Document 87y9xLogprEQwmKEb9Q0n18o

INTRODUCTORY REMARKS David Garrett This session w ill deal with the uses, sources, and identification o f PCB's, their disposal, reclaiming, and their treatment. A ll o f us here on the podium have been required many times to share or contribute to many meetings involving discussions on PCB problems, and we are on a day-to-day basis directly involved w ith these problems. Since discovery and commercialization of these sub stances with such marvelous commercial properties for which there appears to be no universally perfect sub stitute, some 500 m illion pounds have been pumped into our environment. Over this period after some 45 years, considering the PCB's still in service, the quantities de stroyed via incineration, and natural dissipative forces, estimates have been given that some 125 to 135 million pounds are still available fo r biological activities. Our eminent speakers w ill address both the quanti ties and active service life and the quantities still avail able fo r biological activity. GENP 005635 774286 Preceding page blank S3 CHARACTERIZATION OF POLYCHLORINATED BIPHENYLS J. P. Mieure, Ph.D.,* O. Hicks, R. G. Kaley, Ph.D., and V. W. Saeger, Ph.D. A b s tra c t Assessment o f the environm ental im pact o f PCB products cannot be carried o u t w ith o u t a basic under standing o f the physical and chemical properties o f these m ixtures. PCB structure and nomenclature and the approxim ate com position o f A ro clo r products are pre sented. Several physiochem ical properties which a ffe ct the perform ance and environm ental im pact o f current dielectric products are described. 32 2' 3 BIPHENYL CHEMICAL STRUCTUR Polychlorinated biphenyls (PCB's) are made by direct chlorination of biphenyl. The biphenyl molecule has 10 possible sites at which chlorine atoms can be substituted. The numbering system fo r the biphenyl structure is shown in figure 1. By convention, the tw o rings are numbered identically, except the ring w ith the fewest chlorine substituents or substituted in the highest numerical positions is designated as primed. Examples o f nomenclature fo r a tri- and a tetrachlorobiphenyl are included in figre 1. An excellent discussion of PCB nomenclature can be found in a recent te xt by Hutzin* ger, Safe, and Zitko {ref. 1). There are 209 possible chlorobiphenyl isomers dis* tributed as indicated in table 1. However, many of these isomers are not likely to occur at significant levels in commercial PCB mixtures. For example, isomers w ith four or five chlorine atoms on one ring but none on the other ring are not detectable in PCB products. AROCLOR PRODUCTS The major producer o f PCB's in the United States is Monsanto Company, which markets mixtures fo r closed electrical system applications under the Aroclor trade* mark. Aroclor products are identified by a four-digit numbering code in which the first tw o digits, 12, indi cate the parent molecule is biphenyl and the last two digits specify the weight percent o f chlorine. The excep tion is Monsanto's newest product, Aroclor 1016 (41% chlorine), which retained the 1016 designation by which it was known during development. Aroclor products manufactured in the United States are listed in table 2. "Research Group Leader, Monsanto Industrial Chemicals 'ompany, St. Louis, Missouri. Cl Cl Cl 22'r3 ,4 ,-TETRACHLOROBIPHENYL Figure 1. The numbering system for the biphenyl structure. Production of the materials listed as discontinued was terminated in or prior to 1971. AROCLOR COMPOSITION The composition o f the four Aroclor products cur rently marketed in the United States is given in table 3. Aroclor 1221 is prim arily monochlorobiphenyl while Aroclor 1016 and Aroclor 1242 are prim arily trichlorobiphenyls. The major difference between these two products is the lower penta- and hexachlorobiphenyl kJ ' O' 84 774287 AROCLOR 1221 TEMPERATUREC Figure 2. Detailed chromatogram of Aroclor 1221. GENP 005637 Figure 3. Detailed chromatogram of Aroclor 1016. 85 774288 Table 1. 209 possible PCB isomers Degree o f s u b s titu tio n Number o f isomers Mono Di Tri T e tra Penta Hexa Hepta Octa Nona Deca 3 12 24 42 46 42 24 12 3 1 209 Table 2. Aroclor products manufactured in the United States Current D is c o n tin u e d Percent c h lo rin e 1221 1016 1242 1254 1232 1248 1260 1262 1268 21 32 41 42 48 54 . 60 62 68 content o f Aroclor 1016. Aroclor 1254 is prim arily pentachlorobiphenyi. The values in table 3 were calculated from measurements by gas chromatography w ith flame ionization detection after component identification by gas chromatography/mass spectrometry. A ll gas chroma tographic separations were made w ith a high-resolution capillary-column. Average response factors determined fo r each degree of chlorine substitution were applied to all components. 1 ? Detailed chromatograms o f these four products are illustrated in figures 2-5. Specific isomer identifications determined by Webb and McCall (ref. 2) and Sissons and Welti (ref. 31 are listed fo r the major Aroclor 1242 com ponents in figure 4. The complexity of these mixtures was emphasized by amplifying the first and last portions o f the Aroclor 1254 chromatogram in figure 5. Eightyfive components were detected in Aroclor 1254. A .32-mm id x 50-m glass capillary column coated with 0V-101 was used fo r these separations. The flow rate was 2 m l/m in helium and the column temperature was programmed from 150 to 230 C at 2 C/min. High-resolution chromatographic conditions are very useful fo r characterizing PCB products. However, fo r routine m onitoring o f environmental materials, it is more appropriate to use gas chromatography w ith pack ed columns and electron capture detection. Typical chromatograms o f this type fo r Aroclor 1016 and Arod o r 1242 are compared in figure 6. The chromatograms are essentially identical fo r retention times less than 70 relative to p,p'-DDE. However, the higher chlorinated components w ith relative retention times 70 and greater represent a significantly smaller contribution in the A ro clor 1016 chromatogram. These chromatograms illus trate the fe a sib ility-o f distinguishing these unaltered products. However, in environmental materials the char acteristic features o f A ro d o r 1242 are frequently obscured by interfering compounds or by component alteration so the distinction is. less clear or sometimes entirely lacking. These separations were carried out on a 6 f t x 4-mm id glass column packed w ith 3 percent SE-30 on 80/100 mesh Chromosorb W-HP at 190 C. PHYSICOCHEMICAL DIFFERENCES The physical and chemical properties of PCB isom ers and commercial mixtures vary greatly depending o n . the degree and position of chlorine substitution. The effect o f chlorine content on several physicochemical properties is summarized in table 4. Three of these prop erties, volatility, water solubility, and biodegradability, are very relevant to the environmental occurrence of PCB's. V o la tility and water solubility represent potential mechanisms fo r introduction into and transport w ithin the ecosystem.* Biodegradation represents a mechanism fo r removing PCB's from the environment. Illustrations o f the relative significance o f these properties fo r d iffer ent PC8 isomers are evident from the following three examples. Relative volatilities fo r the P f B components in Arod o r 1016 are indicated in figure 7 by comparing chro matograms o f liquid and vapor composition. The higher 86 GBNP 005638 774289 Table 3. Typical percent composition of Aroclor products Homolog # Cl/biphenyl 0 1 2 3 4 5 6 7 8 A ro c lo r 1221 n 51 32 4 2 0 .5 NDa ND NO A ro c lo r 1016 0.1 1 20 57 21 1 0.1 ND ND A ro c lo r 1242 0.1 1 16 49 25 8 1 0.1 ND A ro c lo r 1254 0.1 0.1 0 .5 1 21 48 23 6 ND aND = none d e te c te d , 0.01 p e rc e n t. Table 4. Physiochemical properties for PCB products Property Percent chlorine 21 42 54 Density (g /m l) 1.19 D is t illa t io n range <c) 275-320 F ire point (C) 176 Vaporization ra te (mg/cm2/ h r @100 0 C) 1 .7 4 Water s o lu b ility (ppm) > .2 B iodegradability3 81 1.39 1.50 325-366 None 365-390 None .338 .2 26 .053 .04 15 aPercent d e g ra d a tion/48 hr cycle w ith semicontinuous a c tiv a te d sludge. 774290 87 GENF 005639 1 5 0 174 198 222 230 TEMPERATURE C Figure 4. Detailed chromatogram and isomer identificaton-Aroclor 1242. AROCLOR 1254 Figure 5. Detailed chromatogram of Aroclor 1254. 88 774291 Figure 6. Comparison of electron capture chromatograms of Aroclor 1016 and Aroclor 1242. 89 774292 GENP 005641 Time (Min) Figure 7. Relative volatilities for PCB components in Aroclor 1016. numbered components make successively less contribution to the total vapor composition. Water solubility of Aroclor 1016 components is illustrated in similar fashion in figure 8. Water saturated w ith Aroclor 1016 was extracted w ith hexane and the extract compared chromatographically to an Aroclor 1016 standard. The numbers above significant peaks ex press the percentage contribution of that peak area to the total area. Earlier eluting, lower chlorinated compo nents are more soluble and contribute more to the water saturated composition, A related study has shown that PCB's leaching from Aroclor 1016 impregnated soils after the equivalent of 40 years annual rainfall consist of lower chlorinated biphenyls {ref. 4) (figure 9). Microbial degradation also affects PCB isomers to different degrees. For example, figure 10 shows chro matograms depicting Aroclor 1016 composition after ex posure to a naturally occurring mixed microbial popula tion for 1/2 hour (above) and 14 days (below). The number above each GC peak indicates the percent biode gradation for that component. These percentages range from 17 to > 9 8 and in general are higher fo r lower chlorobiphenyls. The exposure was carried o ut w ith acti vated sludge from a domestic sewage treatment facility. The sludge was previously acclimated to a mixture of industrial organic compounds before addition o f 3 ppm Aroclor 1016. PCB composition was determined by ex tracting a representative aliquot of mixed liquor with hexane followed by analysis by gas chromatography using a glass capillary column and electron capture de tection. It is apparent from these examples that introduction of PCB's into .the ecosystem by volatility or water solu b ility would enhance the ratio o f lower to higher chlori nated biphenyls in the environment. PCB removal from the environment by either o f these mechanisms or by microbial degradation would reduce this ratio. These and related factors combine to make assessment o f PCB envi ronmental impact a very complex problem. In view of the recognized complexity in studying commercial PCB mixtures, it would seem expedient to substitute fo r the m ixture a single isomer product having o o 90 ON 774293 AROCLOR 1016 22.6 18.4 10.1 STANDARD 6.7 Figure 8. Water solubility of Aroclor 1016 components. GENP 005643 91 774294 J o % Figure 9. Composition of PCB's leaching from Aroclor 1016 impregnated soil. 92 774295 SEMI-CONTINUOUS ACTIVATED SLUDGE TIME {MIN) Figure 10. Aroclor 1016 biodegradation. the desired electrical and physical properties. The envi ronmental properties o f this isomer would be much simpler to characterize and control. However, no such PCS isomer exists. Most PCS isomers are solid crystalline materials when isolated at 25 C. Commercial products are liquids only because o f the mutual melting point depression exerted by the PCB components o f the m ix ture. CONCLUSIONS Commercial PCB products are mixtures of many d if ferent isomers w ith varying chlorine content. The prop erties of these isomers, and hence the products, are vast ly different and are complex to study. The environmen tal impact fo r each product must be accurately assessed and compared to the functional benefit. REFERENCES 1. 0 . Hutzinger, S. Safe, and V. Z itko, 'T h e Chemistry o f PCBV ' CRC Press, Cleveland, 1974. 2. R. G. Webb and A. C. McCall, J. Assoc. O fftc. Anal. Chem., Vol. 55 (1972), p. 746. 3. D. Sissons and D. Welti, J. Chromatog., Vol. 60 (L971J, p. 15. 4. E. S. Tucker, W. J. Litschgi, and W. M. Mees, Bull. Environ. Contain. Toxicol., Vol. 13 (1975), p. 86. 93 774296 GENP 005645 OVERVIEW OF ANALYTICAL IDENTIFICATION AND SPECTROSCOPIC PROPERTIES Stephen Safe, Ph.D.* A b s tra c t The analytical problems associated w ith PCB analy sis involve many factors including sampling techniques, extraction and cleanup procedures, quantitation o f PCB, confirm ation o f structure, and ide n tifica tio n o f metab olites and im purities. Recent studies in these areas o f PCB analysis w ill be discussed and examples given. Polychlorinated biphenyls (PCB) are among the most persistent and widespread environmental pollut ants. Commercial PCB formulations can consist o f up to 100 different chloro biphenyl isomers and this is a com plicating factor in the conventional gas chromatographic analysis o f environmental samples. The chemical stabili ty of PCB does, however, facilitate their analysis in that a variety of cleanup procedures can be used to remove coextractive material w ithout modification of the PCB. The determination o f PCB has been described in'detail (ref. 1) and therefore most o f the data and results re ported herein w ill be associated w ith more recent publi cations. The analytical problems associated w ith PCB analy sis can be summarized under six major headings, which w ill be discussed in detail: 1. Sampling methods, 2. Extraction o f PCB from environmental samples, 3. Cleanup procedures, 4. Quantitation o f PCB levels, 5. Confirmation of structure, and 6. Identification of toxic impurities and metabo lites. 1. Sampling Methods PCB analysis is primarily concerned w ith determina tion o f the pollutant concentrations in biological, sedi ment (or solid), water, and air samples. Specific sampling methods are required. a. Biological samples and sediments. The sampling must insure that sufficient material is collected and ex tracted so that the analytical data obtained are repre sentative of the sample. b. Water samples. The sampling o f water is compli cated by the need to distinguish between dissolved PCB, which are usually low, and PCB adsorbed on particulate Guelph Waterloo Centre for Graduate Work in Chemistry, Department of Chemistry, University o f Guelph, Guelph, Ontar io, Canada. matter. The separation o f the two fractions can usually be obtained using suitable filtratio n or centrifugation techniques (ref. 1). c. A ir samples. A ir samples are usually obtained by passage of a known volume o f air through an impinger or a similar device in which a suitable solvent prefer entially extracts or removes airborne PCB (refs. 2,3). 2. E xtraction o f PCB from Environm ental Samples a. Biological samples. A number o f methods have been described fo r the semiquantitative extraction of PCB from biological samples (e.g., > 90 percent recov ery) (ref. 1). The sample can be macerated then freezedried, or dehydrated and extracted directly or by the soxhlet technique using an appropriate solvent. The choice o f solvents can vary from nonpolar hexane or pentane to the more polar chloroform, acetone, or meth anol. The more polar water-soluble solvents are useful in the extraction o f w et tissue; however, the polar aqueous extracts are usually diluted w ith water and extracted w ith hexane to preferentially remove the nonpolar chlo rinated aromatics. This partitioning technique is also u ti lized as a cleanup procedure to remove polar coextrac tives. b. Sediments. Sediments and other solid samples are usually extracted w ith more polar solvents and u lti mately the PCB are partitioned as described above (ref. 1) . c. Water. The simplest approach w ith water is by direct extraction w ith hexane. The removal o f PCB from water has also been effected using polyurethane-foam plugs and resins (refs. 4-6). Using this technique, th e' water is passed through a column containing the solid support and the PCB are adsorbed on these supports. Subsequent passage of a polar organic solvent through the columns removes the adsorbed organics, which can be further cleaned up using the partitioning technique. d. A ir. PCB are readily extracted from air by pas sage o f the air through sintered glass funnels or suitably contracted glass impingers filled w ith solvents (e.g,, amyl acetate, sec-butanol or ethylene glycol) (refs. 2,3). The PCB can then be isolated by the standard partitioning technique. 3. Cleanup Procedures The major aim of a cleanup procedure is to selec tively remove coextractive natural material and xenobiotics from an extract containing PCB. Solvent parti tioning has already been discussed and is an excellent 94 774297 method fo r removing water-soluble and highly polar co extractive organics. The two additional important clean up techniques are methods 'based on column or thinlayer chromatography and chemical treatment of the extract to m odify either the PGB or the coextractives. a. Chromatographic methods. Most chromato graphic procedures include column chromatography on activated florisil and/or alumina using hexane to elute the PCB (refs. 7,8)* Thin-layer chromatography w ith si licic add and alumina can also be used. An example o f a typical chromatographic cleanup procedure is outlined in figure 1, b. Chemical methods. Since PCB are thermally and chemically stable, it is possible to saponify extracts by both acidic and basic treatment w ithout altering the PCB. This procedure is particularly useful in the inver sion o f lipid esters, which have chromatographic proper ties similar to PCB, into more polar products. One o f the major problems in PCB cleanup is to remove ODE, which has similar chromatographic properties to PCB. A J*v recent paper describes an oxidative technique which quantitatively converts DDT, DDE, and their analogs into more polar products (ref. 9). Dehydrochlorination w ith mild base converts DDT and DDT-like compounds into die corresponding bisdiarylethylenes (e.g., DDE); treatment o f the olefin w ith chromic acid gives the cor responding benzophenones, which are readily separated from PCB. The PCB are not affected by this chemical modification procedure. Raney nickel reduction and sul furic acid treatment o f crude PCB extracts are also use ful in the cleanup o f river water extracts (ref. 10). The analysis of PCB is always complicated by the large number of isomeric chlorobiphenyls that are pre sent and this results in a complicated gas chromatogram even after cleanup (figure 2). In addition, polychlorinat ed terphenyls (PCT) and polychlorinated naphthalenes (PCN) are also industrial environmental pollutants which are composed o f several isomeric components that can co-occur w ith PC8. A perchlorination procedure was re ported in which the isomeric mixtures can be converted into their respective perchloro derivatives (refs. 11,12), as shown in figure 3. These compounds can then be readily analyzed and quantitated by conventional gas chromatography (figure 2). The comparative (ps chro matographic retention times of several perchlorinated pollutants are; decachlorobiphenyl, 1.0; octachlorodibenzofuran, 2.55; octachlorodibenzo-p-dioxin, 2.60; dodecachloro-DDE, several peaks > 1.9; tetradecachloro-o-terphenyl, 11.9; tetradecachloro-ro-terphenyl, 19.2; tetradecachloro-p-terphenyl, 22.2. It should be noted that this procedure is markedly dependent on the purity and source o f the commercial antimony pentachloride reagent and the composition or degree o f chlorination o f the PCB. A drawback o f this Generl Cleanup Procedure ( s u ita b le f o r most a i r , w a te r b io lo g ic a l and sedim ent a n aly s es ) Crude E x tra c t I solvent p a rtitio n I (hexane: p o lar so lven t) R a tio n a le p o la r imputi tie s remain in p o la r s o lv e n t hexane e x tra c t I chromatography on a c tiv a te d alunna Removal o f nonpolar l i p i d s , im p u r itie s , and some c h l o r i nated p o llu ta n ts p u r if ie d PCB chromatography on activated s ilic a gel 4 p u r if ie d PC8 Removal o f nonpolar l i p id s and s e p a ra tio n o f PCB from DDT and i t s m e ta b o lite s Figure 1. General cleanup procedure. 95 774298 GENP 005647 "d ' O O O P* CO 96 774299 technique is the reported formation of varying quantities of a sideproduct which has been identified as bromo nonachlorobiphenyl (refs. 13,14). This introduces a second peak which is observed in the gas chromatogram and this side reaction can also reduce the overall yield of the decachlorobiphenyl product. 4. Q uantitation o f PC8 Gas chromatography is the method o f choice for PCB analysis and electron-capture detection is by far the most sensitive procedure for-detecting these chlorinated aromatic compounds (ref. 1). A comparison o f the rela tive molar responses of electron-capture and flameionization detector to some isomeric chlorobiphenyls is given in table 1. It is evident that the electron capture detector is the more sensitive and that the relative molar response is both a function of the degree of chlorination and the.position of the substituent (refs. 15,16). Since the precise composition o f PCB mixtures, is not known, the quantitation of the complex chromatograms can only be an estimated value. A more consistently accurate method would involve perchlorination since the relative molar response and chromatographic properties of deca chlorobiphenyl are known. Quantitation of the PCB mixtures is usually obtained by measuring the total peak heights or areas o f key diagnostic peaks that are present in the environmental PCB extract and comparing this result w ith the heights or areas obtained in the gas chro matogram of the appropriate commercial PCB mixture (e.g., Aroclor 1254, Clophen A*60). An example is shown in figure 4, in which the chromatograms of Clophen A-60 and river water extracts are compared and the quantitation is carried out using three diagnostic peaks present in the environmental and commercial PCB sample (ref. 10). 5. C onfirm ation o f Structure PCB in the environment was originally detected by gas chromatography and later confirmed by mass spec trometry and this technique is the most sensitive and Table 1. Relative molar responses of electroncapture and flame-ionization detectors to some chlorobiphenyls C h io ro b ip h e n y l R e la tiv e molar response E le c tro n Flame capture io n iza tio n 2342 ,2 '-di 2 ,4 '-di 2,6 -d i 3 ,3 '-d i 3 ,4 -d i 4 ,4 '-di 2 ,4 ,4 '-tri 2 ,2 ',4 ,4 '-te tra 2 ,2 ',6 ,6 '-te tra 3 ,3 ',4 ,4 '-te tra 3 ,3 ',5 ,5 '-te tra 2 ,3 ,4 ,5 -te tra 2 ,3 ,5 ,6 -tetra 2 ,2 ',4 ,4 * ,6,6 '-h e x a a . S M ^ ' . S . S ' -hexa 2 ,2 , , 3 , 3 \ 4 , 4 , ,6 ,6 ` -octa 2 ,2 ' ,3,3* .5 .5 ' ,6 ,6 '-acta deca 1.00 0.20 1.10 5.15 17.7 32.0 6.10 15.2 5.97 135 106 20.6 396 320 367 259 347 726 1180 1150 1410 1.00 0 .9 2 0.87 0.99 0.86 0.91 0 .9 4 0.86 0.81 0 .7 8 0.87 0.90 0.87 0.85 0.87 0.71 97 ??430Q GENP 005649 Quantitation of PCB 1 . The method of choice is gas chromatography (GC) using an electron capture (EC) detector. The major problem is selecting suitable standard peaks to use as quantitative standards for comparison with the commercial PCB standard samples. CUOPHEN A -6 0 6.5nq O$% ' 0 GOTA RIVER SAMPLE 19 15 Figure 4. Gas chromatographic analysis w ith electron capture detector. The injected volume of river water extract corresponds to 1.6 liters water. widely used spectroscopic method fo r the confirmation b. Mass fragmentography GC-MS (ref. 18). The o f PCB. The mass spectrometry o f isomeric chlorobi- mass spectrum o f a sample is obtained by scanning tne phenyls and the applications o f this technique in envi entire mass range in order to record all*the ions that are ronmental analysis has been reviewed (ref. 17) and only generated. If a mass range of 400 is scanned in a period recent applications of this analytical technique w ill be of 4 seconds, then the mass spectrum is held for only mentioned. 1/100th o f a second at each mass unit; fo r the remaining a. Gas c h ro m a to g ra p h y --mass spectrometry 3.99 seconds the ion current at that mass value is lost. (GC-MS). Gas chromatographic analysis o f PCB can be Mass fragmentography is a technique which simultane carried out by combination GC-MS so that the mass ously monitors the ion current at one or more mass spectrum o f the individual peaks which elute from the values fo r the complete duration o f the sample spectrum gas chromatograph can be recorded. This technique in (i.e., fo r 4 seconds rather than 0.01 second). The mass combination w ith a computer has been extensively used values which are monitored are the most intense and in environmental analysis fo r both the detection and diagnostic ions generated by a compound. For PCB this confirmation o f environmental PCB, related metabolites, is usually the isotopic molecular ion species or the iso and toxic impurities (refs. 1,17). A GC-MS of an envi topic M-CI3 ions. The sensitivity o f a GC-MS instrument ronmental sample may generate hundreds o f spectra; operating in the mass fragmentography mode can surpass however, using the computer the analyst can recall indi that o f an electron capture detector. An example of this vidual spectra as well as conduct limited mass searches technique is shown in figure 5, in which the mass frag- on key diagnostic ions. mentograms of standard Clophen A-60 and river water CLOPHEN A - 0 lOng aa ! 324 GENP 005651 Figure 5. Mass fragmentograms of PCB Standards and river water extracts. 99 774302 extracts are compared (ref. 19). The diagnostic ions 6. Identification o f Toxic im p urities and PCB Metabo which were used are the isotopic hexachlorobiphenyl lite s (m/e 362, 360, and 358), pentachlorobiphenyl (m/e Analysis of commerciajl PCB preparations showed 328, 326, and 324), and tetrachiorobiphenyl (m/e 294, that higher chlorinated naphthalene isomers were pre 292, and 290) molecular ions. sent as trace impurities and their structures were con c, High-resolution photoplate mass spectrometry. firmed by mass spectromejtry (ref. 22). More recently The relatively large mass deficiencies of both chlorine the highly toxic chlorinated dibenzofurans have also isotopes cause the exact masses o f ions which contain been identified in commercial preparations; the flow chlorine to be usually less*than ions o f the same nominal chart in figure 6 outlines jchromatographic procedures mass that contain only isotopes o f C, H, N, and 0 (see fo r the isolation o f these components (ref. 23). table 2). Thus,, a typical lipid coextractive would appear The metabolism o f PCB in diverse animal and micro at mass positive integer values whereas the molecular ion bial systems has been investigated and the results indi fo r a te tra ch io ro b ip h e n yl isomer (accurate mass cate the conversion o f these substrates into a range o f 289.9224) appears at 776 millimass units below the inte hydroxylated metabolites (ref. 24). Figure 7 summarizes ger value. Mass negative PCB ions are therefore readily a composite scheme fo r the separation and identification distinguished from mass positive ions which occur at the o f PCB metabolites and it should be noted that all the same nominal mass by high-resolution techniques. A steps are used in the cleanup procedure only when it is photographic plate can be used as an integrating ion necessary. Recent data from seal extracts has confirmed detector and the subsequent identification of the PCB the presence o f hydroxylated PCB in their fa tty tissue on the plates is readily carried out. This technique has (ref. 25). These metabolite: are therefore a new class o f been used in the detection o f PCB in biological samples chlorinated aromatic pollutants derived from PCB. as well as confirming the presence o f hydroxylated PCB The financial support o f Environment Canada is metabolites (refs. 20,21). gratefully acknowledged. Table 2. Confirmation of PCB by high-resolution phosphate MS B asic p r in c ip le s : X e n o b io tic s c o n ta in in g mass d e f i c i e n t atoms ( e . g . f Cl ) appear a t low er mass values than most " n a tu ra l c o e x tr a c tiv e s " ; these d iffe r e n c e s can be measured using the above technique. Atom o r compound A c c u rate mass D e v ia tio n from in te g e r value (in m illim ass u n its ) 12c 14n 160 35C1 3*C1 Lipid coextractive 12.000 1.0078 14.0031 15.9949 34.9688 36.9659 v a ria b le - +78 +31 -51 -312 -341 100 KC-400 la hexaoa loludoa i F lo r i s t l Coluam PCI l(adisscluaircde) A Cl-DBF la sluice S / A lta(tIOn aRIEMSic, ro19C7o1alu) sa /\ PCS(dlaiscaalurda)cs 1 Cl-DBF la eluace 2 Figure 6. Procedure for separation of chlorinated dibenzofurans from chlorinated biphenyls in KC-400. Laboratory experiments show that PCB isomers are metabolized to hydroxylaced PCB which can be isolated and Identified as indicated. rine Sample Rationale Strang acid hydrolysis and ether .extraction Hydrolysis of glucuronldes Ethereal Extract further cleanup via base extraction of phenols ,,(optional) Separation of phenolic from ocher coextractives Crude Hydroxy PCS TIC, then extraction of "Hydroxy Sand" ] "Hydroxy Band" I formation of acetate | or oechoxy derivative I then TLC, and | ..hydrolysis (optional) i l_________ Purified Hydroxy P C S Structures proven by M.S. and iJMR spectra and by synthesis^*^ ______ Figure 7. A composite scheme for the separation and identification of PCB metabolites. 101 774304 uiiNP 005653 REFERENCES 1. O. Hutzinger, S. Safe, and V. Z itko, The Chemistry o f PCB's, CRC Press, Cleveland, Ohio, 1974, pp. 2. J1.97D-2. 2T0e.ssari and D, L. Spencer, J. Assoc. O ffic. Anal. Chem., Vol. 54 (1971), p. 1376. 3. D. C. Staiff, G. E. Quinby, D. L. Spencer, and H. G. Starr, B ull. Environ. Contam. Toxicol., Vol. 12 (1974) , p. 455. 4. H, D, Gessar, A . Chow, F. C. Davis, J. F. Uthe, and J. Reinke, Anal. Letters, Vol. 4 (1971), p. 883. 5. J. W. Bedford, B ull. Environ. Contam. T oxicol., Vol. 12 (1975), p.622. 6. G. Sundstrom, 0 . Hutzinger, S. Safe, and D. Jones, Proc. Toxicology Symposium, Wageninger, Nether lands, 1975. 7. A. V. Holden and K. Marsden, J. Chrom ., Vol. 44 (1969), p.481. 8. J. A. Armour and J. A. Burke, J. Assoc. O ffic. Anal. Chem., Vol. 53 (1970), p. 781. 9. W. J. Trotter, J. Assoc. O ffic. Anal. Chem., Vol. 58 (1975) , p. 461. 10. M. A h n o ff and B. Josefsson, Bull. Environ. Contam. Toxicol., Vol. 13 (1975), p. 159. 11. O. W. Berg, P. L. Diosady, and G. A . V. Rees, flu//. Environ. Contam. Toxicol., Vol. 7 (1970), p. 538. 12. O. Hutzinger, S- Safe,.and V. Z itko,./. Assoc. O ffic. Anal. Chem., (in press). 13. W. J. Trotter and S. J. V. Young, J. Assoc. O ffic. Anal. Chem., Vol. 58 (1975!, p. 466. 14. J. N. Huckins, J. E. Swanson, and D. L. Stallings, J. Assoc. O ffic. Anal. Chem., Vol. 57 (1974), p. 416. 15. A . S. Y. Chau and R. C. J. Sampson, Environ. Letters, Vol. 8 (1975), p. 8l, 16. B. Bush, F. Baker, R. DelTjacqua, C. L. Houck and F-C. Lo, J. Chrom., Vol. 109 (1975), p. 287. 17. S. Safe and O. Hutzinger, Mass Spectrom etry o f Pes ticides and Pollutants, CRC Press, Cleveland, Ohio, 1973. 18. E. J. Bonelli, P. A . Taylor, and W. J. Morris, Am eri- can Laboratory, July 29,1975. 19. M. A h no ff and B. Josefsson, Anal. Letters, Vol. 6 (1973), p.1083. 20. S. Safe, N. Platonow, 0 . Hutzinger, and W. D. Jamieson, Biomed. Mass Specfrom ., Vol. 2 (1975), p. 201. [ 21. 0 . Hutzinger, W. D. Jamieson, S. Safe, L. Paulmann, and R. Ammon, Nature, Vo|l. 252 (1974), p. 698. 22. J. G. Vos, J. H. Koeman, H. L. vander Maas, M. C. tenNoever de Brauw and R..H. deVos, Food Cos- met. Toxicol., Vol. 8 (1970 , p. 625. 23. J. A. G. Roach and I. H. Pomerantz, B ull. Environ. Contam. Toxicol., Vol. 12 1974), p. 338. 24. S. Safe, O. Hutzinger, and |D. Jones, J. Agric. Food Chem., Vol. 23 (1975), p. 851 and references cited. 25. B. Jansson, S. Jensen, M. Otsson, L. Renberg, G. Sundstrom, and R. Vaz, A m bio., V ol. 4 (1975), p. 93. GENP 005654 102 774305 PRODUCTION AND USAGE OF PCB's IN THE UN ITE D STATES Robert L. Durfee, Ph.D.* A b s tra c t A b ou t 99 percent o f the PCB's used in U.S. industry are produced by Monsanto in a single fa c ility a t Saget, HUnois, These materials, termed A rodors, are used in the production o f capacitors (70 percent) and transformers f30 percent). Im ported PCB's, comprising sligh tly over 1 percent o f U.S. usage, are used in investm ent casting operations (80 to 90 percent; decachtorobiphenyi) and semiciosed heat transfer applications (10 to 20 percent). Capacitor and transform er production processes are sim ilar in th at process steps involving PCB's include fib tration, flo od o r individual fillin g o f the products, and removal o f excess PCB's p rio r to sealing and individual testing o f the products. M ost losses occur from pump leaks to cooling water, spills, personaI hygiene practice, and the like. Many o f the discharges containing PCB's are to m unicipal sewers. In tro d u c tio n Polychlorinated biphenyls (PCB's) represent a class of compounds produced commercially by the chlorina tion of biphenyl. Most PCB's currently used ,in the United States are mixtures of chlorobiphenyls contain ing up to seven chlorine atoms per molecule, although some decachlorobiphenyl (10 chlorines per molecule) is imported. The production and the types of uses for PCB's increased steadily from initiation of production in 1929 until industry-imposed restrictions in 1971 cur tailed production and essentially eliminated use of domestic production in all but "closed** electrical equip ment (specifically, capacitors and transformers). PCB's have been increasingly identified as a signifi cant environmental pollutant. In our work fo r the Office of Toxic Substances, Versar is studying the economics and other aspects of possible regulatory alternatives as applied to PCB's. We are also studying treatment meth ods which might be applied to control of waterborne PCB's in industrial effluents. The purpose of this paper is to define current PCB production and use, including process technology and sources of wastes containing PCB's. Domestic Production and Im ports Monsanto, the sole domestic manufacturer of PCB's, ` Vice President, Versar, Inc., Springfield, Virginia. manufactures this chemical in its Sauget, Illinois, plant. The basic raw material is biphenyl, which is manufac tured from pure benzene in another Monsanto plant. The PCB manufacturing operation is conducted in two steps. .First biphenyl is chlorinated w ith anhydrous chlorine in presence of ferric chloride to produce crude PCB's and then the crude PCB's are distilled to obtain the finished product. A schematic flow diagram o f this process is given in figures 1 and 2. Monsanto currently produces Arodors 1221, 1016, 1242, and 1254 (chlorine contents approximately 21, 41, 42, and 54 percent by weight, respectively). For the production of a given product, biphenyl and catalyst are heated to melting and chlorine gas is introduced while the charge is circulated w ith a pump. The time of chlo rine contact controls the degree of product chlorination. Vapors from the chlorination (HC1) are scrubbed and removed to another part o f the plant. The crude product is held at temperature and blown w ith dry air for several hours, and then is sent to storage where a small amount o f lime is added to remove .remaining HCI or ferric chloride. The blown air is scrubbed and vented to the atmosphere through a demister. Purification, as typified by figure 2, varies some what between the different products. The 1016 material is processed in a retort and a vacuum distillation (steam jet ejection) to remove the more highly chlorinated compounds. The first cut from the tower is recycled to the retort. When a preset overhead temperature is reached, the product is removed and sent to storage and shipment. The other Aroclors are vacuum distilled (steam jet ejectors), the product being the condensate. The still bottoms (called Mantars) are incinerated. Monsanto's production in 1974 was 40,466,000 lb, o f w h ic h 34,406,000 was sold domestically and ' 5,395,000 lb exported. Production has been about at the 40-mill ion-pound level since 1971, and reached a high of 85 m illion pounds in 1970, Company expectations are for a sizeable increase in sales in 1976, followed by small, steady growth. Imports in 1973 and 1974 amounted to 1.2 to 1.5 percent of Monsanto's domestic sales in those years. Importation appears to be steady or slightly increasing. The major source of imported PCB's is Italy, from which decachlorobiphenyl made by Caffaro is imported by one company for use in investment casting waxes. This constitutes 80 to 90 percent of the imports; the other 10 to 20 percent originates in France (Pradelec) and is used GENP 005655 103 774306 959500 N 3 0 * t 774307 Figure 1. Preparation of crude chlorinated biphenyls Monsanto Krummrich plant. 2 STEAU H ,0 VAPOR cH iO 1 STEAU JET RAW AROCLOR GAS FIRED RETORT BOTTOMS VACUUM DISTILLATION OVERHEAD | CI- I T HCI TO PURIFICATION A IR T O H iO (CASCADE REACTORS) SCRUBBER ^ALKALI ~CHLORINATION----SECTION STORAGE 4- SHELL & TUBE CONDENSER I NONCONTACT COOLING WATER STILL (VACUUM) EJECTOTS H ,0 CONDENSATE AR0CL0R 1016 ` STEAM HaO VAPOR 3 ___ L T AIR STEAM JET EJECTORS . H jO CONDENSER CONGENSATE - AROCLOR 1254 DETAILS SAME AS ABOVE MONTARSTO INCINERATION ' Figure 2. Distillation of crude products Monsanto Krummrich plant. VAPOR FROM JET EJECTORS ------------------------------EXHAUSTS FROM THE SCRUBBER------------------------SURFACE AREA EVAPORATION (IN GENERAL)----- * AIR CONDENSATE FROM STEAM EJECTORS NONCONTACT COOLING WATER---------SCRUBBER LIQUOR--------------------------- TO SEWERS MONTARS---------------------------------------BOTTOMS FROM SEPARATOR SUMP -- COLLECTION FROM ALL DRIP PANS INCINERATION RAPS FOR CLEANING ---------FLOOR DRY-------------------------SPENT FILTER PAPERS & ` FULLERS EARTH------------------ LANDFILL Figure 3. Nonproduct PCB discharges at Monsanto's Krummrich plant. in semclosed heat transfer applications. U ntil recently PCB's were used in some U.S. built mining machines, but this use has been discontinued. In the Monsanto process, PCB's can be released to the environment through the sources listed on figure 3. Waterborne discharges of PCB's at this plant have been reduced greatly over the past few years, and are now below 1 pound per day, according to Monsanto. Capacitor and Transformer Production Producers of capacitors and transformers utilize essentially all of Mqnsanto's domestic sales of PCB's. About 70 percent of the usage is in capacitor produc tion, and, of this total, roughly half is for small capaci tors and half for large capacitors. Lists and locations of capacitor and transformer producers are presented in tables 1 and 2, respectively. Transformers containing PCB's comprise only about 5 percent of the U.S. transformer market, and are used only where safety and reliability are of prime impor tance. On the other hand, about 95 percent o f capacitors made in the United States utilize PCB's. According to General Electric, about 100 X 106 capacitors containing PC8's are made in the United States yearly, most for first-time use in products. Life expectancy fo r capacitors is over 10 years fo r lighting applications and over 20 years in electric u tility service. Life expectancy o f trans formers containing PCB's is over 30 years, and some 135,000 have been put into service since 1932 (virtually all are still in service). The steps involving PCB's used in the manufacture o f capacitors and transformers include filtration of PCB's, filling (under vacuum), removal of excess PCB's, sealing of units, and heat and electrical testing. Sources of nohproduct discharges of PCB's are roughly similar for capacitor and transformer production plants, and are listed in table 3. Most Of the in-plant PCB wastes which reach water ' streams originate in the filling area. A brief description of the various filling processes is presented below. Small capacitor bodies, each containing a machine- 105 774308 r n r A A Ikl'nn Table 1. U.S. transformer manufacturing industry using PCB's Company name Westinghouse Genera] E le c tr ic Company R e s e a rc h -C o ttre ll Niagara Transformer Carp. Standard Transformar Co. Helena Corp. Hevi-Duty E le c tric Kuhlman E le c tr ic Co. E le c tro Engineering Works R.E. U p te g ra ff Mfg. Co. H.K. P o rte r Van Tran E le c tr ic Co. Esco M anufacturing Co. Location o f the pla n t South Boston, Va. Sharon, Pa. Rome, Ga. P i t t s f ie l d , Mass. Flndem e, N .J. B u ffa lo , N.Y. Warren, Ohio Medford, Oreg. Helena, A la. Goldsboro, N.C. C rystal Springs, Miss. San Leandro, C a lif. S co ttsd a le , Pa. Belmont. C a lif. Lynchburg, Va. V andalla, 111. Waco, Tex. G re e n v ille , Tex. s 2 Table 2. U.S. capacitor manufacturing industry using PCB's Company name ( I n o rd e r o f PCB's usage) Location o f the p la n t General E le c tr ic Company Hudson F a lls , N.Y. F t. Edward, N.Y. Aerovox - New Bedford, Mass. Universal Manufacturing Corp. B rid g e p o rt, Conn. Totowa, N .J. Westinghouse E le c tr ic Corp. Bloomington, Ind. Cornell O u b llie r New Bedford, Mass. P.R. M a llo ry & Co., In c. Waynesboro, Tenn. Sangamo E le c tr ic Co. Pickens, S.C. Sprague E le c tr ic Co. North Adams, Mass. E le c tric U t i l i t y Co. L a S a lle , 111. Capacitor S p e c ia lis ts , Inc. Escondido, C a lif. JARO Corp. Bennington, Vt. York E le ctro n ics Brooklyn, N .Y . HcGraw-Edison Greenwood, S.C. RF In te ro n ic s Bayshore, L . I . , N.Y. Axel E le c tro n ic , Inc. Jamaica, N.Y. Tooe Deutschmann Labs. Canton, Mass. Ci.n^-O.rome Lab, In c . Palo A lto . C a lif . C P 106 ? ?4 Table 3. Sources o f nonproduct discharges o f PCB's Source Vacuum pumps Evaporation and ventilation Transfer spillage Vacuum pump cooling water or condensate (steam jet) Personal hygiene Reject products Floor and equipment cleanup wastes Drip pan collection Filter media Type of effluent/ typical disposal A ir A ir -Water Water Water (Muridpai Sewer) Landfill Landfill Incineration Landfill wrapped helix o f alternating paper and aluminum fo il, are placed in a chamber, the chamber is evacuated, and prefiltered dielectric oil is introduced until it covers the capacitors. The vacuum assures that the paper w ill be well soaked (impregnated) w ith the fluid. A fte r the fillin g operation the vacuum is released, excess fluid is removed to a holding tank, and the capaci tors are sealed and then deoiled. Then they undergo heating electric tests and, if specifications are met, are packaged. Reject capacitors and, in many cases, solid wastes containing PCB's are landfilled. Large capacitors are produced similarly, although some differences can be observed: 1. Large capacitors (over 2 to 3 lb o f PCB's) are typically filled through a small fill hole, while the fill tank is under vacuum. Large capacitors may be filled separately or flood-filled in a chamber. Some plants use a multicell "carou sel" arangement where loading and unloading occurs at one station, and the capacitor(s) in each cell are progressively dried, evacuated, filled, and the fluid drained from the cell at stations along the carousel. 2. Following the fillin g operation, the fill holes in the large capacitors are sealed or plugged with solderj deoiled, and then tested prior to packag ing and shipment. Transformer fillin g is very similar to the filling of the larger capacitors, but transformers are all filled individually. Individual fillin g appears to generate less waste PCB's from spills, drip, and deoiling operations. If a transformer does not meet test specifications, the fluid is drained, filtered, and returned to the supply tank, and the windings assembly and other parts are inspected to identify the cause. Once repaired, the transformer reenters the assembly line. Investment Casting Process Imported decachlorobiphenyl (deka) is used as a fille r fo r investment casting waxes; the estimated yearly usage is about 400,000 lb, some o f which is in exported waxes. In investment casting, a pattern is made o f the wax and a ceramic mold is formed on the wax. The wax Is melted out, and the mold, after baking out in a furnace, is ready fo r use. The wax used to form the pattern contains about 60 percent used wax and 40 per cent virgin pattern wax. Significant losses of PCB's to the atmosphere can occur in the melting out process and in the furnace. Used wax can possibly be reclaimed, but most appears to be landfilled. Polychlorinated triphenyls are also used as pattern wax fillers. GENP 005659 107 774310 PCB DISPOSAL, RECLAIM ING, AND TREA TM EN T Thomas E. Kopp* A b s tra c t The Environm ental Protection Agency in 1975 sought inform ation about the uses, disposal, and effects o f PCBs from 84 purchasers and im porters o f PCB's. Responses indicate th a t while PCB's were fo rm e rly dis posed o f in lan dfills, high-temperature incineration is now prevalent There is no proven technology fo r re m oval o f PCB's from water, and emphasis is on prevent ing production-line PCBs from entering waste water. EPA is presently form ulating criteria fo r am bient PCB levels in water and is developing a new toxic e fflue nt standard. On' August 16, 1975, the Office of Enforcement, EPA, sent out 84 letters (figure 1) to companies in the United States that purchase PCB's from Monsanto, to those that im port them, and to others that may be users. This letter has been modified to include polychlorinated terphenyls, PCT's, both because of their similar structure and because they are a type of chemical that we will have evaluated in the whole program of PCB's. This letter concluded w ith four pages of questions which covered the uses, importation, reclaiming, disposal of PCB's (figure 2) and which concerned effluents, trans* portation, spills, health and environmental effects, and other data the companies had on file (figure 3). Since then, we have received 83 responses and we are in the process of evaluating and assembling the infor mation into a useable form for making decisions within the Federal Government. This information w ill be made available to the public and to local and State govern ments. This information w ill be handled in accordance with the confidentiality requested by the companies and the Trade Secrets Act. Starting in 1972, industry had developed a standard fo r handling and disposal of PCB's (figure 4). In 1974, this standard was finalized and published. It covers the following points (figure 5): housekeeping, disposal, effluents, analytical methods, and several other impor tant areas. This is a voluntary standard fo r industry and for the Federal Government. We encourage the imple mentation of this standard support by everybody and also support the proposal by the National Electrical "Environmental Protection Agency, Office of T o x ic Subnances (WH-557), Washington, D.C. Manufacturers Association to revise and update it in the near future. Disposal of PCB's has historically been to the local landfill site or to a scrap oil w ith the environmental problems associated with PCB's has become evident, industry has developed several ways o f disposing o f its PCB waste (figure 6). High-temperatura incineration is the most effective way we know today because it w ill completely destroy PCB's. The other methods are only to contain the material and not to let PCB's get out into the environment. In Canada, there is a study going on about which we have little knowledge (figure 7). It appears to be a method by which PCB's may be reclaimed after their useful lives. On Thursday, December 27, 1973, EPA issued its proposed toxic pollutant effluent standards under Sec tion 307a o f the Water Act. During the hearings in May, 1974, effluent treatment was discussed (figure 8). Westinghouse stated that " A review o f techniques for re moval o f materials such as PCB's from the water has revealed that no commercial operation is now in effect. Furthermore, there is no proven technology on which such a technique might be based." General Electric stated that 'T h e control o f PCB's from current produc tion is basically a containment process. Water is not an essential component of the manufacturing process, so the problem is not one of removing a contaminant from an aqueous process stream, but of preventing the adven titious loss of PCB's from the production line to a waste water line." Monsanto stated fo r its production facility that "the bathtub approach, which really involves pav ing, curbing, Rotating the drains, ... etc.," is the only known method for treatment. We are basically at the same place today as we were in May o f 1974. As EPA develops its reproposed toxic effluent standard, which should be published the first half o f next year, we w ill be looking at carbon absorbtion, reverse osmosis, and ozonation. EPA is almo.st ready to send out fo r interagency and State review o f the Criteria forj Water Quality, Section 304a o f the Water A ct (figure^ 9|. This is not a rulemaking procedure so it does not have to go through hearings and rulings. This is the ambient level which we desire w ill not be exceeded in thp Nation's waters. There have been 20 spills identified at this time which have involved PCB's (figu re 10). Only six o f these were reported to EPA, and only over these did we have any control during the cleanup. There is only one out of g e H P 005660 108 774311 UNITED STATES ENVIRONMENTAL PROTECTION AGENCY W a s h in g t o n ; d .g 204 AUG16 1975 wTtcr CKroReEWENr Gcntltstni Reeent governmental sampling data Indicate the preaenee of Polychlorinated Biphenyls (PCBa) and comparable chemical aubatanees In the air, in vaeer badlea , and In fish in several areas of the. country* In order to determina the nature and extent of the possible adverse effects resulting from the presence of PCB compounds in tha environment! the Environmental Protection Agency (EPA), In cooperation with other federal and State agencies, is attempting to determine the sources and amounts of PGBs entering the environment. It la Important that this effort be carried out without delay. It Is our understanding that your company, handles PCB compounds or mixtures or comparable chemical substances in Its operations* I am therefore requesting, pursuant to the authority provided by Section 308 of the Federal Water Pollution Control Act, as amended, 33 U.S.C. 1318, and Section 114 of the Clean Air Act, as emended, '42 U.S.C. 1857c-9, that your company furnish EPA with Information pertaining to your use and handling of PCBs and comparable chemical substances. In addition to a general description, which should Include Information as to sources, quantities, uses, snd ultimata disposition, you should respond In detail to the enclosed questions. If any question is not applicable to your company or operations, please so Indicate by responding "not applicable." Tht Information requested herein muse be provided notwithstanding Its possible characterization as confidential' information or trade secreta. Should you so request, however, any Information (other than effluent or eolation data) which the Administrator.of thla Agency determines to constitute methods or processes entitled"to-protectlon a trade secrets will be maintained as confidential, pursuant to proetdurea apeclfled In 40 CFR Part 2. Figure 1. Letter from EPA to purchasers, importers, and users of PCB's. 109 774312 GENP 005661 2 Within 14 days of receipt of this letCar, your company must provide all Information concerning your current status and activities and covering the twelve month period Immediately preceding receipt of this letter. Within 30 days fallowing receipt of this letter, your company must provide all Information for all of the prior years Indicated. The Information required herein should be sent directly to the address Indicated below. If you have any questions you may cell the person Indiested below or Hr. Blake A. Biles of our office at (202) 755-8731. We appreciate your prompt cooperation In this mattar. Sincerely yours. Stanley V. Legro Assistant Administrator for Enforcement Enclosure Regional Contact: Mr. Richard O'Connell Director, Enforcement Division Environmental Protection Agency 100 California Street San Francisco, California 94111 Telephone: (415) 556-0102 Figure 1. Letter from EPA to purchasers, importers, and users of PCB's (con.). 110 GENP 005662 i2 POLYCHLORINATED BIFHEHYL (PCR) COHFOUHDS OK HIXTURgS 2. (continued) Within 14 days of receipt of this letter, your company must provide all Information concerning your current status and activities and covering the twelve month period immediately preceding receipt of of this letter. e. For each product the name and address of each sourcs from which your company obtained each FCB compound or mixture, and the amount of each PCB compound or mixture obtained from each source. Within 30 days following receipt of this letter, your company must provide all information for all of the prior years indicated. For purposes of this letter, the phrase "PCB compound or mixture" includes all chemical substances known or believed by you.to be PCB compounds or mixtures or of a similar chemical nature, irrespective of trade name. 1. For each PCB compound or mixture produced or imported by your company, for each company facility, during each year of 1971, 1972, 1973, 1974, and the first two quarters of 1975i a. The total amount of each PCB compound or mixture produced, or Imported. d. The name and address of each of your company's facilities which handle such products (including production facilities and wholesale and retell outlets), and the emount of each product distributed through each- facility. a. The name and address of each customer of each product, and the amount of each product obtained by each customer from each facility. For consumer products list only the total production of each product at each facility and the total number of customers. Do not provide the name and address of each customer of consumer products. 3. For each PCB compound or mixture used by your company in Its operations other than for incorporation Into lta products, for each company.facility, during each year of 1971, 1972, 1973, 1974, and the first two quarters of 1975: b. The name and address of each of your company's facilities which handle PCB compounds or mixtures (Including production facilities and wholesale end retail outlets), and the amount of each PCB compound or mixture distributed through each facility. c. The nemo end addrese of each customer of each PCB compound or mixture, and the amount of each PCB compound or mixture obtained by each customer from each facility. a. A description of each uae. b. For each uae the total amount of each PCB compound or mixture. c. For each uae the name and address of each source from which your company obtained each PCB compound or mixture, end the amount of each PCB compound or mixture obtained from each source. 2* For each PCB compound or mixture incorporated by your company into its products, for each company facility, during each year of 1971, 1972, 1973, 1974, and the first two quarters of 1975; 4. For each FCB compound or mixture reclaimed by your company, for each company facility, during each year of 1971, 1972, 1973, 1974, and the first two quarters of 1975: a. The total amount of each FCB compound or mixtur reclaimed. a. A description of each product. b. For each product tha total amount Incorporated of each FCB compound or mixture. b* The name and address of each aouree from which your ^company obtained PCB compounds or mixtures, and tha amount of each PCB compound or mixture obtained from each source. Figure 2. Questions sent by EPA to PCB users, concerning uses, importation, and reclaiming of PCB's. 774313 9900 JNJ57D ,,9 9 5 0 0 a t o 3 5. For each PCB compound or olxCurt disposed of by your company (with or without the Involvement of other parties), for each tompany facility, during each year of 1971, 1972, 1973 1974, and Che first two quarters of 1975x a. A description of each method of disposal. b. For each method of disposal the total amount of each PCB compound or mixture. c. For each method of disposal, the location of every disposal site, the name and address of each party Involved In the disposal of each PCB compound or mixture, and the amount of each PCB compound or mixture disposed of by each party. 6. The composition of each PCB compound or mixture produced, Imported, sold, reclaimed, used, and/or disposed of by your company since January 1, 1971. 7. Tha reaulta of arty arid all sampling and analysis performed by -- your company, Its agents or Contractors since January 1, 1971, ro concerning the followlngl a. Concentrations of PCB compounds or mixtures in the effluent of any discharges by the company (into voters of the United States or Publicly Owned Treatment Works), or In the emissiotlfe of the company Into tha air. b. The flow and/or composition of any discharges or emissions by the company (into waters of tha United States or Publicly Owned Treatment Works, or into the sir) which contain PCB compounds or mixturesi c.__Concentrations of PCB compounds or mixtures In receiving ___________waters (both upstream and downstream) of any discharges by the company which contain PCB compounds or mlxcures~and concentrations of PCB compounds or mixtures In the sir In the srea of the company. 6. The methods by which PCB compounds or nlxtures are transported to, by, and/or from your company, Including: a. A description of each method of transportation, and the form In which- PCB compounds or nlxtures arc trans ported by each method. -Where different methods of trans portation are used at different facilities specify which transportation method is used at each facility. b. ' The names and addresses of all known transporters of PCB compounds or mixtures. 9. All occasions (including spills) of which you are aware on which PCB compounds or mixtures have or may have been Introduced Into the environment. In particular, describe such occasions Insofar as they involved PCB compounds or mixtures in their liquid state, as Incorporated Into closed systems, or as Incorporated into open systems. For each occasion, indicate name and address of party Involved; dates, time, and location of the discharge or pill; and the amounts involved. ID* A description of any adverse health or environmental effects ' which you know or believe to have resulted from the Introduction of PCB compounds or mixtures into tha environment. Indicate any specific occasions Including dates, times, locations, amounts, and parties involved for which; such effects are known. 11. Any and all other Information w)ilch you possets concerning: a. The production, Importation, radamatlon, use, distribution, and disposal of PCB compounds or mixtures. b. The discharge of PCB compounds or mixtures Into the adVlTohEienC. In addition to the above, EPA would appreciate*receiving any other Information which you possess concerning the distribution and discharge of PCB compounds or mixtures by sources other than your company, Including your company's customers and sources. Figure 3. Questions sent by EPA to PCB users, concerning disposal, effluents, transportation, spills, hearth and environmental effects, and other data about PCB's. 774314 ANSI C107.1-1974 American National Standard Guidelines for Handling and Disposal of Capacitor- and Transformer-Grade Askarels Containing Polychiorinated Biphenyls Sacntariat National Electrical Manufacturers Association Approvati January 9. 1974 American National Standards Institute, Inc Figure 4. Cover of industry standard for handling and disposal of PCB's. 113 774315 005665 American National Standard An American National Standard implies a consensus o scope and provisions. An American National Standard fisthim0f!ensduebdstaasnatiagluliydecotnocaeirdnethdewmitahniut-s facturer, the consumer, and the general public. The existente of an American National Slan- dard does not in any respect preclude anyone, whether he has approved the standard or not. fcroonmfomrmainnugfatoctuthriensgt,amndaarkrde.tiAngm,epruicracnhaNsiantgio, noarluSstianngdparroddsjcrtes,supbrojeccetssteos,poerripodroiccerdeuvireews naontd users are cautioned to obtain the latest editions. CAUTION NOTICE: This American National Standard may be revised or withdrawn at any ttiamkeen. Ttohereparfofciremdu, rreesviosef,thoer wAimthedrriacwantNhiastisotannaldSartdanndoarldatseIrntshtaitnutfeivreeyqeuairres fthroamt atchteiodnabtee of publication. Purchasers of American National Standards may receive current information on all standards by calling or writing the American National Standards Institute. Published by American National Standards Institute 1430 Broadway, New York, New York 10018 CAollpryigrihgthstrese1r9v7ed4. by American National Standards Institute, Inc No part o ih ti publication may b t reproduced In anr form . In an electronic retrieval ly ile m or otharwiae, w ithout the prio r w ritte n perm beton o f the publish. Printed in the United States of America A IM 1074/6 Figure 4. (con.). 114 774316 C o n te n ts S1.ECSTcI0oNp e..................................................................................................................................................... 7 2. General Information............................................................................................................................. 7 2.1 G eneral........................................................................................................................................ 7 2.2 Benefits........................................................................................................................................ 7 22.34 Risks............................................................................................................................................ A lternatives................................................................................................................................ 7 8 2 J Interdepartmental Task Force on P C B s........................................... 8 3. Capacitor Guidelines *....................................................................................................................... 8 3.1 G eneral........................................................................................................................................ 8 3.2 Capacitor-Grade Askarel.......................................................................................................... 9 3 J Plant Housekeeping and Employee S a fe ty ......................................................................... 9 3.4 Control of Water E ffluents....................................................................................................... 11 3.5 Scrap-Disposal Procedures..........................................................................................................12 3.6 Labeling.............................................................. 13 4. Transformer Guidelines.....................................................................................................................13 4.1 G eneral...........................................................................................................................................13 4.2 Specific Guidelines........................................................................................................................15 5. References........................................................................................ 5.1 References to the T e x t...................................... "....................................................................17 5.2 General R eferences.....................................................................................................................17 6. Revision of American National Standards Referred to in This D ocum ent............................18 1 Table 1 Typical Properties of Arodor 1 0 1 6 .................................................................................... 9 Appendixes Appendix A Disposal Services......................................................... ....,....................................... 19 Appendix B Analytical Procedures and Laboratoiy Service Organizations.........................20 B l. G eneral.....................................................................................................................................20 B2. Laboratories.............................................................................................................................20 B3. An Analytical Procedure for the Determination of Airborne PCBs........................... 20 B4. Analysis o f Water and Sediment for PCBs.......................................................................31 Figures Fig. Bl Arodor 1016Electron Captuse Chromatogram ...................................................21 Fig. B2 Comparison of Electron Capture Chromatograms for Arodor 1221,1242,1248,1254, and 1260 ......................................................... 22 Fig. B3 Arodor 1221Electron Capture Chromatogram......................................................23 Fig. B4 Arodor 1242Electron Capture Chromatogram......................................................24 Fig. B5 Arodor 1248Electron Capture Chromatogram......................................................25 Fig. B6 Afodor 1254 Electron Capture Chromatogram.......................................................26 Fig. B7 Arodor 1260 Electron Capture Chromatogram.......................................................27 Fig. B8 Sampling Train.................................................................................., .........................28 Fig. B9 Calculating Column E fficiency.................................' ............................................ 30 Fig. BIO Calculating the Tailing F acto r..................................................................... 30 Figure 5. Points covered in industry guideline for handling and disposal of PCB's. 115 774317 DISPOSAL METHODS THERMAL INCINERATION FOR LIQUIDS Incineration at 2200-2600F with a retention time of 1-1.5 seconds. Venturi scrubber eliminates possibility air contamination. Cooling water is recycle^ and routinely checked for contamination. High aqeous wast are also incinerated by side injection into the system. PHYSICAL CHEMICAL TREATMENT FOR HIGH AQUEOUS WASTE Waste are pH controlled, settled, and filtered and passed through two carbon beds in series. Water parsed throughhas invariably met at specs. No detectable iPCB's (less than 2 ppb). SOLIDIFICATION Solidification means solidifying liquids and sludges using a silicates-cement powder technique. After solidification, materials are disposed of in lined scientific landfill. GELLATION Liquids and sludges are polymerized or gelled in steel of fiber drumswhich are placed in a scientific .andfill SCIENTIFIC LANDFILL Series of reinforced hypalon or reinforced chlorinatedpolyethylene lined cells in clay oil areas ipto which solid, sludges, stabilized chemicals, gelled liquids, solidfill liquids or sludges are disposited. A sump at the bottom of each cell recycles leachate to the physicalchemical treatment plant. A three-dimensionl inventory is kept of waste in each cell." Surrounding ground and surface waters are routinely checked each month. Figure 6. Methods developed by industry for disposal of PCB waste. 116 774318 AS A FUEL TO PRODUCE LOW ALKALI CEMENT POWDER In Canada, there is being pioneered the concept of utilizing chlorinated chemical waste as a fuel and a supply of chlorine to produce low alkali cement powder. The waste material is fed into the fire box to supple ment the fuel oil and burns at 2200 - 2600 f. The waste breaks down to water, carbon dioxide and hydrochloric acid. The acid neutralizes the potassium hydroxide present in the raw feed thus reducing the alkali in the cement powder. The cement kiln is perhaps the safest way to destroy PCBs. The temperature and retention time, approximately 16 - 18 seconds, are sufficient to reduce the PCBs. This test program is currently under way at the St. Lawrence Cement Co. in Hamilton, Ontario, Canada. Participants are: Ontario Water Resources Commission St. Lawrence Cement Company Chem-Trol Pollution Services, Inc. Figure 7. Description of Canadian PCB study. GEN P 005669 117 774319 THURSDAY, DECEMBER 2 7 , 1973 WASHINGTON. D.C. Vefluim 3S Numbtr 247 PART II ENVIRONM ENTAL PROTECTION AGENCY WATER PROGRAMS Proposed Tonic Pollutant Effluent Standards M o .N 1 -W. Figure 8. EPA proposed toxic pollutant effluent standards. 118 774320 GENP 005670 35388 PROPOSED RULES smpp7erppmIpppbelsfatanpeeepotu4d(oepuetoDtabtvCFAftt33teisihhhobpunnoo-pforhofehriaoinboxoalooosossfasnli00oeliodefofaedToDsmrma5D789aT8aca4ss-uWD33drulxusqpoaestetutcSexdJlMllrblaEd7tpprpmlt7e.cse...eronubln...la.tua.idtnantoh.c.ninhtxnnhleDtODotert(uliiueUolPlw)Tns(oMhNeeedohce(Ctneuitbnialopoaottedyod-ideElyyoAePacnpsDl*agttnrCtabodntrhiaxlTEnswsaMemglotmraohtrtVahifsslrosy)touos-rDodaeoetdeet)tbbett!pnmodcanmexea)yDtx.lisnalpixi..snah1boSee(alpclbplrrempdonaelIs.neesi-wrr,esfsred.(e-drotoe,l1puaystoBeoeoTMRMntDntoaroAslrhitolspo4l.a1lotnidelrneaattrbpimao-tanrpootoowapdse.f)iicpaf.iyfpcWhbb,sclsAueoOeblf.ltloe5do--lttnn*lU1nId4sco.tuerirmwinah4Irhppefnnlhuus3,Cahol-nnyexiei*mffemtral,ch-n1ollutd(dtNtetoe)pstudsut[oe.dlWcihdBd(lu0erisaro-ea3eMz:pleThoahna4.ae.oct(pma4tmevyloa(Mnhueem5taesPhnelctt7ooMaCniab*rtlpa,phioa,a-aaefrDArwtnrtocd.ealelJ(tn,nny8sTs2eo0heSyo(ndftirourdrnbtelnria0ellgJlyllUfAhTuarisdnietarioyEacnudeof-reii.iEnilnlnledsobl,dc.nanafoaatnisa(3AFnedtcntCEcetd7aua)ion)fal8neh!toats.(sctesNgle3b.ctlyt)ndnsdfenhfodteadwaghb.d..)ieoonerA4ReePnlertt,lti(1,GtlaPtutit8hv4ietu.lsf7cadnmianaodoerTielpotd3rcneorydnn4et.tad8boeiPsoo.abfioscnleroc.nlaonn1Eoftnh,tld8dlrb-r[).drtatturhcr7Afadleeof.as8nPnsannheeeteterleailde1tol0-1odpetnsalteteaaNcn3tltoa)ewrjlotruhrs.scRawta.aas3LdatppuqobbanaegtrAssua.u.,i0ue-ea8anyntMlbalihreeuseenI1llCRi4lhdnonlOr-ar2rrcraAnbdtumessurlrnt.,rolan(laeirrwodfscd,ndoidooIt0de1i-PoottcpneSpdps9sAtsYf,aeetiunG-dlcnnP-btihotodmpttye-2hfnveWdlr,ta-beia0en3uoofsahtdbhon1egctaeal(bactimgoseuRnRahdnc(ipite-iabeynrotob-cdaloxiple,aersbedmoid2pphnrdsebsdtiwlebontngeeldoOAdhitgatoOnptllxrrnedodxbseItaitat,urautpldrel9daeUlexLpirb,oatloIenMoithfhaae(otyohoCiiryesshmapnsatsiltulbTchAsgmehcsbpp]cpacupxcacotipuasnpsn1ptutnbmatdlrctbyc'starsrttoer-eyaaaoycsoEr.-hhr,s(iuEi3tntnaalooortplddmlbaapahteotydomea.nuletspmashathaodepAoani8ase-ttc)rCUaotf-bcdiseaPbdsleompeelb(hi.nhrnyomeyohf-llram3.xlroh(totrotrtispd4dfadpproeoTslolduceouocaiurtrlroflPtanhiaoaoaaur.edrfl1alsymibi,stsas,boohornhy3aehturlIolrplrurt4otbCasrlefset3eosnose*o-aon-licoeyrOieiceyuevclrwlcfeeepll*tltbrn*yb-totuStencosoofactoiehBcfoeo-a-of.onauooilionaaidos>6notbNzt3-11ht1rlEjstttn1caoAooetowanstulurremfetimntmoiidd>i'-t.fltioe(til.ea.,ilto.tdrason.mnobhntdosoot7bssoo.b4nboc8*4e)coioae1elts4ndaecsd)co')hdbd*)*-.)ae-n--sngahd-nahn-esn--sse.)r,.:--rfrt,.ttt,mltiemIfmInmtapettaepfwpcrwueabttttdtt-atfrasstwettcWs3tFtlAtfpbdcBEttabitalm1rceohntioohorehhohiesieihxeehfmhiinoegrteocormetobsuse4naoryaaon9esoscaioRmeanracafsaxgaracmaarxieBToraercpareWsauadsve3Ttrntlwhaastshyaned7tnstrtatisdmdrgtsnbinioiineylteetiettgiiosyr4ieaiieiatsottofhicscenaegtaplep3.rcethhbacucnoninaosaicsdisydamadpelodttnef3eysciaray3octacddnwe"reriirdtt)meuahrdsecsesedoedannurniwsuicros.laarsancme9ao.atnocltopp.in.edWaSmnuteyaelrsoceef.aeetroeicettbrcatrrlofv8suitabopipQtsird1Tehndlontiut,adtFpr.raeeecitolerotodfnrdcofugameTatdoIt4loooymuesnayrnooo9oeamreevw7eieTccrosalwslwusdrirhaobutenngitdssgnser8ipcnlfiiQcn7lpzfrtocqhwscscndeh.istctiehtlamodinsldaoeieeiduraebesamohcacaeoohe3ledeteatafawpeeuadtsluuamginapeentfloelsgueiatplrohrdaseeitiunedeicrondsesrrtrr1tendetl,lltiofsiaircweeuoatnwniwdfiwtasemterbaeioiidnf.seetntih,rpinn0rdtfatrde,enerthrpaQaotorelotdnWylrtrneaarifssorehlhrosdoalonr7yihtderceeoyodwiedidtuinelpedeie,sirimenpftrsoIrtnanaseEbprfcosyat3teitmtrucirtfncwrriCoelx.fcttudtsaeatothoigtgyecsooeethneaohntcegat,aeebtidniheoeyoirnIvaoebsebRttiiotserroteamstmarqeatxh,ftrshatmssenricnhecnooeeTipi.neipnldiweieevnfltCohexecbmaisseTtfenrcovift3tivnIaptes-tioechxIfnafanrttlslhirrctepfvosifohhtirticeeanptdhdNsbipoiieeeahntot0rrii(tsoedtrosiydeocihteraey.eNtstetcdsaairriansuvnheQLiiTl.csaelohpurFrihpts4Ihhoccstscoseytmfoecoantecaealeic5teWh"oiaagtentaaCoteedapuenWeeittcotih(utrlraiauaxaansatodtenwrnthnWphasnwaneotbpc0catod3oiiftxiresedshrmmorsseerrcllotneaatvhbndiayocnobsamdreliwg)aitua8esulrdsnecociefa^crthdaottafhuucltlpiaueeeientecoarencrutvoaitPaotee,liwdhtapodrueiatyn,osoft9neetntgtioisowtcaiedriiotdtti,eeyuldgttenamnireaa.rlNhmeaocceesploerpnnhfdyoorgie8woiNoaaeendertriIrgnagacsrl,ldtgaotahdadhintsrnenuerntenpr.gnvlgbgfnell-lcfr9oaeeamspfTalctaaiaC9tdolwliftaaoetaQfmerhcuQgbdytcA,irrnirtaasmdelQlntO8eeA,:ullnatroa.wO8cnasodahntiofngphioa,saoaueupclniisahnisnirtfgue-oc&nuriset.acbclPtil-nbanirIenaecnucotmt.reharrdtsrefuaumhshocteildetesosie1rtThtaineannonaaeedyoceeofaat,stourddnnegTmgealtwehatolrmoinsdt7lfodltoofdliocdccntmocdeadscn,htichflcstrcrtlciaotiAhtlei3nncuoehcfhbearpiaepIaosfltuttawdttrotuhtntsueboLhoytasireorehoetaodf,ethsreaygshhesrensaywr,mscacspeniobieorinmicryu.bsxpfegwyaumiCtfritedat,mfrottcaorcerbticgnftwpttitpScaworbnpeiphphopepogpdmttpyCoftCmtaLCealrystfTnecataptrtIpfiehfeenaounrovnieeroitltairettneriurarerebeaeni(rebmmaiaiip3Ctntiiohcrrnoaherhharilrogahoeoeopv3xcboaueoodaialsntsotcfetiyersarlrraeIliil8ilirsthyynedldhncaysndee,,ehe8eefeseefeleeerttrffs,,t,,,f, . . . codlgaaQvesblmttmdwpwremdcisAovctabshetutmcvdeeirtespwciatcampwwwaCciettTdtaeaioniehehcnnehebexereaeraiealtaaeterxeonsaoosiinhlaynrieosoritbotucieinimhvgdarhreciahcgarfdasrsersggelrastptsneeTSeteststeTatlwletcnnnraydtalvnittueteutofyiiataeeinetciaeylihteitecrteeatgdaarmy.dlotehsheiaohrasssciutonrachweeeaass,ialtblraurge.endhIsnhd"na.oigwr.orfeedisdosacwiuabiiho.oenehsmtsartisrrc,eIonrviirtlcIedatiiaaptcnarauanudhditeorflndtentnandsiilhwstfaniymIasnumtuawaretfvyurtecioatltsreessgreailespbrmtorraimuontemohleirotetotindovagestnrIgetripinedeosroehwhiodptnsahnvfChraoIaolorbeuo(e,otnlpadlesrlicyotoirI.tecierna,evmoerwwysuniudo.sfioveiateudnra,enofaoausrsclslefeuaaorstefsidtctohodteastttsetnwisetgeeassgrlynecr.dciinai,oaoaasuhxolilmttcoatohEidsssmhhttddfd,erntz-rtoeuftsoptitttydhehyTatpzfue.cytsrhawerpufrphtgmtpxeoa,eauoaieofed.erreoifsfreienirrrnidruiaeaastIttlisotnalgllircefraoohuixlhe.fmtewdlsncacnqeoeidihtxeiehneeucdtftvwusfsTesimlerilifysofannsttdrhle3ltdrhnuipavsierucnaruptasleisaehehfeuomeoaeTeedehsotgsncaldiahidog0essarsatebsareeemagototucaumaot.saunvnporndttuerihhaeenriuydie3toshsiwnefuelhmonirplnmuenetcoecnhbmrsnsgrrecmttxnhtlnnlolbeo,tsgdncrapd,fsaarrp,reafattTbhldieeedhatorfnoledrotadaeffpykeeeantvurr,ioeraeeirphiaolsseaogorsdsloarydfli.entishfmslebgasftteoefenpwcIsciaicwuigylndeehgcerb.tltttcoelyfehhatwoeohtnnvmntqacnp)ee-aecrtlshohaaoetcoeleetcethiheWeetaTvpaeasphtuftaueereoetodasgheostushamnetphtninnnervetfdItwnnhiwroestniieteoerlseeidttceshsmtoxhmrllaptteneieofigdeeettrtidsdmmczeaedlaa,rhdeaahfrvedernhafhdadpwh,vldoidbatiettorciulndrwvliapeercarmneaofeosttinynaer,eontylcAaesaoiidseeratepaiepeuaewhoetrectlednasiatirbtcrnlcsarxadeabdtEtpripWftotr.rtwnsldoiiodneteqectonodnnvrdrtotccospdcmnothsegtetdanlcuordrhtaleaessieravTainizeawrenrpIuep-tIottedahrleofesIondbdacotcspenobae,nme.srscnQareneapnlwiidavonarohsarehgmssaqobttsohtluhyds,dvad9auttnIudolllitaTtrrp,orodrlilrcu,trseheostentaaasrruibaIfbeed6ue4ftaattriifsosruftrtueriyratrahoaIleoaegeuvooomnaneibhslloisastatocerhoraa0seilinitwaedinvalrttolclzrddsyn,aiendcefoenceesafcrfmlnghepnimfeeennlhal3oternrelenduamifemtarglandsoolcidetgotnieimi"snnQotrdcanoiciticceemewtorrlrydgisflsofttnrnwsihadiiwoc.cwmoonwiiufobyddivewWeeeewoiyouesifeaefetofdwateenntgxltbutnemsniao.nelafferaeeifecacaniiditdmdeenfadhvtrftesuaos)pdawtchielfkpdhiaavomvihrCtctrcdnntrkneeiTsndcuriahtuninduefittcaoeoeocitrltaptgdeieetlntboigiinretiaofniceiiizeoentteiiethhisoibdrharixtcrnlnIrbhMapdecensxnxorvveannooereootatatltetssmththrlalirsistnwitdis^njnoehkeyeoenhdheedoegyyegtyes-frrfstlf-fr,rt,lt.t HDISAl ((OWES, VOL 3S, NO. 347-- THUISOAT, DECEMIft 37, IV73 GENP 00567] Figure 8. (con.). 119 774321 N O T IC E .This document is a preliminary d ra ft. I t has not been formally released by EPA and should not at th is stage be construed to represent Agency policy. I t is being circulated for comment on its technical accuracy and policy implications. POLYCHLORINATED BIPIIENY S CRITERION: 001 uangd/1ffoorr cfornesshumw aetresr thanedremofa. rine aquati z life Figure 9. Preliminary draft of EPA standard for water quality. 120 774322 IL9500 dHHO OATT / 9/71 10/12/71 1/73 i/ a/7i 1/ 1/71 a/ */7J a/7i- 1/ l/7k /7 3/30/7 a/13/7 10/79/7 Unknown eraantsTANCSs TT STATS Druaa cantInIn| 1,600 lb Cn reuta tartcd to In k in rout O n a l i i k i n i an ro u t* , nt beck Cn reuta AMOUNT SPILLED Unknown Unknown AMOUNT RCCOVEUD Unknown Nona MDEISTPHOOSDA0LT Mona Nona con WORTES TO ET* No Ho M i l r/r dovolopn lank tn route Unknown Truck ac c id e n t, 1 trene- loanoka 1000 f a l l rem n lap id a, K Inartaan Unknown Unknown Unknown Unknown Nu No Truck 1 rout d m le p td lalk Truck accident Tranaforaar la lk Kingston, Tenn. Havana, 111. Andereon, Znd. 30 p al FCla 00 pal 19 pal 11,300 druaa o f 35 g a l aaalad eontaainated a o il in concrate Unknown Unknown Unknown Unknown 1.7 m illio i Tea Tea No' Tranaforaar lak Tranaforaar lak Truck ic cid a n t Trinsforaar f a l l Into Duamiah liv e r Traitaforaar laak TTaneforaar laak Tuacalooaa 0-100 pal Ala. Louisburg, 00 pal Kansas Bedford, Unknown Znd. S e a tt le , 2B1 pal Naah. E lis a b e th , 10-100 Iba M .J. Unknown 10-100 lba Unknown Unknown Unknown 70-90 gal Unknown Unknown Unknown Unknown Unknown Entoabed in titan aiaala Unknown Unknown l l,0 0 0 No Ho No Yaa NO No 7/ 5/7 */ia/7 11/11/7 12/1/7 12/27/7 1/33/7 1/9/75 Tranaforaar laak R1 Tranaforaar laak II Truck aceldant TTuek accident Truck aeoident Truck accident Laakin drua on dock Stanford , 10-100 lba Conn. Unknown Unknown B at. P h il, 10-100 lb a a Paoli, Pa. Unknown Unknown T rio n , da ISO gala 3,300 druaa o f Entoabed eontaainatod to il E r ie , Pa 300 ga la PCI* Unknown Unknown tawranoa 1)0 galaPCQBI ,300 druaa o f Entoabed Al oontaainatad ao il Roae Ca 7 gala PCfla 1)3 druaa o f a o il Entoabed Charlaatow i 90 gala SC PCBe 3 druaa o f a o il la n d f ill NO Ho 1173,000 373,000 ra No Tea 13,000 Unknown Tea Figure 10. The 20 identified spills that have involved PCB's. GENP 005673 121 774323 "OIL AND HAZARDOUS SUBSTANCE LIABILITY" Sec. 311 of FWPCA, PL92-500, October 18, 1972 311(b)(2)(A) Designation of Hazardous Substances Polychlorinated biphenyls PCB Aroclor Rolychlorihated diphenyls 311(b)(2)(B)(i) Removability Determinatio;:i . "...cannot actually be removed." 311(b)(2)(B)(ii-iv) Rates of Penalty for Non-Removable PCB's Category A, Unit of Measurement lb - 1,$360/UM 311(b)(3) Non-Harmful Quantities (being developed) S l K b M 1*) Harmful Quantities PCBrs Category A, HQ in lb - 1 311(f)(2) % Small Facilities Liability Limitations (being developed) 311(j)(l)(A) Methods of Removal (being developed) 31l(j)(l)(c) Prevention (being developed) Figure 11. List of subjects covered in proposed EPA regulation under Section 311 of the Water Act. the 20 in which PCB's reached the water. This is the Duwamish River incident. The majority of the spills are transportation-related. ERA is finalizing its proposed regulations under Sectian 311 of the Water Act. "O il and Hazardous Sub- stance L ia b ility " {figure 11). A t the present time, only four areas w ill be covered in the proposed regulation and the other four sections w ill be following next year, we hope, 900 <JN30 123 774325 \ SOURCES OF POLYCHLORINATED BIPHENYLS IN WISCONSIN Stanton J. Kleinert* A b s tra c t The past and present users o f PCB's are discussed and e fflu e n t sampling data are presented fo r m unicipal wastewater treatm ent plants and industries in Wisconsin. Data are also presented covering PCB levels in surface waters, fish, sediments, and snow m e lt A general assess m ent o f the PCB problem in Wisconsin is made w ith comments concerning the need fo r fu rth e r study and regulation. My report w ill summarize the work completed by the Wisconsin Department o f Natural Resources and others to determine concentrations o f PCB's in fish and to identify discharge sources in Wisconsin. Our interest in PCB's began in the late 1960's, when interfering sub* stances were detected in the gas chromatograms o f fish being tested for DDT. Later we were to learn these inter fering substances were PCB's. In 1970, the department collected fish samples along the Mississippi River bordering Wisconsin. Analysis revealed that fish from the Upper Mississippi River be tween Prescott and Pepin, Wisconsin, commonly exceed* .ed the Food and Drug Administration tolerance level o f 5 ppm (ref. 1). During 1971, Lake Michigan fish were collected and later tested in studies conducted by Dr. Veith in a University o f Wisconsin study (ref. 2). Mean concentrations o f PCB's expressed as Aroclor 1254 (wet weight) in the fish ranged from 2.7 ppm in smelt to 15 ppm in lake trout. Subsequent studies confirmed the presence of PCB's in fish in Lake Michigan and other waters of Wisconsin (ref. 3). The search for PCB's in water was also underway at this time. Veith and Lee (ref, 4) sampled water from the Milwaukee River in 1969 and sampled effluents from selected municipal and industrial outfalls to the river in 1970. The analysis o f water from the Milwaukee River indicated that PCB's were present in the river from West Bend to Lake Michigan and were being discharged through municipal and industrial effluents. In .1971, 11 municipal wastewater treatment plant effluents in Wis consin were sampled by Dube, Veith, and Lee (ref. 5). Nine of the plant effluents contained PCB's identified as Aroclor 1254 and one contained Aroclor 124B. Studies of the Cedarburg wastewater treatment plant indicated ` Chief, Surveillance, Wisconsin Department of Natural Resources, Madison, Wisconsin. that more than 70 percent of the PCB's coming into the plant were removed during the treatment process and comparatively high concentrations of PCB's were found in the digester and primary settling sludges. The department surveyed many municipal wastewater treatment plant effluents in Wisconsin from 1972 through 1974. PCB's were| detected in concentrations exceeding .05 ppb (the detection level fo r screening pur poses) in more than half o f Ihe treatment plant effluents tested, even where there were no suspected industrial sources. In most cases, the discharge o f PCB's was well below 1 ppb and .01 pounds per day. However, the high er concentrations of PCB's were found in sewage treat ment plant effluents from inidustrial areas. Tracing sources o f PCB's reaching a large municipal wastewater treatment plant is a d iffic u lt and timeconsuming task. The department is attempting to trace sources o f PCB's reaching jtreatment systems where the final effluent- exceeds 1 ppb. A t the present time, we know of only two municipal wastewater treatment plants in Wisconsin which exceed 1 ppb--the Sheboygan and Portage facilities. The main source o f PyB's being discharged to the Portage treatment plant was found to be a facility that had used PCB's in the manufacture o f carbonless copy papers prior to the summer o f 1971. A fte r ceasing the use of PCB's and after repeated cleanings o f the holding tanks o f the facility, the company substantially reduced the discharge. Residuals still remain, however, in the sewer system and the sewer sludges, resulting in an e fflu ent of several ppb at the municipal sewage treatment plant. We are continuing to check sources o f discharge to the Sheboygan treatment plant. The department has checked effluents from iron and steel foundries and aluminum foundries. The testing has shown that the cooling water effluents from five to seven aluminum foundries contained PCB's ranging from 11.5 to 335 ppb'. Close Investigation revealed the com mon source to be leaking| hydraulic fluids containing PCB's, which were used in die cast machines. We are working w ith company officials to correct the problem. PCB's have been found in ,|he cooling water effluent of only one of nine iron antjl steel foundries checked to date and these were at a concentration o f .9 pob. The Department o f Natural Resources has tested the effluents of 17 pulp and paper mills fo r PCB's. The test ing has revealed that nine o f the mills that recycle wastepapers had measureable discharges ranging from .* to GENF 005676 124 774326 more than-25 ppb. M ill representatives indicate that the paper industry no longer uses PCB's and those found in wastepapers come primarily from carbonless copy papers that were produced prior to 1972. The old carbonless copy papers were widely used in forms and continue to enter the wastepaper market as old files are discarded. Aroclor 1242 is the principal form found in wastepaper, however, some Aroclor 1254 has also been reported. Be cause their solubility in water is low, we believe that most o f the PCB's discharged from wastepaper mills are absorbed on fibers and other particulate matter. Mill wastewater treatment systems, which effectively remove particulate matter, should also remove PCB's. The electrical industry continues to use PCB's as dielectric fluids in some capacitors and transformers. A l though the units are sealed, some fluids may be lost as a result of accidents or disposal practices. In March 1975, the department corresponded with the major electrical companies in Wisconsin to determine current handling practices fo r capacitor and transformer fluids. The cor respondence was followed by visits to many facilities. The companies contacted were aware o f the PCB prob lem, but some were not aware o f the recommended Guidelines of the American National Standards Institute (1974) fo r Handling and Disposal o f Capacitor and Transformer Askarels (Fluids) Containing PCB's (ref. 6). We also found that some facilities were storing defective capacitors until a proper disposal method could be found. As a result of this survey, specific guidance was given to Wisconsin electric utilities for the proper han dling and disposal o f PCB's. Snow samples were collected early in 1975 to deter mine if PCB's were deposited on land and water as fall out from the air. Analysis of the snow melt water from Racine, Kenosha, Madison, and Milwaukee revealed con centrations from -.17 to .24 ppb. These values suggest that fallout of PCB's from the air may be a principal source o f PCB's entering the waters o f the State. PCB's are present in sediments in harbors and streams near industrial areas. The sediments act as a res ervoir where PCB's may be released slowly over a long period o f time. Sediment samples have tested 3.5 ppm in the Milwaukee River near the Capital Drive Bridge, 9 ppm in Superior Harbor, and 72 ppm in the Fox River below the outfall of the Portage sewage treatment plant. We have tried to work out a materials balance for PCB's entering the environment using the domestic sales figures provided by the Monsanto Company as well as other data. There are so many pieces missing from the puzzle, though, that our efforts to work out a materials balance have been unsuccessful. Some general comments can be made, however. 1. PCB's have been sold by the Monsanto Company for more 'than 45 years (ref. 7). The company has reported domestic sales of 795 m illion pounds of PCB's for the years 1957 through 1974, A rodor 1242 accounted for 15 percent, Aroclor 1260 accounting for 11 percent, and Aroclor 1248 accounting fo r 7 percent of the sales. In 1974, the Monsanto Company's domestic sales of PCB's were reported to be 34 m illion pounds for use in closed electrical systems. In addition, the Office o f Toxic Sub stances, EPA (ref. 8) has reported that foreign sales of PCB's in the United States in 1974 exceeded 375,000. 2. The PCB problem in Wisconsin is a fishery problem caused because residues have accumulated in certain fish in Green Bay and Lake Michigan and the Upper Missis sippi River in excess o f FDA tolerance level o f 5 ppm. Laboratory experiments have shown that fish accumu late PCB's more than 100,000 times the levels present in the water (ref. 9). Therefore, PCB's in the water, even at ppt levels, have significance to the fishery resource. 3. Our data indicate that levels o f PCB's in fish in the Upper Mississippi River have declined in recent years. We have not detected a corresponding decline in levels in Lake Michigan fish. If Lake Michigan water contains an average of 10 ppt PCB'5, then there are more than 100,000 pounds of PC8's in solution in the lake waters and there is proba bly a much larger poundage in the sediments. We have tested the major effluents of both municipalities and industries discharging to the Lake Michigan drainage in Wisconsin and estimate a discharge of about 2 pounds per day or 730 pounds o f PCB's per year to Wisconsin's drainage to Lake Michigan. Most o f PCB's identified in our testing of major effluents occur in the wastewaters of pulp and paper mills that recycle wastepapers. Discharges o f PCB's from pulp and paper mills that recycle wastepapers w ill diminish as the mills meet their discharge permit requirements. Wisconsin mills that recy cle wastepapers are required to reduce their discharge of suspended solids from 131,000 pounds per day (for cal endar year 1973) to 45,000 pounds per day by the 1977 compliance date. Recently one m ill in the State, which uses only recycled papers, began operation of a new treatment system that has reduced the discharge of sus pended solids from 40,000 pounds per day to 3,000 pounds per day. Tests at this facility revealed 39 ppb PCB entering the treatment system w ith only 1 ppb being discharged in the final effluent. 4. In our search for sources of PCB's entering the envi ronment, we have not looked closely enough at fallout from the air. Our testing of snow melt suggests that fallout may be contributing much greater amounts of PCB's than are being contributed by industrial and muni cipal effluents. Trace concentrations in fallout over Lake Michigan and its watershed, which cover 67,900 square A K \ hI O 125 774327 miles, could result in appreciable amounts o f PCB's en tering the waters of Lake Michigan, Because PCB's are stable compounds w ith Tow vapor pressures, little loss is expected to occur through vapori zation from disposal sites where capacitors and other equipment and materials have been disposed and covered w ith overburden. Entry into the air may be expected to occur at locations where papers are incinerated, at foundries where imported casting waxes containing PCB's are heated to high temperature, and at manufac turing facilities. PCB's adsorbed on fine particulate mat ter may also be entering the air, as windblown dust. 5. Further information is needed to define the amount of PCB's contributed to Lake Michigan and other waters through past accumulations in sediments. A University o f Wisconsin study is currently underway in Southern Lake Michigan; this should provide some o f the answers. The Department o f Natural Resources does not have the authority to regulate the sale or use o f PCB's, but can adopt effluent standards. The department held hear ings on two proposals fo r effluent limitations for PCB's on August 28-29, 1975. The first proposal would prohib it the discharge o f PCB's and the second would lim it the discharge to .005 mg/l or 5 ppb. The hearing record is being reviewed by the Natural Resources Board. No final decision has been made on an effluent standard as yet. On September 10,1975, Congressman Aspin o f Wis consin introduced a bill (HR 9525) to prohibit the intro duction or delivery for introduction into commerce of PCB's. This bill is pending in the House Interstate and Foreign Commerce Committee, Subcommittee on Con sumer Protection and Finance. This legislation would be come effective 3 years after enactment providing indus try w ith a 3-year changeover period to alternate sub stances. REFERENCES 1. P. Degurse and J. Ruhland, Occurrence o f Chlorh nateti Biphenyls in Mississippi River Fish, Wisconsin Department o f Natural Resources, Bureau o f Fish Management Report No. 5 2,1 97 2 ,13 pp. .2 G. D. Veith, Chlorinated Hydrocarbons in Fish From Lake Michigan, Watt r Quality Office, U.S. En vironmental Protection Agency, Project 16020, 1973, 129 pp. 3. P. Degurse and V. Duter, 'Chlorinated Hydrocarbon Residues in Fish from M ajor Waters o f Wisconsin, Wisconsin Department of Natural Resources, Fish Management Section Repart No. 79, 1975, 21 pp. 4. G. D. Veith and G. F. Lee, "Chlorobiphenyls (PCBs) in the Milwaukee River, Water Research, Voi. 5 (1 9 7 1 ), Pergam on Pfess, Great Britain, pp. 1107-1115. 5. J. G. Dube, G. D. Veith, and G. F. Lee, "Polychlori nated Biphenyls in Trectment Plant Effluents,' Journal o f the Water P ollution C ontrol Federation, 6 Voi. 46, No. 5 (May 1974) , pp. 966-972. . American Standards Institute, Am erican National Standard Guidelines fo r Handling and Disposai o f Capacitor and Transformer Grade Askarels Contain ing Polychlorinated Biphenyls, ANSI C107, 1-1974, 35 pp. 7. W. B. Papageorge, Testimony provided at the E fflu ent Standards Hearings fo r Polychlorinated Biphenyls held on August 28-29 1975, by the Wisconsin Department of Natural R ^sources in Madisop, Wis consin; Wisconsin Department o f Natural Resources Public Hearing Record files, Madison, Wisconsin, 1975. 8. G. H. Schweitzer, Testimony provided at the E fflu ent Standards Hearings fo r Polychlorinated Biphen yls held on August 28-29, 1975, by the Wisconsin Department o f Natural Resources in Madison, Wis consin; Wisconsin Department o f Natural Resources - Public Hearing Record f|les, Madison, Wisconsin, 1975. 9. A. V. Nebeker, F. A. Piighisi, and D. L. DeFoe, "E ffe ct o f Polychlorinated Biphenyl Compounds on Survival and Reproduction o f the Fathead Minnow and Flagfish,'' Transactions o f the Am erican Fishertes Society, Voi. 103. No. 3 (July 1974), pp. 562-568. 126 G0 7745128 POLYCHLORINATED BIPHENYL USAGE AND SOURCES OF LOSS TO THE ENVIRONMENT IN MICHIGAN John L. Hesse* A b s tra c t Polychlorinated biphenyls {PCB's} are used in a wide variety o f applications including dielectric flu id s in transformers and capacitors; plasticizers in paints, inks, plastics, and coatings; hydraulic systems; heat transfer systems; investm ent casting waxes; and many moire. This paper describes industrial uses o f PCB's in Michigan and focuses on those uses which were found to be sources o f environmental contam ination. I t describes PCB use fig ures supplied b y several industries and concentrations detected in industrial and m unicipal effluents and sludges. INTRODUCTION Polychlorinated biphenyls (PCB's) are complex mix* tures o f chlorine*substituted biphenyl compounds and have been produced commercially in the United States since 1929. Their properties o f nonflammability, stabili ty, resistance to acids, alkalis, and other caustic chemi cals, and low volatility under prolonged heating have made them useful in a wide range o f industrial products. Monsanto Chemical Company, the sole U.S. manu facturer o f PCB's, recently released production and sales figures through 1974 (ref. 1). These showed that produc tion and sales roughly doubled between 1960 and 1970, with nearly 80 m illion pounds sold annually in the United States by 1970. Broadhurst (ref. 2) has summarized many of the uses of PCB's, The five largest uses fo r PCB's prior to 1970 were dielectric fluids in capacitors, plasticizer .applications, transformer fluids, hydraulic fluids and lubricants, and heat transfer fluids. The list of other uses is lengthy. Because of the widescale usage of PCB's, they have became distributed throughout the world. Since 1967, reports of PCB residues in fish, birds, water, sediments, and other environmental samples have been common. They are of concern in the environment because o f their persistence, potential for biological magnification, and chronic toxicity. 'Supervisor, Toxic Material Unit, Department of Natural Resources, Lansing, Michigan. By 1971, Monsanto recognized the environmental problems which had developed because o f PCB's and initiated a program to phase out sales for all open-ended uses, finally lim iting sales to uses in electrical capacitors and transformers. Many officials believed this action would result in rapid reductions in environmental con tamination but little evidence o f this has yet been docu mented. Michigan officials have been studying the PCB situa tion since 1969 when excessive PCB residues were de tected in Great Lakes fish. A fter development of ade quate laboratory capabilities, we instituted a monitoring program fo r PCB's early in 1971 consisting o f a state wide water sampling survey in inland waters and trib u taries to the Great Lakes. Supplementary sampling has since been conducted on fish from inland and Great Lakes waters, stream sediments, potable water intakes, sanitary landfill runoff, municipal wastewater treatment plant effluents, and industrial discharges. Limited ques tionnaire surveys o f industrial usage have also been con ducted. This paper w ill report briefly on the industrial uses o f PCB's that we have identified in Michigan and focus' on those uses which were found to be sources of environmental contamination. E lectrical Applications Prior to the 1971 Monsanto lim itation o f sales to the so-called "closed-system" uses, approximately 60 percent o f U.S. sales were fo r electrical capacitor and transformer applications. In 1968, annual capacitor and transformer sales totaled approximately 30 and 16.8 m il lion pounds, respectively (ref. 3). While losses from the use o f PCB's in these applica tions have been estimated as minimal (ref. 3), incorrect disposal practices and accidental losses from equipment and storage areas -do occur and can result in environ mental contamination. In response to an industrial questionnaire sent to a cross section of Michigan industries in 1971, one major power company in Michigan reported an annual use of 562,000 pounds o f PCB's (250,000 in precipitator trans formers and 312,000 in capacitors). Company records showed annual losses o f approximately 300 pounds of PCB liquids to soils from burst capacitors and 12,000 pounds from salvaged capacitors. This fluid from the capacitors was reportedly disposed o f through waste GENP 005679 127 774329 . - CO haulers. Waste haulers then dispose o f these wastes in many ways, including dust control on roads, sale o f oils as fuel in low-temperature boilers, and treatment and discharge to municipal sewerage systems. Fluid recover ed from precipitator transformers was returned to Mon santo fo r incineration. In the same industrial question naire survey, a smaller power company reported that it had been disposing o f approximately 700 pounds of PCB's per year by mixing w ith other waste oils and using the oils for dust control on their driveway and parking lot. In October 1975, a 55-gallon drum o f PCS trans former oil on inventory at a Michigan power- company developed a leak from a defective seam. Approximately 45 gallons of the fluid soaked into the ground, resulting in more than 100 cubic yards of contaminated soil hav ing to be removed and disposed o f in an approved land fill. This situation illustrates the lack o f such proper safe guards as diking around storage areas and represents an example o f environmental loss from a so-called "closedsystem" use. Most industries other than u tility companies using electrical transformers containing PCB's contract either the transformer manufacturer or smaller companies for servicing and do not concern themselves w ith the prob lem of disposal of the waste fluids. Frequency o f servic ing appears to differ between industries, varying any where from every 6 months to 10 years. While water sampling programs in Michigan have failed to identify any electrical applications o f PCB's as major point sources of loss to aquatic situations, envi ronmental losses do occur which have the potential of indirectly reaching watercourses through atmospheric fallout or leaching from contaminated soils at spill or disposal sites. Losses directly to water may occur on occasion but would be d ifficu lt to detect because of their interm ittent nature. Plasticizer Applications Plasticizer applications represent the single largest "open-ended" or dissipative use o f PCB's. PCB's are or have been used as plasticizers in most countries in a wide variety o f consumer products, including paints, inks, copying paper, adhesives, sealants, plastic products, and textile coatings, many o f which are traded international ly (ref. 4). Monsanto's U.S. sales figures fo r 1970 showed a volume of nearly 20 m illion pounds fo r plasti cizer applications (ref. 1). Sales for this use were discon tinued in 1971. Environmental losses from past sales w ill likely continue fo r a long.period of time. Papers .used in the thermographic, xerographic, or pressure-sensitive copying processes have had PCB's added as plasticizers either in the ink or paper coatings, Recycling o f these papers can result in contamination of food packaging materials and other paper products (ref. 3). Effluents from paper re ve lin g or deinking plants also become contaminated. In Michigan, paper industry effluents have been found to commonly contain from 1 to IO pg/1 of PCB's. Conta nination o f fish has been identified as high as 110 mg/kg in the Kalamazoo River downstream from Kalamazoo, Michigan, where Michi gan's paper industry is prim arily centered. Stream sedi ments in the Kalamazoo area contain as much as 360 mg/kg PCB's; this is believed to be a result o f past deink ing processes in the area. Lower level contamination con tinues from processing o f recycled paper but most deink ing mills have ceased operation over the past 10 years. While Monsanto stopped sales o f PCB's fo r paper applications in 1971, one Michigan paper company re cently reported to the Michigan Department o f Natural Resources that several raw products that they purchase still contain PCB's. Two coloring compounds reportedly have 23 and 500 mg/kg PC B's and nearly all o f their wood pulp contains from 0.5 to 1.0 mg/kg. Burning o f waste papers containing PCB's, which occurs every day, undoubte dly results in atmospheric losses. PCB's have been deteuted in snowfall samples in Wisconsin (ref. 5). The largest quantities of PCB's in plasticizer applica tions end up in dumps and landfills. Much o f the materi al is in sealed containers or impregnated in plastics and is slowly released to the environment. Nisbet and Sarofim (ref. 6) reported that vaporization directly from paints, coatings, and plastics does o^cur, w ith losses as great as 20 percent. Open burning in landfills also releases PCB's to the atmosphere. Another source is loss to leachate from landfills. Samples of surface run off water from nine landfills in Michigan shwed five o f the nine sampies having PCB concentrati ons ranging from 0.04 to 0.30 pg/1, while the others contained less than 0.01 ig/L In 1970, the U.S. Food and Drug Administration identified m ilk contamination in Ohio, Georgia, and Florida resulting from use of a PCB-containing sealant in silos (ref. 3 j. In 1975 the Michigan Department o f Agriculture investigated problems from this usage and found 76 dairy herds in Michigan with PCB's in m ilk ranging from a trace to 14 mg/l on a fat basis. Scrapings from silos on these farms contained PCB's up to 10,000 mg/kg. Eighty additional silos have been Identified as having the PCB sealant and have been removed from use until a protective coating an be apolied to eliminate transfer of PCB's to the cattle feed. 128 7 /4 3 3 0 H ydraulic Fluids PCB's have found wide usage in hydraulic systems involving extreme pressure and high-temperature condi tions. Annual U.S. domestic sales o f PCB's fo r hydraulic uses totaled approximately 8 m illion pounds in 1970 (ref. 1). In Michigan, the automotive and metal finishing industries have used PCB-containing hydraulic fluids ex tensively. Industrial inspections and questionnaires documented past usage to have been as much as 878,000 pounds/year in individual plants, w ith most being col lected and disposed o f through waste haulers. Large losses of PCB's from these plants to municipal sewers or directly to surface waters have also been identified. W astew ater discharges from identified users of PCB-hydraulic fluids have had concentrations as high as 7.1 mg/l PCB's, indicating losses as great as 30 pounds per day. In a materials balance study, one industry which showed in its records that it was replacing approx-, imately 30,000 pounds PCB's/year in hydraulic systems calculated that 10,000 pounds/year were entering the atmosphere through vaporization losses, 8,000 pounds/ year in absorbents placed in landfills, 6,000 pounds/year lost to soils and drainage systems on plant property, 5,000 pounds/year going to waste haulers, with the re mainder incinerated. A ll industries that we have identified as using PCB's in hydraulic systems have converted to substitute prod ucts, mostly phosphate esters. Complete elimination of PCB residues from the systems has proved ineffective even w ith repeated flushings. Sampling o f replacement fluids indicates PCB contamination as high as 100 mg/I. Residues in discharge lines combined w ith loss o f con taminated replacement fluids appear to result in con tinued low-level discharges. Because of existing invento ries and possible purchase from foreign sources or re processing companies, it is unlikely that all hydraulic systems not included in our surveys or questionnaires have been switched to replacement fluids. One facility which we investigated had an inventory o f 9,000 gallons of PCB fluids in storage. In summary, Michigan's surveys o f hydraulic system usage of PCB's suggests that this has been a major source o f environmental contamination and may continue to contribute to the problem to a lesser but still significant degree. Heat Transfer Systems PCB's heat transfer fluids have been used in place of steam or superheated water in many industries and large building complexes. They provide advantages of reduced explosion hazards, absence o f corrosion problems, and have good heat transfer characteristics (ref. 4). In 1970, Monsanto sold approximately 4 m illion pounds o f PCB's fo r this application but phased out all sales in 1972 (ref. 3). From 1971 through 1973, Michigan identified at least 12 facilities discharging PCB's to surface waters or municipal sewers from this usage. Concentrations in some discharges were as high as 5.2 mg/l. One automotive company in Michigan reported using 34,000 pounds o f PCB's per year in heat transfer systems at three of its plants. The waste fluids were reportedly disposed o f by industrial waste haulers. Another smaller plant reported loss of 800 pounds in 1972 and that approximately 700 pounds o f this total was incinerated, 75 pounds disposed of in dumps, and 25 pounds lost to sewers and drains. In another Michigan survey, a chemical company complex was found to have an effluent concentration of 35 pg/l resulting from heat transfer system losses. Heat transfer losses are not all from industrial facilities. Samp ling o f interceptor lines o f the D etroit, Michigan, sewer age system resulted in the identification of heat transfer usage from two residential building complexes and one hospital as large sources o f PCB input to the system. Miscellaneous Uses In 1971, Michigan officials found a PCB concentra tion of 6.6 jig/1 in the waste lagoon o f a soap and deter gent company. The source was traced back to the com pany's usage o f PCB's as a dedusting agent at 0.7 percent in one o f its powdered products. The company had dis continued this usage in June 1970 and the PCB's were apparently leaching from contaminated lagoon sedi ments. The investment casting wax industry has been re cently identified as another user o f PCB's (ref. 7). This casting method, which has largely replaced sand casting for production of low-tolerance-quality metal castings, uses formulated waxes as a basic molding mode. The waxes are injected into metallic dies to form the part shape and then coated w ith ceramic to form a final mold. The wax is removed by insertion o f the mold in an autoclave, which melts the wax. Residues o f wax are also secondarily removed by insertion o f the molds in a fur nace at 1,600 to 1,800 F. During these two proce dures, the bulk o f the wax is collected and usually recy cled but a portion is lost to vaporization, cooling water contact, and poor housekeeping practices. The waxes in use are obtained from a few major suppliers, one of whom is a major importer of decachlorobiphenyl from an Italian source. We have found twelve firms in Michigan using this casting process and several firms that reprocess their waxes. Our preliminary investi gations indicate that most of the waxes contain approxi mately 20 percent of PCB's or polychlorinated terphen- o n iN r u u ju o i 129 774331 yls (PCT'sl; one recent sample indicates the range may extend as high as 60 percent content in the wax. The nature of these casting operations, including both opera* tional and storage modes, at many plants indicates strong potential fo r environmental loss. An effluent sampie from one of the Michigan companies using invest ment casting wax contained 2.5 pqi\ of PCB's. During a telephone survey of 39 industries in Michigan during May 1975, several industries reported use o f a toilet hand soap containing 0.05 percent PCB's by weight. Followup on these reports indicated that this product actually contains a chlorinated diphenyl oxide rather than PCB's. Three industries in the telephone survey reported use o f a hydrated lime product that contained about 0.5 mg/kg PCB's. This product was being used fo r water treatment and in production of glass pellets. No explana tion was available on why the lime contained PCB's but it is assumed to be a contaminant rather than an addi tive. Concentrations in M unicipal Wastes Because o f the diversity of PCB usage, municipal wastewater is likely to receive PCB's from numerous domestic and industrial sources, many of which are list ed above. Buckley (ref. 3) estimated that municipal out falls would likely contribute less than 5 percent (300 tons) o f total annual loadings (6,000 tons) to aquatic environments o f the North American continent. His esti mate was based on an assumed average PCB concentra tion of 10 pg/l in wastes serving a sewered population of 150 million people producing 130 gallons of sewage per person per day. Sampling of 58 municipal wastewater treatment plant (WWTP) effluents throughout Michigan in 1973 showed an average concentration o f 0.52 pg/l (table 1). This is considerably lower than Buckley's value of 10 jug/l used in his calculations but still exemplifies wide spread contamination in municipal wastes, and docu ments that they are indeed a source o f PCB loss to sur face waters. Much of the PCB's entering municipal waste treat ment facilities are removed and become incorporated into the waste sludge. Table 2 shows PCB concentrations in the sludges from Michigan municipal plants sampled in 1973. Concentrations are much higher than in the effluents from the same plants. The average for all plants was 15.6 mg/kg, w ith individual values as high as 350 mg/kq. Disposal of these sludges may add to environ mental PCB levels. Sewage sludges are commonly dispos ed of by incineration, spreading on agricultural land, or placing in landfills. Discussion While I have characterized in this report possible and proven sources o f environment loss of PCB's in Michigan from several applications, I want to acknowl edge that not all industrial effluents tested in Michigan contain measureable PCB levels. We have tested over 900 industrial samples, w ith appro):imately 40 percent of ef fluents sampled containing PCB's above our 0.1 jig/l laboratory sensitivity lim it. Twenty-three percent o f the industries tested had greater than 0.5 pg/l, 18 percent greater than 1 jig /l, 6 percent greater than 10 Mg/I, and 2 percent greater than 100 ig/l. This represents a diversity of industries showing contamination and in many cases the source o f effluent contamination could not be deter mined. Since new industrial sources of loss are continuously being found, we feel we are far from eliminating the PCB inputs to surface waters by searching fo r p oint sources and taking corrective measure; on a case-by-case basis. We are far from understand!nij the impact or compara tive contribution o f atmospheric losses but we feel these are probably very significant also. In light o f considerable environmental damage and economic impact o f PCB contamination, an absence of any apparent decline in environmental concentration w ith current control methods, the ubiquitous nature of usage, the general lack o f adequate disposal facilities, and the indication that atmospheric transport and depo sition is also significant, the Michigan Department of Natural Resources urges that a national ban be pursued on all domestic and imported PCB's destined fo r use other than in transformers and capacitors, and that the critical or essential use o f PCB's in transformers and capacitors be immediately and critically reviewed in light o f current potential replacement products. Feeling that existing legis ation was inadequate to control PCB's, a group o f Michigan legislators introduced a bill on August 14, 1975, to prohibit the manufacture, sale, and use o f PCB's in Michigan fo r all applications other than fo r transformers and capacitors. The bill would provide fo r labeling, reporting, and disposal re quirements and specifies penalties fo r violations. The bill calls fo r a stepwise elimination o f PCB's w ith the sale, manufacture, and use of products containing 25 percent or more PCB's forbidden by January 1, 1976; 10 ppm or more forbidden after January 1, 1977; and 5 ppm or more forbidden after January 1, 1978. Public hearings on the bill are currently being: conducted by the Michigan House Committee on Mari ne Affairs. [The bill was amended and voted out of committee on December 11, 1975. The amendment changeq the maximum allowable concentration after January 1, 1977, to 1,000 ppm and 100 after January 1,1978.] GENP 005682 130 774332 Table 1. Concentrations of PCB's in the final effluent from wastewater treatment plants throughout Michigan, Spring, 1973. Concen trations in micrograms per liter, dry weight. City Date h-- TCTs ' 1'4 1242:12 Adrian A lb io n Ann Arbor Bay C ity B a ttle Creek. Benton H arbor- S t. Joseph Brighton C adillac C h a rlo tte Constantine D etroit Dexter East Lansing Escanaba E s s e x v llle F lin t Gladstone Grand Haven Grand Rap1ds Holland Houghtan-Hancock Iran Mountain- Kingsford Xranwood Jackson Kalamazoo L'Anse Lansing Han1st1que Marquette Harshal1 Menominee Midland M ilford Monroe Mt. Clemens Mt. Pleasant Muskegon Muskegon Heights N ile s Norway Owosso Pontiac (Auburn) Pontiac (E. B lvd.) P ort Huron Saginaw Sault Ste. Marie S t. Ignace Three*Rivers Traverse C ity Trenton Warren Wayne County Wyoming Y psilanti Y p s ila n ti Twp #1 Y p s ila n ti Twp #2 3/7/73 2/22/73 3/1/73 3/1/73 2/28/73 2/28/73 3/1/73 3/28/73 5/1/73 2/28/73 2/28/73 3/1/73 5/2/73 ` 3/28/73 3/1/73 2/22/73 3/28/73 2/21/73 2/21/73 2/21/73 3/27/73 3/28/73 3/27/73 2/22/73 2/29/73 3/27/73 4/18/73 3/28/73 3/27/73 2/22/73 2/28/73 3/1/73 3/8/73 5/4/73 3/8/73 3/28/73 2/28/73 2/28/73 2/20/73 3/28/73 2/21/73 3/12/73 3/12/73 3/8/73 3/1/73 3/28/73 3/28/73 2/21/73 3/7/73 2/28/73 2/27/73 2/28/73 2/21/73 2/28/73 3/1/73 3/1/73 3.20 2.15 0.34 0.2S * <0.10 0.20 0.53 0.34 0.46 0.23 0.18 0.10 <0.10 0.44 <0.10 1.05 <0.10 0.18 * 0.69 <0.1 0.22 0.63 0.29 0.15 0.57 <0.10 <0.10 0.29 0.88 0.18 0.48 <0.10 0.12 0.73 0.31 <0.10 <0.10 <0.10 <0.10 0.40 0.22 ` <0.10 <0.10 0.26 0.33 0.28 0.29 1.12 0.31 2.20 2.90 0.60 0.54 1.80 0.77 0.31 1r2e4*l2oC, .oAn-creandtroarc 1lo2a5s4,baasreda monixbteusree aflcAorfadCohrre1e24s2: aannddar12s5:4 Alaraada1r:1 GENP 005683 131 774333 Table 2. C ity Concentrations of PCB's in the sludge from fifty-seven municipal wastewater treatment plants in Michigan, Spring 1 9 7 i Concen trations in milligrams per kilogram, dry weight. PCB's Date 1242:1254 Adrian A lb io n Ann A rb o r B a y *C ity B a ttle Creek Benton Harbor- S t. Joseph B rig h to n C adillac C harlotte C o n s ta n tin e Q etrolt Oexter E. Lansing Escanaba E ssexville F lin t Gladstone Grand Haven Grand Rapids H o lla n d Howell Hougntdn- Hancock Iron MountainK in g s fo rd Ironwood Jackson Kalamazoo - L ' Anse Lansing M a n lstiq u e Marquette M a rsh a ll Menominee M id la n d M ilfo rd Monroe M t. Clemens Mt. Pleasant Muskegon Muskegon Heights N iles Norway Owosso Pontiac (Auburn) Pontiac (E. 31v d .) P o rt Huron Sag1naw S ault Ste. Marie S t. [gnace Three Rivers Traverse C ity Tren ton Warren Wayne County Wyoming Y p s U a n tl Y p s ila n ti Twp #1 Y p s lla n tl Twp 42 3/7/73 2/22/73 3/1/73 3/1/73 2/28/73 2/28/73 3/1/73 3/23/73 5/1/73 2/28/73 n2 /2 8 / 7 3 3/1/73 5/2/73 3/28/73 3/1/73 2/22/73 3/28/73 2/21/73 2/21/73 2/21/73 4/26/73 3/27/73 3/29/73 3/27/73 2/22/73 2/29/73 3/27/73 4/18/73 3/28/73 3/27/73 2/22/73 2/28/73 3/1/73 3/8/73 5/4/73 3/8/73 3/28/73 2/28/73 2/28/73 2/20/73 3/28/73 2/21/73 3/12/73 3/12/73 3/8/73 3/1/73 3/28/73 3/28/73 2/21/73 3/7/73 3/28/73 2/27/73 2/29/73 2/21/73 2/28/73 3/1/73 3/1/73 352.0 32.1 23.3 175.0 2.0 1.5 1.1 2.8 13.8 <0.1 <0.1 6.8 2.1 3.2 4.6 5.9 3.9 6.3 4.1 4.1 11.8 0.8 15.0 5.5 9.5 5.2 3.0 4.4 5.3 1.5 2.8 3.9 4.2 2.9 3.3 6.5 12.7 11.0 7 .8 <0.1 2.0 - , 5.0 2.4 1.5 4.1 1.8 <0.1 <0.1 0.53 2 .0 <0.1 <0.1 24.0 50.5 12.1 9.2 9.2 124a2C, oAacreobcelorarC1la2n54b, asoerdaoanixbteusrte foi tf Aofr otchlroere stan 1242 dard and, :5L:254AIrno calo1r :1 ratio GENP 005684 132 774334 REFERENCES 1. William Papageorge, "PCB Manufacture and Sales, Monsanto Industrial Chemicals Company, 1957 through 1974," handout to Governor's Great Lakes Regional Pesticide Council, Chicago, Illinois, Janu ary 30, 1975. 2. Martin G. Broadhurst, " Use and Replaceability of Polychlorinated Biphenyls/' Environm ental Health Perspectives, Exp. Issue No. 1 (April 1972), pp. 81-102. 3. Interdepartmental Task Force on PCB's, "Polychlor inated Biphenyls and the Environment," National Technical Information Service, Springfield, Virginia, COM-72-10419, May, 1972. 4. Organization fo r Economic Co-Operation and Devel opment, "Polychlorinated Biphenyls--Their Use and C ontrol," Paris, November, 1973. 5. Stanton Kleinert, "Statement Before the DNR Rulemaking Hearings to Consider Effluent Standards for PCB's," Room 421, South Capital, Madison, Wis consin, August 28,1975. 6. 1. C. T. Nisbet, and A. F. Sarofim, "Rates and Routes of Transport o f PCB's in the Environment," presented at International Scientific Meeting on PCB' s, Rougemont, North Carolina, December 20-21,1971. 7. Vincent J. DeCarlo, EPA Monitoring and Informa tion Systems Branch, memo to James M. Conlon, EPA A ir and Hazardous Materials Division, Washing ton, D.C., May 12, 1975. GENP 005685 133 774335 GENERAL DISCUSSION OF SESSION II CHAIRMAN GARRETT: I applaud all the speakers for MR. W ILLIA M H. BUSCH (Illinois EPA, Springfield, their interesting insights in these matters. A t this Illinois): This is not so much a question as a con point I'd like to call for questions from the floor. cern. I t seems like therej is another open-ended MR. DON SKINNER (Environment Canada, Ottawa, source of PCB's in that most electrical capacitors, Canada): I am from Canada, and I would like to the small ones, end up as a throw-away item in address myself to Mr. Tom Kopp. Tests going on at St. Lawrence Cement in Ontario, to set the record straight, are being financed by the Government of Canada and the Government of Ontario. The partici pation in that program other than the suppliers of hom e entertainment products. Television sets, radios and motor-starting capa citors ultim ately fail and are discarded in landfills. It seems like we should be [giving more attention to groundwater around landfills. This was touched on the waste is stilt up to EPA? MR. THOMAS E. KOPP (Environmental Protection earlier today. | CHAIRMAN GARRETT: We'have been considering this Agency, Washington, D.C.): Yes, sir. MR. HOWARD A. FORMAN (United Electrical Work ers, New York, New York): I would like to address aspect | MR. JACK M ED VILLE; Dr. purfee described the con trol of U.S. manufacture o f PC8's. Does the presen my question to Mr. Kopp. You had mentioned how EPA is surveying the use and disposal of PCB's. I tation indicate that the I nited States has shut o ff * foreign manufacturers of PCB's? 1 know that at least our use was not surveyed, we MR. KOPP: We have no lega authority to control im represent a very valuable source of information on portation of PCB's into the United States. PCB use, especially regarding capacitor plants and MR. M ED VILLE: I w ill phrase the question differently. transformer plants. Does EPA plan to survey and try We have received here a [number o f figures of the to get information from the various labor unions amount that is going o u t and being reentered each involved in the electrical manufacturing industry? year from U.S. manufacturing; is there an outlet on MR. KOPP:' That is a very interesting idea, to survey the what is coming in from foreign nations? unions. I w ill discuss this w ith our Office of En MR. KOPP: The information jwe get is from the Bureau forcement. We'll get together and discuss it and if o f Customs. That is maintained confidential, which you'll let me have your name and address, we'll get is upon their request. Only bulk PCB's are reported. back to you. The amount o f PCB's ente ring in equipment, such as CHAIRMAN GARRETT: I have one question I'd like to transformers, we have no idea, but we are trying to ask Bob Durfee. There may be some question that identify the importers .of capacitors and trans may arise from this, but Bob, would you please describe the differences between the two terms formers to the United Staties. MR. MARK WILSON: I am from Canada. I am not ad mentioned just now, Aroclors and askarels. dressing my question to any particular member. DR. ROBERT L. DURFEE (Versar, Inc., Springfield, Does anyone know if PC8's are still used in aircraft, Virginia): Well. Aroclors are a trademark of Mon and secondly, what w ill the offshore oil lines do? santo Company, and askarels are a class of fluids Are they- bringing their own European hydraulic which by their nature do not form combustible facilities in? products during an electrical breakdown in a dielec MR. KOPP: We have thought about this a great deal. We tric system. There are several types of askarels; have also thought about ships that are coming into among them is the metalated PCB. the United States from overseas, because of their MR. RICHARD FERRY (Bio International, Inc., Woods hydraulic systems. We do not know o f any PCB's Hole, Massachusetts): You told us about filtration being used in aircraft except in capacitors. of PCB's. Do you have a handle on the quantity of These things we are trying to get information PCB's and how they are disposed of? o n , and we hope to get more consultation with DR. DURFEE: The disposal of all solid wastes contain the members of the Organization of Economic Co ing PC3's is by landfill. There is no incinerator operation Development. operating at the present time that w ill accomodate solids and destroy the PCS. As far as the quantities arc concerned, I really do not know what the total is going to be. I f you say that all transformer fluids are cleaned up once every 5 years or something like that, then perhaps the quantity w ill be less than 1 percent, and this w ill be replaced by fresh PC8's. 134 OEM? 005686 774336 20 November 1975 Session III: ENVIRONMENTAL FATE AND OCCURRENCE Ian C.T. Nisbet, Ph.D.* Session Chairman ` Director, Scientific Staff, Massachusetts Audubon Society, Lincoln, Massachusetts. 135 774337 GENP 005687 774338 GENP 005688 INTRODUCTORY REMARKS Ian C. T. Nisbet, Ph.D. This is Session III on Environmental Fate and Occurrence of PCB's. We have eight papers on residue levels of PCB's in the environment, followed by four papers on transport and transformation in the environ ment. We are very short o f time to present 12 papers in 4 hours, so I am going to be pressing on the speakers to cut down the time they spend as much as possible. I hope you w ill forgive them if they om it supporting details o f some o f what they say. We w ill not be able to entertain any questions or discussion until the end of the session. J have been asked to introduce this session by ex plaining what we knew about PCB's in 1971 when Monsanto first made its voluntary restrictions on sales, so that we can see what has been learned in the last 4 years. A t the end o f 1971, Adel Sarofim and I reviewed the data that were available on the occurrence of PCB's in the environment and tried to construct a transport model. We wrote two papers; a preliminary version was p u b lish e d in E n v iro n m e n ta l Health Perspectives (1:21-38, 1972), and a considerably fuller version came out a few months later in the journal EnvironmentalResearch {5:249-362, 1972), incorporating additional data, corrections, and a comparison of our transport model with observations of residue levels in the environ ment. It seems that almost no one has read this second paper in Environm ental Research, the main reason prob ably being that it cost $8. The moral o f the story fo r us scientists is that if we want our w ork to be read and quoted, we have to release large quantities of reprints into the environment, and direct them down environ mental gradients into compartments where they w ill have maximum biological impact. In these papers we did four things. The first was to review the data on production of PCB's in the United States and their uses. We reviewed what data were avail able os releases of PCB's into the environment, bath deliberate releases and accidental ones. We filled in this information with what was essentially guesswork about the remaining releases into the environment, based on our knowledge of the lifetimes of products containing PCB's, disposal practices, and the likely behavior of PCB's in the environment, including their behavior during incineration. Our conclusion was there were three major routes of release of PCB's into the environment as of 1971. The most important, amounting to about three quarters of the total, we believed would be deliberate discarding of PCB's and products containing them, mostly into dumps and landfills. Much of this discarded material would be incorporated in sealed containers and plastic. We had no knowledge whatsoever whether the material put into dumps was leaching out or not. th e second most important route, accounting for two-thirds to three-quarters o f the remaining disposal, we believed was into water. This was primarily attribut able to losses o f industrial fluids, including hydraulic fluids, dielectrics, heat exchange fluids, fluids in com pressors, and disposal of scrap fluids from manufacturing operations. The third route o f release, which we thought accounted for the balance of the total, was into the air. We thought that there were several substantial contribu tions to release to the atmosphere, the major one being evaporation from plasticized products. We thought there were probably also substantial releases from incomplete burning in dumps and poorly operating incinerators, together with some releases from burning of scrap prod ucts. There was also known to be some release into the environment from dedusting agents containing PC8's used on roads and parking lots. The second thing we did was to review what was known about transport o f PCB's in the environment. This appeared to fall into two major categories, trans port in air and transport in water. We guessed that most aerial transport was due to passive movement of PCB's trapped on airborne particulates, eventually returning to earth in rain and dustfall. We reviewed transport in water with particular respect to transport downstream into the Great Lakes and the sea. We thought there were a num*. ber of different methods of transport, all of which were significant. These included transport in solution, move ment of sediment containing PC8's, dredging o f contam inated sediment followed by dumping at sea, deliberate dumping at sea of industrial waste, dumping at sea of sewage sludge, transport in sewage to ocean outfalls, leaks directly into estuaries from coastal industries, and finally disposal from ships. The third thing that we did was to compare our estimates of releases and ` transport to levels that had been reported in the environment. We found five major discrepancies. 1. Surveying the environment, we could not account for more than a very small fraction of PCB's that were being released or had been released in the past. CjENP 005689 137 Preceding page blank 774339 We concluded that most o f the PCB's that had been discarded in the past were still in dumps and land* fills. 2. The amount that we estimated as being released into freshwater was very much larger than anything we could estimate as being transported to the sea. We concluded that PCB's were accumulating in sedi ments in rivers and lakes. We also thought that they were accumulating in sediments, at sea on the con tinental shelf.3. Most environmental residues were o f pentachlorobiphenyls and higher chlorinated species, although about half of the releases into the environment at that time and in the past had been of tetrachlorobiphenyts and lower chlorinated species. Our con clusion was that the tetrochlorobiphenyls and lower chlorinated species were being rapidly degraded in the environment. This conclusion was based on the fact that we could not find any evidence for d iffer ential transport and dispersion of the lower isomers away from points o f release. 4. PCB levels in the ocean and in marine organisms-- plankton, fish, and birds--were much higher than could be accounted fo r by aerial transport. We suggested speculatively that the major source of PCB's in the ocean might be marine hydraulic fluids. 5. There were higher residues in terrestrial birds than could be accounted fo r by considering known dis persive uses. Accordingly we posed in 1972 six major questions about PCB's in the environment: 1. What happens to chlorinated dibenzofurans in the environment? Are they released, are they persistent, and are they bioaccumulative? 2. Are the PCB's being discarded into dumps going to stay there or are they going to leak out in the future? This is perhaps one of the biggest environ mental questions to be solved, because our estimate was that over the past few decades something of the order o f 300,000 tons of PCB's had gone into dumps and landfills. 3. Are the PCB's that are r ow in sediments in freshwaters and the shallow sea going to be covered up and sequestered away from us, or are they going to be continually recycled llack into the environment in future years? 4. Is it correct that the tetrachlorobiphenyls and the lower chlorinated species really are rapidly de graded, and is there significant human exposure to these lower chlorinated species? 5. What is the extent of human exposure, both the average and the extremes? We suggested some num bers in our papers, but we concluded that they were very ill-defined and that fhe extent o f human expo sure was very variable. 6. Finally, what w ould be the effect o f Monsanto's curtailment of dispersive uses in 1971? We con jectured that this action would cut out only part of the influx into the environment, and that it would be -a long tim e before some compartments in the environment show decreases in environmental levels. These are the questions which I th in k w ill be ad dressed in part by our 12 speakers this morning. In my summary statement, I w ill corn back and see how far we have come in answering those questions in the last 4 years. s ^3 ON vo 138 774340 RESIDUES OF POLYCHLORINATED BIPHENYLS IN THE GENERAL POPULATION OF THE UNITED STATES Frederick W. Kutz, Ph.D., and S. C. Strassman* A bstract Residues o f polychlorinated biphenyls have been found in human adipose tissue end in m ilk collected from the general population o f the U nited Sates. In a national survey o f human adipose tissue during fiscal yean 1973 and 1974, 35.1 and 40.3 percent, respective ly , o f the tissue collected contained levels o f 1 ppm o r m ore o f polychlorinated biphenyls 'o n a w et-weight basis. Electron capture-gas chromatographic analysis o f this tissue revealed th a t the compounds found in adipose tissue were m ost comparable to those prevalent in A ro clo r 1254 and A ro clo r 1260. A d d itio n a lly , semiquantitative estim ation o f these residues was accomplish ed b y thin-layer chromatography. Evidence from gasliq u id chromatography-mass spectrom etry indicated th a t th e m o s t fre q u e n tly encountered polychlorinated biphenyl residues were penta-, hexa-, and heptachlorobiphenyl compounds. Human m ilk samples collected in selected counties o f Arkansas and Mississippi were found to contain trace quantities 1 ppm ) o f polychlorinated biphenyls on a wet-weight basis. Human exposure to polychlorinated biphenyls may come from direct contact w ith industrial products con taining these compounds, from association w ith contam inated environmental components or from many combi nations of the two. Intak of these compounds may occur by three routes: (1) ingestion, (2) respiration, and (3) absorption through the skin and mucous membranes. Most probably, all contribute to the total body burden of these chemicals; none o f these routes o f exposure can now be identified as the most important. Polychlorinated biphenyls have been found in human adipose tissue collected fo r the National Human Monitoring Program as reported by Yobs (ref. 1). This program is a continuing ambient monitoring activity which functions to determine, on a national scale, the exposure of the general population to pesticides and to assess changes in these parameters when they occur. Polychlorinated biphenyls, in addition to certain organochtorine pesticides, are detected in human adipose tissue following a multiresidue analytical procedure sti- Ecological Monitoring Branch, Technical Services Division (WH-5691, U.S. Environmental Protection Agency. Washington, D.C. puiated by the National Human Monitoring Program for Pesticides. The objective o f this paper is to report the findings o f polychlorinated biphenyls during the human m onitor ing sDrveys conducted in fiscal years 1973 and 1974. These results are compared to those obtained in the 1971 survey. Additionally the results o f the analysis of human m ilk fo r polychlorinated biphenyls are presented. Data from gas-liquid chromatography-mass spectrometric analysis of the polychlorinated biphenyls in human adipose tissue and m ilk are also reported. Early confirmation of polychlorinated biphenyls in human depot fat was accomplished in 1967 by Widmark (ref. 2) using combined gas chromatography mass spec trom etry. An article by Biros et al. (ref. 3) reported that two human adipose tissues examined by combined gas chromatography mass spectrometry were shown to con tain substantial quantities o f polychlorinated biphenyls ran gin g fro m pentachiorobiphenyl to decachlorobiphenyl and included at least 14 isomers and chlorine homologs. These samples, supplied by the National Human Monitoring Program for Pesticides, were selected because of indications of unusually high levels of these chemicals. One of the laboratories routinely engaged in human tissue analysis, under contract to the National Human Monitoring Program for Pesticides, published data re garding the polychlorinated biphenyl content of human adipose tissue (ref. 4). According to this study, 41 to 45 percent of the general population had levels o f 1 ppm or .more of polychlorinated biphenyls w ith isomers contain ed in Aroclors 1254, 1260, 1262, and 1268. The pre sence of these compounds, ranging from pentachlorobiphenyl to decachlorobiphenyl, was confirmed in three samples by combined gas chromatography mass spectro metry. Polychlorinated biphenyls were found in measurable amounts in 31.1 percent of 637 samples o f human adipose tissue collected from the general population as part o f the Human Monitoring Survey during 1971 (ref. 1). Sample collection involved 18 states and the District of Columbia. Positive samples were obtained from each political jurisdiction sampled. Residues o f these compounds have also been detect ed in other human tissues and m ilk. In a study of human m ilk collected in Colorado, 8 of 40 samples contained residues of polychlorinated biphenyls ranging from 40 to 100 ppb (ref. 5). 139 774341 GENP 005691 METHODS AND MATERIALS Samples of adipose tissue from individuals of the general population were obtained through the coopera tion o f pathologists and medical examiners in 75 select ed collecting sites throughout the contiguous 48 States. Sampling: A stratified random design, with samp ling proportioned to populations, was followed for selecting cities in which tissue samples were collected. The strata were the nine census divisions as designated in the 1970 Census; the sampling units in each census re gion were cities with populations in excess of 25,000 people. The number o f cities designated within each census division was based on population. The cities which served as collecting sites are shown in figure 1. This design provided samples which are statistically representative o f the general population. For each collec tion site, an annual sample quota was established to re flect the demographic distribution in that census divis ion. The sample quota in each of these groups was allo cated proportionally according to the age, sex, and race distribution, as determined by the 1970 Census. Adipose tissue was collected by cooperating patho logists and medical examiners from postmortem exami nations and from specimens which had been removed during therapeutic surgery. Thus] tissues were received from patients having pathological conditions as well as those dying from sudden acute illness or from trauma. Information recorded fo r each iissue sample included age, sex, race, and pathological diagnosis. Geographic residence was assumed to be in :he general location of the hospital. Since the objective of the program was to reflect the pesticide and other pollutant burden in the general population, samples were not collected from cases in which a diagnosis o f pesticide poisoning was suspected or known, from cachectic patients, or from patients who had been institutionalized for extended periods. Further details o f the program were presented by Yobs (ref. 6). Chemical Analysis: Samples were analyzed chem ically by contract laboratories using only methodologies specified by the program. A ll laboratories were required to maintain acceptable performance levels in an interlaboratory quality assurance program established and moderated by the EPA Pesticides and Toxic Substances E ffe c ts L a b o ra to ry , Research T ria n g le Park, N.C. 27711. This laboratory also provided technical assistance fo r the analytical portion o f the program. Samples were analyzed fo r selected chlorinated hydrocarbon insecticides (table 1 1, and polychlorinated g e n p 005692 Figure 1. Map of the United States showing census divisions and collection sites for the National Human Monitoring Program for Pesticides. 140 774342 Table 1. List o f chem icals detectable in human adipose tissue o.p'-DDT p,p'-DDT o,p'-DDE p , p `-DDE o,p'-DDD p.p'-DDD a-BHC 6-BHC lindane 6-BHC aldri n dieldrin heptachlor heptachlor epoxide endrin mi rex oxychlordane transnonachlor polychlorinal biphenyls hexachlorobenzene biphenyls, using a modified Milts-Olney-Gaither proce dure (ref. 6). Gas-liquid chromatography with electron capture detection was employed fo r basic compound identification and quantification. The analytical deter minative procedure fo r polychlorinated biphenyls in tissue involved: (a) extraction, partitioning, and Florisil column chromatographic purification o f the residues to gether with the chlorinated hydrocarbon pesticides pre sent in the tissue sample, and (b), thin layer chromatog raphic (TLC) semiquantitative estimation o f residues in the purified extract following elimination o f interfer ences from o p %` and p jo'-DDE, DDD, and ODT residues by chemical conversion to the respective isomer of dichlorobenzophenone. The details of the TLC proce dure included treatment of the extract w ith ethanolic potassium hydroxide to effect dehydrochlorination of DDT and its analogs to DDE. This was followed by oxi dation with chromium trioxide in acetic acid to convert DDE residues to dichlorobenzophenone, which may be c o n v e n ie n tly separated from the polychlorinated biphenyl residues by the TLC procedure. The plates were coated w ith silver nitrate-impregnated aluminum oxide G and developed w ith 5 percent benzene in hexane. Ultraviolet visualization of the eluted poly chlorinated biphenyl residues and semiquantitative com parison of sample, spot intensity w ith those observed for standard materials completed the polychlorinated bi phenyl determination. A total of 140 human adipose tissue sample extracts from the general population have been subjected to analysis by combined gas chromatography-mass spectro metry (GC-MS) to confirm and identify polychlorinated biphenyl components stored in human tissue. Levels of total polychlorinated biphenyls in the samples based on TLC determination ranged from 0.4 to 3.5 ppm. The adipose tissue samples had been extracted and subjected to the purification procedures described earlier. Con version of the DDT-type residues to dichlorobenzo phenone was effected by the combined dehydrochlorina tion, oxidation, chemical procedures. A final Florisil column chromatographic step was included to further purify the polychlorinated biphenyl residues and remove the dichlorobenzophenones present at relatively high levels in the extract RESULTS AND DISCUSSION The levels of polychlorinated biphenyls found in general population samples o f adipose tissue during fiscal years 1973 and 1974 are presented in table 2. Results presented by Yobs (ref. 1) are included fo r comparative purposes. During fiscal years 1973 and 1974, 35.1 and 40.3 percent, respectively, of the tissues collected con tained levels o f 1 ppm or more o f polychlorinated bi phenyls on a wet-weight basis. These frequencies are slightly higher than the 32.5 percent figure reported by Yobs (ref. 1) and are slightly lower than th rje (41-45 percent) reported by Price and Welch (ref. 4). The per centage of tissues which contained quantifiable amounts o f polychlorinated biphenyls appears to be remaining relatively constant However, there does seem to be an increase in the percentage o f tissues which contained trace levels of this chemical although the lim it of detec tion (1 ppm) remained constant. It should be interesting to determine whether these trace values w ill be conver ted to quantifiable amounts as the exposure of the general population continues over time. National frequencies for fiscal years 1973 and 1974 were compared to frequencies for each census division and are presented in figure 2. The New England, Middle Atlantic, South Atlantic, and East North Central Census Divisions had frequencies of quantifiable levels exceed ing the national frequencies for both survey years. The Mountain and East South Central Census Divisions had levels higher than the national levels for one survey year and lower fo r the other survey year. The Pacific, West North Central, and West South Central had levels lower than the national levels for both-survey years. f'/'n r A A rk in r r \ 141 7 7 4 3 4 3 Table 2. Levels of polychlorinated biphenyls in hum an adipose tissue Data source Sample s iz e Yobs, 1972 FY 1973 Survey FY 1974 Survey 688 1277 1047 Percent nondetected 34.2 24.5 9.1 Percent Percent Percent < 1 ppm 1 -2 ppm > 2 ppm 33.3 27.3 5 .2 40.2 29.6 5 .5 50.6 35.4 4 .9 GENP 005694 Figure 2. Map of the.United States depicting census divisional frequencies of polychlorinated biphenyls. 142 774344 The most frequently encountered polychlorinated biphenyl residues in the human adipose tissue extracts examined by combined gas chromatography-mass spec trometry were the penta-, hexa- and heptachlorobiphenyl compounds. As polychlorinated biphenyls enter a biological system, the less chlorinated isomers are apparently either metabolized or excreted. These biochemical -reactions alter the original Aroclors, so that electron capture chro matograms o f these compounds from biological systems do not exactly match available laboratory reference standards. However, it can be noted that results do indi cate that the polychlorinated biphenyls found in human adipose tissue most closely resemble Aroclor 1254 and Arocior 1260. The National Human Monitoring Program also collected and analyzed 57 samples o f human m ilk from selected areas of Arkansas and Mississippi. The survey design was related to rice culture areas in which the herbicide 2,4,5-T was used. A ll o f these samples contain ed trace amounts of polychlorinated biphenyls, the pre sence of which were confirmed by combined gas chro matography-mass spectrometry in a composite sample. REFERENCES 1. A. R. Yobs, ''Levels o f Polychlorinated Biphenyls in Adipose Tissue o f the General Population of the N a tio n ," Environ. Health Perspectives, Vol. 1 (1972), pp. 79-81. 2. G. Widmark, "Possible Interference try Chlorinated Biphenyls," J. Assoc. O ff. Anal. Chem., Vol. 50 (1967), p. 1069. 3. F. J. Biros, A. C. Walker, and A. Medberry, "Poly chlorinated Biphenyls in Human Adipose Tissue," B ull. Environ. Contamin. Toxicol., Vol. 5 (1970), pp. 317-323. 4. H. A . Price and R. L. Welch, "Occurrence of Poly chlorinated Biphenyls in Humans," Environ. Health Perspectives, Vol. 1 (1972), pp. 73*78. 5. E. P. Savage, J. D. Tessari, J. W. Mai berg, H. W. Wheeler, and J. R. JBagby, "Organochlorine Pesticide Residues and Polychlorinated Biphenyls in Human M ilk, Colorado -- 1971-1972," Pesticide M onitoring J., Vol. 7 (1973), pp. 1-5. 6. A. R. Yobs, "The National Human Monitoring Program fo r Pesticides," Pesticide M onitoring J., Vol. 5 (1971), pp. 44-46. 7. J. F. Thompson, e d ,, Analysis o f Pesticide Residues in Human and Environm ental Samples (Manual of . Analytical Methods), prepared by Pesticides and Toxic Substances Effects Laboratory, U.S. Environ mental Protection Agency, Research Triangle Park, N.C. 27711. GENP 005695 143 774345 PCB RESIDUES IN HUMAN ADIPOSE TISSUE AND MILK Donald L. Grant, Ph.D.*, J. Mes* and R. Frank** A bstract Surveys. o f PCB residues in human adipose tissue suggest th a t females have tower residues than mates, th a t residents o f Centra/ Canada (Manitoba and Saskatche wan} have tow er levels than die rest o f Canada, and th a t the m a jo rity o f Canadians have an adiposa tissue residue o f 1 to 2 mg/kg. PCB residue in human m ilk o f O ntario residents was found to be approxim ately 1 m g/kg fat. Data on PCB residues in adipose tissue obtained in a national survey by Health and Welfare Canada and data obtained in a survey of residents o f Ontario w ill be pre sented. Human m ilk PCB residue data obtained in Ontario w ill also be presented. The Ontario surveys were carried out by the Ontario Ministries o f Health and of Agriculture and Food. The adipose tissue samples were collected at autop sy. In all surveys, organochiorine pesticides as well as PCB residues were determined. The PCB and organo chiorine pesticide residues were separated by column chromatography prior to gas-liquid chromatography and quantitation w ith an electron capture detector. PCB residue data fo r human adipose tissues ob tained in the Health and Welfare Canada survey are pre sented in tables 1 and 2. A ll adipose tissues had detectable levels o f PCB's and 30 percent o f the samples had PCB residues greater than 1 mg/kg. The range of residues present was 0.11 to 6.60 mg/kg. Tnere are some regional differences; 49 per cent of The adipose tissues samples collected in Ontario had PC8 residues greater than 1 mg/kg, while only 9 percent of the samolas collected in Manitoba and Sas katchewan (Central Region) had PCB residues greater than 1 mg/kg. The other three regions were very similar w ith approximately 25 percent o f the samples having residues greater than 1 mg/kg. The mean PCB residue for all adipose tissues collect ed was 0.907 mg/kg (table 2). The residue present in adipose tissue from males was greater than that present *Toxicaluqical Evaluation Division, Foods Directorate, Health Protection Branch, Depanment of Health and Welfare, Ottawa, Ontario. Canada. "P ro vin cia l Pesticide Residue Testing Laboratory, Ontario Ministry of Agriculture and Food, Guelph. Ontario, Canada. in adipose tissue from femal es. Residues present were highest in samples collected in Ontario, w ith means of 1.165 and 0.B59 mg/kg for males and females, respectively, and lowest in samples collected in Central Canada (Manitoba and Saskatchewan , w ith means of 0.621 and 0.377 mg/kg fo r males and females, respectively. AIthough differences were noted when the data were broken down (0 to 25 years, 26 to 50 years, 50+ years) to study the effect o f age, these differences were not statistically significant. The results o f the survey^ carried out by the Ontario government during the years 1969-1974 (table 3) suggest that'the mean PCB residue in human adipose tissues col lected in Ontario is higher than that reported in the survey by Health and Welfare Canada. However, the Ontario survey results are expressed on a fat basis, while the Health and Welfare Canada surveys are presented on a whole wet tissue basis. The adipose tissue contained approximately 80 percent extractable fat. Although the 1969-70 mean residue value is half that reported fo r the years 1971-72 and 1973-74, the authors believe this is due more to method refinement than to an actual doubling o f PC8 residue. The PCB residue datii obtained fo r the years 1971-72 and 1973-74 are broken down so that an age comparison fo r PCB residues can be made (table 4). A l though the results have not been statistically analyzed, the 21- to 40-year age group did show somewhat lower residues than the 41- to 60- and 61- to 80-y`ear groups. Residue surveys were *lso carried o ut during the period (1969-1974) on hum in m ilk. The residue results suggest no change in PCB residue concentration during the years 1969-74 (table 5). In summary, surveys of PCB residues inhum an adi pose tissue suggest that fern:lies have lower residues than males, that residents o f Central Canada (Manitoba and Saskatchewan) have lower levels than the rest of Canada and that the majority of Canadians have an adipose tis sue residue of 1 to 2 mg/kg . PCB residue in human m ilk of Ontario residents was fo|und to be approximately 1 mg/kg fat. REFERENCE 1. M. Holdrient, H. E. Braun, R. Frank, G. J. Stopps, and J. W. McWade, unpublished results, 1975. GENP 005696 144 774346 Region O n ta rio Quebec A tlan tic Central Western Canada Table 1. PC B residues in hum an adipose tissue Samples w ith PCB > 1 mg/kg T o ta l No. samples Percent samples w ith PCB T mg/kg 28 57 11 50 4 16 2 22 6 27 51 172 49 22 25 9 22 30 Table 2. PC8 residues (mg/kg) in human adipose tissue Sex A t la n t ic Quebec O n ta rio C e n tra l3 Western** Canada M 0.758(13) 1.125(30) 1.165(38) 0.621(11) 0.977(19) 1.020(111) F 0.593(3) 0.723(19) 0.859(17) 0.377(11) 0.684(7) 0.685(57) M&F 0 .7 2 7 (1 6 ) 0 .9 6 9 (4 9 ) 1 .0 7 0 (5 5 ) 0 .4 9 9 (2 2 ) 0 .8 9 8 (2 6 ) 0 .9 0 7 (1 6 8 ) aC e n tra l = Saskatchewan and M anitoba. bWestern = A lb e rta and B. C. 145 774347 vjcinp 005697 Table 3. PCB residues (mg/kg)a in human*1adipose tissue Year Samples Range Mean 69-70 20 1 . 0 - 2 . 0 1 .2 71-72 282 ND-18 2 .5 73-74 129 0 .6 -1 1 .0 2 .3 aFat basis. ^Ontario re s id e n ts , H o ld rie n t, e t a l. (re f. 1). Table 5. PCB residues (mg/kg)a in human*1 milk Year Samples Range Mean 1969-70 43 0 .7 -1 .2 1 .0 1971-72 34 0 .2 -3 .0 1 .2 1973-74 19 0 .1 -2 .5 1 .2 aFat basis. ^Ontario re s id e n ts , H o ld rie n t e t a l. Table 4. PCB residues (mg/kg)a in human*1adipose tissue Year 1971-72 Mean Samples 1973-74 Mean Samples 21-40 Age 41-60 61-80 0 .5 -6 .0 2 .2 40 0 .6 -6 .0 2.1 13 N D -8 .0 2 .6 96 0 .7 -7 .0 2 .2 47 0 .5 -1 0 .0 2 .6 119 0 .6 -1 1 2.5 54 aFat basis. b0 n ta r io r e s id e n ts , H o ld r ie n t e t a l . O O KJ* \000 146 774348 LEVELS OF PCB's IN THE U.S. FOOD SUPPLY Charles F. Jelinek, Ph.D., and P. E. Comeliussen* A b s tra c t The Food and Drug Adm inistration has taken regu la to ry action since Iate 1969 to p ro te ct the consumer from foods found (d contain hazardous levels o f PCB's. I t has m onitored fo r PCB's in (1) specific products such as m ilk, (2) raw agricultural products, (3) commercial fish a t the wholesale levels, and (4) the to ta l d ie t The foods examined were com m ercial products, essentially a ll in interstate commerce. Data w ill be presented on the concentration o f PCB's obtained in d iffe re n t food com m odities from 1969 through mid-1975. These data show th at there has been a significant decrease in PCB levels in a lt foods w ith the exception o f fish, where no p articular trend has been noted. In the case o f fish, alm ost a ll lo ts containing more than the FDA tolerance level o f Sppm in the edible p o rtio n originated from the Great Lakes area. I t is concluded th at the procedures institute d to exdude die use o f PCB's in die "o p e n " app/icadons have been effective, b u t th a t more needs to be done to pre vent th eir entry in to die aquatic environm ent The Food and Drug Administration (FDA) has taken regulatory actions since late 1969 against foods or feeds containing hazardous amounts of PCB's. The pur pose o f this paper is to summarize the data FDA has obtained on PCB levels in the different types of foods, and to cite the trends which have taken place since our first actions. Table 1 summarizes the highlights from FDA's anal ysis of approximately 15,000 samples from November, 1969, through June, 1971. It w ill be noted that fish, cheese, m ilk, eggs, and byproducts used in animal feeds were the main commodities contaminated by PCB's. Such foods o f animal origin were frequently found to contain significantly high levels of PCB's. This table does not include data developed by the United States Department of Agriculture (USDA) in its surveillance o f meat and poultry during this period. In addition, the data do not reflect the food contamination that occurred later as a result of the leakage o f PCBcontaining heat exchange fluid into a pasteurized fish meal, which in turn was fed to poultry and catfish. This was by far the most serious incident of PCB contamina *C. F. Jelinek is Director of the Division of Chemical Tech nology, Bureau of Foods, Food and Drug Administration, Wash ington, D.C. P. E. Comeliussen is Assistant to the Director of the Division of Chemical Technology, Bureau of Foods. tion o f our food supply and led to very extensive regu latory actions by FDA and USDA, such as seizures and recalls of poultry, eggs, fish, and feeds. During the surveillance period summarized in table 1, PCB's were not found in cereal grain and fresh fruits and vegetables. In late 1971, FDA established the fact that food packaging made from recycled paper which contained PCB's caused contamination of the contents, such as infant foods and cereals. As a result of the above findings, FDA proposed certain regulations for PCB's in 1972. Table 2 shows our current regulations pertaining to PCB's in foods, animal feeds, and food packaging (ref. 1). The first category o f regulations covers the tempo rary tolerances fo r PCB's in products selected as a result o f our monitoring activities, namely, m ilk, dairy prod ucts, poultry, eggs, animal feeds and their components, infant foods, and paper food packaging. Of these, fish are the only products which the PC B'i contaminate pri marily through the environment, in this case the water ways. The sources o f the PCB's in the other foods and in food-packaging material were mainly industrial and agri cultural uses which enabled PCB's to enter into food or animal feeds. The second category o f regulations is the prohibi tion o f use o f PCB's in such applications as heat transfer fluids, hydraulic fluids, paint components, adhesive com ponents, etc., in plants that produce food, animal feed, or food-packaging materials. These regulations were proposed in 1972 and are now officially established, w ith the exception of the maximum permissible level o f PCB's in paper foodpackaging material, which is an administrative guideline, pending the results o f a hearing which has been granted. Turning to the more recent period since 1972, the results obtained in FDA and USDA monitoring programs in fiscal years 1973, 1974, and 1975 are summarized in table 3. It can be seen that PCB's now contaminate far fewer types o f foods than they did form erly. Although PCB's were reported in fish, m ilk, eggs, cheese, feed components, and poultry in fiscal years 1974 and/or 1975, the rates and levels of occurrence have declined drastically in all categories except fish. The samples of fish FDA has analyzed were ob tained through several different activities in the field. In fiscal years 1973 and 1974 we carried out Compre hensive Fish Surveys in which we analyzed freshwater and saltwater fish obtained at the wholesale level for ,T k n rr\ o r fin 147 774349 Table 1. PCB findings, Nov. 1969-June 1971a Food commodi ty P ositive fin d in g s Avg. o f p o s itiv e s (ppm) Max. le (ppm) F in fis h 317 Oysters 12 Fish byproducts 6 Cheese 44 M ilk 60 Eggs 17 Potato byproducts 12 M is c e lla n e o u s 11 2.1 Trace 1 .8 0 .3 b 2 .5 b Trace 1.1 1 .9 3 5 .3 Trace 5 .0 1 .0 b 2 2 .8b 0 .5 4 .2 6 .5 a p p ro x im a te ly 15,000 samples examined. ^Fat basis. Table 2. FDA regulations, PCB's I. Commodi ty Temporary tolerances PCB cone, (ppm) M ilk ( f a t basis) D airy products ( f a t basis) P oultry ( f a t basis) Eggs Finished animal feed Animal feed components Fish (e d ib le p o rtio n ) In fa n t and ju n io r foods Paper food-packaging m a te ria l w ith o u t PCBimpermeable b a r r ie r 2 .5 2 .5 5 .0 0 .5 0 .2 2 .0 5. 0 .2 1 0 .oa I I . Use p ro h ib ite d in fo o d , fe e d , food packaging p la n ts A d m in is tr a tiv e g u id e lin e , pending hearing. 148 774350 GEtfP 005700 Table 3. Summary of PCB's in foods, FY 7 3 , 7 4 , and 7 5 Food Commodi ty FY '7 3 Percent p o s itiv e M ax.. (ppm)a FY '7 4 Percent p o s itiv e M ax., (ppm) FY '7 5 Percent p o s itiv e Max _ (ppm)a Fish M ilk Eggs Cheese Feed components Animal feeds Processed f r u it s In f a n t & j r . foodsi 6 0 .4 2 .2 ' 1.1 0 .9 12.7 7.2 4 .5 1.1 123.0 1.6 Trace 0 .5 9 .0 199.5 19.2 Trace 44.0 2 .6 4 .2 2 .6 ,0 .0 . 0 .0 0 .0 0 .0 16.8 2 .3 11.0 2 .8 N .D . N.D. N.D. N.D. 17.8 0 .7 0 .0 0 .0 0 .3 0 .0 0 .0 0 .0 9 .0 1 .9 N.D. N.D 0 .9 N.D. N.D. N.D. Percent p o s itiv e Percent above 5 ppm Percent p o s itiv e Percent above 5 ppm Percent p o s itiv e Percent above 5 ppm Meats & p o u ltry (USDA) 1.9 0 .1 9 1 .2 0.07 0 .3 aM ilk , cheese, meats and p o u ltry re p o rte d as ppm, f a t b a s is . 0.06 in/ cnn a Man PCB's, pesticides, and certain heavy metals. In addition, we analyzed fish obtained from our regular surveillance program fo r pesticides and PCB's, primarily in the raw products. Finally, we collected samples as a compliance followup after high levels of PCB's had been found in a particular species or area. The data obtained from these activities are valuable in showing which species and which areas are apt to be o f concern, but it is d iffic u lt to determine whether there have been any significant trends because o f the diversity o f the sources o f the fish samples and o f the reasons fo r collecting them, Figure 1 depicts the results obtained in the Compre hensive Fish Survey conducted in fiscal year 1973.'I t should be stressed that almost all the samples collected were commercial species intended for interstate com merce, and thus would not ordinarily include sports fish. No PCB's could be detected in over 70 percent of the samples collected. Only about 3 percent contained over 1 ppm, and 0.5 percent had over 5 ppm PCB's. It is interesting to note that the various species containing over 1 ppm were generally freshwater fish, or those which were apt to be near the shore. The only fish in this particular survey that contained more than the 5 ppm tolerance fo r PCB's were carp, w ith a maximum level of 20.5 ppm. The results obtained in the Comprehensive Fish Sur vey fo r fiscal year 1974 are shown in figure 2. Over 80 percent of the samples analyzed in this survey did not contain PCB's, and no samples contained more than 2 ppm PCB's. However, it cannot be concluded that there was a down-trend, since it was necessary to stop this survey before it was half finished because of the neces sity to divert manpower to the canned mushroom crisis. Nevertheless, freshwater fish again were most likely to contain the highest levels o f PCB's. Figure 3 depicts the results obtained with all sam ples of domestic finfish analyzed in fiscal years 1973, 1974, and 1975, from all FOA programs. The percentage of fish samples containing PCB's decreased in 1974 and 1975, but on the other hand, the percentage of PCBcontalning samples which were above 5 ppm increased. Significantly, all these samples were from the districts in the Great Lakes area, and included such species as chubs, carp, and coho salmon. 149 774351 80- ? 3 of 17 Carp 3 of 3*1Catfish 3 of 29 Herring 2 of 36 Flounder OF2 of 16 Scup-Porgie 1 2 Buffalo 1 of 1 White Bass 1 of 39 Mackerel Hot Daebtleect aa - .5TO0 ' 1T,0O0 2.T0O0 5.tCoO 10.0 20.0 to (Max. C R ( ) 99 ' PCS o1n.c9e9ntrati4o.n99 ange-s 9p.p9m9 19.9 20.5) Figure 1. *FY 1973 Comprehensive Fish Survey (41 species. 600 sample total). ISO 774352 O LSO O Percent of Survey Samples 80 70 60 50 40 30 20 2 11 of of of 5219BCaMurafpfcakleorel *1 of 2,4 Perch* 10 0 DeNtaoebctlte .49 PCB .5T0O Concen.t9r9ation 1.00 2.0t0o (Max.1>34) Ranges (ppm) Figure 2. FY 1974 Comprehensive Fish Survey (38 species, 269 sample total). vxjiiNj- 005703 151 774353 CO Ui LU co o _ X LS 3 LUCU u a. X LULA X co aZ lu a- 2 LA -- C3 to 2 5 -- a- LU LULU oo X X LU FISCAL YEAR '73 w a Q_ X IS a= O ___ LUS LUC L . LUQ_ X LULA X CO g a. P LA LS GO o a- a LU LU LU o>U X M LU FISCAL YEAR '74 L:>U 1-- to o QX o a UJ LU seuc UJ C_ X LU LA X xz <oo_ LUQ_ --> LA --ts COsc o-- eu o LU LULU O tu X LU FISCAL YEAR 7 5 Figure 3. PCB's in fish, ail programs. As mentioned previously, it is d iffic u lt to draw any conclusions as to whether there is a significant trend, because o f the changing sources and objectives from year to year. The percentage o f samples examined which con tained more than 5 ppm PCB's stayed in the same gener al range (2.2 to 3.5 percent). These results from FDA's surveillance. programs show that PCB's do not generally occur in significant levels in saltwater fish, and indeed that only a small percentage o f freshwater fish in interstate commerce contain more than 5 ppm PCB's. Further, the waterways in which commercial fish are likely to contain high levels of PCB's are those which are contiguous with industrial ized areas. Thus far, we have reviewed the general levels of PCB's in individual food types. What do these findings mean in terms o f average intake o f PCB's from the entire diet? FDA conducts a continuing survey of the Total Diet, in which composites o f 12 different food catego ries are analyzed. Table 4 presents the composites in which PCB's were found in thu FDA Total Diet Surveys from fiscal years 1971 through the firs t half of fiscal year 1975. It can be seen tljiat the meat-fish-poultry composites contained PCB's much more frequently than any other o f the food groups. With regard to the findings o f PCB's in the composites o f fruits, vegetables, and cereals in fiscal years 1972 ana 1973, it should be noted that these composites include; processed and packaged 152 774354 GENP 005704 Table 4. Total Diet Studies-American teenage male Percent of composites containing PCB's Food class composites Fiscal Year Dairy products Meat, fish & poultry Grain & cereal products Potatoes Legume vege- tables Root vege Garden tables fruits Oils, fats & shortening Sugars and adjuncts 1971 1972 1973 1974 1975 (1st half) 6 10 47 46 33 43 40 13 6 17 3 # 6 3 3 17 3 6 3 Fiscal year Table 5. Estimates of daily PCB intakes (Total Diet Study-teenage male) Average daily intake of PCB'sa Total diet ' (ug/day) Meat-fish-poultry food class (yg/day) 1971 1972 1973 1974 1975 (1st half) 15.0 12.6 13.1 8.8 8.7 9.5 9.1 8.7 8.8 .8.7 alower limit of quantitative reporting = 0 . 0 5 ppm with analytical method employed. GENP 005705 153 774355 foods as well as raw foods purchased in retail stores. Since we have hardly ever detected PCB's in the raw products, the PCB's probably contaminated these foods during processing or from the packaging. This hypothesis is borne out by the fact that no PCB's have been found in these composites in 1974 or 1975. after our regula tions had a chance to take effect. FDA chemists have found that the source of the PCB's in the meat-fish-poultry composite is almost always due to the fish component. It is interesting to note that the frequency o f findings in this composite has remained quite constant since fiscal year 1971. Signifi cantly, PCB's are now generally found only in this fishcontaining composite of the Total Diet Survey. This reflects the beneficial results of FDA and USDA in their efforts to prevent the uses o f PCB's that could lead to direct contamination o f foods, and of the U.S. manu facturer in limiting the sales o f PCB's to " closed" electri cal uses. In calculating the average daily intake from the Total Diet Survey, we must be aware of the short comings in the use of composites, where the level of occurrence of the contaminant in the composites may be at or just below the lim its o f detection. How we handle "Trace" and "N o t Detected" can have a significant effect on our estimates of the daily intake. Table 5 gives the estimated average daily intakes o f PCB's by a young male adult, for fiscal years 1971 through the first half of 1975, where we have ascribed a certain level to all "Trace" in all composites and to "N o t Detected" in the meat-fish-poultry composites where PCB's are still com monly detected. It can be seen that there has been a marked decrease in the estimated total intake. However, the estimated intake w ill tend to continue at the FY 1975 level, as long as (1) fish remain almost the sole source of detectable PCB's and (2) the entry of PCB's into the waterways is not decreased. In summary, the breadth of occurrence of PC8's has narrowed to the point where freshwater fish are now the primary source o f PCB's in pur diet. Thus, the daily PCB intake fo r the average citizen is low, since his consump tion o f freshwater fish is loijv, and even here, most of the commercial freshwater fish contain less than 5 ppm PCB's. However, the estimated intake o f the average consumer is only a guidepost. and the Food and Drug Ad ministration must consider the dietary consumption patterns o f significant sectors o f the population which are significantly different from the average. For example, PCB intake could be quite different fo r those people whose diets include substar tial quantities of sports fish. For the future, (1) we rjnust continue to m onitor fo r PCB's in foods and food-packaging materials to maintain the beneficial results already obtained, and (2) means must be employed by the responsible Federal and State agencies to effectively halt the entry o f PCB's into the aquatic environment. REFERENCE 1. Food and Drug Adm inistration, " Polychlorinated . Biphenyls (PCB's),'* Federal Register, Vol. 38, No. 129 (July 6,1973), pp. 18096-18104. 154 774356 LEVELS OF PCB's IN CANADIAN COMMERCIAL FISH SPECIES John M. Graham* A b s tra c t F o r purposes o f examining PCB levels in various environments, Canada is divided in to fo u r study areas: area 1 is the Pacific sector; area 2 is Central Canada; area 3 covers the Great Lakes; and area 4 is the A tla n tic sector,: The tables included give detectable levels o f PCB's in various species--ground fish, estuarial and pelag ic fish, and crustaceans and moHusks--fo r the respective areas. I w ill briefly summarize the work that the Inspec tion Branch has done in analyzing marine and freshwater species. And I am going to start by reporting on four areas in Canada (figure 1). Areas 1 and 4 involve marine species; area 2 is the central part of Canada excluding the Great Lakes; and area 3 contains the Great Lakes, which are o f quite a b it of interest to us. Table 1 is a brief summary of the PCB's that we have found in our marine species, subdivided as ground fish, pelagic, estuarial, mollusks and crustaceans, and miscellaneous. The landings are given in pounds, the levels are mean levels o f PCB's, and the samples analyzed are in parentheses. One thing worth noticing is the high level in bluefin tuna, which is 2.65 ppm. We explain this by the fact that bluefin tuna is usually landed at 600 to 700 pounds. It is a very large fish and at the top of the food chain. Another point of interest that you might note is the fish oils with a mean level of 5.1 ppm. Finally, fish meal is at a level o f about 0.16 ppm. This is because, during the manufacture of fish meal, most of the oil is ex tracted. As shown in figure 1, area 2 is the central part of Canada, excluding the Great Lakes. Table 2 gives PCB levels fo r freshwater species in that area. The production amounts to same 70 m illion pounds of fish annually. There are detectable levels of PCB's, but usually very, very Jow. These are from large northern lakes, and usual ly no industry is close by. The median level is 0.10 ppm. All our samples are based on the'edible portion of the fish and that portion that would normally be con sumed by the consumer. The samples are taken either by commercial fishermen or by our inspectors, so that we know the exact location at wt)ich the samples are col lected. Sample size is usually 15 pounds of the fille t or edible portion and a minimum o f five fish. I have subdivided the Great Lakes--St. Lawrence River system into the lakes and the river. Table 3 shows our finding on Lake Superior, which amounts to close to 3.3 m illion pounds o f fish per year. As you can see, the lake trou t is the highest in this lake, based on our fin d ings. We also find th at it varies between the inshore lake trout or shallow-water lake trout and the deepwater, or fa tty, take trout. Table 4 shows Lake Huron, Canadian side, amount ing to some 2.1 m illion pounds. Chub at the 2-ppm level, and carp and suckers are relatively high. Coho salmon is not normally considered a commercial species in Canada. There is quite a volume available to sports fishermen and commercial fishermen. They sell it as part of an inciden tal catch. Now we come to Lake Erie (table 5), which some people say is a dead lake, but it has an annual planting of some 31 m illion pounds of fish. Atewives, rock bass, and carp are slightly high. The highest is catfish and again coho salmon, which is 3.14 ppm. Table 6 shows Lake Ontario, which, as you can see, has a little b it of a problem (or a lot o f problems). Smelt is at 4.16, and eels are 17.14 ppm. Again the coho sal mon is up there. The eels in Lake Ontario are quite high. The eels in the St. Lawrence river system (table 7) show about 8 ppm. I have broken the eels down into their size range and given the medians. Note the last line. A 4%-pound eel ranges from 3 to 30 ppm, so that we really cannot manage this fishery on a size or weight basis. It is going to be extremely d iffi cult. It looks as if we are going to have to terminate the licenses fo r this fishery. These eel figures are in contrast to the figures that we had for eels in the Maritime Provinces. The eels in Maritime Provinces are 0.56 ppm. So it is apparent that we will be able to keep one section of this fishery open and must try to manage or close the other one. We presently have a 2,500-sample survey for the Great Lakes. Health & Welfare, Canada, established a temporary guideline o f 2 ppm in fish; this means that we are going to have to break some o f our lakes down into areas, geographic areas, and put restrictions on them either by length or weight. I do n ot see the problem getting any better in the next year. / f i / C A f k tht 155. 774357 80LS00 MHO Figure 1. Four fish species areas in Canada. Table 1. Polychlorinated biphenyls in com m ercial fish and fishery products, areas 1 and 4 (marine) D e s c rip tio n and .species Landings (pounds) PCB's (mean ppm) Groundfish (c a tfis h , cod, flounder, haddock, h a lib u t, lin g co d , p o llo ck, re d fis h , red snapper, ro ckfish , s ab le fis h , skate, s o le , p la ic e , tomcod) 1 ,1 9 1 ,7 0 1 ,0 0 0 0.07 (141) Pelag ic -e s tu ria l (A lew ife; cap elin ; dogfish; h e rrin g ; m ackerel; salmon; sm elt; swordfish; tuna: alb acore-skipjack-yellow fin; w h a le ) B luefin Eel - M aritim e Provinces 1,131,868,000 0.39 ( 73) -- 2.65 762,000 0.S6 ( 19) Mollusks & Crustaceans M iscellan eo u s Clams; crab s; (dungenessqueen-red-rock) lo b ster; mussels; o y sters ; s ca llo p s; shrimp Fish o ils Fishmeal 100,144.000 0.12 ( 56) -- 4.51 ( 12) 0.16 ( 71) UENP 005709 Table 2. Polychlorinated biphenyls in commercial fish and fishery products, area 2 (freshwater) Species Landings3 (pounds) PCB's (mean ppm) B uffalo fis h , carp, goldeye, m a lle t, perch, p ike, p ic k e re l, sauger, tro u t, w hitefish 70,000,000 0.10 (113) la n d in g s o f le s s than 2 5 ,0 0 0 pounds per species: are not included. 157 774359 Table 3. P olychlorinated biphenyls in com m ercial fish and fishery products, (area 3) Location Lake S up erio r (A) M a jo r species chub lake herring lake tro u t w hitefish sm elt y e llo w perch Landing^" PCB (pounds) (mean ppm) 306.000 1 ,6 1 1 ,0 0 0 195.000 328.000 788.000 67,000 3,295,000; 0.96 ( 8) 1.17 (10) 02 ..60 28 11( 3 7 ) () 0.35 ( 6) 0.31 ( 5) la n d in g s o f le s s than 2 5,0 00 pounds p e r species a re n o t in c lu d e d . i Table 4. Polychlorinated biphenyls in commercial fish and fishery products, (area 3) Location Major species Landingsj'a* PCB (pounds)! (mean ppm) Lake Huron (B) chub 6 7 1 ,00d w hitefish 950,000 carp 56,000 suckers 176,000 yellow pickerel 2 6 9 ,00d sheepshead (drum) 29,000 coho salmon noncommercial! 2 ,1 5 1 ,0 0 0 2.09 0.95 1.55 1.33 0.61 0 .7 5 5.11 (17) ( 8) ( 4) (12) ( 9) ( 2) ( 6) aLandings o f le s s than 2 5 ,0 0 0 pounds p e r speci es a re no t in c lu d e d . GENP 005710 158 774360 Table 5. Polychlorinated biphenyls in com m ercial fish and fishery products, (area 3) Location Lake E rie - M a jo r species Landings3 PCB (pounds) (mean ppm) alew ife 332,000 rock bass 49,000 carp 41,000 y e llo w perch 12,190,000 smel t 15,760,000 yellow pickerel 234,000 w h ite bass 2 ,3 4 6 ,0 0 0 c a tfis h 88,000 bullhead 109,000 sheepshead (drum) 354,000 coho salmon noncoumercial 31,503,000 1 .2 2 -(1 4 ) 0.27 ( 2) 1.27 ( 7) 0.19 (10) 0.42 (21) 1.16 ( 9) 1.26 (28) 2.04 ( 8) 0.26 ( 4) 0.74 (15) 3.14 ( 8) la n d in g s o f less than 2 5 ,0 0 0 pounds p e r species are not included. Table 6. Polychlorinated biphenyls in commercial fish and fishery products, (area 3) Location M a jo r species Lake O ntario (D) bullhead y ello w perch sm elt w hite perch sunfish carp rock bass eel coho salmon Landings3 (pounds) PCB (mean ppm) 248,000 699,000 103,000 290,000 203,000 395,000 42,000 222,000 noncommercial 2 ,2 0 5 ,0 0 0 0 .7 3 1 .2 3 4 .1 6 1 .8 4 0 .7 4 1.69 1.76 17.14 4 .9 7 (12) (10) (17) (22) ( 6) (10) (18) (49) ( 3) la n d in g s les s than 2 5,0 00 pounds p e r species are n o t in c lu d e d . 159 774361 GENP 005711 Table 7. Polychlorinated biphenyls in com m ercial fish and fishery products, (area 3) Location M ajor Landings3 PCB species (pounds) (mean ppm) S t. Lawrence R iv e r (E) sturgeon 77,000 2 .3 2 ( 5) eel 435,000 7.94 (216) Species eel S iz e <Zh pound Range Mean PCB 0.11( 7 .9 9 ) 2 .9 5 (66) 25s pound-45s pound 1 . 6 8 - 2 2 . 8 ) 8 .1 9 (7 2 ) >45s pound 2.82^29.7 ) 12.37 (43) la n d in g s o f le s s than 2 5 ,0 0 0 pounds p e r species are no in c lu d e d . S 160 774362 THE OCCURRENCE OF PCB IN THE N A TIO N A L FISH AND W ILDLIFE MONITORING PROGRAM Charles R. Walker* A b s tra c t The N ational Fish and W ildlife M onitoring Program has as its objective to ascertain, on a national scale, the amounts o f pesticides and contaminants in some fish, birds, and mammals. Testing is done through repeated sampling over time. The species chosen to be m onitored are freshwater fish, m allard and black duck, and starling. PCB residues in freshwater fish were found to be highest in certain rive r systems th a t lie in industrial areas. For mallards and black ducks, concentrations were greatest in ducks in the A tla n tic flyways. Starlings from a ll over the Nation showed PCB contam ination; how ever, over the 1970-1974 period, there was an apparent decline in residue levels, except in certain specific areas such as A ustin, Alabama. Related m onitoring indicates th at PCB may be especially threatening Id endangered species, w ith serious effects on the survival o f their young. The National Fish and Wildlife Monitoring Program was initiated in 1967 as a cooperative Federal effort conducted join tly by the Bureau of Commercial Fisher ies and the Bureau o f Sport Fisheries and W ildlife in the U.S. Department of the Interior, and the Water Supply and Sea Resources Program of the National Center for Urban and Industrial Health, Public Health Service, U.S. Department o f Health, Education, and Welfare (ref. 34). The current National Pesticide Monitoring Program is sponsored by the Monitoring Panel o f the Federal Work ing Group on Pest Management that includes compo nents drawn from the Environmental Protection Agency, the Tennessee Valley A uthority, the National Science Foundation, and the Departments o f Agriculture, De fense, Commerce, Interior, and Health. The monitoring objective was to ascertain on a na tional scale the amount of pesticides and related materi als in components o f the environment and trends of these levels with time through repeated sampling and analysis of environmental components (refs. 34,37,38). The Fish and Wildlife Service program consists of three elements: (1) freshwater fish, (2) mallard and black duck, and (3) starlings. The Freshwater Fish Program originally consisted of sampling fish from 50 stations in the continental United 'Charles R. Walker, Senior Environmental Scientist, U.S. Fish and W ildlife Service, Department of the Interior, Washing ton, D.C. States as it was initiated in 1967 (refs. 24,25). In 1970 this was expanded to include 100 stations sampled an an annual basis and included the conterminous United States and Alaska (ref. 30). Criteria fo r selection of spe cific sampling station locations included the following, in the order of p riority: (1) availability o f desired species of fish; (2) relationship to station locations for other phases o f the National Pesticide Monitoring Program (refs. 11,14,19,67,69), particularly those stations used for monitoring surface water samples; (3) existence of State-sponsored monitoring programs or cooperative par ticipation by a State conservation agency; and (4) availa bility of suitable manpower and facilities to make field collections. In the late 1960's, the toxicological signifi cance and the detection of polychlorinated biphenyl compounds in fish and w ildlife along w ith the interfer ences with organochlorine pesticide analysis became apparent (refs. 31,32,33,43,45,50,54,66). This problem stimulated the development of analytical methods for the separation and identification o f PCB in fish samples fro m th e N a tio n a l M o n ito rin g Program (refs. 26,28,52,53.57,58). The cleanup of solvents (refs. 20,56), selective partit i o n of PCB f r o m p e s t i c i d e s (refs. 1.3,4,7,16,18,26,53,55,58,59), quantitative determina tion (refs. 2,9,46,54,57,62), and confirmation methods (refs. 2,6,8,29,51,52) utilizing gas chromatography-mass spectrometry became practical for Federal agencies to use in the National Pesticide Monitoring Program by 1970. In the Freshwater Fish Program, samples of three to five fish were taken of three species representing d if ferent tropic levels to comprise each composite sample. A ll composite samples of white fish vre analyzed for the most common organochlorine insecticides, including DDT, DDE, TDE. dieldrin, aldrin, endrin, BHC, heptachlor epoxide, chlordane, toxaphene, and beginning w ith the 1970 collections, polychlorinated biphenyl com pounds (PCB), as well as the percent lipid content of the fish (ref. 61), Whereas these analysis were contracted to private and other Federal laboratories, a cross-check quality assurance program was conducted on about 10 percent of the samples by our Fish-Pesticide Research Laboratory at Comlumbia, Missouri. The number of pesticides and related contaminates that were detected in the cross-check analyses grew from 19 compounds in 1970 to 33 parent compounds, homologs, or metabolites by 1973 (table 1). The mallard and black duck monitoring program I / . C 0 n ,rlMTrr\ 161 774363 Table 1. Organochlorine pollutants detected by initial and confirmatory laboratories from 1967-1974 Pollutant DDE DDD q ip1Isomers DDT DDE DDD ,1isomers DDT 1232 1242 1248 1254 1260 .' p Aroclor* dieldrin aldrin endrin BHC lindane heptachlor heptachlor expoide chlordane cis-chlordane toxaphene hexachlorbenzene (KCB) heptachlor norborene oxychlordane hexachlor norbornadiene 2,4-D PGBE pentachlorobenzene hexachloro-113-butadiene ethylhexylphthalate dibutylphthalate dioctylphthalate DEHP 1967 Ia I I 1968 I I I 1969 I I I I 1A970 I cb Ic I cccc c c Ic c 1971 Xc Ic I ,C c cc & c c Ic c 1972 I- c Ic Ic c c c 0 0* c Ic c 1973 Ic Xc Ic c c c 0 0 0 I0 I0 X I I Ic Xc Ic Ic c cI I 0 I c X c 0 0 I c I I 0 Ic Ic I Ic XI Ic Ic Ic I I 0 0 0 0 0c c c cI I I I 0 0 0 c c c cI I I X I I c c c cI I I 0 X I 0 cc c c c c cI I 0 0 I X I ccc c c c c c c c cc c0 0 0 00 00 0 vUSOOdHUO I-indicates a pollutant was reported in the results from the Initial analyses. ^C-indicates a pollutant was reported in the results frfcom the confirmatory analyses. O-indicates a pollutant was found in previous years but not reported later. 162 ?W 64 was conducted in cooperation w ith State agencies in conjunction with the fall migration of waterfowl and the hunting season in each of the conterminous States (refs. 17,21,22,23,64). Through a process o f systematic sub sampling, a series o f wings, approximately 12,500 an nually, are drawn from each State. These are composited fo r analysis into samples o f 25 wings each representing a sample from each State in proportion to the harvest. Mallard duck wings are collected in the Pacific, Central, and Mississippi flyways whereas both the mallard and black duck were represented in those samples from the Atlantic flyway, depending on the availability o f species. Pesticide analysis included chlorinated hydrocarbon pes ticides and beginning with the 1969 sampling also in cluded polychlorinated biphenyl compounds. The National Monitoring Program fo r starlings, a widely distributed and abundant species, was especially designed to sample five degree latitude/iongitude blocks covering the contiguous 48 States w ith up to four ran domly selected collecting sites w ithin each block (refs. 34,41,42,63). Ten birds were collected at each sample site and composited fo r analysis in the fall of even years at approximately 125-130 sites. Organochlorine pesti cides were analyzed in the 1967-68 samples and begin ning with the 1970 samples polychlorinated biphenyl compounds were analyzed in 1970-72 and 1974 samples. Freshwater Fish M onitoring Program Polychlorinated biphenyl compounds have been detected in certain rivers and areas in unusually high concentrations and confirmed in a qualify control cross check analysis among several laboratories (refs. 54,61). PCB residues have been found in 40 to 60 percent of the samples in residue concentrations exceeding 0.5 mg/kg (figure 1). More than 98 percent of the samples during the period o f 1969-71 contained residues in at least one composite sample exceeding these criteria. Geographically, the higher concentrations appear to be V J C iIN I' U U J / 1 J Figur 1. Percentage of fish sampled from 1969-1973 in the National Pesticide Monitoring Program that contained either no detect able residues (white), residues (cross-hatched), or levels exceeding the criteria established to be biologically signifi cant (solid black: > 0 .5 mg/kg PCB: > 1 .0 m g / k g DDT; and > 0 .1 mg/kg dieldrin, BHC, or toxaphene) (ref. 69). 163 774365 associated with certain river systems having industrial activity (refs. 54,61) (tables 2 and 3). PCB residues ex pressed as Aroclor 1254 were found in five major river systems in the A tlantic coastal region, w ith residues ex ceeding 5 mg/kg. Four of these stations had residues exceeding 10 mg/kg during the last 5 years. Fish in four o f the Great Lakes stations had PCB concentrations exceeding the 5 mg/kg level and all stations reported concentrations exceeding 0.5 mg/kg. In the Mississippi River system, the Allegheny and Ohio were the hot spots, w ith seven out o f the eight stations reporting resi due concentrations in excess o f 5 mg/kg.' Thirty-one of thirty-five stations in this river system reported residues in excess of 0.5 mg/kg in the 1970-73 sampling pro grams. The highest residues, often exceeding 10 mg/kg were found in the Allegheny, Kanasha, Cumberland, Tennessee, and Ohio Rivers along with stations on the Mississippi River at Memphis, Tennessee, and the Mis souri River at Herman, Missouri. Other m onitoring sta tions that were found to have residue levels exceeding 5 mg/kg during the sampling periods 1970-73 included: the Williamette River on the Columbia system; the Rouge River in the Pacific coastal drainage; the Sacra mento River in California; the Chena River tributary of the Yukon in Alaska; and the Rio Grande, Alabama, and Mississippi Rivers in the Gulf States region. Only in two sample periods o f 1972-73 and in the current monitoring samples, which are still yet to be fu lly analyzed, has there been a downward trend, but this occurs only in those samples where residues are not being detected. The stations where high residues have been noted in the past still remain relatively contaminated w ith PCB. Unlike the decline o f DDT in Great Lakes fishes, PCB concen trations do not show significant changes and may trend upward in salmonids, as indicated in special investiga tions conducted by W illford (ref. 69), and Veith (ref. 60). Just as it is exceedingly im portant to distinguish PCB from organochlorine pesticides, we must also make positive identifications o f the different Aroclors so that they may be correctly expressed in stoichiometric calcu lation. For example, in table 4, let us examine some of those stations with high PCB concentrations. The com position o f PCB residues in selected fish samples taken during the National Pesticide Residue Monitoring Pro gram illustrates the difficulties in equating all residues to one type of Aroclor, such as 1254. In this illustration we can readily show that the expression o f PCB from the Ohio, Mississippi, and Hudson drainage would certainly misrepresent the true distribution o f PCB isomers if they were all stoichiometrically expressed as 1254. The best analogy I can offer to illustrate this is if we were to express all of the hardness or alkalinity o f water as calci um carbonate, when indeecj the actual chemical analysis indicated that most o f the carbonates existed as magnesi um carbonate. This relationship has tw o dimensions. The first is that the lower Aroclor serie^ are more highly biodegrada ble than are the higher series such as 1254 and 1260. A PCB residue in fish taken downstream following degrada tion would thus appear to be composed primarily of the 1254 or 1260 isomer. However, the to x ic ity and poten tial biological effect w ouldjbe more serious w ith regard to the Aroclors 1232, 1242, and 1248, as noted in table 4. This was particularly evident in the 1970 cross-checks, in which we were finding tfla t results of two other labor atories typically expressed PCB levels at concentrations o f only 5 to 20 percent of that found in the sample by the more sophisticated procedures used by our FishPesticide Research Laboratory (refs. 52,54,55,57,58). M allard and Black Duck M onitoring Program White and Heath report that polychlorinated bi phenyl residues were highest in the A tlantic flyways; the mean value of 1.36 ppm occurred in black duck in both 1969 and 1972 (ref. 64). Mallards from the same fly way averaged 1.24 and 1.29 ppm for samples taken in 1972 and' 1969 respectively (figurn 2 and table 5). These levels compared to mallard duck wings from the Mississippi flyw ay, where average values were found to be 0.66 and 0.44 ppm on a wet weight basis fo r the years 1972 and 1969. Both'the Central and Pacific flyways had residues of approximately 0.1 ppm during 1972 and 0.2 ppm in 1969. The overall trend in the concentration of PCB would appear to be downward in the Central and Pacific flyways; however, this was significantly different at the P < 0.05 in the analysis o f variance calculation. The increase in concentration Observed in the Mississippi flyway and status quo fo r the A tlantic flyw ay have not been significantly changed over the same period o f time (refs. 21,22,23,64). The recent studies by White andKaiser (ref. 65) on the m ortality o f ruddy ducks in the Delaware system, however, |did indicate the seriousness of PCB residues. They found Aroclor 1260 residues or the bioaccumulation o f pentachloro and hexachloro bi phenyl compounds that exceed the levels found in our National Monitoring Program by almost tenfold. Starling M onitoring Program PCB has been found in all o f the starling samples taken in 1970, 1972, and 1|974 (figure 3). The level of residues appears to be declining throughout this period; however, some areas continue to report exceedingly high concentrations--for example, in the Austin, Alabama, 9u s o o a ^ 164 ^4366 Table 2. Stations with residues in at least one composite exceeding 0.5 mg/kg total PCB's, from an estimate based on Aroclor 1254 (asterisk and double asterisks denote residues in excess of 5.0 and 10.0 mg/kg, respectively) River (location) - 1970 1971 1972 1973 Atlantic Coastal Streams Penobscot R. (Old Town, ME) (Stillwater R.) Kennebec R. (Hinckley, ME) L. Champlain (Burlington, VT) Merrlmac R. (Lowell, MA) Connecticut R. (Windsor Locks, CT) Hudson R. (Poughkeepsie, NY) Raritan R. (Highland Park, NJ) Delaware R. (Camden, NJ) Susquehanna R. (Conowingo, MD) Potomac R. (Little Falls, MD) James R. (Richmond, VA) Roanoke R. (Roanoke Rapids, NC) Cape Fear R. (Elizabethtown, NC) Pee Dee R, (Dongola, SC) Cooper R. (Summerton, SC) Savannah R. (Savannah, GA) Altamaha R. (Doctortoun, GA) St. Johns R. (Welaka, FL) St. Lucie Canal (Indiantown, FL) X X X XX X* X** X** X** X* X** X** X* X** X** X** X** X* X X* X X X X** X** XX X X XXXX XX X XXXX XXX X XX X XX X. X X XX XX X X Gulf Coastal Streams Suwanee R. (Old Town, FL) XX Apalachicola R. (Jim Woodruff Dam, FL) X X X X Alabama R. (Chrysler, AL) X X X*- X Tombigbee R. (McIntosh, AL) XX Mississippi R.' (Luling, LA) Brazos R. (Richmond, TX) Colorado R. (Wharton, TX) Nueces R. (Mathis, TX) cX X X* X XX X X XX X X L > \L S 0 0 r lK iZ l 165 774367 River (location) Table 2. (con.) 1970 1971 197.2 1973 Rio Grande (Brownsville, TX) Rio Grande (Elephant Butte, NM) Rio Grande (Alamosa, CO) Pecos R. (Red Bluff Lake, TX) X* XX X X* X XX Great Lakes Drainage Gennessee R. (Scotsville, NY) St. Lawrence R. (Massena, NY) L. Ontario (Port Ontario, NY) L. Erie (Erie, PA) L. Huron (Bay Port, MI) L. Mighigan (Sheboygan, WI) L. Superior (Bayfield, WI) XXX X X* X* X** X X X** X* X* XXX X X* X X* X X** X* X* XXXX Mississippi iver System Allegheny R. (Natrona, PA) Kanawha R. (Winfield, WV) Wabash R. (New Harmony, IN) Ohio R. (Marietta, OH) Ohio R. (Cincinnati, OH) Ohio R. (Metropolis, IL) Cumberland R. (Clarksville, *TN) Tennessee R. (Savannah, TN) ' Wisconsin R. (Woodman, WI) Des Moines R. (Keosauqua, IA) Illinois R. (Beardstown, IL) Mississippi R. (Little Falls, MN) Mississippi R. (Guttenburg, IA) Mississippi R. (Cape Girardeau, MO) Mississippi R. (Memphis, TN) Arkansas R. (Pine Bluff AR) Arkansas R. (Keystone Reservoir, OK) Arkansas R. (John Martin Reservoir, CO) Verdigris R. (Oologah, OK) Canadian R. (Eufaula, OK) X** X** X** X* X** X X** X* XX XX X** X** X** X** X** X** X** X** X X* X* X X X X** X* X X X** X* XXXX XX XX X XX X X XXX X XXX X X X X** X** XX XXX X X GENP 005718 166 774368 Table 2. (con.) River (location) 1970 White R. (DeValls Bluff, AR) Yazoo R. (Redwood, MS) Red R* (Alexandria, LA) Red R. (Lake Texoma, OK) Missouri R. (Hermann, MO) Missouri R. (Nebraska City, NE) Missouri R. (Garrison Dam, ND) Missouri R. (Great Falls, MT) Big Horn R. (Hardin, MI) Yellowstone R. (Sidney, MT) James R. (Olivet, SD) N. Platte R. (Lake McConaughy, ME) S. Platte R. (Brule, NE) Platte R. (Louisville, NE) Kansas R. (Bonner Springs, KS) X X X X X X X X X X 1971 X X X X** X X X X X 1972 X X* X X X X* X X X 1973 X X* X X X X X X Hudson Bay Drainage Red R. (North) (Noyes, MN) XXXX Colorado River System Green R. (Vernal, UT) Colorado R. (Imperial Reservoir, AZ) Colorado R. (Lake Havasu, AZ) Colorado R. (Lake Mead, NV) Colorado R. (Lake Powell, AZ) Gila R. (San Carlos Reservoir AZ) XX Truckee R. (Fernley, NV) Utah L. (Provo, UT) Bear R. (Preston, ID) Interior Basins X X XX X XX X X GENP 005719 167 774369 River (location) Table 2. (con.) 1970 1971 1972 1973 California Streams Sacramento R. (Sacramento, CA) San Joaquin R. (Los Banos, CA) X X X* X XX Columbia River System Salmon R. (Riggins, ID) Snake R. (Hagermann, ID) Snake R. (Lewiston, ID) Sanke R. (Ice Harbor, WA) Yakima R. (Granger, WA) Williamette R. (Oregon City, OR) Columbia R. (Bonneville, OR) Columbia R. (Pasco, WA) Columbia R. (Grand Coulee, WA) XX X X X. X XXX XXX X XX X X X* X X XX XXXX XXXX Pacific Coastal Streams Klamath R. (Hom b rook CA) Rogue R. (Gold Ray Dam, OR) X X X X* Alaskan Streams Chena R. (Fairbanks, AK) Renai R. (Soldatna, AK) X X X* X Hawaiian Streams Waikele Stream (Waipahu, HI) Manoa Stream (Honolulu, HI) XXXX X GENP 005720 168 774370 Table 3. Environmental contaminants in fish (refs. 52, 53, 54, 55) ' a Residue (pg/g whole body) 1970 1971 1972 1973 Hudson, R ., Poughkeepsie, N.Y. Ohio R. M arietta, Ohio 122 38 C in cin n ati, Ohio 133 66 M etropolis, 111. Lake Michiqan Sheboygan, 7 .8 Wis. - Merrimac R. Lowel1, Maine 98 CO CM 93 61 104 76 118 69, 77 16 7 .5 - 6.0 156 20 45 - 43 8 .6 2.6 n 53 4 .9 4 .4 45 8 .8 8 .5 aEach valu e re p res e n ts a n a ly s is o f single fis h . River Ohio OOhhiioo OHAYhlaulzideoogsoohneny CDaeplaewFaerear Lake Ontario MMiesrsriismsiapcpi Table 4. Composition of PCB residues in selected fish, samples from the 1970 National Pesticide Residue Monitoring Program (ref. 54) Location Species PCB residue ns ,Aroclor type (j*g/g whole body) 1232 1248 1254 1260 total Cincinnati, O. CMianrciientntaa,ti0, .O. RMeadrwieototad,, 0M. iss. PNoautrgohnkae,epPsai.e, N.Y. CElaimzadbeent,h NToJw. n, N.C. PMoermt Ophnitsa,rTioe,nNn..Y. Lowell, Mass. Carp WCChhhaainntenneecllraccpaapttffiiiesshh Smallmouth buffalo GWoalldlfeiyseh WGihzzitaerdpesrhcahd WDYerhluloimtwe*ppe recrhc h 1105..29 3718--825..66 -- 18.9 . 1112..29 13.8 271357 --5 . 2 173 5.2 --8 . 0 7----5 42 211712.6 1.4 2352 26..68 44..56 6.1 6.0 --5--44...696 4.6 31..19 1.2 33 .. 42 133 6767 3783 213 2311139599 98 169 774371 c IZL00 jmo 1.5 0.15 m m m m u im m tm m m m im tim itn m -- iiiiiiiiiiiiiinii limn ilium IIIIIIUIIIIIIIIIIIIIUIII1I III llll cf e no :: j TaI \ | Illlllllilllllllllllllllllilll mini iiiiiiiiiii i- 0.5 O a .o. u 0 " . g ~ j| "a ~ J Sc S IJ S 1 ^ ; u i (Sc 1969 j 1972 ~0 3~; Ue *0y L, c *5 ~ "Z o 4! o :e sy i : i * U* i 5 v i l3 13 55 i II =-CoX <y ueo 'Z0. w *JCz j* i5 ^tca ^`3* e} *2 1965-6j 1969 1972 1965-6 196j9 y_ ,<552 5<.* uic0 5-y0 1972 PC B D O T + m e fa b o /ife s D ield rin Figure 2. Trends of PCB and organochlorine pesticide residues m easured in samples of duckwings.from each flyway in the Natio nal Pesticide Monitoring Program: black duck (Solid bar);: nallard (broken bar). Q 1 to to station, the 1970 analysis showed 24.3 ppm in 1972 and 19.9 ppm and a 1.8 ppm concentration in 1974 (table ). PCB's appear to be ubiquitous throughout the Nation and occur generally in a concentration of less than 5 ppm, with an arithmetic mean for 1970 o f 0,65 ppm, for 1972 of 0.43 pom, ana for 1974 of 0.12 ppm on the wet weight basis (figure 4). Related investigative M onitoring Programs fo r W ildlife The widespread occurence of PCB in ecosystems may be most serious to fish-eating species (refs. 5,10,13) and to the rates of bioaccumulation up the food chain (refs. 36,43,49). Special investigative monitoring activi ties of the U.S. Fish and W ildlife Service laboratories at Patuxent, Maryland, have been reported on the bald eagle relative to pesticides and PCB levels vs. autopsy and analysis (refs. 15,40,44). In endangered or threaten ed species, PCB residues may have serious effects on survival of young since some effects have been docu mented on certain behavioral patterns (refs. 35,36). Residues observed in the National Monitoring Program may pose a hazard to animals that have demonstrated particular sensitivity to PCB conce.i .rations affecting organ function, behavior, growth, v>-:/o r reproduction (refs. 27,36,48,50,52). ACKNOWLEDGMENTS Special recognition is d je th e U.S. Fish and Wildlife Service Regional Pesticide Specialists and the cooperat ing State agencies and individuals fo r the collection of samples in the National Pesticide M onitoring Program. Dr. Donald H. White, Mr. David F. Walsh, and Dr. David L. Stalling deserve fu ll credit and authorship fo r the tab ulated materials used in this presentation. Chemical anal yses were performed by WjARF Institute, Inc., and the U.S. Fish and W ildlife Service Laboratories at Denver, Colorado, Columbia, Missouri, and Laurel, Maryland. Analytical methods development and quality control assurance were conducted by the Fish-Pesticide Research Laboratory. Management o f the contracts, handling of data, and statistical analyses were the responsibility of the Patuxent W ildlife Research Center for duckwings, the Division o f Technical Services fo r starlings and fish. The author shared responsibility fo r coordination of this program w ith Mssrs. Jerry Longcore, Donald Donahoo, Bernard Berger, Paul Nicke son, and Anthony Inglis for the period o f time reporting these results. 170 774372 100 a a u a xti a. I < ZUl uaUaeJ. 0 NATIONAL PESTICIDE MONI TORI NG PROGRAM T RE ND O f PESTICIDE RESIDUES IN STARLI NGS 1 967- 74 Figure 3. Percentage of starling samples containing PCB and organochlorine pesticides in the National Pesticide Monitoring Program. 97/ cnn rTWiTT 171 774373 Table 5. Mean residues of PCB in wing-pools by major flyway, 1972 and 1969 Residues (ppm wet wei ght) Species Flyway Year No. of Pools Mean Std. Error Black Duck M allard M allard M allard M allard A tla n tic A tlan tic M ississippi C e n tra l P acific 1972 1969 44 42 1972 1969 21 19 1972 1969 61 51 1972 56 1969 . 49 1972 1969 55 51 1.36 1.37 1.24 1.29 0.66 0 .4 4 0 .1 0 a 0 .2 0 o .n a 0 .2 0 0.149 0.161 0.230 0.457 0.303 0.061 0.013 0.039 0.009 0 .0 1 4 aP < 0.05 (Analysis o f v a ria n c e ). Table 6. Means, ranges, and geometric mean PCB i i starlings from each collecting period, 196 h 68 through 1974 No. o f Year Pools 1967-68 1970 1972 19 7 4 * * * a 360 125 130 126 PCBb (ppm wet w e ig h t) X + S.E. Range ' -- 0.663 + 0.196 0.09 - 24.30 0.425 + 0.153 0.037 - 19.90 0.112 + 0.016 0 . 0 0 6 - 1.88 x_Geom. - 0 .3 5 8 0.215 0.068 Mean re sid u es f o r 1974 were s ig n if ic a n t l y lo w er than For 1972: * * * = P<0.001. 'PCB were not analyzed in 1 9 6 7 -6 8 . 172 774374 GENP 005724 NATIONAL PESTICIDE MONITORING PROGRAM hO .9 .8 Trends in sfar/ings iJ 1* Sa .5 01 A Q1 !c 3 . 0.2 .1* 1967*88 1970 1972 1974 CO i Ss s 3 0 00 o _ r; O 3O K Ot a <e n N0 9 K0 0is*0 6 k O* 0JNi J A r i f f i . x I S e e m . "x PCa A r jfh . x 1 Geom. x DDE i Figure 4. Trends of PCB and organochlorine pesticide residues measured in pooled samples of starlings taken in the National Pesticide Monitoring Program. UliNP .005725 173 774375 REFERENCES 1. B. Ahling and S. Jensen, " Reversed Liquid-Liquid Partition in Determination o f Polychlorinated Bi phenyl (PCB) and Chlorinated Pesticides in Water," A n a i. C hem ., Vol. 42, No. 13 (1970), pp. 1483-1486. 2. J. A. 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Ingiis, "Organochlorine Insecticide Residues in Fish," N ational Pesticide M onitoring Program, Vol. 3, No. 3 (,1969), pp. 145-171. 26. R. J. Hesselberg and J. L. Johnson, "Column Ex traction o f Pesticides From Fish, Fish Food, and M ud," B ull, Environ. Contam. and Toxicol, Vol. 7, No. 2/3 (1972), pp. 115-120. 27. J. W. Hogan and J. L. Brauhn, "Abnorm al Rainbow T rout Fry From Eggs Containing High Residues o f a PCB (Aroclor 1242)," unpublished manuscript, 19.... p. 5. 28. J. N. Huckins, J. E. Swanson, and D. L. Stalling, "Perchlorinatiori of Polychlorinated Biphenyls," J. Assoc. O fficia l Anal. Chem., Vol. 57, No. 2 (1974), pp. 416417. 29. 0 . Hutzinger and W. 0 . Jamieson, "Identification of Polychlorinated Biphenyls and ODT in Mixtures by Mass Spectrometry," Nature, Vol. 225, No. 5246 (1970), p. 664. 30. A. Ingiis, C. Henderson, and W. L. Johnson, "E x panded Program fo r Pesticide Monitoring o f Fish," Pesticides M onitoring J .. Vol. 5, No. 1 (1971), pp. 4749. 31. S. Jensen, " A New Chemical Hazard," New Sfc/.,Vol. 32 (1966), p. 612. 32. S. Jensen, "Chlorinated Hydrocarbon in Fauna and Flora," G rundfoerbattring, Vol. 23, SpeciaKnummer 5 (1970), pp. 81-84. 33. S. Jensen, A. G. Johnels, M. Olssem, and G. Otterlind, "D O T and PCB in Marine Animals From Swed ish Waters," Nature, Vol. 224 (1969), pp. 247-250. 34. R. E. Johnson, T. C. Carver, and E. H. Dustman, "Residues in Fish, W ildlife, and Estuaries," Pesti cides M onitoring 7., Vol. 1, No. 1 (1967), pp. 7-13. 35. J. R. Longcore and B. M. Mulhern, "Organochiorine Pesticides and Polychlorinated Biphenyls in Black Duck Eggs From United States and Canada - 1971," Pesticides M onitoring J ., Vol. 7, No. 1 (1973), pp. 62-66. 36. F. L. Mayer, P. M. Mehrle, and H. O. Sanders, "Resi due Dynamics and Biological Effects of PCB's in Aquatic Organisms," Archives o f Environ. Contam. and Toxicol., manuscript, 21 p., (in press). 37. Monitoring Panel, FWGPM, "Criteria fo r Defining Pesticide Levels to be Considered an Alert to Poten tial Problems," Pesticides M onitoring J., Vol. 5, No. 111971), p. 36. 38. Monitoring Panel, FWGPM, "Guidelines on Sam pling and Statistical Methodologies fo r Ambient Pes ticide M onitoring," Federal Working Group on Pest Management, Washington, D.C., 1974,60 pp. 39. r Monitoring Panel, FWGPM, "Catalog of Federal Pes ticide Monitoring Activities in Effect July 1973," Federal Working Group on Pest Management, Wash ington, D.C., 1975,450 pp. 40. B. M. Mulhern, W. L. Reichel, L. N. Locke, T. G. Lamont, A. A. Belisle, E. Cromartie, G. E. Bagley, and R. M. Prouty, "Organochiorine Residues and Autopsy Data fo r Bald Eagles, 1969 and 1970," Pes ticide M onitoring Jm Vol. 6, No. 3 (1970), pp. 133-138. 41. P. R. Nickerson and K. R. Barbehenn, "Organochio rine Residues in Starlings, 1972," Pesticides M oni toring J^VoU 8, No! 4 (1975), pp. 247-254. 42. P. R. Nickerson and K. R. Barbehenn, "D D T Resi dues in Starlings, 1974," brief. Pesticides M onitor ing J. Vol. 9, No. 1 (1975), p. 1. 43. Ian C. T. Nisbet and Adel F. Sarofim, "Rates and Routes o f Transport o f PCB's in the Environment," Environm ental Health Perspectives, Exp. Issue No. 1, DHEW, Nat. Inst. Environ. Health Sci., 1972, pp. 21-33. 44. W. L Reichel, E. Cromartie, T. G. Lamont, B. M. Mulhern, and R. M. Prouty, "Pesticide Residues in Eagles," Pesticides M onitoring J., Vol. 3, No. 3, (1969), pp. 142-144. 45. L. M. Reynolds, "Polychlorinated Biphenyls (PCB's) and Their Interference W ith Pesticide Residue Anal ysis," B ull. Environ. Contam. and Toxicol., Vol. 4 (1969), pp. 128-143. 46. L. M. Reynolds, "Pesticide Residue Analysis in the Presence o f Polychlorinated Biphenyls (PCB's)" in "Residues of Pesticides and Other Foreign Chemi cals in Foods and Feeds," Residue Reviews, F. A. Gunther and J. D. Gunther, eds., Vol. 34 (1971), pp. 27-57. 47. A. Richardson, J. Robinson, A. N . Crabtree, and M. K. Baldwin, "Residues o f Polychlorinated Biphenyls in Biological Samples," Pesticides M onitoring J., Vol. 4, No. 4 (1971 ) / pp. 169-176. 48. R. K. Ringer, R. J. Aulerich, and M. Zabik, "E ffect o f Dietary Polychlorinated Biphenyls on Growth and Reproduction of M in k," Am er. Chem. Soc. A ir, 175 774377 I Water, and Waste, New York, N.Y., 1972, pp. 149-154. 49. R. W. Risebrough and B. deLappe, "Accumulation o f Polychlorinated Biphenyls in Ecosystems," Environm ental Health Perspectives, No. 1, DHEW, Nat. Inst, of Environ. Health ScL, 1972, pp. 159-164. 50. R. W. Riseborough, P. Rieche, D. B. Peakail, S. G. Herman, and M. N. Kirven, "Polychlorinated Bi phenyls in the Global Ecosystem," N ature,Vo\. 220 (1968) , pp. 1098-1102. 51. S. Safe and 0 . Hutzinger, "The Mass Spectra o f Polychlorinated Biphenyls," J. Cham. Soc. Vol. 5 (1972), pp. 689-691. 52. 0 . L. Stalling and J. N. Huckins, "Gas-Liquid Chro matography-Mass Spectrometry Characterization o f Polychlorinated Biphenyls (Arodors) and 36ClLabeling o f Aroclors 1248 and 1254," J. Assoc. O fficia l Anal. Chem., Vol. 54, No. 4 (1971), pp. 801-807. 53. D. L. Stalling and J. N. Huckins, "Reverse Phase Thin Layer Chromatography of Some Aroclors, Halowaxes and Pesticides," J. Assoc. O fficia l Anal. Chem.,Vol. 56, No. 2 (1973), pp. 367-372. 54. 0 . L. Stalling and F. L. Mayer, "Toxicities o f PCB's to Fish and Environmental Residues," Environm ent ta! Health Perspectives, No. 1, DHEW, 1972, pp. 159-164. 55. D. L. Stalling, R. C. Tindle, and J. L. Johnson, /'Cleanup of Pesticide and Polychlorinated Biphenyl Residues in Fish Extracts by Gel Permeation Chro matography," J. Assoc. O fficia l Anal. Chem., Vol. 55. No. 1 (1972), pp. 32-38. 56. R. C. Tindle, "Purification Procedure fo r Low Polar. -ity Solvents," J. Agric. 'Food Chem., Vol. 17, No. 4 (1969) , pp. 900-901. 57. R. C. Tindle, "Handbook o f Procedures fo r Pesti cide Analysis," U.S.D.I. Bur. Sport Fish, and W ild life, Technical Paper No. 65, 1972,88 pp. 58. R. C. Tindle and D. L. Stalling, "Apparatus for Automated Gel Permeation Cleanup fo r Pesticide Residue Analysis," Anal. Chem., Vol. 44, No. 11 (1972), pp. 1768-1773. 59. W. J. Trotter, "Removingthe Interference o f DDT and Its Analogs in the Analysis fo r Residues o f Poly chlorinated Biphenyls," J. Assoc. O ffic ia l Anal. Chem.,Vol. 58, No. 3 (1975), pp. 461-465. 60. G. D. Veith, "Baseline Concentrations o f Polychlo rinated Biphenyls and DDT in Lake Michigan Fish, 1971," Pesticides M onitoring J ., Vol. 9, No. 1 (1975), pp. 21-29. 61. D. F. Walsh, "Organochlorine and Heavy Metals Detected in Fish A Partial Review o f the FWS Contribution to the National Pesticide Monitoring Program, 1967*1973," (JSFWS administrative re port, Atlanta, Ga., 1975,35 pp. 62. H. Weingarten, D. W. Ross, J. M. Schlater, and G. Wheller, Jr., "Gas Chromatographaphic Analysis of Chlorinated Biphenyls," A nal. Chem. A cta., Vol. 26 (1962), pp. 391-394. 63. D. H. White, "Nationwide Residues o f Organochlorines in Startings, 1974," Pesticides M onitoring J., (in press). 64. D. H. White and R. G. Heath, "Nationwide Residues o f Organochlorines in Wings o f A dult Mallards and Black Ducks," Pesticides M onitoring J ., (in press). 65. D. H. White and T. E. Kaiser, "Residues o f Organochlorines and Heavy Metals in Ruddy Ducks From the Delaware River, 1973," brief, Pesticides M oni toring J., (in press). 66. ' G. Widmark, "Possible Interference by Chlorinated Biphenyls," J. Assoc. O fficia l Anal. Chem., Vol. 50, No. 5 (1967), p. 1069. 67. G. B. Widmark, H. Tai, and P. F. Sand, "Pesticide Residue Levels in S o il," FY-1969-National Soils Monitoring Program, Pesticides M onitoring J ., Vol 6, No. 3 (1972). pp. 194-201. 68. G. B. Wiersma, P. F. Sand, and E. L. Cox, "A Sam pling Design to Determine Pesticide Residue Levels in Soil of the Conterminous United States," Pesti cides M onitoring J ., Vol. 5, No. 1 (1971), pp. 63-66. 69. W. A. W illford, "Contaminants in Upper Great Lakes Fishes," Great Lakes Fishery Commission Meeting, Milwaukee, Wis., March 25-26, 1975, Appendix V, 1975, pp. 31-39. lsoo 176 774378 TRENDS OF POLYCHLORINATED BIPHENYLS IN THREE LAKE MICHIGAN FISHES Wayne A. Willford,* Robert J. Hesselberg,t and Lawrence W. Nicholsont A b s tra c t C o n c e n tra tio n s o f polychlo rin ate d biphenyls (PCB's) were determined from 1972 through 1974 in three species o f fish collected in the fa it from eastern Lake Michigan. Mean concentrations in whole fish ranged in d iffe re n t years from 5.24 to 5.66 ppm in bloaters fCoregonus hoyiL 10.4 to 12.2 ppm in coho salmon fOncorhynchus kisutchj, and 1 29 to 2 2 9 ppm in lake tro u t fSalvelinus namaycushj. There was no evidence o f a decline in average PCB residues in the fish sampled a fte r the introduction in 1970-71 o f voluntary controls on the safe o f PCB's in the U nited States. INTRODUCTION Past investigations have shown that substantial levels o f polychlorinated biphenyls (PCB's) were present in fish from the open waters o f Lake Michigan during the late 1960's. Veith and Lee (ref. 1) reported residues o f Aroclor 1254 ranging from 14 to 25 ppm in three coho salmon (Oncorhynchus kisutch) and 6 to 25 ppm in eight rainbow tro u t {Salmo gairdneri) collected from western Lake Michigan during the spring o f 1969. Stalling and Mayer (ref. 2) reported a PCB concentration (sum of Aroclors 1248 and 1254) o f 13 ppm in a single coho salmon collected from eastern Lake Michigan during the fall of 1969. Extensive collections and analyses of fish from Lake Michigan in 1971 confirmed the approximate levels of PCB contamination found in 1969, and further demonstrated that residues in excess o f 5.0 ppm were common in several species o f fish (refs. 3,4). Because o f the potential effects o f PCB's on fish and consumers of fish, the Great Lakes Fishery Laboratory in 1972 incorporated analysis of PCB's w ith its routine program of pesticide analysis in Lake Michigan fishes. The program is designed to permit the accurate deter mination and statistical evaluation o f contaminant levels and trends with time in fish from Lake Michigan. Partic ular emphasis is placed an the yearly evaluation of con taminants in samples of bloaters (Coregonus h oyi) that Chiof. Section of Physiology and Contaminant Chemistry, U.S. Fish and W ildlife Service, Great Lakes Fishery Laboratory, Ann Arbor, Michigan. tResaarch Chemists, U.S. Fish and W ildlife Service. Great Lakes Fishery Laboratory, Ann Arbor, Michigan. are similar in terms of fish size, location of catch, and time o f year sampled. Bloaters are particularly useful for contaminant evaluation fo r several reasons:they repre sent an important commercial species that concentrates pesticides and PCB's; they reflect local conditions be cause they are essentially nonmigratory; and they are generally easy to catch in adequate numbers. Lake trout [Saiveiinus nam aycush) and coho salmon are also sampled annually because o f their current importance as sport fishes and their role in salmonid restoration pro grams. In addition, the analysis of lake trout provides an estimate of contaminant levels in a long-lived predatory species from the same geographic location as the bloat ers; and coho salmon serve as potential indicators of lakewide contaminant trends because of their extensive migrations. This report presents the trends o f average PCB con centrations in Lake Michigan bloaters, lake trout, and coho salmon in 1972-74. The data provide a basis for determining the effectiveness o f past efforts to reduce the contribution of PCB's to the Lake Michigan environ ment, as evidenced by the level of contamination in the fisheries. Voluntary restrictions on PCB sales in the United States.were introduced in 1970-71. FISH SAMPLING PROCEDURES Bloaters (240-280 mm total length) and lake trout (500-700 mm) were collected by gill net each fall (September-October) in southeastern Lake Michigan, o ff Saugatuck, Michigan. Coho salmon (600-750 mm) were collected in east-central Lake Michigan near Ludington, Michigan, in 1972, near the entry to Portage Lake in 1973, and from the lower weir on the Platte River in 1974. A ll fish were placed in plastic bags previously deter mined to be free of pesticides and PCB's. The packaged fish were frozen whole or packed in ice, transported to the Great Lakes Fishery Laboratory, apd stored at ap proximately -30 C. Before analysis, the bloaters were measured and weighed, sorted according to sex and length, grouped into 10-fish composite samples, and homogenized (whole fish) by repeatedly passing them through a meat grinder. A portion of the sample was then further homogenized in a food blender. Individual lake tro u t and coho salmon were measured, weighed, sexed, and the whole fish similarly homogenized. GENP 005729 177 774379 A N A LY T IC A L PROCEDURES Ten grams o f homogenized fish were mixed w ith anhydrous sodium sulfate and extracted by the method of Hesselberg and Johnson (ref. 5). Lipids were removed from the extract by gel permeation chromatography in an automated system simitar to that described by Stalling et al. (ref. 6), after which the pesticides and PCB's were separated on either silicic acid w ithout Celite 545 (ref. 7) or on silica gel (ref. 8). The PCB's were quantitated on a gas chromatograph equipped w ith electron-capture detectors (63Ni, $pc) and a 5-ft x l/8-in. ID glass column packed w ith 1.5 percent OV-101 on 80-100 mesh glass beads or Chromosorb W. Recov eries o f PCB's from fo rtifie d samples o f fish tissue aver age 88 percent by the described method. We performed confirmatory analyses on each sample using a second, 10-g portion of tissue saponified in alcoholic potassium hydroxide (ref. 9). Results were calculated by summing the heights o f all peaks on the chromatogram attributable to PCB's, and comparing them with the sum o f peak heights o b ta in e d f r o m analytical standards composed o f Arodors 1248, 1254, and 1260 (1:1:1). No corrections were made fo r losses incurred during analysis or the pres ence o f PCB's in blanks. A ll results are reported as total PCB's in wet weight o f tissue. TRENDS OF PCB's Mean concentrations o f total PCB's during 1972-74 ranged from 5.24 to 5.66 ppm in bloaters, 10.4 to 12.2 ppm in coho salmon, and 12.9 to 22.9 ppm in lake tro u t (table 1}. A plot o f mean PCB concentrations in bloaters venus year of collection (figure 1) suggests no change in PCB's during the 3 years o f sampling. Statistical analysis involving Student's t test (ref. 10) and the annual sam ples representing 110 to 160 fish showed that minor differences between mean PCB concentrations fo r the three sample dates were not significant. We therefore conclude that mean PCB concentrations have remained essentially unchanged since 1972 in large, adult bloaters o ff Saugatuck, Michigan. A p lot o f mean PCB concentrations in coho salmon from 1972 to 1974 also fails to show any definite change pattern (figure 2). The mean concentrations of PCB's in these fish appear to have varied randomly between 10.4 and 12.2 ppm. Statistical analyses show that the decline between 1973 and 1974 is highly signif icant (P >0.01) but that th 1972 samples do not differ significantly from either the 1973 or 1974 samples. Thus despite the evidence of significant variation among the three sample groups, there is no statistical evidence of a Bra E ft s k r VEAR Figure 1. Trends of PCB's in Lake Michigan bloaters off Saugatuck, Michigan. Mean concentrations in whole fish (wet weight) with 95 percent confi dence intervals (vertical lines). N u m b e r o f 10-fish composites shown in parentheses. Figure 2. Trends of PCB's in coho salmon from eastern Lake Michigan. Mean concentrations in whole fish (wet weight) with 95 percent confidence in intervals (vertical lines). Number of fish in parentheses. GENP 005730 178 774380 Table 1. Concentrations of PCB's in fall collections of Lake Michigan bloaters and lake trout taken off Saugatuck, Michigan, and coho salmon from between Ludington, Michigan, and the Platte River Species and Year Date c o lle c te d Number o f fish Mean length (mm) Mean Mean Range o f w eig h t l i p i d t o t a l PCB's ( g ) (p e rc e n t) (ppm) Mean t o t a l PCB's (ppm)a B loater 1972 1973 1974 Coho salmon 1972 1973 1974 Lake tro u t 1972 1973 1974 10/19 9/27 10/9 9/19 9/21 10/1 9 /2 8 9 /1 9 10/9 120(12)!* 255 160(16)P 250 110(11) b 257 10 693 29 620 30 665 9 648 30 602 30 616 177 21.6 165 2 0.0 175 2 1 .6 3 .1 2 -8 .1 7 4 .2 0 -6 .3 3 4 .8 3 -6 .2 2 5 .6 6 (0 .9 5 ) 5 .24(0.37) 5 .5 7 (0 .3 1 ) 4,156 7.3 4 .9 3 -1 5 .4 1 0 .9 (2 .1 ) 2,967 6 .0 8 .2 4 -1 6 .6 1 2 .2 (0 .8 ) 3,148 5 .4 6 .9 9 -1 6 .3 1 0 .4 (0 .9 ) 2,576 2,353 2,514 18.5 16.0 16.5 3 .5 3 -2 5 .3 9 .3 6 -3 0 .6 7.0 5 -4 7.4 1 2 .9 (4 .8 ) 1 8.9 (2 .1) 22.9 (3 .7) C o n c e n tra tio n s in whole f is h , wet w eig h t, w ith 95 percent confidence in te rv a l In parentheses. bNumber o f composite sam ples, 10 fis h /s a m p le , given in paren th eses. (jENIj UU373I general increase or decrease during 1972*74 in mean PCB concentrations in coho salmon from eastern Lake Michigan. Mean concentrations of PCB's in lake trou t collect* ed o ff Saugatuck, Michigan, appear to have increased from 1972 to 1974 (figure 3). Although statistical analy* ses show no significant differences between consecutive years, the increase between 1972 and 1974 is highly significant (P >0.005). Because of the comparatively small number of lake trout collected in 1972 (9 fish) and the high variability in PCB residues generally encoun tered between individual lake tro u t (table 1), the level of confidence in the results is low and interpretation of the apparent trend must be approached with considerable caution. Although PCB's appear to have increased in lake trout, there is no evidence of an upward trend of resi dues in bloaters (which represent the most reliable indi cator o f trends) o r coho salmon; consequently additional sampling w ill be required to determine if the apparent upward trend of PCB's in lake trou t is real. We can safely conclude, however, that mean PC8 concentrations have n o t declined in lake tro u t taken o ff Saugatuck, Michigan. TRENDS OF OTHER CHLORINATED HYDROCARBONS Mean concentrations o f DDT and its metabolites (total DOT) in the same samples o f Lake Michigan fishes employed fo r the PCB study declined 69, 48, and 26 percent respectively in bloaters, coho salmon, and in lake trou t during the period 1972-74 (ref. 11). Total DDT residues in fish decreased significantly w ithin 1 year after the ban (1969-70) on the use of DDT in the 179 774381 1972 m YEAR Era Figure 3. Trends of PCB's in Lake Michigan Lake trout off Saugatuck, Michi gan. Mean concentrations in whole fish (wet weight), with 95 percent confidence intervals (vertical lines). Number of fish in parentheses. States bordering Lake Michigan. During 1970-74, mean concentrations of total DDT dropped 87, 73, and 56 percent in bloaters, coho salmon, and lake tro u t respec tively. Mean concentrations of dieldrin in the same fish samples showed no definite trend from 1970 to 74 (ref. 11). The lack o f change is probably due to the common use of dieldrin during the early 1970's. The rapid reduc tion of DDT residues in Lake Michigan fishes and the lower bioaccumutation characteristics o f dieldrin lead us to believe'that the recent ban (1974) on the manufac ture and use of aldrin and dieldrin w ill result in a rapid decline of dieldrin residues in Lake Michigan fishes. SUMMARY AND CONCLUSIONS Mean concentrations o f PCB's in Lake Michigan b lo a te rs coIlected o ff Saugatuck, Michigan, have remained essentially unchanged since yearly analyses were initiated in 1972.' Similarly, PCB residues in coho salmon from eastern Lake Michigan show no definite pattern of change. Residues o f PCB's in lake tro u t col lected o ff Saugatuck, Michigan, are highly variable and indicate a possible, but unconfirmed, upward trend in mean PCB concentrations. Thus, voluntary restrictions in 1970-71 on the sale o f PCB's the United States have not led to a decrease in PCB concentrations in the Lake Michigan fishes sampled. REFERENCES 1. Gilman D. Veith and G. Fred Lee, "PCB's in Fish from the Milwaukee River," Proceedings o f the Fourteenth Conference on Great Lakes Research, April 1971, pp. 157-169. 2. David L. Stalling and Foster Lee Mayer, ` Jr., "Toxicities o f PCB's to Fish and Environmental Residues," Environm ental Health Perspectives, Vol. 1 (April 1972), pp. 159-164. 3. Great Lakes Fishery Laboratory, Progress in S port Fishery Research -- 1971, Resource Publication 121, U.S. Bureau o f Sport Fisheries and W ildlife, Washington, D.C., 1973, pp. B6-120. 4. Gilman D. Veith, "Baseline Concentrations o f Poly chlorinated Biphenyls and DDT in Lake Michigan Fish, 1971," Pesticides M onitoring Journal, Vol. 9, No. 1 (June 1975), pp. 21-29. 5. R. J. Hesselberg and J. L. Johnson, "Column Ex traction of Pesticides from Fish, Fish Food and M ud," BuJletin o f Environm ental Contam ination and Toxicology, Vol. 7, No. 2/3- (1972), pp. 115-120. 6. David L. Stalling, Roger C. Tindle, and James L. Johnson, "Cleanup o f Pesticide and Polychlorinated Biphenyl Residues in Fish Extracts by Gel Permea tion Chromatography," Journal o f the Association o f O fficia l A n alytica l Chemists, V ol. 55, No. 1 (1972), pp. 32-38. 7. J. A. Arm our and J. A. Burke, "M ethod for Sepa rating PCB's from DDT and Its Analogs," Journal o f the Association o f O ffic ia l A n a lytica l Chemists, Vol. 53, No. 4 (1970), pp. 761-768. * 8. Diane Snyder and Robert Reinert, "Rapid Separa tion o f Polychlorinated Biphenyls from DDT and its Analogues on Silica G el," B ulletin o f Environm ental Contam ination and Toxicology, Vol. 6, No. 5 (1971), pp. 385-390. 180 774382 9. Robert E. Reinert, "Pesticide Concentrations in Great Lakes Fish,*' Pesticides M onitoring Journal, Vol. 3, No. 4 {1970}, pp. 233-240. 10. George W. Snedecor, Statistical Methods, Iowa State University Press, Ames, Iowa, 1957. 11. Wayne A. W illford, "Contaminants in Upper Great Lakes Fishes," report presented at the Upper Great Lakes Committee Meetings of the Great Lakes Fishery Commission, Milwaukee, Wisconsin, March 25-26,1975,9 p. GENP 005733 181 . 774383 U A NOTE ON POLYCHLORINATED BIPHENYLS IN AIR Frederick W. Kutz, Ph.D.* and Henry S. C. Yang A b s tra c t Samples o f am bient a ir were collected using an ethylene-glycol im pinger sampler, and analyzed fo r selected pesticides and polychlorinated biphenyls in sub urban locations in F lorida, Mississippi, and Colorado. P relim inary results fo r samples taken in A p ril, May, and June o f 1975 show th at PCBs were present a t a ll loca tions. Samples o f ambient air were collected and analyzed for selected pesticides and polychlorinated biphenyls. Suburban locations in Miami, Florida, Jackson, Mississip pi, and Fort Collins, Colorado, were sampled using an ethylene-glycol impinger sampler essentially the same as reported by Enos et al. (ref. 1) except that an improve ment o f air flow rate was made. The air flow rate was maximized and calibrated at ca. 30 l/m in. Each sampler was operated fo r a 24-hour period to collect one sample. The analyses o f samples were done by extraction w ith hexane fo llo m d by cleanup w ith fluorsil column chromatography, using a mixture o f diethyl ether and petroleum ether fo r elution; the'fraction containing the polychlorinated biphenyls and some organochlorine "Project Officer, Notional Human Monitoring Program for Pesticides, Ecological Monitoring Branch, Office of Pesticide Pro grams, Environmental Protection.Agency, Washington, O.C. pesticides underwent further separation by silicic acid column chromatography. Quantitation of the poly chlorinated biphenyls was done by summation o f major peaks employing the dual-column gas chromatography w ith electron capture detector. Preliminary results fo r samples taken in April, May, and June of 1975 show that PCB's were present at alt locations. Although the data varied, the average con centration at each of the three locations was approxi mately 100 nanograms per cubic meter. The presence of polychlorinated biphenyls in ambient air samples taken in Miami and Jackson has been confirmed by combined gas chromatography-mass spectrometry. Initial identifi cation o f the polychlorinated biphenyls indicates that they were most comparable to the Aroclor 1254 stand ard. In July the number o f sampling sites was expanded to five with the addition of Lafayette, Indiana, and Harrisburg, Pennsylvania. Results from all sites should be available in the near future. REFERENCE 1. H. F. Enos, J. F. Thompson, J. B. Mann, and R. F. Moseman, " Determination of Pesticide Residues in A ir," (022-Pesticide Chemistry), Division of Pesti cide Chemistry, 163rd Meeting Proceedings, Ameri can Chemical Society, Boston, Massachusetts, April 1972. O t-n X> 182 774384 POLYCHLORINATED BIPHENYLS IN THE SURFACE WATERS AND BOTTOM SEDIMENTS OF THE MAJOR DRAINAGE BASINS OF THE UNITED STATES D. Steve Dennis, Ph.D* A b s tra c t Data gathered from m onitoring activities indicate die widespread occurrence o f PCBs in surface waters and bottom sediments o f the m ajor drainage basins o f the United States. A preiim inary assessment o f PCS levels shows median residue levels o f the positive detecdons fo r the years 1971 to 1974 ranging between 0.1 to 3.0 p g /l fo r unfiltered water samples and from 1.2 to 160.0 pg/kg fo r bottom sediments. The highest levels were found in basins east o f die Mississippi and bottom sediments may contain concentrations o f PCBs many times higher than those in the overlying water. age basins o f the United States and Puerto Rico (figure 1) fo r the years 1971 to 1974. A ll data were obtained from STORET, which is EPA's computerized informa tion system that draws on both State and Federal agen cies fo r parametric data relating to water quality. Although there is not a nationwide program specifi cally designed to assess PCB levels in the aquatic environ ment, the present Geological Survey and EPA water monitoring programs are expanding and gradually in creasing to more adequately determine PCB levels in the surface waters o f the United States. These programs are also being designed to determine both national and regional trends in the concentration o f PCB's. INTRODUCTION Within the past few years, particularly in the past year, polychlorinated biphenyls (PCB's) have been iden tified as a major contaminant o f natural waters. PCB's in the hydrologic environment can originate from several sources including: 0 ) runoff from sewage sludges dis posed of on land, (2) discharge of industrial and munici pal wastes {this includes treated as well as untreated wastes}, (3) accidental spills or improper waste disposal practices, and (4) formerly as ingredients of pesticides or as carriers fo r pesticides. Probably the largest amount of PCB's in the environment results from industrial and municipal discharges to inland and coastal waters (refs. 1-5). Although much attention has been focused on estimating levels of PCB's in aquatic organisms, and the potential hazards involved, few data are available on the occurrence of PCB's in water and bottom sediments. The U.S. Department of Interior's Geological Survey and the U.S. Environmental Protection Agency's (EPA) Office o f Pesticide Programs, Technical Services Division, through their National Water Monitoring Program for Pesticide Residues and various water-resource-assessment projects, are accumulating data which permit a preliminary assess ment of PC8 contamination of the Nation's drainage basins. The data presented here were gathered by the Geological Survey. They show the occurrence o f PCB's (PCB mixtures predominately resemble Aroclor 1254) in whole water samples (i.e., water samples which are un filtered) and in bottom sediments in the 17 major drain- *Project Officer, National Water Monitoring Program for Pesticides, Ecological Monitoring Brandt, Office of Pesticide Programs, Environmental Protection Agency. Washington, O.C. METHODS AND PROCEDURES Water samples were collected either by depth inte gration at the center o f flo w or by the equal-transit-rate method. In the latter method a standard suspended- sediment sampler, such as the US D-49 suspended- sediment sampler, was used to collect a velocity- and * discharge-weighted sample. Samples were taken at a number o f equally spaced verticals across a stream, depending on stream width (usually three sites were . sampled across a stream). The transit rate of movement of the sampler from the water surface to the stream bed and back to the surface was the same at all verticals. Samples collected at each vertical were composited into a single sample intended to represent the entire flow across the stream. Bottom sediments were sampled by collecting a series of coresacross the stream bed using piston type or US BMH-60 or US BM-54 bed material samplers or a commercial core sampler. When a core sampler was used, cores were composited to form a representative sample of the stream bed (see refs. 5,6 fo r a description of sampling procedures). Once the samples were collected, PCB residues were analyzed by the multiple-pesticide-residue methods for water, suspended sediment, and bottom sediment de scribed by Goerlitz and Brown (ref. 7). Basic identification of PCB residues was made by dual-column electron capture/gas-liquid chromatography > and confirmed by gas-liquid chromatography or mass spectrometry. The amount of PCB's was determined by matching the peaks on the chromatogram with the near- ^ est commercial form ulation. The reported values are sub- ^ ject to some error because of the complexity of multiple -> peaks resulting from mixtures of PCB's in environmental samples. ^ 183 774385 9S00 dNHO Figure 1. Map showing the major drainage basins in the United States and Puerto Rico. 774386 Table 1. PCB 's in w hole water samples in the major drainage basins o f the U nited States and Puerto R ico fo r 1971 Drainage basin Sample s iz e % of p o s itiv e d e te c tio n s Median o f p ositive d e te c t i ons in yg/1 Range o f p o s itiv e d e te c tio n s in ug/1 1. North A tla n tic Slope 2. South A tla n tic Slope and Eastern G u lf o f Mexi co 3. Ohio R iv er 4. S t. Lawrence R iv er 5 . Hudson Bay and Upper M ississippi River 6. Missouri R iver 7. Lower M is sis s ip p i 8. Western G u lf o f Mexico 9. Colorado R iver 10. G reat Basin n . P a c ific Slope Basins in C a lifo rn ia 12. P a c ific Slope Basins in Washington 13. Snake R iv er 14. P a c ific Slope Basins in Oregon and Lower Columbia R iv er 15. Alaska 16. Hawaii 17. Puerto Rico 12 5 8 .3 12 0 -15 2 6 .7 -- 10 1 100.0 9 44.4 ---- -- -- --- -- Note: - = no samples; ND = not detected. 0 .2 0.1 - 2.1 ND ND -0 .3 0.1 - 0 .5 -- ND ND 3 .0 3.0 0 .3 0.1 - 0 .7 -- -- -- -- ---- GENP 005737 185 774387 Table 2. P C B 's in w hole water samples in the m ajor drainage basins o f the United States and Puerto R ico for 1972 Drainage basin 1. North A tla n tic Slope 2. South A tla n tic Slope and E astern G u lf o f Mexico 3 . Ohio R iv e r 4 . S t. Lawrence R iv er 5 . Hudson Bay and Upper M ississippi River 6 . Missouri R iver 7. Lower M is s is s ip p i 8 . Western G u lf o f Mexico 9. Colorado R iver 10. G reat Basin n . P a c ific Slope Basins in C a lifo rn ia 12. P a c ific Slope Basins in Washington 13. Snake R iv e r 14. P a c ific Slope Basins . i n Oregon and Lower Columbia R iv e r 15. Alaska 16. Hawaii 17. P uerto Ri co Sample s iz e % of p o s itiv e d e te c tio n s Median o f ' p o sitive d e te c tio n s in ng/1 Range o f p o s itiv e d e te c tio n s In ug/1 112 17.0 122 0 .8 0.1 0.1 - 0 .3 NO ND 10 29 12 34 39 93 ` 24 9 20 14 3 20.0 13.8 16.7 o 2 .6 8 .6 0 0 0 0 0 -- 10 30 0 .2 0.1 - 0 .2 0.1 0.1 - 0 .2 0 .3 0.2 - 0.3 ND ND 0.1 6.1 0 .3 0.1 - 2 .6 ND ND ND ND ND ND ND ND -- ND ND -- ND ND ND ND Note : - = no sam ples; ND = not d e te c te d . 8isoo 186 774388 Table 3. PCB 's in w hole water samples in the m ajor drainage basins o f the United States and Puerto Rico for 1973 Drainage basin Sample s iz e % of p o s itiv e d e te c tio n s Median o f p o s itiv e d e te c tio n s in ug/1 Range o f p o s itiv e d e te c tio n s in yg/1 1, North A tla n tic Slope 109 3 .7 0.1 0.1 2. South A tla n tic Slope and E astern G u lf o f Mexi co 114 4 .4 0.1 0.1 - 20.0 3 . Ohio R iver 60 ND ND i . S t. Lawrence R iv e r 31 3 .2 0 .1 0 .1 5. Hudson Bay and Upper M ississippi R iver 30 10.0 0 .2 0.1 - 0 .4 6. Missouri R iver 95 0 NO ND 7. Lower M is s is s ip p i 291 0 .7 1.6 0 .2 - 2.9 8. Western G ulf, o f Mexico 362 1.7 . 0 .3 0.1 - 0.6 9. Colorado R iver 64 0 ND ND 10. G reat Basin 12 o . ND ND n . P a c ific Slope Basins in C a lifo rn ia 73 0 ND . ND 12. P a c ific Slope Basins in Washington 33 0 ND ND 13. Snake R iv e r 20 ND ND 14. P a c ific Slope Basins in Oregon and Lower ' Columbia R iv er 90 ND ND 15, Alaska -- -. - 16. Hawaii 10 ND ND 17. Puerto Rico 37 0 ND ND Note: - = no samples; ND = n o t d e te c te d . GENP 005739 187 774389 Table 4. P C B 's in w hole water samples in the major drainage basins o f the United States and Puerto R ico for 1974 Drainage basin 1. North A tla n tic Slope 2. South A tla n tic Slope and E astern G u lf o f Mexico 3. Ohio R iv er 4 . S t. Lawrence R iv e r 5 . Hudson Bay and Upper M ississippi River 6. Missouri R iver 7. Lower M is s is s ip p i 8 . Western G u lf o f Mexico 9. Colorado R iv er 10. G reat Basin 11. P a c ific Slope Basins in C alifo rn ia 12. P a c ific Slope Basins in Washington 13. Snake R iv er 14. P a c ific Slope Basins in Oregon and Lower Columbia R iv e r 15. Alaska 16. Hawai i 17. Puerto Rico Sample s iz e % of p o s itiv e d e te c tio n s 51 2 .0 0151 Median o f p o s itiv e d e te c tio n s in pg/1 0.1 ND ' Range o f p o s itiv e d e te c tio n s in ug/1 0.1 ND 24 0 38 0 33 0 28 0 269 2 .6 325 1 .2 52 0 12 0 74 2 .7 13 7 .7 11 0 80 ND ND ND NO ND ND ND ND 0.1 0.1 - 0 .2 0.3 0 .2 - 0.7 ND ND ND ND 0.1 0.1 0.1 0.1 ND ND ND NO -- 10 -- ND ND 68 1 .5 0 .8 0 .8 Note: - - no samples; NO = n ot d e te c te d as 0 8 188 O' 5 774390 Table 5. PCB 's in bottom sediments in the major drainage basin o f the U nited States and Puerto Rico fo r 1971 Drainage basin 1. North A tla n tic Slope 2. South A tla n tic Slope and E astern G u lf o f Mexi co 3. Ohio R iver 4 . S t. Lawrence R iv er 5 . Hudson Bay and Upper M ississippi River 6. Missouri R iver 7. Lower M is s is s ip p i 8. Western G u lf o f Mexico 9. Colorado R iver 10. Great Basin 11. P a c ific Slope Basins in C a lifo rn ia 12. P a c ific Slope Basins in Washington 13. Snake R iv e r 14. P a c ific Slope Basins in Oregon and Lower Columbia R iv er 15. Alaska 16. Hawai i 17. Puerto Rico Sample s iz e % of p o s itiv e d e te c tio n s Median o f p o s itiv e d e te c tio n s in ug/kg Range o f p o s itiv e d e te c tio n s in ug/kg 3 100.0 19 6 3 .2 50.0 64.5 10.0 - 100.0 10.0 - 200.0 1 100.0 1 100.0 -- 8 .8 10.0 - 8 .8 10.0 - 2 100.0 1.2 0.3 - 2.0 4 100.0 , 3 0 .0 10.0 - 80.0 20 100.0 10.0 2.0 - 290.0 -- - - -- - - -- - - -- - - -- - - --- - - - Note; - = no samples; ND = not d e te c te d GENP 005741 189 774391 Table 6. P C B 's in bottom sediments in the major drainage basins o f the United States and Puerto Rico for 1972 Drainage basin 1. North A tla n tic Slope 2 . South A tla n tic Slope and E astern G u lf o f Mexi co 3 . Ohio R iv er 4. S t. Lawrence R iv e r 5 . Hudson Bay and Upper M ississippi R iver 6. Missouri R iver 7. Lower M ississip p i 8 . Western G u lf o f Mexico 9. Colorado R iver 10. G reat Basin 11. P a c ific Slope Basins in C a lifo rn ia 12. P a c ific Slope Basins in Washington 13. Snake R iv e r 14. P a c if ic Slope Basins in Oregon and Lower Columbia R iv er 15. Alaska 16. Hawaii 17. Puerto Rico Sample s iz e _ Median o f % of p ositive p o s itiv e detections* detections in ug/kg Range o f p ositive d e te c tio n s in ug/kg 56 57.1 101 . 3 2 .7 10.0 30.0 S.O - 8 00 .00 5 .0 - 500.00 -10 9 0 .0 30 22 8 1 .8 25 4 8 .0 66 4 3 .9 7 71.4 9 66.7 6 83.3 9 44.4 10 1 100.0 20.0 ND 2 .0 2 .0 4 .0 2 .0 2 .0 20.0 2 .0 NO 2 .0 2.0 - 800.0 ND 2 .0 2 .0 - 2400.0 2 .0 - 250.0 2 .0 2 .0 2 .0 - 190.0 2 .0 ND 2 .0 -10 -- ND - ND -' Note: - = no samples; ND = not d e te c te d . O Q O' 190 7 ?4392 Table 7. PCB's in bottom sediments in the major drainage basins of the United States and Puerto Rico for 1973 Drainage basin Sample s iz e % of p o s itiv e d e te c tio n s Median o f p o s itiv e d e te c tio n s in yg/kg Range o f p o s itiv e d e te c tio n s in ug/kg 1. North A tla n tic Slope 2. South A tla n tic Slope and E astern G u lf o f Mexico 3. Ohio R iv er 4. S t. Lawrence R iv e r 5 . Hudson Bay and Upper M ississippi R iver 6. Missouri R iver 7. Lower M is sis s ip p i 8 . Western G u lf o f Mexico 9. Colorado R iver 10. G reat Basin 11. P a c ific Slope Basins in C a lifo rn ia 12. P a c ific Slope Basins in Washington 13. Snake R iv e r 14. P a c ific Slope Basins in Oregon and Lower Columbia R iv er 15. Alaska 16. Hawai i 17. Puerto Rico 58 123 70.7 4 8 .8 4 25.0 24 9 1 .7 14 0 17 0 57 1 .8 188 3 .7 40 70 14 0 12 0 10 20 10 6 16.7 10.0 10.0 4 .0 - 4000.0 5 .0 - 600.0 20.0 20.0 NO ND 20.0 50.0 ND. ND ND ND ND * 20'. 0 5 .0 -13000.0 ND ND 20.0 14.0 - 180.0 ND ND ND ND ND ND ND ND . ND 5.0 5.0 Note: - = no samples; ND = not d e te c te d . GENP 005743 191 7 7 4 393 Table 8. P C B 's in bo tto m sediments in the major drainage basins o f the United States and Puerto R ico fo r 1974 Drainage basins Sample s iz e % of ' p o s itiv e d e te c tio n s Median o f p ositive d e te c tio n s in ug/kg Range o f p ositive d e te c tio n s in ug/kg 1. North A tla n tic Slope 2. South A tla n tic Slope and E astern G u lf q f Mexico 3. Ohio R iv e r 4. S t. Lawrence R iv e r 5 . Hudson Bay and Upper M ississippi River 6. Missouri R iver 7. Lower M ississip p i 8 . Western G u lf o f Mexico 9. Colorado R iver 10. G reat Basin 11. P a c ific Slope Basins in C a lifo rn ia 12. P a c ific Slope Basins in Washington 13. Snake R iv e r 14. P a c ific Slope Basins in Oregon and Lower Columbia R iv er 15. .Alaska 16. Hawai i 17. Puerto Rico 99 171 6 40 26 5 81 157 3 4 26 5 4 1 18 56.6 25.7 33.3 60.0 0 0 9 .9 21.7 0 0 11.5 0 0 0 27-2 31.0 11.0 2 .0 - 800.0 2.0 - 530.0 3 5 .0 ' 9 .0 - 61.0 20.0 3 .0 - 700.0 ND ND ND 10.5 27.0 ND ND 2 .0 ND 1.0 - 39.0 2 .0 - 330.0 ND ND 2 .0 - 65.0 ND ND ND ND ND ND - - 160.0 - 10.0 - 640.0 Note: - = no samples; ND = n o t d e te c te d 192 774394 RESULTS Tables 1 through 8 present the PC8 residue data by year fo r water and bottom sediments. For each year the following is given: number of samples, percent of posi tive detections, median of positive detections, and maxi mum o f positive detections in g/l for water and g/kg fo r bottom sediments (one g/l and one g/kg are rough ly equivalent to one ppb). Not all drainage basins had detectable levels of PCB's in both water and bottom sediments. However, it should be noted that this may be in part due to the location of sampling stations within drainage basins and/or the small number o f samples within drainage basins. Median residue levels o f the positive detections in whole water samples ranged from 0.2 to 3.0 g/l, 0.1 to 0.3 g/l, 0.1 to 1.6 g/l, and 0.1 to 0.8 for all drainage basins fo r 1971, 1972, 1973, and 1974, respectively (tables 1 to 4). For both these data and the data fo r each basin there is no indication of an increase in PC8 levels and in many instances the levels decreased. The highest PCB level was found in the South Atlantic Slope and Eastern Gulf of Mexico basin and in general, the highest levels- were found in basins east o f the Mississippi. One might speculate that this is due to the presence of cer tain industries in the eastern United States. Bottom sediments showed a pattern similar to that of water with the highest PCB residue levels occurring in the eastern United States (table 5 to 8). Median residue levels of the positive detections for all basins ranged from 1.2 to 64.5 xg/kg, 2.0 to 30.0 /kg, 5.0 to 50.0 g/kg, and 2.0 to 160.0 g/kg for 1971,1972,1973, and 1974, respectively. The data indicate that, as with the whole water samples, the levels decreased in some basins. However, it appears as if PCB's are more persistent in bottom sediments. DISCUSSION The data which I have presented here indicate that PCB's are widespread in the surface waters and bottom sediments of the Nation. Crump-Wiesner et al. (ref. 9) also found PCB's to have a ubiquitous occurrence and distribution in surface water, ground water, and bottom sediments. According to Veith and Lee (ref. 8) " . . . the chlorinated biphenyls may be'one of the more wide spread. . environmental contaminants. It is well documented that bottom sediments may contain concentrations of pesticide residues many times higher than the overlying water (refs. 10-13). The data presented here and previously published data (refs. 1,4,9,14) indicate that a similar relationship holds true fo r PCB's. Even in drainage basins, where PCB's were not detected in water samples such as the Missouri River, they were present in bottom sediments. It is assumed that this is due to the low water solubility and high specific gravity of PCB's (ref. 14). According to Nisbet and Sarofim (ref. 14), " . . . it is expected that most of the PCBs discharged into the environment w ill be resting as sludges or adsorbed in the sediment at the bottom of rivers or lakes near their point o f discharge, and that transport in streams w ill be primarily by means of water borne particles." Finally, it is important to note that although PCB's are found in water and bottom sediments, this informa tion must be related to the entire aquatic environment before the data can be adequately evaluated. This is because (1) PCB's in solution and sorbed on organic and inorganic particles are available for introduction into food chains, (2) PCB's are accumulated in the tissues of animals which are exposed to water and bottom sedi ments containing PCB's, (3) biological magnification may occur in food chains, and (4) all components in an aquatic ecosystem are interrelated. REFERENCES 1. Interdepartmental Task Force on PCBs, P olychlorin ated Biphenyls and die Environm ent, National T e c h n ic a l Information Service COM-17-10419, 1972,181 pp. 2. A. V. Holden, "Source o f Polychlorinated Biphenyl Contamination in the Marine Environment," A/a* ture, Vol. 228 (1970), pp. 1220-1221. 3. T. T. Schmidt, R. W. Risebrough, and F. Gress, " In put of Polychlorinated Biphenyls into California Coastal Waters from Urban Sewage O utfalls," Bull. Environ. Contam. Toxicol., Vol. 6 (1971), pp. 235-243. 4. T. W. Duke, J. I. Lowe, and A. J. Wilson, Jr., "A Polychlorinated Biphenyl (Arocior 1254) in the Water, Sediment, and Biota of Escambia Bay, Flori d a," B ull. Environ. Contam. Toxicol., Vol. 5 (1970), pp. 171-180. 5. H. R. Feltz and J. K. Culbertson, "Sampling Proce dures and Problems in Determining Pesticide Resi dues in the Hydrologic Environment," Pestic. M onit. J.. Vol. 6 (1972), pp. 171-178. 6. H. P. Guy and V. W. Norman, "Field Methods for Measurement o f Fluvial Sediment," Techniques o f Viater-Resources Investigations o f the U.S. Geologb cal Survey: Book 3 . Chapter C2, 1970,59 pp. 7. D. F. Goerlitz and E. Brown, "Methods for Analysis GENP 005745 193 774395 o f Organic Substances in W ater/' Techniques o f Water-Resources Investigations o f the U.S. Geologi cal Survey: Book 5, Chapter A 3 ,1 9 7 2 ,4 0 pp. 8. G. D. Veith and G. F. Lee, " A Review of Chlorin ated Biphenyl Contamination in Natural Waters," Water Research, Vol. 4 (1970), pp. 265-269. 9. H. J. Crump-Wiesner, H. R. Feitz, and M. L. Yates, " A Study of the Distribution o f Polychlorinated Bi phenyls in the Aquatic Environment," Pestic. M o n it J., Vol. 8 (1974), pp. 157-161. 10. H. R. Feitz, W. T. Sayers, and H. P. Nicholson, "National M onitoring Program fo r the Assessment o f Pesticide Residues in Water," Pestic. M o n it J ., Vol. 5 (1971), pp. 54-62. 11. T. E. Bailey and J. H. Hannum, "D istribution of Pesticides in California," Amer. Soc. C ivil Eng. Proc., J. Sanit. Eng. D iv., Vol. 93 (1967), pp. 27-43. 12. W. E. Odum, G. M. Woodwell, and C. F. Wurster, "D D T Residues Absorbed From Organic Detritus by Fiddler Crabs," Science, Vol. 164 (1969), pp. F76-577. 13. J. 0 . Keith and E. G. Hunt, "Levels' of Insecticide Residues in Fish and W ildlife in California," Tran scrip t T h irty-F irst N. Am er. W ildlife C onf., 1966, pp. 150-177. 14. I.C.T. Nisbet and A. F, Sarofim, "Rates and Routes o f Transport o f PCBs in the Environment," Environ, Health Perspec., Vol. 1 (1972), pp. 21-38. 194 774396 PCB's IN AG RICULTURAL AND URBAN SOIL A b s tra c t A. E. Carey and J. A. Gowen* SAMPLING PROCEDURES Polychlorina ted biphenyls in soil have been m oni tored since 1972 as p a rt o f the N ational Soils M onitoring Program, originally established to measure pesticide resi due levels in agricultural soils, raw agricultural com m odi ties, and urban soils across the Nation. The PCB's are m onitored as p a rt o f this program because o f their chem ical sim ila rity to certain chlorinated pesticides. The PCB's have rarely been detected in agricultural soils o f the United States. O nly 0.1 percent o f the soil samples collected in the N ational Soils M onitoring Pro gram fo r 1972 contained detectable PC8 levels. How ever, detectable levels o f PCB's occur more frequently in urban soils. O f the 19 m etropolitan areas sampled since 1971, 12 o f the cities, o r 63 percent showed detectable PCB levels. The m ost com m only encountered PCB was A m clor 1254, which was ide ntifie d in approxim ately 40 percent o f the positive samples, w hile A ro c/or 1260 was prevalent in about 20 percent o f the positive samples. In the rem aining 40 percent o f the positive samples, no identification was made o f the specific A roclor. The occurrence o f these compounds appears to be more prev alent in die "u rb a n "p o rtio n (w ithin the c ity lim its } than in the "suburban" p o rtio n (remainder) o f these m etro politan areas. INTRODUCTION The occurrence of polychlorinated biphenyls (PCB's) in environmental media has been known and well-documented for several years; it is only recently that the magnitude of the contamination has created widespread concern. These compounds have been monitored in agricul tural and urban soils since 1972 as part of the National Soils Monitoring Program. This program was established to measure pesticide residue levels in agricultural soils, raw agricultural commodities, and urban soils across the Nation. It was initiated by the U.S. Department o f Agri culture and is now operated by the U.S. Environmental Protection Agency. The PCB's are monitored as part of this program because of their chemical similarity to cer tain chlorinated pesticides. Soil Scientist a n d Agronomist, respectively. National Soils Monitoring Program, Technical Services Division, U.S. Environ mental Protection Agency, WH-569, Washington, O.C. 20460. For cropland sampling, 50 cores 5.1 x 7.6 cm in size were collected over an evenly spaced 5 x 10 grid on each 4-hectare site (ref. 1). In urban sampling, this procedure was modified to collect 16 cores on a 4 x 4 grid over a 225-ma plot (15 x 15 m) (ref. 2). Field processing was similar fa r both types o f samples; the cores were com posited, thoroughly mixed, and sieved through a 6.3-mm mesh, and a 24 subsample was sent to the EPA Technical Services Division's Pesticide Monitoring Laboratory in Bay St. Louis, Mississippi, fo r chemical analysis. A N A LY T IC A L PROCEDURES Sample Preparation A 300-g subsample was dampened w ith water and extracted w ith 600 ml o f 3:1 hexane:isopropanol sol vent. The isopropanol was removed by three distilled water washes and the hexane extract was dried through anhydrous sodium sulfate and stored at low temperature fo r subsequent gas-liquid chromatographic analysis. JSas-Uquid Chromatography Analyses were performed on gas chromatographs equipped w ith tritiu m fo il electron a ffin ity detectors. A multiple system o f polar and nonpolar columns was u ti lized fo r identification and confirmation. Instrument parameters ware as follows: Columns: Glass, 6 mm o.d. x 4 mm i.d., 183-cm long, packed w ith one o f the following: 9% QF-1 on 100/120-mesh Gas-Chrom Q; 3% DC-200 on 1 0 0 /1 20-m esh G as-C hrom Q ; or 1.5% OV-17/1.95% QF-1 on 100/120-mesh Sepul- coport. Carrier Gases: 5% methane-argon at a flo w rate of 80 m l/min; prepurified nitrogen at a flow rate of 80 ml/min. Temperatures: Detector 200C Injection port 250 C Column QF-1 166C Column DC-200 170--175C Mixed column 185--190C. Sensitivity or minimum detection levels were 0.05 to 0.1 ppm. The average recovery rate in soil was 90 to 110 percent. GENP 005747 195 774397 DISCUSSION A g ricu ltura l Soils PCB's have rarely been detected in the Nation's a g ri-. cultural soils. O f the 1,556 soil samples collected in 1972 as part of the National Soils Monitoring Program, only 2 samples or 0.1 percent contained detectable levels of PCB's. Urban Soils Detectable levels o f PCB's occur more frequently in urban soils than in agricultural soils. O f the 19 metropoltan areas sampled since 1971, 12 of the cities, or 63 percent showed detectable levels o f PCB's. Correspond* ing data are presented in tables 1-4. The most commonly encountered PCB was Aroclof 1254, which was identi fied in 39 percent o f the positive samples, while Aroclor 1260 was prevalent in 21 percent of the positive sam ples. Although no attempt was made to identify the spe cific Aroclor in 39 percent of the positive samples, it is likely that a majority contained Aroclor 1254. A ll sites sampled within a metropolitan area were classified into tw o of four categories. First, sites were identified as either "la w n " o r "w a s te ,"-to indicate whether or not they seemed likely to receive regular maintenance. Secondly, each site was classified as urban if it was w ithin the city limits, and suburban if it was located in the remainder o f the metropolitan area. When the positive sites in the 12 cities were catego rized in this manner, 42 percent were lawn sites (main tained), while 58 percent were waste sites (not main tained). This difference was not considered significant. However, the second categorization showed that 70 per cent of the PCB-positive sites were urban, or within the city limits, whereas only 30 percent were classified as suburban sites. In comparison, the ratio o f urban to sub urban sites fo r these 19 cities was 37 percent to 63 percent In summary, PCB occurrence in agricultural soils is extremely rare and is not considered a problem. How ever, the occurrence o f these compounds is more preva lent in metropolitan areas, particularly w ithin city limits, and monitoring should be continued to determine trends over time. REFERENCES 1. G. B. Wiersma, P. F. Sand, and E. L. Cox, " A Sam pling Design to Determine Pesticide Residue Levels in Soils o f the Conterminous United States," Pestic. M o n it J ., Voi. 5, No. 1 (1971), pp. 63-66. 2. G. B. Wiersma, H. Taj, and P. F. Sand, "Pesticide Residues in Soil From Eight Cities--1969," Pesto. M o n it J .. Vo). 6, No. 2 (1972), pp. 126-129; Table 1. Occurrence of polychlorinated biphenyls in soils of five U.S. cities sampled in 1971. U.S. Environmental Protection Agency Urban Monitoring Program Location B altim ore, Md. Gadsden, A la. H a rtfo rd , Conn. Macon, Ga. Newport News, Va. Total. No. o f . Percent o f Oetected values Geometric PCB No. o f p o s itiv e p o s itiv e (ppm) A r1 th m e tic mean typ e -if s ite s detections detections Minimum Maximum mean (ppm) estimate (ppm) Id e n tifie d 156 6 3.9 0.09 0.74 0.02 55 1 1.8 11.94 0.21 48 NDa 43 NO - 78 1 1.3 3.30 0.04 0.001 *b 1260 not Iden tifie d * 1254 aND = Not detected. ^ * ~ Geometric mean estimate not calculated when less than two p o s itiv e values present. GENP 005748 1S6 774398 Table 2. Occurrence of polychlorinated biphenyls in soils of five U . cities sampled in 1972. U.S. Environmental Protection Agency Urban Monitoring Program Location Total No. o f Percent o f Detected values Geometric PCB No. o f p o s itiv e p o s itiv e (ppm) A rlthm etit mean type-i f s ite s detections detections Minimum Maximum mean (ppm) estimate (ppm) Id e n tifie d Oes Moines, Iowa 82 3 3.7 0.34 0.94 0.03 0.002 F itchburg, Mass. Lake Charles, La. P ittsburgh, Pa. 35 70 189 NDa 1 1.4 1 0.5 1.31 1.01 0.02 0-. 01 * Reading, Pa. 49 NO - aND Not detected. -* * a Geometric mean estimate not calculated when less than two p o s itiv e values present. not id e n tifie d 1254 not id e n tifie d ! Table 3,. Occurrence of polychlorinated biphenyls in soils of five U.S. cities sampled in 1973. U.S. Environmental Protection Agency Urban Monitoring Program Location Evansville, Ind. G re e n ville , S.C. P it t s f ie ld , Mass. Tacoma, Wash. . Washington, O.C. Total No. o f Percent o f Detected values Geometric PCB No. o f p o s itiv e p o s itiv e (ppm) Arithm etic mean typ e -if s ite s detections d e te c ti ons Minimum Maximum mean (ppm) estimate (ppm) id e n tifie d 82 N0a 86 3 3.5 0.13 1.59 0.02 0.001 45 ND 95 6 6.3 0.18 0.63 0.03 0.003 116 2 1.7 0.32 0.80 <0.01 0.001 1254 1-1254 5-not id e n tifie d 1-1254 1-not id e n tified aND a Not detected. GENP 005749 197 774399 Table 4. Occurrence of polychlorinated biphenyls in soils of five U.S. cities sampled in 1974. U.S. Environmental Protection Agency Urban Monitoring Program L o c a tio n T o ta l No. o f s ite s No. o f p o s itiv e d e te c tio n s Percent o f p o s itiv e d e te c tio n s D e te cte d v a lu e s (pp m ) M inim um Maximum A rith m e tic mean (p H G e o m e tric mean e s tim a te (ppm) PCB ty p e - if Id e n tifie d Percent o f A n a ly s e s C om pleted Durham , N .C . G ary, Ind. GG 89 San F ra n cisco * C a lli. 119 S p r in g fie ld , 111. P ire B lu ff, A rk. 72 59 1 l. S 0 .4 0 0 .01 5 5 .6 0 .50 3 .3 3 < 0.01 3 2 .5 0 .39 1 .15 < 0 .0 1 NGa A n a ly s e s n o t co m p le te d 0 .00 3 0 .0 0 1 1254 1 -n o t Id e n tifie d 4 -1 2 5 4 1 -n o t id e n tifie d 1-1254 1-1260 94 100 71 100 aND N o t d e t e c t e d . b * = G e o m e tric mean e s tim a te n o t c a lc u la t e d when le s s th a n tw o p o s it iv e v a lu e s p r e s e n t. GENP 005750 198 774400 MARINE INPUTS OF POLYCHLORINATED BIPHENYLS OFF SOUTHERN CALIFORNIA David R. Young, Deirdre J. McDermott, and Theadore C. Heesen* A b s tra c t Rates o f polychlorinated biphenyl (PCB) transport via p ote ntia l in p u t routes to the coastal waters o ff south ern C alifornia have been quantified. Submarine discharge o f m unicipal wastewater was found to be the single larg est source, contributing 5,400 kg o f these synthetic or ganics in 1974. However, inputs via this route appear to be decreasing, as the corresponding estimate fo r 1971 exceeded 19,000 kg. Bottom sediments around the larg est outfalls contain up to 10 ppm PCB. D ry aerial fa llo u t also appears to be an im portant source. The estimated deposition rate o f 1254 PCB onto the coastal waters during 1973-74 was 1,800 kg /yr; highest inputs were measured o ff the Los Angeles Basin. This region also contributed the m ost PCB in surface ru n o ff, although less than 800 kg were discharged annually during 1972-73 via storm and dry-weather flow . D irect indus tria l discharges to San Pedro and San Diego Harbors d id n o t appear to be a significant PCB source, totaling less than 250 kg/yr. Although a ntifo uling paints may have been a very significant source in the past, present inputs are negligible. Also, despite high contam ination levels measured in three m ajor harbors, we found no evidence o f significant PCB transport from these harbors to the adjacent coastal waters. INTRODUCTION Polychlorinated biphenyls (PCB's) have been used for more than 4 decades in a wide variety of industrial products (refs. 1,2), Within the last 10 years, the prob lem of environmental contamination by these synthetic organic compounds has become a subject o f increasing concern (refs, 3,4,5), Here we report the results obtained to date on the routes by which PCB's enter one coastal * David Young is Senior Environmental Specialist in Chomicai Oceanography, Southern California Coastal Water Research Project, El Segundo, California; Deirdre McDermott and Thea dore Heesen are also with Southern California Coastal Water Research Project, El Sogundo, California. This research was supported in part by the National Coastal Pollution Research Program of the Environmental Protection Agency. Grant R801153, Investigations into the harbor dis charges of PCB's were conducted in connection w ith State of California Agreement M-11 w ith the Marine Research Com mittee, Department of Fish and Game. Contribution 54 of the Southern California Coastal Water Research Project. marine ecosystem, the Southern California Bight, and the rates at which inputs occur. MUNICIPAL WASTEWATERS Every day, over 1 billion gallons (approximately 4 x 109 I ) o f municipal wastewaters are discharged from submarine outfalls to the Southern California Bight. Almost 95 percent o f these wastewaters are released by five major treatment plants.t By sampling these five plants, we have been able to obtain a reasonably repre sentative picture of PCB inputs to the Bight via this route. Resultant effluent concentrations and estimated annual mass emission rates for 1972-75 are summarized in table 1; details o f sampling and analytical procedures are presented elsewhere (ref. 6). These data indicate that in recent years there has been a significant decrease in the amount o f PCB's discharged through these outfall systems. The municipal wastewater discharges have resultedin obvious contamination of the bottom sediments around the larger outfall systems. Figure 1 illustrates concentrations of total PCB measured in surface sedi ments collected around the Hyperion outfalls in Santa Monica Bay. The maximum concentration measured near the longer Hyperion outfall (the sludge line) and the JWPCP outfalls were similar, on the order of 10 ppm (mg/dry kg). However, w ithin a few kilometers of the Hyperion sludge discharge, the surface sediment concen trations o f PCB had fallen to about 0.2 ppm. Near the JWPCP outfalls, large vertical gradients were observed, w ith values decreasing by one to two orders of magni tude over a 30-cm depth. We estimate that the load of 1254 PCB in these Palos Verdes Shelf sediments (50 sq km) is on the order of 6 metric tons (ref. 7), Surface sediments around the Orange County outfall did not exhibit large gradients of total PCB in 1975; the median value was 0.1 ppm, w ith values ranging from 0.04 to 0.3 ppm. Similar concentrations were measured 6 months after discharge commenced in 1971, indicating little buildup o f PCB's in these sediments since then. tThese treatment plants are located near the following sta tions indicated in figure 2: Oxnard-Port Hupneme: Hyperion* Santa Monica; JWPCP-Palos Verdes Peninsula; Orange Co.Newport Beach; Point Loma-midway between La Jolla and the U.S.-Mexko border. FC/CAA 199 774401 Table 1. Representative PCB concentrations and mass emission rates^ from major municipal wastewater discharges to the Southern California Bight, 1972-75 ` Discharger Total Susp. Solids (nw/l) 1972 ' JWPCP Hyperion Effluent Sludge Orange Co. Point Loma Oxnard Total 290 90 7,670 150 140 70 1973 JWPCP Hyperion Effluent Sludge Orange Co. Point Loma Oxnard Total 260 80 7,500 150 160 130 1974 JWPCP Hyperion Effluent - Sludge Orange Co. Point Loma Oxnard Total 280 SO 7,300 110 140 170 1975 JWPCP Hyperion Effluent Sludge Orange Co. Point Loma Oxnard Total Concantration (u q /l) 24 HD 280 28 HD HD 3.9 HD HD HD HD HD 1.9 0.11 72 8.0 6.6 0.1 0.6 0.06 34 5.2 1.1 0.03 Mass Emission Rate (Wvrl 11,600 - 1,780 5,800 - >19,180 1,930 - - >1,930 910 50 470 1,890 950 1 4,270 .290 30 220 1,230 160 0.4 1, 930 Concentration fo q /i) ND 0.3 HD HD 0.9 0.2 1.6 0.38 26 1.4 0.48 0.35 0.76 0.24 50 0.89 0.74 0.24 0.52 0.18 28 0.63 0.39 0.16 Mass Emissign Rate fka/vr) 140 - 120 3 >260 790 180 170 290 70 6 1,510 360 110 320 210 110 3 1,110 250 80 180 150 60 2 720 ceOafmf*llcTauuhredel--anfttio--1ol0ln3.os4w0oi;nfgHpy1rpe9el7ri4mionifnloaswlruydvg1ae9lu--75es4m,7(am;ssiOlelrimaoningsesgioCanlol.o--rnasc17ep0s:;erPJdoWaiyPnC)tP--wLoem3re5a--0u; 1seH0d0y;pfeorrion tLSO 200 774402 Figure 1. Concentrations of total PCB (mg/dry kg) measured in the top 2 cm of bottom sediments collected during July 1971 off the Hyperion submarine outfalls in Santa Monica Bay. We have found that benthic organisms trawled from these regions are highly contaminated with PCB's. Crab and flatfish muscle tissue contain on the order o f 1 ppm total PCB, approximately 100 times the levels measured in specimens from uncontaminated control stations. De tails of these studies are presented elsewhere in these proceedings (ref. 8) and a background paper (ref. 9). SURFACE RUNOFF In water year 1971-72, we conducted a detailed sur vey o f chlorinated hydrocarbon inputs to the Southern California Bight via storm runoff. During the major storms of the year, time series o f depth-in tegrated samples were collected in an all-metal sampler near the mouths of four major drainage channels--the Santa Clara River, Ballona Creek, the Los Angeles River, and the Santa Ana River.* Analyses o f the preserved samples "These channels discharge-surface runoff near the following station! indicated in figure 2: Santa Clara R.-Port Huaneme; Ballona Ck.-Santa Monica; Los Angeles R.-midway between Palos Verdes Peninsula and Newport Beach; Santa Ana R.-New port Beach. were conducted by Dr. R. Risebrough and B. de Lappe at Bodega Marine Laboratory (University of California at Berkeley). The following year, we resurveyed one o f these channels on a limited basis. Los Angeles River run o ff was sampled during four storms and analyzed in our laboratory. Subsequently, tw o seasonal collections o f dry-weather flo w were made from channels located throughout the Bight (ref. 6). Table 2 presents final flow-weighted mean PCB con centrations in 1971-72 storm runoff in the four channels samples. In table 3 we list flow-weighted mean PCB con centrations for the four Los Angeles River storm flows sampled in 1972-73, and compare the yearly averages for this channel with those for 1971-72. To aid in the com parison, we also list corresponding results for total DDT and dieldrin. In light of the variation measured in con centrations during any given storm, and the fact that two water years and two laboratories were involved, the agreement between the flow-weighted means is remark ably good. Because of this general agreement, we con cluded that the data from the 1971-72 Bight-wide storm runoff survey could be extrapolated to the following year, on the basis of relative flow rates. 201 774403 GENP 005753 - Table 2. Flow-weighted mean concentrations Ug/I) of PCB in storm runoff via major channels in southern California, 1971-72 Channel Santa C lara B a llo n a Los Angeles Santa Ana Volume3 do6 cu m) 9 .0 2 .6 ' 9. 1.0 1242 PCB 0 -0 .1 3 0 -0 .4 3 1 .2 -1 .9 NO 1254 PCB 0 -0 .1 6 0.47 0 .9 -1 .1 0 .1 1 -0 .2 3 T o ta l PCB 0 -0 .2 9 0 .4 7 -0 .9 0 2 .1 -3 .0 0 .1 1 -0 .2 3 A ccum ulated storm flo w from which samples were obtained f o r c h lo rin a te d hydrocarbon a n a ly s is . Table 3. Flow-weighted mean concentrations (aiq/I) of chlorinated hydrocarbons in Los Angeles River storm runoff, 1971-73 Date Total DDT D ie ld rin 1242 PCB 1254 PCB Total PCB 4 -7 Dec 72 27 Feb to 1 Mar 73 6 -9 Mar 73 11-12 Mar 73 Average blank Averages 1972-73 1971-72 0.66 1 .5 0 .7 8 0 .6 0 <0.004 0.92 0 .9 3 0.12 0.16 0 .1 6 0 .0 8 <0.001 0 -1 .1 0 -3 .2 0 -1 .0 0 -2 .6 <0.002 0.51 1 .0 0 .8 3 0.71 <0.001 0 .5 -1 .6 1 .0 -4 .2 0 .8 -1 .8 0 .7 -3 .3 <0.003 0 .1 4 0 .1 6 0 -1 .9 1 .2 -1 .9 0 .7 7 0.9 -1 .1 0 .8 -2 .7 2 .1 -3 .0 S s> 202 774404 ss& The results indicate that the Los Angeles River carried an order o f magnitude more PCB's via storm run o ff than any other channel in the Bight. Further, the estimated input of 1254 PCB in storm runoff from the major channels in the Los Angeles Basin was 235 kg, constituting 86 to 98 percent of the estimated total storm runoff input o f this contaminant to the Bight. These channels also carried more than 80 percent of the dry-weather input o f 1254 PCB. A comparison o f mass emission rates fo r all areas via the dry-weather and storm runoff fo r water year 1972-73 is presented in table 4. This summary illustrates that, although dry-weather flow constituted almost 20 percent o f the total surface runoff volume during the year, it carried only-about 5 percent of the measurable PCB's. Thus, it appears that storm runoff is the dominant mode fo r surface runoff inputs of PCB to the Bight, and that the Los Angeles Basin is the principal source region. AERIAL FALLOUT We conducted our aerial fallout surveys by exposing glass plates sprayed with mineral oil fo r about 1 week at 13 coastal and 5 island stations between Point Concep tion and the U.S./Mexico border. Two 13-week surveys ware conducted in summer 1973 and spring 1974, and a 3-week survey was conducted during fall 1974. Although fallout rates o f 1242 PCB were not obtainable, apparent ly because of poor retention o f this relatively volatile mixture, the collection efficiency fo r 1254 PCB over 1-week exposure was determined to be about 50 percent (ref. 6). During the first tw o surveys, net flu x values for 1254 PCB generally ranged between 50 and 150 ng/sq m/day; values at certain coastal stations at the edge of the Los Angeles Basin were higher. During the third sur vey, however, values were higher by a factor o f 2, on the average. The fall and winter seasons in southern Cali fornia are characterized by desert (Santa Ana) winds, which occur periodically and transport the polluted air of the Basin out over the `Bight. These data yielded seasonal fallout estimates fo r spring, summer, and fail of about 1,400, 1,430, and 2,700 kg/yr, respectively. Giving equal weight to each seasonal survey results in an estimated annual input of about 1,800 kg/yr 1254 PCB to the study area via dry aerial fallout. (Rainfall is so infrequent in this region that its overall effect is judged to be negligible.) The estimated annual aerial inputs o f 1254 PCB to the individual sectors of the study area are shown in Table 4. Estimated 1972-73 mass emission rates of PC8 via storm and dry-weather runoff to the Bight Type V o lume (10 cu m) 1242 PCB ( k q /y r ) 1254 Total Storm Dry weather Total % dry weather 574 0-520 240-270 240-790 127 0 -3 0 7-8 . 7-40 700 0-550 250-280 250-830 18 2 7 3 -5 ^ JS P 005755 203 774405 figure 2. Highest values (each over 100 kg/yr) occurred in the five sectors o ff Los Angeles and Orange Counties (centering around the Palos Verdes Peninsula). This portion of the coastal plain o f southern California is most affected by air pollution. The three sectors between Zuma Beach and Newport Beach (100 km by 50 km), which' account fo r only about 10 percent o f the 50,000-sq-km study area, received approximately 25 per cent of the total measured PCB input. Thus, we find a pattern similar to that fo r surface runoff: The central basin area appears to be the single most important source of 1254 PCB transported via the atmosphere to the waters o f the Bight. DIRECT INDUSTRIAL DISCHARGE Most of the industrial wastewaters released directly to marine waters o ff southern California occur in San Pedro and San Diego Harbors. These harbors also receive a wide variety of industrial discharges, Thus, we were able to study a number of different types o f industrial effluents under similar conditions by surveying the tw o harbors (ref. 6). Estimates fo r overall industrial inputs of 1254 PCB to San Pedro Harbor were obtained by calcu lating flow-weighted concentrations in three types of effluents--power plant cooling water, fish cannery wastes, and "other industrial" discharges. The flowweighted concentrations were then m ultiplied by the reported total flows o f each o f the three classes o f indus trial wastewaters into San Pedro Harbor to obtain esti mates o f annual mass emission rates. The values are pre sented in table 5. Corresponding data fo r San Diego Har bor are given in table 6. These data provide no indication of significant release of PCB's to the harbors from the industrial e fflu ents studied. However it should be noted that shipyardrelated discharges into Los Angeles Harbor had the high est 1254 PCB concentrations of the industrial discharges surveyed; vessel cooling water, ballast effluent, and oil tanker clean-down water contained 0.6, 1.5, and 2.1 O O' Figure 2. Estimated annual input of 1254 PCB (kg/yr) to sectors of the Southern California Bight via dry aerial fallout during 1973-74. 204 774406 Table 5. Flow-weighted mean concentrations and estimated 1973 mass emission rates of 1254 PCB in industrial discharges to San Pedro Harbor Discharge type Total flow (mgd). C o n c e n tra tio n (yg /1) Mass e m is s io n ra te (kg /yr) Power p la n t cooling w ater Fish cannery wastes Other in d u s tria l v wastes Total 1,020 15 250 0.01 0.09 0 .1 0 14 2 35 50 Table 6. Flow-weighted mean concentrations and estimated 1974 mass emission rates of PCB in industrial discharges to San Diego Harbor Discharge type Total flo w (mgd) 1242 PCB Concen tratio n (ug/1) * Mass e m issio n rate (kg /yr) 1254 PCB Concen tra tio n (ug/l) Mass em is s io n rate (kg /yr) Cooling waters Brine waters Flume w aters Total 757 0 .5 2 .8 - <0.03 <0.01 <0.02 <30 <0.01 <0.07 <30 0.01 0.05 0.01 10 0.03 0.05 10 p g /t 1254 PCB respectively. These relatively high levels are consistent with our observations that highest levels of this contaminant in harbor mussels occurred in regions of greatest vessel activity (ref. 8-11). VESSEL ANTIFOULING PAINT ' In 1973, we surveyed numerous drydock or haulout facilities in southern California harbors and marinas (ref. 12). Our objective was to obtain a representative picture of antifouling paint usage in southern California. In only 7 of the 28 wet paint samples analyzed, 1242 PCB or 1254 PCB were detected; levels were generally on the order of 1 mg/1 or below. Although two samples had total PCB concentrations o f approximately 40 m g/I, median values for 1242 and 1254 PCB were 0.3 mg/I and 0.7 mg/1, respectively. Combination of these medi an values w ith the estimated 300,000 titers of antifoul ing paint applied annually to recreational, commercial, and naval vessels in marinas and harbors of the Bight 205 774407. UtUNJ- U05757 indicates that marine inputs o f PCB from this source now are completely negligible. However, four samples o f old paint scraped from vessel bottoms yielded total PCB concentrations of 270, 3,300, 56,000, and 150,000 ppm, respectively. Further more, the two highest concentrations (approximately 5 and 15 percent on a dry weight basis) correspond w ith an observation by Dr. V. McClure,* who found that a paint chip collected in a zooplankton trawl in 1970 con tained approximately 10 percent PCB, Polychlorinated biphenyls are reported to have been used extensively as a plasticizer in paints before such use was banned in this country in 1971. Our survey revealed that, on the aver age, the density o f antifouling paints used in southern California is about 1.5 dry k g /t. Therefore, if such paints did contain 10 percent PC8 in the past, an appli cation rate of 300,000 I /yr would correspond to a PCB usage o f 45,000 kg/yr. Antifouling paints are designed to slough o ff w ith time, and an estimated 5 to 10 percent of the old paint removed from vessel bottoms is believed to be carried back to the harbor waters (ref. 13). Thus these observations point to the possible importance of antifouling paints in the past as a source of PCB's to the coastal marine environment. National Marins Fisheries Service, La Jolla, personal com munication. HARBOR FLUSHING In view o f the relatively high levels of PCB contam ination found in southern California harbors (refs. 8-11), we attempted to determine if any significant levels of PCB's could be detected in the waters moving from such harbors into the open ocean during periods of peak tidal flow (ref. 6). Figure 3 illustrates the results obtained from the San Diego Harbor survey; net concentrations of 1254 PCB for the replicate samples of each collection period are plotted against tidal flow . Although there is some evidence o f increased PCB concentrations near the time t>f tide reversal, when the greatest influence of "back harbor" water would occur near the harbor mouth, the measured concentrations were extremely low; flow-weighted mean concentrations fo r San Pedrot and San Diego Harbors were 1.5 and 1.8 ng/l, respec tively. By combining the measured concentrations w ith tidal flo w values obtained from the current meter meas urements and channel geometries, we obtained estimates fo r maximum net transport of 1254 PCB from the har bors to the adjacent coastal ecosystem. Because of the extremely low concentrations observed, none of the tLocated ju it eest of Palos Verdes Peninsula (figure 2). 6000 2000 wUui 0 3 O -3000 0700 1100 TIME 1500 1900 Figure 3. Concentrations of 1254 PCB in surface seawater collected over a semidiurnal tidal cycle at the mouth of San Diego Harbor, November 12, 1974. Positive flow represents outflowing water; negative, inflowing. Vertical bars indicate individual replicate values. 206 774408 values exceeded 50 kg/yr when extrapolated to an annual basis. Thus, these pilot seawater surveys have provided no indication that any of the three harbors is now a significant source of polychlorinated biphenyls to the coastal marine ecosystem. OCEAN CURRENT ADVECTION As a part of this inputs study, we attempted to estimate the quantities o f measurable chlorinated hydro* carbons in surface seawater annually flowing through the Southern California Bight. In October 1973, we sampled surface seawater at seven stations along a north/south transect (12035'W) at the northwestern edge of the Bight (ref. 6). The transect began o ff Point Conception and ended approximately 300 km west o f Oceanside. Circulation patterns (ref. 14) indicated that the transect chosen should have intersected California Current water flowing into the Bight. Replicate 40-liter samples'were collected in a stain* less steel bucket, which was lowered from the bow o f a research vessel that was slowly underway. Immediately upon collection, the replicate samples were passed through polyurethane foam columns and taken to Bodega Marine Laboratory fo r analysis. The results indi cated average concentrations fo r total DDT and 1254 PCB o f 0.7 and 0.4 ng/l, respectively. These data may be used to obtain rough estimates of the quantity of these synthetic organics carried into the Bight via ocean current advection. Taking the length of the Bight as 500 km and the width influenced by the coast as 100 km, the effective study area is 5 x 1010 sq m. Assuming the mixed surface layer to be 50 m, the volume of the mixed layer is 2.5 x 1012 cu m. It has been shown that the mean residence time o f water in this mixed layer is on the order o f 3 months (ref. 14). Thus, the estimated advectiye flow rate of California Current water through the Southern California Bight is 1013 cu m /yr, equal to 1014 l/y r . Corresponding estimates fo r advective flu x rates of measurable DDT and 1254 PCB compounds are 7,000 and 4,000 kg/yr, respectively. CONCLUSIONS Table 7 summarizes input rates o f polychlorinated Table 7. Inputs of PCB's to the Southern California Bight Route Year 1242 PCB's ( k o /v r ) 1254 Total M u n ic ip al w as te w a ter Surface ru n o ff A erial fa llo u t In d u s tria l discharges A ntifouling p a in t Harbor . flu s h in g 0 Ocean currents 1974 1972-73 1973-74 1973-74 1973 1974 1973 4,300 . < 550 - < 180a <1 - 1,100 250 1,800 60 <1 < ISO 4,000 5,400 < 800 < 250 <1 - aAssuming th a t the maximum 1242/1254 PCB r a t i o ( 3 : 1 ) found in San Diego Harbor a ls o a p p lie s to San Pedro Harbor in d u s tria l discharges. ^San Pedro, Newport, and San Diego H arbors. 207 774409 GENP 005759  0 -* S uy s biphenyls to the marine waters o ff southern California. These data indicate that, in recent years, municipal wastewaters have been the dominant source of PCB's to this coastal marine ecosystem. In 1974, more than 5 metric tons of this synthetic organic material were dis charged via the five major treatment plants in the Bight; the fact that the 1254 PCS values fo r municipal wastewaters and ocean current transport were of the same order o f magnitude testify to the importance of the wastewater input route. Aerial fallout is the other important route by which PCB's enter the waters o f the Bight. The 1973-74 esti mate of 1,800 kg fo r 1254 PCB exceeded the 1974 input from municipal wastewaters (1,100 kg), and the fact that PCB levels in municipal wastewater are continuing to decrease suggests that aerial transport of these con taminants may become the dominant input mode in the future. Finally, these studies have demonstrated that, in southern California, surface runoff is only a secondary PCB source, while contributions from industrial dis charges and antifouling paint use in the major harbors appear to be insignificant. Although intertidal mussels in these harbors had an order o f magnitude more PCB in their soft tissues than did nearby coastal specimens, we found no evidence that harbor flushing constitutes a sig-.. nificant source of polychlorinated biphenyls to the coastal marine ecosystem. REFERENCES 1. S. Jensen, "PCV as a Contaminant: History," in PCB Conference, pp. 6*17, National Swedish Envi ronment Protection 8oard, Solna, Sweden, 1970. 2. P. Jay, "PC3: Uses in Industry," in PCB Confer ence pp.* 18-25, National Swedish Environment Pro tection Board, Solna, Sweden, 1970. 1 3. R. W. Risebrough, P. Rieche, D. B. Peakall, S. G. Herman, and M. N. Kirven, "Polychlorinated Bi phenyls in the Global Ecosystem," Nature, Vol. 220 (1968), pp. 1098-1102. 4. VI. Kuratsune, T. Yoshimura, J. Matsuzaka, and A. Yamaguchi, "Epidemiologic Study on Yusho, a Poisoning Caused by Ingestion of Rice Oil Contami nated with a Commercial Brand o f Polychlorinated Biphenyls," Environ. Health Perspectives, Vol. 1 (1972), pp. 129-36. 5. R. L. de Long, W. G. Gilmartin, and J. G. Simpson, "Premature Births in California Sea Lions: Associa tion with High Organochlorine Pollutant Residue Levels," Science, Vol. 181 (1973), pp. 1168-70. 6. D. R. Young, D. J. McDermott, and T. C. Heesen, "Polychlorinated Biphenyl Inputs to the Southern California Bight," background paper prepared for the National Conference on Polychlorinated Bi phenyls, 19-21 November 1975, Chicago, Illinois, Rept. TM 224, So. Calif. Coastal Water Res. Proj., El Segundo, Calif., 1975. 7. D. R. Young, D. J. McDermott, and T. C. Heesen, "Polychlorinated Biphenyls O ff Southern Califor nia," to be published in the proceedings Volume o f the International Conference on Environmental Sensing and Assessment, 14-19 September 1975, Las Vegas, Nevada. 8. D. J. McDermott, D. R. Young, and T. C. Heesen, "PCB Contamination o f Southern California Marine Organisms," in the proceedings o f the National Con ference on Polychlorinated Biphenyls, 1975. 9. D. J. McDermott, . R. Young, and T. C, Heesen, "Polychlorinated Biphenyls in Marine Organisms O ff Southern California," Rept. TM 223, So. Calif. Coastal Water Res. Proj.. El Segundo, Calif., 1975. 10. D. R. Young, and T. C. Heesen, "Inputs and Distri butions o f Chlorinated Hydrocarbons in Three Southern California Harbors," Rept. TM 214, So. Calif. Coastal Water Res. Proj., El Segundo, Calif., 1974. 11. D. R. Young, D. J. McDermott, T. C. Heesen, and T. K. Jan, "P ollutant Inputs and Distributions O ff Southern California," to be published in the pro ceedings volume o f the 169th National Meeting of the American Chemical Society, Symposium on Marine Chemistry in the Coastal Environment, 8-10 April 1975, Philadelphia, Penn. 12. p . R. Young, T. C. Heesen, D. J. McDermott, and P. E. Smokier, "Marine Inputs o f Polychlorinated Bi phenyls and Copper From Vessel Antifouling Paints." Rept. TM 212, So. Calif. Coastal Water Res. Proj., El Segundo, Calif., 1974. 13. J. N. Barry, "Wastes Associated w ith Shipbuilding and Repair Facilities in San Diego Bay," staff report, California Regional Water Quality Control Board, San Diego Region, 1972. 14. J. H. Jones, "General Circulation and Water Charac teristics in the Southern California Bight," Rept. TR 101, So. Calif. Coastal Water Res. Proj., El Segundo, Calif., 1971. 208 PCB CO NTAM INATIO N OF SOUTHERN CALIFORNIA MARINE ORGANISMS Deirdre J. McDermott, David R. Young, and Theadore C. Heesen* A b s tra c t in the past, the submarine discharge o f m unicipal wastewater has been the dom inant source o f PCB to the marine environm ent o ff southern California. However, the level o f in p u t from this source has steadily decreased during the period 1972 O 19J0Q0 kg /yr) to 1975 (2JB00 kg /yr). Despite the significant decrease in this inp ut, no significant decrease was observed over the 3-yearperiod 1971-72 to 1974-75 in the level o f PCB in musc/e tissue o f Dover sole, Microstomus pacificus, collected from die m ajor m unicipal wastewater discharge sites In contrast, sim ilar surveys o f the in te rtid a l mussel, Mytilus californianus, indicated th at the PCB levels in this marine orga nism had significantly decreased oyer the same time period. Bight-wide surveys o f M. califomianus and the yel low rock crab. Cancer anthonyi, indicate that PCB con tam ination o f these marine animals is lo w b u t wide spread. Levels o f PCB in the harbor mussel, M. edulis, were highest in specimens collected from areas o f intense vessel activity. A convenient and effective system fo r continuously m onitoring PCB levels in the marine envi ronm ent is described. INTRODUCTION Over the last 4 years, the Southern California Coastal Water Research Project has been studying the inputs of PCB's to the Southern California Bight. A number of sources of PCB's (most closely resembling Aroclors 1242 and 1254) to the marine environment o ff southern California have been identified and their inputs quantified. The submarine discharge of municipal wastewater has been the dominant source of PCB to the marine environment o ff southern California. However, Deirdre McDermott is Assistant Environmental Specialist in Chemical Oceanography, Southern California Coastal Water Research Project, El Segundo, California. David Young and Theadone Heesen are also w ith Southern California Coastal Water Research Project, El Segundo, California. This research was supported In part by the National Coastal Pollution Research Program of the Environmental Protection Agency, Grants R801153 and R801152. Investigations into the harbor distributions of PCB's were conducted in connection with State of California Agreement M-11, w ith the Marine Research Committee, Department of Fish and Game. Contribution 53 of the Southern California Coastal Water Research Project. the level o f input from this source has steadily decreased during the period 1972 O 19,000 kg/yr) to 1975 (2,600 kg/yr). Dry aerial fallout also appears to be an important source and if wastewater inputs continue to decrease, fallout may become the dominant input mode of the future. PCB inputs from surface runoff are o f secondary importance, and those from direct industrial discharges and vessel antifouling paints are relatively insignificant. Detailed results o f our inputs studies are presented else* where in these proceedings (ref. 1) and in a background paper (ref. 2). Other workers have studied PCB contamination o ff California and elsewhere in the United States in the past decade. During the summer of 1975, several reports of high PCB levels in fish collected from Lake Michigan and the Hudson River caused public concern about PC8 residues in commercial fish and sport fish (refs. 3-6). Munson's w ork in California (ref. 7) indicated that, in 1972, concentrations o f these chlorinated hydrocarbons were low but widespread in the southern California marine community. The work of Allen and his colleagues (ref. 8) w ith rhesus monkeys attests to the toxic effects of short term, low-level (25 ppm) exposures to PCB's on non human primates. Later results of their experiments on the monkeys showed that exposure to PCB's at the 2.5and 5-ppm levels was related to spontaneous abortions and the birth o f undersized infants (ref. 9). Also, de Long et al. (ref. 10) found PCB's to be associated with premature births in the California sea lion. In conjunction with our studies of PCB sources, we undertook research into the fates and effects o f PCB's in marine animals. Our research involved several organisms common locally (the Dover sole, Microstomus pacificus. a b en thic flatfish; the yellow rock crab. Cancer anthonyi; and an open coast and a harbor mussel, M ytilus califom ianus and M. edulis, respectively), and three distinct programs: * Regional surveys of PCB levels in the flatfish, the crab, and the mussels. Specimens from stations through out the Southern California Bight (fig. 1) were analyzed ' to determine the levels of PCB's present in their tissues and plot the distribution of the substances in the Sight. Changes over time wer noted, as were relationships between the concentration levels and man's centers of activity along the coast (wastewater discharge, major harbors). We also sought to identify the dominant PCB ( f Q / CA/1 _i .Krnr 209 774410 12I*W I20*W 119* W I IS*W 117*W Figure 1. The Southern California Bight. Outfall systems are (1) Oxnard City, (2) Hyperion, Los Angeles City, (3) Whites Point, Los Angeles County, (4) Orange County, and (5) San Diego City. Major harbors are (6) San Pedro, (7) Newport, and (8) San Diego. GENP 005762 present by determining if the PCB's found most closely resembled Aroclor 1242 or Aroclor 1254.* Finally, we investigated the PCB levels in specimens o f the flatfish afflicted w ith a fin erosion disease prevalent around several southern California wastewater outfalls. * A study of the relative amounts o f PCB's in the various tissues of the flatfish and the crab. The design of a convenient and effective system fo r continuously monitoring PCB levels in the marine environment. This paper presents a brief summary of the results o f these studies. SAMPLING PROCEDURES AND CHEMICAL ANALYSIS McDermott et al. (ref. 11) report in detail the procedures used for the collection and preparation of Throughout the text, 1242 PCB and 1254 PCB have been used to distinguish between substances most closely resembling Aroclor 1242 and Aroclor 1254, resoectively. biological samples as well as the subsequent PCB anal yses by electron-capture gas chromatography for all research programs discussed in this paper. RESULTS AND DISCUSSION Regional Surveys o f PCB's in Marine Anim ats Two Bight-wide surveys of PCB contamination in the benthic flatfish', Dover sole, were conducted during 1971*72 and 1974-75 (ref. 11). The results of these regional surveys (table 1) revealed that PCB levels in specimens collected near the three largest municipal wastewater discharge sites o ff Palos Verdes, Santa Monica, and Orange County were significantly higher than levels found in specimens from regions w ith little or no wastewater discharge. Despite the high levels of PCB in the fish from the outfall areas, less*than 2 percent of all Dover sole taken in the two surveys had muscle tissue PCB concentrations that exceeded the Federal Food and Drug Administration's tolerance of 5 mg/wet kg in the edible portion of fish intended fo r interstate commerce. Over the 3-year study period, municipal wastewater 210 774411 Table 1. Total PCB concentrations (mg/wet kg) in muscle tissue of Dover sole M ic r o s to m u s p a c ific u s .3 Region 1971-- 7 2 (nb = no) Region median S tation range 1974-75 (nc = 165) Region mdian S tation range P o in t Hueneme Santa Monica . Palos Verdes Orange County Dana P o in t San Diego Santa C atalin a Is la n d 0.1 1 .5 1 .9 0 .7 0 .0 6 0 .0 4 0.1 0 .4 -2 .8 1 .1 -6 .3 0 .1 -1 .2 0 .0 3 -0 .0 9 0.0 3 -0 .04 0 .0 6 2 .0 1 .3 0 .6 0 .7 0 .2 0 .0 5 0 .0 5 -0 .0 7 1.0 -2 .3 0 .0 6 -2 .5 0.3 -2 .8 0.0 3 -0 .14 0 .0 9 -0 .6 0 .0 3 -0 .0 7 aA f t e r r e f . l l . There is no s t a t i s t i c a l l y s ig n if ic a n t d iffe r e n c e between th e 1971-72 and the 1974-75 le v e ls . ^Composite samples o f Dover s o le muscle tis s u e . i n d i v i d u a l samples o f Dover s o le muscle tis s u e . emissions o f total PCB decreased (ref. 1). Yet we observed no statistically significant decrease in the levels of total PCB In the Dover sole. This finding Indicates that other factors or inputs o f these chlorinated hydro* carbons are involved in maintaining the total PCB levels in this fish. During 1971 and 1974, Bight-wide surveys o f the open coast mussel were also conducted (refs. 11,12). The results are shown in table 2. A regional survey o f the yellow rock crab was also conducted during 1971 (ref. 11). Table 3 presents the median concentration of total PCB in the muscle tissue o f the crabs collected in each region. These surveys indicate that the PCB contamina tion levels in these animals are low but widespread. Levels of total PCB in specimens near the major outfall systems were generally 10 to 100 times higher than levels in specimens collected from coastal or island control sites; however, the Federal tolerance level for PCB compounds was not exceeded in the edible portion of any specimens of these tw o species. The two surveys of Af. californ/anus indicate that the level o f PCB contamination in these mussels had decreased signifi cantly over the 3-yeair interval, 1971-74, w ith a median percent decrease o f 54 percent The dominant PCB observed in the three species surveyed was 1254 PCB; the other PCB identified was 1242 PCB. The percent composition o f total PCB in the muscle tissue samples from the crab and mussel speci mens was similar to that in the Dover sole muscle samples. The median 1974-75 composition o f total PCB in muscle tissue o f Dover sole taken near the five major discharge sites was'67 percent 1254 PCB and 33 percent 1242 PCB. This contrasted w ith the median 1974 co m position o f municipal wastewater emission of PCB: 29 percent 1254 PCB and 71 percent 1242 PCB. These data, along w ith a comparison of total PCB levels in Dover sole muscle tissue, surface sediments, and municipal wastewater emissions (table 4), indicate that the PCB levels in Dover sole are n ot dependent only upon the level o f PCB discharged in wastewaters and that other factors, such as the solubility, vo la tility, the sediment load, or the relative biological uptake and GENP 005763 211 774412 Table 2. Concentrations fmg/wet kg) of the PCB most closely resembling Aroclor 1254 in the whole soft tissues of M y tilu s c a fifo r h ta n u s .a S t a t i on 1971 1974 Coastal G av io ta Santa Barbara P o rt Hueneme P o in t Dume Palos Verdes Peninsula Point Vicente Royal Palm San Clemente P o in t Loma Is la n d Anacapa Santa Barbara Santa C atalin a San N ic o la s San Clemente 0 .0 5 0 .0 3 0 .1 2 0 .0 8 0 .3 8 0 .5 2 0 .0 5 , 0.12 0.01 0 .0 7 0 .0 2 * 0.02 0 .0 2 0.01 0 .0 2 0 .3 7 0 .0 4 0 .1 0 0 .1 4 0 .0 2 0 .0 6 0.01 0 .0 2 0.01 0.01 0 .0 2 aA f t e r r e f s . 1 1, 12. GENP 005764 Table 3. Regional survey of total PCB concentrations (mg/wet kg) in the muscle tissue of individual yellow rock crabs, C a n c e r a n th o n y i, 1971 *72.a Region No. o f samples Region median S tation range Santa Monica Palos Verdes O utside San Pedro Harbor Orange County Ensenada^ 12 16 5 9 3 0 .6 8 0 .8 2 0 .4 9 0 .3 2 0 .0 1 4 0.13 -2 .2 0.30 -1 .8 0.32 -0 .8 3 0.23 -0 .5 4 0 .0 1 2 -0 .0 1 8 aA ft e r r e f . 11. ^Three chelae {Cancer species) purchased in fis h m arket. 212 774413 Table 4. Comparison of total PCB levels in muscle tissue of Dover sole, M ic ro s to m a s p a c ific a s , and bottom surface sediments and PCB mass emission rates in municipal wastewater.3 Region Dover sole (mg/wet kg) Pal os Verdes Santa Monica Orange County San Diego P o in t Hueneme 1.9 1 .5 0 .7 0 .1 1971-72 S e d i ments (m g /d ry kg) 3 .6 0.53 0 .0 2 0.01 0.004 Muni c ip a l waste (kg /yr) 11,600 1,920 5,800 118 3 1974-75 Dover sole (m g /w et kg) Muni c ip a l waste (kg /yr) 1 .3 1,270 2 .0 956 0 .6 2,100 0 .2 1,050 0.1 5 aA ft e r r e f s . 1 ,2 ,1 1 . retention rate of a given PCB are involved in the result* ing levels o f PCB's in this marine animal. D istribution o f PCB's in Tissues o f a Benthic Flatfish and Crab in February 1975, special collections o f Dover sole were made o ff Palos Verdes and Orange County fo r the analysis of PCB's in the muscle, liver, gonad, heart, and kidney tissues (ref. 11). The results are presented in table 5. The level of PCB in the liver tissue was 10 to 20 times higher than the levels observed in the other tissues analyzed. To determine the liver and muscle tissue burdens o f the two sets of fish, the median concentra* tions of PCB in the specific tissue was applied to the average wet weight o f that tissue: Lbiuvredren bMuursdcelen Ratio, liver to muscle Palos Verdes Orange County 0.04 mg 0.02 mg 0.02 mg 0.03 mg 2 0.7 The liver-to-muscle tissue burden ratio for PCB in Palos Verdes Dover sole was 2; fo r Orange County specimens, the ratio was 0.7. There are two possible explanations fo r the high liver-to-muscle tissue burden ratio in the Palos Verdes fish. A review o f the literature indicates that (1) in metabolic disturbances, the lipid (fat) content in liver tissue may significantly increase, and (2) chlorinated hydrocarbons, which are hepatic poisons, induce fatty livers. As chlorinated hydrocarbons are associated w ith lipids, if either one or both o f these situations had occurred in the Palos Verdes Dover sole, it would have resulted in an increase in the total PCB levels in the liver and a higher liver-to*muscle tissue burden ratio. The lipid content of these tissues is being studied, and further work on the physiological and ecological implications of these tissue burdens is underway. Analysis o f the PCB concentrations in the reproduc tive organs o f C. anthonyi indicate that the gonadal tissues generally contain PCB levels five to ten times higher than the muscle tissue levels (ref. 11). Also, in females, the gonad had an absolute tissue burden o f PCB that was 25 percent higher than the muscle tissue burden (see table 6). As the reproductive organs o f this crustacean are exposed to considerably higher levels o f this synthetic organic than is the muscle, spawning may represent a significant' distribution mechanism o f these contami nants in the marine environment, and a significant factor in the elimination of a large percentage o f the body burden of these materials from the crab. The long-term effects of PCB concentrations on reproduction or other biological processes in this crustacean are unknown. Fin Erosion and PCB Levels in a Benthic Flatfish The Dover sole collected o ff Palos Verdes are fre quently affected by fin erosion; the disease has recently also become prevalent o ff Orange County. Data on specimens w ith eroded fins and those w ith healthy fins taken in 1974 in single trawls were paired. U tilizing the 213 774414 GENP 005765 Table 5. Total PCB concentrations {mg/wet kg) in composite samples of tissues of Dover sole, M ic ro s to m a s p a d fic u s , 1975a Tissue Muscle L iv e r Gonads H e a rt K1dney Palos Verdes Median Range 0 .7 15 1 .4 1 .8 o;8 0.1 -1 .1 11-18 0 .8 -5 .2 1 .5 -3 .2 0 .6 -1 .1 aA f t e r r e f . 1 1. Orange County - Median Range 1.1 0 .6 -1 .4 8.3 4.8-13 0.8 0 .7 -4 .6 0.5 0 .4 -0 .8 0.6 0 .6 -0 .8 Table 6. Analysis of PCB concentrations in the reproductive organs of C a n c e r a n th o n y i P ercent o f combined gonad/muscle tis s u e w eight Gonad Muscle T is su e burden (mg) Gonad Muscle Male 7 93 0.009 0.025 ' Female 27 73 0.031 0 .0 2 5 Wilcoxon signed-rank test, the levels of PCB in the muscle tissue o f the unaffected fish and the diseased fish were found to be different at the 90 percent confidence level (p 0,10). Although this level is not considered to be statistically significant, it shows a strong tendency fo r the total PCB levels to be higher in the diseased fish. The median values fo r the diseased and unaffected groups were 2 and 1 mg/wet kg, respectively (refs. 11,13). If this association^ was dependent upon the input level o f PCB, one would expect fin erosion to be dominant o ff Orange County where the input level o f _3 PCB is the greatest. One. would also expect to find it o ff 0 s Santa Monica and San Diego where the level o f input is similar to Palos Verdes. However, this is not the case. There are several possible reasons fo r the association between high PCB levels and fin erosion. The disease is predominantly found in the Palos Verdes region: Palos Verdes sediments have the highest levels o f PC8 in the Bight, thus contaminated sediments could be the dominant factor. Also, PCB--in combination w ith other constituents present in this region (DDT, hydrogen sulfide, trace metals)--could be involved in the develop ment o f the disease. It is also possible th at PCB uptake is enhanced in diseased fish; hence the higher levels could be the result of the disease rather than a cause. These relationships are being studied further. 214 774415 Surveys o f PCB's in H arbor Mussel Composite samples o f the whole soft tissues of M ytilus edutis collected from three major southern California harbors (San Pedro, Newport, and San Diego) were analyzed fo r PCB's (ref. 11). The survey showed that the harbor mussels had contamination levels up to 20 times those found in specimens o f the same species collected from nearby coastal sites. Highest levels were found in mussels taken near regions o f heavy vessel activity. Figure 2 shows the data fo r San Diego Bay, where the range o f total PCS values near the commercial docks and navy moorings {0.80 to 1.3 mg/wet kg) is three to four times higher than die values observed at other inner harbor sites, and ten times greater than levels in nearby coastal mussels. The levels of 1254 PCB in seawater at the mouths of the harbors, were generally on the order o f 1 part per trillio n (ref. 1,2). The values of 1254 PCB in the whole soft tissues of the harbor mussels were 100,000 times these seawater levels. Although most antifouling paints presently applied to vessel bottoms in southern California contain PCB concentrations o f less than 1 mg/dry kg, a few samples o f pre-1970 paint chips averaged about 10 percent PCB or 100,000 mg/dry kg (ref. 14). Thus it is possible that thousands o f kilograms of this synthetic material could have been released annually to the harbor and coastal marine ecosystems, before' the widespread use o f nonrecoverable PCB's was discontinued in the United States in the early 197Q's. Bouy Mussels: A n Offshore B iom onitoring System In June 1974, 4- to 6-cm long specimens of M. califom ianus were collected from Point Sal, an area known to be relatively free of PCB contamination. W ithin 1 day of collection, these mussels were trans ported to a taut-line bouy anchored o ff Whites Point, where wastewaters from Los Angeles County's Joint Water Pollution Control Plant discharged (ref. 11). The mussels were placed in net bags fastened at five levels between the sea surface (0.5 m) and the bottom sedi ments (35 m), which are highly contaminated w ith trace metals and chlorinated hydrocarbons at this site (refs. 15-17). The mussels transported to the bouy system o ff Palos Verdes appeared to survive well under the test conditions: Less than 10 percent m ortality was ob served at any of the five levels (0.5 to 35 m) at which the mussels were suspended during the 3-month study. On the average, mussels living at Royal Palm Beach, inshore o f the buoy, contained 17 times as much PCB as the control specimens at the time o f their transfer to the buoy northwest of the outfalls. Thus, exposure of these mussels to PCB was greatly increased upon their transfer to the discharge region. ` The results indicated that there was a direct rela tionship between uptake o f PCB and proxim ity o f the bioindicator to the contaminated bottom sediments and to the wastewater plume, which is trapped beneath the thermocline. The bottom specimens became approxi mately 10 times as contaminated as did the surface specimens. A t the end of the 13-week period, the 1254 PCB concentrations in the whole soft tissues o f specimens collected from Level 5 (closest to the bottom sediments) were approaching 0.4 mg/wet kg; those specimens from Level 1 (at the surface) were at 0.04 mg/wet kg. To date, the highest 1254 PCB concentration measured in the water above the outfalls is 4 ng/1 (ref. 12). This suggests a concentration factor on the order of 100,000 for 1254 PC8 in the whole soft tissues of M. califom ianus, a number in good agreement w ith the estimate for M. eduiis in the harbors. SUMMARY 1. No statistically significant decrease in the Bight wide levels of PCB in the muscle tissue of Dover sole was observed over the 3-year period 1971-72 to 1974-75. 2. The level of PCB contamination o f the open coast m.ussel decreased significantly over the 3-year interval, 1971-74, w ith a median percent decrease of 54 percent. 3. Regional surveys of the yellow rock crab and open coast mussel indicate that PCB contamination levels in these animals are low but widespread, 4. For all three species surveyed, PCB levels in specimens collected near major outfall systems were generally 10 to 100 times higher than levels in specimens collected from coastal or island control sites. 5. The dominant PCB observed in the three species surveyed most closely resembled Aroclor 1254; the other PCB identified most closely resembled Aroclor 1242. In contrast, the dominant PCB discharged via municipal wastewaters most closely resembled Aroclor 1242. 6. The liver tissue o f Dover sole generally had concentrations of PCB's 10 to 20 times greater than the levels found in the muscle, gonad, heart, and kidney tissues. 7. The liver-to-muscle tissue burden ratio for total PCB in Palos Verdes Dover sole was three times higher than the ratio fo r Orange County specimens. 8. The reproductive organs of the yellow rock crab generally contain PC8 levels five to ten times higher than the muscle tissue levels. GENP005767 215 774416 S CP Figure 2. Total PCB concentrations (mg/wet kg) in whole soft tissues of M y tU u s e d u s in San Diego Bay, January 1974. (After ref. 11). 216 774417 9. PCB's were found to be associated w ith the fin erosion disease prevalent in Dover sole collected around major municipal wastewater discharge sites at the 90 percent confidence level (p = 0.10). 10. Harbor mussels had PCB contamination levels up to 20 times those found in specimens of the same species collected from nearby coastal sites. Highest levels were found in mussels taken near regions o f heavy vessel activity. 11. Although the mussel used in the buoy system was an intertidal organism, less than 10 percent mor ta lity was observed at depths to 35 m. This mussel's hardiness, its ubiquitous distribution along many coast lines around the world, its very high a bility fo r concen trating chlorinated hydrocarbons above seawater values, and its apparent ability to rapidly respond to changes in environmental levels of such contaminants make it a very useful bioindicator, both in natural intertidal communities and on offshore substrates, The widespread use o f nonrecoverable PCB's was curtailed in the United States during the early 1970's. However, the inputs o f these persistent substances are still diffuse and d iffic u lt to control. There is a need for more knowledge o f the effects o f these materials in the marine environment; in particular, uptake rates, persis tence, and biological effects should be studied. REFERENCES 1. D. R. Young, D. J. McDermott, and T . C. Heesen, "Marine Inputs of Polychlorinated Biphenyls O ff Southern California," in the proceedings o f the National Conference on Polychlorinated Biphenyls, 1975. 2. D. R. Young, D. J. McDermott and T. C. Heesen, "Polychlorinated Biphenyl Inputs to the Southern California Bight," background paper prepared for th e N a tio n a l Conference on Polychlorinated Biphenyls, 19-21 November 1975, Chicago, Illinois, Rept. TM 224, So. Calif. Coastal Water Res. Proj., E! Segundo, California, 1975. 3. R. H. Boyle, "Poisoned Fish, Troubled Waters," Sports Illustrated, 1 September 1975, pp. 14-17. 4. R. Server, "State Says Some Striped Bass and Salmon Pose a Toxic Peril," New York Times, 8 August 1975. 5. R. Server, "Warning Ignored on Striped Bass," New York Times, 9 August 1975. 6. R. Server, "Reports o f Chemical in Fish In itially W ithheld," New York Times, 17 August 1975. 7. T. O. Munson, "Chlorinated Hydrocarbon Residues in Marine Animals o f Southern California," Bull, Environ. Contam. T oxicol., Vol. 7 (1972), pp. 223-228. 8. J. R. Allen, L. A. Carstens, and D. A. Barsotti, "Residual Effects o f Short-Term, Low-level Expo sures of Nonhuman Primates to Polychlorinated Biphenyls," Toxicol, and A pplied Pharm,, Vol. 30 (1974), pp. 440451. 9. D. A. Barsotti and J. R. Allen, "Effects of Poly chlorinated Biphenyls on Reproduction in the Primate," paper presented at the meeting o f the American Societies fo r Experimental Biology, 18 A p ril 1975, A tla ntic C ity, N J . 10. R. L. de Long, W. G. Gilmartin, and J. G. Simpson, "Premature Births in California Sea Lions: Associa tion With H igh' Organochlorine Pollutant Residue Levels," Science, Vol. 181 (1973), pp. 1168-70. 11. D. J. McDermott, D. R. Young, and T, C. Heesen, "Polychlorinated Biphenyls in Marine Organisms O ff S o u th e rn C a lifo rn ia ," background paper prepared fo r the National Conference on Polychlo rinated Biphenyls, 19-21 November 1975, Chicago, Illinois, Rept. TM 223, So. Calif. Coastal Water Res. Proj., El Segundo, California, 1975. 12. 8. de Lappe and R. Risebrough, personal communi cation. 13. D. J. McDermott and M. J. Sherwood, "D D T and PCB in diseased Dover sole," in 1975 Annual Report, So. Calif. Coastal Water Res. Proj., pp. 33-5, 1975. 14. D; R. Young, T. C. Heesen, D. J. McDermott, and P. E. Smokier, "Marine Inputs of Polychlorinated Biphenyls and Copper from Vessel Antifouling Paints," Rept. TM 212, So. Calif. Coastal Water Res. Proj., El Segundo, California, 1974. 15. J. N. Galloway, "Man's Alteration of the Natural Geochemical Cycle o f Selected Trace-Elements," Ph. D. dissertation, University o f California, San Diego, 1972. 16. Southern California Coastal Water Research Project, 'T h e Ecology.of the Southern California Bight: Im plications fo r Water Quality Management," Rept. TR 104, So. Calif. Coastal Water Res. Proj., El Segundo, California, 1973. 17. D. J. McDermott, T. C. Heesen, and D. R. Young, "D D T in bottom sediments around five southern California outfall systems," Rept. TM 217, So. Calif. Coastal Water Res. Proj., El Segundo, Califor nia, 1974. 005769 217 774418 TRANSPORT OF CHLORINATED HYDROCARBONS IN THE UPPER CHESAPEAKE BAY T. O. Munson, Ph.D., H. D. Palmer, Ph.D., and J, M. Forns* A b s tra c t Under contract to the M aryland State Departm ent o f N atural Resources, the s ta ff o f die Westinghouse Ocean Research laboratory (together w ith subcon tractors a t Johns Hopkins U niversity and the U niversity o f M aryland} recently com pleted die Upper Bay Survey--a program having as the central task the study o f the routes, rates, sources, sinks, and reservoirs o f ch lo rin ated hydrocarbons (CHC's) in the upper Chesapeake Bay. Data from die fie ld p ordon o f this program w ill be presented; in particular, the levels o f PCB's, chlordane, and DDTR found in bottom sediments, suspended particulates, zooplankton, and shellfish w ill be summa rized* The discussion w ill include the role o f sediment deposits as traps fo r CHC's; suspended particulates as transport vehicles fo r CHC's; movement o f CHC's from the suspended particulate reservoir in to the biological system, p a rticu la rly shellfish and zooplankton; and die sources o f CHC's in the upper Chesapeake Bay. INTRODUCTION The concept o f the Upper Bay Survey grew directly from the Chester River Study (ref. 1), a program of more limited scope, which was completed in the fall o f 1972. An objective o f that program was to provide the Maryland Department of Natural Resources w ith envi ronmental and resource management information essen tial to the local shellfish industry. These studies were directed toward determining the source and fate of chlorinated hydrocarbons and selected trace metals in the waters and sediments o f this estuary. The approach was multidisciplinary. The project as a whole was con sidered experimental, since it was to encompass many aspects o f an estuarine ecosystem w ith the declared pur pose o f supporting the practical needs o f natural re source managers. Thus, the Chester River Study was a program o f focused, applied research rather than a more basic program to. extend knowledge in estuarine sciences. As a result of this program, it became clear that the upper Chesapeake Bay was the most likely source of sediment-borne materials considered potentially harmful to the living resources of the Chester River. An exten sion of the Chester River project encompassing the bay between the Severn and Susquehanna Rivers became the "Westinghouse Ocean Research Laboratory, Annapolis, Maryland. next logical step in assessing the impacts of man-made substances in the bay ecosystem. The Upper Bay Survey (funded by the Mayland Department o f Natural Re sources) was begun in December 1973-once again m u lti disciplinary, but also m ultiinstitutional w ith the partici pation o f scientists from the University of Maryland and The Johns Hopkins University. A 12-month research progrartf was implemented w ith the following five defini tive objectives: 1. To determine concentrations, distributions, and sources fo r chlorinated hydrocarbons (CHC's) in cluding pesticides and polychlorinated biphenyls (PCB'SI, and to determine the nature of transport paths, mechanisms, and rates in the Chesapeake Bay's waters, sediments, and organisms. 2. To determine immediate and longer-term biological consequences o f chlorinated hydrocarbons and PCB'S on commercially important species. 3. To determine the distribution of bacteria on sedi ments and suspended particles o f the upper bay, and to perform toxicological studies o f the combined effects o f pesticides and bacteria on oysters. 4. To institute numerical models fo r projecting con taminant distribution relative to the sources and to develop interrelations to biological impacts resulting from changes in the upper Chesapeake Bay's input stresses. 5. To report results in a format convenient fo r re source management and in a form at fo r computer storage, retrieval, and augmentation. In this paper, the data resulting from the chlorin ated hydrocarbon analyses of bottom sediments, sus pended sediments, zooplankton, and shellfish w ill be presented and discussed. METHODS Sample C ollection. The bottom sediments were col lected as grab samples using either a Wildco-Eckman Bot tom Sampler or a Ponar Grab Sampler. In the labora to ry, a portion o f the sample was retained fo r sediment grain-size and clay mineralogy analyses, and the remainder air-dried fo r about 1 week. The shellfish samples were collected w ith a modified bottom trawl or a Ponar Grab Sampler and frozen fo r later analysis.* Suspended particulate samples were collected from surface, midwater, and 0.5 m from the bottom at the sampling stations illustrated in figure 1. The suspended GENP 005770 218 774419 UPPER CHESAPEAKE BAY .CONOWINGQ DAM , <? iA GENP 00577J 75151A002 Figure 1. The principal stations at which samples and measurements were taken in the Upper Bay Survey. 219 774420 particulates were collected by filtratio n through Gelman type-A glass-fiber filters having nominal pore diameters of 5-8 p (the functional pore size appeared much smaller because our tests w ith Chesapeake Bay water showed that nothing which passed through this filte r could be retained on a 0.45 p Millipore filte r). In order to get sufficient sample for chlorinated hydrocarbon analysis (in excess o f 0.3 g dry weight) as much as 100 I of water was filtered depending upon the concentration o f sus pended particulates in the water (usually in the range, 3 to 30 mg/l). Figure 2 shows the filte r apparatus and a filte r loadad w ith suspended particulates. It was determined'em pirically that filtering until tw o filters 14.5 cm in diam eter became clogged provided the minimum amount o f ample required. The bay water entered a % inch garden lose suspended at the appropriate depth, passed through he filte r, through die pump, and into a calibrated vessel or volume estimation. The wet filters were folded, vrapped in aluminum fo il and transported to the laborapry. In the laboratory the samples were air-dried (about days) and stored wrapped in fo il until analysis. The eight of sample collected (and subsequently extracted) as determined by a calculation using the volume of 'ater filtered and the concentration o f suspended paniclates in the water. Two procedural restrictions prevented direct detern a tio n o f th e suspended paniculate sample eights: first, the filters had to be preextracted with Ivents to remove interfering substances and sealed in il until use, which made preweighing undesirable; and cond, had preweighing been done, the subsequent ;ights would have been dubious because these filters id to shed and flake. A t each point in time and space iere a suspended paniculate sample was collected for iorianted hydrocarbon analysis, tw o suspended panic,-te samples were collected on 4.7 cm diameter M illi's or Nucleopore membrane filters (pore size 0.45 and ) p respectively)--one fo r determing the suspended ticulate concentration and one fo r determining the pended paniculate grain-size diameters (ref. 2). Zooplankton samples were collected as oblique tows h paired half-meter standard oceanographic nets using o n e rinsed 202-p Nitex netting. A calibrated K.-type mechanical flowmeter was placed in the ith of each o f the two nets to record the volume of ?r passing through'. Upon completion o f each tow, nets were carefully washed to concentrate the plank- in the cod end. A fter removal o f the larger, gelatinmaterial by passage through a 4-mm sieve, the lies were concentrated w ith a 202-p sieve. From pair o f net samples, one net collection was preid fo r taxonomic and biomass enumerations, and the other sample was pasted through a hexane-extracted Gelman glass-fiber filte r to collect the zooplankton. The resultant pad of zooplankton (including the filter) was frozen and retained fo r later analysis. Sample Preparation. A ll of the samples were ex tracted using Soxhlet extraction w ith 2:1 hexaneacetone (the biological samples were first dried by being ground w ith anhydrous sodium sulfate). A ll o f the ex tracts were subjected to fuming sulfuric acid cleanup procedures (refs. 3,4) prior to gas chromatographic anal ysts. Before the acid treatment procedure, the bottom sediment extracts were treated w tih activated alumina. Most o f the bottom sediment extracts, some o f the sus pended sediment extracts, and several of the zooplank ton extracts'contained sulfur, which was removed by treatment w ith elemental mercury (ref. 5). C hlorinated Hydrocarbon Analysis. The chlorinated hydrocarbons were identified and quantitated by multicolumn, electron-capture, gas-liquid chromatography. Peak relative retention times and peak heights (or areas) were compared to those o f standard compounds. The amounts o f PCB's and chlorinated pesticides were esti mated by a manual subtraction procedure correcting for the overlapping peaks. RESULTS AND DISCUSSION Table 1 summarizes the chlorinated hydrocarbon levels found in the various types o f samples collected in the upper Chesapeake Bay. The standard deviation values given in table 1 em phasize the fact that the range of CHC values observed w ithin any particular sample type was very broad. The values fo r CHC*s on suspended sediment and zooplank ton varied y e a tly from one station to the next during the same collection period or at the same station from one collection period to the next. Apparently these values flu c tu a te ra p id ly . enough (temporally and spatially) that only the unusually large events in terms o f time and/or space w ill be observed at enough points to describe a trend when the sampling is lim ited to a fairly smalt number o f samples, as in this program. The m ulti disciplinary approach of this program, however, circum vents this problem somewhat by providing many d iffer ent types of data that are comparable in space and time. As w ill be seen below, these data then can be examined for interrelationships .relevant to the understanding of the dynamics of chlorinated hydrocarbon movements in the upper Chesapeake Bay. For the purposes o f this discussion, the PCB's w ill be discussed as total PCB (the sum o f the values reported as Aroclor 1242, 1248,1254, and 1262), and in some 220 774421 C o * 774422 500 dNHO Figure 2. aFnildteariGngelampapnarfaitlutesrfcoornctoailnleicntginsgusspuesnpdeneddesdedsiemdiemntesn.t samples T ab le 1. Average chlorinated hydrocarbons found in the upper Chesapeake Bay (S tandard deviations are in parentheses) Sample type Number of samples Total PCB Total chlordane Total DDT Shellfish (wet,ppm)a 26 0.052(0.037) 0.016(0.017) 0.035(0.041) Plankton (wet,ppm) 70 0.50(1.4) 0.041(0.032) 0.16(0.68) Suspended, sediment (dry,ppm)D 66 0.92(0.87) 0.061(0.086) 0.057(0.066) Bottom sediment (dry,ppm) 54 0.28(0.57) 0.0052(0.014) 0.051(0.067) Plankton (H20,ppt)c 69 Suspended sediment (H20,ppt) 68 0.042(0.164) 0.0038(0.0083) 0.010(0.035) 12(14) 0.53(0.88) 0.78(1.5) aThe values are expressed as pg CHC found per g wet weight of material extracted. ^The values are expressed as pg CHC found per g dry weight of material extracted. CThe values are expressed as ng of CHC found per 1 of water filtered to collect the material extracted. GENP 005774 cases, all of the CHC's found will be summed and dis cussed as total CHC. The PCB residue pattern observed most often matched Aroclor 1254 or a mixture of Aforuoncdlorins m1a2n5y4 oafntdhe1s2a6m2p.le(sA.)rocJor 1242 or 1248 was By comparing the bottom sediment data with the suspended sediment (dry) data, one can see that the PCB and chlordane concentration are 4 to 10 times higher in the suspended sediments. The higher values in the sus pended sediment probably occur for one, or most likely, both of the following reasons: the average grain-size of the suspended sediments is much smaller than that of the bottom sediments, resulting in a greater surface area for adsorption per unit weight; and although the sus pended sediments are primarily inorganic materials, the phytoplankton, which were included in these samples, probably bioconcentrated chlorinated hydrocarbons to some extent. If one accepts the above discussion, one is left with the dilemma that the DDTR does not appear higher in ttBhhueet esanulldspuoesnfesd1eo9df72Ds.eOdIifTmtwheniestrsebabansandhnaoeddththienePtehCfefBeUcatnnoidtfedcdheSlcotraredtaeassnineag.t the ODT levels flowing into the Chesapeake Bay, the concentrations of DDT residues in the suspended sedi ments would be less relative to those in the bottom sedi mmaetnetrsiablsecdauepseostihteed bdouttroinmg sthedeimsaemntplsianmg pyleesarcoannsdistproef svaiomupslesyecaornssisats pwriemlla,rilwyhiolef mthaeterisaulsspethnadtedentseerdeidmtehnet bay during the sampling year. While this explanation is plausible, it seems somewhat suspicious that samples 222 774423 were taken fortuitously at just the right time to yield exactly thu same DOT residue levels in both the sus pended w'difnentt and the bottom sediments. The data In labia 1 also show that the CHCs are biuconcaritratad in passing from the suspended sediment into the zooplankton. To evaluate the magnification, one must first convert the plankton (wet) values to plankton (dry) to allow comparison w ith the suspended sediment (dry) values. If one conservatively uses 0.10 as the plankton dry weight to wet weight ratio (ref. 6), one then multiplies all o f the plankton (wet) values by 10 to convert to plankton (dry) and then calculates the follow* ing bioconcentrations as the CHC's pass from the sus* pended sediments to die zooplankton: PCB, 5.4; chlordane, 6.7; and DDTR, 28. The DDTR value seems un reasonably high, and it probably is. If two anomalously high DDTR values are excluded from the total and the average is computed from the other 68 values, the aver age DDTR in plankton (wet) become 0.045, leading to a magnification o f 7.9--a value more compatible w ith the others. The CHC data fo r suspended sediments and zoo plankton are expressed in tw o ways, as mentioned earlier, but further amplification should be made. Envi ronmental residues o f chlorinated hydrocarbons (chlo rinated pesticides and polychlorinated biphenyls) usually are reported as parts per m illion (ppm) dry weight (or wet weight) based upon the dry weight (or wet weight) of sample which was extracted fo r the analysis. If the levels are very low, parts per billion (ppb) or parts per trillio n (ppt) also are used. The data then represent the concentration of CHC's present in that sample. In the consideration of transport o f CHC's (rates, routes, etc.) the amount o f CHC being transported by a water move ment frequently is o f more interest than the concentra tion of the CHC's on the suspended sediments in the water. Therefore, in addition to the data being presented in the usual fashion, the zooplankton and suspended sedi ment CHC data are presented as nanograms (10^g) of CHC on zooplankton or suspended sediment per titer of water (by definition, ppt). These values represent the amount of CHC associated w ith the suspended sediments or the zooplankton contained in a 1 liter sample o f bay water. In a sense, the numbers can be compared directly because they have been normalized to a u nit volume o f water. For instance, referring to table 1, one finds the average PCS values in the bay water on suspended sedi ment and zooplankton to be 12 ppt and 0.042 ppt. respectively. On the average, a given volume of bay water w ill have about 300 times as much PCB in the suspended sediment fraction as in the zooplankton frac tion. Using these values, one also could calculate approxi mate biomagnification values from the shellfish data. The concentrating ability o f shellfish usually is expressed as the level accumulated in the shellfish tissue (wet weight) divided by the exposure concentration in the water. Using the values fo r CHC in the water column on suspended sediment, the shellfish concentration factors are approximately: PCB, 4,000; chlordane, 30,000; and DDTR, 45,000. These values should be considered rough estimates, because the average values used fo r CHC's in the water column probably do not represent accurately the values at the water-bottom sediment interface in habited by these shellfish. Figure 3 is a log-log p lo t of total CHC concentration in the water column on suspended sediment (ppt) versus the concentration of suspended sediment in the water (mg/l). Although the data points are widely scattered, the data could best be enclosed in an oblong field w ith an upward t ilt to its long axis. This indicates a positive relationship between the parameters plotted (if the parameters were unrelated-that is, varied independent ly--the long axis o f the oblong would be either vertical or horizontal). The correlation obviously is not followed closely by all of the data, but in general, it indicates that the bay water samples which had high suspended sedi ment concentrations also had high levels o f CHCs In the water on suspended sediments. I f all suspended sedi ments in the water contained the same amounts of CHC's (ppm, dry weight), a perfect correlation would have been observed in figure 3. The variations in the concentrations of CHC's on suspended sediments are responsible fo r the scattering o f the data. Figure 4 is a log-log p lo t o f total CHC's in the water on zooplankton (ppt) versus the zooplankton biomass in the water (mg/m3). Although the data are'somewhat scattered, there is an obvious positive relationship--as the zooplankton population in the water increases (in creasing biomass), the amount of CHC's in the water on zooplankton increases. The existence o f this relationship establishes th at there is movement o f CHCs Into the aquatic food chains which include the zooplankton com munity. The fa ct that the zooplankton population con tains only a small fraction o f the CHCs present in the water column, considered w ith the relationship observed in figure 3, suggests that the movement of CHCs into the biological system (via zooplankton) from the nonbiological system (suspended sediments) is not influ enced by changes In the concentration o f suspended sediment but is regulated by whatever regulates the zoo plankton population. One could visualize the suspended sediments in the water column as being a reservoir o f CHCs, which flo w into the biological system when zoo plankton blooms occur. OU5775 223 774424 K TOTAL CHC IN WATER ON SUSPENDED SEDIMENT (PARTS PER TRILLION) Figure 3. sActheoedpniclwmoetanetnotertfra(tt(hipmoaenirltllosiinggprtoeahmrfettsrhwiplelaeitsoreunrlsi)pta.esersn)odvceiedartsesuedsdwtihmietehlnottghceoofsnucthsepenettnroadtteaiodl nCHinC- Obviously, this concept is an over simplification o f a tion in the water column. These parameters appear to be very complex system. More likely, the phytoplankton independent variables. A similar plot (not shown) o f die are im portant in the transport o f CHCs from the non- chlorophyll-a concentration versus the concentration of biological reservoir into the zooplankton food-chain. Un CHCs in the water column on zooplankton yielded a fortunately, the sampling procedure fo r gathering sus very similar result. If the phytoplankton have a direct o pended sediments involved pumping the water through a filter, so the phytoplankton were included in the frac role in the pathway o f CHCs into the zooplankton com m unity. the chlorophyll-a data shown here do not indi tn tion called suspended sediments. To overcome this lim i cate it. tation, it had been hoped to estimate the influence of Whatever the details o f the pathway fo r CHCs from oo changes in the phytoplankton population through the use o f measurements o f the chlorophyll level in the water column. Figure S presents a log-log plot o f the the suspended sediment reservoir into the zooplankton, it seems that only a very small percentage o f the CHC's in the water column are associated w ith the zooplankton zooplankton biomass versus the chlorophyll-a concentra- (average of 12 ppt PCB in the water column on suspend- -o as 224 774425 Figure 4. aApsesprolccouitabtoiecfdtmhweeittehlor)gthvoeefrzszouoosoppthllaaennklkottgoononf(bptihaoermtstaopstsaelr(mtCriiHllllCiigorinna)m.thsewweiagthetr ed sediment versus 0.042 on zooplankton). However, to quantify the rate of movement of the CHC's via this pathway one would need information about turnover rates in the plankton community. Regarding resource management, one should consider that a change in bay conditions that would increase the zooplankton popula tion would probably have the effect of increasing the flow of CHC's from the suspended sediment reservoir into the biological system. This could create adverse con sequences as ail aquatic species o f commercial interest at some time in their lifecycle make up a part o f the zoo plankton community. By far, the largest route fo r the transport of CHC's from the suspended sediment reservoir probably is a result o f sediment deposition. The areas of deposition of fine-grain sediments can be visualized as sinks where the CHC's attached to suspended sediments collect. As in the Chester River Study (ref. 1), the chlorinated hydro carbons, in the bottom sediments were found highest where the median g-ain-size diameters were the lowest. Baltimore harbor is a trap fo r fine-grain sediments in the upper Chesapeake Bay and, as such, functions as a sink fo r CHC's from the suspended sediment reservoir. Figure 6 shows that PCB, fo r instance, was much higher in the sediments o f Baltimore harbor than elsewhere in the bay. It would be necessary to analyze core slices and establish the three-dimentional concentration gradient in order to estimate the mass o f CHC's contained in the bottom sediment sinks. (A core from the Chester River Was found to contain layers of widely varying levels of CHC's to a depth o f 50 cntimeters-referencs 1.) A number o f mechanisms exist fo r movement of GENP 005777 225 774426 (MICCHRLOOGRROAPHMSY/LLIL-TAER) Figure 5. Awtoanptelborito(ommfiactshrsoeignlroatgmheosfwpteharteelricthe(rml)oirlvoleipgrshruaymsllts--hpaeeclroocgnucobefinctthmreaetzitooenro)p.inlatnhke i r f \ r \/ jrKTar^ Figure 6. A representation of the concentration of PC8's in bottom sediments samples from the upper Chesapeake Bay. 227 774428 GENP 005780 Figure 7. gSiAnraatmpopohptrlhtetieasoknuwepneoprfeeAarptnaCrkiEhleea3nsr,at1ahpt9eRs7atke4aset,oiosBuhnraocy"wesf1irn3Tog"me.cshtuhnseopleSonugdsyeqduSesahetaednlilmaiteeR--nitv1einrp.fhluoxto 228 774429 Chic's out o f the bottom sediment sinks. When one considers the fine-grain fractions in the upper Chesa peake Bay as a whole, resuspension of this material by tidal scour probably is the major reentry route from the sinks to the suspended sediment reservoir (ref. 7). In the Baltimore harbor area, however, maintenance dredging of navigational channels is a major mechanism fo r removal of sediments containing chlorinated hydro carbons from the bottom sediment sink. Although the subsequent fate o f this dredged material is a subject clouded by great controversy, during the dredging and subsequent overboard discharge of this material, un doubtedly, a substantial quantity returns to the suspend ed sediment reservoir. The Susquehanna River appears to be the major source o f chlorinated hydrocarbons to the upper Chesa peake Bay. Nearly all o f the suspended sediment in the upper bay originates from the Susquehanna River-enter ing prim arily during the few brief periods o f high flo w (ref. 7). Figure 7 is an ERTS-1 (Earth Resource Tech nology Satelite-1) photograph showing the sediment in flu x at the beginning of a freshet period in April 1974. During this freshet period, suspended sediment samples were collected at the location designed " 1 3 " in figure 7. Analysis o f these samples (together w ith other samples collected during the study) indicated that, when they enter the bay, the suspended sediments appear to carry sufficient burden o f PCB's and DDT residues to account for levels observed at the lower stations w ithout postu lating additional sources. The chlordane values appear low. however, suggesting substantial inputs from other sources. As is discussed in greater detail elsewhere (ref. 4), the urban-industrial activities concentrated in and around Baltimore harbor appear to generate locally high concentrations o f PCB and DDT residues, but seem not to contribute a major portion o f the total budget of these materials in the upper bay. It seems likely, how ever, that the harbor area does contribute a large portion of the chlordane found in the upper bay. REFERENCES 1. W. D. Clarke, H. D. Palmer, and L. C. Murdock, eds., Chester River Study, Volume 11, Westinghouse Electric Corporation, Annapolis, Maryland, 1972, 251 pp. 2. H . D. Palm er and J. R. Schubel, "Chapter 4: Estuarine Sedimentology," Upper Bay Survey, F inal R eport fo the M aryland Departm ent o f N atural Resources, Volume II, T.-O. Munson, D. K. Ela, and C. Rutledge, eds., Westinghouse Oceanic Division, Annapolis, Maryland, 1975, in press. 3. T. O. Munson, "Chlorinated Hydrocarbon Residues in Marine Animals o f Southern California," Bull. B n v ir. Contam. Toxicol., Vol. 7 (1972), pp. 223-238. 4. T. 0 . Munson, "Chapter 6: Biochemistry," Upper Bay Survey, F inal R eport to the M aryland D epart' w en t o f N atural Resources, Volume II, T. 0 . Munson, D. K. Ela, and C. Rutledge, eds., Westing house Oceanic Division, Annapolis, Maryland, 1975, in press. 5. D. F. Goerlitz and L. M. Law, "N ote on Removal of Sulfur Interferences from Sediment Extracts fo r Pesticide Analysis," B ull. Bnvir. Contam. T oxicol., Vol. 6 (1971), pp. 9-10. 6. J. M. Forns, "Chapter 2: Marine Biology," Upper Bay Survey, F ina l R eport to the M aryland Depart m ent o f N atural Resources, Volume II, T. O. Munson, D. K. Ela, and C. Rutledge, eds., Westing house Oceanic Division, Annapolis, Maryland, 1975, in press. 7. 'J. R. Schubel, "D istribution and Transportation of Suspended Sediment in Upper Chesapeake Bay," Geol. Soc. Am er. M em oir 133, 1975, pp. 151-167. GENP 005781 229 774430 RECENT STUDIES OF TRANSPORT OF PCB'S TO M A R IN E ENVIRO NM ENTS Robert W. Risebrough* A bstract The deep ocean waters and sediments are a p ote ntia l sink fo r chlorinated biphenyl compounds, removing them from food webs which provide in p u t to man. Data on PCB levels in seawater are as y e t unsatisfactory o r too few to p e rm it a reliable estimate o f the amounts o f PCB th a t have so fa r entered the oceans. Form ulation o f a global mass balance equation fo r the m ajor kinds o f PCB compounds w ould be useful in p redicting fu tu re contam ination levels. Chlorinated biphenyl compounds have been report* ed in many marine environments, including those o f the Arctic (ref. 1) and the Antarctic (ref. 2); w ith the DDT compounds they have become contaminants throughout the global ecosystem. Concentrations reported are occa sionally high, including those in seawater o f the North Atlantic (ref. 3), in marine birds of coastal areas (refs. 4,5,6), in birds feeding on the eggs of other sea birds (ref. 7) and in peregrine falcons [Faico peregrinus) o f Amchitka Island in the Aleutians (ref. 8). The high levels which have been reported from both coastal and marine environments raise two questions, Do these levels represent a threat to local ecosystems and to human consumers? And do the high levels indicate that the oceans, particularly the deep waters and marine sedi ments, can be considered an ultimate sink in which poly chlorinated biphenyls are unlikely to enter food webs that provide nourishment to man? Deposition in marine sediments might then be a significant pathway of remov al of these pollutants from the biosphere. Attempts to answer the latter question would require form ulation of a global mass balance equation o f the chlorobiphenyts, which would express the present burden o f PCB's in the oceans in terms o f global production figures and use patterns. A preliminary formuation of such a global mass balance equation based on North American production and use of PCB has been presented by Nisbet andSarofim (ref. 9). The present paper reviews some of the work relating to the transport of polychlorobiphenyl com pounds to marine environments that has been carried out since Nisbet and Sarofim presented their preliminary model. Just as it has become misleading to speak of "DDT'* in the environment w ithout reference to the individual "Bodega Marine Laboratory, University of California, Bode ga Bay, California 94923, and Canadian W ildlife Service, Depart ment of the Environment, Ottawa, Canada K1A OH3. compounds, so has it become misleading to speak of " PCB" in the environment w ithout reference to the kind o f PCB. Thus, the m ajority of the chlorinated biphenyls used in the United States has consisted o f the trichlorinated preparations (ref, 10), whereas PCB reported in marine environments usually consists of penta- or hexachlorobiphenyts. I t is therefore meaningless to discuss PCB concentrations in seawater in reference to input from rivers if the form er consist predominately of pentachlorobiphenyls and the latter o f trichlorobiphenyls. Nature o f PCB Compounds in Marine Environm ents The higher vapor pressures of the lower chlorinated PCB compounds (ref. 11) and the production and use figures (refs. 9 ,10 ) suggest that larger quantities o f these have entered the marine environment than have the penta- and hexachlorobiphenyls. Thus Bidleman and Olney (ref. 12) found that the majority o f the PCB resi dues in air over the Sargasso Sea consisted o f tri- and tetrachlorobiphenyls. Sim ilarly, PCB entering the sea as a component o f the wastewaters o f Southern California has consisted predominately o f trichlorobiphenyls (D. R. Young, R. W. Risebrough, B. W. de Lappe, T . C. Heesen, and D. J. McDermott, unpublished data). Trichloro biphenyls have occasionally been detected in seawater of the Southern California Bight (ref. 13), but PCB usually reported in seawater has consisted of pentachlorobiphenyls (refs. 3, 14, 15, 16). Bidleman and Olney (ref, 12) have reported that the chlorobiphenyls in their seawater extracts from the Sargasso Sea were predominately hexachlorobiphenyls. Tri- and tetrachlorobiphenyls have been detected in marine fish from the Aleutians and in ptarmigan [Lagopus m utus), an arctic grouse that feeds on the tundra (ref. 8). Many extracts of marine species, however, do not contain tri- or tetrachlorobiphenyls in concentrations equivalent or approaching those of the penta- and hexachlorobiphenyls. Bacterial degradation o f the lower chlorinated compounds (ref, 17) is a possi ble pathway of breakdown but the low concentrations o f PCB in seawater might not prompt bacteria to synthe size the necessary enzymes fo r their metabolism, unlike the bacterial response in artificial environments where PCB compounds are the only carbon source. A major d iffic u lty in recording the lower chlorinated compounds in seawater has been the presence in the majority of extracts of high concentrations o f other compounds which interfere w ith the analysis. The higher vapor pres sures o f the lower chlorinated compounds and the!' GBtfP 005782 230 774431 longer residence time in the atmosphere might result in higher rates of breakdown by ultraviolet light, but evi dence to support this hypothesis is apparently lacking. In higher vertebrates, metabolism to hydroxylated deriv atives of unknown significance in the marine environ ment accounts fo r the disappearance of some of the triand tetrachlorobiphenyls. Formulation of a global mass balance equation of "PCB" therefore makes little sense unless it is done w ith reference to individual compounds or at least to the major classes o f chlorobiphenyls. Chlorinated Dibenzofurans in the Environm ent Other papers presented at this symposium have ex pressed the current concern over the possible exposure of man to chlorinated dibenzofurans. Preparations of PCB have been shown to produce birth defects in birds (refs. 18,19, 20), similar to those which have occasional ly been observed in populations of terns. Sterna hirundo, and S. dougai/ii, breeding in Long Island Sound and feeding on small fish (ref. 21). The observed defects are comparable to those produced by the chlorinated dibenzodioxins (ref. 22). The presence of the chemically relat ed chlorinated dibenzofurans in PCB preparations (refs. 23, 24, 25) suggests that the defects may be caused by these contaminants rather than by chlorobiphenyls. Extracts of mallards (Anas pfatrhynchos) that had been fed PCS o f known dibenzofuran content were examined fo r the presence of chlorinated dibenzofurans. The chlorinated dibenzofurans originally present in the Aroclor 1254 were found to be metabolized or other wise excreted at a much faster rate than the pentachlorobiphenyls and were not found in the extracts (re. 26). It would therefore appear unlikely that these compounds would be accumulated in marine food webs. In the tight of other results that have been presented at this symposi um, it might be worthwhile to look in the environment fo r those individual PCB compounds from which diben zofurans might be formed in vivo, and to examine tissues of species exposed to these compounds fo r the presence of the furans. Comparative PCB Levels in Marine Environments Relative contamination levels o f different oceanic areas by PCB compounds have recently been reviewed by Ohlendorf et al. (ref. 27) and by Risebrough et at. (ref. 13); marine birds were used as indicator organisms. In the North Atlantic, PCB contamination appears to increase from west to east; contamination levels in the vicinity of Iceland appear comparable to those in the Aleutians in the North Pacific. In the southern hemi sphere, levels in biocoenetic equivalents of northern spe cies are approximately one order of magnitude lower. The difference between the tw o hemispheres reflects therefore the relative industrialization of the two areas. Data that would permit a more detailed comparison be tween the Atlantic and the Pacific are as yet insufficient. PCB in Seawater Determinations o f the PCB levels in seawater have been reported from both the Pacific and the Atlantic. Williams and Robertson (ref, 15) have reported PCB, p, p'-DOT, and p, p '-DDE values in subsurface water from the outer California Current and at two stations in the North Central Pacific Gyre, both in the vicinity of 31 N . 155 W. Water was collected in 2.5- liter glass bottles, 10-15 cm below the surface. Reported PCB values in the subsurface water, including filtrate and filtered fractions, were 2.5 x 10*12 g/g in the California Current and 4.5 x 10*12 g/g at one o f the North Central Pacific Gyre sta tions. # Scura and McClure (ref. 16) utilized a column con taining 5% activated carbon powder, 10% MgO, and 85% refined diatomaceous earth fo r the determination of chlorinated hydrocarbons in 1-1iter samples o f seawater collected o ff the Southern California coast. Reported PCB concentrations at five stations in the Southern Cali fornia Bight ranged from 3 ppt to 9.6 p pt (10'12 g/g) at the surface; concentrations reported in five samples ob tained at depths from 500 to 1,500 meters ranged from 2.3 to 10.3 ppt. In the majority o f samples, p,p'-DDE and p.p'-DDT were detected; DDE concentrations ranged from <0.1 ppt to 1.0 ppt at the surface and from O. 3 to 1.2 p pt at depths from 500 to 1,500 meters. Concentrations of p.p'-DDT were somewhat lower. Bidleman and Olney (ref, 12) have reported PCB and DDT concentrations at eight stations in the Sargasso Sea in 1973. PCB concentrations in subsurface water were lower than detectability 0 .9 x 10*11 g/g) at four of the stations and ranged from 1.0 to 3.6 x 10` 12 g/g at the others. Concentrations of p,p -DDT were 0.5 x 10'12 g/g at one station but were below detectability 0 .1 5 x 10' 12 g/g) at the'others. Samples were collected in 3.8liter glass jugs at depths approximately 30 cm below the surface. Substantially higher concentrations were meas ured in the surface microlayer. These concentrations were calculated by reference to Aroclor 1260. Concen trations calculated by reference to Aroclor 1254 may have been up to two times higher (ref. 28). Because of the difficulties in extracting large vol umes o f seawater w ith organic solvents, Harvey et al. (ref. 3) developed a column extraction system using Amberlite XAD-2 resin. Seawater samples in volumes ranging between 19 and 80 liters were obtained in a large volume sampler and passed through the resin on board 231 8soojKr?tn 774432 ship. Also, the extracts were analyzed on board ship. Rnpnrti'il PCB concentrations, calculated by reference to Arrtdor 1754, .ivernqcd 35 x 10M3 g/fj at the surface and 10 r>P< ;ii 200 meter';. A t depths o f 100, 1,500, and 3.000 mu iits ret)orted concentrations were >1 ppt. Sam* pies were obtained in the summer o f 1972 (ref. 3). In 1973 and 1974, substantially lower values were recorded and it was concluded that PCB concentrations in North A tla ntic surface waters had declined 40-fold over the 2-year period as a result o f restrictions on PCB use (ref. 14). A t two stations sampled in 1973 (09 N. 40 W. and 32 N. 70 W.) samples were obtained through the water column. PCB concentrations ranged from 4.3 ppt at 10 meters to 1 p pt at 3,000 meters at the former site and from 0.4 to 1.9 p pt at depths be tween 10 meters and 5,100 meters at the latter. Harvey et al. (ref. 14) estimated that the decline of PCB concentrations would require removal o f 2 x IQ4 tons of PCB from the upper 200 meters over the 2-year period, assuming a mean concentration in 1972 o f 20 x 10*13 g/g in the upper 200 meters of the North A tlantic between 26 N. and 63 N,; the volume was assumed to be 10*8 liters. The estimate o f the volume over this area at a depth of 200 meters appears, however, to be low, perhaps by an order o f magnitude since the correspond ing area would be 5 x 10* km3. The area of the Atlantic, including the North and South Atlantic, is 82 x 10* km3 (ref. 29). Thus, since the PCB reported consisted pre dominantly of pentachlorobiphenyls, in the order o f 10s metric tons o f pentachlorobiphenyls would have to be removed from the upper 200 meters. From 1957 through 1974, a total of only 124 m illion pounds, equiv alent to 5.6 x 104 metric tons of pentachlorobiphenyls (Aroclor 1254), was sold in the United States (ref. 10), Sales in 1970, the peak year o f U.S. production, amounted to 5.6 x 103 tons. Since the mean depth of the A tlantic is 3,926 meters (ref. 29) and since PCB was recorded at depths to 3,000 meters, the estimated pentachlorobiphenyl content o f the North Atlantic would be correspondingly higher. If the average concentration throughout the water column were assumed to be 1,pot, the average depth assumed to be 3,900 meters and the area of the North Atlantic between the equator and 65 N. were assumed to be in the order o f 47 x 106 km3, the pentachlorobiphenyl content would be in the order of 180.000 metric tons, higher than the total U S. domestic use. Similarly, the PCB concentrations reported from the Pacific by Scura and McClure (ref. 16) and by Williams and Robertson (ref. 15) appear to be too high. If a mean value o f 1 ppt were assumed fo r the upper 200 meters of the North Pacific and the area from the equator to 65 N. is 82 x 106 km3, 16,000 tons o f pentachlorobiphen yls would be present in this volume. This represents three times the U.S. use in 1970. Nisbet and Sarofim (ref. 9) and the Panel on Haz ardous Trace Substances (ref. 30) estimated that 1.5-2.5 x 103 tons per year of PCB.had been discharged into the atmosphere from North America. A large fraction of this amount can be expected to consist of lower chlorinated PCB compounds such as the tri- and tetrachlorobiphen yls. To eliminate the very significant problems of con tamination during collection and extraction, and the d if ficulties of working w ith low yojumes of seawater, we have worked towards the development o f an in situ sam pling system, such that all materials in contact w ith sea water that is sampled can be cleaned in the laboratory to a,desired background level and wrapped in clean contain ers, to be unwrapped only immediately prior to use. The system would extract water at a desired depth and could be rewrapped immediately upon retrieval and stored under appropriate conditions until analysis. Our own values obtained w ith this system have been substantially lower than those recorded by other investi gators. Thus 23 extracts of seawater obtained o ff Western Mexico in 1975 contained no detectable chlorobiphenyls; volumes extracted were in the order o f 100 liters. In *22 o f these samples, concentrations o f penta chlorobiphenyls were less than 100 parts per quadrillion (TO*15 g/g); in 11 samples, concentrations were less than 50 x 10"1S g/g (ref. 13). We believe these values to be more consistent w ith the requirements o f a global mass balance equation, yet intercalibration o f all methodolo gies used to determine organochlorines in seawater is urgently required. River Transport o f Ch/orobiphenyis to the Marine Environm ent Nisbet and Sarofim (ref. 9) estimated that 4 to 5 x 10s tons/year o f PCB were discharged into fresh and coastal waters in the peak year o f PC8 use. This estimate was based upon use figures and industrial and disposal practices in effect at that time. Of the to ta l PCB, about 1,000 tons may be assumed to have consisted o f penta chlorobiphenyls. Analysis o f wastewaters and o f surface runoff entering the Southern California Bight since 1971 has shown that trichlorobiphenyls have constituted the majority of the total PCB residues. In this area, PCB input into the sea from wastewaters is considerably high er than the input from surface runoff. Estimated total PCB input into the Bight from these sources in 1972 was 20 tons; in 1974 total input was estimated to be 6.5 tons (Young et al., op. tit.) . 232 GENP 005784 774433 Atm ospheric Transport o f PCBs to Marine Environ m ents Peel (ref. 31) was unable to detect PCB compounds in samples o f Antarctic snow obtained in December 1969 inland from the British Antarctic Station at Halley Bay (7531 'S . 264 2'W .). The samples represented the previous 5 to 10 years' accumulation. Total concentra tions of p .p ^ D T and p,p'-DDE ranged from 0.1 to 2.0 x 10*" g/g. On this basis, the argument was advanced that on a global scale the atmosphere is not the predomi nant mode of transport o f PCB. These results, therefore, appear inconsistent w ith those o f Bidleman and Olney (ref. 12) and Harvey and Steinhauer (ref, 32), who were able to detect PCB in samples of marine air at concentra tions considerably in excess o f those o f the DDT com pounds. In 1975 we extracted Antarctic snow in situ on Doumer Island in the Antarctic Peninsula (6335.5'W . 6451.3'S .); eggs o f three species o f antarctic penguins [Pygosce/is adeiiae, P. papua, P. antarctica) were ob tained to look fo r PCB in the food webs and to compare residues with those obtained 5 years previously (ref. 2). Eleven 99-liter samples o f snow were extracted by tech niques described elsewhere (R. W. Risebrough, W. Walker II, B. W. de Lappe, unpublished manuscript). PCB concentrations, as pentachlorobiphenyls, ranged from 30 to 1,200 x 10'15 g/g; median concentration was 300 x 10*1S g/g. The median total DDT:PCB ratio in these samples was 6. Pentachlorobiphenyls were detected in all o f 27 penguin eggs of the three species obtained in 1975. In addition, 15 eggs of the Adelie penguin obtained in A rthur Harbor on Anvers Island, near Palmer Station, on 25 December 1973 also contained pentachlorobiphenyls. The median DDE:PCB ratio was 3.0. Concentrations of p,p'-DDT were low compared to those o f p,p'-DDE: Fur thermore, reexamination o f extracts o f 14 Adelie pen guin eggs obtained at the same site in A rth u r Harbor in 1970 showed the presence o f PCB compounds in all extracts. A variety of unknown compounds had previ ously interfered w ith the detection o f pentachlorobipherv'ls. These however, could be destroyed by rigorous saponification (R. W. Risebrough and T. T. Schmidt, unpublished data). Total DDT:PCB ratios recorded in several of the subantarctic samples from the Auckland Islands ranged between 2 and 4 (ref. 33), comparable to those recorded in the Antarctic penguin eggs. Moreover, concentrations of DDE and PCB were equivalent north and south of the Convergence. Thus, fallout patterns o f chlorinated hydrocarbons appear to be equivalent north and south of the Antarctic Convergence, which separates waters derived both from the melting of the Antarctic Icecap and from upwelling from waters of the southern Atlan tic, Pacific, and Indian Oceans. Residues in the Antarctic have therefore derived from atmospheric transport rath er than from oceanic circulation, The possibility that the residues of organochlorine pollutants in Antarctica have resulted from human activities at the scientific bases has been examined and discounted (ref. 34). Changes in PCB Contam ination Leveis in the Marine Environm ent PCB levels in mussels, M ytiius, at several sites in the Southern California Bight, have declined between 1971 and 1974 (B. W. de Lappe, R. W. Risebrough, P. M illikin, and D. R. Young, unpublished data). As dis cussed above, the reporte'd decline o f PCB values in the North A tlantic mixed layer (ref. 14) appears unlikely. The seabird data (refs. 35, 7, 27) do not indicate a de cline in the North Atlantic between 1971 and 1973. Most meetings, particularly international meetings discussing pollution problems o f the marine environ ment, have recommended monitoring programs that would follow w ith time changes in the levels o f particu lar pollutant classes. These recommendations have yet to be implemented; indeed, we might be reluctant to sup port such recommendations w ithout assurance that the numbers obtained would be meaningful. A " Mussel W atch" (ref. 36) w ill shortly be underway in the United States which w ill examine mussels, principally M. edufis and M. catifornianus, from coastal sites fo r PCB and other chlorinated hydrocarbons, as well as fo r plutonium isotopes, petroleum compounds, and selected metals. Many variables, including salinity, temperature, particu late content o f the water, gonadal condition, time of year, size of the organism, microhabitat, etc., can be expected to affect the variance o f the determinations obtained in such m onitoring programs. Nevertheless, the program does provide a beginning, which hopefully w ill determine how levels o f chlorobiphenyls change in a marine environment in response to changes in produc tion and use practices. Summary The deep ocean waters and sediments are a potential sink for chlorinated biphenyl compounds, removing them from food webs which provide input to man. Data on PCB levels in seawater are as yet unsatisfactory or too few to permit a reliable estimate o f the amounts o f PCB that have so far entered the oceans. Formulation o f a global mass balanco equation fo r the major kinds o f PCB GENP 005785 233 774434 compounds would be useful in predicting future contamnation levels. ACKNOWLEDGMENTS Research was supported by the International De cade of Ocean Exploration Program o f the National Science Foundation, grant numbers GX32885 and ID072-06412 A02; the Office o f Polar Programs, Nation al Science Foundation, grant numbers OPP74-21254 and OPP75-23520; and by the Canadian W ildlife Service. REFERENCES a% *0 G. W. Bowes and C. J. Jonkel, "Presence and Distri bution of Polychlorinated Biphenyls (PCB) in A rctic :.nd Subarctic Marine Food Chains," Journal o f die Fisheries Research Board o f Canada Vol. 32, No. 11 (19751,pp. 2111-2123. R. W. Risebrough and G. M. Carmignani, "C hlorin ated Hydrocarbons in Antarctic Birds," Proceedings o f the Colloquium, Conservation Problems in A n t arctica, B. C. Parker, ed.r Allen Press, Lawrence, Kansas, 1972, pp. 63-78. 3. G. R. Harvey, W. G. Steinhauer, and J. M. Teal, "Polychlorobiphenyls in North A tlantic Ocean W ater," Science, Vol. 180 (1973), pp. 643-644. 4. J. H. Koeman, H. C. W. Van Velzen-blad, R. de Vries, and J. G. Vos, "Effects o f PCB and DDE in Cormorants and Evaluation o f PCB Residues From an Experimental S tudy," J. Reprod. F e rt, SuppL 79,1973, pp. 353-364. P. R. Spitzer, R. W. Risebrough, J. W. Grier, and C. R. Sindelar, "Eggsshell-Thickness-Pollutant Rela tionships Among North American Ospreys," Proc. N orth American Osprey Symposium, J. Ogden, ed., (in press). S. M Wiemeyer, P. R, Spitzer, W. C. Krantz, T. G. Lamont. anu . Crcmartie. "Effects o f Environmen tal Pollutants on Connecticut and Maryland Os preys," J. W ild!. Manage,, Vol. 39, No. 1 (1975), pp. 171-139. W. R. P. Bou-.-e .jnd J. A. Bogan, "Polychlorinated Biphenyls in North Atlantic Seabirds," Marine Pol- lu t. B u ll., Vo'. 2 (1972). pp. 1 7 M 7 5 . C. M. While and R. W. Risebrough, "Polychlorin- atr-! Biphenyls in the Ecosystems of Amchitka Is la n d /' The Environm ent o f Am chitka Island, Alas ka, M. L. M erritt and R. G. Fullers, erfs.. Oak Ridge, Tennessee, Technical Information Center, Atom ic Energy Commission, 1976, (in press), s; i. C. T. Nistwt and A. F. 3-`ic im , "Rates and Ruutes of Transport of PCB's Environment," Environ. Health Perspectives, No. 1 (1972), pp. 21-38. 10. Monsanto Chemical Company, St. Louis, Mo., Octo ber 23,1975, (in litt.). 11. D. Mackay and P. J. Leinonen, "Rate o f Evapora tion o f Low-Solubility Contaminants From Water Bodies to Atmosphere," Environ. Sci. and Tech., Vol. 9, No. 13 (1975), pp. 1178-1180. 12. T. F. Bidleman and C. E. OIney, "Chlorinated Hydrocarbons in the Sargasso Sea Atmosphere and Surface W ater," Science, Vol. 183, No. 4124 (1974), pp. 516-518. 13. R. W. Risebrough, B. W. de Lappe, and W. Walker II,. "P ollutant Transfer to the Marine Environ m e n t: S y n th e tic Organics," Proceedings of a symposium held at the Skidaway Institute o f Ocean ography, H. L. Windom, ed., Savannah, Georgia, January 7-9,1976, (in press). 14.. G. R. Harvey. W. G. Steinhauer, and H. P. Miklas, "Decline of PCB Concentrations in North A tlantic Surface Water," Nature, Vol. 252 (1974), pp. 387-388. 15. P. M. Williams and K. J. Robertson, "Chlorinated .'Hydrocarbons in Sea-Surface Films and Subsurface Waters at Nearshore Stations-and iri the North Cen tral Pacific G yre," Fishery B u ll., V ol. 13 (1975), pp. 445-447. 16. E. D. Scura and V. E. McClure, "Chlorinated Hydro carbons in Seawater: Analytical Method and Levels in the Northeastern Pacific," M arine Chem istry, Vol. 3, No. 1975 (1975), pp. 337-346. 17. P. T. S. Wong and K. L. E. Kaiser, "Bacterial Degra d a tio n o f Polychlorinated Biphenyls. II. Rate studies," B ull. Environ. Contam. T oxicol., Vol. 32, No. 2 (1975), pp. 249-255. 18. R. W. Carlson and R. T. Duby, "E m bryotoxic Ef fects of Three PCB's in the Chicken," B ull. Environ. Contam. T oxicol., Vol. 9 (1973), p. 261. 19. C. F. Tumasonis, B. Bush, and F. D. Baker, "PCB Levels in Egg Yolks Associated W ith Embryonic M ortality and D eform ity o f Hatched Chicks," Arch. Environ. Contam. T oxicol., Vol. 1 (1973), pp. 312-324. 20. H. C. Cecil, J. Bitman, R. J. Lillie, G. F. Fries, and ,J. Verrett, "E m bryotoxic and Teratogenic Effects in Unhatched Fertile Eggs From Hens Fed Polychlorin ated Biphenyls (PCB's)/' B ull. Environ. Contam. Toxicol., Vol. 11 (1974), p. 489. 21. H. Hays and R. W. Risebrough,-"Pollutant Concen trations in Abnormal Young Terns From Long Is land Sound," The A u k, Vol. 89 (1972), pp. 19-35. 22. J. Verrett, Statement before the Subcommittee on Energy, Natural Resources, and the Environment of c o 234 0 s 774435 the Committee on Commerce, United States Senate, Ninety-First Congress, Second Session on Effects of 2,4,5*T on Man and the Environment, Serial 91-60, U .S. G overnm ent Printing Office, 1970, pp. 190-360. 23. J. G. Vos, J. H. Koeman, H. L. Van der Maas, M. C. Ten Noever de Brauw, and R. H. de Vos, " Identifi cation and Toxicological Evaluation o f Chlorinated Dibenzofuran and Chlorinated Naphthalene in Two Commercial Polychlorinated Biphenyls," FoodCosmet. T oxicol., V ol. 8 (1970), pp. 625-633. 24. J. G. Vos and J. H. Koeman, "Comparative Toxico logic Study W ith Polychlorinated Biphenyls in Chickens W ith Special Reference to Porphyria, Ede ma Formation, Liver Necrosis and Tissue Residues," Toxicol. A p pl. Pharmacol., Vol. 17 (1970), pp. 656-668. 25. G. W. Bowes, M. J. M ulvihill, B. R. Simoneit, A . L. Burlingame, and R. W. Risebrough, " Identification of Chlorinated Dibenzofurans in American Poly chlorinated Biphenyls," Nature, Vol. 256 (1975), pp. 305-307. 26. R. J. Norstrom, R. W. Risebrough, and D. J. Cart wright, " Elimination o f Chlorinated Dibenzofurans (CDFs) Associated W ith PCBs Fed to Mallards (Anas p/atyrhynchos)/* (unpublished ms.). 27. H. M. Ohlendorf, R. W. Risebrough, and K. Ver meer, " Exposure o f Marine Birds to Environmental Pollutants," Proc. Pacific Seabird Congress, (in press). 28. R. W. Risebrough and B. W. de Lappe, " Accumula- tion o f Polychlorinated Biphenyls in Ecosystems," Environ. Health Perspectives, No. 1 (1972), pp. 39-45. 29. H. V. Sverdrup, M. W. Johnson, and R. H. Fleming, 'T h e Oceans: Their Physics, Chemistry and General Biology," Prentice Hall, New York, 1942,1087 pp. 30. Panel on Hazardous Trace Substances, "PCBs -- Environmental Im pact," Environ. Research, Vol. 5 (1972), pp. 249-362. 31. D. A . Peel, " Organochlorine Residues in Antarctic Snow," Nature, Vol. 254 (1975), pp. 324-325. 32. G. R. Harvey and W. G. Steinhauer, "Atmospheric Transport of Polychlorobiphenyls to the North A t la n t ic , " Atm ospheric Environm ent, Vol. 8 (1974) , pp. 777-782. 33. S. Bennington, P. G. Connors, C. Connors, and R. W. Risebrough, "Patterns o f Chlorinated Hydrocar bon Contamination in New Zealand Subantarctic and Coastal Marine Birds," Environ. P o llu t, V ol. 8 (1975) , pp. 135-147. 34. R. W. Risebrough,'Transfer o f Organochlorine Pol lutants to A ntarctica," Adaptations W ithin A ntarc tic Ecosystems, Scientific Committee fo r Antarctic Research, G. A . Llano, ed., 1976, (in press). 35. J. A. Sproul, Jr., R. L. Bradley, Jr., and J. J. Hickey, "Polychlorinated Biphenyls, DDE, and Dieldrin in Icelandic Seabirds," Pesticides M onitoring J ,, (in press). 36. E. D. Goldberg, " The Mussel Watch -- A First Step in Global Marine M onitoring," M arine P o llu t B u ll., Vol. 6 (1975), p. 111. GENP 005787 235 774436 UPTAKE OF THREE POLYCHLORINATED BIPHENYLS, DDT AND DDE BY THE GREEN SUNFISH, L e p o m is C y a n e llu s Raf James R. Sanborn, Ph.D., William F. Childers, and Robert L. Metcalf* A bstract The ubiquitous occurrence o f polychlorinated b i phenyls (PCB's) in aquatic organisms demonstrates the extreme persistence o f these m aterials and their resist ance to being m etabolized in fish to water-soluble prod ucts (refs. 12,3,4,5). The com plex m ixtures o f chlorin ated biphenyls in com m ercial PCB's makes quantitative research on the physiological effects o f these compounds and th e ir susceptibility to metabolism very d iffic u lt. However, die availability o f three 14C biphenyls-- 2 ,2 ' ,5-trichlorobiphenyl, 2,52?,& -tetrachlorobiphenyl, and 2,4,5,2?,i>-pentachiorobiphenyf--provides a p a rtia l solution to this problem as these three pure isomers are m a jo r components o f three im p orta nt comm ercial PCB's, nam ely, 1242, 1248, and 1254 (ref. 6). Recently the fate o f these pure chlorinated biphenyl isomers has been examined in a m odel ecosystem. The substantial accum ulation o f both the tetra- and pentachlorobiphenyl isomers b y the m osquito fish, Gambusia affinis Baird and G irard, 15.6 and 119.7 ppm .(parts p er m il lio n ), respectively, clearly dem onstrated the necessity fo r the exam ination o f the uptake o f these m aterials from water b y fish (ref. 7). This com m unication reports the uptake o f three pure 14C PCB's, D D T, and DDE by the green sunfish, Lepomis cyanellus Raf. MATERIALS AND METHODS The three pure ( > 99 percent by tic, thin-layer chromatography, and radioautography) chlorinated bi phenyls were obtained from Mallinckrodt and had the following specific activities in mCi/mM: 2,2 \5 -t rich lorobiphenyl 9.83; 2,2\5,5'-tetrachlorobiphenyl 9.78; and 2,4,5,2',5*-pentachlorobiphenyl 9.78. The ring-labeled 14C DDT and DDE were available from previous work and had specific activities of 0.264 and 5.59 mCi/mM, respectively (ref. 8). Fifteen green sunfish weighing 50-150 mg were placed in 2 liters o f aged tap water for a 24-hour acclimation period, then two concentrations, 'Illin o is Natural Historv Survey, Illinois Agricultural Experi m e n t S ta tio n and th e U n iv e rs ity o f Illin o is , Urbana, Illinois 61801. All figures and tables reproduced from and text adapted from Bullentin of Environmental Contamination & Toxicology. Vol. 13, No. 2 11975), pp. 209-217. 31975 by Springer-Verlag New York Inc. Used by permission approximately 1 and 3 ppb, of the five compounds in acetone were added to the jars. Each concentration was run at 22 C in triplicate and the fish were fed Daphnia magna Straus twice a week during the experiment. The experimental design as described in table 1 is taken in part from the study on the uptake of DDT and methoxychlor by several species of fish (ref. 9). This type of .experiment models the pulsed introduction of pesticides or industrial chemicals into the aquatic envi ronment. Each point on the graphs represents the aver age of three fish and when the standard deviation for each point was divided by the average fo r each point, an average of 22 percent was obtained fo r all o f the experi ments. ' Analysis of concentrations of the various com pounds in the fish was accomplished by solubilizing the fish individually in scintillation vials w ith one ml Protosol (New England Nuclear) at 60 C fo r 4 to 6 hours and then adding Aquasol (New England Nuclear) for scintillation counting. This method assumes that all the radioactivity is parent compound, which, except fo r the trichlorobiphenyl which undergoes substantial metabo lism, (see table 3) was an excellent assumption. A t the end of* the experiment the remaining fish were ground in acetone and the extracts were spotted on tic plates (silica gel GF-254, Qrinkmann, 0.25 mm) and developed in Skellysolve B fo r metabolite distribution by radioautography (Blue Brand X-ray film , Eastman Kodak) and liquid scintillation counting. The flu id used for counting contained PPO (7 g), POPOP (0.05 g), and napthalene (120 g) in 1 liter dioxane. Quenching for both the fish and tic analysis was corrected using an external standard. RESULTS AND DISCUSSION Tables 1 and 2 show the experimental design of the uptake study and the amounts o f 14C compounds added to the environment o f the fish. The data in table 3 des cribe the metabolite distribution o f the compounds at the end of this uptake investigation. Table 4 contains data showing the bioconcentration o f the three 14 C PCB's, DDT, and DDE. Figures I through 5 show the time-dependent uptake o f the five compounds by Lepomis cyanellus Raf. Figure 6 shows the relationship for the three PCB's and DDE between the unextractable radioactivity in Gambusia a ffints Baird and Girard in the GENP. 005788 236 774437 Table 1. DTDimTe, taanbdleDfDorEebxypeLreimpoemntisoncyuapnteaUkuesoRfatfhree PCB's, Day Treatment 0 Add l**C in acetone 2 Take out one fish, weigh and count ll*C 3 Take out one fish, weigh and count lt*C 9 Change water and add in acetone 10 Take one fish, weigh and count lkC 13 Take one fish, weigh and count lt*C 16 Take one fish out, weigh and count ^ C , grind remaining fish up in acetone, spot acetone ex tracts on tic for metabolite distribution Table 2. Aenmvoiruonntms oenftthorfeLeePpCoBm'iss, DDT, and cyaneUus RDaDfE added to First Second Trichlorobiphenyl Low High PPb PPb 0774 2 7 W 2.80 5.61 Tetrachlorobiphenyl Low 2.50 1.57 High 7.50 5.00 Pentachlorobiphenyl Low 1.77 1.77 High 5.31 5.31 DDT low High DDE Low High First Second PPb PPb OTTl OTTT 0.33 0.33 1.13 2.25 3.40 6.75 GENP 005789 TableD3D.E Paterecnedntodfiesxtrpiberuitmioenntofin14LCep-loamheilsedcyPaCneBU'su,sDRDaTf, and Trichlorobiphenyl Tetrachlorobiphenyl Pentachlorobiphenyl DDE DDT Parent 18.39 98.84 99.41 99.00 97.23 Polar* 81.61 1.16 0.69 1.00 2.27 *Rf = 0 Skellysolve B 237 774438 Table 4. Bioconcentration of 14C-labe!ed PCB's, DDT, and DDE in L e p o m is c y a n e f/u s Raf. after 15 days Trichlorobiphenyl Tetrachlorobiphenyl Pentachlorobiphenyl DDE DDT 54 460 1,510 890 17,500 by L e p o m is c y a n e i/u s Raf Figure 2. Time-dependent uptake of tetrachlorobiphenyl by L e p o m is c y a n e itu s Raf 238 774439 10.0 Figure 3. Time-dependent uptake of pentachlorobiphenyl by L e p o m is c y a n e llu s Raf GENP 00579J 0 3 Tim 1(0O i y i ) 13 30 Figure 4. Time-dependent uptake of DDE by L e p o m is c y a n e llu s Raf 239 774440 Figure 5. Time-dependent uptake of DDT by Lepom is cyanetlus Raf Figure 6. The relationship for the three PCB's and DDE be tween the unextractable radioactivity in Gambusia affinis Baird and Girard in the 33-day ecosystem and the average change in concentration of radio activity from day 3 to day 9 and day 10 over day 16. 240 774441 \Q to 33-day ecosystem (ref. 7) and the average change in con centration of radioactivity from day 3 to day 9 (ppm day 9/ppm day 3) and day 10 over day 16 (ppm day 16/ppm day 10). Each point on figure 6 on the abscissa is an average of four values. tt is quite clear from examination of figures 1 through 5 that three of the compounds--namely the pentachlorobiphenyl, DDT, and DDE-have similar uptake curves in that the fish retain the radiolabeled compound after it is added to the environment of the fish. The point fo r the last day fo r DDT is not shown, as th fish died before final value could be measured.The tetrachlorobiphenyl is retained somewhat less than pentachlorobiphenyl, DDT, and DDE, in th at a few days after a peak concentration is reached after addition of labeled biphenyl the curve begins to drop. The trichlorobiphenyl differs dramatically from the preceding four compounds, in that after the peak concentration the curve drops o ff sharply. This type o f metabolic susceptibility fo r chlorinated biphenyls, namely that the lower chlorinated biphenyls undergo metabolism more readily than the higher chlo rinated PCB's, has been shown fo r the complex commer cial mixtures using rats (ref. 10) and Japanese quail (ref. 11 ). However, the literature appears to be lacking in metabolism studies on pure isomers of the PCB's except fo r some work on 4-chlorobiphenyl in the rabbit (refs. 12, 13). A comparative metabolism study with pigeons, rats, and trou t and 4-chlorobiphenyl, 4,4*-dichlorobip h e n y l, 2 ,5 ,2 ',5 '-te tra c h lo ro b ip h e n y l, and 2,4,5,2',4',5*-hexachlorobjphenyl has been reported (ref. 13). These authors found that the tro u t could not hydroxylate any of these compounds while the pigeon and rat were able to hydroxylate all but the hexachlorobiphenyl. Recently an elimination study w ith the rhesus monkey and two pure 14C biphenyls--2,4*dichlorobiphenyl and 2,5,2'-trichlorobiphenyl--has been reported but no metabolite structure or distribution was reported (ref. 14). The first hydroxylated metabolite from a higher chlorinated biphenyl has been reported in a study of the excretion products o f 2,4,3,,4l-tetrachlorobiphenyl in rats (ref. 15). These authors identified two hydroxylated species as the 2- and 5-hydroxy derivatives of the tetrachlorobiphenyl. Further, the 5-hydroxy bi phenyl was determined to be about four times more toxic to the rat than the tetrachlorobiphenyl. The data reported in this paper corroborate quite well the information already available, except for the trou t, on the metabolism o f PCB's by organisms. In the present work the data indicate rather convincingly that the green sunfish is able to transform the trichlorobi phenyl into polar species as only 18 percent (table 3) of the radioactivity in the fish was parent material at the end of the experiment. Perhaps species differences and temperature optimum of detoxifying enzymes account fo r the discrepancy between the relative abilities of the trout and green sunfish to metabolize chlorinated bi phenyls. Further, previous Investigations have shown that tro u t liver microsomes as compared to mouse liver microsomes are very inefficient at introducing a hydrox y l group into an aromatic nucleus such as biphenyl (ref. 16) and therefore the reported inability of tro u t to hydroxylate any chlorinated biphenyl is not surprising. F in a lly * fig u re 6 clearly demonstrates an inter esting relationship between the dynamics o f uptake in the present study, that is, the change in concentration of the biphenyls in the fish after labeled compounds are added to the water of the fish, and the percent unextractable radioactivity in Gamhusia a ffin is Baird and Girard in the 33-day model ecosystem experiment. This is a logical relationship, as it would be expected. The greater the metabolic susceptibility, the larger the amount of incorporation o f 14 C radioactivity into unextractable polar compounds. This study emphasizes the need fo r further research and information on uptake and metabolism of polychlo rinated biphenyls by aquatic organisms. It has been established that 2,5,2'-trichlorobiphenyl is quite suscep tib le to m etabolism by the green sunfish, and 2,5,2',5'-tetrachlorobiphenyl and 2,4,5,2',5'-pentachlorobiphenyf are much less susceptible. These latter two chlorinated biphenyls, especially the pentachloro isomer, resemble the relatively metabolic inert chlorinated hydrocarbons DDT and DDE. Much of the previous w ork, and this paper, deal w ith the qualitative assess ment of metabolic susceptibility as a function of number of chloro substituents. This type of information is useful as it provides the background data for w ork that desper ately needs to be done on the effect of chlorine isomer distribution on metabolic susceptibility, and, even more important, the further structural elucidation of the hydroxylated chlorinated biphenyls. ACKNOWLEDGMENTS The authors want to thank Dr. Ching-Chieh Yu, Janet Matusumoto, and M. Kathryn McClendon for their skillful assistance during this work. This investigation was supported in part by the Illinois Natural History Survey, the Illinois Agricultural Experiment Station, Regional Project NC 96; U.S. Environmental Protection Agency Grant No. EPA 800736; U.S. Department o f the Interior Grant No. 14-31-000-3879; and a grant to RLM fro m U.S. D epartm ent o f the In te rio r No. 14-31-0001-3273, Project No. B-050-ILL. GENP 005793 241 774442 REFERENCES 1. C. Henderson, A. Inglis, and W. L. Johnson, "Fall 1969 National Pesticide Monitoring Program/' Pest. M onit. J ., Vol. 5 (1971), p. 1. 2. J. H. Koeman, M. C, Ten Noever De Brauw, and R. H. Devos, Nature, Vol. 221 (1969), p. 1126. 3. V. Z itko, Butt. Environ. Contam. Toxicol., V ol. 6 (1971), p. 464. 4. R. W. Risebrough, R. Reiche, D. B. Peakall, S. G. Herman, and Min Kirven, Nature Vol. 220 (1968), p. 1098. 5. J. Jensen, A. G. Johnels, S. Olsson, and G. Otter* find. Nature, Vol. 224 (1969), p. 247. 6. R. G. Webb and A. C.* McCall, J. Assoc. O ffice. A gri. Chem., Vol 55 (1972), p. 746. 7. Robert L. Metcalf, James R. Sanborn, Po-Yung Lu, and Donald E. Nye, unpublished data, 1974. 8. Robert L. Metcalf, Gurchuran K. Sangha,and Inder P. Kapoor, Environ. Sci. Techno/., Vol. 5 (1971), p. 709. 9. Keturah A. Reinbold, Inder P. Kapoor, William i . Childers, Willis N. Bruce, and Robert L. Metcalf, t i l Nat. Survey B utt., Vol. 30 (1971), p. 405. 10. D. L. Grant, W. E. T. Phillips, and D. C. Villeneuve, D.C. Butt. Environ. Contam. Toxicoi., Vol. 6 (1971) , p.102. 11. S. Bailey and P. J. Bunyan, Nature, Vol. 236 (1972) , p. 34. 12. W. D. Block and H. H. Cornish, J. Bio/. Chem., Vol. (1959). p.3301. 13. 0 . Hutzinger, A. Inglis, and W. L. Johnson, "Fall 169 National Pesticide Monitoring Program," Pest. M o n it J ., Vol. 5(1971), p. 1. 14. W. Greb, W. Klein, F. Coulston, L. Goldberg, and F. . Karte, Chemosphere, Vol. 2 (1973), p. 143. 15. Hidetoshi Yoshimura and Hiroaki Yammamoto, Chem. Pharm. Butt., Vol. 21 (1973), p. 2239. 16. P. J. Creaven, D. V. Parke, and R. T. Williams, Biochem. J., Vol. 96 (1965), p. 889. 242 774443 LABORATORY MODEL ECOSYSTEM STUDIES OF THE DEGRADATION AND FATE OF RADIOLABELED TRI-, TETRA-, AND PENTACHLOROBIPHENYL COMPARED WITH DDE Robert L. Metcalf, James R. Sanborn, Ph.D., Po-Yung Lu, and Donald Nye* A bstract Radiolabeled tri-, tetra-, and pentachlorobiphenyls (PCB) and DDE were studied in a laboratory m odel eco system fo r degradation pathways, and biom agnification in alga, snail, m osquito, and fish. Trichlorobiphenyl was degraded in a ll die organisms o f the m odel ecosystem much more rapidly than tetrach/or- and pentachlorobiphenyt. Pentachlorobiphenyl was approxim ately as per sistent as DDE. There was a linear relationship between Hpid/water p a rtitio n and ecological m agnification and between water s o lu b ility and ecological m agnification. No evidence o f conversion o f DDE to PCB was detected. The laboratory model ecosystem previously de scribed (ref. 1) has been employed fo r the estimation of the environmental fate of DDT and a number of its analogues (refs. 2,3,4) and fo r study of aldrin, dieldrin, endrin, mirex, lindane, and hexachlorobenzene (ref. 5). The methodology developed has yielded useful informa tion about (1) the degradation pathways of the various xenobiotics, (2) the toxic effects of the compounds and their degradation products, (3) their comparative biomagnification and food chain concentration, and (4) their comparative biodegradability; all in organisms of five phyla linked in several food chains. This information has proved o f value in characterizing the potential envi ronmental pollutant effects o f candidate insecticides (refs. 4,6) and of plasticizers (ref. 7). In this paper we report the application of these techniques to a better understanding of the comparative environmental prop erties o f trichloro-, tetrachloro-, and pentachlorobi p h e n y l (PCB's), and o f dichlorodiphenyl-dichloroethylene (DDE) the persistent DDT degradation prod uct. Methods and materials The laboratory model ecosystem evaluation was carried out in a small glass aquarium w ith a sloping ter restrial-aquatic interface of pure white sand exactly as ` Department of Entomology and Environmental Studies Institute. University of Illinois and Illinois Natural History Sur vey, Urbana-Champaign, Urbana, Illinois 61801. A ll figures and tables reproduced and text adapted from Archives of Environmental Contamination & Toxicology. Vol. 3, No. 2 (1975), pp. 151-165. 1975 by Springer-Verlag New York Inc. Used by permission. previously described (ref. 1). The 14C-radiolabeled com pounds were applied quantitatively from acetone solu tion at 5.0 mg (or ca. 1 kg per ha) to Sorghum vulgare seedlings grown in die terrestrial portion. The treated leaves were consumed by fourth instar salt marsh cater pillar larvae Estigmene acrea, whose activities and fecal products contaminated the aquatic portion of the system. The radiolabeled products were transferred through several food chains, e.g., alga iOedogonium cardiacum) -* snail {Physa); plankton -* water flea (Daphnia magna) -* mosquito {Cu/ex pipiens quinquefasciatus) - fish [Gambusia a ffin is). A fter 33 days in an environmental chamber at 26 C and a 12-hr photoperiod at 5,000 foot candles simulated daylight, the organisms were extracted w ith acetonitrile and the 14 C-radiolabeled compounds evaluated by TLC on silica gel containing fluorescent marker (E. Merck GF-254) and radioautography on noscreen X-ray film . Liquid scintillation counting of the individual components was done in cocktail D (5 g PPO and 100 g naphthalene in dioxane to make 1 liter) and counts were corrected to dpm by using channels ratio quenching correction. The residues, after extraction, were counted by total combustion to 14C 0 3 by the Schoniger oxygen flask technique (ref. 8) to determine the unextractable radioactivity. Whenever possible, the identity cvf individual components on the TLC plates was determined by cochromatography w ith known standards and by extraction and mass spectrometry. Radiolabeled Compounds. The individual R e labeled PCB's were obtained from M ailinkrodt, St. Louis, Missouri. They were: 2, 5,2'-trichlorobiphenyl (2,5-dichlorophenyl-ring-UL-14C), 9.91 mCl per mmole w ith > 9 B percent radiopurity and 41.5 percent Cl, and a p rin c ip a l c o n s titu e n t o f Aroclor 1242 (ref. 9); 2,5,2',5'*tetrach Iorobi phenyl (ring-UL-14C), 9.87 mCi per mmole w ith > 9 8 percent radiopurity and 48.7 per cent Cl, and a principal constituent o f Aroclor 1248 ( r e f.9 ); and 2,4,5,2',5'-pentachlorobiphenyl (2,,5*dichlorophenyl- ring-UL-14C), 9.87 mCi per mmole with > 9 8 percent radiopurity and 54.4 percent Cl, a principal constituent of Aroclor 1254 (ref. 9). 14 C la b e le d 2,2-bis-(p-chlorophenyl)-1,1-dichloroethylene (DDE) was prepared from 14C-ring-UL p,p'-DDT obtained from the Radiochemical Centre, Amersham, England, 5.48 mCi per mmole, by dehydrochlorinating with 1.0 M alcoholic KOH, and purifying on GENP 005795 243 774444 a silicic acid column with hexane elution to 99 percent radiopurity. Results PCB's. The movement of ,4 C radioactivity from Sorghum plants into the water phase of the model eco system is shown in figure 1. AH three chlorinated bi phenyls reached a maximum concentration in water at about 7 days after treatment and the levels of contam ination declined as the PCB's were taken up by the organisms o f the system. The levels o f the chlorinated biphenyls in the water phase (table 1) were in the ppb range, below the water solubility o f the compounds as determined by radiotracer technique (table 2). Radioautographs of the extracts from the compo* nents o f the model system after TLC are shown in figure 2. The data in table 1 represent the quantitative distribu tion of the l 4 C in the spots on the TLC plates. The results fo r the three PCB's are also expressed in table 2 in terms o f ecological magnification (E.M.) (ppm in organism/ppm in water) and of biodegradability index (B.l.) (ppm polar degradation products/ppm nonpolar products). The E.M. values for the parent compounds increased substantially w ith the number o f chlorine atoms, from tr ichlorobiphenyl (41 . percent Cl) to tetrachlorobiphenyl (48.7 percent Cl) to pentachlorobiphenyl (54.4 percent Cl). Conversely, the B.l. values decreased with increasing degree o f chlorine. This con sistent and regular behavior gives added confidence that these parameters are ecologically significant (ref, 4) and must be a function of the number of C-H bonds available fo r hydroxylation by microsomal oxidations in the v a rio u s o rg a n is m s . The spots o f low Rf value (0.02-0.06), figure 2, are presumably hydroxylated PCB compounds and the polar radioactivity (Rf 0.0) is thought to consist o f conjugates o f these compounds. Wallnofer et al. (ref. 10) have found 4-chloro-4'-hydroxybiphenyl as a metabolite of 4-chlorobiphenyl from soil fungus, Rhizopus faponicus. Yoshimura and Yammamoto (ref. 11) have reported the 5-hydroxy Iated de rivative as the major and the 3-hydroxy lated derivative as the minor excretion product o f 2,4,3',4'-tetrachlorobiphenyl in the rat. Hutzinger et al. (ref. 12) have show n th a t ra t and pigeon could hydroxylate 2,5,2',5'-tetrachlorobiphenyl but they could not detect hydroxylated metabolites in brook trou t. However, the 96LS0 Figure 1. Movement of total 14C radioactivity from plants into the water phase of the model ecosystem and uptake by organisms. 244 774445 Table 1. amDniodsdtretihlbeeuicrtioodsneygsorteafmdcahtlioorninpartoeddubcitpshienntyhles Chlorinated biphenyl equivalents (ppm) Hs O 1.2,5,2'-trichlorobiphenyl total 14C 0.03845 Unknown I t r i(cRh lfo0r o.6b6ip)h e n y l U n(Rknfo`0w.5n61)1 U n(Rknfo0w.2n3I)II U n(Rknfo0w.1n0I)V U n(Rknfo0w.0n6V) PUon((lRRkarnffo(00Rw..00fn340V)).0I) U nex tractab le 0.00015 0.00020 0.00005 -- 0.00055 0.00040 00 ..00 20 20 6450 0.01405 Oed(oaglgoan)ium 23.2155 15.9575 1.4630 0.0520 00 .. 05 61 88 55 5.1560 (Pshnyasial) (mCosuqleuxito. ) Ga(mfibshu)sia 31.2015 18.9720 1.1590 0.6480 0.9735 0.5460 0.2205 0.4410 3.9315 4.3100 2.7030 1.1995 0.1630 + -- 0.4795 0.8610 3.2055 0.2085 1.2800 0.1595 * -- 0.9985 0.5590 11.2te,t5b(rR,ia2pcfh'hl0Sel.on'4<ry8tole1btt)roiaptcahhleln1o4yroCl Unknown I (Rr 0.23) ' U n(Rknfo0w.0n4I)I PUonleaxr(trRafct0a.b0l)e. 0.02065 0.00120 0.00005 00 ..00 01 12 52 55 0.00560 23.6845 21.5975* 0.3220 0.1030 0.3275 1.3345 53.7465 47.3275 0.7560 0.4360 3.9850 1.2420 14.5333 12.6745 0.1070 -- 0.9670 0.7850 15.5685 14.2360 0.0890 -- 0.8S45 0.3900 III.2 t5clh2l'o,4ro',5b'i-ppheenntyalp etnotat ac hl 1io4rCo biphenyl U n(Rknfo0w.5n5I ) U n(Rknfo0w.4n6I)I U n(Rknfo0w.3n9I)II U n(Rknfo0w.2n1I)V U n(Rknfo0w.0n4)V PUon(lReaxrf t(r0Ra.c0f t20a)b.0le) 0.04340 * 0.00985 -- 0.00020 0.00015 0.00030 000 ...000 020 308 855 550 62.4660 53.8440 0.6850 0.5080 0.1425 -- 01..26527650 5.4330 TLC with hexane (Skellysolve B,bp 60-68 C). 633.0165 181.4565 127.6945 587.3545 8.6210 2.2490 1.9365 0.5000 176..45956550 8.3040 170.8480 2.4070 _ 1.3195 1.0520 -- -- 2.6745 3.1555 119.7060 2.5380 0.5810 0.3285 021...734436551000 ' GENP 005797 245 774446 Table 2. Ecological magnification (E.M.) and biodegradability index (B .U of PCB's and DDE compared with water solubility and partition coefficient Chemical H?0 solubility (ppb) tri-CI-PCB 16 tetra-Cl-PCB 16 pcnta-CI-PCB 19 DDE 1.3 Partition coefficient Ecological magnification (E.M.) Alga Snail Mosquito Fish 7,803 7,315 5,795 815 6,400 8,126 17,997 39,439 10,562 11,863 16,037 5,464 59,629 17,345 12,152 18,893 11,251 36,342 S9.390 12,037 Biodegradability index (B.l.) Alga Snail Mosquito Fish 0.30 0.17 0.35 0.60 0.015 0.082 0.076 0.060 0.029 0.027 0.0134 0.019 0.069 0.049 0.033 0.050 ci ci Cl ct * Cl Cl Cl A F M STD S H20 H20 hyd. Figure 2A. Radioautogram of TLC plate con taining extracts of water and organisms treated with 2,5,2*trichlorobiphenyl. A (alga), F (fish), M (mosquito larva), S (snail) and STD (,4 C-radiolabeled compound). A F M STD S H20 H20 hyd. Figure 2B. Radioautogram of TLC plate con taining extracts of water and or ganisms treated with 2,5,2',5'tetrach loro biphenyl. A (alga), F (fish), M (mosquito larva), S (snail) and STD (14C-radiolabeled compound). 246 774447 A A F M STD S Hz0 H20 hyd. Figure 2C. Radioautogram of TLC plate con taining extracts of water and or ganisms treated with 2,4,5,2',5'pentachlorobiphenyl. A (alga), F (fish), M (mosquito larva), S (snail) and STD ( 14C-radiolabeIed compound). A F M STD S HzO Figure 2D. Radioautogram of TLC plate con taining extracts of water and or- . ganisms treated with DDE. A (alga), F (fish), M (mosquito larva), S (snail) and STD (14C-radiolabeled compound). amounts of polar material in Gambusia (figure 2, table 1) suggest that this fish is able to slowly hydroxylate this tetrachlorobiphenyl. The pentachlorobiphenyl with B.l. values of 0.019 to 0.027 in fish and snail is very comparable in model ecosystem behavior to DDT, B.l. 0,015 and 0.044 (ref. 4) and this suggests that the two compounds should behave similarly in the environment (ref. 13). Properties of the tetrachlorobiphenyl were similar to those o f the pentachlorobiphenyl (figure 2) but the trichJorobiphenyl was much more degradable. A prominent degradative product (R f 0.66) is stored in alga, snail, and mosquito larva in much greater quantities than the parent com pound. This compound is less polar (higher R^) in the hexane solvent than any of the three PCB isomers. As shown in table 1, it is magnified to very high values, 106.382X in alga and 126.480X in snail, is stored in lipids, and is highly persistent. Its presence in high amounts in alga and in the snail and mosquito, which are alga feeders, suggests that it might be formed by photo chemical processes during photosynthesis in the alga. This compound forms slowly and no traces of it were visible in 3-day uptake studies of trichlorobiphenyl by alga, snail, daphnia, mosquito, or fish (ref. 14) although it appeared in alga in 14-day studies. To date we have been unsuccessful in identifying the unknown by mass spectrometry.. DDE. This compound has been implicated as a possible environmental precursor o f PCB isomers through photooxidation reactions involving radical re arrangements to 3,6-dichlorofluorenone intermediates (refs. 15,16,17). Although such rearrangements could logically produce 4,4'-dichlorobiphenyl, it is d iffic u lt to see how trichloro- and tetrachlorobiphenyls could be 247 GENP 005799 774448 formed as suggested by Maugh (ref. 18). Moreover, Kerner <;t al. (ref. 19) could detect only bis-(p- chlorophenyl) chloroothylune (DDMU) after ultraviolet irradia tion of DOE. Because of the ecological importance of these possible rearrangements, we have reinvestigated the behavior of DDE in the model ecosystem (ref. 1) to determine if any PCB-like products could be formed un der the simulated daylight o f the model ecosystem (5,000 fo o t candles) in an environmental chamber. The radioautograph showing the fate o f pure DDE is present ed in figure 2. When the extracts o f water and organisms were developed on TLC plates w ith Skellysolve B (hex ane fraction) there was no trace of any 14C-labeled com pounds w ith f y values between 0.05 and 0.47 (DDE) or o f any less polar materials w ith higher values. Under these conditions, as shown in figure 2, trichlorobiphenyl has R, 0.43, tetrachlorobiphenyl R^ 0.50, and pentar chlorobiphenyl 0.53. Detection levels w ith the tech niques used are approximately 0.1 ng (e.g., spot at alga origin in DDE, figure 2) or about 0.00002 percent o f the total 14C applied. Thus under the model ecosystem con ditions, there is no evidence o f formation o f PCB isomers from DDE. DDE is extremely stable in the tissues of the living * organisms of the model ecosystem and is stored as ap- . proximately 92, 93, 95, and 97 percent of the total 14C in snail, alga, fish, and mosquito larva. The percent of unextractable l 4 C in these organisms ranged from 0.10 to 0.93 (table 3). The B.l. value fo r DDE in fish was 0.049 and the E.M. value 12,037 (compared w ith 0.032 and 27,358 found by Metcalf et al.) (ref. 1). From these values it is apparent that DDE is a more stable environ mental pollutant than 2,4,5,2',5r-pentachlorobiphenyl (table 1), which was stored in the organisms at 86 to 94 percent of the total radioactivity, w ith from 1.12 to 8.67 percent o f unextractable I4 C, and had a B.l. of 0.019 and an E.M. of 12,152 in fish. It is of interest that Sodergren (ref. 20), using a model aquatic ecosystem, found no major metabolic changes in DDE occurring in passage through a food chain into fish, although similar experiments w ith a polychlorinated biphenyl mixture (Clophen A) showed that the lower fractions w ith low chlorine content were degraded when transported through the food chain, as was 2,5,2'-trichlorobiphenyl in our experiments. How ever, m our studies (figure 2, table 3), the water phase contained several polar radiolabeled degradation prod ucts. These were resolved on silica gel into at least 11 d is tin c t c o m p o u n d s u sin g a s o lv e n t of benzene:dioxane:acetic acid (90:30:1) and we are pre sently attempting to identify the pathway o f DDE degra dation in the environment. Biomass Recovery. To determine the relative avail ability o f the various organisms o f the model ecosystem as reservoirs fo r the bioaccumulation o f the m icropol lutants studied, the total amounts o f 14C-labeled prod ucts recovered from the principal organisms o f the m od el ecosystem s treated w ith tri-, tetra-, and pentachloro-PCB's, and w ith DDE were evaluated, as shown in table 4. The evaluations were made on the basis o f total recovery o f the applied pollutant: o f recov ery o f the maximum amount o f pollutant in water (figure 1) fo r each of the four principal organisms, alga, snail, mosquito, and fish; and o f biomass recovery (four organisms) o f the total amount o f pollutant lost from water (figure 1). The figures o f table 4 are very revealing Table 3. Distribution of DOE and degradation products in the model ecosystem HzO Total i*C 0.00384 DDE (Rf 0.49J) 0.00062 Unknown 1(Rf 0.05) 0.00009 Polar ( Rf 0.0) 0.00223 Unextractable 0.0009 DDE equivalents (ppm) Oed(oaglgoan)ium (Pshnyaiial) (mCo suqleuxito ) 7.4720 6.9759 0.4881 0.0080 38.1958 H22.5325 0.8035 1:1612 0.3616 24.8588 36.8223 1.2448 0.1087 Ga(mfibshus) ia 7.8653 7.4632 0.3746 0.0275 aTLC w ith hexane (Skellysolve B, bp 60-68C). 248 774449 Table 4. Bbofiipomhmeoandsyesllsr,eeccaoonvsdyesrDyteDmoEf cfrholmorionragtaendisms % Recovery Alga Snail Mosquito % trichlorobiphenyl 14C in solution 0.18 0.015 0.0017 total *4C 0.033 0.0028 0.00032 (biomass) o f ,4 C lost from solution -- -- 0.45 te tra c h lo ro b ip h e n y l >4C in solution total 4C 3.33 0.28 1.04 0.088 0.23 0.019 (biomass) o f ,4 C lost from solution -- -- 8.7 pen tachlorobiph enyl 14C in solution total 4C 4.57 0.74 19.0 3.06 2.32 0.37 (biomass) o f i 4C lost from solution -- -- 57.2 * 4C in solution 22.4 4.03 total *4C 0.24 0.044 (biomass) o f 14C lost from solution -- -- 65.8 DDE 2.25 0.055 Fish 0.12 0.021 1.91 0.16 11.8 1.90 20.2 0.22 in terms of the biodegradability of the various com* pounds. The highest recoveries o f the 14C lost from solution were obtained from the organisms with DDE, 65.8 percent, and pentachlorobiphenyl, 57.2 percent. With tetrachlorobiphenyl, recoveries of 8.7 percent were still substantial, but with trichlorobiphenyl (recovery 0.45 percent), the compound was nearly completely degraded and excreted. Degradation in Salt Marsh Caterpillar. This animal was chosen, after considerable study, as the dispersing agent fo r the model ecosystem because it was able to ingest a large variety of organic compounds w itho ut apparent injury (ref. 14). The effects of passage o f the PCB isomers through the insect are of interest as repre senting the first stage in the biodegradation of these compounds. Figure 3 shows radioautographs o f TLC plates of extracts of feces and body homogenates from larvae feeding on about 30 pg of l 4 CPCB incorporated in a synthetic diet. Figure 3 and the quantitative evalua tion of the radioactivity in the various spots shown in table 5 demonstrate conclusively the much greater degra* d a b ilit y o f the tric h lo ro b ip h e n y l over the tetrachlorobiphenyl and pentachlorobiphenyl. With the trichloro compound, the caterpillar feces contained 91 percent o f the recovered 14C, w ith the remainder in the body hqmogenate, while w ith the tetrachloro- and pentachlorobiphenyls, the feces contained 21 percent and 24 percent o f the radioactivity. The unknown (Rf 0.05) found in feces after trichlorobiphenyl is probably the principal hydroxylated degradation product leading to the very large amount o f polar radioactivity. Whereas only low levels of trichlorobiphenyl were retained in the salt mar.sh caterpillar body, w ith tetrachloro* and pentachlorobiphenyl the major portion of I4 C was retained in the insect body. DDE passed through the salt marsh caterpillar largely unchanged, w ith 81 percent of the total radio activity recovered retained in the body homogenate and 19 percent in the fecal excreta (table 5). Ecological Magnification. The uptake and concen tration o f organic compounds by living organisms either directly or through food chains appear to be a function of two important factors: (1) their high lipid solbility and low water solubility, e.g., a large lipidAvater parti tion coefficient, and (2) their resistance to degradation by enzymatic processes, especially the m ultifunction 249 774450 GENP 005801 tri-Ci. tetra-CI pnto-CI Figure 3. Radioautogram of TLC plate con taining extracts of bodies and feces of salt marsh caterpillar larvae fed 14C-labeled 2,5,2'-tri-, 2,5,2',5'tetra-, and 2,4,5,2',5'-pentachlorobiphenyis. B (body homogenate), and F (fecal excreta). 250 774451 GENP 005802 Table 5. Metabolism of 14C-radiolabeled compounds by salt marsh caterpillar3 Body Feces A. 2,5,2'-trichlorobiphenyl total l4 C (%) Unknown I (Rf 0.531) trichlorobiphenyl (Rf 0.43) Unknown II (Rf 0.31) Unknown III (Rf 0.13) Unknown IV (R f 0.05) Unknown V (Rf 0.02) Polar (Rf 0.0) B. 2f5,2 ',5 ,-tetrachlorobiphenyl total *4C (% ) tetrachlorobiphenyl (Rf 0.50>) Unknown I (R f 0.41) Unknow n II (R f 0.05) Unknown III (Rf 0.03) Polar (R f 0.0) C. 2,5,2,,4',5'*pentachlorobiphenyl total I4C(% ) pentachlorobiphenyl (Rf 0.53a) Unknown 1 (Rf 0.46) Unknow n II (R f 0.39) Unknown III (Rf 0.03) Polar (R f 0.0) D. 2,2-M i-(p-chlorophenyl)-l,l-dichlaroethylene (DDE) total i 4C(%) DDE (Rf 0.49a) Polar (Rf 0.0) aTLC with hexane (SkeUysolve B, bp 60-68C). 8.66 0.64. 5.84 0.27 0.05 0.10 0.11 1.65 78.68 75.60 0.99 0.13 trace 1.96 75,86 74.00 0.74 0.62 0.08 0.42 80.59 76.88 3.71 91.34 8.91 0.37 0.12 4.67 0.92 76.35 21.32 15.08 1.36 0.20 4.64 1 24.14 20.70 0.74 0.56 0.08 2.06 19.41 19.37 0.04 utsiw UU5803 oxidase enzymes (ref. 14). Hamelink et al. (ref. 21) have suggested that the water insolubility of highly lipid* so lu b le compounds provides the driving force in producing lipid storage, through a series of simple parti tionings from water to lipids. We have correlated the E.M. values for the PCB's and DDE from the fish o f the model ecosystems with both water solubility (table 2) in figure 4, and with the octanol/water partition value (table 2) in figure 5. Because the values fo r the PCB's and DDE fall closely together, the relationships have been extended using values for aniline, anisle, benzoic acid, chlorobenzene, and nitrobenzene taken from other model ecosystem studies (ref. 22). For the limited num ber o f compounds included, the correlation between physical properties and biomagnification is excellent. The regression equation for log water solubility vs. log E.M. (figure 4) was: y = 4.4806 - 0.4732X: n = 9, r = - 0.9677. The regression equation fo r log partition coefficient (Mansch's n) vs. log E.M. (figure 5) was: y = -0 .7 5 0 4 + 1 .1 5 8 7 *: n = 9 , r = 0.9771. Thus fo r the organic compounds studied, the prop erties o f water solubility and octanol/water partition coefficient appear to provide a realistic estimate of the biological magnification found in living organisms. 251 774452 Figure 4. Plot o f log E.M. (ecological magnification) for fish vs. log water solubility (ppb). Figure 5. Plot of log E.M. (ecological magnification) for fish vs. log octanol/water partition coefficient. 252 774453 GENP 005804 ACKNOWLEDGMENTS This research was supported in part bv research grants from the U. S. Department of Interior, Office of Water Resources Research through the University of Illinois Water Resources Center Project B-050, Illinois; the National Science Foundation Grant Gl 39843X; the U. S. Environmental Protection Agency Grant R802022 and Grant R800736; and the Bureau o f Veterinary Medicine, Food and Drug Adm inistration, Contract FDA 72-116. REFERENCES 1. R. L. Metcalf, G. K. Sangha, and I. P. Kapoor, "A L a b o ra to ry Model Ecosystem/' Environ. Set. Techno!., V o l. 5 (1971). p. 709. 2. I. P. Kapoor, R. L. Metcalf, R. F. Nystrom, and G. K. Sangha, "C o m p ara tive M etabolism o f Methoxychlor, Methylchlor, and DDT in Mouse, In sects and in a Model Ecosystem/' J. Agr. Food Cftem., Vol. 18 (1970), p. 1145. 3. I. P. Kapoor, R. L. Metcalf, A. S. Hirwe, Po-Yung Lu, J. R. Coats, and R. F. Nystrom, "Comparative Metabolism o f DDT, Methylchlor, and Ethoxychlor in Mouse, Insects, and in a Model Ecosystem/* J. Agr. Food Chem., Vol. 20 (1972), p. 1. 4. I. P. Kapoor, R. L. Metcalf, A . S. Hirwe, J. R. Coats, and M. S. Khalsa, "Structure A ctivity Correlations o f Biodegradability o f DDT analogs," J. Agr. Food Chem., Vol. 21 (1973), p. 310. 5. R. L. Metcalf, I. P. Kapoor, Po-Yung Lu, C. K . Schuth, and P. Sherman, "Model Ecosystem Studies o f the Environmental Fate o f Six Organochlorine Pesticides," Environ. Heatth Persp. E xperi., Issue 4 (1973a), p. 35. 6. J. R. Costs, R. L. Metcalf, and I. P. Kapoor, "Metabo lis m o f th e M e th o x y c h lo r Isostere, Dianisylneopentane in Mouse, Insects, and a Model Ecosystem," Pesticide Biochem. Physio/., Vol. 4 (1974), p. 201. 7. R. L. Metcalf, G. M. Booth, C. K. Schuth, D. J. Hansen, and Po-Yung Lu, "Uptake and Fate of Di-2-ethylhexyl Phthalate in Aquatic Organisms and' in a Model Ecosystem," Environ. Heatth Persp. Expert., Issue 4 (1973b), p. 27. 8. R. G. Kelly, E. A. Peets, S. Gordon, and D. A . Buyske, "Determination o f l 4 C and 3 H in Biolog ical Samples by Schoniger Combustion and Liquid Scintillation Technique," AnaL Biochem., Vol. 2 (1961), P.267. 9. R. G. Webb and A. C. McCall, "Identities o f Poly chlorinated Biphenyl Isomers in Aroclors," J. Assoc. O ffic. Agr. Chem., Vol. 55 (1972), p. 746. 10. P. R. Wallnofer, G. Engelhardt, S. Safe, and D. H u tz in g e r, "M ic ro b ia l H yd ro xyla tio n of 4 -c h lo ro b ip h e n y l and 4,4*-dichlorobiphenyl," Chemosphere, Vol. 2 (1973), p. 69. 11. H. Yoshimura, and H. Yammamoto, "Metabolic Studies on Polychlorinated Biphenyls III. Complete Structure and Acute T o x ic ity o f the Metabolites of 2,4 ^ l ,4,-tetrachlorobiphenyl," Chem. Pharm. B u il., (Japan), 21,2239 (1973). 12. O. Hutzinger, D. M. Nash, S. Safe, A. S. W. DeFreitas, R. J. Norstrom, D. J. Wildish, and V. Zikkos, "Polychlorinated Biphenyls: Metabolic Be havior o f Pure Isomers in Pigeons, Rats, and Brook T ro u t," Science, V ol. 178 (1972), p. 312. 13. R. W. Risebrough, P. Rieche, D. B. Peakall, S. G. H e rm a n , and M. N. Kirven, " Polychlorinated Biphenyls in the Global Ecosystem," Nature, Vol. 220 (1968), P.1098. 14. R. L. Metcalf, Po-Yung Lu, and I. P. Kapoor, "Environmental D istribution and Metabolic Fate of Key Industrial Pollutants and Pesticides in a Model Ecosystem/' U nivJlII. Water Resources Center, Re port No. 69, Project B-050 Illinois, 1973. 15. J. R. Plimmer, U. I. Klingelbiel, and B. E. Hummer, "Photooxidation of DDT and D D E ," Science, Vol. 167 (1970), p. 67. 16. D. B. Peakall and J. L. Lincer, "Polychlorinated Biphenyls, Another Long-Life Widespread Chemical . in the Environment/* Bioscience, Vol. 20 (1970), p. 958. , 17. K. W. Moilanen and D. G. Crosby, "Vapor-Phase Phbtodecomposition o f p.p'-DDT and its Relatives," Abstract No. 27, 1973, 165th Meeting American Chemical Society. 18. T. H. Maugh, II, "D D T : An Unrecognized Source of Polychlorinated Biphenyls," Science, Vol. 1180 (1973), p.578. 19. I. Kerner, W. Klein, and F. Korte, "Photochemische R e a ctio n e n von 1,1-dichloro-2*(p,p- D ie h l o r oethylene) D D E/* Tetrahedron, Vol. 28 (1972), p. 1575. 20. A. Sodergren, 'T ransport, Distribution, and Degra dation of Chlorinated Hydrocarbon Residues in Aquatic Model Ecosystems/* Oikos, Vol. 24 (1973), p. 30. 21. J. L. Hamelink, R. C. Waybrant, and R. C. Ball, " A Proposal: Exchange Equilibria Control the Degree Chlorinated Hydrocarbons are Biologically Magni fied in Lentic Environm ents/' Trans. Am . Fisheries Soc., Vol. 100 (1971), p. 207. 22. Po-Yung Lu, and R. L. Metcalf, "Degradation and Environmental Fate o f Radiolabeled Benzene Deriv atives in a Model Aquatic Ecosystem/* manuscript in preparation. GENP 005805 253 774454 ENVIRONMENTAL TRANSPORT AND OCCURRENCE OF PCB'i IN 1975 Ian C. T. Nisbet, Ph.D.* o o o oug o\ CN A b s tra c t Despite curtailm ent o f some dispersive uses, envi ronm ental levels and rates o f transport o f PCB's have n o t changed greatly since 1972. This is probably due in p a rt io the continued release o f m aterials in service p rio r to 1971 and in p a rt to rim e lags in environm ental transport and dissipation. Surprisingly high concentrations o f PCB's m atching A ro clo r 1254 are s tilt being found in a ir, in precipita tion, and in d ry fa llo u t As yet, there is little evidence th at significant quan tities o f PCB's are being leached from dumps. Human exposure to PCB's is h ig ly variable. Some sport fishermen and breast-fed infants have especially high intakes. A lm ost nothing is known about the environm ental behavior o f chlorinated dibenzofurans. I think the organizers o f the conference may have expected me to compose a global transport model while this session was going on. I have not attempted to do this, except to make some quick calculations on the back of an envelope. My general conclusion from what I have heard to* day and yesterday about the release and concentrations of PCB's in the environment in 1975 is that most of what we have learned since 1972 is reasonably consistent w ith the very crude model that Sarofim and I con structed in 1972. That is not to say that the model was right. A ll it says is that our ignorance about the exact rates and routes o f transport o f PCB's in the environ ment is nearly as profound in 1975 as it was in 1972. I have found only one area where there does seem to be substantial quantitative discrepancy between our 1972 model and the data generated subsequently; that is,the numbers reported to us here and published in the interim ,t on concentrations in air and air transport. We have heard some numbers o f the order o f 200 parts per trillio n of PCB's in snowmelt, reports o f numbers o f the ` Director. Scientific Staff, Massachusetts Audubon Society, Lincoln, Massachusetts 01773. tP e ris a n , B., O rn is S c a n d in a v ic a , 2:127-135 (1971); SOdergren, A P C B -C o n fa re n c e / / J 9 7 2 :15-18 (National Swedish Environment Protection Board, 1973); Bengtson, A. A. and A. Sddergren, A m b io , 3:84-86 (1974); Munson, T. O., Ch. 6 in U p p e r B a y S u rv e y (Westinghouse Electric Corporation, Final Re port to the Maryland Department of Natural Resources, in press). order o f 100 nanograms per cubic meter for concentra tion o f PCB's in air, and the number of the order o f 70 -- 200 and locally up to 2,000 nanograms per square meter per day fo r rates o f dry deposition. These are all somewhat higher than we anticipated on the basis of our model. If we extrapolate up on the back of an envelope basis from 200 nanograms per square meter per day over the whole continent, that comes out to be something of the order of 1,000 tons. Similarly, if you extrapolate up from 100 parts per trillio n in rainfall over the entire continent, you get something o f the order of 1,000 tons. Now, it may be that the numbers we heard were biased toward urban areas, where the concentration of PCB's may be higher than they ere in the United States at a whole. Even so, we are now being given numbers that suggest that at least 1,000 tons of PCB's per year are falling out onto the terrestrial environment of the United States in rain and particulate matter. That is about as large as numbers we had envisaged fo r total releases o f PCB's into the air in 1971. What makes the problem worse is that nearly all the PCB's that are found in dry fallout, in the air, and in precipitation look like Aroclor 1254,wherea$ we had thought that only about half o f the materials released into the environment even in 1971 would be Aroclor 1254, and a good deal of them would be Aroclor 1242. So it seems to me that aerial releases and aerial transport are rather larger than anything we could account for according to our knowledge o f the uses and , releases that we surveyed in 1972. We need to find out where all this material in the air resembling A ro do r 1254 is actually coming from . One possibility is that it may be coming from leaks . from supposedly sealed uses. Perhaps we ought to be looking at transformers to see how much PCB's vaporize from them. I would now like to go to the six questions which I posed at the beginning o f this session and see what we have learned in the course o f this conference toward solving these outstanding problems. 1. What happens to chlorinated dibenzofurans in the environment? I think the answer is that still we know almost nothing. We know they are being released into the environment, since they are present in smalt quanti ties in commercial PCB's. Dr. Kuratsune in his presenta tion yesterday indicated that they are actually formed in the environment during use, and Dr. McKinney's presen tation suggested they might be formed by metabolism 254 774455 -ider certain circumstances. On the other hand, Dr. iehroutjh's presentation suggested that they are not retained in the bodies of birds even when they are ingested; that conflicts with Dr. Kuratsune's information that they are retained extraordinarily efficiently in human tissue. 2. What happens to PCB's in dumps? Again, we know almost nothing. Some numbers were mentioned yester day fo r water leaking out of dumps; I did some back-ofthe-envelope calculations which suggested that the quantities of PCB's escaping are not yet very significant. One is talking about quantities of the order of hundreds of kilograms per year nationwide--certainly not more than a few tons. 3. Are PCB's in sediments going to be covered up or are they going to be continually recycled? There have been some hints in what has been said today that they are going to be recycled. The information from Ms. McDermott about PCB's in areas where there is shipping activity, and information from Dr. Munson about the movement of PCB's in suspended sediments around Chesapeake Bay suggests that these PCB's in shallow waters are not going to stay there and be covered up and disappear. They are going to be w ith us fo r a long time into the future. 4. Is it correct th at tetrachioro-biphenyls and lower hlorinated species are rapidly degraded and is there sig nificant human exposure to these lower species? I think that we have had very adequate evidence here that tetrachloro isomers are indeed degraded rather rapidly, but not as rapidly as we would like. Dr. Sanborn's pres entation just now suggested that in fish the major d iffer ence in the efficiency o f uptake, retention, and metabo lism comes between trichlorobiphenyls and tetrachiorobiphenyls, and that fish do indeed retain tetrachlorobphenyls fairly efficiently. That was supported by data from the National Fish Monitoring Program, which suggested that a substantial fraction of the PCB's in the fish look like Aroclor 1242 and 1248; that means that they include substantial quantities o f tetrachlorobiphenyls. This in turn implies that humans are exposed to tetrachiorobiphenyls. Although the tetrachlorobiphenyls appear to be rare in human tissue, what that tells us is that humans do n ot retain tetrachlorobiphenyls. It does not tell us that they are not exposed to them. This has some important implications from the regu latory point of view. We may have to consider, fo r ex ample, whether Aroclor 1016 is environmentally " safe/' in the sense that modest releases can be regarded as acceptable. These data indicate that releases of Aroclor 1016 into water w ill lead to human exposure, at least to tetrachlorobiphenyls. 5. What is the extent of human exposure? The data derive from tw o sides, monitoring o f human tissue and monitoring of human food. Human tissue monitoring tells us that human exposure is very widespread. Human food monitoring tells us that most PCB's in human food are in fish. Unfortunately, that makes it very d iffic u lt to esti mate human exposure quantitatively, because we know from the fish monitoring program that the levels of PCB's in fish are extraordinarily variable in space. Despite the large number o f samples that have been taken by the Canadian program and by the FDA, it is very d iffic u lt to define an average exposure. I would go so far as to say that an " average" exposure is a meaning less concept, because some individuals who live, in areas where fish residues are high w ill get exposures 100 times greater than the average, whereas those persons who live in areas where there is little contamination, or who do not like fish, w ill get very tittle. Nevertheless, we do have some numbers for human dietary exposure. The Total Diet Program in the United States gave a figure o f the order of 9 micrograms per day fo r the intake of the average adult. I also did some calcu lations from Mr. Graham's figures on the Canadian com mercial fish to see how many kilograms of PCB's were brought in in Canadian commercial fish and what frac tio n was eaten. That led me to a figure around 5 micrograms per day fo r the average intake of the average per son in the Canadian population. We have to remember that the average adult does not eat much fish. Unfortunately, these figures are quite misleading because it is very easy fo r an individual who is a sports fisherman and who catches salmon, or trou t, or chub to take in very much more than that. One calculation in our 1972 paper indicated that it would be very easy for a fisherman or a member o f his fam ily to average 300 micrograms per day: this would represent about 4 micrograms per kilogram per day fo r an adult. One important point is that exposure o f breast-fed infants is likely to be very much greater than that o f any adult, even- an individual who likes fish. Although Dr. Kutz did not give numerical estimates of PCB levels in human m ilk in this session; earlier data suggest that a typical level would be around 30 parts per billion .* This leads to an estimate o f 4--5 micrograms per kilogram per day intake for the average breast-fed infant. There would PCS levels reported in human m ilk have been in the range 10--100 ppb: Risebrough, R. W-, and V. Brodlne, E n v iro n m e n t 12:16-27 11969): Westoo, G., Noren, K., and M. Andersson, Var F d d a , 22:10-31 (19701; Acker, L., and E. Schulte, N a tu rw is s e n sch a fte n . 57:497 (1970); Savage, E. P., Tessari, J. D., Malberg, J. W., Wheeler, H. W., and J. R. Bagby, P e s tic id e s M o n i to r in g J o u rn a l, 7:1-5 (1973). A concentration of about 30 ppb would correspond to the median level of about 1 ppm reported in human fat. GENP 005807 255 774456 be many above the average and many below. -Accordingly, when considering averages, we should remember that certain individuals are going to get 10 to 100 times the exposure o f the average person, as calcu lated from an average diet. 6. The m ost c o m p lic a te d q u e s tio n posed in 1972: what would be the effect o f Monsanto's curtail* ment o f dispersive uses? A number o f speakers yesterday and today have talked about decreases o f PCB levels in certain areas or compartments of the environment. For example, there have been decreases in the total dietary intake estimated from the FDA Total Diet Program, in the frequency o f findings o f PCB's in m ilk and fish in the FDA's surveillance samples, and in runoff into the Southern California coastal waters. On the other hand, we have also heard about some levels that have not changed, particularly levels in fish in Lake Michigan. There are three reasons why the curtailment o f sales by Monsanto in 1971 should n ot have been expected to lead to an immediate reduction in environmental levels. One is that not all the closed system uses are actually closed. There are some losses that we heard about today, even from transformer and capacitor uses, which are systems as closed as we are likely to get. Secondly, and more important, there is still a large backlog of products containing PCB's, that were in service prior to 1971, which are still in service and are still being discarded and still leaching. Some o f the users o f hydraulic fluids, he? transfer fluids, compressors, and so on, are probably stii. using PCB's that they had several* years ago. Certainly the scrapping o f capacitors and any losses that may result from disposal o f transformers are going to lead to releases fo r years into the future. Finally, there is an environmental inertia: it takes a long time after the input into the environment is cut o ff fo r the levels in fish, fo r example, to go down. The tim e lags w ill depend on the part of the system under con sideration; i t is evidently quite short fo r mussels in Southern California, but Is longer fo r the fish in the same area. Time lags have been quite short fo r the star lings, which reflect terrestrial uses, and fo r soil residues. The time lag is likely to be long fo r somewhere like Lake Michigan, which is a closed system, w ith a large reservoir of PCB's in the sediment. So I think we should not have hoped fo r a very rapid decline in PCB's since 1971. On the other hand, it has been somewhat dis-* appointing that i t has been so d iffic u lt to fin d any change in the firs t 3 or 4 years. One of the longest time lags o f all is likely to be in human tissue, because there is evidence that PCB's are retained fo r an extremely long tim e in human tissue. We w ill probably have to wait- fo r some considerable tim e after PCB levels have declined in fish before we see a significant decline in human tissue residues. o oo oo o co 256 7?4457 GENERAL DISCUSSION OF SESSION III D R . JOSEPH HIGHLAND (Environmental Defense Fund. Washington, D.C.): I want to ask Dr. Jelinek about the survey for fresh fish. Were there many differences in the last several years in the program which might lead to differences in the levels of the species. 1 was wondering if you could tell us a little b it more about that. I am not very clear on what differences you are talking about. DR. CHARLES JELINEK (Food and Drug Administra tion, Washington, D.C.): First of all, one of the big differences is in the fact that all o f our activities included compliance followups when we found any species or areas that had high levels. And we are going to dig in on that to find o ut just how much of a problem it is. Obviously, from a statistical standpoint, that would throw things way o ut o f whack. You are not getting representative sampling. That is one big difference, in the years where you have a higher proportion o f that, you are apt to have a higher proportion o f violative samples. In our comprehensive fish survey program, which we carried out in 1973 and half of 1974, we included saltwater and freshwater fish. So again, you are probably going to have pretty low fre quency o f high findings, because we did pick up a lo t o f saltwater fish there. In our regular pesticide surveillance program, that is carried out more w ithin the confines o f the United States, although there are some coastal water fish that might be picked up, so that would sort o f be in between these two activi ties. Where you try to combine all these together, it is just impossible to decide, at least w ith the data that we have, whether there have any changes. DR. JAMES R. SANBORN (Illinois Natural History Survey, Urbana, Illinois): Our national monitoring program does look at three types of fishes, the predator, and one intervening. Locating the fish in each sampling does create a problem. So we get a cross section of the fish's species. We do notice that many species have a much higher fat content than others. And even if there is a variation within those species as to their body conditions, you would find a correct relationship in the amount o f fat and the age o f the fish. Consequently, when we look at those fish -lake tro u t can exist in those environ ments w ithin a period o f time and gather a rather substantial amount o f adipose tissue. The goldfish, fo r example, is a very fat fish. You w ill find it loaded with PCB's and pesticides. MR. DONALD TESLACK (EPA): I'd like to find out if there is any data--how does 99 percent average? DR. JELIN EK : I don't believe I have that figure here, and I would hate to speak from memory, sir. If you want to, you know, you can leave me your name and I can see-- DR. IAN C. NISBET (Massachusetts Audubon Society, Lincoln, Massachusetts): Speaking from memory, I believe it would be 95 percent. DR. ROBERT GOLDEN (Environmental Protection Agency, Washington, D.C.): I understand that fish meal is used to feed poultry extensively. Is there any information available possibly on secondary exposure to humans? DR. JELIN EK: Well, these levels that we are finding now in poultry, or rather USDA is the one who monitors poultry, are exceedingly low. In the one slide there, the 1 percent o f poultry that the fin d ings were on were down around 1 ppm or something like that. Also, I would say this; our tolerance for PCB's in finished animal feed is two-tenths of a ppm, which is just above the limits of our analytical methods fo r accurate reproducible quantitative results of animal feed. So we set the tolerance there at almost what you would call the analytical nondetectable method fo r enforcement purposes. GENP 005809 257 774458 20 November 1975 Session IV : ECOLOGICAL EFFECTS AND EXPOSURE Donald I. Mount, Ph.D.* Session Chairman ' Director, Environmental Research Laboratory, Environmental Protection Agency, D uluth, Minnesota. Preceding page blank 259 "774459 GENP 005810 INTRODUCTORY REMARKS Donald I. Mount, Ph.D. Not being a back*of-the envelope modeler like Dr. Nisbet, I am not going to try to play the role that he did. But I do thinkothere are two or three very quick com ments that might help in moving into our discussion. First of all, it is worth pointing out that there are three primary reasons to be concerned about the impact o f pollutants on aquatic organisms. First and most ob vious are the effects of pollutants on the organisms themselves. Perhaps less obvious is the warning that when residues accumulate in aquatic organisms, poten tial hazards to human health may exist. We have heard about the impact o f residues in human food on humans. I think it is worth emphasizing that essentially 100 percent of the organism's diet has residues unlike those in humans. Therefore, the signifi cance of a given concentration o f PCB's in the food of an animal such as the mink may be quite different than it is to a human. I had talked with Dr. Nisbet before the conference and we agreed in the upcoming session to discuss resi dues only where they relate to effects on the organisms carrying them. I have noted as I have sat in the audience that it has been very d iffic u lt to tell whether the speaker is saying parts per billion or parts per m illion. So I have asked our speakers if they can refer to micrograms per liter and milligrams per liter. For those who cannot make the conversion, that is parts per billion and parts per m illion, respectively. So, if a speaker says milligrams per liter, that is parts per m illion. I would like now to start w ith our papers and we would like to reverse the position o f the first two papers, because the first one is to deal with the information that was available up to 1972 regarding the effects o f PCB's in nonhuman organisms. We are referring, o f course, to those organisms in the environment more so than domes tic animals. If you wonder why 1972 was picked, it correlates roughly w ith the report o f the PCB task force. GENP 005811 Preceding page blank 261 774460 SUMMARY OF RECENT INFORMATION REGARDING EFFECTS OF PCB's ON BIRDS AND MAMMALS A b s tra c t Rey C. Stendell* The significance o f PCB 5 to w ild animals depends both upon their lethal to x ic ity and th eir sublethalphys iological effects. The lethal dietary toxicides o f m ost A rociors to experim ental b ird s generally are less than those o f DDE, DDTt o r dieldrin. Effects o f PCBs on reproduction are a pt to have the m ost serious im pact on populations. These effects are d iffic u lt to evaluate. The ch ie f reproductive effects in chickens are reduced egg production and hatchability. D eform ities in chicks are common, and grow th rates o f young sometimes are de pressed. A dm inistration o f lo w d ietary levels o f PCBs to chickens, bobw hite quail, ringdoves, and mallards have n o t resulted in thinning o f eggshells. No tests o f shell thinning have been made w ith birds o f prey o r other c ritic a l species. Residues o f PCB s in w ild birds often are a t levels known to have caused reproductive im pairm ent in chickens. Species differences m ust be considered, however, and the significance o f these levels to w ild birds is very uncertain. PCBs have been im plicated in the reproductive failure and m o rta lity o f m ink from the Great Lakes re gion. High levels o f PCB s and organochlorine pesticides have been found in marine mammals and have been lin k ed w ith prem ature b irths in some species. Recent studies have shown th at some species o f bats m ay be sensitive to a lo w level o f PCB contam ination. INTRODUCTION The widespread distribution o f PCB's in the environ ment and their effects upon populations o f w ild birds and mammals are matters o f growing concern. Their presence has stimulated research to evaluate their role in the biosphere. This paper reviews recent literature (1972-1975) on the effects o f PCB's upon birds and mammals. EFFECTS ON BIRDS Lethal T o xicity Outright m ortality can affect populations. Measure ment of direct toxicity is an important first step in the evaluation of a chemical. Toxicities of different PCB's to young pheasants (Phasianus cotchicus), mallards (Anas ` Patuxent W ildlife Research Center, U.S. Fish and W ildlife Service, Laurel, Maryland. platyrhynchos), bobwhite quail {Colin us virginianus), and coturnix quail (C oturnix cotum ix) have been com pared w ith the toxicities o f DDT, dieldrin, and other insecticides (ref. 1). LCS0's fo r the PCB's were high. Tests o f six PC8 mixtures, containing 32 to 62 percent chlorine, showed that the toxicity increased w ith the percentage o f chlorine. The dietary toxicities of the Arociors were, w ith few exceptions, less than those of the four organochlorine pesticides used fo r comparison. Special tests w ith cotum ix quail showed that the toxic effects o f DDE and Aroclor 1254 were additive b ut not synergistic. In other studies, Aroclor 1254 was approxi mately as toxic as DDE to four species o f blackbirds (ref. 2). Redwinged blackbirds (Age/aius phoeniceus) were somewhat more susceptible to DDE than to PCB's. Regular oral doses from 10 to 210 mg Aroclor 1254 produced some m ortality among subadult pheasants (ref. 3). The amount and timing o f the m ortality were related to the dose. Heavier birds lived longer and lost the great est percentage of their body weight before death. Residues of PCB's in brains o f blackbirds given heavy doses o f Aroclor 1254 were diagnostic o f death (ref. 4); residues in brains o f birds that died varied from 349 to 763 ppm (wet weight) and were n ot above 301 ppm in survivors. In studies w ith pheasants given daily doses o f 210 mg o f Aroclor 1254, a brain residue level of 300 to 400 ppm generally indicated death due to PCB toxicosis (ref. 3). Residues of PCB's in livers and other tissues were more variable and of lesser value fo r diagn osing death. PCB residues in brains o f bald eagles [Haliaeetus leucocephalus) found dead from various causes in the United States between 1969 and 1972 varied from 0.10 to 230 ppm (refs. 5,6). Even the highest levels in the eagle brains weretjelow the lethal range determined w ith captive blackbirds. However, there may be at least two distinct modes o f death from PCB's (ref. 7). A sudden heavy intake may cause death from neurotoxicity, w ith brain residues high and diagnostic o f death. Long, low intake, which may occur in the field, may k ill by causing edema and related phenomena; signs vary between in dividuals and between species. Under these circum stances, m ortality resulting from PCB's would not nec essarily be accompanied by high residues of PCB's in brains, and fo r these birds no good diagnostic technique is available, fo r the signs are nonspecific and the residue levels vary greatly. GENP 005812 262 774461 PCB\ were implicated in a dieoff of guilemots (Uria aufge) which occurred in the Irish Sea region in 1969 (ref. 8). The body load of PCB's in birds that died was about twice that in healthy hirds collected in the same general region. Moreover, livers o f shot birds contained only 0.9 percent of the total body burden compared to 22.5 percent for birds found dead. PCB residues in brains were not determined. Uptake and Loss Rates PCB's are readily taken up by animal tissues, and loss rates are reasonably slow. Like )DT and other lipid-soluble pesticides, PCB's accumulate in adipose tissue and have been shown to move out of adipose tissue during lipid mobilization. In experimentally dosed birds, highest PCB levels accumulated In adipose tissue, followed by kidney, liver, brain, muscle, and blood (refs. 3,9). In e x p e rim e n ta lly dosed grackles (Quiscatus quiscuia), half of the PCB's were gone from the tissues in about 1 month, compared to an estimated 6 months for DDE (ref. 4 ) . Continued Igss of PCB's after the first month, however, was exceedingly slow and there was no significant further loss occurring during the next 12 weeks. A fter 32 weeks, about 15 percent o f the original burden o f PCB's remained in the body. PCB's are readily excreted in the egg. PCB levels in the eggs of double-crested cormorants (Phalacrocorax auritus) reflected carcass levels, but this relationship did not hold fo r white pelicans (Pefacanus erythrorhynchos) (ref. 10). In ringdoves {Streptopel/a risoria), Aroclor 1254 fed at 10 ppm reached an equilibrium level of 17 ppm wet weight in the eggs; this was about 2 percent of the level found in the fat o f the adult birds (ref. 9). PCB's stored in the adipose tissue are readily m obil ized during periods of stress that cause loss of body weight. Alternate starving and feeding of pheasants dos ed with PCB's increased the to x ic ity o f the PCB's (ref. 11). Birds that died from starvation had mobilized their fat reserves and had considerably higher PCB's in the brain and other tissues than did PCB-treated birds that were not starved. Similarly, increased levels of PCB in muscle, brain, and liver of PCB-treated ringdoves fo llo w ed depletion of fat reserves by starvation. A t death, PCB' concentration in the brains of starved birds had increas ed 56-fold (ref. 9). Reproductive Effects Effects of PCB's on reproduction are d ifficu lt to evaluate but arc apt to have the most serious impact on populations. Few data are available for wild species, so work done with chickens must be relied upon. Numer ous good studies have shown that chickens are sensitive to PCB'Si. The chief reproductive effects in chickens are lowered egg production and reduced hatchability. De formities in chicks are common, and growth of young may be depressed. Survival of young sometimes is affect ed. Feed consumption, adult survival and body weight, eggshell characteristics, and gametogenesis usually are not affected. Most embryo m ortality occurs during the latter stages o f incubation, although this may depend upon the PCB residue in the egg. Many chicks may die after pipping. The most severe effects are produced by Aroclors in the middle o f the range--from 1232 through 1254. Chickens fed 2 ppm of several Aroclors in the diet fo r 9 weeks were not adversely affected (ref. 12). Others fed 20 ppm were affected differently by the different types of Aroclors. A. odors 1221 and 1268 did not affect egg production or hatchability. Aroclor 1248 pro duced the most severe effects, causing some m ortality of adults and nearly eliminating hatching of eggs. Aroclor 1242 produced effects that were very nearly as severe. Aroclor 1232 produced less effect. The lack of effects o f 2 ppm o f dietary PCB on chicken reproduction was supported by a 39-week feed ing test w ith Aroclor 1254 (ref. 13), Five ppm of 1254 reduced egg production erratically over the 39-week period. With 50 ppm, however, m ortality began, and dosage was stopped after 14 weeks. Egg production fell sharply. Hatchability dropped nearly to zero; residues in eggs were then about 25 to 50 ppm. As residues in eggs dropped after 6 weeks of clean food, hatchability rose. Residues ever 10 to 15 ppm in eggs were accompanied by heavy em bryotoxicity, b ut those below 5 ppm show ed no effect. A t the start of the 50-ppm dosage, deaths of embryos came late in development, but as residues b u ilt up deaths came progressively earlier. The effects on reproduction were further investi gated in another study in which chickens were given 50 ppm A ro c lo r 1254 in water fo r 6 weeks, and then were given untreated water fo r 20 weeks (ref. 14). Hatchabi lity dropped to zero w ithin 3 weeks after dosage began and stayed nearly at zero through 8 weeks of clean water, then rose to approximately normal levels after 16 weeks of untreated water. The amount o f embryonic m ortality associated w ith a given amount of PCB residue in the egg became higher as the study progressed. Thus, 50 percent m ortality of embryos was correlated with 50 ppm of PCB in the yolk after 1.6 weeks of dosage, but with 10 ppm after 18.7 weeks, a fivefold difference. The 18500 rTKnin 263 *774462 greatest toxicity per unit o f PCB came after 11 weeks of untreated water. Late in the study, 6 to 8 ppm o f PCB in yolks was correlated w ith 14 to 36 percent m ortality of embryos. This would represent about 3.6 ppm in the whole egg. The authors concluded that the increase of toxicity with time was caused by the accumulation of some persistent isomer or homolog of 1254 or by a met abolite. In another study w ith chickens, egg production was reduced by 10 percent and hatchability by 44 percent when eggs from hens dosed w ith Aroclor 1248 contained only 3 ppm {ref. 15). When levels in the eggs reached 4.5 ppm, production was further reduced and hatchability was almost completely eliminated. PCB residues in eggs of w ild birds have often equalled or exceeded the levels known to have caused reproductive problems in chickens. For a few examples, 11 eggs o f bald eagles from the United States contained from 2 2 to 27.7 ppm of PCB's with a median of 9.7 ppm (ref. 16). PCB residues in osprey {pandion haiiaetus) eggs collected in Connecticut in 1968 and 1969 varied from 3.6 to 51 ppm {ref. 17) and brown pelican (Pefecanus Occidents/is) eggs from the Eastern United States contained from 1.9 to 36.5 ppm PCB's, w ith many readings over 5 ppm (ref. 18). Species differ ences in response must be considered in the interpreta tion of the effects of these levels upon reproduction of w ild birds. The number o f species that may respond like chickens is not known. PCB's caused deformities in chicks from hens dosed with 50 ppm Aroclor 1254 (ref. 19). Many deformities appeared when residues in yolks were 10 ppm or more. In another study in which hens were dosed w ith 20 ppm of Aroclors 1232, 1242, 1248, or 1254, 34 percent of 843 embryos that died during incubation showed signs of abnormal development (ref. 20). PCB's or related chemicals were suspected of causing deformities in a small number of young in a tern colony in which PCB residues were high {ref. 21). Other species of birds may be less sensitive to PCB's than chickens. Mallards showed no decline in reproduc tive success during 2 years of dosage w ith 25 ppm of Aroclor 1254 (ref. 1). Similar results have been reported for coturnix quail (refs. 15,22) and bobwhite quail (ref. 1). Pheasants given oral doses o f Aroclor 1254 showed depressed eyg production and hatchability, suggesting a response similar to that of chickens (ref. 23). Decreases in eggshell thickness and associated de clines in populations of certain species of w ild birds have been linked with elevated levels o f DDE in their eggs (for review sec ref. 24). The effect of DDE upon eggshell thickness has been demonstrated experimentally w ith several species (ref. 24). Recent experimental studies w ith PCB's, however, have failed to demonstrate tha low dietary dosages cause significant eggshell thinning in mallards (ref.. 1), bobwhite quail (ref. 1), pheasants (ref. 23), ringdoves (ref. 25), or chickens (refs. 12,15,26,27). In earlier tests, chickens fed Aroclor 1242 at 10 ppm or 100 ppm and Aroclor 1254 at 100 ppm laid eggs w ith thinner shells than did controls (ref. 28). Coturnix qu- I hens given 10 ppm Aroclor 1242 in the feed for 40 days produced eggs with shells 5 percent thinner than did hens given untreated.feed (ref. 29). Similarly, 50 ppm of Aroclor 1254 in the diet produced a small decrease in shell thickness and an increase in the percentage of cracked eggs o f coturnix quail (ref. 22). No tests of egg shell thinning have been made w ith birds o f prey or other critical species. Statistical evaluation o f the role that different che micals may play in thinning the eggshells o f brown pel icans in the field has.shown that DDE residues correlate much better w ith shell thinning than do residues of PCB's (ref. 18). Similar relationships have been shown fo r other species (ref. 30). E ffe c t on Chromosomes Few cytogenetic studies have been conducted to de termine effects o f PCB's on chromosome structure. In one study, no chromosomal aberrations were detected in chicken embryos follow ing injection o f Aroclor 1242 into the egg to levels o f 10 and 20 ppm (ref. 31). A t these levels m ortality o f embryos was high. In another study, embryos from ringdoves treated w ith Aroclor 1254 at 10 ppm had a higher frequency of chromosome aberrations than did controls (ref. 32). Chromosomal aberrations may contribute to the ab normalities o f developing embryos observed in some studies, or perhaps to a decreased reproductive success during successive generations of exposure to PCB's. When ringdoves were exposed to - 10 ppm Aroclor 1254 during two generations, the reproductive success o f the first generation was normal, but the success of the second generation was greatly reduced (ref. 32). Effects on Behavior Alterations in behavior may bring about depressed survival and reproductive success o f w ild species. Exper imental studies have shown that PCB's may alter be havior. Caged European robins {Erithacus rubecufa) fed PCB's showed increased migratory activity compared w ith untreated controls (ref. 33). PCB's caused a similar tendency in redstarts {Phoenicurus phoenicurus) (ref. GENP 005814 264 774463 34) . Hi.'linviur, on a visual cliff, of pheasant chicks hatch* ml from Ihiik ijivon bO mg Aroclor 1254 weekly was =.iljnificanlly ciiffurent from controls or those receiving 12.5 mg (ref. 23); more chicks from the 50-mg group jumped to the visually deep side or made no choice of sides than chicks from other groups. The avoidance re sponse to a moving silhouette o f cotum ix quail chicks fed 200 ppm o f Aroclor 1254 was greatly reduced (ref. 35) ; there was no significant recovery in response after the birds were again given clean feed, suggesting an effect upon the maturing central nervous system. Embryonic m ortality of ringdoves fed 10 ppm Aroclor 1254 was higher when the eggs were incubated by the parent birds than when they were incubated arti ficially (ref. 36). Egg temperatures suggested that the increased m ortality was due to decreased parental atten tiveness. Recent studies have shown that certain species of bats are sensitive to PCB's. In big-brown bats [Eptesicus fuscus), PCB's crossed the placenta 2 to 3 times more readily than DDE (ref. 41). Concentrations of PCB's were significantly greater in litters that included dead young than in litters in which both young were born alive. In further studies, big-brown bats fed 250 ppm DDE in the diet gained weight and none died, but indi viduals fed only 10 ppm Aroclor 1254 gained weight more slowly and some died (ref. 42). PCB's have been shown to be toxic to some non human primates over a wide dose range. A d ult rhesus monkeys developed signs o f PCB intoxication w ithin 1 to 2 months at doses as low as 2.5 and 5.0 ppm of Aroclor 1248 in the diet (ref. 43); these levels also caused a marked decline in reproductive success. EFFECTS ON MAMMALS CONCLUSIONS Certain species o f mammals appear to be. especially sensitive to ingestion o f low leveis o f PCB's. An extreme example was provided by the declining reproductive success and increasing m ortality o f mink that was ob served by commercial mink ranchers in the Great Lakes region in the 1960's. The problems developed when mink ranchers began to use coho salmon from the Great Lakes in mink rations (ref. 37). Other fish from Lake Michigan had similar effects, but coho from the Pacific coast caused no trouble. Feeding trials were conducted w ith several contaminants that had been identified in the fish (ref. 38). Neither DDT nor dieldrin caused these effects in mink, even at levels far higher than those in the fish. In the first test, a mixture o f PCB's at 30 ppm in the diet killed all the adult mink. With dietary dosages o f 5 and 10 ppm of Aroclor 1254, no reproduction occurred. A t 10 ppm, five of the six adults died. In further tests, 1 ppm o f PCB in the diet reduced repro ductive success. More drastic results were observed when the mink were fed meat from cows that had been dosed w ith Aroclor 1254 (ref. 39). When the concentration of PCB in the diet was 3.57 ppm, there was no reproduc tion and all breeders died. When the concentration was 0.64 ppm, some adults died and no surviving young were produced. High levels of PCB's and organochlorine insecticides have been found in marine mammals and a link w ith premature births in some species has been suggested. Pre m a tu re pups from California sea lions (Zafophus caUforntcus) contained higher levels of these compounds in the blubber, liver, and brain than did full-term pups (ref. 40). The effects o f PCB's upon w ild populations are d if fic u lt to evaluate and many important questions remain to be answered. 'Residues in w ild species may be derived from different commercial mixtures that have undergone metabolic changes fo r varying time periods before reach ing the target organism. Residues o f PCB's in w ild birds often are at levels known to have caused reproductive impairment in chickens. Nevertheless, species differences must be considered and it is not known how many spe cies respond in the same manner as chickens. The great sensitivity of mink raises the question o f haw many other mammals may be equally sensitive to reproductive impairment or m ortality. REFERENCES 1. R. G. Heath, J. W. Spann, J. F. Kreitzer, and C. Vance, "Effects of Polychlorinated Biphenyls on Birds," Proc. X V th fn t. O rnith. Congr., 1972, pp. 475-485. 2. E. H. Dustman, L. F. Stickel, L. J. Blus, W. L. Reichel, and S. N. Wiemeyer, 'T h e Occurrence and Significance of Polychlorinated Biphenyls in the En vironm ent," Trans. 36th N. Am . WHdl. Nat. Res. Conf., 1971, pp. 118-131. 3. R. B. Dahlgren, R. J. Bury, R. L. Linder, and R. F. Reidinger, Jr., "Residue Levels and Histopathology in Pheasants. Given Polychlorinated Biphenyls," J. WHdl. Manage., Vol. 36 (1972), pp. 524-533. 4. W, H. Stickel, unpublished report, Patuxent Wildlife Research Center. GENP 005815 265 774464 $0* s OOP' 0s 5. A. A. Btilisli:, W. L. Reichtil, L. N. Locke, T. G. Lament, B. M. Mulhern, R. M. Prouty, R. B. DeWolf, and E. Cromartie, "Residues of Organochlorine Pesticides, Polychlorinated Biphenyls, and Mercury and Autopsy Data fo r Bald Eagles, 1969 and 1970," Pestic. M onit. J., Vol. 6 {1972J, pp. 133-138. 6. E. Cromartie, W. L. Reichel, L. N. Locke, A. A . Belisle, T. E. Kaiser, T . G. Lamont, B. M, Mulhern, R. N. Prouty, and D. M. Swineford, "Residues of Organochiorine Pesticides and Polychlorinated Bi p h e n y ls and Autopsy Data for Bald Eagles, 1971-72," Pestic, M o n it J., Vol. 9 (1975), pp. 11-14. 7. W. H. Stickel, "Some Effects o f Pollutants in Terres trial Ecosystems," Proc. NATO Conf. P ollution by Heavy Metals and Organoha/ogens, in press. 8. J. L. F. Parslow and D. J. Jefferies, "Relationship Between Organochiorine Residues in Livers and Whole Bodies o f Guillemots," Environ. P o ilu t, Vol. 5 (19731, pp. 87-101. 9. J. L. Lincer and D. B. Peakall, "PCB Pharmaco dynamics in the Ring Dove and Early Gas Chroma- . tographic Peak D im inu tio n," Environ. P o ilu t, Vol. 4 (1973), pp. 59-68. 10. Y. A. Greichus, A. Greichus, and R. J. Emerick, "Insecticides, Polychlorinated Biphenyls and Mer cury in Wild Cormorants, Pelicans, Their Eggs, Food and Environment," Bull. Environ. Contam. Toxi co l.. Vol. 9 (1973). pp. 321-328. 11- R. B. Dahlgren, R. L. Linder, and W. L. Tucker, "Effects of Stress on Pheasants Previously Given Polychlorinated Biphenyls," J. W ifdl. Manage., Vol. 36(1972), pp. 974-978. 12. R, J. Lillie, H. C, Cecil. J. Bitman, and G. F, Fries, "Differences in Response of Caged White Leghorn Layers to Various Polychlorinated Biphenyls (PCBs) in the D iet," P oultry Sci., Vol. 53 (1974), pp. 726-732. 13* N. S. Platonow and B. S. Reinhart, `T h e Effects of Polychlorinated Biphenyls (Aroclor 1254) on Chick en Egg Prouut lion. F ertility, and H atchability," Can. J. Comp. M ed.. Vol. 37 (1973), pp. 341-346. 14. B. Bush, C. F. Tumasoms, and F. D. Baker, 'T o x icity and Perrrstence of PCB Homologs and Isomers in the Avian System," Arch. Environ. Contam. Tox ic o l., Vol, 2 (1974), pp. 195-212. 15. M. L. Scott, J. R. Zimmerman, S. Marinsky, P. A. M ullenhoif, G. L. Rumsey, ana R.W . Rice, "Effects of PCBs, DOT, and Mercury Compounds Upon Egg Production, Hatchability and Shell Quality in Chick ens anri Japanese Quail," P oultry Sci., Vol. 54 (1975), pp. 350-368. 16. S. N. Wiemeyer, B. M. Mulhern, F. J. Ligas, R. J. Hensel, J. E. Mathisen, F. C. Robards, and S. Postupalsky, "Residues of Organochiorine Pesti cides, Polychlorinated Biphenyls, and Mercury in Bald Eagle Eggs and Changes in Shell Thickness -- 1969 and 1970," Pestic. M o n it J., Vol. 6 (1972), pp. 50-55. 17. S. N-. Wiemeyer, P. R. Spitzer, W. C. Krantz, T. G. Lamont, and E. Cromartie, "Effects of Environmen ta l P o llu ta n ts on Connecticut and Maryland Ospreys." J. W ild!. Manage., Vol. 39 (1975), pp. 124-139. 18. L. J. BIus, B. S. Neely, Jr., A. A. Belisle, and R. M. Prouty, "Organochiorine Residues in Brown Pelican Eggs: Relation to Reproductive Success," Environ. P o ilu t. Vol. 7 (1974), pp. 81-91. 1 9 . C. F, Tumasonis, B. Bush, and F. D. Baker, "PCB Levels in Egg Yolks Associated w ith Embryonic M ortality and Deformity o f Hatched Chicks," Arch. Environ. Contam. T oxicol., V ol. 1 (1973), pp. 312-324. 20. H. C. Cecil, J. Bitman, R. J. Lillie, G. F. Fries, and J. Verrett, "E m bryotoxic and Teratogenic Effects in ` ilnhatched Fertile Eggs From Hens Fed Polychlori nated Biphenyls (PCBs)," Bull. Environ. Contam. T oxicol., Vol. 11 (1974), pp. 489-495. 21. H. Hays and R. W. Risebrough, "P ollutant Concen trations in Abnormal Young Terns From Long Island Sound, A u k , Vol. 89 (1972), pp. 19-35. 22. E. S. Chang and E. L. R. Stokstad, "E ffe c t o f Chlor inated Hydrocarbons on Shell Gland Carbonic An hydrase and Egg Shell Thickness in Japanese Q uail," P o ultry Sci., Vol. 54 (1975), pp. 3-10. 23. R. B. Dahlgren and R. L. Linder, "Effects o f Poly chlorinated Biphenyls on Pheasant Reproduction, Behavior, and Survival," J. W ild/. Manage., V ol. 35 (1971), pp. 315*319. 24. L. F, Stickel, "Pesticide Residues in Birds and Mammals," Environm ental P ollution b y Pesticides, C. A, Edwards; ed.t Plenum Press, New York, 1973, pp. 254-312. 25. D. B. Peakall, "E ffe c t o f Polychlorinated Biphenyls (PCBs) on the Eggshells of Ring Doves," B ull. Envi ron. Contam. T oxicol., Vol. 6 (1971), pp. 100-101. 26. W, M. Britton and T. M. Huston, "Influence o f Poly chlorinated Biphenyls in the Laying Hen," P o ultry Sci., Vol. 52 (1973), pp. 1620-1624. 27. R. H. Teske, B. H. Armbrecht, R. J. Condon, and H. J. Paulin, "Residues of Polychlorinated Biphenyls from Poultry Fed Aroclor 1254," J. Agric. Food Chem., Vol. 22 (1974), pp. 900-904. 266 774455 PRE-1972 KNOWLEDGE OF NONHUMAN EFFECTS OF POLYCHLORINATED BIPHENYLS Charles R. Walker* A bstract Research conducted worldw ide on the effects o f PCB on aquatic organisms, birds, and mammals is herein summarized. The ecological effects o f PCB are s till n o t fu lly understood, n or is the long-term im pact o f PCB on anim al populations. I t Is know n th at PCB are h ig hly per sistent contaminants th a t bioaccum ulatein die food chain. They produce both chronic and acute effects on the grow th, reproduction, and behavior o f fish, birds, and mammals. O f these, freshwater fish accumulate PCB to die greatest e xte n t The birds and mammals th a t feed on freshwater fish in turn take in hazardous amounts o f PCB residues and become subiect to th eir serious to x i cological effects. INTRODUCTION Polychlorinated biphenyls were under investigative development as early as 1881 (Schmidt and Schultz) and yet very little knowledge of their toxic effects was evi dent until they had gained wide use during the 1930's and pnthological studies on laboratory animals were con ducted (refs. 5,41). These polychlorinated biphenyls, napthlenes, terpenes, etc., were marketed under a variety of trade names--Aroclor, Chlorphen, Kanechlor, Phenochlor -and a series o f numerical synonyms such as we have become familiar w ith in Aroclors--1221, 1232, 1242, 1248,1254,1260, 1268, etc. (refs. 8, 33, 51). Almost 20 years lapsed until McLaughlin et al. re ported that Aroclor 1242 was highly toxic and produced teratogenic effects in chick embryo at low dosage levels (ref. 44). Many studies were initiated at about this time, when analytical chemists monitoring environmental components observed a number of unidentified peaks in gas chromatographic analysis that were most frequently associated with aquatic species of birds and fishes (refs. 3, 19, 20, 21, 22, 24, 25, 26, 27, 32, 33, 34, 45, 46, 48, 53, 54, 55, 56, 58, 59, 61, 64, 66, 67, 68, 83, 84, 85, 86, 88, 93, 94), The annual research reports by the U.S. Fish and Wildlife Service since 1969 gave technical de tails in the developments of our work on the toxicity of PCB and chlorinated hydrocarbon pesticides, which " Senior Environmental Scientist, U.S. Fish and W ildlife Service, U.S. Department of Interior, Washington, D.C. 20240 NOTE; Scientific names for fish and wildlife listed in text are given at the end of the paper. coincided with m onitoring investigations of persistent chemicals such as DDT (refs. 3, 12, 16, 17, 38, 39, 40, 47, 52, 57, 71, 77, 78, 79, 80, 81, 82, 89, 90, 91, 92). The development o f the silicic acid method allowed for the separation o f PCB from other pesticide components and permitted detailed investigation of these environ mental contaminants (refs. 1,71). The December 1971 conference on polychlorinated biphenyls sponsored by the National Institute of Envi ronmental Sciences at the Quail Roost Conference in Rougemont, North Carolina, provided fu ll array of the effect of PCB on experimental animals, fish, and w ild life. The Fish and W ildlife Service National Pesticide Monitoring Program discussed at this conference concen trations of PCB in fish samples (ref. 89). These residue levels were confirmed in the cross-check analysis by the Fish Pesticide Research Laboratory, which in turn has spurred more toxicological research in to the significance o f these residues (refs. 18,40, 71, 74, 7 5 ,7 6 ,8 0 ). EFFECTS ON AQUATIC ORGANISMS Chronic and acute to xicity studies on aquatic orga nisms were conducted in which 96-hour LC50 values were determined fo r eight o f the Aroclor series from 1221 through 1268 (refs. 40,71). The 96-hour LC values ranged from 1,170 to 50,000 mg/1 fo r cutthroat trou t (table 1) (refs. 40,71). In another test, the acute oral toxicities of Aroclors 1242, 1248, 1254, and 1260 were found to be greater than 1500 mg/kg in rainbow trout. Interm ittent flo w for Aroclors 1242, 1248, and 1254 indicated that these compounds were much more toxic at high temperatures and at longer exposure periods. Comparable results were obtained on channel catfish and rainbow tro u t (table 1) (refs. 40,71). The effect of Aroclors on invertebrate forms gave an even wider distribution o f effects (table 2) (refs. 40,69,71), w ith Aroclor 1248 being the most toxic to Daphnia magna and levels above 5 mg/l causing inhibi tion in reproduction (ref. 45). Similar results were ob tained on Gammarus pseudolimnaeus (ref. 45). The 96-hour LCSo values for Aroclors 1248 and 1254 were 52 and 2400 mg/l respectively (ref. 40). Another species of scud (Gammarus fasciatus) was found to concentrate PCB by 27,000 times the exposure level compared to the Daphnia, which concentrated Aroclor 1254 by 48,000 times (figure 1) (ref. 40). Both crayfish and the scud were found to be much more sensitive to Aroclor 1242, w ith the uptake being 268 co 28. Monsanto Company, unpublished report prepared by Industrial Biotest Laboratories, Inc., N orth brook, Illinois, 1970. 29. E. F. H ill. R. G. Heath, and J. D. Williams, "E ffe ct o f Dieldrin and Aroclor 1242 on Japanese Quail Eggshell T hickness," unpublished manuscript, Patuxent W ildlife Research Center, 30. R. A. Faber and J. J. Hickey, "Eggshell Thinning, Chlorinated Hydrocarbons, and Mercury in Inland Aquatic Bird Eggs, 1969 and 1970," Pestle. M o n it J ., Vol. 7 (1973), pp. 27-36. 31. W. F. Blazak and J. B. Marcum, "A ttem pts to In duce Chromosomal Breakage in Chicken Embryos w ith Aroclor 1242," P oultry Set. , Vol. 54 (1975), pp. 310-312. 32. D. B. Peakall, J. L. Lincer, and S. E. Bloom, "E m bryonic M ortality and Chromosomal Alterations Caused by Aroclor 1254 in Ring Doves," Environ. Health Persp., Vol. I (1972), pp. 103-104. 33. S. Ulfstrand, A. Sodergren, and J. Rabol, "E ffe c t of PCB on Nocturnal A ctivity in Caged Robins, Erithacus rubecu/a L., N ature, Vol. 231 (1971), pp. 467-468. 34. B. Karlsson, B. Persson, A. Sodergren, and S. Ulfst rand, "Locom otory and Dehydrogenase Activities o f Redstarts Phoenicurus phoenicurus L. (Aves) Given PCB and D D T," Environ. P o llu t, Vol. 7 (1974), pp. 53-63. 35. J. F. Kreitzer and G. H. Heinz, "The Effect of Sublethal Dosages o f Five Pesticides and a Polychlori* nated Biphenyl on the Avoidance Response of Coturnix Quail Chicks," Environ. P o llu t, Vol. 6 (1974), pp. 21-29. 36. D. B. Peakall and M. L. Peakall, " Effect o f a Poly chlorinated Biphenyl on the Reproduction o f A rti ficially and Naturally Incubated Dove Eggs," J. A p p iE c o l., V ol. 10 (1973), pp. 863-868. 37. R. J. Aulerich, R. K. Ringer, H. L. Seagran, and W. G. Youatt, "Effects o f Feeding Coho Salmon and Other Great Lakes Fish on Mink Reproduction," Can. J; Zoo/., Vol. 49 (1971), pp. 611-616. 38. R. J. Aulerich, R. K. Ringer, and S. Iwamoto, "Reproductive Failure and M ortality in M ink Fed on Great Lakes Fish," J. Reprod. Pert. SuppL, Vol. 19 (1973), pp. 365-376. 39. N. S. Platonow and L. H. Karstad, "D ietary Effects o f Polychlorinated Biphenyls on M in k ," Can. J. Ccmp. M ed., V ol. 37 (1973), pp. 391-400. 40. R. L. DeLong, W. G. Gil martin, and J. G. Simpson, "Premature Births in California Sea Lions: Associa tion W ith High Organochlorine Pollutant Residue Levels," Science, Vol. 181 (1973), pp. 1168-1169. 41. D. R. Clark, Jr., and T. G. Lamont, " Organochlo rine Residues and Reproduction in the Big-Brown B a t/V . W ild!. Mange., in press. 42. D. R. Clark, J r ,, unpublished data, Patuxent W ildlife Research Center. 43. J. R. Allen, "Response o f the Nonhuman Primate to Polychlorinated Biphenyls Exposure," Fed. Proc., Vol. 34 (1975), pp. 1675-1679. .GENP 005817 267 774466 PCB Aroclor 1242 T a b le 1. T o x ic it y o f P C B to fish (refs. 40,71) I n v( sepr et ecbiersa)t e . DDCSS(((((GMGOIccarrsuuaaaamracddmmgcychsoormmfneoinnaaslumeffrrhrluluclyyaasstevsbffaapencc.r)laltaailcsttuu)assl))is) mBleotahsoada!y/ C c A A A A rodor 1248 Aroclor 1254 2,4b,-ipDhlecnhylol ro- S(Gcuadmmarus faclatus) DDGCS(((((MGFIOcarrlsuaaaaamracdmslgycchassoorfmeneoinnmlsaumsfferhhrlluoclyyarasntieme.vssftpapeencs.r)latakilcstau)adsli)iask)ensls) S(Gcuadmmarus psuedollmnaeus) .A A C C c A A 4 , 4 '-bDlpl chhe nl oyrlo - S(Gcuadtmarus psuedollmnaeus) 213,b4l1p-Thernicyhl loro- S(Gcuadmmarus psuedollmnaeus) 2 ,4 ,c5h,l2o'rIo5b,-ipPheenntay-l S(Gcuadmmarus psuedollmnaeus) 2 ,4 ,c6h,2lo,r,o4b',ip6h1e-Hnyexl a- S(Gcuadmmarus psuedollmnaeus) A A A A 1/ A - Acute toxieity by static test procedure C Chronic toxicity by flow through procedure Extpimoseure 4 10 7 4 7 LCS0 (hr/ r) 10.0 5.0 30.0 400.0 , 800.0 4 52.0 4 2400.0 7 3.0 7 80.0 4 200.0 7 100.0 4 120.0 4 100.u 4 70,0 4 210,0 4 150,0 GENP 005819 269 774467 Table 2. T o x ic ity o f PCB to aquatic invertebrates (refs. 40,69,71) PCh (Aroclur) Pieh Teap <C) 1221 1232 1242 1248 1254 1260 1262 1268 Cutthroat trout 8.9 Cutthroat trout 8.9 Cutthroat trout Rainbow trout Blueglll Blueglll Channel catflah Channel cetfleh 8.9 17.0 20.0 17.0 20.0 17.0 Cutthroat trout Rainbow trout Blueglll Blueglll Blueglll Channel eotflah Dianne1 catflah Channel catflah Channel catflah 8.9 17.0 18.3 20.0 17 18.3 27.0 20.0 17.0 Cutthroat trout Rainbow trout Rainbow trout Blueglll Blueglll Blueglll Channel catflah Channel catflah Channel catflah 8.9 20.0 17.0 18.3 20.0 17.0 18.3 20.0 17.0 Cutthroat trout 8.9 Rainbow trout 20.0 Rainbow trout 17.0 Blueglll 20.0 Blueglll 17.0 Channel catflah ' 20.0 Channel catflah 17.0 Cutthroat trout 8.9 Cutthroat trout 8.9 Bloeeae1 aathodi.!ff 4d A 1170 A 2500 A 4530 C-- C-- c-- c-- c-- A 5750 C-- A 278 C-- C-- A 6000 C-- C --W c-- A 42500 c-- c-- A 2740 c-- c-- A 12000 c-- c-- A 60900 c c-- c-- c-- c-- c-- A 50000 A 50000 LCjq value lb ig/1 at expoaure tine of 5d lOd 15d l i d " 303* ---- -- -- ---- ---- -- -- ---- 67 48 18 10 12 -- 154 72 54 -- ---- ---- 164 125 120 84 -- 174 107 -- ---- ---- 219 ISO 132 87 54 38 ---- 307 160 136 115 ---- -- 94-- 225 -- 121 156 -- -- -- -- -- -- -- 156 -- -- -- -- -- 8 160 -- 443 -- -- -- 303 __ 5 326 -- -- 535 -- - 16 -- 76 111 -- 57 127 121 __ 64 -- 204 303 -- 741 286 -- 143 -- -- -- 482 -- -- 6.4 -- 10 106 __ *-- -- 115 __ 39 -- 135 260 -- 300 293 3.4 __ __ 100 __ __ __ 78 __ -- 104 __ 27 -- 54 239 -- 113 181 __ 75 Mm __ __ -- -- 177 -- -- 139 -- ---- 78 49 51 245 212 151 -- -- 400 296 166 137 512 465 433 ---- -- ---- 1/ A Acute toxicity by atatic teat procedure. O Chronic toxicity by flow-through procedure. o z # 00 270 7?4468 GENP 005821 IXPOSURf TIMf Figure 1. Bioaccumulation of Aroclor 1254 for various aquatic inverte brates exposed to water concentrations: 1.1 /ig/l for D a p h n ia m a g rta ; 1.6 jxg/1 for G a m m a ru s p s e u d o fim n a e u s ; 1.2 #ig/l for O r c o n e c te s n a ts ; 1.3 /ig/l for P a /a e m o n te s k a d ia k e n s is ; 2.8 /ig/l for P t e r o n a r c y s d o r s a ta ; 1.1 t ig / \ for C o r y d a iu s c o r n u t u s ; 1.5 Aig/I for Cu/ex ta rs a /is ; 1.3 jig/l for C h a o b o r u s p u n c t ip e n n is (ref. 40). 271 774469 a i oo CO to somewhat enhanced w ith tme. Glass shrimp (,Pa/aemonetes kadi'akensis) were also found to be quite sensi tive to Aroclor 1254, with an LCS0 value of 3 mg/1 in a 7-day exposure. On the other hand, dragon fly (Macromia species) and damsel fly (Iscbnura verticalis) were a great deal more resistant to Aroclors 1254 and 1242 (table 1 and figure 1). Aroclor 1254 was found to be extremely toxic to immature pink shrimp, of which more than 50 percent died within 15 days of continuous exposure to 0.94 mg/l (ref. 47). A similar concentration factor was noted for Aroclor 1254 in two estuarine fish species (Lagondon rhomboides and Leiostomus xanthurus). While between 14 and 45 days of exposure to 5 mg/l did product some m ortality, the 1 mg/l during the same exposure time resulted in no m ortality, but concentration of residues did occur at rates similar to those fo r freshwater fis h 10,000 to 50,000 times the environmental levels (refs. 12,16). In studies conducted in Sweden on salmon eggs, PC8 residues on a lipid basis ranging from 7.7 to 34 pg/g caused mortalities between 16 to 100 percent (ref. 26). The regression analysis gave a coefficient of correlation of 0,85, w ith a significance of P = .001. PCB residues in these Atlantic salmon eggs on a wet weight basis were from 0.4 to 1.9 pg/g. This indicates that the threshold for egg m ortality was about 0 3 jig/g PCB. Such residues would be comparable to whole fish residues of 2.5 to 5.0 pg/g or very close to those values found in many fish sampled in our National Pesticide Monitoring Program and in Sweden (refs. 6,89). The oral toxicities of Aroclors 1242, 1248, 1254, and 1260 were found to be in excess of 1500 ig/kg for adult rainbow trou t (ref. 40). However, tro u t fry from eggs containing 2.7 pg/g o f Aroclor 1242 along w ith a DDT residue of 0.09 pg/g caused a 75 percent cumula tive m ortality 30 days after hatching (ref. 18). In five other groups of less contaminated eggs, 10 to 28 percent m ortality was noted 30 days after hatching. A bout 60 to 70 percent of the fry that survived were deformed and teratology was evident. Generally speaking, the more chlorinated PCB were not as acutely toxic as the less chlorinated ones. For example, in cutthroat trout, A ro clors 1221, 1232, 1242, 1248, 1254, and 1260 had LCJ0 values for 96-hour exposure of 1.2, 2.5, 5.4, 5.7, 42, and 61 mg/l respectively. - In tests with individual homologs, to xicity decreases as the percentage o f chlorine increases in amphipods against 5 PCB formulations (ref. 40). The dichlorobiphenyls and trichlorobiphenyls dominate the Aroclor 1242, whereas the trichlorobiphenyls and tetrachlorobiphenyls dominate in Aroclor 1248 and the pentachloro- biphenyls and hexachlorobiphenyls dominate in the A ro clor 1254. The most toxic PCB formulations appear to be those that contain 4 to 5 chlorine atoms; these pre dominated in Aroclor 1248, which was found to be the most toxic of all of the Aroclors tested on fish. A noticable shift in residue components follow ing exposure to Aroclor 1254 was observed in experiments conducted on amphipods (ref. 71). An apparent tw ofold increase in concentration of less chlorinated isomers and homologs occurred in the trichlorobiphenyls and tetrachlorobiphenyls. The higher chlorinated pentachlorobiphenyls and hexachlorobiphenyls were decreased by half in ex periments conducted on fish (ref, 40). Tests showed that residue accumulation o f PCB in invertebrates ranged from 160 to 6,300 times that in water. In channel cat fish, after 77 days of exposure, the concentration of Aroclors 1248 and 1254 accumulated in channel catfish to 56,270 and 61,190 times, respectively, than in water (figure 1). The more chlorinated components accumu lated more than the less chlorinated ones, and upon ter mination of the exposure, PCB elimination by fish was more rapid fo r the less chlorinated components (refs. 40,71). The researchers also found evidence that the ac tual uptake is less or the turnover rate is more rapid in the invertebrates. This is in agreement w ith observations by other investigators (refs. 48, 64, 65,66, 67). In other experiments conducted by our Fish Pesti cide Research Laboratory, we found that inclusion o f Aroclor 1254 in fish food at the rate o f 0.448 jug/g resulted in a 52 percent increase in fish thyroid activity. In a high-treatment group that received 480 /ig/g, th y roid stimulation was 119 percent over that of the con trol group (figure 2) (ref, 40). In these tests we found that the lowest detectable stimulation thyroid activity occurred in salmon dosed at 1/1,000th the dosage that would cause m ortality. This test was further duplicated in channel catfish w ith comparable results, which sug gests that the laboratory studies may be realistic indica tors of the physiological effects o f PCB on fish and the aquatic environment (figure 3) (refs. 40,71). The true effects of thyroid stimulation, however, on respiration, carbohydrate metabolism, oxygen consumption, ammo nia metabolism, osmoregulation, growth, oxidative phos phorylation, central nervous system function, and behav ior of fish are yet to be determined. Nevertheless, we can postulate that these must be im portant and interrelated factors in'the physiological and biochemical function of fish and any alteration of this normal function could effect fishes' ability to adapt to stress or such changes in the environment as salinity and temperature. The effect of environmental stress on the health of fish is very well illustrated by Snieszko (figure 4) (ref. 70). Subtle effects 272 774470 Figure 2. Whole-body residues and thyroidal uptake o f 1151 in coho salmon fed diets containing Aroclor 1254 for 260 days (ref. 40). on microflora, fauna, and plankton must also be investi gated fo r potential impacts on trophic level ecology (refs. 29,30). Enzymatic and compositional changes of the micro* somes occur where possible lipids are concentrated in the membrane and manifestation of enzyme malfunction is suspect in the proxim ity of hydrophobic chlorinated aromatic hydrocarbons such as PCB, DDT, and other organochlorine pesticides that would accumulate (ref. 50). Meyer, Mehrfe, and Sanders conducted experiments w ith incorporation o f Aroclor 1248 into the diet o f juve nile lake trou t in concentrations of 0.2 to 6 mg/kg of food (ref. 40). These levels, comparable to those found in natural food, suppressed growth and serium cortisol levels, but stimulated thyroid activity during the first 160 days of the experiment (ref. 40). A fter 320 days, however, control and treated fish were similar. Histopathological examination of fish exposed to Aroclor and chlordane showed a very high incidence o f gill lesions after 6 months exposure; 6 percent of the PCB-treated fish were affected, compared to 15 percent after 9 months {refs. 76-78). Progressive and diffuse degeneration changes in liver were noted in 80 percent o f the fish after 4 to 6 months exposure to the chlor dane or PCB d ie t A nonspecific degeneration of liver pyrenchema and cytoplastic vaculation o f liver cells occurred in addition to pleomorphism. The severity of liver tissue degeneration throughout the 6- to 9-month exposure period exceeded the controls by at least three fold. A fter this, we noted that focal areas in liver degen eration decreased in size and by the following year no liver lesions could be observed in this lo t of fish. This observation was complemented by the decrease in sever ity o f gill lesions in PCB-treated fish. The gill lesions also improved after 9 to 12 months of exposure and no sig nificant difference between treated and control fish could be detected the follow ing year. In parallel experiments, whole-body residues had o M oo oo 273 774471 p s /9 PC B ( A r o c l o r ) in d i e t 193 d a y s Figure 3. Whole-body residues and thyroidal uptake of 125 I in channel catfish fed diets containing Aroclors 1 23 2 ,1 2 48 ,1 25 3 , and 1260 for 193 days (ref. 40), s >3 O O CO increased from 0.13 mg/kg at the lower dosage of 0.1 mg/kg in the food to a residue of 9.7 mg/kg at the higher food dosage 6 mg/kg after 320 days (ref. 40). A fter the trout were fed uncontaminated food fo r 60 days, the residues declined an average o f 31 percent, 15 percent, and 12 percent in the 0.6-, 1.8-, and 6.0-mg/kg treat ments respectively. Lake tro u t growth was retarded by the dietary intake of Aroclor 1248. These results suggest that although fish have a remarkable ability to recuper ate and regenerate tissue, the extent and lethality of damage through intoxication by PC8 are not clear. How ever, precise toxicological implication o f Aroclors on the general well being and health of fish is certainly suspect (ref. 70). EFFECTS ON BIRDS AND MAMMALS Behavioral effects o f organochlorine pesticides and PCB have been noted in the studies conducted on Japa nese or coturnix quail fed sublethal concentrations and subjected to a simultaneous test fo r avoidance behavior by rapidly moving away from strange objects (refs, 79,82). This behavior appears in the very early stage of development of galinaceous chicks and is almost certain ly essential to their survival in the w ild. Seven-day-old coturnix chicks were given Aroclor 1254 in their diet for 8 days and in untreated food fo r 6 more days. Avoid ance behavior was measured daily, and a group avoid ance response was significantly suppressed by chlordane. 274 774472 Figure 4. ssg(Rrtuareesneflcis.asestm7pioi0tmin)ab.ssplheosispuhegodbgseetbts,wytaeednPedCnbBytehnaeSvnndidirieoszpenkeamossteeicnoitdarels, dieldrin, and Aroclor 1254, although DDE had no appar ent effect. Whereas the behavior of untreated birds re turned to normal after 2 days on untreated feed, the response of chicks that were on dieldrin- and chlordanetreated feed improved somewhat during the 6 days o f untreated food. However, the response of birds treated with Aroclor 1254 showed no improvement during the period. Investigative monitoring for pesticide and PCB resi dues indicated that the highest residues occur in or near urban and industrialized areas. If these data are transfer able to many other species o f birds, we would expect to see the avoidance reaction suppressed, mortalities would increase from accidents, and predation would be maxi mized through the encroachment o f man on the habitat of the species. The causes of m ortality were subjected to autopsy study plus chemical analysis in studies conduct ed from 1969 through 1970 on 39 bald eagles found dead in various areas in the United States (refs. 42, 57, 79-82). The median residues of DDE in carcuses were 7 ppm in 1969 and 19 ppm in 1970, and mean residues of dieldrin were 0.4 ppm in 1969 and 0.7 ppm in 1970. Six of the eagles had dieldrin residues in the brain of 4.6 to 11 ppm, which is w ithin the lethal range. One eagle con tained 385 ppm of DDE and 235 ppm of PCB. In sum mary, environmental poisons were credited w ith 18 per cent of the deaths, illegal shooting w ith 46 percent, acci dents w ith 15 percent, natural disease w ith 8 percent, and miscellaneous and unknown causes w ith the remain ing 13 percent. In a survey to determine the degree of eggshell thin ning and the extent of chemical contamination in aquat ic birds in the Texas Coast area, eggs from 21 species were collected in 1971 (refs. 52, 78-80). Chemical analy sis completed fo r 14 species showed that DDT in metab olites existed in all samples, whereas dieldrin residues were found in the Texas Rice Belt and the highest PCB residues were near urban and industrial areas again (ref. 79). The most noticably high PCB residues were found in some eggs o f inland feeding species, including: dou ble-crested cormorant {Phalacrocorax auritus), which contained 32 ppm; Caspian terns (Hydroprogne caspia), 16.5 ppm; and Foster terns (Sterna forsteri), 12.5 ppm (ref. 80). However, PCB were present in only 66 percent of the 158 eggs that were analyzed in another study conducted on ospreys (Pandfon haliaetus) in the Gulf of California. During 1971, the residues o f DDT were found to be generally low compared to those in osprey populations showing poor reproductive success in other parts of the range. PCB residues were detected in four of eight eggs and when present were higher than DDE resi dues; however, eggshell thinning was minor (averaging -3 percent), as expected from their low residues. An experimental study on the absorption and me tabolism of the PCB m ixture A roclor 1254 showed that all the components in the m ixture were absorbed in es sentially equal proportions from encapsulated dosages (ref. 81). The dietary dosage fo r quail of 300 ppm of Aroclor 1254 fo r 14 days followed by 14 or 42 days of untreated food showed that the various components of the Aroclor were excreted at greatly different rates. A t the end of the 42 days of clean food, the PCB compo nents changed entirely from the proportions of com pounds that were originally fed to birds. Changes in pat terns of gas chromatographic peaks that were detected m ilitate against the dependable measurement of the quantities of PCB by gas chromatographic methods that can be related to the environmental or diet intake of the birds. In a n o th e r s tu d y , the combined effects o f p,p'--DDE, and PCB were measured in mallard ducks. The ducks were fed diets containing 40 ppm of each chemical in the diet for 2 months prior to breeding and throughout the reproductive season (ref. 81). Average decreases in eggshell thickness were almost identical between the two compounds, w ith -17.5 percent for DDT only and -17.0 percent fo r DDE plus PCB in the diet (refs. 38, 79-80). No eggshell thinning occurred in birds fed PCB alone or in untreated diets except for a SZSeOOrlMRD 774473 slight decrease in shell thickness near the end of the egg laying period. However, the birds fed the DDE-plus-PCB diet layed fewer eggs and egg production dropped off significantly 8 weeks before that of birds that were re ceiving other treatments. Egg breakage and egg eating were also highest in the DDE-plus-PCB groups and the The effects of polychlorinated biphenyls and organotecrhaltoiorinneofpeesntizcyidmees aanpdpeharortmoobnee mbiaoncihfeesmteisdtryin. tIhneuanl published work by Street and his coworkers, Vos repor ted that in inductions of hepatic microsomal enzymes, the sleeping time of experimental animals was decreased combination of the chemicals seemed to increase the after treatment with hexobarbitol. An enhancement of amount of egg loss through some effect--possibly on in vitro rates of aniline hydroxylation and para-nitro- behavior. Therefore, overall production problems were anisole demethylations occurred in direct proportion to most severe when PCB were fed in addition to the DDE. an increase to chlorine content of different PCB isomers In the Upper Great Lake States, 9 of 13 species of in Aroclors 1221 through 1268 (ref. 86). PCB prepara fish-eating birds were investigated in 1969-1970, and tion of Aroclor 1221 and Aroclor 1254 at 1 and 10 were found to sustain statistically significant decreases in mg/kg for 28 days in pregnant rabbits resulted in liver eggshell thickness since 1946 (ref. 82). Maximum enlargement with increased activity of drug metabolizing changes in thickness index occurred in great blue herons enzymes aniline hydroxylase and aminopyrine n-deme- (-25 percent), red breasted mergansers (-23 percent), thylase at the rate of 10 mg/kg of Aroclor 1254, while common mergansers (-15 percent) and double-crested no effects could be measured at the other levels and with cfroommorLaonutsisi(a-n1a5 gpeenrecrealnlty).diGsprleaaytedblusme ahlleerrocnhaengggesstsaiknecne 1946 than herons in the Midwest. On a lipid basis, mean osPpfCeBctiheaesnsedinDsLpDeocEuiiesrsieasniinda.uetThheleevLealavskeereaxgcSeetaeDtdeDesdEa:1Pn0Cd0Bopnrpaemtiooisfn issneevvtheenne two regions were 1.25:1 and 3.9:1 respectively. These ratios contrast with some around 0.3:1 previously re ported in oceanic birds in the Bay of Fundy and with ratios of roughly 5:1 and 10:1 that were reported by others on the Pacific Coast. The relationship between shell thinning and DDE content of eggs was apparent for the other levels and with the other Aroclors (ref. 86). PCBVfoors mcoamndmuacltsedandanbierxdtsen(rseifv.e86re)v. iHewe coofnctoluxdiecditythoaft ePnCzBy'ms ehaviendseuvcetiroaln,subploertphhalyreofgfeecntisc, sauccthioans, meicstrroosgoemnaicl activity, and immunosuppression. Aroclor 1254 adminis tered to rabbits during the first 28 days of gestation had embryo-toxic effects at levels of 12.5, 25, and 50 mg/kg of body weight, which demonstrates the direct effects on microsomal enzyme activity in pregnant rabbits (ref. 77). In previously cited work by McLaughlin (ref. 44), edema and beak deformities in chicken embryos have most species, but for herons DDE was the only com pound correlated (ref. 52). Partial correlation carried out on a somewhat been described after yoke sac-injection of 10 and 25 mg of Aroclor 1242 resulted in a 95 and 100 percent em bryonic mortality respectively. PCB have also been questionable family basis showed that PCB also corre found to cause neural pathology in rats when administer lated with shell thinning in mergansers, in a study of ed at a rate of 0.3 to 0.5 ml/kg per day for 14 or 21 chlorobiphenyl poisoning with formation of myelin figures in both mouse and monkey liver (ref. 49). Mice were subjected to daily dosages of .001 ml for 12-26 days. The pathology is characterized by impairment of motor function and decreased motor velocity with loss of large nerve fibers (ref. 76). weeks and cornification of smooth surface membranes A high dose of Aroclor was required before liver of the cytoplasmic reticulum was observed (ref. 50). necrosis developed in chickens (ref. 88). Moderate dos This was also accompanied by a displacement of rough ages in rabbits produce mottled liver with subacute surface membranes and endoplasmic proliferation and an increase in microbodies, lyosomes, and lipid content. Sfriommiladroosabgseesrvoatfio3n2s0wmerge gmivaedne oivnerth4e6sqduaiyrrse.l Lmivoenrkeeny largement was noted but the main cause of death was attributed to penumonia or diarrhea (ref. 49). A similar experiment was run on the cynomolgus monkey, which received 641 mg in 40 days to 348 mg in 239 days with venerzyymsiemiilnadr urcetsiuolnts w(reerfe. 4c9o)r.reSluabteldethwalithefftehcetsborefahkedpoawtinc yellow atrophy and fatty degeneration with marked gn/edcaroysiscaautseddosadgeeathratebsefoorfe0.l3ivearndpa0th.6ologg/dyayd,evbeultop0e.d9 (refs. 86,87). Miller (1944) observed 100 percent mortal ity between 17 and 98 days with similar skin applica tions of 34.5 mg during an 11-day period caused 100 p(reerfc.en4t1).mCoretnatlriatyl awtriothpihny 2o8f dliavyesr cwehllisleococnurtrreeda,tmweintht opcecriunruricnlegairn abafesowpohfilitchegarnainmualalst.ion and focal necrosis \o of estradiol and the increase in cytoplasmic RNA in Nichizum i (1970) utilized light and electron kestrels fed 0.5 to 5.0 ppm of Aroclors 1254 or 1262 for microscopy to confirm the formation of so-called myelin 5 months (ref. 53). figures in mouse liver associated with a minimum effec o o 276 CO to 774474 tive dose of 5 mg/kg of a 48% chlorine PCS (refs. 73,88). Japanese quail demonstrated porphyrogenic action when dosed with PC8 fo r 7 days at dosage rates of 1 to 100 mg/kg o f Aroclor 1260 (ref. 86). Nichizumi measured the formation of aminoevulinic acid by liver mitochondria; significant increases of greater than 10.5 to 120 m/moles A L A per gram of liver per hour were found. PCB concentrations in the liver ranged from 1.4 to 478 ppm between the 1 mg/kg and 100 mg/kg dosage rates. The most marked effect was noted at the 100 mg/kg dosage rate, in which microscopic tissue fluores cence was seen in three o ut o f five cases and two out of five cases respectively. Domestic chickens demonstrate an acute susceptibi lity to Aroclor intoxification; liver enlargement occurs at dosages ranging from 100-1,000 ppm of Aroclor 1242 and m ortality occurs at rates above 200 ppm (ref. 88). However, Aroclor 1258 causes m ortality at dosages above 100 ppm and partial mortalitites at dosages above 30 ppm when fed in a diet fo r 4 to 5 weeks. One hun dred percent m ortality occurs in chickens fed Aroclor 1254 above 250 ppm. Pathologically, clinical observa tions demonstrate that general edema occurs at all toxic dosages (refs. 7, 10, 35, 43, 55, 56). Internal haemorrh aging and tubular dilatation in kidneys are accompanied by enlargement o f the kidneys, in addition to defeather ing and dermatitis (refs. 86,88). Depression and second ary sexual characteristics occurred at levels as low as 30 ppm o f Aroclor 1248 (ref. 7). Sublethal effects caused by enzyme induction and increased steroid metabolism have been demonstrated in pigeons. American kestrels fed Aroclor 1254 and 1262 at levels of 0.5 and 5 ppm fo r 5 months affected hor mone metabolism (refs. 53, 6 6 ,6 7 ). In an interaction o f polychlorinated biphenyls and duck hepatitis virus, 10-day-old ducklings fed Aroclor 1254 at levels o f 25, 50 and 100 ppm had significantly higher m ortality than those birds not exposed to PCB (ref. 13). Vos and Koeman (1970) found direct effects on the lymphoid system in chickens (ref. 88). Peakall and Lincer (1972) observed embryonic m ortality and chromosomal aber rations in ring doves fed Aroclor 1254 at 10 ppm over two generations (ref. 54). They found that 13 o f 17 PCB-treated embryos had aberration rates exceeding the mean control. Results thus indicate possible cfastogenic (i.e., chromosome-breaking) action of PCB in dove em bryos. Eggshell thinning was not observed in either the first or second generation. Dahlgren et al. observed that pheasant fe rtility and eggshell thickness were not affec ted by PCB exposure (ref. 10). The chief effects on re production occurred through PCB taken in by the hen b ut not by the cock. In laying pheasant hens, the major effects were observed in egg production, hatchability. and viability o f the embryo. There also was a subtle effect on behavior, as the visual c liff and ability of o ff spring to avoid hand capture was adversely affected. Among the most profound demonstrations of the adverse effects of PCB was the inhibition of mink repro duction that was caused by feeding them coho salmon containing PCB residues (refs. 2, 62, 63). CONCLUSIONS Polychlorinated biphenyls are highly persistent en vironmental contaminants that bioaccumulate in food chains and produce direct acute and chronic effects as well as subtle impact on the growth, reproduction, be havior, and health of fish, birds, and mammals. Fresh water fish are particularly susceptible to chronic effects since PCB residues concentrate at high levels that are known to elicit serious toxicological effects. Fish-eating birds and mammals are thus subject to hazardous levels o f residues. However, the actual mode of action and ecological effects are poorly understood, as is the long term impact o f PCB on animal populations. ACKNOWLEDGMENTS The staff o f the Fish-Pesticide Research Laboratory under the direction of Dr. Richard A. Schoettger contri buted the major portion of the information on effects o f PCB on aquatic organisms. The detailed Q uarterty and A nnual Reports o f the Research D ivisions o f the Bureau o f S port Fisheries and W ild life during 1969-1972 were especially helpful in addition to the publications and unpublished manuscripts from which the tables and figures were developed. The technical assistance of Drs. David L. Stalling, Paul M. Mehrle, Foster L. Mayer, and Mr. Jerry R. Longcore and Mrs. Laura Crane was partic ularly helpful. SCIENTIFIC NAMES C utthroat tro u t (Sa/mo c la rk i); rainbow trout {Salmo gairdneri) ; A tla n tic salmon (Sa/mo sa/ar); coho salmon [Oncorhynchus kisutch); lake tro u t [Salvelinus nam aycush): Japanese or coturnix quail (C otum ix cotum in); bald eagle (Hafiaeetusleucocephafus); doublecrested cormorant [Phalacrocorax auritus); Caspian tern (Hydroprogne caspia); Fosters tern [Sterna fosteri); osprey (Pandion ha/iaetus); mallard duck [Anus p/atyrhynchos); great blue herons (Ardeo herodias); red breast ed merganser (Mergus serratus); common merganser [Mergus merganser); American kestrel [Falco sparverius); ring dove (Steptopelia riso rla); pigeon (Columba Itvia): pheasant [Phasianus colchicus) ; squirrel monkey (Satm iri UfcNP 005827 277 774475 sciureus); cynomolgus monkey (Macaca sp.); mink (Mustela vison). REFERENCES 1. J. A. Armour and J. A. Burke, "Method for Separa ting Polychlorinated Biphenyls From DDT and Its ANon.al4og(1s,9"7J0.),Apsps.oc7.61O-7ff6ic8i.al Anal. Chem., Vol. 53, 2. R. J. Aulerich, "Effects on Feeding Coho Salmon and Other Great Lakes Fish on Mink Reproduc 3. tion," G. E. BCaagnlaeyd,iaWn .ZIo.oR!.e,icVhoell., 49 (1971), p. 611. and E. Cromarie, "Id e n tification of Polychlorinated Biphenyls in Two Bald Eagles by Combined Gas-Liquid Chromatography- Mass Spectrometry,"J. Assoc. Vol. 53 (1970), pp. 251-261. O fficial Anal. Chem., 4. S. Bailey and P. J. Bunyan, "Interpretation of Per sistence and Effects of Polychlorinated Biphenyls in Birds," 34-36. Nature, Vol. 236, No. 5340 (1972), pp. 5. G. A. Bennett, C. K. Dinker, and M. F. Warren, "Morphological Changes in the Livers of Rats Re sulting From Exposure to Certain Chlorinated Hydrocarbons," (1938), p. 97. J. Indust. Hyg. Toxicol., Vol. 20 6. Fredrick Berglund, "Levels of Polychlorinated Bi phenyls in Foods in Sweden," sSpeei.c,ti(v1e9s7, 2N),op. p1., DHEW, 67-72. Nat. IEnsntv.irEonnv. irHoena. ltHh ePalethr 7. Joel Bitman, Helene C. Cecil, and S. J. 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G, Heath, "Nationwide Residues of Organochtorines in Wings of A dult Mallards and Black Ducks" Pesticides M onitoring J. (in press). 93. G. Widmark, "Possible Interference by Chlorinated Biphenyls," J.' Assoc. O ffic ia i Anal. Chem., Vol. 50 (1967), p. 1069. 94. V. Z itko, 0 . Hutzinger, and P, M. K. Choi, "C on tamination o f the Bay of Fundy-Gulf o f Maine Area With Polychlorinated Biphenyls, Porychlorinated T e rp h e n y ls , C h lo rin a te d Dibenzodioxins and Dibenzofurans," Environ. Health Perspectives. No. I , DHEW, Nat. Inst. Environ. Health Sci., (1972), pp. 47-54 GENP 005831 281 774479 PCB's: EFFECTS ON AND ACCUM ULATIO N BY ESTUARINE ORGANISMS David J. Hansen-* A b s tra c t E ffects o f PCB's on and.accum ulation b y estuarine organisms were studied in laboratory bioassays. A roclors 1016, 1242, and 1254 were acutely to xic to certain estuarine organisms a t concentrations greater than 10 pg/i, b u t these bioassays underestim ated toxicides o f PCB's, as shown b y data from exposures th at fasted long er than 2 weeks. Concentrations th a t were letha/ to selected invertebrates and fishes in chronic exposures ranged from 0.1 to 5 pgA. Reproduction o f sheepshead m innows was im paired b y concentrations o f A ro clo r 1254 in th eir eggs> 5 pgfl, b u t this was n o t observed in eggs th at contained up to 77 pg/g o f A ro clo r 1016. B io accum ulation o f PCB's in estuarine organisms generally exceeded 10* times the concentration in water in labora to ry studies and /0 s times in the estuary. Following the discovery o f PCB's in Escambia Bay, Florida, in 1969 (ref. 1), the Environmental Research Laboratory at Gulf Breeze, Florida, began studies w ith PCB's to determine their effects on and bioaccumufation by estuarine organisms. Estuarine organisms studied in cluded bacteria (ref. 2); protozoans (ref. 3,4); oysters (refs. 5,6); shrimp (refs. 7,8,9,10,12,13); fishes (refs. 14,15,16,17,18,19); and communities o f benthic orga nisms (ref. 20). The following discussion is confined to research on Aroclor 1016, 1242,1254 because these PCB's are presently produced in the greatest quantities. Aroclors 1016, 1242, and 1254 are acutely toxic to certain estuarine organisms. The 48- or 96-hour LC50's, in pg/l, range from 9 to 32 fo r penaeid shrimp, 12 to 16 for grass shrimp, > 1 00 for pinfish and EC50 (reduction of shell growth fo r oysters) from 10 to 32 pgfl (refs. 1,15,21). Laboratory bioassays lasting longer than 2 weeks demonstrate that acute bioassays underestimate the toxicities of Aroclors 1016 and 1254. Aroclor 1254 is toxic to commercially valuable shrimps \Penaeus spp.) and grass shrimp {Pafaemonetes pugio) at concentrations of 1 Pgfl (refs. 8,11). Exposed shrimp are particularly sensi tive to salinity stress (ref. 11) and possibly to viral dis ease (ref. 13). Aroclor 1254 decreases growth rates of Environmental Research Laboratory, Environmental Pro tection Agency, Gulf Breeze, Florida. 32561 Registered Trademark, Monsanto Company, St. Louis, Missouri. oysters {Crassostrea virginica), at 4 pgfl (ref. 5). A t con centrations of about 5 p g fl, Aroclor 1254 is lethal to juvenile fishes: spot (Leiostomus xanthurus), pinfish (L ag od on rh o m b o id e s ), and sheepshead minnow (Cyprinodon variegatus) (refs. 14,19). A t Aroclor 1254 concentrations o f 0.1 p g fl, some sheepshead minnow fry die (ref. 19). Aroclor 1016, at 15 pg/l, was lethal to pinfish and sheepshead minnows; susceptibilities of fry , juvenile, and adult sheepshead minnows were similar (refs. 15,18). Aroclor 1254 affects reproduction o f the sheep shead minnow, an estuarine fish (ref. 16). A dult fish exposed fo r 4 weeks to 0.1 pgfl appeared to be unaffect ed, but when eggs from these fish were fertilized and placed in PCB-free water, the survival o f fry was diminshed. M ortality was observed also in fry from eggs that contained greater than 5 pgfg o f the PCB and increased as PCB content o f the eggs increased. Reproductive suc cess of A tla ntic salmon (ref. 22) and striped bass (ref. 23) may also be affected by PCB's in their eggs. A dult sheepshead minnows that had been exposed fo r 4 weeks to from 0.3 to 3 pgfl of Aroclor 1016 produced eggs that contained from 3 to 77 pgfg o f this PCB, yet fry that hatched from these eggs were apparently unaffected (ref. 18). Estuarine organisms accumulate PCB's from water. Maximum concentration factors (concentration in ani mals divided by concentration in water) in laboratory exposures o f various species to Aroclor 1254 were: oys ters, 101,000 (ref. 5) to 165,000 (ref. 6); shrimp, 26,000 (ref. 9); and fishes, 37,000 (refs. 14,19). The maximum concentration factor determined from exposures of fishes to Aroclor 1016 was 34,000 (refs. 15,17). Fishes exposed continuously to Aroclors 1016 and 1254 accu mulated both Aroclors in increasing concentrations fo r about 4 weeks; thereafter, the quantity stabilized (refs. 14,15), Maximum concentrations were found in the liver, gills, and skin of the fish, but the lowest concentra tion found in fishes' and shrimps was in the muscle (refs. 14,15,8). Bioconcentration factors calculated from data from Escambia Bay (refs. 1,10) were greater than 230.000 fo r shrimp, 670,000 fo r fishes, and greater than 100.000 fo r oysters, indicating that laboratory data can underestimate bioconcentration potentials o f Aroclor 1254. 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Forester, "Effects of the Polychlorinated Biphenyl Aroclor 1254 on the American Oyster, Crassostrea virginica," Mar. B io l., Vol. 17, No. 3 (1972), pp. 209-214. 6. Patrick R. Parrish, "A ro clor 1254, DDT, and DDD, and Dieldrin: Accumulation and Loss by American Oysters (Crassostrea virginica) Exposed Continuously fo r 56 Weeks," Proc. Nat. Shellfish Assoc., Vol. 64 (1974), p .7 . 7. D. R. Nimmo, P. D. Wilson, R. R. Blackman, and A. J. Wilson, Jr., "Polychlorinated Biphenyls Absorbed F ro m Sediments by Fiddler Crabs and Pink Shrim p," Nature, Vol. 231 (1971a), pp. 50-52. 8. D. R. Nimmo, R. R. Blackman, A. J. Wilson, Jr., and J. Forester, 'T o x ic ity and D istribution of A ro c lo r 1254 in the Pink Shrimp, Penaeus duorarum ," Mar. B io l., Vol. 11, No. 3 (1971b), pp. 191-197. 9. D, R. Nimmo, J. Forester, P. T. Heitmuller, and G. H. Cook, "Accumulations o f A roclor 1254 in Grass Shrimp (Pataemonetes pugio) in Laboratory and Field Exposures," B ull. Environ. Contam. Toxicol., Vol. 11 (1974), pp. 303-308. 10. D. R. Nimmo, D. J. Hansen, J. A. Couch, N. R. Cooley, P. R. Parrish, and J. I. Lowe, 'T o x ic ity of Aroclor 1254 and Its Physiological A ctivity in Several Estuarine Organisms," Arch. Environ. Concam. Toxicol., Vol. 3, No. 1 (1975), pp. 22-39. 11. D. R. Nimmo, and L. H. Bahner, "Some Physiologi cal Consequences of Polychlorinated Biphenyl- and Salinity-Stress in Penaeid Shrim p," P ollution and Physiology o f Marine Organisms, F. John Vernberg and Winona B. Vernberg, eds.. Academic Press, New York, (1974) pp. 427-443. 12. DelWayne R. Nimmo, and Lowell H. Bahner, "Metals, Pesticides, and PCB's Toxicities to Shrimp, Singly and in Com bination," Proc. Estuarine Res. Fed., Third Intematl. Estuarine C onf,, October 7-9, 1975, Galveston, Texas. 13. John A. Couch, and DelWayne R. Nimmo, "U ltrastructural Studies of Shrimp Exposed to the Pollut ant Chemical, Polychlorinated Biphenyl (Aroclor 1254)," B ull. Soc. Pharm. Environ. Pathol., Vol. 11 (1974) , pp. 17-20. 141 D. J. Hansen, P. R. Parrish, J. I. Lowe, A. J. Wilson, Jr., and P. D. Wilson, "Chronic T oxicity, Uptake and Retention of Aroclor 1254 in Two Estuarine Fishes," B ull. Environ. Contam. T oxicol., Vol. 6, No. 2 (1971), pp. 113-119. 15. D. J. Hansen, P.. R. Parrish, and J. Forester, "A ro clo r 1016: T o xicity to and Uptake by Estuarine Animals," Environ. Res., Vol. 7 (1974a), pp. 363-373. 16. D. J. Hansen, S. C. Schimmel, and J. Forester, "A ro clor 1254 in Eggs o f Sheepshead Minnows: Effect on Fertilization Success and Survival of Embryos and F ry ," Proc. 27th A nn. Conf. S.E. Assoc. Game Fish Comm., 1974b, pp. 420-426. 17. D. J. Hansen, S. C. Shcimmel, and E. Matthews, "Avoidance o f A roclor 1254 by Shrimp and Fishes," B ull. Environ. Contam. T oxicol., Vol. 12 (1974c), pp. 253-256. 18. D. J. Hansen, S. C. Schimmel, and Jerrold Forester, "E ffe c t of Aroclor 1016 on Embryo, Fry, Juvenile and A d u lt Sheepshead Minnows (Cyprinodon va rie g a tu s)T ra n s. Am . Fish. Soc., Vol. 104, No. 3 (1975) , pp. 582-586. 19. S. C. Schimmel, D. J. Hansen, and J. Forester, "Effects o f Aroclor 1254 on Laboratory-Reared E m b ry o s and F ry o f Sheepshead Minnows (Cyprinodon variegatus)," Trans. Am . Fish. Soc., Vol. 103, No. 3 (1974), pp. 582-586. 20. David J. Hansen, "A ro clo r 1254: Effect on Com position of Developing Estuarine Animal Com munities in the Laboratory," C ontrib. Mar. Sci., Vol. 18 (1974), pp. 19-33. 21. Jack J. Lowe and Patrick R. Parrish, U.S. Environ mental Protection Agency, Environmental Research Laboratory, G ulf Breeze, Florida, unpublished data. 22. Nils Johannsson, S. Jensen, and M. Olsson, "PCB -- Indicators of Effects on Fish," in "PCB conference, Wenner-Gren Center," Sept. 29, 1970, pp. 59-68. Natl. Environ. Prot. Bel., Stockholm. 23. A n o n y m o u s , 'T h e Striper -- This Century's Dinosaur," Stripers U nlim ited, 1971 D irectory and Guidebook, 1971, pp. 11-62. 8C00 rri'J'qA 283 7 7 4 4 8 1 SUMMARY OF RECENT INFORMATION REGARDING EFFECTS OF PCB'S ON FRESHWATER ORGANISMS Alan V. Nebeker, Ph.D.* A bstract Polychlorinated biphenyls (PCB's) are to xic to freshwater organisms a t concentrations below 5 p gfl (ppb), and new ly hatched fish and sm all insects and crustaceans w ith short life cycles are m ost sensitive. A ro clo r 1254 a t 0.45 pgA produced a 5 0 percent de crease in midge reproduction; 1.3 p g /l caused a 50 per cent reduction in Daphnia reproduction; and 1.8 pgA produced 50 percent reduction in fathead minnows. The in d ire ct to x ic ity o f PCB's to predators through accumu latio n o f PCBs in tissues o f fo o d organisms causes death. Fish can accumulate 200,000 times more PCB's in their flesh. than can be held in the surrounding water. The concentration o f A ro clo r 1260 in the water resulting in a tissue residue o f 0.5 pg/f is approxim ately 0.002 pgA. A ro clo r 1016 and 1242 have been shown to have sim ilar to x ic ity to freshwater organisms. The Environm ental Protection Agency proposed water q u a lity criterion fo r PCB's is as follow s: " M axi mum acceptable concentration o f PCB's in water is 0.001 mV and the residues in the general body tissues o f any aquat ic organism do not exceed 0.5 pg/g. The Environmental Protection Agency (ref. 2) also proposed water quality criteria fo r PCB's as follows: "Maximum acceptable concentrations o f PCB's in water are 0.002 pg/I, and maximum acceptable levels of resi dues in general body tissues o f any aquatic organism are 0.5 p g /l"; follow ing the proposed criteria recommended by the National Academy "Blue Book." However, these criteria have not been promulgated. Recently, the En vironmental Protection Agency (ref. 3), using the latest information available, has proposed 0.001 pg/l PC8 as a maximum permissible concentration in freshwater, but has proposed no tissue level criterion. The purpose o f this paper is to present a summary o f recent inform ation dealing w ith the toxicity o f p oly chlorinated biphenyl compounds to freshwater fish, crustaceans, and aquatic insects, and to present impor tant recent information on the bioconcentration of PCB's in fish tissues and its effect on consumer orga nisms. Polychlorinated biphenyls (PCB's) are toxic to freshwater fish and other aquatic organisms at very low levels and direct toxic effects are evident within a few hours, but much greater harm is caused by longer ex* posure at lower concentrations. PCB levels that kill fish, Crustacea, and aquatic insects are similar to those o f DDT and several other pesticides. Environmental occur rence o f these materials is increasing and there is mount ing evidence that they are causing widespread harm in the freshwater aquatic environment. One of the significant accomplishments since the discovery of the to xicity of PCB's to freshwater orga nisms was the synthesis o f known data and their publica tion in the "Blue Book," or Water Q uality C riteria-- 1972, sDonsored by the U.S. Environmental Protection Agency and prepared by the National Academy of Sciences, National Academy o f Engineering Committee on Water Quality Criteria (ref. 1). It was recommended in this report that aquatic life should be protected where the maximum concentration of total PCB in unfiltered water does not exceed 0.002 pgA at any time or place. ` Western Fish Toxicology Station, Corvallis Environmental Research Laboratory, U.S. Environmental Protection Agency, Corvallis, Oregon. Fish A significant amount o f new inform ation dealing w ith the to x ic ity of PCB's to fish has been collected during the last 3 years. Acute and longer term studies have been conducted w ith a variety of freshwater sport and forage fish species. Tests w ith fathead minnows at the National Water Quality Laboratory, D uluth, Minne sota, (ref. 4) have shown that Aroclor 1242, A-1248, and A-1254 are toxic below 5 pg/l. Ninety-six-hour LCSo values (that concentration which kills half the fish in 96 hours) fo r newly hatched fathead minnows were 15 pql\ fo r Aroclor 1242 and 7.7 pgA fo r A-1254. F ifty percent died at 8.7 pg/l A-1248 after 30 days. A fte r 60 days, half were dead at 8.8 pg/l A -1242 and 4.6 pg/l A-1254 (table 1). Two 9-month continuous-flow bioassay tests were conducted (ref. 4) w ith the fathead minnow to deter mine the effects of Aroclor 1242 and A-1254 on survival and reproduction (table 2). Concentrations of Aroclor 1242 above IOpg/1 were lethal to newly hatched fry and all minnows were dead after 96 hours in 51 pg/l A-1242; none survived to the end o f the test at 15 pg/l. Fry survived when reared in the same concentrations at which their parents lived and spawned; however growth o f newly hatched fish was retarded p rior to their death 284 774482 co Table m1.innAocwuste, GtoaxmicmitayruosfaAnrdocDloarph1n2i4a,2,in1c2o4n8t,inaondus-1f2lo5w4 ttoesftasthead Test temp. 96-(phrg/DLC503 ____6_0_-d(auyg/DLC_5_0___ (C) 1242 1248 1254 1242 1248 1254 Fathead minnow, newly hatched 24 15 h 7.7 8 . 8 8 .7C 4.6 Garnnarus oo o G^JJ --29 8 .7C 5.Ie Daphnia 18 12.9 6.4 - 2 .6 d 1 .8 d Concentration where 50 percent died after 96 hours. bNo mortality after 96 hours . cThirty-day LC50* dFourteen-day LC5Q. Table 2. Spawning andAegrogcplorrod1u2c4t2ioanndof1f2a5th4ead minnows exposed to Aroclor (ug/Dconcentrati on Number of spawnings per female Number of eggs per spawning Number of eggs per female Percent eggs hatched Aroclor 1242 51.0 15.0 5.4 2.9 0.9 0.0 Aroclor 1254 15.0 4.6 1.8 0.5 0.2 0.0 0 0 2.5 3.9 1.3 4.6 0 0 1.0 5.2 3.0 2.4 0 0 30 63 28 90 0 0 63 105 64 104 00 00 151 81 283 38 35 84 442 53 00 00 106 79 556 63 221 55 253 75 285 774483 G EN P 005835 lAarrvoacl:onrl 1il25:4m. ossuqrvuiivtoedCuwleelxl taanrsdalpisu,peaxtpeods,ebduttom1a.n5ypyo/lf the pupa.1were unable to metamorphose into the adult form. Control organisms pupated with success. BiocoBnicoecnontrcaetinotnration, biological magnification, bioaccu mulation, PCB or tissue residues, and residue dynamics, are some of the terms used to describe the intake of PCB's from food or direct water contact into the animal and accumulation in the tissues to concentrations many thousands of times those in the water or food they were exposed to. Polychlorinated biphenyls are much more soluble in fatty tissues (lipids) than water and are selec tively concentrated in those tissues. Animals that feed on aquatic invertebrates or fish that have bioaccu mulated significant tissue concentrations of PCB's are threatened even when the prey species are not adversely affected. Exposure of fish to water containing PCB's demon strates that they can bioconcentrate PCB's directly from the water, in addition to uptake in food, and in most cases direct uptake from water is more rapid and leads to much higher accumulation in the tissues. The bioconcen tration factor (concentration in fish tissue/concentration in the water) for PCB's is essentially independent of the PCB concentration in the water. The bioconcentration factor (whole body) for adult male fathead minnows at 25 C is approximately 1.2 X 105 (120,000) for Aroclor 1248 and 2.7 X 105 (270,000) for Aroclor 1260. Fe male fathead minnows accumulated about twice as much PCB's as the male fatheads and the difference is largely The residue of PCB's in the tissues of fathead min nows studied by DeFoe et al. (ref. 7) was directly pro portional to the concentration of the toxicant in the water. The concentration of Aroclor 1248 in the water mreasutelltying0.0in04a/jgti/s|.suTeherecsoidnuceenotrfat0io.5n oufg/Agrowcalosra1p2p6ro0xiin the water resulting in a tissue residue of approximately 0.002 /-ig/l. They showed 0.5 that tuhge/gmworaes highly chlorinated PCB mixtures are bioconcentrated to a greater extent in the lipids of the fish than the lower chlorinated compounds. They also showed that the PCB residues in the fish reached an apparent steady state after approximately 100 days, and when exposed fish were placed in untreated Lake Superior water they eliminated less than 18 percent of the body burden after 60 days. Nebeker et al. (ref. 4) showed that the bioconcen tration factor for Aroclor 1254 in fathead minnows ranged from 1.1 X 10s to 2.4 X 10s and that the bio concentration factor for several PCB's in the fathead minnow ranged from about 0.3 X 10s to 2.7 X 105 with the more highly chlorinated PCB's accumulating to a greater extent. Adult fathead minnows accumulated up to 430 ppm A-1242 in whole body residues, with con centrations up to 270,000 times that of water, and up to 1,000 ppm of 1254, with concentrations up to 230,000 times that of the water over 500 ppm 1248 and (ref. 400 4p)p,mGa1m24m2a,ruwsitahcccounmcuelnattread tions over 100,000 times that of the water (ref. 14). Sodergren and Svensson (ref. 19) showed that the tnoymbipohcoonfcEenpthreamtioenrafadcatnoircsa accumulated Clophen A of 3 X 103. After 60 days 50 of exposure to Aroclor 1242 and A-1248, the maximum bioconcentration factor was approximately 3 X 1in04Gaanmdm5arXus 1p0s4e,urdeosplimecntiaveeulys (ref. S1a4n)d. ers and Chandler (ref. 18) showed that the uptake and biological magnification of Aroclor 1254 by some aquatic invertebrates was very rapid. When Dtaainpihnngia1.m1 apggn/1a owfeAre-1e2x5p4o,stehdeyfoarcc4umdauylsatetod water total con body concentrations 48,000 (4.8 X 104) times greater than those posed in to water. water The mosquito containing 1.5 nlga/rlvaAe-1C2u5l4exactcaursmahu'slateexd psA1es9-ne1tuu2sgd5/o4gal,imo1rfne2aat,h6ecih0use0sdc-,foomealdxnppoomeusqneauddginlwiibfciirtocihuanimtntiion2nuc4.oouhnSsoccluyeurndsts,rt,awotGhioiac1nmh.6mrineajpurrug1e/4sl days. Total body 27,500 times that residues were in the water. 44 ug/g. a concentration Some evidence exists that the bioconcentration fac tors measured in the laboratory are essentially the same as those found in the river environment. Veith and Lee (refs. 20, 21) reported that goldfish in the lower Mil waukee River accumulated Aroclor 1248 approximately 0.7 X 105 to 2 X 10s times (depending on the lipid content) the estimated PCB concentration in the river water. The maximum concentration of Aroclor 1254 in Saginaw River concentrations shad was averaged 165 1.1 upgg//g1, whereas with a typical water maximum of 2.9 Mg/I (ref. 22). This indicates a bioconcentration of 0.6 X 10s to 1.5 X 10s . Studies resulting from the reproductive failure of mink fed Great Lakes fish led to the conclusion that it was PCB residues in the fish that caused the adverse effects. Ringer et al. (ref. 23) demonstrated that 10jug/g of Aroclor 1254 in coho salmon produced 71 percent mamnoodrrtt0aa.ll5iittyyu.gi/nNgodmikeinlidtksrianwnedinretchobahotoranfemaelidixvetpurrwoedhuoecfne1dt0h1eu0g0d/igpeetPrCcceoBnn'st tctoaoinnbceeedlnet5srsauttghio/agnn or greater o1f.0P/iCgB/g.s Aroclor alone. The ''no effect" in the mink diet was estimated Platonow and Karstad (ref. 24) presented similar GE N P 005836 286 774484 at h itte r PCB concentrations. Reproduction occurred and good egg hatching took place at and below 5.4>ig/l A-1242. Eggs produced by control fish but maintained at the higher concentrations of 15 and 51 jig/l hatched w ith good success but none o f the fry survived. Aroclor 1254 was more toxic to the fathead min now than A-1242 (ref. 4|, as they did n ot survive and reproduce above 1.8 /g/l A-1254 (table 21. A ll fish in the long-term study were dead after 96 hours at 15 jig/l, and growth was delayed at 4.6 Mg/I. Spawning occurred at 1.8 Atg/I but was significantly less than at the lower concentrations. Egg hatchability and fry survival were good at and below 1.8 Mg/I. Eggs produced by the con trol fish and, maintained at 15 /tg/l hatched readily, but all young fish were dead w ithin 96 hours. Growth o f young fathead minnows was affected above 2.2 Mg/I A-1248, and none survived above 5.1 ig/l after 30 days. Young flagfish did not survive at Aroclor 1248 concentrations above 5.1 /g/l and did not grow well above 2.2 pg/l (ref. 4). Due to low PCB solubility, 96-hour LC30 values do not adequately reflect PCB toxicities to fish. For Aro clor 1221-1268, 96-hour LCS0 values ranged from 1,170 to 50,000 M9/I fo r cutthroat trout. The acute oral to xic ity o f Aroclors 1242, 1248, 1254, and 1260 was greater than 1,500 mg/kg in rainbow trout. Interm ittent-flow bioassays of A-1242, 1248, and 1254 to bluegills re sulted in 15-day LCS0 values o f 54, 76, and 204 jxg/l, respectively. Exposures to channel catfish gave 15-day L C j0 values of 107, 127, and 741 tigA fo r the same Aroclors. All LCjq values decreased significantly w ith longer exposure, indicating the much greater PCB hazard with increased exposure time (ref. 5). Direct water expo sures appear to represent a greater hazard to fish than dietary exposures, but dietary sources are important as PCB's have a high affinity fo r sediments and readily enter the food chain. Schoettger et al. (ref. 6 ) showed that the growth of lake trout was retarded by Aroclor 1248 in the diet fo r 3 months. Concentrations of 1.2, 3.8, and 12 pg/g de creased weight gain by 6 , 1 0 , and 28 percent, respectively, below that o f controls. The growth of the high-exposure group (1 2 /tg/g in diet) was only about half that of the controls after 6 months. Fathead minnows were exposed to Aroclor 1248 and A-1260 (ref. 7), in flow-through bioassays to deter mine the acute (30-day) and chronic (240-day life cycle) effects on the fry and adult fathead minnows. Newly hatched young were the most sensitive lifestage to the exposure of PCB's. Total m ortality occurred when newly hatched fatheads were exposed for 30 days to 8.5 pg/l A-1248. All fish exposed to 9.0 pg/1 A-1260 died after a 30-day exposure. The calculated 30-day T L S0 fo r newly hatched fathead minnows 8 hours old} was 4.7 g/l fo r A-1248 and 3.3 pg/l fo r Aroclor 1260. PCB's did not measurably affect the ability of fathead minnows to re produce at concentrations which were acutely toxic to the larvae. With reproduction occurring at and below 3 jug/l fo r A-1248 and at below 2.1 M9/I fo r A-1260, the 20 percent reduction in the standing crop in the second generation of minnows at concentrations as low as 0.4 pg/1 is due to the m ortality of the fathead larvae soon after hatching. Aroclor 1016, a compound chemically similar to A-1242, has been introduced recently to replace PCB's of the Aroclor 1200 series in many applications. Work has been completed w ith this compound with freshwater organisms and what is available indicates that the toxic ity of Aroclor 1016 is similar to that o f Aroclor 1242. Mayer (ref. 8 ) presents data on the toxicity of Aroclor 1016 to nine species of freshwater fishes. Bluegills had a 4-day LC jo o f 260 jig/1 A-1016; rainbow trout, 135 /jg/l; Atlantic salmon, 134 /zg/f; and yellow perch, 185/ig/l A-1016. Johnson (ref. 9) presented data comparing the effects o f A-1242 and A-1016 on rainbow trout and bluegill sunfish. Rainbow tro u t had a 10-day LCj 0 of 39 pg/l fo r A-1242 and 17-day LC30 o f 49/xg/I fo r A-1016. Bluegills had a 15-day LC30 o f 54 /ig/l A-1242 and a 35-day LCjo of 43 ugA for A-1016. They had 96-hour LCS0 values o f 125 /ig/l A-1242 and 46 g/I A-1016. A test comparing the to x ic ity o f Aroclor 1242 and Aroclor 1016 using fathead minnows was completed by Veith (ref. 10). There was no difference in the survival of fry after 96 hours between A-1242 and A-1016 at 28 M9/I; both had 50 percent m ortality. In 30-day tests, 100 percent m ortality o f fry occurred at 42 pg/TA-1242 and 95 percent m ortality occurred at 42 /ig/l A-1016. Approximately 50 percent had died after 30 days at 25.5 pg/l A-1242 and 30.5 /zg/1 A-1016. The effects of Aroclor 1242 on the guppy Poeciiia reticulata were studied by Morgan (ref. 11) in static tests. The guppy had 100 percent m ortality at 20 and 2 ppm, but only 25 percent m ortality at 0.2 ppm after 7 days. In prelim inary investigations, Jensen, e ta li (ref. 12) reported a possible relationship between PCB residues in salmon eggs and egg m ortality in Sweden. When residues in groups of eggs ranged from 0.4 to 1.9 /zg/g on a whole-weight basis (7.7 to 34 pg/g on a fat basis), related mortalities ranged from 16 to 1 0 0 percent. No adverse effects were observed on survival, growth, and reproduction of brook tro u t exposed for 71 weeks to 0.94 /ig/1 and lower concentrations o f the PCB GENP 005837 287 774485 O o oLGAO LP GO Aroclor 1254. Survival and growth to 90 days of alevmjtwinilns from exposed parents were also unaffected. PCB concentrations in the brook tro u t were directly pro* portions! to the water exposure concentration. PCB tis sue concentrations appeared to have reached a steady state by the first sampling following 14 weeks o f expo sure. PCB residues (wet tissue basis) in chronically exposed fish were approximately 2 pg/g in the fille t and 9 pg/g in the "whole body" (minus one fille t and the gonads) at the highest water concentration, 0,94 jig /1 . The higher residue in the "whole b od y" compared to the corresponding fille t was due to the higher fa t content of the former (ref. 13). Thyroid stimulation in coho salmon ranged from a 52 percent increase in fish fed 0.48 #ig/9 Aroclor 1254 of food to a 119 percent increase in the high-treatment group (480 jug/g). The lowest detectable stimulation of thyroid activity occurred in salmon dosed w ith 1/ 10 0 0 th that caused m ortality. In channel catfish, 2.4 ^ 9/g and 24 pg/g A -1254 in food caused significant increases in thyroid activity when compared to control fish (ref 15). Crustacea Freshwater crustaceans are very sensitive to low concentrations o f PCB's. Because o f their generally short life cycles they wilt be eliminated from PCB contaminated waters quite rapidly, causing not only their loss from aquatic systems but impairment o f fish populations because of a decrease in fish food organisms. To assess the danger of PCB compounds to fish food organisms, bioassays were conducted w ith Daphnia magna (ref. 14) using the eight commercially available PCB's, Aroclor 1221, 1232, 1242, 1248, 1254, 1260, 1262, and 1268 (table 3). Aroclor 1248 was the most toxic to Daphnia magna of the eight Aroclors tested in static tests; the 3-week LCS0 was 25 pg/l. Aroclor 1232, 1242, and 1254 had similar to xicity values to A-1248. Jn continuous-flow Daphnia tests, Aroclor 1254 was the most toxic, w ith a 3-week LC$o o f 1.3 pg/l. No repro duction occurred at 3.8 pg/l A-1254, and no adults sur vived 3.5 pg/l. The Aroclors were much more toxic in continuous-flow conditions due to continual replace ment of fresh PCB. Almost one-third of the PCB added to the test water was lost to the air, w ith some lost to bacteria, algae, waste materials, test container surfaces, and test animal tissues. The difference between static and continuous-flow results (table 3) illustrates how critical test methodology can be for certain chemicals. The freshwater scud Gammarus pseudo/imnaeus was also studied by Nebeker and Puglisi (ref. 14) in con tinuous-flow test systems to determine the effects of A-1242 and A-1248 on survival and reproduction. Nine ty-six-hour LCjo values were 7 3/ig /l fo r A-1242 and 29 Table 3. Toxicity of eight Aroclors to D aphnia m agna in static and continous flow bioassays A ro c lo r 3-week LC-n* (PCB) ( u g / l) 50 50 percent reproductive** Instalm ent ( p9 /1 ) Continuous-flow te s t conditions 1248 2.6 1254 1.8e 1254 1.3 S ta tic te s t conditions 1221 180 . 1232 72 1242 67 1248 25 1254 31 1260 36 1262 - , 43 1268 253 2.1 1.1 1.3 125 66 63 24 28 33 41 205 C o n c e n tra tio n where 50 percent d ie d . bFf f t y percent loss o f young. cTwo-week.LCgg. pqf\ fo r A-1248. F ifty percent were surviving after 60 days at 8.7 pg/l A-1242 and 5.1 pg/l A-1248. No live animals remained after 2 months at 26 pg/l A-1242 or 1 8/ig /l A-1248 (table 4). Good reproduction occurred at and below 2.8pg/l A -1242 and 2.2 pg/i A-1248. Static and flow-through to x ic ity tests w ith aquatic invertebrates (ref. 5) indicate that they are generally more susceptible to acute toxic effects o f PCB's than fish. Gammarus faciatus in flow-through tests had a 96-hour LCso o f 10 pg/l A-1242 and a 10-day LCjo of 5 pg/1 A-1242. The glass shrimp Palaemonetes kadiakensis was very sensitive to A-1254, w ith a 7 day LC90 of 3 Atg/I- In static tests w ith the amphipod Gammarus pseudo/imnaeus, Mayer et al. (ref. 15) found that of four PCB homologs tested', the trichlorobiphenyl was slightly more toxic than the di-, penta-, and hexachlorobiphenyls. The trichlorobiphenyl had a 96-hour LCj 0 of 100 pq/l, two dichlorobiphenyls tested had 96-hour LCjo values of 1 0 0 and 1 2 0 pg/l, the hexa- and pentahomologs had 96-hour LCS0 values o f 150 and 210pg/) respectively. The crayfish Orconectes nais was reported by Stal ling and Mayer (ref. 5) to have a 7-day LC50 of 30pg/l for Aroclor 1242 and a 7-day LCjo o f 80 pg/l for A-1254. 288 774486 Table 4. Survival and reproduction of Gam m arus pseudo/im naeus after 2 months exposure to Aroclor 1242 and 1248 A ro c lo r concentration (us/l) A ro c lo r 1242 234.0 81.0 26.0 8.7 2.8 0.0 A ro c lo r 1248 18.0 5.1 2.2 0.5 a.2 0.0 S u rv iv a l o f adults (percent) 0 0 0 52 77 48 0 53 73 71 73 64 Young per s u rv iv in g a d u lt d 0 0 0 4 7 0 7 22 . 20 11 11 Daphnia puiex were quite sensitive to Aroclor 1242 (ref. 11). Young Daphnia p uiex died at levels as low as 0.02 ppm in 4-day static tests. The to x ic ity of Aroclor 1242 and OOT to the ostracod Cypidopsis vidua appear ed to be approximately the same in static tests. A t 20 ppm, there were no survivors out of 20 ostracods in the Aroclor cultures, and some m ortality occurred at 2 ppm. Studies by Moorman and Biesinger (ref. 16) compar ing the lethality of Aroclor 1016 and Aroclor 1242 to Daphnia magna have shown similar to x ic ity fo r both compounds in static tests. No young survived after 3 weeks at 125 pg/l A-1016 or A-1242. A t 100-pg/l, 80 percent o f the young (percent o f control) survived after 3 weeks in A-1016.and 19 percent of the young survived A-1242. Good survival occurred at 50 pg/l fo r both compounds. A study of tiie to xicity o f isomers of Aroclor 1242 and 1254 to Daphnia magna by Biesinger (ref. 17) showed significant reproductive impairment in static tests at 50 pqA for trichloro- and tetrachlorobiphenyls, indicating that there was tittle difference in the to xicity o f the tri- and tetra- chlorabiphenyl compounds. A quatic insects Aquatic insects also appear to be very sensitive to longer exposures o f PCB's, though response is variable when exposed to brief, or acute, concentrations. The midge Tanytarsus dissim i/is was tested through its full life cycle (ref. 14) and found to be affected at levels below 1 pg/1. Survival and growth of the midge, when tested with Aroclor 1254, were excellent in control chambers but were reduced by 50 percent at the lowest test concentration o f 0.45 pg/l (table 5). A t 1.2 pqA, the numbers of larval cases were reduced to 35 percent of the control, and the numbers o f pupal cases were reduced to 18 percent of the control. No adult emer gence occurred above 3.5 tg/l, and abundant adult emergence did not occur above 3 pg/l, even though lar vae were present. No pupal cases were constructed at 9 fiqA and no larval cases were formed at 33 pg/l A-1254. The calculated 3-week LCSo fo r A-1254 (50-percent re duction based on control <as 100 percent) was 0.65 pgA fo r larvae and 0.45 pqA fo r pupae. A d ult midges emerged at concentrations up to 9 pqA Aroclor 1248. Larvae were present at 18 pgA, but adult emergence did not occur. Abundant emergence did not occur above 5.1 /ig/l (ref. 12). Mayer et al. (ref. 15) report some acute data for other aquatic insects. Dragonfly and damselfly nymphs, Maeromia sp. and ischnura verticalis, were tolerant to Aroclor 1242 and A-1254 in short-term static tests. The dragonfly had a 7-day LCS0 o f 800 pgA fo r Aroclor 1242 and 1,000 pqA fo r A-1254. The damselfly, tested under continuous-flow conditions, had a 4-day LCS0 of 400 /ig/l fo r A-1242 and 200/xg/l fo r A-1254. a Studies by Sanders and Chandler (ref. 18) have shown that larvae of the stonefly Pteronarcys dorsata, the dobonfly Corydatus com utus, and the phantom midge Chaoborus punctipennis survived concentrations o f up to 2.8 jig /l A-1254 for up to 21 days w ithout significant m ortality. However, in similar experiments. Table 5. Effect of Aroclor 1254 on the growth and survival of the midge Tany tarsus dissim i/is A ro c lo r concentration (u g /1 ) N u tte r o f nature la r v a l eases (percent o f co n tro l) 33.0 9.0 3.5 1.2 0 .4 0.0 (co n tro l) 0 0.2 7 # 35 52 100 . Hunter o f pupal cases (percent o f c o n tro l) 0 0' 7 18 55 100 ; GENP 005839 289 774487 o o o 5CO evidence fo r mink fed diets enriched w ith Aroclor 1254. The data show that 0.64 ug/g o f PC8 in the rations resulted in only 1 o f 12 m ink producing 3 kits, all of which died on the first day. Research w ith nonhuman primates indicates that the to xicity of PCB residues to consumers are not limited to m ink. Barsotti and Allen (ref. 25) and Allen et al. (ref. 26) have shown that PCB enriched diets were toxic to primates. Female primates fed 2.5 fig/g Aroclor 1254 in their diet had periorbital edema, acneform lesions on face and neck, and substantially reduced fe rtility after 2 months. SUMMARY There is ample evidence that PCB's are toxic to freshwater organisms at very low concentrations. Newly hatched fish and small insects and crustaceans with short life cycles appear to be the most sensitive life forms. In larger animals or those w ith longer life cycles, toxic effects are delayed and acute or short-term testing does not adequately reflect the chronic or longer term effects that PC8's have on the test animals. Concentrations of polychlorinated biphenyls commonly found in contami nated waterways today, such as Aroclor 1242 and 1254, are directly toxic to fish and aquatic invertebrates in the range o f 0.1 to 10.0 pg/l. Aroclor 1016 and 1242 have been shown to have similar to x ic ity to freshwater orga nisms. The indirect to xicity o f PCB's to predators through accumulation of PCB's in tissues of food orga nisms may cause deaths from water concentrations that do n ot cause direct lethality. REFERENCES 1. National Academy o f Sciences, National Academy o f Engineering, Water Q uality C riteria 1972. Report o f the Committee on Water Q uality C riteria, EPAR3-73-033, March 1973. U.S. Environmental Pro tection Agency, Washington, D.C. (Blue Book), 1973. 2. U.S. Environmental Protection Agency, Proposed C riteria fo r Water Q uality, U.S. Environmental Pro tection Agency, Washington, 0 . C ,, Vol. 1 (1973). 3. U.S. Environmental Protection Agency, Proposed Water Q uality C riteria, U.S. EPA, Washington, D.C., (White Book), 1976. 4. A. V. Nebeker, F. A. Puglisi, and D. L. Defoe, "E f fect of Polychlorinated Biphenyl Compounds on Survival and Reproduction of the Fathead Minnow and Flagfish," Trans. Amer. Fish. Soc., Vol. 103 No. 3 (1974), pp. 562-568. 5. D. L. Stalling and F. L. Mayer, 'T o xicitie s of PCB's to Fish a n d ' Environmental Residues," Environ m e n ta l H ea lth Perspectives, A pril, 1972, pp 159-164. 6 . ` R. A. Schoettger, B. Grant, H. 0 . Kennedy, F. L. Mayer, H. O. Sanders, and D. Swedberg, "Special Report on Polychlorinated Biphenyls (PCB's)," Progress in S port Fishery Research, Fish-Pesticide Research Laboratory, Division -of Fisheries Re search, Bureau o f Sport Fishery and W ildlife, Wash ington, D.C., 1970, pp. 1-23. 7. D. L. DeFoe, G. D. Veith, and R. W. Carlson, " E f fects o f Aroclor 1248 and 1260 on the Fathead M innow ," J. Fish. Res. Board, Canada, 1976, (in press), 8. F. L. Mayer, 'T o x ic ity o f Aroclor 1016 to Fresh water Fishes," Fish-Pesticide Laboratory, USDI, Fish and W ildlife Service, Columbia, Mo., 1975. 9. W. Johnson, Unpublished report on to x ic ity of Aroclor 1016, Fish-Pesticide Laboratory, Columbia, Mo., 1973. 10. D. Veith, personal communication. PCB test data, National Water Quality Laboratory, D uluth, Minn., . 1975. 11. J. R. Morgan, "E ffe c t of Aroclor 1242 (a Polychlo rinated Biphenyl) and DDT on Cultures o f an Alga, Protozoan, Daphnid, Ostracod, and G uppy," Bull. Env. C on t and T oxicol., Vol. 8, No. 3 (1972), pp. 129-137. 12. S. Jensen, N. Johansson, and M. Otsson, "PCB-- Indications o f Effects on Salmon," PCB Conference, Stockholm, September 29, 1970, Swedish Salmon Research Institute Report LF1 MEDD 7/1970, 1970. 13. V. M. Sharski, and F. A . Puglisi E ffects o f A ro clo r 1254 on Brook T ro u t, salvelinus fontinalis, Final Report, Environmental Research Laboratory, EPA, Duluth, Minn,, 1975. 14. A. V. Nebeker and F. A . Puglisi, "E ffe c t o f Poly chlorinated Biphenyls (PCB's) on Survival and Re production o f Daphnia, Gammarus, and Tanytar sus," Trans. Am er. Fish. Soc., Vol. 103, No. 4 (1974), pp. 722-728. 15. F. L. Mayer, P. M. Mehrle, and H. O. Sanders, "Resi. due Dynamics and Biological Effects of PCB's in Aquatic Organisms," A rch. Env. Cont. and Toxic., 1975, (in press). 16. K. Moorman and K. E. Biesinger, "Polychlorinated . Biphenyl Research--A Static Bioassay Using Aroclor 1016 and Related Experiments," National Water Quality Laboratory, Duluth, Minn., 1973, unpub lished report. 290 774488 17. K. Biesinger, unpublished reports on to x ic ity of isomers of Aroclor 1242 and 1264 to Daphnia magna, National Water Quality Laboratory, ERA, Duluth, Minn., 1974. 18. H. 0 . Sanders and J. H. Chandler, " Biological Mag nification o f a Polychlorinated Biphenyl (Aroclor 1254) from Water by Aquatic Invertebrates," B ull. Env. Cont. and T oxic., V ol. 7, No. 5 (1972), pp. 257-263. 19. A . Sodergren and B. Svensson, " Uptake and Accu mulation of DDT and PCB by Ephemera danfea in Continuous-Flow Systems," B u ll. Environ. Contam. T oxicol., V ol. 9 (1973), pp. 346-354. 20. G. D. Veith and G. F. Lee, "P C B 'sinF ish From the Milwaukee River," Proc. 14th Conf. Great Lakes Res.. (1971a), pp. 157-169. 21. G. D. Veith and G. F. Lee, " Chlorobiphenyls (PCB's) in the Milwaukee River," Water Res., Vol. 5 (1971b), pp. 1107-1115. 22. M ichigan, " Monitoring fo r Polychlorinated Bi phenyls in the Aquatic Environment," R eport to dte Lake M ichigan T oxic Substances Com m ittee, M ay, Michigan Water Resources Comm., Bureau of Water Management, East Lansing, 1973, p. 26; 23. R. K. Ringer, R. J. Aulerich, and M. Zabick, " Effect o f Dietary Polychlorinated Biphenyls on Growth and Reproduction o f M ink," presented at the Amer ican Chemical Society Meeting, Division o f A ir, Water, and Waste, New York, N.Y., 1972, pp. 149-154. 24. N. S. Platonow and L. H. Karstad, " Dietary Effects o f Polychlorinated Biphenyls on M ink," Can. J. Comp. M ad., V ol. 37 (1973), pp. 391-400. 25. D. A . Barsotti and J, R. Allen, " Effects o f Polychlo rinated Biphenyls on Reproduction in the Primate," meeting abstract, 1975 American Society fo r Exper imental Pathology. 26. J. R. Allen, L. A. Carstens, and D. A. Barsotti, " Residual Effects o f Short-Term, Low-Level Expo sure o f Non-Human Primates to Polychlorinated Biphenyls," Toxicol. Appl.> Pharmacol., Vol. 30 (1974), pp. 1-12. GENP 005841 291 774489 DISTRIBUTION AND EXCRETION OF [ ' 4C] -2,4,5,2',5'-PENTACHLOROBI PHENYL IN THE LOBSTER [Homarus americanus) AND THE DOGFISH SHARK [Squa/us acanthias)* John R. Bend, Ph.D.,t, Larry G. Hart, Ph.D.,T, Anthony M. Guarino, P h .D .,tt, David P. Rail, M.D., Ph.D.,T, and James R. Fouts, Ph.D.t A b stra ct S ignificant am bient concentrations o f p olychlo rinated biphenyl (PCB) residues were present in lobster hepatopancreas (1.57 ppm w et weight) and dogfish shark liv e r (1.87 ppm w et weight). PCB concentrations in muscle were o nly 10-20 percent o f hepatic values. A fte r inje ction o f [ l AC ]- 2 ,4 ,5 ^ -pentachlorobiphenyl ( l 4C -2,4,52' -PCB) (0.2 m g/kg) in to the pericardial sinus o f the lobster, the hepatopancreas contained more than 90 percent o f the recovered rad io a ctivity a t a ll times investigated (24 hr-8 wk). V irtu ally a ll o f the hepa topancreas radioactivity was unaltered 2 ,4 ,5 /2 ,5*-PCB. The rad io a ctivity was very persistent in hepatopancreas, female egg mass, stomach, g ill, and intestine o f lobsters (t% > 3 wk). Follow ing intravascular adm inistration o f XAC -2,4J5jtJ> -PCB (0.03 m g/kg) to dogfish, alm ost a ll o f the dosed radioactivity was found in liv e r a t each tim e studied (6 h r-1 2 days). M ost o f die benzene extractable m ateria! was also unaltered 2,4,5J?J5?-PCB in each in stance. Small amounts o f rad io a ctivity were excreted in bite b u t o nly traces in urine. Microsomes from lobster hepatopancreas had no detectable aniline hydroxylase, benzphetamine demethylase, 7-ethoxycoum arin 0-deethy/ase, o r benzpyrene hydroxylase a c tiv ity although dogfish shark live r microsomes had lo w a c tiv ity w ith e a c h s u b s t r a t e te s te d . The p e rs is te n c e o f 14C -2 ,4 ,5^',51-PCB in the tw o marine species is prob ably related to the lo w hepatic m icrosom al m ixedfunction oxidase activities observed and die high lip id content o f lobster hepatopancreas and dogfish shark liver. INTRODUCTION The polychlorinated biphenyls (PCB's) possess high chemical and thermal stabilities and have been used extensively in the United States fo r certain industrial applications during the past 45 years (ref. 1). PCB's were first recognized as environmental contaminants in 1966 *W ork fo r this project was done at Mount Desert Island Biological Laboratory, Salsbury Cove, Maine. tPharmacology Branch, National Institute of Environmental Health Sciences, National Institutes of Health, Research Triangle Park, North Carolina. ttL ab orato ry of Toxicology, National, Cancer Institute, National Institutes of Health, Bethesda, Maryland. (ref. 2). Subsequently, the widespread occurrence of PCB residues was verified in w ildlife species (ref. 3) (both terrestrial and marine) all over the world, in hu man adipose tissue (ref. 4), in waters o f the North A tlan tic (ref. 5), and in marine species indigenous to Maine (ref. 6f. The chemical stability and lipid solubility of certain PCB's contributes to their bioaccumulation. Commercially available PC8's are complex mixtures of many different species w ith varying chlorine content. Aroclor 1254, fo r example, was resolved into more than 50 individual compounds, o f which the pentachlorobi phenyl derivatives were the major constituents (ref. 7). The present study describes the distribution and e x c re tio n o f [ ' 4C]-2,4f5,2',5'-pentachlorobiphenyl (l4 C-2,4,5,2*,5'-PCB) in the lobster [Homarus am eri canus) and the dogfish shark [Squa/us acanthias) after parenteral administration. The in vivo data is correlated w ith in vitro microsomal mixed-function oxidase activi ties of lobster hepatopancreas and dogfish shark liver. A single, radiolabeled PCB isomer was used in the disposi tion experiments. Use o f pure isomers has obvious advantages over similar experiments w ith commercial PCB mixtures. The isomer chosen is a constituent of Aroclor 1254, and should be representative of several Aroclor 1254 components. PCB residues were also deter mined in certain tissues of lobsters and dogfish sharks. MATERIALS AND METHODS Male or female lobsters (320-560 g) were purchased locally (Mt. Desert Island, Maine) and female dogfish sharks (3.0-5.1 kg) were caught by hook in Frenchman Bay, Maine. Both species were maintained in tanks equipped w ith circulating fresh seawater before and after treatment w ith 14C-2,4,5,2',5-PCB. The lobsters main tained fo r longer-than 1 week after dosing were sub merged in a lobster crate in Frenchman Bay. They were fed small pieces o f mackerel or flounder three times a week when the traps were lifted to remove any dead or ill animals. Only lobsters that were alive and in apparent good health were dissected at the indicated times. 2 ,4 ,5 ,2 ',5 '-p e n ta c h lo ro [ I4 C] bip he nyl (14C-2,4,5,2',5'-PCB), (10.98 mCi mmole) was obtained from Mallinckrodt Nuclear and was shown by thin-layer chromatographic analysis (TLC) to be greater than 98.5 percent radiochemically pure, 14C-2,4,5,2>,5'-PCB was injected into the pericardial GENP 005842 292 774490 sinus of lobsters (0.2 mg/kg, 1.4 X 107 dpm/kg) or into the caudal vessels of dogfish sharks (0.03 mg/kg, 2.2 X 106 kpm/kg) as a solution in Emulphor water (36-38 percent v/v). Lobster plasma samples were withdrawn from the pericardial sinus just prior to sacrifice and placed in vials containing citrate. Dogfish blood samples (serially in disappearance studies or terminally in distribution stud ies) were taken from the caudal vessels and placed in heparinized vials. A t various times after administration of M C-2.4,5,2',5,-PCB, animals were sacrificed andvar-., ious tissues and fluids were removed from lobsters and dogfish. Duplicate aliquots o f plasma, blood, bile, or cerebrospinal fluid (100 p i ) or tissue (70-200 mg) were solubilized in ,2 m l NCS (Amersham/Searle) by incuba tion at 50 C overnight. Liquid scintillation solvent (18 ml; 5.0 g PPO; and 250 mg POPOP/I toluene) was added and the radioactivity determined in a Nuclear Chicago Mark I scintillation spectrometer. Counting efficiency was determined using the channels ratio technique and varied from 50-80 percent fo r the solubilized biological samples. A ll counts were converted to disintegrations per minute. TLC was performed on precoated silica gel GF . plates (5 X 20 cm, 250 pm thick; Analtech) that were activated at 110 C for 60 min before use. Plates were developed in hexane (solvent A) or benzene:ethyI ace tate, 12:1 (solvent B) and were sequentially scraped (1 cm bands). The radioactivity present in each segment was determined by counting the silica gel in vials con taining 10 ml Fluoralloy (Beckman)-dioxane liquid scin tillation cocktail. Radioactive recovery from the plates was normally greater than 95 percent w ith this proce dure. Statistical analysis of the data was performed using Dunnetts' multiple comparisons test. Log transformation was used to equal the variances. Microsome5 were prepared from lobster hepatopancreas or dogfish liver homogenates (in 1.15% KC1 buffered to pH 7.6 w ith 0.013 M HEPES) by centrifuga tion; microsomal protein concentrations were deter mined and mixed-function oxidase activities were meas ured toward aniline, benzphetamine, benzo [a] pyrene, and 7-ethoxycoumarin as described in detail elsewhere (ref. 8). PC8 residue analyses were performed according to Armourand Burke (ref. 9) following caustic hydrolysis of a preliminary extract which removed DDT, PCB's, and related chemicals from the tissues to be studied (ref; 10). In e s tim a tin g the degree o f metabolism of l 4 C-2,4,5,2\5'-PC8, 25 percent w /v aqueous homoge nates of lobsters hepatopancreas and green gland were extracted four times with equal volumes o f warm hexane and/or acidified toluene. Homogenates o f livers from dogfish were extracted in a similar manner with benzene. RESULTS Of the various lobster tissues investigated, the fe male egg mass was found to contain the highest residual level of PCB's (table 1) although the hepatopancreas also contained a significant amount. This is interesting since the tomale (i.e., hepatopancreas o f the cooked lobster) is considered a delicacy by some people. The PCB concen tration in lobster muscle was about an order o f magni tude lower than that o f egg mass or hepatopancreas and was well below the 5 ppm lim itation on PCB residues in human foodstuffs. Dogfish shark liver also had appreciable PCB resi dues (table 1), whereas muscle contained only about one-fifth the hepatic concentration (per gram wet weight). These residual PCB's are not unexpected in either dogfish shark liver or lobster hepatopancreas since both tissues have high lipid contents (50 to 60 percent w et weightHref. 11). The specific activity o f several lobster tissues, plas ma, and feces w ith time, after parenteral administration o f 14C-2,4,5,2',5'-PCB, is shown in table 2, and the per centage o f dosed radioactivity present in the various organs at each time point is outlined in table 3, The hepatopancreas contained much higher amounts of radioactivity (per mg tissue) than any other organ (table "2J and accounted fo r between 91 and 96 percent of the total recovered radioactivity at all times. The half-life (tK ) fo r radioactivity in tissues was estimated from semi logarithmic plots of the specific activity (dpm/mg) versus tinfla (days). The tissues could be classified into two categories (table 2): those in which labeled com pound had a t K o f 3 weeks or longer and those in which the t j j was 1 week or less. ` Almost all of the radioactivity in lobster hepato pancreas at 2, 4, or 8 weeks after treatment was un changed 2,4,5,2',5'-PCB. More than 90 percent of this hepatopancreas activity was extracted into hexane after shaking homogenates four times w ith this solvent (93 3%, mean S D jn = 4). Over 95 percent o f the hexane soluble radioactivity cochromatographed with authentic 2,4,5,2',5'-PCB (Analabs) on TLC plates developed in solvent A (Rf 0.7-0.8) or solvent B (Rf 0.9-1.0). Similar ly, more than 90 percent o f the radioactivity in hexane extracts of green glands from lobsters sacrificed 2 or 4 weeks after dosing was 2,4,5,2',5'-PCB, although in this case only about 50 percent of the total activity was hexane and toluene (acidified) extractable, the remain der residing in the aqueous phase of green gland homo genate. Only about 10 percent of the fecal radioactivity was extracted into hexane and acidified toluene (four 293 774491 Table 1. Residue levels of polychlorinated biphenyls (PCB's) in some tissues of the lobster ( H o m a r u s a m e ric a n u s ) and the dogfish shark ( S q u a fu s a c a n th ia s ) Species ppm w et w e ig h t PCB's3 Lobster*5 Dogfish sharkc Egg mass 4.41 (2 .7 8 -5 .9 8 ) L iv e r 1.87 Hepatopancreas Muscle 1.57 (1 .1 3 -2 .2 7 ) ,0.097 (0 .0 7 -0 .1 3 ) Muscle Kidney 0 .4 2 R e p o r te d in terms o f t o t a l A ro c lo r 1242 and 1254 re s id u e s . bMean and ranges f o r 4 a n im a ls . cMean values f o r 2 d o g fis h w eighing 4 -6 kg. ^Detection lim it in dogfish kidney. Table 2. Specific activity of various lobster tissues and fluids with the following pericardial injection of 14 C -2 ,4, 5, 2 1, 51, -pentachlorobiphenyl (0.2 mg/kg)a> Tim e a f t e r a d a in is t r a t io n T is s u e 24 h r 1 wk . 2 wk 4 wk 8 wk t^ t days) H epatopancreas G reen g la n d I n te s tin e H eart T a ll m u scle C la w m u sc le Stom ach G ill M a le gonad Egg m asses P lasm a Feces dmp/mg t is s u e o r / u l p la sm a 183.4 X 2 4 .7 ( 6 ) b 20.1 1 3 .0 {6} 14.0 X7 .0 (6 ) 8 .8 i 5 .4 (6 ) 5.1 1 .8 (6) 5 .0 3.1 (6 ) 4 .5 X 1.1 (6} 3 .4 X1 .8 (6) 8 .3 (1) 1 6 .6 9 .7 (5} 1 .3 3 X0 .4 1 (6}- - 192.9 X 3 3 .'* (7 ) 8 .4 t 2 .4 (7) 1 4 .3 X5 .9 (7) 2 .7 X0 .4 (7) 1 .6 X0.1 (7 ) 1 .5 X0 .2 (7 ) 4 .8 t 2.1 (7 } 3 .2 + 1 .5 (7 ) 1 .6 (1) 7 .7 6 .6 (6) 0 .49 X0 .1 7 (7} - 1 7 0 .9 * '` 4 0 . 0 ( 5 ) 6.1 l 1 .9 (5 ) 17.6 X 1 8.7 (5) 2 .2 X0 .7 (5) 1 .3 X0 .3 (5) 1 .3 X0.1 (5 ) 4 .3 2 .0 (5) 3.1 X 2 .3 (5) 2 .9 (2) 10.2 X6 .0 (3 ) 0 .6 2 t 0 .0 7 142.5 X7 0 .7 (5) 1 3 1 .2 X34,3f (6 ) 4 .8 t 1 .2 (6 ) 4 .3 t 0 .9 (6) r.6 X0 .3 (5 0 .8 X0 .2 (6) 0 .8 X0 .1 (5) 2 .2 X1 .0 (6) 1 .4 X0 .9 (6) 2 .1 (2 ) 8 .6 X4 .0 (6) 0 .3 6 X0 .1 3 (5) 2 1.5 X 6 .6 (6) 7 7.4 t 2 8 .'\ (9 ) 3 .4 1 .4 (9} 2 .2 t 1 .5 (9) 1.1 t 0 .3 (9 ) 0 .4 X0 .2 (9) 0 .6 t 0 .2 (9) 1 .3 X0 .4 (9 ) 0 .8 1 0 .3 (9) 1.1 X0 .2 (5} 7 .7 X4 .0 (4) 0 .2 0 X0 .0 5 (9} 2 0.1 t 10.!S (9 ) 45 <7 23 <7 <7 <7 28 24 <7 39 <7 a Data from Send e t a l. ( r e f . 12}. bHean x SD (N ). 294 774492 GENP 005844 Table 3. Percent administered radioactivity remaining in tissues of lobster with time after pericardial injection of 14C -2 ,4, 5, 2 1,5^ -pentachlorobiphenyl (0.2 mg/kg)a T iss u e H epatopancreas Green, g la n d I n te s tin e H eart T a ll m u scle Stom ach G ill M ale gonad Egg m asses Kean to ta l re c o v e ry 24 h r Tw k Tim e a f t e r 1 n le c t io n 2 wk 6 1 .4 8 .3 (6 )b 0 .1 9 0 .1 2 (6) 0 .1 0 0 .09 (6) 0 .09 0 .0 4 (6) 4 .36 0 .84 (6) 0 .36 t 0 .1 4 (6) 0.61 i 0.31 (6) . 60.5 1 0.8 (7) 0 .0 7 0 .1 1 0 .0 3 4 0.01 + 0 .05 0.01 (7) (7) (7) 1.57 0 .2 6 (7) 0.53 0 .39 (7) 0 .5 9 4 0.31 (7) 0 .0 6 (1) 0 .48 0 .3 4 (5) 0 .0 2 0) 0.37 t 0 .56 (6) 6 1 .4 1 4.6 (5) 0 .0 7 * 0 .03 (S) 0.21 0 .2 7 (5) 0 .0 4 t 0 .02 (5) 1 .5 4 0.41 (5) 0 .45 i 0 .22 (5) 0 .6 0 0 .4 1 (5) 0 .0 3 . (2) 0 .46 0 .44 (3) 4 wk 55.2 i 1 3.4 (6) 0.05 0.01 (6) 0 .0 4 0 .01 (6) 0 .02 0 .01 (6) 0 .9 6 i 0 .26 (6) 0 .20 0 .1 0 (6) 0.25 0 .1 5 (6) 0 .04 (2) 0 .64 0 .3 8 (4) . '8 wk 3 1.2 0 .0 4 0 .0 3 4 12.5 0 .02 0 .02 (9) (9) (9) 0.01 0 .01 (9 ) 0.45 0 .02 (9) 0.12 0 .04 (9) 0.16 4 0 .07 (9) 0.01 4 0.01 (5) 0.67 X 0 .5 3 (4) 6 7.6 1 64.8 1 6 4.8 1 5 7 .4 1 32.7 1 a D ata from Bend e t a l. ( r e f . 1 2 ). M ean SO (N ). extractions w ith each solvent), but about 70 percent of the organic extractable material was chromatographically identical to 2,4,5,2',5'-PCB. Neither the water soluble fecal metabolites nor green gland metabolites were investigated further. Total recovery experiments in which lobster carcas* ses were homogenized after dissection accounted fo r as much as 90 percent o f the injected radioactivity. The specific radioactivity (dpm/mg tissue) was high er in dogfish shark liver than in any other tissue fo llo w ing parenteral administration o f l4 C-2,4,5,2',5'-PCB (table 4). There was an apparent increase in specific radioactivity of liver between 6 and 24 hours, concomi tant with a statistically significant decrease in the radio activity of most other tissues. Liver radioactivity re mained at, or above, the 6-hour level throughout the course o f the experiment (20.3 dpm/mp at 12 days, the longest period sharks could be maintained). A t all times subsequent to administration of 14C-2,4,5,2',5'-PCB to dogfish sharks, almost all of the recovered radioactivity was located in the liver (table 5), and initially all o f the benzene extractable activity from hepatic tissue was unchanged l4 C-2,4,5,2',5'-PCB. Only trace amounts o f radioactivity were present in all other tissues (less than 1 percent) with the exception of mus cle which contained 7 to 9 percent of the dosed activity 3 and 7 days after treatment. This observation was at tributable more to the large muscle content o f the dog fish (about 23 percent) (ref. 14) than to the specific radioactivity of the tissue. Urine was collected continuously from a few sharks w ith cannulated urinary papillae. Only trace amounts of radioactivity were excreted in the urine o f these fish after injection o f M C-2,4,2',5'-PCB. The delayed biliary excretion o f radioactivity and the excretion o f only very small quantities o f biliary metabolites suggested that dogfish sharks biotransformed the dosed compound very slowly. Unaltered 2,4,5,2',5'-PCB was not excreted in the bile and the biliary radioactivity was not converted to organic soluble material by 0-glucuronidase hydrolysis indicating that glucuronide conjugates o f phenols were not major biliary metabolites. The decline in blood radioactivity following the in travenous administration of 14C-2,4,5,2',5'-PCB is illus trated in figure 1. The disappearance of radioactivity follows a multiple exponential decay relationship w ith time. Using least squares technics (fig. 2), we resolved this blood decay curve into three components by com puter anlysis. Th t ^ of l4 C-2,4,5,2',5'-PCB was esti mated for each component; the a, 0, and y components of the radioactivity disappearance curve had t ^ values of 4, 27, and 730 minutes, respectively. It is interesting that the a and 0 components fo r blood disappearance of the PCB isomer tested had similar t,A values to those reported by Dvorchik and Maren (ref. 14) for DDT blood disappearance in this same species (3 and 30 minutes, respectively). The initial, rapid phase of radioactivity removal from blood after injection of 14C-2,4,5,2',5'-PCB is probably related to the rapid uptake into liver. 295 774493 GENP 5845 O o KJ\ 00 4* O' Table 4. Specific activity of various dogfish shark tissues and fluids with time following intravenous injection of 14C -2 ,4 ( 5, 2 1, 5 1 -pentachlorobiphenyl (0.03 mg/kg)a T iss u e L iv e r K id n e y S a lt g la n d Pancreas S p le e n G ill B ra in H eart K u s cle B lo o d B ile CSF Tim e a f t e r a d m in is t r a t io n 6 h rb 24 h rb 3 daysb dptn/mg t i s s u e o r / u l f l u i d 1 4 .0 0 i 2 .1 5 2 1 .6 3 4 .8 0 5 .3 9 i 0 .72 1 .0 4 0 .2 2 e 3 .1 2 0 .91 0 .7 2 4 0 .0 7 e 2 .31 0 .7 7 0 .4 9 0 .0 8 * 1 .8 6 1 1.04 0 .5 9 0 .0 5 e 1 .8 4 i 0 .3 8 0 .7 8 4 0 .05 * 0 .9 2 4 0 .3 0 1 .0 7 4 0 .24 * 0 .8 2 0 .1 0 0 .3 6 4 0 .0 2 e ---- 0 .8 0 i 0 .0 2 0 .3 2 4 0 .0 8 d 0 .4 1 4 0 .21 1 .3 5 4 0 .5 1 d 0 .0 2 0 .03 0 .0 3 4 0 .05 1 8.9 8 t 5 .7 7 0 .65 * 0 .0 5 e 0 .6 0 4 0 .07 * 0 .5 3 4 0 .16 * 0.61 4 0 .0B * 0 .55 4 0 .1 3 * 0 .4 0 4 0 .1 6 * 0-41 + o . n * 0 .87 0 .4 2 0 .5 0 0 .2 3 2 .71 0 .5 8 * 0 .0 6 0 .0 5 7 daysc 14.0 5 4 2 .3 9 0 .4 9 4 0 .05 * 0 .3 6 4 0 .05 * 0 .3 3 4 0 .05 * 0 .46 4 0 .0 6 * 0 .7 0 4 0 .2 1 d 0 .1 6 4 0 .03 * 0 .1 5 4 0 .04 * 0 .6 6 4 0 .0 8 0 ;14 4 0 .1 3 e 1 2.0 3 4 4 .83 * 0 .0 4 0 .04 *D ata fro m H a rt e t e l. ( r e f . 1 3 ). bHean SD (N 3 ) . eMean t SD (N - 4 ) . dp < 0 .0 5 com pared w ith 6 h r . *p < 0 .01 Table 5. Percent administered radioactivity remaining in tissues of Dogfish shark with time after intravenous injection of 14C -2 ,4 ,5 , 2 1, 51 -pentachlorobiphenyl (0.03 mg/kg)a T is s u e 6 h rb L iv e r K id n e y S a lt g la n d P a n cre a s S p le e n B ra in H eart Mean t o t a l re c o v e ry 7 5.22 4 6.11 0 .4 3 0 .1 6 0 .0 8 4 0 .02 40 . 2 5 0 . 0 3 40 .2 1 0 .0 4 0 .0 3 4 0 .01 0 .0 5 0 .01 76.3% T im e a f t e r I n j e c t io n 24 h rb 3 daysb 49 4 . 0 2 2 4 . 6 5 0 .0 6 4 0 .01 0 .0 2 4 0 .00 2 0 .0 5 4 0 .0 2 0 .0 8 t 0 .02 40 . 0 3 0 .01 0 .01 4 0 .0 0 2 7 9.55 4 1 2.7 7 0 .0 6 4 0.01 0 .01 l 0.00 1 0 .0 5 4 0 .02 0 .0 6 i 0 .0 2 0.01 0.001 0 .0 2 i 0 .00 4 7 days6 8 9 .4 2 4 1 1.1 7 0 .0 6 4 0 .0 2 0 .01 4 0.001 0 .0 3 4 0 .0 0 4 0 .0 7 4 0 .0 3 0 .01 4' 0 .00 2 0 .01 4 0 .00 3 94.3% 7 9 .8 8 9 .6 X *0ta from H a rt e t a l. ( r e f . 1 3 ). b Hean SD (N - 3 ) . e Mean SD (N - 4 ) . 296 774494 dpm/ml blood 100,000 Figure 1. Decline in blood activity following the intravenous administration of 14 C -2,4, 5 , 2 I , 5 1-PCB. 297 774495 GENP 005847 GE^P 005848 Figure 2. Three components of blood decay curve. 298 774496 Microsomes prepared from lobster hepatopancreas had no detectable aniline hydroxylase, benzphetamine N -dem ethylase, 7-ethoxycoumarin O-deethylase; or benzpyrene hydroxylase activity (table 6), whereas dog* fish shark liver microsomes had appreciable (but low, relative to the little skate, Raja erinacea, another marine elasmobranch indigenous to Maine) mixed*function oxidase activity toward each substrate tested. These assays were run at 30 C, the optimal in vitro tempera ture fo r 7-ethoxycoumarin 0-deethylation in the dogfish (ref. 8). A t 12 C, which is w ithin the range o f summer water temperature in Maine, specific 7-ethoxycoumarin 0-deethylase activity was only about 20 percent o f that found at 30 C. D IS C U S S IO N Although the accumulation and to xic ity o f commer cial PCB mixtures, consisting of many isomers of varying chlorine content, were demonstrated in many aquatic species (refs. 15-22) few such studies have utilized single, purified PCB isomers. Hutzinger et al. (ref. 23) demon strated .that 4<h loro biphenyl, 4,4'-dichlorobi phenyl, and 2,2',5,5'-tetrachlorobiphenyI were hydroxylated by rat and pigeon but not by brook trou t, a freshwater s p e c ie s . No h y d r o x y la te d m etabolites of 2,2',4,4',5,5'-hexach loro biphenyl were found in rat, pigeon, or brook trout. In previous studies from our laboratory, we found that many marine species have some hepatic microsomal mixed-function oxidase activity, but that this activity is generally considerably lower than that found in mam malian liver (refs. 8, 24-26). Reduced rates o f oxidative xenobiotic metabofism in marine vertebrates and inverte brates would partially account fo r the persistence of lipophilic compounds, such as the PCB's, in these species. The distribution, excretion, and metabolism of 14C-2,4,5,2',5*-PCB in the rat was studied by Matthews et al. (refs. 27-31), working in our laboratory. This com pound is metabolized readily by rats and the major m e ta b o lite s are 3-hydroxy-, 3',4'-dihydroxy-, and 3 ', 4 #- d ih y d r o - 3 ',4 '- d i h y d ro x y -2 ,4,5,2',5'-pentachlorobiphenyls; the firs t half-life in rats is only about 2.5 days. This varies markedly from both the lobster (tables 2 and 3) and the dogfish shark (tables 4 and 5), where excretion o f radioactivity occurs very slowly and the fa tty hepatopancreas and liver, respectively, act as stor age depots f o r 14C-2,4,5,2',5'-PCB. The very slow metabolism (and excretion) of 14 C-2,4,5,2',5'-PCB in the lobster is probably related to the very low microsomal mixed-function oxidase activi ties of lobster hepatopancreas (table 6). In separate experiments, we found only traces o f benzpyrene hydro xylase or aniline hydroxylase activity in gill or hepato pancreas homogenate. The much lower concentrations of PCB's (tables 1 and 2) in lobster muscle and dogfish muscle (vs. hepatopancreas or egg mass) suggest that portions o f marine species might be used fo r foodstuffs even in certain organs exceed the FDA recommended Table 6. Mixed-function oxidase activity in lobster hepatopancreas and dogfish shark liver microsomes3 S p e c ie s A n ilin e h H y d ro x y la s e B e n zp h e ta m in e . 7 -E th o x y c o u m a rin N -d e m e th y la s e D 0 -d e e th y la s e b B enzpyrene H y d ro x y la s e L oEabomsatraeireru,amnua . 0 .01 (3 )* D o g fis h SSahqoauarank l,tuhaiaa 0 .0 7 - 0 .01 , (3 )T 0 .0 6 (3) 0 .1 5 i 0 .0 5 (3) 0 .01 (3 ) ' 0 .0 8 t 0 .0 2 (3) 0 .01 (3 ) 0 .0 7 i 0 .0 2 (3) a0 a ta ta ke n from P oh l e t a l. ( r e f . 8 ) . ^ m o le s/m in /m g m ic ro s o m a l p r o t e in , f lu o r e s c e n c e u n its /m ln /m g m ic ro s o m a l p r o t e in . ^M inim um m e t a b o lis m d e t e c t e d b y a s s a y p r o c e d u r e u s e d . eH1crosom es from th re e lo b s t e r s w ere te s te d s e p a r a te ly . f Hean x SO ( N ) . 299 774497 GENP 005849 PCB levels, provided that care is taken in preparation and that no PCB metabolites or degradation products with high toxicity to humans are present (ref. 32). Although hepatic microsomes from dogfish shark have mixed-function oxidase activity, this activity is low relative to mammals and some other marine species (ref. 8). Furthermore, dogfish liver is very fatty and the microsomal protein yield is very low (only 1-3 mg protein/g liver vs. 6-15 mg/g liver in the little skate), mean ing that whole liver xenobiotic-metabolizing activity per gram tissue in the dogfish is even lower relative to the skate than is specific activity (per mg microsomal pro tein). The liver appears to function both as the major site of 14C-2,4,5,2,,5,-PCB uptake and storage in the dogfish shark, probably due to its high lipid content. The delay ed excretion may be related to poor partitioning of the compound from liver lipid into metabolically active parenchymal cells, and to the low mixed-function oxi dase activity, especially at 12 to 15 C which is the Maine water temperature in summer. T he p e r s is te n c e of trace doses of m C-2,4,5,2,,5,-PCB, an isomer that is metabolized rapidly by rats, in the two marine species studied sug gests that the problem of PCB residues in marine and freshwater species will be with us for some time, especi ally in the face of continued PCB release into the aquatic environment. ACKNOWLEDGMENT We are grateful to Ms. S. Bend, Ms. T. Devereux, and Ms. R. Pohl for excellent technical assistance and to Dr. J. Haseman for the statistical analysis. REFERENCES 1. 2. 0. oS.f Hutzinger, S. Safe, and PJeCnBs'esn. ,CR"RCePproesrst, 1974. of a V. Zitko, The New Chemical C h e m istry Hazard," 3. NRe. wWS. cRieisnetbisrto,uVgho,l. a3n2d (B1.9d7e2)L, apppp.e3,9"-A45c.cumulation 4. roHof.n.PAoH.leyPacrihltchleo,rPianenardstpedeRc.tB.L,ip.VhWoelne.ylc1lhs(,1in"9O7E2cc)c,ouspryrpes.nte3cm9e-s4o,5"f.EPonlvyi 5. chlorinated Biphenyls in Humans," PGe.rsRp.ecHt.,arVvoeyl., 1W(1. 9G7.2)S, tpepin. h7a3u-7er8,. Environ. Health and J. M. Teal, "Polychlorobiphenyls in North Atlantic Ocean 6. WR.atHe.r,A" dSacmiesnocne,, Vol. 180 (1973), pp. 643-644. and A. M. Guarino, "Natural Levels of DDT-Related Compounds and Polychlorinated Biphenyls (PCB's) in Vanr js Marine Species," Bull. M6-t9.. Desert Island Biol. Lab., Vol. 12 (1972), pp. 7. D. Sissons, and D. Welti, "Structural Identification of Polychlorinated Biphenyls in Commercial Mix tures by Gas-Liquid Chromatography, Nuclear Mag 8. netic Resonance, and Mass Spectrometry," CRh. rJo.mPaotohgl,raJp. hRy,. Vol. 60 (1971), pp. 15-32. Bend, A. M. Guarino, and J. J. R. Fouts, "Hepatic Microsomal Mixed-Function Oxi dase Activity of Several Marine Species from Coastal M54a5i-n5e5,"5.Drug Metab. Disposition, Vol. 2 (1974), pp. 9. Ja.raAti.ngArPmoolyucr,hlaonrdinJa.teAd . Burke, "A Biphenyls Method for From DDT Sep and (It1s9A70n)alo, gpsp,." 7J.61A-s7s6o8c.. O fficial Anal. Chem., Vol. 53 10. P21e1st-i1c3idae, A22n1a.l1y4ti,ca2l2M1.a1n5u. aFl o1o9d68a,ndVoDl.ruIg, Sections Admini stration, U.S. Department of Health, Education and Welfare, second edition. 11. A. M. Guarino, J. B. Pritchard, J. B. Anderson, and D. P. Rail, "Tissue Distribution of (14C) DDT in the Lobster After Administration via Intravascular or Oral Routes or After Exposure From Ambient S(1e9a74W),aptepr.,"27T7-o2x8ic8o.l. Appl. Pharmacol., Vol. 29 12. J. R. Bend, S. G. Bend, A. M. Guarino, D. P. Rail, and J. R. Fouts, "Distribution of 14C-2,4,5,2',5'- cS(Pa1ienn9nou7tsas3,c)",halfpBotpeur.rollb.1ai-p4M.hStei.nngDylleesineInrttjheIcestliaLonondb sIBtnetiroolH. tohLmeaabPr.,uersVicaoamlr.dei1ar3il 13. L. G. Hart, J. R. Fouts, and J. R. Bend, "Distribu tion and Blood Disappearance of 14C-2,4,5,2',5'- Pentachlorobiphenyl in the acanthias After Intravascular 56-59.M t. Desert Island Biol. Lab .D,AoVdgmofilsi.nhi1sS3trha(at1riko97ns3,"q)u,Bauplulpls.. 14. B. H. Dvorchik, and T. H. Maren, 'The Fate of p,p'-DDT (2,2-bis(p-chlorophenyl)-1,1,1-trichlo- roethane) in the C20o5m-p2.11B. iochem. P hDysoigofl.i,sh,VoSl.qu4a2luAs (a1c9a7n2th),iapsp,". 15. D. J. Hansen, P. R. Parrish, J. I. Lowe, A. J. Wilson, Jr., and P. D. Wilson, "Chronic Toxicity, Uptake, and Retention of Aroclor 1254 in Two Estuarine F(1is9h7e1s),", pBpu. ll1. 13E-1n1v9ir.on. Cont. Toxicol. Vol. 6 16. M. L. Hattula, and O.Karlog, 'Toxicity of Polychlo 17. rinated Biphenyls cNo.l.JoThoaxnicssool.n, ,VAo.l. (3P1CB(1)9t7o2G),oplpd.fi2sh3,8"-2A4c0ta. Pharma Larsson, and K. Lewander, "Meta bolic Effects of PCB (Polychlorinated Biphenyls) on G EN P 005850 300 774498 the Brown Trout [Salmo tru tta )," Comp. Gen. Pharmacol., Vol. 3 (1972), pp. 310-314. 18. W. B. Kinter, L. S. Merkens, R. H. Janicki, and A. M. Guarino, "Studies on the Mechanism of T oxicity of DOT and Polychlorinated Biphenyls (PCB's): Dis ruption of Osmoregulation in Marine Fish," Envi ron. Health Perspect., Vol. 1 (1972), pp. 169-173. 19. V. Z itko, "Uptake o f Chlorinated Paraffins and PCB from Suspended Solids and Food by Juvenile Atlan tic Salmon," B ull. Environ. C on t Toxicol. Vol. 12 (1974), pp. 406-412. 20. D. R. Nimmo, J. Forester, P. T. Heitmuller, and G. H. Cook, "Accumulation o f Aroclor 1254 in Grass Shrimp [Palaemonetes pugio) in Laboratory and Field Exposures," Bull. Environ. C o n t Toxicol. Vol. 11 (1974), pp. 303-308. 21. A. J. Lieb, D. D. Bills, and R. O. Sinnhuber, "A c cumulation o f Dietary Polychlorinated Biphenyls (Arocior 1254) by Rainbow Trout {Salmo gairdneri) ," J. Agric. Food Chem., Vol. 22 (1974), pp. 633-642. 22. H. Nestel, and J. Budd, "Chronic Oral Exposure of Rainbow T rout (Salmo gairdneri) to a Polychlori nated Biphenyl (Aroclor 1254): Pathological Ef fects," Canad. J. Comp. M edicine, Vol. 39 (1975), pp. 208-215. 23. O. Hutzinger, D. M. Nash, S. Safe, A. S. W. De Freitas, R. J. Norstrom, D. J..Wildish, and V. Z itko, "Polychlorinated Biphenyls: Metabolic Behavior of Pure Isomers in Pigeons, Rats, and Brook T ro u t," Science, Vol. 178 (1972), pp. 312-314. 24. J. R. Bend, R. J. Pohl, and J. R. Fouts, "Further Studies of the Microsomal Mixed-Function Oxidase System of the Little Skate, Raja erinacea. Including Its Response to Some Xenobiotics," B ull. M t. Desert B iol. Lab., Vol. 13 (1973), pp. 9-13. 25. R. J. Pohl, J. R. Bend, T. R. Devereux, and J. R. Fouts, "Hepatic Chemical and Drug Metabolizing Enzymes in Coastal Maine Marine Species," Bull. M t Desert Island B iol. Lab., Vol. 13 (1973), pp. 94-98. 26. R. J. Pohl, J. R. Fouts, and J. R. Bend, "Response o f Hepatic Microsomal Mixed-Function Oxidases in the L ittle Skate, Raja erinacea, and the Winter Flounder, Pseudopieuronectes americanus to Pre tre a tm e n t w ith TCDD (2,3,7,8-Tetrachlorodibenzo-p-dioxin) or DBA (1,2,3,4-Dibenzanthracent)," B ull. M t Desert Island Biot. Lab., in press. 27. H. B. Matthews, P. R. Chen, H. M. Mehendale, and M. W. Anderson, "The Metabolism, Storage, and Excretion o f Highly Chlorinated Compounds by Mammals," ACS Symposium Series No. 2., Mech anism o f Pesticide Action, American Chemical Society, 1974, pp. 54-68. 28. P. R. Chen, and H. B. Matthews, "Metabolism and Excretion of 2,4,5,2f,5'-Pentachlorobiphenyl (PCB) in the Male R at," Toxicol. A ppl. Pharmacol., Vol. 29 (1974), p. 88. 29. H. B. Matthews, and M. W. Anderson, "The Distri bution and Excretion o f 2,4,5,2',5'-Pentachlorobiphenyl in the R at," Drug Metab. D isposition, Vol. 3 (1975), pp. 211-219. 30. H. B. Matthews, and M. W. Anderson, "E ffe ct o f Chlorination on the D istribution and Excretion of Polychlorinated Biphenyls," Drug Metab. Disposi tio n , Vol. 3 (1975). pp. 371-380. 31. H. B. Matthews, "PCB Chlorination vs. PCB Distri bution and Excretion," this conference. 32. J. D. McKinney, "Correlating Biological Effects w ith Chemical Structure," this conference. GENP 005851 301 774499 20 November 1975 Session V: ECONOMICS AND SUBSTITUTES Warren Muir, Ph.D.* Session Chairman Senior Staff Member for Environmental Health, Council oh Environmental Quality, Washington, D.C. Preceding page blank 303 774500 GENP 005852 INTRODUCTORY REMARKS Warren Muir, Ph.D. I guess we have all had an opportunity to hear about health and ecological impact and other aspects o f PCB's in the last day and a half. The history of PCB's, as I am sure most o f you are aware. Is several years old. By 1971 and 1972 there was sufficient concern over their potential environmental effects that a Federal task force was created under the sponsorship o f the Council on Environmental Quality and the Federal Council fo r Sci ence and Technology, which looked into the situation and made a variety o f recommendations. In addition, at that time the Monsanto Chemical Company developed a restricted sales policy w ith regard to uses of PCB's, and also shortly thereafter, the Organi zation fo r Economic Cooperation and Development had an international agreement with regard to uses of PCB. A ll of these actions were directed in one fashion or another toward inappropriate uses o f the chemical. Yet, as o f this date, there is no Federal authority to control the use o f these chemicals, despite 5 years o f consider ation o f toxic substances control legislation. This particular session o f the conference deals w ith economics and substitutes; we w ill have a presentation or a brief description o f two economic case studies that have been done on PCB's, and then several speakers w ill discuss the substitutability or nonsubstitutabiiity fo r uses o f PCB's. In dealing w ith environmental problems such as PCB's and a variety o f other chemicals, I am sure you are aware that there is a great deal of scientific uncertainty with regard to particular health or ecological impacts. For example, there is a certain amount o f uncertainty as to whether or not something is carcinogenic or whether it can bioaccumulate. JThere typically appears to .b e, however, a much greater uncertainty about the economic implications or the economic impacts of any action that might be taken to mitigate the suspected problems. Much of this arises from uncertainty, about substitutes and also about the inability to predict the actual individual or corporate responses th at would be made under a given type of regulatory action or other type of mitigating action. Thus in my view, there is much greater economic uncer' tainty in many o f thesq issues than there is scientific uncertainty. Also, irrespective of all the uncertainties, we know that the further along in the chemical marketing and development process, the longer it has been manufac tured, and the larger the market, generally the greater the health and environmental effects o f the particular chemicals and tne greater the economic impact there is o f mitigating action, to the extent that they are neces sary. Thus, if we are to deal w ith problems such as PCB's, ` we must change our approach toward environmental phemical problems; we must get out o f a reactive pos ture. We must undertake the task o f identifying poten tial hazardous chemicals early in the development process. By so doing, health and ecological problems can be avoided before they develop. And, by so doing, the economic dislocation and impacts from any potential regulatory action w ill be eliminated or minimized to the benefit o f all. GENP 005853 Preceding page blank 305 774501 PCB's IN CAPACITOR APPLICATIONS Richard L. Rollins* A b s tra c t A lternating current (AC) capacitors have used a grade o f polychlorinated biphenyls (PCB's) since the 1930's. Long life , high re lia b ility and a high degree o f flam e retardancy are im parted to the capacitors b y these flu id s . The la tte r characteristic is very im p orta nt in applica tions where high exposure to the general population exists such as in fluorescent lights and television sets. The main disadvantage w ith the flu id is its long persist ence in nature. When the capacitor industry became aware o f the environm ental problem , it generated guide lines fo r handling and disposal o f the m aterial, then vo lu ntarily imposed these restrictions upon itse lf. Now o f the 70,000 pounds per day processed, o n ly 7 pounds are being discharged in to p la n t water effluents. L iq u id waste m aterials are sent to proper incineration fa cilitie s and solid waste m aterials are placed in sanitary lan dfills to prevent escape in to the environm ent F or 4 years the ,industry has been using a sign ifican tly more biodegrad able grade o f A ro c/or id e n tifie d as 1016 b y Monsanto. In th a t tim e, A ro cto r 1016 has n o t been id e n tifie d as a PCB com m only found in the environm ent Non-PCB mate rials are continuing to be evaluated, b u t there are n o t dielectric flu id s available today which can be considered an acceptable substitute fo r PCB's in the broad range o f AC capacitors. On behalf o f the electronic industrial association and the manufacturers of PCB capacitors, I appreciate this opportunity to present our point of view. I w ill discuss' PCB capacitors, the industry's response to the environmental problem, and possible alternative candi dates to PCB's. Manufacturers o f AC capacitors have used PCB's since the early 1930's, and have used them almost ex clusively sine? World War II. They are presently used, for example, in capacitors for fluorescent lighting, atr con ditioners, and television sets. These capacitors are in the plant where you work, in the home, and in public gathering facilities. They are therefore near you a high percentage of the time. Manufacturers are very cognizant of their responsiblities in providing a capacitor that w ill operate satisfactorily in these applications fo r providing long life and high reliability at a reasonable cost. * V ic e P re sid e n t for Engineering, Jard Corporation, Bennington, Vermont. The consequence o f these requirements in a com petitive marketplace is that the products and their com ponents are constantly being reevaluated to increase life, increase reliability, decrease size, and decrease cost. The capacitor manufacturer indeed daily sees pressures fo r improvements. It is, therefore, an obvious question to ask w hy are PC8's still used after 40 years during which the best capacitor research and development scientists in the United States were constantly seeking substitutes. One o f the reasons lies in the nonflam mability of the PCB material. Because o f applications, such as light ing, where personnel and equipment safety are para mount, capacitors must be manufactured since they not only fail infrequently but also fail safely. In applications such as the World Trade Center in New York, where 250,000 fluorescent lights are installed, it is obvious that high reliability and a nonflammable capacitor character istic are mandatory. A capacitor which fails violently and contains a flammable flu id could create a serious problem, especial ly in densely populated buildings, giving visions o f a towering inferno. The Consumer Products Safety Com mission, as an example, has shown considerable concern over television set fires and has requested Underwriters' Laboratories to develop standards fo r safety fo r tele vision set receivers. A second reason lies in the reliability o f the product as it is known today. Presently, the capacitors our com panies manufacture have a survival rate per year greater than 99.9988 percent. The requirement that more than 95 percent o f our capacitors must survive after 13 years of normal application conditions must also be met. The test time and the amount o f test necessary to guarantee the above reliability is mind boggling to say the least. Many thousands o f units and m illions o f unit hours at or referred to application conditions are required to satisfy our statisticians that any change in product w ill conform to these present day standards. Even w ith the large amount o f previous testing and history on the PCB-containing capacitor, there have been many instances which despite all controls in existence cause consumer concern due to extreme failure rates. That is at a rate greater than 10 percent. The first occurred in 1957, when a variation in the quality of the PCB flu id , as synthesized, resulted in a highly unstable capacitor. Standard analytical tests in use at the time did not detect the quality difference. The result was a large number o f capacitors failing in a very short period o f application life. GENP 005854 306 774502 The consequence was the requirement by the customer that the capacitor manufacturer not only pro* vide compensation fo r the cost o f the capacitor, but the cost of the equipment which contained the capacitor, plus the labor charge fo r placing the equipment in the installation. The total replacement cost the manufac turer 100 times the original price o f the capacitor. The second instance o f numerous failures occurred 6 years later, this time involving the capacitors o f most manufacturers. In this circumstance reduced-size capaci tors were tested and approved by industry-accepted accelerated life testing and a new size was shipped to customers. Approximately 1 year later, up to 15 percent of these capacitors began failing in some applications. A subsequent modification in the accelerated-life testing based upon findings in the field failure analyses now provides proper screening to eliminate the chance of such a problem occurring. Therefore the AC capacitor industry now does very extensive evaluations before1re leasing new designs or using new materials. The capacitor industry became aware that PCB's were possible environmental problems in 1970. Soon thereafter, in 1971, a committee was formed under the sponsorship o f the American National Standards Insti tute, ANSI, to develop standard industry guidelines fo r the handling and disposal o f capacitor grade PCB's. An interim standard was published as an official standard proposal by the National Electric Manufacturers Associa tion, NEMA, in January 1973. And a final document, C l07.1 1974, was published in January 1974. Briefly, properly planned housekeeping, considera tions fo r employee safety, and scrap disposal procedures were detailed. Today, to the best of my knowledge, all manufacturers o f PCB capacitors in the United States have applied these guidelines fo r the handling and dis posal of PCB's. The success o f the manufacturer's control in han dling practices is apparent from the fact that of the approximately 70,000 pounds per day used, less than .01 percent or 7 pounds per day is discharged into die water effluents of the plants. The ANSI guidelines also recommended that the capacitor companies change from Aroclor 1242 to a PCB w ith less toxic effects which Monsanto identified as Aroclor 1016. Here it must be pointed out that various grades of PCB's cannot, as so often is assumed, be classified as having the same chemical, physical, or biological charac teristics. For instance, in "A Comparative Study of Two Chlorinated Biphenyl Mixtures . . by Goldstein et al., significant differences were shown to exist in the biologi cal effects of Aroclor 1242 and 1016 on equal doses of the two mixtures. Aroclor 1016 also-reduces by greater than 94 percent those higher homologs existing in Aroclor 1242 which were the most persistent in nature. W ith these benefits, and w itho ut sacrificing the capacitor characteristics, all capacitor manufacturers began using the new material by 1972, despite the fact that it was 50 percent more expensive. A fter 4 years o f use by the capacitor industries, Aroclor 1016 has not been identified as a PCB that is commonly found in the environment. Nor should it be suspected that 1016 would be commonly found, because the industry is exercising control over waste disposal from its capacitors, so th at there is tittle or no oppor tu n ity fo r leaking PCB's. Our industry believes it is much more important to reduce the environmental problems and to allow con tinued use o f the capacitor-grade PCB than to be con cerned w ith the material cost increase and immediately turn to a substitute which is not thoroughly evaluated and may be flammable. Alternates have been considered ever since the origi nal introduction of PCB's. The substitutes must be not only a satisfactory dielectric fluid providing acceptable life, reliability, and safety, but in addition must not cause environmental problems. Our experience w ith PCB's has demonstrated that some material w ill escape into the environment through processing and handling. Therefore, alternate fluids must be evaluated on this basis. The effects on man and his environment must be determined before the product is introduced. It would be a very serious error to replace capacitor-grade PCB's w ith a fluid which eventually becomes a greater threat to man. Further PCB m odification which would provide even less to xicity and persistence in nature but still maintain good dielectric properties and good non flam m ability would seem to be one alternative to A r o c lo r 1 0 1 6 . O u r companies respectfully urge Monsanto to pursue this possibility. Non-PCB alternatives are now being offered and suggested. Some are new and some have been available fo r many years. The industry's position on these is as follows. Mineral oil is a flammable fluid which was replaced by PCB's in the 1930'$. Capacitors using it are 50 to 100 percent larger, much less reliable, and much less safe than those using PCB's. The substitution of mineral oil necessitates redesign of equipment to utilize the larger capacitor, an increase in the capacitor manufacture facil ity, and w ill result in increased use of basic materials which are presently in short supply. Modified synthetic hydrocarbon oils have been developed which while flammable would allow capaci tors to approximate today's size. Samples have been dis- r r o r n n _t k t c i i ^ v 307 774503 tributd fo r testing, but the material is not commercially available. Phthalate ester, also a flammable flu id and also w ith biodegradability problems, has been used in certain restricted applications where conditions o f lim ited tem peratures exist. The unknown factors o f reliability and safety in the broad consumer use areas such as lighting now prevent its use. Evaluations, however, are continu ing. Substituted aromatic compounds are possible candi dates, and one has been proposed that has less fire resist ance than PCB's; it is suggested to be a good dielectric fluid but only fo r high-voitage power factor correction. This, to our estimation, represents only 17 percent of the PCB used in closed systems, and leaves completely unanswered an alternative or alternatives fo r the remain ing 83 percent of the applications. Some material has been produced but the fluid has not been made commer cially available. In fact, our companies are having trouble obtaining samples from the manufacturer. When samples become available, the time-consuming testing can begin. It has been estimated that 3 years are required before final commercial use after initial testing o f a change in capacitor fluids. Also proposed fo r limited applications is the use o f a plastic film replacing the kraft paper dielectric in the AC capacitor. Although evaluations w ith the highest quality film have been underway fo r more than 2 years using the current processing techniques, the reliability o f the, product is only 1/20th o f that of present capacitors in most applications. Significant additional testing is required to determine if the cause of poor reliability is totally inherent or if improvements can be made by modifications in capacitor design. In summary, there are no commercially available fluids which today can be considered a to ta lly accept able substitute fo r PCB's in the broad range of AC capacitors, nor are there substitute dielectric systems which would satisfy the requirements of reliability and safety in most applications. - I would like to reiterate that our companies have shown responsiveness to the environmental problems of PCB's by the follow ing actions. 1. Working as a group w ith government and consumers ini providing guidelines fo r proper handling and dis posal of capacitor- and transformer-grade PCB's. 2. Reducing discharge levels o f PCB's in a 16-capacitor plant. Further reductions are now being planned. 3. Converting to a more expensive grade o f PCB's which is less persistent and has less to xic effects. Finally significant differences do exist between Aroclor 1016, which capacitor manufacturers are now using, and material which is predominantly being found in the environment. Our industry believes that all concerned should be aware o f the differences. W respectfully urge this awareness in environ mental studies and in drafting o f regulations. GENP 005856 308 774504 THE ECONOMIC IMPACT OF A BAN ON POLYCHLORINATED BIPHENYLS Duncan MacArthur* and Stephen F. Nagyt A b s tra c t The study described below assessed the effects o f a hypothetical to ta l ban on PCB's. In order to com pile a realistic scenario, the proposed Toxic Substances Con tro l A c t was used as a m odel. A complete phaseout was estimated to take 76 m onths, and w ould involve publica tion o f rules, testing, hearings, halting o f im ports and m anufacturing o f PCB's, and depletion o f stocks o f PCB-containing products. M ineral o il was assumed to be the prim ary substi tute fo r PCB's, since a m ajor technological breakthrough in the development o f alternate flu id s is u n like ly in the near future. M inim um estimates are given fo r the one-tim e and annual capita! expenditures by industry o f a ban on PCB's, and fo r the prim ary and secondary im pact costs. Intangible issues, such as the e ffe ct o f a PCB ban on p ub lic safety, are also discussed. In the course o f our work w ith private and public clients, we have examined polychlorinated' biphenyls, PCB's, in a number o f areas, ranging from product design to economic impact. The work to be discussed here was completed in 1975 as part of a study to examine the effects of the proposed Toxic Substances Controls A ct, as illustrated by Senate Bill S776 (20 Feb. 75). We selected as an example a case study to com pletely ban an existing product following the procedures outlined in the proposed bill. We use the case study for following reasons. It provides an example o f the com plete analysis required to assess the impact of a ban; it illustrates the direct and secondary impact on industry; and it enables us to estimate the economic consequences of a ban on one specific product. In our study, we also highlighted the unquantifiable factors. In our methodology, and again this was done in the early part of the year, we assume all the steps in the proposed Toxic Substance Control A ct as illustrated by Senate Bill S776 are taken. The end result of this is a total ban on PCB manufacture and use. We selected PCB's fo r illustrative purposes only. Our discussion was not intended to reflect on the actual health or environ mental aspects of the example.product. * Associate Research Director. Foster D. Snell, Inc., Division of Booz, Allen, & Hamilton, Inc., New York, New York. tResearch Director, Foster D. Snell, Inc., Division of Booz, Allen, & Hamilton, Inc., New York, New York. The scenario fo r banning the product is estimated to require about7 6 months fo r complete phaseout of prod uct use. Thirty-eight months were estimated fo r publica tions o f the rules, testing, hearings, and so forth. The key element in this period is the 24-month period that we estimated would be required fo r testing. The key element in months 39 through 76 is phasing out the sale o f some manufactured goods, particularly appliances. We also assumed that no legal action would be taken by industry until publication o f the final ban on substances occurring after the 38 months o f testing and hearings. A possibility in the scenario o f the second 38 months is that industry reguests a judicial review but complies w ith the review. We estimated the judicial review takes 2 years and results in a complete product ban. In the second 38-month period the following types o f activity would go on: documentation fo r control purposes; m onitoring o f shipments; lim ita tio n o f stock piling of PCB products; refining methods to prevent PCB's from entering the environment, such as controlled use and control proposal; stopping the production and im port o f PCB's or equipment containing PCB's, and finally banning the manufacture and sale o f PCB-con taining products. In the analysis o f our PCB's we have tried to consid er the complete life cycle o f the product. PCB's are pro duced by one manufacturer in the United States--the trade'name is Aroclor--and about 40.5 m illion pounds were produced in 1974. The sale of PCB's is currently restricted to electrical use and casting waxes. In the past they were used as transfer fluids from heat exchangers, hydraulic fluids, and so fo rth . However, as you know, to avoid potential adverse environmental impact, Monsanto restricted domestic and export sales in 1972 to electric installation equipment applications in which the product is enclosed in a relatively well-maintained container throughout its use. Monsanto and others offer PCB dis posal service. We found that PCB applications are characterized by their long-term utilization w ith the majority con trolled by utilities. Transformers, fo r example, were re ported to .last 20 to 30 years, and capacitors to last 7 to 10 years. The number o f transformer manufacturers vary; anywhere from 2 to 10 have produced PCB-containing transformers. Primary use is as nonflammable electric insulating oil. Previous estimates report approximately 5,000 transformers were produced per year w ith an aver- GENP 005857 309 774505 \ age PCB amount of about 5,000 pounds per transformer. Value of shipments (1974 data) is estimated at $35 to $45 million. The number of people using capacitors varies. Esti* mates range from 16 up to 50 capacitor manufacturers. There are approximately 90 to 100 million units per year produced w ith a value about $105 to $147 m illion. There are primarily tw o types: large u tility capacitors, using about 9 to 13 m illion pounds o f PCB's per year, and small industrial capacitors, using about 17 m illion pounds per year. In the case of casting wax, there is only one manufacturer in the United States. PCB's represent 30 percent o f the components o f the wax. The annual usage is about half a m illion pounds. Primarily, it is imported. We also found another indirect importation o f PCB's--in capacitors in electrical equipment. The primary transformer users are.utilities; others include manufacturers of and users o f electrically power ed rail equipment, furnace equipment, and electrostatic precipitators. About 85 percent o f PCB transformers are used as network transformers by the utilities, and we estimate that approximately 90 percent o f the trans former uses are controlled by the utilities, either through ownership or service contracts. With respect to the capacitor users, electric utilities use large capacitors and manufacturers and consumers of goods use small capacitors. Electric utilities use them prim arily fo r power'factor correction, and smaller units are used fo r starting and other uses such as fluorescent lighting. We estimate that about 2 to 3 percent o f large capacitors are consumed as replacements and about 5 to 10 percent of the small capacitors were consumed as replacements. With respect to the casting wax, approximately 98 percent of that is now recycled and the people in the business maintain that the remaining 2 percent that is left in the mold is destroyed when the mold is prepared at high temperatures. The final step is disposal. Monsanto and others have specialized incincerator facilities fo r PCB liquids, primar ily fo r large uses such as transformers and capacitors used by utilities. The ban of PCB's was estimated to result in a one time cost of $13.7 m illion. There would be additional expenditures of $110 m illion annually. The ban would also affect regulatory codes, public safety, and other intangible areas, and, as always, the net result would be an increase in consumer costs. The primary impact, which is on the manufacturer and users, is estimated at $8.8 billion fo r one-time costs and approximately $16 m illion for annual costs. Key elements in this, surprisingly enough, were "red tape" required by Senate Bill S776. There are also disposal costs, plant rebuild costs, and salary costs. Secondary impact on users o f PCB's, PCB-containing products or services, and disposal organizations is estimated at $4.9 billion fo r one-time costs and $93 b il lion fo r annual costs. Elements o f secondary impacts are primarily new plant rebuilds fo r increasing the capacitor output o f the United States, disposal, and the increased cost o f substitutes. The annual costs reflect the forecasted increased costs of electrical equipment manufacture and use, in cluding replacements o f existing equipment. Since the lifetime o f large transformers and capacitors is 20 to 30 years, the additional annual cost, over $110 m illion, was forecast fo r the same period. In the proposed 38-month time period, industry representatives indicated that fo r primary and secondary transformer use, there would essentially be a shift to mineral oil as a replacement fo r PCB's, since the environ ment and performance characteristics o f other substi tutes are not thoroughly researched. Major technological breakthroughs, such as development o f substitute fluids, were not forecast We d id ` use minimum cost estimates. The cost of replacing a PCB transformer, fo r example--n ot necessari ly the transformer but the vault which is surrounded by the building-has been estimated as varying anywhere from $5,000 to $50,000. We used a figure o f about $10,000, which we consider low and very conservative. The economic impact o f changing the regulatory codes cannot be accurately quantified w ith o u t a detailed survey. However, the impact of the changeover fo r those localities w ith regulations was estimated not to cause major dislocation in building activities. We do know that many cities permit only nonflammable, essentially PCB, electrical equipment to be installed in tall buildings; however, others do permit non-PCB transformers w ith a vault. Intangible issues include public safety, which would be impacted by a ban on PCB's. Analysis would require a detailed analysis o f the tradeoffs between the benefits of the product versus the benefits o f the ban. Electrically driven- trains use PCB transformers and it has been re ported that the flammable liquid in the transformer would be a potential hazard. Uses o f other transformers in rail cars, if possible, w ould require redesign and over haul of existing equipment. Use o f large quantities--over 20 gallons o f liquid--in buildings would present a poten tial danger even in walls. Insurance underwriters have reportedly studied the problem but nothing has been presented as a request to change rates. Other intangible areas are in replacements fo r all types o f equipment. D ry transformers, fo r example, are 310 774506 GENP 005858 reported to have a low reliability. There are also specific areas, such as replacement capacitors fo r compact equip* ment in which the capacitors cannot be replaced w ith a non-PCB-containng unit similar in size and characteris tics, forcing either salvage or scrappage o f the equip* ment. In assessing all these costs, we forecasted pass through to the consumer. GENP 005859 311 774507 THE USE OF DOW CORNING 02-1090 DIELECTRIC LIQ UID IN POWER TRANSFORMERS Richard H. Montgomery* A bstract D ow Corning has developed Q2-1090 D ielectric L iq u id to replace askareis in transformers. Five years o f laboratory and fie ld testing have shown i t to be both e ffic ie n t and safe. I t is now being sold in comm ercial quantities both fo r new transform ers and fo r re tro fillin g o ld transformers. W ith some redesign, com petitive en tries, and fu rth e r restrictions on PCB use anticipated, i t is expected to have favorable economics. A 3 - to 5- year phase-in to com pletely com m ercially q u a lify the liq u id in a il applications is planned. Thank you for the opportunity to come here today to represent the silicone industry, which in the United States consists o f the Dow Coming Corporation, the General Electric Corporation, Union Carbide, and Stauffer Chemical. The global silicone industry is now 5 years into a program to qualify dielectric flu id replace* ments in both transformers and capacitors. The Japanese silicone industry and Dow Corning Corporation have led this effo rt to date. As a result o f this extremely large effo rt by the industry, I am very pleased today to make two major announcements. First, the technology to commercially manufacture a capacitor dielectric fluid w ith superior dielectric pro* perties is being developed. This material appears to w ith stand any of the high electrical stresses the material would normally be used fo r in the industry. We plan to make this product commercially available during 1976. A t its present state o f development, we know of no environmental problems w ith this particular p ro du ct No chemistry would indicate there should be any. But this w ill be continually studied, as have other products from the silicone industry. Second, Dow Corning now has commercial produc tio n available to manufacture silicone transformer liquids in sufficient capacity to handle the global trans former market, and that is a very large investment. So let me now turn in some detail to the transformer industry and the role silicones can play. We must remember that today three environ mentally safe transformer systems are available to re place transformers filled with PCB liquids. Gas-cooled, New Product Market Manager, Fluids and Lubricano M arketing, Dow Corning C orporation, M idland, Michigan. air-cooled dry types, and liquid-silicone-filled trans formers w ill meet almost every need where PCBcontaining transformer fluids are used. T h e silicone industry has produced insulating materials fo r transformers fo r 25 years. The industry's newest material, a silicone transformer liquid, is now in use in Japan as a direct replacement fo r PCB-containing transformer oils. In the United States, extensive field testing has been under way fo r 4 years and at the present time this material is being examined fo r inclusion in the U.S. National Electrical Code. Now, to underscore Dow Coming's personal assur ance in the safety, the efficacy, and the efficiency of this liquid, Dow Corning has notified its vendors that we w ill be specifying silicone-filled transformers fo r all the new transformers in our production plants around the world. Our existing askarel transformers, in which we have a very heavy investment, are being phased o ut rapidly through a silicone re tro fit program. Over 6 transformers have been installed new or retrofitted in the past year, and this program w ill accelerate in the spring. I t is, of course, not possible in Michigan during the winter months to drain the PCB's satisfactorily and replace these materials w ith a silicone flu id . The material that we are talking about is known today as Q2-1090 dielectric liquid. Basically, Q2-1090 transformer liquid is a dim ethyl silicone that has been specially formulated and qualified fo r use in electrical applications. The technical feasibility o f using the sili cone in transformers has been shown in over 20 years o f experience in m ilitary transformers, in several years of use on the Japanese National Railway, and in a number o f power transformers in the Midland, Michigan, area; several other areas around the United States w ill also test silicone transformers in the next few months. In addition to these actual applications, which today are well known and have worked o ut nicely, sup port fo r'th e use o f a silicone dielectric fluid in power transformers is contained in over 30 years o f accumula ted data on dielectric properties and com patibility w ith the common materials of transformer construction. The present concern for fire, explosion, health, and environmental hazards are all strong reasons fo r an evo lutionary approach to using silicones and qualifying them in this application fo r all major power transformer uses over the next few years. The silicone liquids o f this type are much less S 312 774508 $09 flammable than typical mineral oils. They actually have a higher flash point than many PCB-containing trans former fluids. Although they w ill burn, they have an extremely low heat of combustion, extremely high flash points and firepoints, and they have been shown in catastrophic testing to be self-extinguishing. They appear to offer a level o f fire safety greatly superior to mineral oils. The silicone that we are now recommending, a dimethyl silicone, has been evaluated by Underwriters Laboratory, and has received an extremely low flamma b ility classification number. In Japan and the United States, transformer cases containing PCB's, silicones, and mineral oil were subjected to catastrophic failure testing. In both tests, all liquids exploded. Most im p orta nt fo l lowing this test, only the mineral oil continued to bum. Both the polychlorinated biphenyl materials and the sili cone fluid self-extinguished. Normally, in a test o f this type you would fuse the circuit c u to u t The fault in the silicone fluid self-cleared, thereby extinguishing die arc. With the other materials, the backup fuse blew and ex tinguished the arc. Following the review of some very extensive data (which is available to all of you by w riting to me at Dow Corning, provided you are w illing to put in 4 or 5 hours in reading it), the major insurance companies have given their permission to use silicone flu id in indoor trans formers. Because it is a new material and since no gen eral policy has been established, the insurers have indi cated that they w ill evaluate each application on an in dividual basis; this is a conservative approach which we highly applaud. Dow Corning feels that we should look at a 3* to 5-year evolutionary approach o f gradually putting a larger and larger number o f transformers into operation. We are offering financial inducements to companies who do this in order to collect a large body of case history data that can be used to convince ourselves and the in dustry that there are no fatal flaws that have been over looked. It's an extremely conservative approach. Silicones are often used in small concentrations in the preparation o f certain foods. A ny time you eat a jam or jelly or drink a glass of some o f that good old Milwau kee beer, you are eating a food-grade dim ethyl silicone. And if you have an ulcer and you eat Di-Gel, you are also eating it. They are excellent deflaccuants. The to xicity of dimethyl silicones to mammals, aquatic life, and plants has been very thoroughly investi gated. The extremely low to xicity o f silicones has made it d iffic u lt to detect any toxic reactions in test subjects. Studies directed toward determining the tendency of sili cone to bioconcentrate have been negative. It has not been possible to date to show that any bioaccumulation was occurring. It has been often stated that silicones are persistent in the environment because they do not biodegrade, under the evidence available at the present time. How ever, there is considerable evidence that silicones do chemically degrade in the environment. Contact w ith soil and water causes the liquid to depolymerize to lowmolecular-weight species, and known chemistry de fin ite ly suggests that these degrade in water or in the atmosphere. Silicones cost more money than the current liquids being used in transformers, but they are not outrage ously expensive. Referring to the entire market of capacitors and transformers, and making some assump tions which would include the shipment o f present pro ducts such as PCB's to the manufacturer's site, if we include the shipping costs, my estimate is that the in dustry PCB purchases would be about $19.2 m illion. I f good engineering practices are followed to reduce the amount o f flu id needed, which has never been a design criteria in the major manufacturer's mind, as mineral oil, of course, is cheap, those costs would prob ably rise w ith the use o f silicone to an industry figure of $25 m illion. So the total increased cost to the electrical and electronics market would be about $5.8 m illion or 29 percent If we made the assumption that the dielectric fluids cost is 20 percent o f the total material cost going into a transformer or capacitor, we are talking about an average cost increase o f about 5.8 to 6 percent at the manufacturing level on new equipment. I feel that this slightly higher initial cost o f silicone liquid-filled transformers is more than offset by the cost of monitoring and controlling of PCB-filled transformers over their lifetimes. And w ith silicone, no known envi ronmental hazards are incurred. PCB-filled transformers currently in service can be changed over to Q2-1090 transformer liquid w ith o u t un due problems. I th in k the work we have done over the past 4 years-some o f it in conjunction w ith Dow Chemical, a lo t o f it in conjunction w ith leading trans form er manufacturers--shows this. I th in k you w ill be' hearing not only from Dow Coming in more detail on this subject I highly suspect that our w orthy competitors, who can manufacture dim ethyl silicones to the same specifications once they learn what they are, w ill go into the market. A t that particular time, the law of supply and demand w ill come into effect. The silicone industry at the present tim e has more capacity than it can sell. I anticipate the economics w ifi be extremely favorable fo r further consideration o f this product in both transformers and capacitors over the next three years. GENP 005861 313 774509 DOW XFS-4169L: AN ENVIRONMENTALLY ACCEPTABLE CAPACITOR FLUID it-rn.iv w ^ ' T A bstract -wr* w IM Dean Branaon, N IH ' H J * i"' Ph1 .D.* >U x>*Ttir<V>rf of power factor correction;''" "' ",r .'.'rT r': Y^ lV U J'.i , , D ow and McGraw^Edfson Companies have devel oped a new capacitor flu id which is electrically, ecologi ca lly, and econom ically acceptable. Chemically, the new flu id can be- described as butyfated m onochlorodiphenyt oxide. . .... ' ? In 1971, Monsanto lim ited the sa le 'o f PCB's fo r dielectric uses where'acceptable alternatives were not' yet ovailable. Since then,Tindustry has been rearching ^fbr alternatives which were ecologically, electricallyi and economically acceptable, ,T Today, we want to report to you that Dow and McGraw-Bdison have developed a buty fated monoch)o-" rodiphenyl oxide known as XFS 4169L. it meets ail tne above criteria and can be used in. highW ta g e capacitors. In itia lly, over 60 fluids representing several chemical families were selected as possible dielectric fluids bn the basis o f their chemical and physical properties, .There fluid* were then scmnecl fo r both electrical, pei^forrrv ance in miniature capacitors and fo r potential hazard to the health and the environment in a battery o f indicative tests. Daw XFS4169L capacitor flu id The conclusion o f there screenings was that the most promising chemical fam ily was the alkylated mono* D ow XFS-4169L capacitor flu id perform s equal to o r better than A ro c lo r 1016 in pow er capacitors. This conclusion is based on dielectric losses, discharge incep tio n voltages, capacitor size, Ora hazard, re lia b ility , economics, and a vailab ility: Dow XFS-4169L capacitor flu id and its components are acceptable in farms o f chlorodiphenyl oxides. ./V " Electrically, several members o f this fa m ily per* formed equal to or better than Aroclor 1016. I t was the health and environmental data that'dem onstrated the significant advantages o f the buty fated m onobhjorodi*. ptnnyl oxide.. health and environm ent according to an assessment o f biodegradability, bioconcentration in fish, to x ic ity to animals, and to x ic ity to fish. -Other capacitor manufac turers are cu rren tly evaluating XFS-4169L fo r applicabil ity in th e ir respective companies. F ield trails have been started w ith u tility companies across d ie country. E lectrical Performance 1 '!" *' : ^ * -'"l, T, - The confidence that McGrarw-Edison'Company ,has in high-voltage capacitors' made w ith the XFS flu id i based on the following assessment ;o f these six key elec trical performances.. 1. D ielectrical losses. The dielectric losses are as low 'or The contents o f this presentation represent 4 years o f jo in t research between Dow and McGraw-Edison Company which has culminated in the development o f an environmentally and electrically acceptable capacitor fluid. When PCB's replaced mineral oils some 40 years ago in power capacitors, this represented another step for* ward in the electrical industry's continuing e ffo rt to pro* vide the public w ith low-cost electrical power and safer electrical equipm ent As a result o f the use o f PCB's, there has been a downward trend in the cost per kUdvar slightly lower than fo r capacitors w ith a PCS known as.. Aroclor 1016. This Is true fo r both paper-film and all film high-voltage power capacitors. This means that the( capacitors w ill operate under normal temperatures an^J that the operating costs wit) be m inimal. This is one o f . the same significant advantages th at PCB's have relative ' to mineral o il. "* v ' ' 2. Discharge inception voltages. Discharge inception voltage is significantly higher than fo r A ro d o r 1016 In both paper-film and all-film capacitors. This means th a t' operating voltages may surge a t least"20 to 30 percent' higher w itho ut resulting in temporary malfunction due ' a 'C apacitor F luid H.N.E., Project Manager, Health and Em f* ronm ant Research Laboratories, Dow Chemical, Inc*. M idland, M ichigan. to electrical discharges known as corona. 3. System siza. The size or volume per u n it o f highvoltage power capacitor correction known as kilovar is 3s 00 314 774510 flammable than typical mineral oils. They actually have a higher flash point than many PCB*containing transformer fluids. Although they w ill burn, they have an extremely low heat of combustion, extremely high flash* points and firepoints, and they have been shown in catastrophic testing to be self-extinguishing. They appear to offer a level of fire safety greatly superior to mineral oils. The silicone that we are now recommending, a dimethyl silicone, has been evaluated by Underwriters Laboratory, and has received an extremely low flamma b ility classification number. In Japan and the United States, transformer cases containing PCB's, silicones, and mineral oil were subjected to catastrophic failure testing. In both tests, all liquids exploded. Most important, fo l lowing this test, only the mineral oil continued to burn. Both the polychlorinated biphenyl materials and the sili cone fluid self-extinguished. Normally, in a test of this type you would fuse the circuit cutout. The fa ult in the silicone fluid self-cleared, thereby extinguishing the arc. With the other materials, the backup fuse blew and ex tinguished the arc. Following the review of some very extensive data (which is available to all o f you by w riting to me at Dow Corning, provided you are willing to p ut in 4 or 5 hours in reading it), the major insurance companies have given their permission to use silicone flu id in indoor trans formers. Because it is a new material and since no gen eral policy has been established, the insurers have indi cated that they w ill evaluate each application on an in dividual basis; this is a conservative approach which we highly applaud. Dow Corning feels that we should look at a 3- to 5-year evolutionary approach o f gradually putting a larger and larger number o f transformers into operation. We are offering financial inducements to companies who do this in order to collect a large body of case history data that can be used to convince ourselves and the in dustry that there are no fatal flaws that have been over looked. It's an extremely conservative approach. Silicones are often used in small concentrations in the preparation o f certain foods. Any time you eat a jam or jelly or drink a glass of some o f that good old Milwau kee beer, you are eating a food-grade dimethyl silicone. And if you have an ulcer and you eat Di-Gel, you are also eating it. They are excellent deflaccuants. The toxicity of dimethyl silicones to mammals, aquatic life, and plants has been very thoroughly investi gated. The extremely low .toxicity of silicones has made it d iffic u lt to detect any toxic reactions in test subjects. Studies directed toward determining the tendency of sili cone to bioconcentrate have been negative. It has not been possible to date to show that any bioaccumulation was occurring. It has been often stated that silicones are persistent in the environment because they do not biodegrade, under the evidence available at the present time. How ever, there is considerable evidence that silicones do chemically degrade in the environment. Contact with soil and water causes the liquid to depolymerize to lowmolecular-weight species, and known chemistry de fin ite ly suggests that these degrade in water or in the atmosphere. Silicones cost more money than the current liquids being used in transformers, b ut they are not outrage ously expensive. Referring to the entire market of capacitors and transformers, and making some assump tions which would include the shipment o f present pro ducts such as PCB's to the manufacturer's site, if we include the shipping costs, my estimate is that the in dustry PCB purchases would be about $19.2 m illion. I f good engineering practices are followed to reduce the amount o f flu id needed, which has never been a design criteria in the major manufacturer's mind, as mineral oil, of course, is cheap, those costs would prob ably rise w ith the use o f silicone to an industry figure o f $25 million. So the total increased cost to the electrical and electronics market would be about $5.8 m illion or 29 percent If we made the assumption that the dielectric fluids cost is 20 percent of the total material cost going into a transformer or capacitor, we are talking about an average cost increase o f about 5.8 to 6 percent at the manufacturing level on new equipment. I feel that this slightly higher initial cost o f silicone liquid-filled transformers is more than offset by the cost o f monitoring and controlling o f PCB-filled transformers over their lifetimes. And w ith silicone, no known envi ronmental hazards are incurred. PCB-filled transformers currently in service can be changed over to Q2-1090 transformer liquid w itho ut un due problems. I th in k the work we have done over the past 4 years-some o f it in conjunction w ith Dow Chemical, a lo t o f i t in conjunction w ith leading trans former manufacturers--shows this. I think you w ill be hearing not only from Dow Corning in more detail on this subject I highly suspect that our w orthy competitors, who can manufacture dim ethyl silicones to the same specifications once they learn what they are, w ill go into the market. A t that particular time, the law o f supply and demand w ill come into effect. The silicone industry at the present tim e has more capacity than it can sell. I anticipate the economics w ill be extremely favorable fo r further consideration o f this product in both transformers and capacitors over the next three years. GENP 005863 313 774511 DOW XFS-4169L: AN ENVIRONMENTALLY ACCEPTABLE CAPACITOR FLUID Dean Branson, Ph.D.* A b s tra c t D ow and McGraw-Edison Companies haw devel oped a new capacitor flu id which is electrically, ecologi cally, and econom ically acceptable. Chemically, the new flu id can be described as butylated m onochlorodiphenyl oxide. n - 0 ,1,2,3 Dow XFS-4169L capacitor flu id D ow XFS-4169L capacitor flu id perform s equal to o r b etter than A ro clo r 1016 in pow er capacitors. This conclusion is based on dielectric losses, discharge incep tio n voltages, capacitor size, Ore hazard, re lia b ility , economics, and a vailability,. D ow XFS-4169L capacitor flu id and its components ere acceptable in terms o f health and environm ent according to an assessment o f biodegradability, bioconcentration in fish, to x ic ity to animals, and to x ic ity to fish. -Other capacitor manufac turers are cu rren tly evaluating XFS-4169L fo r applicabil ity in th eir respective companies. F ield trails have been started w ith u tility companies across the country. The contents o f this presentation represent 4 years o f jo in t research between Dow and McGraw-Edison Company which has culminated in the development of an environmentally and electrically acceptable capacitor fluid, When PCB's replaced mineral oils some 40 years ago in power capacitors, this represented another step for* ward in the electrical industry's continuing e ffo rt to pro* vide the public w ith low-cost electrical power and safer electrical equipment. As a result o f the use of PCB's, there has been a downward trend in the cost per kllovar ' Capacitor F luid H.N.E., Project Manager, Health end Envi- ronm ent Research Laboratories, Dow Chemical, Inc., M idland, M ichigan. of power factor correction. In 1971, Monsanto limited the sale of PCB's for dielectric uses where acceptable alternatives were not yet available. Since then, industry has been searching for alternatives which were ecologically, electrically, and economically acceptable. Today, we want to report to you that Dow and McGraw-Edison have developed a butylated monochlo rodiphenyl oxide known as XFS 4169L. It meets all the above criteria and can be used in high-voltage capacitors. In itially, over 50 fluids representing several chemical families were selected as possible dielectric fluids on the basis o f their chemical and physical properties. These fluids were then screened fo r both electrical perform ance in miniature capacitors and fo r potential hazard to the health and the environment in a battery o f indicative tests. The conclusion o f these screenings was that the most promising chemical fam ily was the alkylated mono chlorodiphenyl oxides. ' Electrically, several members o f this fam ily per formed equal to or better than A roclor 1016. It was the health and environmental data that demonstrated the significant advantages o f the butylated monochlorodi phenyl oxides. E lectrical Performance The confidence that McGraw-Edison Company has in high-voltage capacitors made w ith the XFS flu id is based on the follow ing assessment o f these six key elec trical performances. 1. D ielectrical losses. The dielectric losses are as low or slightly lower than fo r capacitors w ith a PCB known as Aroclor 1016. This is true fo r both paper-film and all film high-voltage power capacitors. This means that the capacitors w ill operate under normal temperatures and that the operating costs w ill be m inimal. This is one o f the same significant advantages that PCB's have relative to mineral oil. . 2. Discharge inception voltages. Discharge inception voltage is significantly higher than fo r A ro d o r 1016 in both paper-film and all-film capacitors. This means that operating voltages may surge at least 20 to 30 percent higher w ith o u t resulting in temporary malfunction due to electrical discharges known as corona. 3. System size. The size or volume per u n it o f highvoltage power capacitor correction known as kilovar is GENP 005864 314 774512 flammable than typical mineral oils. They actually have a higher flash point than many PCB-containing trans former fluids. Although they w ill burn, they have an extremely low heat of combustion, extremely high flash points and firepoints, and they have been shown in catastrophic testing to be self-extinguishing. They appear to offer a level o f fire safety greatly superior to mineral oils. The silicone that we^ are now recommending, a dimethyl silicone, has been evaluated by Underwriters Laboratory, and has received an extremely low flamma b ility classification number. In Japan and the United States, transformer cases containing PCB's,silicones, and mineral oil were subjected to catastrophic failure testing. In both tests, all liquids exploded. Most im p orta nt fo l lowing this test, only the mineral oil continued to burn. Both the polychlorinated biphenyl materials and the sili cone fluid self-extinguished. Normally, in a test of this type you would fuse the circuit c u to u t The fault in the silicone fluid self-cleared, thereby extinguishing the arc. With the other materials, the backup fuse blew and ex tinguished the arc. Following the review of some very extensive data (which is available to all of you by writing to me at Dow Corning, provided you are w illing to put in 4 or 5 hours in reading it), the major insurance companies have given their permission to use silicone flu id in indoor trans formers. Because it is a new material and since ,no gen eral policy has been established, the insurers have indi cated that they w ill evaluate each application on an in dividual basis; this is a conservative approach which we highly applaud. Dow Corning feels that we should look at a 3- to 5-year evolutionary approach o f gradually putting a larger and larger number o f transformers into operation. We are offering financial inducements to companies who do this in order to collect a large body of case history data that can be used to convince ourselves and the in dustry that there are no fatal flaws that have been over looked. It's an extremely conservative approach. Silicones are often used in small concentrations in the preparation of certain foods. A ny time you eat a jam or jelly or drink a glass of some of that good old Milwau kee beer, you are eating a food-grade dimethyl silicone. And if you have an ulcer and you eat Di-Gel, you are also eating it. They are excellent deflaccuants. The to xicity of dimethyl silicones to mammals, aquatic life, and plants has been very thoroughly investi gated. The extremely low to xicity o f silicones has made it d iffic u lt to detect any toxic reactions in test subjects. Studies directed toward determining the tendency of sili cone to bioconcentrate have been negative. It has not been possible to date to show that any bioaccumulation was occurring. It has been often stated that silicones are persistent in the environment because they do not biodegrade, under the evidence available at the present time. How ever, there is considerable evidence that silicones do chemically degrade in the environment. Contact with soil and water causes the liquid to depolymerize to lowmolecular-weight species, and known chemistry de fin ite ly suggests that these degrade in water or in the atmosphere. Silicones cost more money than the current liquids being used in transformers, b ut they are not outrage ously expensive. Referring to the entire market o f capacitors and transformers, and making some assump tions which would include the shipment of present pro ducts such as PCB's to the manufacturer's site, if we include the shipping costs, m y estimate is that the in dustry PCB purchases would be about $19.2 m illion. I f good engineering practices are followed to reduce the amount o f fluid needed, which has never been a design criteria in the major manufacturer's mind, as mineral oil, o f course, is cheap, those costs would prob ably rise w ith the use o f silicone to an industry figure of $25 million. So the total increased cost to the electrical and electronics market would be about $5.8 m illion or 29 percent If we made the assumption that the dielectric fluids cost is 20 percent o f the total material cost going into a transformer or capacitor, we are talking about an average cost increase o f about 5.8 to 6 percent at the manufacturing level on new equipment. I feel that this slightly higher initial cost o f silicone liquid-filled transformers is more than offset by the cost o f monitoring and controlling o f PCB-filied transformers over their lifetimes. And w ith silicone, no known envi ronmental hazards are incurred. PCB-filled transformers currently in service can be changed over to Q2-1090 transformer liquid w itho ut un due problems. I th in k the work we have done over the past 4 years--some o f it in conjunction w ith Dow Chemical, a lo t o f it in conjunction w ith leading trans former manufacturers--shows this. I th in k you w ill be hearing not only from Dow Coming in more detail on this subject I highly suspect that our 'w o rth y competitors, who can manufacture dim ethyl silicones to the same specifications once they learn what they are, w ill go into the market. A t that particular time, the law o f supply and demand w ill come into e ffe c t The silicone industry at the present tim e has more capacity than it can sell. I anticipate the economics w ill be extremely favorable fo r further consideration of this product in both transformers and capacitors over the next three years. GENP 005865 313 774513 DOW XFS-4169L: AN ENVIRONMENTALLY ACCEPTABLE CAPACITOR FLUID Dean Branson, Ph.D.* A b s tra c t Dow and McGraw-Edison Companies have devel oped a new capacitor flu id which is electrically, ecologi cally, and econom ically acceptable. Chemically, the new flu id can be described as butyla ted m onochiorodiphenyl oxide. Dow XFS-4169L capacitor flu id Dow XFS-4169L capacitor flu id perform s equal to o r better than A ro clo r 1016 in pow er capacitors. This conclusion is based on dielectric losses, discharge incep tio n voltages, capacitor size, fire hazard, re lia b ility , economics, and availability. D ow XFS-4169L capacitor flu id and its components are acceptable in terms o f health and environm ent according to an assessment o f biodegradabi/ity, bioconcentration in f/sh, to x ic ity to animals, and to x ic ity to fish. -Other capacitor manufac turers are cu rren tly evaluating XFS-4169L fo r applicabil ity in th eir respective companies. F ield trails have been started w ith u tility companies across the country. The contents of this presentation represent 4 years of jo in t research between Dow and McGraw-Edison Company which has culminated in the development o f an environmentally and electrically acceptable capacitor fluid. When PCB'5 replaced mineral oils some 40 years ago in power capacitors, this represented another step for* ward in the electrical industry's continuing e ffo rt to pro* vide the public w ith low-cost electrical power and safer electrical equipment. As a result o f the use of PCB's, there has been a downward trend in the cost per kilovar 'C apacitor F luid H.N.E., Project Manager, Health and Envi ronm ent Reioorch Laboratories, Dow Chemical, Inc., M idland, M ichigan. of power factor correction. In 1971, Monsanto lim ited the sale o f PCB's for dielectric uses where acceptable alternatives were not yet available. Since then, Industry has been searching for alternatives which were ecologically, electrically, and economically acceptable. Today, we want to report to you that Dow and McGraw-Edison have developed a butylated monochlorodipheny) oxide known as XFS 4169L. It meets all the above criteria and can be used n high-voltage capacitors. In itially, over 50 fluids representing several chemical families were selected as possible dielectric fluids on the basis o f their chemical and physical properties. These fluids were then screened fo r both electrical perform ance in miniature capacitors and fo r potential hazard to the health and the environment in a battery o f indicative tests. The conclusion o f these screenings was that the most promising chemical fam ily was the alkylated mono chiorodiphenyl oxides. Electrically, several members o f this fam ily per formed equal to or better than Aroclor 1016. It was the health and environmental data that demonstrated the significant advantages o f the butylated monochlorodi-' phenyl oxides. E lectrical Performance The confidence that McGraw-Edison Company has in high-voltage capacitors made w ith the XFS flu id is based on the following assessment o f these six key elec trical performances. 1. D ielectrical tosses. The dielectric tosses are as low or slightly lower than fo r capacitors w ith a PCB known as Aroclor 1016. This is true fo r both paper-film and all film high-voltage power capacitors. This means that the capacitors w ill operate under normal temperatures and that the operating costs w ill be m inimal. This is one o f the same significant advantages that PCB's have relative to mineral oil. 2. Discharge inception voltages. Discharge inception voltage is significantly higher than fo r Aroclor 1016 in both paper-film and all-film capacitors. This means that operating voltages may surge a t least 20 to 30 percent higher w itho ut resulting in temporary m alfunction due ' to electrical discharges known as corona. 3. System size. The size or volume per u n it o f highvoltage power capacitor correction known as kilovar is at oo O' O' 314 774514 flammable than typical mineral oils. They actually have a higher flash point than many PCB-containing trans former fluids. Although they w ill burn, they have an extremely low heat of combustion, extremely high flash points and firepoints, and they have been shown in catastrophic testing to be self-extinguishing. They appear to offer a level of fire safety greatly superior to mineral oils. The silicone that we are now recommending, a dimethyl silicone, has been evaluated by Underwriters Laboratory, and has received an extremely low flamma b ility classification number. In Japan and the United States, transformer cases containing PCB's,silicones, and mineral oil were subjected to catastrophic failure testing. In both tests, all liquids exploded. Most important, fo l lowing this test, only the mineral oil continued to burn. Both the polychlorinated biphenyl materials and the sili cone fluid self-extinguished. Normally, in a test o f this type you would fuse the circuit cutout. The fa ult in the silicone fluid self-cleared, thereby extinguishing the arc. With the other materials, the backup fuse blew and ex tinguished the arc. Following the review of some very extensive data (which is available to all of you by w riting to me at Dow Corning, provided you are w illing to put in 4 or 5 hours in reading it), the major insurance companies have given their permission to use silicone flu id in indoor trans formers. Because it is a new material and since no gen eral policy has been established, the insurers have indi cated that they w ill evaluate each application on an in dividual basis; this is a conservative approach which we highly applaud. Dow Corning feels that we should look at a 3- to 5-year evolutionary approach o f gradually putting a larger and larger number o f transformers into operation. We are offering financial inducements to companies who do this in order to collect a large body of case history data that can be used to convince ourselves and the in dustry that there are no fatal flaws that have been over looked. It's an extremely conservative approach. Silicones are often used in small concentrations in the preparation o f certain foods. Any time you eat a jam or jelly or drink a glass of some o f that good old Milwau kee beer, you are eating a food-grade dimethyl silicone. And if you have an ulcer and you eat Di-Gel, you are also eating it. They are excellent deflaccuants. The toxicity of dimethyl silicones to mammals, aquatic life, and plants has been very thoroughly investi gated. The extremely low toxicity o f silicones has made it d iffic u lt to detect any toxic reactions in test subjects. Studies directed toward determining the tendency of sili cone to bioconcentrate have been negative. It has not been possible to date to show that any bioaccumulation was occurring. It has been often stated that silicones are persistent in the environment because they do not biodegrade, under the evidence available at the present time. How ever, there is considerable evidence that silicones do chemically degrade in the environment. Contact w ith soil and water causes the liquid to depolymerize to lowmolecular-weight species, and known chemistry de fin ite ly suggests that these degrade in water or in the atmosphere. Silicones cost more money than the current liquids being used in transformers, b ut they are not outrage ously expensive. Referring to the entire market of capacitors and transformers, and making some assump tions which would include the shipment o f present pro ducts such as PCB's to the manufacturer's site, if we include the shipping costs, m y estimate is that the in dustry PCB purchases would be about $19.2 m illion. If good engineering practices are followed to reduce the amount o f flu id needed, which has never been a design criteria in the major manufacturer's mind, as mineral oil, o f course, is cheap, those costs would prob ably rise w ith the use o f silicone to an industry figure of $25 m illion. So the total increased cost to the electrical and electronics market would be about $5.8 m illion or 29 percent If we made the assumption th at the dielectric fluids cost is 20 percent o f the total material cost going into a transformer or capacitor, we are talking about an average cost increase o f about 5.8 to 6 percent at the manufacturing level on new equipment. I feel that this slightly higher initial cost o f silicone liquid-filled transformers is more than offset by the cost o f monitoring and controlling o f PCB-filled transformers over their lifetimes. And w ith silicone, no known envi ronmental hazards are incurred. PCB-filled transformers currently in service can be changed over to Q2-1090 transformer liquid w itho ut un due problems. I think the work we have done over the past 4 years--some o f it in conjunction w ith Dow Chemical, a lo t o f i t in conjunction w ith leading trans form er manufacturers--shows this. I th in k you w ill be hearing not only from Dow Coming in more detail on this subject. I highly suspect that our w orthy competitors, who can manufacture dim ethyl silicones to the same specifications once they leam what they are, w ill go into the market. A t that particular time, the law o f supply and demand w ill come into effect. The silicone industry at the present time has more capacity than it can sell. I anticipate the economics w ill be extremely favorable fo r further consideration of this product in both transformers and capacitors over the next three years. GENP 005867 313 774515 DOW XFS-4169L: AN ENVIRONMENTALLY ACCEPTABLE CAPACITOR FLUID Dean Branson, Ph.D.# A bstract D ow and McGraw-Edison Companies have devel oped a new capacitor flu id which is electrically, ecologi cally, and econom ically acceptable. Chemically, the new flu id can be described as butyla ted m onochlorodiphenyl oxide. n - 0 ,1,2,3 Dow XFS-4169L capacitor fluid D ow XFS-4169L capacitor flu id perform s equal to or better than A ro clo r 1016 in pow er capacitors. This conclusion is based on dielectric losses, discharge incep tio n voltages, capacitor size, fire hazard, re lia b ility , economics, and a vailability. Dow XFS-4169L capacitor flu id and its components are acceptable in terms o f health end environm ent according to an assessment o f biodegradability, bioconcentration in fish, to x ic ity to animals, and to x ic ity to fish. -Other capacitor manufac turers are cu rren tly evaluating XFS-4169L fo r applicabil ity in th eir respective companies. F ield trails have been started w ith u tility companies across the country. The contents of this presentation represent 4 years o f jo in t research between Dow and McGraw-Edison Company which has culminated in the development of an environmentally end electrically acceptable capacitor fluid. When PCB's replaced mineral oils some 40 years ago in power capacitors, this represented another step fo r ward in the electrical industry's continuing e ffo rt to pro* vide the public w ith low-cost electrical power and safer electrical equipment. As a result o f the use o f PCB's, there has been a downward trend in the cost per kilovar C apacitor F luid H.N.E., Project Manager, Health and Envi ronm ent Research Laboratories, Dow Chemical, Inc., M idland, M ichigan. of power factor correction. In 1971, Monsanto lim ited the sale o f PCB's for dielectric uses where acceptable alternatives were not yet available. Since then, Industry has been searching fo r alternatives which were ecologically, electrically, and economically acceptable. Today, we want to report to you that Dow and McGraw-Edison have developed a butylated monochlorodiphenyl oxide known as XFS 4169L. It meets all the above criteria and can be used in high-voltage capacitors. In itially, over 50 fluids representing several chemical families were selected as possible dielectric fluids on the basis o f their chemical and physical properties. These fluids were then screened fo r both electrical perform ance in miniature capacitors and fo r potential hazard to the health and the environment in a battery o f indicative tests. The conclusion o f these screenings was that the most promising chemical fam ily was the alkylated mono chlorodiphenyl oxides. Electrically, several members o f this fam ily per formed equal to or better than Aroclor 1016. I t was the health and environmental data that demonstrated the significant advantages o f the butylated monochlorodi phenyl oxides. E lectrical Performance The confidence that McGraw-Edison Company has in high-voltage capacitors made w ith the XFS flu id is based on the follow ing assessment o f these six key elec trical performances. 1. D ielctrica/ losses. The dielectric losses are as low or slightly lower than fo r capacitors w ith a PCB known as Aroclor 1016. This is true fo r both paper-film and all film high-voltage power capacitors. This means that the capacitors w ill operate under normal temperatures and that the operating costs w ill be minimal. This is one o f the same significant advantages that PCB's have relative to mineral oil. 2. Discharge inception voltages. Discharge inception voltage is significantly higher than fo r Aroclor 1016 in both paper-film and all-film capacitors. This means that operating voltages may surge at least 20 to 30 percent higher w itho ut resulting in temporary malfunction due to electrical discharges known as corona. 3. System size. The size or volume per u n it o f highvoltage power capacitor correction known as kilovar is 898 00 314 774516 the same as fo r comparative capacitors impregnated w ith Aroclor 1016. This means that it w ill not be necessary to redesign capacitors, the capacitor manufacturing, or the application of capacitors. 4. Fire hazards. As indicated w ith PCB's, there is a low risk of explosion and fires from power capacitors im pregnated w ith XFS 4169L. A major problem associated w ith a failure in a paper-film power capacitor is the decomposition of the paper and, to a lesser degree, the film . The resulting pressure of the gases formed is a major cause of tank rupture. A fter failure, the flamma b ility of the fluid may contribute to a fire only if the paper, the film , and the fluid, are above the ignition or flash temperatures. Under normal operating conditions, a capacitor w ill operate between 40e and 80 C. A t a time of failure, this temperature w ill have to exceed the flashpoint of the capacitor fluid before this fluid becomes contributive to the explosiveness or the flam m ability of the system. In this regard, the flash temperature for the existing dielec tric fluids for mineral oil is 164 C; fo r Aroclor 1016, 166 C; and fo r XFS 4169L, //** C. The fire tempera ture fo r mineral oil, 167 PCB, is greater than 316 C; fo r XFL 4169L, it is 199 C. This clearly shows that the flash and fire points are substantially above the operat ing temperatures. The National Electric Code allows the installation of the electrical devices w itho ut a vault if they contain less than 3 gallons o f burnable liquid. The most common size of our capacitor used today is a 200-kilovar unit. These units contain less than 3 gallons of fluid, and are in stalled predominantly outdoors. 5. Capacitor re lia b ility . Power capacitors impreg nated w ith XFS are more reliable than the same type o f capacitors impregnated w ith Aroclor 1016. This con clusion is based on results of comparative evaluations. The following tests have been completed. Three years of accelerated life tests, more than 18 m illion kilovar hours in full-sized units w ithout failures. Hundreds of sample capacitors operating up to 200 percent of the rated vo lt ages fo r a wide range of temperatures, minus 60 to plus 125 C. 6. Economics and a va ila b ility. The long-range price of power capacitors impregnated with XFS 4169L w ill be reasonable. The increased price or expense attributed to the flu id is expected to be less than $20 fo r a 200kilovar unit. Dow has assured the electrical industry that it w ill have the manufacturing capabilities to produce XFS at a m illion pounds per year rate during the first quarter of 1976. Should this fluid prove to be acceptable to the industry. Dow is w illing to make the commitment to produce the fluid in m ultim illion pound quantities per year by the end o f 1976. Health and Environm ental Assessment The Dow Chemical Company's assessment of the health and environmental acceptability o f XFS 4169L as a dielectric fluid in capacitors is based on the following criteria. 1. Biodegradability. The components in XFS 4169L are significantly more biodegradable than the compo nents of Aroclor 1016. W ith micro-organisms, the rates of formation of radioactive carbon dioxide from radio labeled components of XFS 4169L are much faster than for 2,5,2' trichloro biphenyl, a major component of Aro clor 1016. The major component in 4169L is 45 times more biodegradable than the representative PCB isomer. This rate o f biodegradability is comparable to several nonpersistent industrial chemicals. 2. Bioconcentration. The bioconcentration factors in fish o f the components of XFS 4169L are low relative to the components of Aroclor 1016. The environmentally significant components in each flu id show a factor 30 times less bioconcentratable in tro u t muscle fo r XFS. 3. T o xicity to animals. In both acute and 90-day to xic ity tests w ith animals, XFS shows very little to xicity. For example, in rats, a dose o f 10 grams per kilogram of XFS 4169L was administered orally and had no observ able effect on rats. The levels o f the components o f XFS that accumu lated in the fat o f rats fed the XFS in the diet fo r 150 days were significantly lower than fo r the comparable dietary tests w ith Aroclor 1016. For example, the accu mulation in the fa t was 22 times less fo r XFS; the appar ent plateau' level was achieved in 1 to 2 months com pared to 6 to 7 months fo r the PCB, and the estimated half-life of the rat was 7 days w ith XFS compared to 60 days fo r the PCB. This indicates the relatively low degree of to x ic ity associated w ith XFS 4169L in animals. 4. T oxicities to fish . The XFS material is only moder ately toxic to fish compared to capacitor-grade PCB, which is extremely toxic. The concentration o f XFS that was to xic to fathead minnows was 15 milligrams per titer compared to 0.76 milligrams per liter o f Aroclor 1016, which is a factor o f 20 times less to xic to the fathead minnow. Dow and McGraw-Edison Companies have deter mined that XFS 4169L is an acceptable alternative to capacitor-grade PCB in high-voltage power capacitors. ' This is based on the electrical performance and its low potential impact on health and the environment. Today, McGraw-Edison is proceeding w ith field trials o f capacitors at u tility companies across the GENF 005869 315 774517 country Other U.S manufacturers of power capacitors are currently evaluating XFS fo r applicability in their respective companies. The information about XFS in this discussion is only a very brief summary o f the toxicological and ecological data which have been generated. GENP 005870 316 774518 CHLORINATED BIPHENYL DIELECTRICS-- THEIR U T IL IT Y AND POTENTIAL SUBSTITUTES David Wood* A bstract The paper describes the m ajor reasons fo r the use o f chlorinated biphenyl in capacitors and transformers. These lead to establishment o f objectives fo r research in to p o te n tia l substitutes. MCS-1238, a non-PCB capaci to r flu id developed b y Monsanto, is discussed and areas where fu rth e r development work is required are in d i cated. The p articula r problem s associated w ith d e fin itio n o f " fire resistance" relative to transform er, flu id s is raised. I. INTRODUCTION In 1970, Monsanto voluntarily began its program of terminating sales o f chlorinated biphenyls to open applications--those which could result in losses to the envi ronm ent By late 1972, this program was fu lly imple mented and Monsanto was selling these products only to manufacturers of sealed electric equipment such as trans formers and capacitors. Major applications affected by our withdrawal were carbonless paper, fire-resistant hydraulic fluids, heat transfer fluids, and plasticizers. Sales fo r other miscella neous m inor applications were discontinued during the same period. This action resulted in a reduction o f some 45 m illion pounds per year in the use o f chlorinated biphenyl in areas where entry to the environment was less controllable. We decided at that time to continue supply to closed electrical applications because we believed that: 1. Entry of chlorinated biphenyl to the environment was limited and controllable; 2. A more biodegradable, lower chlorinated homolog had been developed which the capacitor industry could use; 3. Withdrawal would have brought to a halt produc tion o f equipment essential to the.safe and efficient distribution and use of electrical energy because there was no known satisfactory replacement for chlorinated biphenyl dielectrics. Today we continue to sell chlorinated biphenyl, observing the follow ing policy: 1, We supply only to manufacturers o f sealedelectrical equipment such as capacitors and transformers. 2, We supply lower chlorinated homologs, Aroclor 1016, to die capacitor industry. 'M anager, Product and M arketing Dielectrics, Monsanto Industriel Chemicals Company, S t. Louis, Missouri. 3. We offer an incineration service fo r liquid PCB wastes. 4. We continue to work w ith.AN SI Committee C107 and other bodies to establish appropriate handling and control procedures fo r equipment containing chlorinated biphenyl. 5. We allocated increased research resources in 1969 to seek and develop effective replacements; this pro gram continues. 6. In seeking possible replacements, we w ill insure that differences between Aroclor and candidate fluids from our program are widely reviewed in order that the potential impact o f any compromises is fu lly evaluated. The implementation o f these and other programs both by ourselves and electrical equipment manufacturers was prompted by the u tility o f this dielectric fam ily and the difficulties inherent in developing substitutes to effec tively and fu lly replace it. II. U T ILITY OF CHLORINATED BIPHENYL IN CAPACITORS 1. F ire Resistance The adoption o f chlorinated biphenyls in 1929 as capacitor dielectrics stemmed from their superior dielec tric properties compared to mineral oil. However, recog nition o f the fire-resistant character o f the fluids in flu enced system and equipment design and standards over the subsequent 45 years. I t t$ probably true that today many people find it d iffic u lt to assess potential capacitor fire hazard purely because A roclor has been used fo r 45 years. Particular examples where fire resistance in a capacitor is o f benefit indude: a. fluorescent lighting ballasts, b. air*conditioner`m otor capacitors, ' c. television capacitors, d. large power capacitors where high fa u lt currents can cause rupture and ejection o f flu id from pole-mounted units close to people and build ings, e. industrial furnace capacitors. 2. S ta b ility The persistence o f chlorinated biphenyl in the environment is associated w ith the high degree o f ther mal, chemical, oxidative, and hydrolytic stability which permits capacitor manufacturers to fu lfill the exacting reliability requirements th at exist today. GENP 005871 774519 3. DThieelseectprircopCeortnisestanart/eDiiemiepcotrritcanSttreinngdthetsermining the size of a capacitor. In a mixed dielectric system, e.g., paper/Aroclor or paper/polypropylene/Aroclor, the dielectric properties of Aroclor permit optimization of stress distribution between the components making up the dielectric layer. This has enabled capacitor manufac turers to reduce paper and film volumes for a given capacitance. I shall discuss under the heading of "poten tial substitutes" the impact that this could have on: a. paper/film availability and usage; b. design of equipment containing capacitors. III. U TILITY IN TRANSFORMERS Chlorinated biphenyl transformers represent less than 15 percent of transformers in service. Their use is associated with the need to lim it fire hazard in installa tions. 1. Railroad Transformers Multiple unit cars as used in rapid transit systems have transformers mounted beneath each car. By nature of the type of service, involving high passenger density, safety is essential. 2. U rban P o w er Substations (e.g.. Underground Vaults) These designs need to take into account city center space limitations and also the safety of the public and maintenance crews. Fire-resistant liquid transformers are helpful to all these objectives. 3. Industrial Load Centers Efficient system designs for large, power intensive, manufacturing plants (e.g., automotive assembly, steel production) often incorporate transformers close to the electrical load centers. The use of Aroclor transformers at these centers, in the heart of the plants, or overhead in roof structures, protects both employees and plant. 4. Transform er/Rectifiers Programs to reduce the emission of particulate matter from stack gases, for example in fossil fuel generating plants, include installation of electrostatic precipitators. The transformer/rectifiers energizing the precipitator field must be located close to the electrodes. In many designs, the multiple transformers are located in a penthouse above the precipitator. A fire in the pent house could lead to shutdown of the precipitator, and thus the generating plant, if pollution control is to be maintained. A fire-resistant fluid is of obvious benefit in this application. In each of these applications, Aroclor protects the system from: a. initiation of a transformer fluid fire by an elec trical fault beneath the liquid level, b. electrical breakdown of the fluid causing emis sion of flammable gases, c. propagation of fire if the transformer liquid content is involved in an external fire. IV. POTENTIAL SUBSTITUTES IN CAPACITORS 1. Research Objectives In seeking potential substitutes, our research objec tives of necessity involved keeping those properties that gave Aroclor its value. We equally recognized the need that an Aroclor replacement should eliminate environ mental concerns. A replacement should ideally operate across the fu ll range of current Aroclor capacitor appli cations while requiring minimum changes in design of capacitors and equipment utilizing capacitors. The use of chlorinated biphenyl is worldwide. Monsanto manufactures chlorinated biphenyls both in America and Great Britain. We supply to the capacitor industry of many countries. We sought potential replace ment products that could be made available w ith the consistent quality control applied to Aroclor on a w orld wide basis. We referred earlier to availability of codielectric components in capacitors. A solution requiring substan tia l changes in availability of polypropylene film (quantity or quality) or a major increase in short-term availability or capacitor paper, we considered unsatis factory. If in 1974 such increased quantities had been required, they would not have been available. Capacitor production would have fallen short of demand, further jeopardizing efficient power supply. Our research objectives can be broadly summarized in table 1. 2. Non-PCB Candidates The capacitor industry is currently examining two Monsanto non-PCB (candidate) dielectrics. These con tain no chlorinated biphenyl and are not chlorinated products. The two fluids are designated MCS 1238 and MCS 1588. Both of these products are blends o f syn thetic hydrocarbons w ith a high dielectric constant additive to give a dielectric constant equivalent to Aroclor 1016. Table 2 lists some of the properties of MCS 1238 and MCS 1588 compared to Aroclor 1016. 318 774520 Table 1. Research objectives in seeking potential substitutes for capacitors 1. Match o r exceed A ro c lo r 1016 c a p a b ility : a . D i e l e c t r i c c o n stan t - Usage o f o th e r components D ie le c tric strength - C o n v e rta b ility b. S ta b ility Power fa c to r - R e lia b ility c. F ire resistance - Safety 2 . Good environm ental c o m p a t ib ilit y : 3 . a . Span e x is tin g a p p li c a tio n s - Complete s o lu tio n . b. In te rn a tio n a lly a v a ila b le - Not s o le ly U.S.A. s itu a tio n . Table 2. Some properties of MCS 1238 and MCS 1588 compared to Aroclor 1016 Property A roclor 1016 MCS 1238 MCS 1588 ooo o DK 25 C Corona IV /E V * 5 .9 4 .8 5 - 6 .0 5.1 - 6.1 5.1 - Hydrolysis s ta b ility 3 (n e u tr a liz a tio n number) 0 .0 0 0 .0 0 . 0.00 D issipation fa c to r flu id tan 6 60 Hz. 100 C 0.0025 0.05 0.05 . D is s ip a tio n f a c t o r model 0.0032 0.0039 0.0035 paper capacitor a t 90 C aSee t e x t e x p la n a tio n , s e c tio n IV 2 . 319 774521 GENP 005873 Corona inception and extinction voltages are more a function of capacitor design than o f the liquid itself. Preliminary industry results demonstrate functioning in capacitors f(uivalent to Aroclor 1016. Further full-scale work is required before final conclusions can be drawn. Dielectric constants relate closely to those of Aroclor 1016 over the temperature range o f capacitor operation. Hydrolysis stability is mentioned because of work carried out on earlier candidates based on esters, which gave concern because of hydrolysis instability. Hydrolysis was assessed by measuring the neutralization number of a sample w ith 0.5 percent water added, which had been heated fo r 168 hours at 210 F in a stainless steel bomb along w ith an aluminum and a m ild steel coupon. 3. Fire Resistance Neither MCS 1238 or 1588 is fire resistant This deficiency versus Aroclor 1016 must be closely con* sidered. 4. Environm ental Considerations The environmental/health evaluation of capacitor replacement fluids must be related to: a. D eg ra d a tio n --If some quantity enters the environment, at what rate and through which mechanism w ill it degrade? b. Tissue accumulation c. T oxicity-O ccupational safety Environmental compatability 5. Degradation Biodegradation has been studied using a semi* continuous activated sludge technique. Forty-eight*hour exposure of Aroclor 1254, Aroclor 1016, and MCS 1238 dielectric fluids to activated sludge using a semicontinu ous procedure resulted in the percent biodegradation rates and 95 percent confidence lim its shown in table 3. For the polychlorinated biphenyl (PCB) materials, the level of chlorination appears to be the most signifi cant factor in their relative biodegradability. The rate of biodegradation decreases as the number of chlorine atoms per biphenyl molecule increases. Chromatograms representing samples after exposure to activated sludge show significant alteration in the Aroclor 1016 isomer distribution, but little fo r Aroclor 1254. Degradation of the nonhalogenated fluid, MCS 1238, proceeds much more rapidly than fo r the halogenated PCB fluids with no evidence o f resistant components. The methodology fo r this technique is described in appendix B. 6. Tissue Accum ulation Figure 1 depicts the results o f rat tissue residue level studies vs. time and compares Aroclor 1242, Aroclor 1016, and MCS 1238. A fraction o f the ingested A roclor 1242 and A ro c lo r'1016 was stored in rats' lipid reser voirs. However, most o f this residue was depleted after the rats had been on the basal laboratory diet fo r several weeks. During the course o f the feeding study, residues o f Aroclor 1016 accumulated more stowly and to a significantly lesser extent than those o f Aroclor 1242. During the recovery period, these PCB residues de creased to lower values fo r Aroclor 1016. The residue concentrations o f MCS 1238 quickly reached a stable level well below the concentration in the feed. The residues did n o t increase w ith continued exposure. A fter feeding o f the treated chow was ceased, the MCS 1238 residues were rapidly metabolized and/or excreted. The tissue residue accumulation and depura tion profile of MCS 1238 shown in figure 1 is markedly different than those o f the Aroclor fluids, especially that of Aroclor 1242. Methodology is given in appendix A . Table 3. Results of biodegradation using a semcontinuous activated sludge technique M aterial A ro c lo r 1254 A ro c lo r 1016 MCS 1238 48-Hour percent biodegradation 15 + 38 33 + 14 70 + 10 Feed c o n c e n tra tio n , .. _ PPm 1 1 3 320 774522 H8S00 25 PPM FEED LEVEL FOR RATS GENP 005875 Figure 1. Results of rat tissue residue level studies vs. time, comparing Aroclor 1242, Aroclor 1016 and MCS 1238. 321 774523 7. T o xicity Before samples o f MCS 1238 could be evaluated in the capacitor industry and w ithin Monsanto, acute to xicity data was gathered: a. R a t--A cute single oral dose UDS0: 3,800 mg/kg. b. Rabbit--Dermal LD50: 5,000-8,000 mg/kg. c. R a b b it--P o te n tia l eye irritation: A slight degree o f irritation resulted when 0.1 ml of undiluted MCS 1238 was placed in the conjunc tival. sac o f the rabbit eye. The average maxi mum score recorded at one and again at 24 hours aftr treatment was 12.0 on a scale of 110.0. AM eyes had regained normal appearance 72 hours after dosing, d. R a b b it--Potential skin irritation: When un* diluted, MCS 1238 was held in continuous 24*hour contact w ith intact rabbit skin, a moderate degree o f irritation resulted. The maximum average score was 3.6 on a scale o f 8.0 . Further programs are in process, or scheduled, to study the following: a. vapor inhalation, b. ultimate degradation, c. 90-day p ilo t feeding study, d. long-term (2-year) feeding studies, and e. fish tissue residues. 8. Conclusions To summarize Monsanto research activities: -- A large number o f single compounds and mixtures have been evaluated in terms o f physical property data, environmental compatability, fire resistance, and model capacitor life testing. -- These have led us to conclude that: d a. Aroclor 1016 may well be sufficiently de gradable to remain in controlled use, b. MCS 1238 is a potentially acceptable replace ment w ith the qualification that it is not fire resistant. -- Further programs must be completed w ith MCS 1238 in order to: a. deepen our knowledge o f its environmental co m p a tib ility . b. permit complete evaluation by the capacitor industry across their range of applications, c. enable utilities, capacitor users, and agencies to evaluate the significance o f decreased fire resist ance. As a closing thought to this section, I would like to comment that since 1929 when Aroclor was first developed as a capacitor dielectric, normal commercial pressures have spurred efforts to find superior replace ments. The awareness o f environmental accumulation of chlorinated biphenyls from other applications added further impetus for more intensive research in the chemical and electrical industries. Aroclor has defied 45 years o f search fo r a superior replacement V. SUBSTITUTE TRANSFORMER FLUIDS Neither Monsanto nor any other company, to our knowledge, has developed a transformer dielectric w ith equivalent fire resistance to that of Aroclor. The d iffi culties that we face in common w ith other workers in this field are tw o fold : 1. Aroclor has become the reference standard fo r fire resistance in transformers because it works and has "worked fo r 45 years. To establish standards to guide research effort, there is a need fo r objective evaluation o f the fire hazard associated w ith the major sectors of transformer use. 2. The chemistry which imparts fire resistance tends also to produce stable molecules. Monsanto seeks replacement products that w ill provide protection against: a. fire from transformer faults under the liquid surface, b. fire from secondary ignition o f gaseous arc decomposition products, c. fire propagation if the transformer is involved in an externally initiated conflagration. We strive to accomplish this and produce Bn environmentally compatible product. We have four candidates which are currently being evaluated by the transformer industry. These materials are in a suffi ciently early stage o f development that it would be premature to give detailed property data at this meeting. GENP 005876 322 7?4524 APPENDIX A METHODOLOGY FOR FEEDING STUDY Feeding and Sampling Rat chow containing 25 ppm Aroclor 1242, Aroclor 1016, or MCB 1238 was prepared by mixing the products into Ralston Purina rat chow. The treated chow was fed ad libitum to adult albino rats fo r an exposure period of 30 days. Following the 30-day exposure period, all remaining rats were placed on the basal laboratory d ie t A t predetermined intervals during the exposure and recovery periods, five rats from each exposed set and a control set were sacrificed. Fat tissue was excised fo r analysis and composited fo r each group. Samples were quick-frozen and stored in glass containers w ith aluminum foil-lined caps to minimize risk o f contamination. Isolation The dielectric flu id residues were isolated from the fat by solvent extraction. A weighed amount o f fat was placed in an Erlenmeyer flask and homogenized three times w ith 25 ml o f pesticide-grade hexanes and anhy drous sodium sulfate using an ultrasonic homogenizer. The combined supernatants and washings were filtered through anhydrous sodium sulfate and diluted to 100 ml w ith hexane. L ip id W eight Determ ination A 5 ml-aliquot o f the extract solution was pipetted into a tared 50-ml beaker. A fte r evaporation o f the solvent under a stream o f nitrogen, the beaker and resi due were reweighed to obtain the lipid weight of the aliquot. A ll residue levels are reported as ppm on a lipid weight basis. PCB Cleanup A nd Measurement Sample cleanup .for the extracts containing A roclor 1242 and Aroclor 1016 residues was accomplished by pipetting an aliquot o f the extract onto a 5 percent deactivated alumina column and eluting w ith 125 ml of hexanes. The column eluate was collected in a KudernaD anish evaporative concentrator, a 3-ball Snyder condenser was attached, and the solution was concen trated to 5 ml. The residue levels in the extracts were measured by gas chromatography using an electron capture detector. Non-PCB Cleanup A n d Measurement Sample cleanup fo r the extracts containing MCS 1238 residues required separation o f the residues from the lipid by preparative scale gel permeation chromatog raphy. Following the GPC separation, the extracts were further cleaned up on an alumina column, collected, and concentrated as above. The residue levels in these extracts were measured by gas chromatography using a flame ionization detector. C alcu la tion s Calibration curves fo r each product were prepared by plotting detector response (total peak area) versus nanograms o f standard injected. Residue levels in the samples were determined by summation o f the total area o f peaks corresponding to peaks in the standard and use o f the appropriate calibration curve. The calculations were done as follows: (NKVp) Residue (ppm) = ----------(V ,)(W ) where N >= A m o u n t o f product from calibration curve (ng), V p * Volume o f final concentrate (ml), V| * Volume injected (ul), W Lipid weight o f original sample (g). GENP 005877 APPENDIX B TECHNIQUE FOR BIODEGRADATION METHOD Biodegradation M ethod Since activated sludge is one o f the most important agents fo r sewage treatment, test procedures evaluating its action are o f great importance. T h e sem continuous activated sludge (SCAS) method has been extensively utilized in the development o f biodegradable detergents. In our SCAS procedure, patterned after the Soap and Detergents Association's 323 774525 standard method (1,2) mixed liquor (activated sludge and supernatant) from a local domestic sewage treat ment plant is charged to magnetically stirred glass vessels of 1.5-1 capacity. Means fo r aeration and sampling are provided. The SCAS u nit ts generally operated using a retention or aeration time cycle o f 24 to 72 hours. A t the beginning of each cycle, synthetic sewage (300 mg glucose, 200 mg nutrient broth, and 130 mg K3 HP0 4 ) and the appropriate test material in ethanol solution are added to the mixed liquor (2,500 mg/l suspended solids concentration). Aeration is maintained until the end of the cycle, at which time the sludge is settled and 1 I o f supernatant drained. The cycle is then reinitiated by the addition of tap water, synthetic sewage, and test mate rial. Operation o f the units can be continued fo r an indefinite period of time until consistent degradation rates are observed. Sample Analysis Biodegradation o f the test material was determined during one cycle each week by analyzing 20 to 50 ml mixed liquor samples withdrawn after feeding and at the end of the aeration cycle. The mixed liquor analytical procedure involved extraction w ith three successive 25-ml portions o f hexane, and drying combined extracts w ith anhydrous sodium sulfate. Extracts were concen trated in a Kuderna-Danish evaporative concentrator equipped w ith a 3-ball Snyder condenser, and measured by electron capture or flame ionization gas chromatog raphy. Calibration curves fo r each product were pre pared by plotting detector response (total peak area) versus hanograms o f standard injected. The percent biodegradation was calculated from the following equation: percent biodegradation (CQ Cn)/CQ x 100 where CQ and Cn use the initial and final concentration o f test material, respectively, on the mixed liquor. REFERENCES 1. J. Am . O il Chem. Soc., V o l. 42 (1965), p. 986. 2. J. A m . O il Chem. Soc.. Vol. 46 (1969), p. 432. 005878 324 774526 SOME COMMENTS ON A LTE R N A TIV E S TO PCB's Bruno Rey Coquais* A b s tra c t In the transform er industry, the benefit o f a non flammable liq u id seems to exceed the risks o f p o llu tio n b y polychlorinated biphenyls; however, to m inim ize eventual contam ination o f the environm ent, i t is suggest ed to use, when possible, a m ixture o f chlorobenzene and trichlorobiphenyl o r even chlorobenzene alone. F or the im pregnation o f capacitors, m ost o f the sub stitutes which can be imagined are n o t very attractive, though they are useful fo r certain applications. I t is p ro posed to use a m ixture o f pure dich/orobiphenyls and th e ir a lkylated derivatives. This im pregnant, named chloralkylene, has dielectric properties very sim ilar to the industrial trichlorobiphenyl. The tests in progress already show th a t chloralkylane is easily biodegradable and has a lo w to x ic ity . This com pound seems to be quite acceptable fo r the environ m ent and should he a p erfect substitute fo r p o ly c h lo ri nated biphenyls in capacitors. To begin w ith , I would insist on the fact that heavy chlorinated biphenyls have been used fo r a long time in dispersive applications as plasticizers and fo r other uses. Although these types of applications have been stopped in accordance w ith the OECD recommendations of the February 14, 1973, it is not surprising to continue to find th e persistent, highly chlorinated PCB's every* where in the environment. It is therefore very d iffic u lt to know if the electrical uses o f PCB's fo r transformers and fo r capacitors have a significant contribution to the pollution of our environment. TRANSFORMERS PCB's are used in transformers only when the fire hazard is high {department stores, theatres, movies, skyscrapers, factories); otherwise o ilfilled transformers, which are cheaper, are always preferred. We do not th ink dry*type transformers would be a competitive alternative in spite o f the fact that silicone and epoxy belong to the range o f products we market. They may be very attrac* tive in some cases, but in addition to certain economical and technical disadvantages, dry transformers do not offer a perfectly safe solution wherever flammable va pors {solvents, oil, gas) may be present accidentally. We believe a nonflammable dielectric liquid is abso * Development Manager, Prodalac, S.A., 25 Duel Paul Doom er, Courbevoie, France. lutely necessary to prevent the risk of fire in transform ers. In table 1 we have listed the different possible solu tions. In the United States, at this tim e, transformers are filled w ith Inerteen 70-30, which is based on pentachlorobiphenyl, or w ith Inerteen 100-42. To minimize the pollution risk, a mixture o f trichlorobiphenyl and chlor obenzene or even the chlorobenzene alone could be used in spite of some technological problems. In any case, the systematic recovery of used PCB's w ill further lim it pollution hazards; our company Prodelec has organized this practice throughout France since 1968, as soon as this pollution problem became known. This systematic recovery has now been enforced in France by the French law o f July 8,1975, on PCB's. CAPACITORS For capacitor impregnation, we have examined vari ous possible ^solutions. We th in k that the performances o f such compounds as silicone; sulfone or synthetic oil (alkylbenzene, poly butene); phthalate; and sebacate-- which we are indeed selling ourselves fo r certain applications-are not really satisfactory enough fo r generalized or widespread use. In our opinion, a substitute to PCB's should be char acterized by: * High perm ittivity; * Nonflam m ability, at least n ot sustaining com bustion; Compatibility w ith polypropylene film ; Being a permanent liquid w ith no crystalliza tion until -25; Good thermal and electric subfteld stability; a Regarding its effect on the environment, being fa irly easily biodegradable, to eliminate the risk o f accumulation, and by having low to xicity. To get a good and nonflammable dielectric flu id means in practice that the compound must be a chlori nated aromatic hydrocarbon. We have studied, fo r in stance, new structures, as shown in figure 1. With chlorobiphenyl oxide, we are afraid o f the risk o f metabolization in highly to x ic dioxins and we feel that products of the fam ily o f the chlorobiphenylethane are technically and environmentally much more promising. Actually, in troducing a to ta lly new compound would require a long and expensive testing program and it seems better to take advantage o f the huge amount o f knowledge gather ed about PCB's and to see how it may be possible to improve the present situation. GENP 005879 325 774527 Table 1. Possible solutions for dielectric liquid IEC type Chlorobiphenyl Chloro benzene Pour Point (C) Viscosity Cst at 20 C t at 20 C Hydrogen index3 Askarels for transfor mer T 1 60% hexa 40* tri <-33 21 T2 45% hexa 55% tri and <-40 tetra T4 70% penta 30% tri <-30 11 20 45% penta 55% tri and tetra T 3 100% tri <-40 <-18 10 65 60% tri 40% t r i ` <-50 7 40% tri 60% tri and tetra 100% tri and tetra <-20 Chrystallize -9 4.5 <0 Pyralene e x c e s s Cl Tj P yrocl o r 5 <0 e x c e s s Cl 5 0 Inerteen 70-30 Pyralene T4 <0 Pyralene e x c e s s Cl T 2 6 16 Pyralene Tg Inerteen 10042 6 10 Pyralene 1460 4 6 <0 excess Cl aHydrogen index = No. hydrogen - No. chlorine Molecular weight " 326 oo oo 774528 CL ,CL 4. FLASHPOINT FIREPOINT Chloro diphenyloxldo 103 C IT I 9C --------------M---a---t-o--b--o--l-l-s--m---------------- i C hlorod toxin e CL Cl CHCI II ch2 + (developed by Telgin) S-si FLASHPOINT ieo c FIREPOINT 25 0 C FLASHPOINT 210 C FIREPOINT NONE 774529 l8 8 S 0 0 d N 3 O Figure 1. New structures for nonflammable dielectric fluids. O Cl dlctiloro biptwnyl 2- 2' 2-4* CHj CM--CHj - Figure 2. Structure of chloralkylene. Table 2. Composition of various imprgnants Composition, percent C h lo ra lk y le n e 12 Biphenyl M o n o c h lo ro b ip h e n yl D ic h lo ro b ip h e n y l T ric h io ro b ip h e n y l T etrach lo ro b i phenyl Pentachlorobi phenyl A 1kylchiorobi phenyl isomers Chlorine content, percent `0 0 20 0 0 0 80 2 5 .8 Pyralene 3010 (tric h io ro bi phenyl) Pyralene 1500 Pyralene 2000 0 0 11.4 57.1 29.4 2 .2 - 0 0 .5 37.5 4 0 .0 2 0 .5 1 .5 - 1 .6 18.4 4 4 .0 2 3 .4 1 1 .7 0 .9 - 42. ` 38.5 3 3 .5 328 774530 Table 3. Comparison of chloralkylene to commercial trichlorobiphenyls C haracteristics Chi o ra lk y le n e 12 Pyralene 3010 (trich io ro d ip h en yl) Specific g ra vity a t 20 C 100 C C o e ffic ie n t o f expansion V isco sity Cst. a t 20 C 100 C Pour p o in t (ASTM D 97) F ire p o in t (Cleveland) P erm itivity a t 20 C 100 C R e s is tiv ity 100 C - 500 V - 1 mn D issipation fa c to r +g5 100 C - 50 cps 1.163 1.097 7 .5 x TO"4 135 3 .2 258 C 6 .0 0 4 .8 6 g >3000 x 10 <0.02 1.391 1.319 6 .8 x 1 0 '4 65 2 .3 -23 C none u n t il b o ilin g 5.93 4 .8 0 Q >3000 x 10s <0.02 (pmnt) i ro tn o o GENP 005883 Figure 3. Excretion by rats, with diet of 2 ppm/day for 5 weeks. 329 774531 / / Figure 4. Excretion by rhesus monkey; single oral dose 1 mg/kg. The studies carried on, in particular by Prof. Korte and Dr. Klein in Germany, seem to prove the easy biode gradability of PCB's when they have a very low chlorine content; therefore, oure mono- or dichlorobiphenyls could be quite acceptable fo r the environment. and abroad. To assess its impact on the environment, we have given chloralkylene to the Institute fo r Ecological Chem istry in Bonn, Germany, Prof. Korte. This institute is engaged in an extensive investigation on "PCB's in the As an impregnant consisting only o f mono- and dichlorobiphenyls would crystallize at room tempera ture, it is necessary t t produce a more complicated m ix Environment." We therefore hope to have next spring the final results on the fate o f chloralkylene in compari son with PCB isomers.' ture to get a permanent liquid at alt temperatures. We have therefore developed a product named "chioralkylene," obtained by addition o f an alkyl chain, actually an isopropyl group, on a mixture of nearly pure dichlorobiphenyl isomers (figure 2). Tests on environmental acceptability are actually being carried out w ith chloralkylene based on 2-4* dichlorobiphenyl labeled w ith 14c. The tests consist o f a study of the balance of the excretion, the storage, and the metabolism in rats and in monkeys (figures 3 and 4); the As shown on table 2, chloralkylene. contains i \o monkey studies are being completed at the Institute of penta- nor tetrachlorobiphenyl and the trichlorobiphen- Experimental Pathology and Toxicology, Albany Medi yl content can be extremely low. Technically, for its cal College, Albany, New Y ork. These tests also examine dielectric and physical properties, the chloralkylene is a the fate o f chloralkylene in a soil plant ecosystem and in O perfect substitute to the commercial trichlorobiphenyls an aquatic ecosystem, as welt as its behavior under at o (Pyralene 3010, Arochlor 1016), as shown in table 3 and mospheric conditions, upon waste composting, and in ooo o as checked by some major capacitot "v-vjfacturers here sewage treatments. The results so far obtained prove that 330 774532 chloralkylene does not accumulate, is metabolized quickly, and behaves generally like the dichlorobiphenyls isomers themselves. Chloralkylene is two times less toxic than trichloro* biphenyl when one compares the acute to xicity values. A t this time, there is no real reason to consider PCB's dangerous fa r the labor manufacturing capacitors, if the necessary precautions are taken. We th in k th at w ith an easily biodegradable compound such as chloralkylene, long-term effects due to accumulation along the food chain do not need to be feared. The chloralkylene price is presently twice that of the currently commercially available polychiorobiphen yls, which would result in an increase o f the capacitor costs o f about 5/10 percent. However, by substituting mineral oil or other substitutes w ith less outstanding characteristics, the increase o f the cost o f capacitors would be much higher. We hope to improve its economy and are quite confident that chloralkylene could thus be an excellent substitute fo r trichlorobiphenyls. GENP 005885 331 774533 PCB's AND TH E IR SUBSTITUTES - A BRIEF LOOK AT SOME EXAMPLES OF PAST TRADEOFFS Dale Hattis; Ph.D., and Albert Murray, Ph.D.* A b s tra c t Some aspects are described o f a study o f the economic, health, legal, and other impacts o f the past voluntary restriction on PCB sales. Examples illustrate the im portance o f exam ining the effects o f substitute technologies in assessing regulatory p o lic y b y showing the p o te n tia l fo r surprises in this regard, in the PCB case, s u b s titu te s may be producing both unanticipated economic benefits and unappreciated health and safety risks. I am Dale Hattis of the Center fo r Policy Alterna tives M.I.T. My colleague at the center, Dr. Albert Murray, who was originally scheduled to speak here--and who would be the most appropriate speaker on this subject--was unfortunately taken ill about a week and a half ago and he is now still recuperating in the hospital. What 1 have done in his place fo r presentation today is to extract some particular examples of tradeoffs from Al's work on PCB's, which illustrate some occasionally surprising features o f the technological changes that arise out of environmental/health concerns. For context, I would (ike to say that our project, sponsored by the Council on Environmental Quality and EPA, and under the direction o f Dr. Nicholas A. Ashford, has for the past year been exploring ways to analyze the economic, environmental health, legal, and other impacts of regulatory decisions related to environ mental chemicals. In this exploration, we are now in the process of completing eight experiments in the analysis of the impacts o f particular regulatory actions, primarily drawn from the past 5 years of history. The first o f our eight experiments, though not strictly resulting from a mandatory governmental action, was the restriction a few years ago of the sale of PCB's fo r particular uses. Because our case studies are experiments to explore the practical use o f methods, and because the resources we could devote to each case were relatively small, we could not perform as comprehensive an elucidation of effects as we would have wished. Nevertheless, we do think that our analyses have revealed important types of questions, similar to those referred to yesterday by Mr. Train, which are d iffic u lt to deal w ith in the single chemical ` Research Associates, Center fo r Policy Alternatives, Massachusetts In stitu te o f Technology, Cambridge, Massachu setts. reactive context of most current regulatory authorities. My initial two examples of such questions on PCB's illustrate the fact that it is sometimes d iffic u lt to be sure that technological changes introduced with the intent of reducing environmental health risks accomplish their purpose on balance, when the risks of substitute prac tices are considered. Sometimes there appear to be legiti mate reasons for concern that particular changes-- especially in the absence o f continuing regulatory follow up--might create environmental health hazards as dangerous or more dangerous than the ones that are eliminated. As a first example, the substitutes fo r PCB's in some large heat exchangers and in some special hydraulic fluids fo r high-fire-risk uses are flammable at elevated temperatures. Concern fo r the lack of fire protection previously provided by PCB's in these situations has reportedly caused a substantial increase, as much as a doubling in some cases, in fire insurance rates on some industrial facilities employing high-temperature heat exchangers. In our case study, A l Murray estimated the total increase in premiums at possibly in the tens of millions o f dollars annually. This, o f course, reflects mainly property damage and not the human cost. How ever, if our information on the increased premiums is correct, and if the apparent perception o f the insurance companies is correct as to the size o f the added chance o f catastrophic fires, then we must consider that such events would be likely to be accompanied by appreciable human casualties. The rise in insurance rates, o f course, may not reflect an actual change in risk, and in that case the increased insurance cost is simply a transfer payment to the benefit of the insurance companies, but the mat ter seems to deserve further exploration w ith the aid of hard statistics on actual fire-risk experience. If the data confirm that appreciable human impact may be ex pected to occur, alternative means fo r reducing this risk might be productively evaluated. Another, although probably less important, example o f potential risk of substitute technology arises in the case of the former use o f PCB's as a dye-solvent fo r carbonless carbon paper. It may be recalled that at some frequency PCB's from this source found their way into recycled paperboard products fo r food contact use, and this was a. source o f concern fo r the FDA. Now the PCB's form erly used fo r this purpose have been replaced, but unfortunately it is not public inform ation what exactly has replaced them. The barrier o f trade secrecy GF.NP 005886 332 . 774534 in this instance, as in many others, can frustrate at tempts to assess the difference in environmental health risk produced by the change in technology, Two other examples illustrate the potential fo r a different category of surprises--those in the economic area. Formerly, PCB's costing on the order of 25 cents per pound were used in many paints and coatings, some times as a major ingredient. In this application PCB's were a chemically stable blender and conferred resist ance to fire, impacts, water, and weathering, Our inquir ies w ith paint manufacturers indicate that chlorinated paraffins now perform essentially all the technical func tions of PCB's at about half the former co st Our industry informants mention some increased problems in a few of their products w ith lowered stability to dechlo rination-causing occasional discoloration and loss o f weathering resistance--but over the great bulk o f their product lines, the industry perception appears to be that th change has been economically beneficial. PCB's had evidently become established as paint additives before t he availability and advantages o f the chlorinated paraffins became widely appreciated. Later, when approximate technical equality and lower prices might have tempted paint manufacturers to substitute, the usual inertial resistance to any change appears to have caused this opportunity to be generally neglected. The real world and the economists* ideal one occasionally behave differently. Another example o f a surprise (at least to us) in the economic area 5 the potential importance of even small adverse impacts on sport fishing. A U.S. Department of Interior survey (ref. 1) indicates that in 1970 a total of about 700 m illion person-days and five billion dollars were spent in pursuit o f this pastime --mainly in fresh water. The five billion dollars must, of course, be con sidered an underestimate o f the actual "value" o f that activity to people. I f PCB's had continued to be used as they were in the past, we m ight speculate that additional concern of people about residues (such as that now publicly in evidence), or possibly some declines in fish populations might have led to small fractional declines in participation or enjoyment o f fishing by some portion of the population. If this were to occur, the loss o f value to society o f even less than a fraction of a percent of national sport fishing activities might be appraised at tens o f millions o f dollars annually--depending on the "value" realized by form er fishers in substitute recrea tional activities. The importance o f examining subtle and uncertain effects, including the effects o f substitute technologies, is illustrated by such occasional insights into their poten tial magnitude. REFERENCES 1. Fish and W ildlife Service, Bureau o f Sport Fisheries, U.S. Dept. Interior, "National Survey o f Fishing and H unting," Resource Publication 95, GPO, Washing ton, D.C., 1972. GENP 005887 333 774535 ENJ-2065--AN ELECTRICAL INSULATING FLU ID E. J. Inchalik, Ph.D.* A b s tra c t The need fo r an electrical insulating flu id whose use w ould avoid the adverse toxicological and ecological e ffe c ts associated w ith polychlorinated biphenyls prom pted a study o f organic esters as possible substi tutes. The study culm inated in the id e n tifica tio n o f diisononyt phtha/ate (ENJ-2065,) as a dielectric flu id o f p o te n tia l interest to the capacitor industry. ENJ-2065 has been made available to th a t ind ustry and i t is now being used in some com m ercial capacitors. In late 1970, a study was begun at Exxon Research and Engineering Company by Drs. A, J. Rutkowski and E. 0 . Forster to develop an electrical insulating flu id whose use would avoid the adverse toxicological and ecological effects associated w ith polychlorinated bi phenyls. This study culminated in the identification of diisononyt phthalate (ENJ-2065) as a dielectric flu id o f potential interest to the capacitor industry. Exxon Chemical Company U.S.A. has made ENJ-2065 available to the industry for its evaluation and it is now being' used in some commercial capacitors. In the preliminary phases o f this study, the dielec tric properties of a significant number o f mono- and dibasic acid esters were determined in order to obtain a general understanding of the interrelation between mo lecular structure and dielectric properties. From these data it was concluded that major attention ought to be directed at the esters o f phthalic acid. The phthalates that we tested all had dielectric constants o f 4-6, close enough to the desired level fo r fluids fo r t)ie widely used paper-based capacitors to justify further evaluation. The optim um dielectric constant fo r these capacitor fluids is one which closely matches the dielectric constant o f the paper. A close match reduces electric field inhomogenei ties, increases dielectric strength and lifetime, and de creases capacitor size. Other im portant property criteria fo r a paper dielectric fluid include a low dissipation fac tor, to reduce energy loss and destructive heat buildup; a high dielectric strength, to reduce capacitor size and im prove service life by permitting short-term exposure o f the flu id to abnormally high stresses w ithout break down; a low gassing tendency, to avoid production o f gases that could lead to pressure buildup in sealed units; stability at elevated temperatures, to prevent capacitor * Research Associate, Chemical Interm ediates Technology Division o f Exxon Chemical Company, Linden, New Jersey. breakdown and stabilize performance; low viscosity, to allow fo r easier impregnation and fillin g o f capacitors and elimination of air pockets; a low order o f to x ic ity ; and com patibility w ith the environment. Consideration o f these factors as well as availability and cost resulted in narrowing the choice of potential candidates to those shown in table 1. From this list, diisononyl phthalate (ENJ-2065) was selected as the most promising fo r additional study. ENJ-2065 was cho sen on the basis that it has (1) a higher dielectric con stant than the phthalates o f higher molecular weight, (2) an advantage in its loss characteristics relative to the lower molecular weight dihexyl and dioctyl phthalates, (3) a relatively high flash p oint o f 430 F, (4) a more highly branched molecular structure than dihexyl and dioctyl phthalates w ith the potential fo r improved hydrolytic stability and (5) a good balance o f other physical and electrical properties. ENJ-2065 is manufac tured in the United States by Exxon Chemical Company U.S.A. from phthalic anhydride and a mixture of branched isomeric alcohols in which C$ alcohols pre dominate. Electrical insulating fluids have to remain essentially unchanged chemically when subjected to temperature cycles. Once having chosen .ENJ-2065 fo r further evalua tion, it was desirable to know what effect certain con taminants m ight have on its stability, how these contam inants might be removed, and what additives, if any, m ight be useful in enhancing its stability. The effects o f small amounts of tw o potential contaminant5, alcohol and water, on conductivity of ENJ-2065 are shown in tables 2 and 3. The results show that alcohol levels o f less than about 1,000 ppm and water levels of less than about 100 ppm can probably be tolerated w ithout affecting performance seriously. To re move small quantities o f these impurities as well as any 8cids or catalyst residues from the production of ENJ-2065, we found percolation through a packed col umn o f activated Attapulgus clay to be effective, but we did not carry o ut extensive studies to optimize a p u rifi cation system. I t is our feeling that systems now being used in the industry fo r purification o f PCB's prior to use In capacitors, or slight m odifications o f them , w ill prove to be satisfactory fo r ENJ-2065. Although the most widely used capacitors today are o f the all-paper type, newer types based on polypropy lene film and paper or on all-poiypropylene film are growing in importance. W ith capacitors o f this type, the dielectric constant o f the flu id is less important. 334 774536 Table t. Electrical and physical properties of phthalate esters P h th a la te Ester D im Dihexyl e th y l hexyl D iis o o c ty l ENJ-2065 D iiso d ecyl D itrid e c y l D ie le c tric constant 5 .6 4 Tan d e lta -- AC conduc n rt i v i t y , 11 ( ohm-cm)* 1 9 .0 Breakdown v o lta g e (K V /0 .1 in .) B oiling p o in t-- mid @ 5 mnHg, C 210 Pour p o in t, C -33 V iscosity, c p s ., 20 C 50 F la s h p o in t, COC, F 380 F irep o in t, COC, F 420 5.33 0 .1 4 2.1 28 230 -50 81 425 475 4 .9 7 0 .3 0 4 .6 6 0.05 4 .4 5 0 .0 2 4 .0 8 0.01 1 .3 27 0.29 30 0 .2 0 36 0 .0 4 29 235 252 256 -45 -4 8 -50 83 95 110 430 430 '452 485 495 515 286 -37 230 470 555 GENP 005889 335 774537 Table 2. Effect of residual alcohol on conductivity of ENJ-2065 Temperature cycle (1 ,0 0 0 V, 60 Hz) 12 1 C onductivity (10 ohm-cm) Wt. p e rce n t alcohol1 added 0 0.01 0.1 25 C 90 C 25 C 0 .7 8 40 3 1.97 65 4 1 .9 8 320 12 Table 3. Effect of residual water on conductivity of ENJ-2065 Temperature cycle (1,000 V, 60 Hz) 12 -1 C onductivity (10 ohm-cm) Wt. p e rc e n t w a te r added 0 0.001 0.01 0.1 25 C 90 C 25 C 0 .7 8 40 3 2 .7 165 10 3 .7 >400 25 135 >400 70 Table 4. Weight gain of PP film in contact with dielectric fluid F lu id Run number 1 2 ENJ-2065 A ro c h lo r 1242 11.0 10.9 13.8 18.8 18.2 2 2 .8 336 774538 Impregnation of the polypropylene film w ith the fluid, however, is of great importance and prompted a brief study, summarized on table 4. These data show that ENJ-2065 swells polypropylene capacitor-grade films satisfactorily, as measured by the film weight gain after 2 days at 60 C, so that film impregnation should not be a serious problem. The next generation of capacitors may well be based on metallized polypropylene film . Polychlorinated biphenyls cannot be used fo r this type of capacitor- since they generate hydrogen chloride, which can lead to premature breakdown. In summary, we believe that ENJ-2065 has a bal ance o f properties such that it w ill find a niche in the capacitor flu id field. GENP 005891 337 774539 GENERAL DISCUSSION OF SESSION V CHAIRMAN M UIR: A ll right. I see that we have reached our scheduled departure hour. I think it's only fair to entertain a few questions from the audience and given the diversity, I would request that people raise a question from the floor and then address their questions to the individual they would like an answer from. MR. BEN KINING HAM (Illinois Lung Association, Springfield, Illinois): I do not have any particular gentleman on the panel to address. I just want to refer to the breakdown o f the film , if anyone could elaborate on how that comes about, and if so, is there any research that is being carried on now in development of films that would be any more stable. MR. RICHARD ROLLINS (Jard Corporation, Benning ton, Verm ont): Are you talking about a biological breakdown? MR. KINING HAM : Biological or chemical or both breakdowns. MR. ROLLINS: It is a reduction type atmosphere in the capacitor so it does not see the oxygen that would normally be considered. The basic problem is not one o f the degradation as much as it is an inherent characteristic of not being able to survive voltage levels or stresses in an AC application. MR. KIN IN G H AM : Would it be feasible to develop an alternative program? MR. ROLLINS: The organic type films have been used or have been attempted to be used in AC capacitors. The basic problem is one o f corona exception and corona distinction voltages, and this is inherently low and goes down to initiation of points 250 to 275 volts and the extinction voltage is extremely low. The meaning o f the corona is that the capacitor slowly deteriorates by this ionic device which is the definition o f corona. The interpretations o f corona I am not going to get into today because every capacitor designer has his own opinion, but every capacitor designer is completely aware of what the corona problems can do. So essentially what we are saying is that organic films have the basic problem o f not being able to withstand high AC voltages, especially in the dry system. On an impregnated system, the circumstances are still there, so you are not really changing the circumstances a great deal in all polypropylene film or any organic film when you impregnate it. VOICE; I have a question fo r Dave Wood. We heard a number of things about environmental factors. How about a still lower chlorinated material than 1016 that might be a more desirable material? I believe Monsanto has passed a given developmental material such as 1043, which is a lower chlorinated material. MR. D A V ID WOOD (Monsanto Industrial Chemicals Company, St. Louis, Missouri): We have done considerable work w ith MCS 1043, but at the present time commercialization of such a product must hang in the balance pending further conclu sions being drawn about the true significance in the differences observed between the trichlorinated materials and bichlorinated materials. Aroclor 1016 was itself a reduction in materials from the Aroclor 1042 widely used by the industry. In order to carry through development of the dichlorinated material, I th in k we need some approvals from the comm unity that they recognize a movement in that direction as one that should be taken. So yes, some data are already available. Acceler ation or stopping of that program depends largely, on some of the things that we hope w ill come out of this conference this week. MS. NANCY STROUP (Environmental Defense Founda tion, Washington, D.C.): I apologize fo r the openhandedness o f m y question, but I hope th at the panel members w ill respond as concisely as possible. One o f the speakers mentioned that his concern was that we not jum p from the frying pan into the fire, and A am sure it's the concern o f everyone at this meeting. To that end I would like to know when the four or five compounds that are now being developed to replace PCB's w ill be tested for the health and safety of these compounds, including carcinogenic, immunogenic, and teratogenic tests before your marketing. And whether this informa tion w ill be available fo r independent review. DR. M UIR: Essentially,-as I already outlined in my talk, we developed a date fo r the work and the work is going forward and we recognize the biphenyl prob lem and that replacing the product inevitably is going to have to satisfy the most thorough and rigorous testing. DR. DEAN BRANSON (Dow Chemical. Inc., Midland, Michigan): In the case o f methosilicones additional data w ill be published very shortly and w ill be publicly available. I th in k this is most in the minds of all manufacturers when they consider substitutes GKNP 005892 338 7*74540 fo r the material which is dielectrically one of the best ever developed. This w ill seem to solve the problem when it comes out. DR. E. J. IN C H ALIK (Exxon Chemical Company, Linden, New Jersey): A great deal o f information is already available. You may recall in 1972 a program sponsored by the National Foundation o f Health Sciences and one subject made by Dr. Tapper, what he observed at comparison o f PCB and mercury, it was like an ideology searching for a disease, and that's a quote. The recent study by Dr. Hartung of the University o f Michigan has concluded that no prob lems attributable to polyesters have been noted due to the constant low level exposure o f the general population, and that occupationally, only mild skin irritation has been observed at high exposures. But he did point out that ecological work should be continued. And I might add that Dr. Tapper sug gested the same. To help answer these questions, particularly related to these items, a research grant has been made by the University o f Missouri to the Manufac turing Chemists Association, and they are starting tests. I think we can hope w ithin the next year or so , results w ill be coming from this study obviously available to all which w ill help answer these ques tions. M R . DUNCAN MacARUTHUR (Booze Allen and Hamilton, Inc., New York, New York): Well, some o f the things that you have asked fo r are in progress and when these tilings are available, they w ill also be made available to the general public. MR. .D AV ID C. MORRIS (Weyerhauser Company, Tacoma, Washington): You stated, sir, that a cost of $4.9 m illion would be necessary fo r I guess you would call them secondary market users like my company, to replace our PCB w ith some substitute. Did I understand you correctly, Mr. Mac* Arthur? MR. MacARTHUR: Yes. MR. MOSS: Just fo r my own sake, I just believe in it very strongly, the cost alone is estimated at $2 m illion and we are right in the midst o f investing. And I think somewhere along the line the investing might not take into account the factors that we initia lly have to face. I would guess it's at least 50 times over. CHAIRMAN M UIR: Yes, sir. VOICE: There are three experimental items coming on the market. Will someone label these transformersMR. ROLLINS: Well, I'm not too sure, but there have been requests that major capacitors manufacturers now conform by labeling all capacitors that have greater than I believe 5 pounds o f A roclor--1 may be wrong, but on small capacitors, the basic problem is the label gets hidden because this is placed into another piece of equipment. M R . STE VE N U M U S (Environmental Protection Agency): I have a question fo r Richard Mont gomery regarding the use o f silicone which was approved by Underwriters Lab fo r indoor use. Do you know the reasons w hy it was approved for indoor use and w hy it was not approved fo r outdoor use? And secondly, can somebody give me an idea of the percent of transformers in the United States used fo r outdoor purposes as opposed to indoor purposes? MR. RICHARD H. MONTGOMERY (Dow Corning C o rp o ra tio n , Midland, Michigan): First of all. Underwriters Laboratory does not approve o f any particular material fo r any given use--once you exceed 600 volts in a transformer. Underwriter's Laboratories has no certification. The only certifica tion received from Underwriters' Laboratories is as to the fire hazard of your particular material on a scale which ranges from 0 to 100, w ith the burnab ility o f water as 0, and gasoline as 100. Therefore, Underwriter's Laboratory does not approve silicone material fo r indoor use. In respect to the use o f dielectric fluids in transformers, the electric code fo r outdoor uses does not specify nonflammable material. It does in subsection 450, paragraph 23 approve the use fo r the indoors. These are the only materials approved fo r use. MR. NUMUS: I want to know the percentage as opposed to indoor use. MR. MONTGOMERY: Well, my research seems to indicate 85 to 90 percent of the transformers sold in the United States are currently outdoor applica tions, and the other 10 to 15 percent are indoor applications, fo r safety is of paramount importance. M R.'W OOD: Essentially the figure that he is using is pretty accurate. Very large power transformers are filled w ith mineral oil because, if they're o ut in the field, there is not a substantial hazard, they can be screened out. In the medium voltage range the use o f askarel is something under 15 percent o f the transformers used in th at medium voltage area. MR. CLIFFORD H. TU TTLE (Aerovox Industries. Inc., New Bedford, Massachusetts): I really have tw o questions--another alternative mentioned up there, the capacitor fo r getting the high voltage can consume 20 to 50 m illion pounds a year. How long GENP 005893 339 774541 would it take fluid to be available in that type of quantity; 1 year, 2 years, 3 years, or what? I don't want to pressure you, I just want to determine. The second question is a third of that market is lighting, fluorescence. If you have an application at 100 C, are any of these fluids or alternatives capa ble of operating at that temperature w ith o u t break ing? MR. MONTGOMERY: Let me answer your second question first. The answer is yes. The answer to the first question is we do have the productive capabili ties capable to handle that market. It could be accomplished very quickly. It would probably be faster than the industry takes to evaluate and qualify new material. MR. WOOD: In terms of Monsanto, alternatives could be made available on a production basis in calendar year 1976, in relationship to the stability of these materials at 100 in the H1B and the fluorescent lighting capacitors, these are test sequences which are going on under our test programs. And the results w ill be forthcoming. We are in a period now o f collective work. We are not ready to go tom or row. S 00 340 774542 20 November 1975 Session V I: GENERAL SESSION Christopher M. Tim m * Session Chairman Director, Surveillance and Analysis Division, Environmental Protection Agency--Region V, Chicago, lilt* nois. 341 774543 GENP 005895 774544 rvPTvTP 005896 OPEN DISCUSSION D R . JO H N BUCKLEY (Environmental Protection Agency, Washington, D.C.): I'd like to call to order the evening session which is our General Session. There are some papers to be presented tonight that are technical papers appropriate to other parts of the session but which just did n't f i t in. In the rest of the sessions we've tried to avoid people expressing their opinions. So w ith that, I'd like to turn it over to our Chairman fo r the evening, Chris Timm , who is the Director o f the Surveillance and Analysis Division fo r EPA here in Chicago. MR. CHRISTOPHER TIM M (Environmental Protection Agency, Chicago, Illinois): Thank you, John. I have at the present time 26 registered speakers. There w on't be any discussion during this session. . I'd like to start o ff by introducing the groups that have been most directly impacted by PCB's in the environment, at least as far as theic livelihoods. They are the real reason we have conferences like this. We have a group o f commercial fishermen, commercial as far as both the market and as far as recreational aspects in the charter fishing, who are here from Lake Michigan and some o f the surround ing areas. I w ill lead o ff w ith them. I'll m ix it up after that w ith technical presentations, industrial viewpoints, environmental groups, etc. MS. JEAN HERMES (Spokesperson fo r Commercial Fishing Interests, Green Bay, Wisconsin): I would like you to know that hardships are already being inflicted on families because o f the PCB poisoning o f our waters. We are fourth-generation commercial fishermen out o f Green Bay. We have four children and have had our livelihood taken away because of high levels o f PCB's in the Green Bay waters. On the last part o f July o f this year, the FDA shut down our business when fish tested from our nets measured 54 ppm o f PCB's. Overnight we've lost a business it's taken 15 years to build. As PCB's are almost indestructible, any further discharge, no matter how small, would only add to an already insurmountable problem. The mills dumping PCB's into the waters have gotten rich at everyone's expense but their own. It is time they make a few sacrifices. Industries have been allowed to pollute and poison the waters long enough. Every commercial fisherman in Wisconsin w ill soon face our situation. The commercial fisherman provides the public w ith a food that is 75 percent protein. In these days of food shortages, it is a crime to let this commod ity be destroyed. But the commercial fisherman will not suffer alone. Sportfishing, all water recreation, and tourist towns are threatened. Even our drinking water w ill become, if it is not already, hazardous. Someone must be held responsible fo r stopping PCB discharge into our waters before they are destroyed beyond repair. Thank you. MS. GLORIANNE HERMES (Spokesperson for Com m ercial Fishing Interests, Green Bay, Wiscon sin): We are from another fam ily w ith seven chil dren that fishes carp commercially from the waters o f Green Bay. We have also lost our livelihood, because o f the high levels o f PCB in carp taken from Green Bay waters. Our fish measured up to 57 ppm when tested by the Agriculture Department and we were forced to release the 15,000 pounds o f carp . that were in our holding ponds at that time. The PCB problem so far has been handled back wards. My husband and his brothers were stopped from fishing carp on Green Bay, while nothing has been done to stop the sources o f PCB's. The fisher man who had no part in the PCB pollution has been inflicted w ith great hardships after many years of building his business. The innocent have been made to.pay the price fo r the destruction caused by a few industries that are getting richer everyday and do not want to rein vest a small part o f their profits into the treatment o f their waste. We believed th at the EPA and DNR were keep ing the waters clean and safe, which is supposed to be their job. How has our water been allowed to become so chemically polluted as to make its fish inedible even fo r animal consumption or even for use as a fertilizer? Some people have not been doing their job. For if the industries' discharges were safe, so would the water and fish be safe. The DNR still plans to plant tro u t and salmon into the waters although the levels o f PCB in these fish tested o ut even higher than some o f our carp. Also, they claim that no money is available to com pensate commercial fishermen fo r their losses due to the PCB problem when they still plan on planting tro u t and salmon into the polluted water. It isn't going to help to lower the lim it o f PCB's GENP 005897 343 Preceding page blan1* 774545 from 5 ppm to 2 ppm , as n o th in g has been done to stop the dumping of PCB's even at the 5-ppm level. To lower the lim it o f PCB's in fish from 5 ppm to 2 ppm would destroy the fishing industry all over the United States. The levels of PCB in all other edible products, such as meat, would also have to be lowered and sport fishing would have to be stopped altogether. The fishermen would have to be compensated fo r their losses, which resulted from other parties' ruthlessness and carelessness. Please attack this problem where it started by stopping all PCB discharges into the water immedi ately. Thank you. MR. GENE LAMBRICH (Spokesperson fo r Commercial Fishing Interests, Green Bay, W isco n sin , and representative o f Lambrich Brothers Live Fish Company): We haul fish from the Hermes Brothers and I th in k something that a lot o f people d on 't realize is that carp is a good fish. It's just not a scavenger, it's something that's a necessity. We have tw o fishing resorts in St. Louis, Missouri. It has cost us roughly over 100 thousand dollars since July o f this year and I think that our load was a sample load that the _Federal Food and Drug Adm inistration to ok the samples o ff o f and said they were polluted. Now if these fish were polluted at the time we inquired, in February 1975, they did state that there were PCB's in the water; w hy weren't they periodically checked and sampled, and if there was pollution at that time, w hy wasn't it stopped? We're just one o f a few fish haulers. This goes all over the United States. For the life o f me I can't figure o ut w hy they cannot do something w ith the people putting these pollutions in the waters. Thank you. LEE WEDDIG (National Fisheries Institute, Washington, D.C.): We're a trade association consisting o f 550 companies engaged in the commercial fish and sea food business. This is somewhat o f an old refrain here. In the last several years we've talked about things like DDT in our waters, which had its to ll. A fte r that it was mercury, and today it's PCB. In each of these situa tions, there was a cost to our business, which is a 6 billion dollar industry in the United States. It represents the livelihood o f 140 thousand people throughout the entire country. In each o f these situations, our industry faces three losses. The first is the direct loss o f income, such as has been related to you by the people who were up here a few m in utes ago, as their products become unsaleable. Then we have the loss that is harder to define yet was alluded to today, and that's the destruction of habitat fo r our resource. Many of our resources are failing. We're running out o f fish, there's been speculation that perhaps we're overfishing. But as we learn what these chemicals do to the ability of fish to reproduce, we would have to believe that the real cause of some o f the failures in our resources is because o f the pollution that has been caused by the unchecked dumping o f chemicals into the water. And then finally we have a loss o f consumer confidence. People d on 't understand that In a case o f PCB's, there are certain fish that are taken from the market because they do exceed the Food and Drug Administration tolerances. The consumer doesn't really understand that this affects only a very small portion o f the total and the reaction is--Well, let's n o t use any fish -w h ich is certainly an unjustifiable attitude, but nonetheless, it does exist. It's also very easy fo r one to say the percentage o f loss is small. We are a 6 billion dollar industry; we supply something like 10 billion pounds o f fish a year to the consumer. One can listen to the folks from Green Bay and say, "W ell, perhaps you could lose several hundred thousand pounds o f fish a year and it doesn't really amount to much in the way o f percentage." But yet fo r these folks, it's 100 percent. Those are the losses that our industry has. What we're recommending to this group to do, is to muster its strength, to come up w ith six different points. We have to solve the problem. We cannot just live w ith the DDT's, the mercury, the PCB's, or whatever it w ill be next year. We have to come to a solution. So we're recommending six things. First fo r the immediate. The Government should immediately ban further sale, production, importation, or recycling of PCB's in any form , w ith perhaps an exception fo r use in existing electrical transformers where usage should be strictly con trolled. But after hearing this afternoon's statement about possible substitutes that have been used in other countries, I'm not too sure I even agree to my exception any more. Efforts should be made to achieve an interna tional agreement to the same goals. If legislation Is necessary to achieve such a ban, then we should all get together to get it passed. Number two, we must establish a national system to provide fo r safe disposal o f PCB's already used in electrical equipment. We were shocked to hear o f the hundreds o f m illions o f capacitors that are in use and we can just envision th a t over the GENP 005898 344 774546 next 30 to 50 years these elements are going to be disposed of w ithout any control whatsoever, and eventually they are going to leak into our environ ment. Number three, the Toxic Substances Control Act must be passed. We must avoid future problems o f this type with other chemicals. I admit our indus try has not worked hard enough to get this bill passed. We did support it as it went through the various stages of the Congress, but we did not really get behind it and scream loud enough. I can assure you we w ill do this from this point on. Number four, we believe the present Food and Drug tolerance o f 5 ppm in fish should be retained pending further research on the toxic effects on humans of PCB's. We believe that any reduction in tolerance should be selective, based on the role and the specific effect of the food in the diet. Five, compensation, in all justice, must be made to commercial fishermen whose livelihood is de stroyed by prohibition of sale of the species of fish in which the presence o f PCB exceeds the Food and Drug tolerance. One element of our society must not pay fo r the mistake of the entire society. And sixth. Congress should investigate the Envi ronmental Protection Agency to determine why effluent standards fo r PCB's have not yet been established despite the clear mandate of the Water Quality A ct to do so. If EPA doesn't have the fund ing, we have to get it. If the deadlines were unrea sonable as set by Congress in 1972, then Congress should know they were unreasonable. Nonetheless, our industry would have expected results from this act at this time. Thank you. PCB BODY BURDENS DENY FULL USE OF THE GREAT LAKES FISHERY RESOURCE Carlos M. Fetterolf, Jr.# The 1954 Convention on Great Lakes Fisheries between the United States o f America and Canada led to establishment o f the international Great Lakes Fishery Commission in 1956. The Commission has two major thrusts, control of the sea lamprey and determination o f research and management strategies to provide sustained productivity in the convention area o f any stock of fish which is o f common concern to the parties. The Com mission works cooperatively with the Canadian and U.S. Federal agencies and the provincial and State govern ments o f Ontario and eight Great Lakes States to improve and perpetuate Great Lakes fishery resources. The statement below is not Commission-approved. It is an expression o f my personal opinions as the Com mission's executive secretary. The U.S. Food and Drug Administration guideline of 5 /g/g (ppm) * in edible tissue o f fish has been exceeded in numerous species in lakes Michigan, Huron, Erie, and Ontario, and in their connecting waters. Several important sport and commercial species are included w ith those that exceed the guideline. This situa tion casts a pall over the social and economic aspects o f Great Lakes fisheries. It creates a very real problem fo r com m erical fishermen, processors, and retailers; a *Extcutive Secretary, Great Lakes Fishery Commission, Ann Arbor, Michigan. shadow of doubt in the minds of every consumer and sport fisherman; an added question fo r the fishery man ager; a symbol o f defeat fo r the water pollution control agencies; and a mark fo r every environmental manage ment critic to flaunt as an example o f the failure of the "system ." It denies fu ll use o f the Great Lakes fishery resource. I hope none of you have the feeling that if residues in Great Lakes fish diminish to below 5 jxg/g that all is well. A few years ago commercial mink ranchers fed their animals Great Lakes fish until they noticed a dis turbing phenomenon, reproduction was falling o ff alarm ingly. This led to studies of the effects o f PCB's in ranch mink. Ringer et al. (ref. 1) demonstrated that 2 ig/g PCB's in fish flesh prevented survival of newborn ani mals, and Platonow and Karstad (ref. 2} demonstrated that reproduction was eliminated in mink fed a beef diet containing 0.64 fiq/g A roclor 1254, a PCB compound. If regulatory agencies consider fish as animal feed a use to be protected, application of a modest 0.2 safety factor provides a tissue level o f 0.1 #ig/g PCB in whole fish. There aren't many adult fish in the Great Lakes system that can meet that objective at this tim e. The presence o f PCB's in Great Lakes fish continues to deny full use o f the fishery resource. The Great Lakes Fishery Commission is not a regulatory agency. We must 345 774547 GENP 005899 depend on legislative action to pass the laws and enforce* mem agencies to furnish the muscle which w ill provide an aquatic environment that w ill produce usable fishery products. It appears to me that some fo o t dragging has been going on. How do we get response from a regula tory agency? Dr. Nisbet expressed disappointment that so few people were aware o f his $8 publication and con cluded that to have impact one must release large amounts o f reprints into the environment. I d on 't th ink that's the answer. How about development o f data and publication by the regulatory agency itself? You heard Charlie Walker state that PCB's in fish were added in 1970 to the Na tional Pesticide Residue Monitoring Program partici pated in by EPA. Data showing PCB body burdens as high as 213 pg/g in the Hudson River and 133 pg/g in the Ohio River were available 5 years ago. FD A guide lines o f 5 pg/g were the same then as they are now. How about the regulatory agency funding a study to recommend allowable levels o f contaminants? EPA funded such a study by the National Academy o f Sciences/Engineering in 1971 and the first draft was deliv ered on schedule to EPA's Washington office in Decem ber 1971. The recommendation fo r PCB's in that draft o f Water Quality Criteria 1972 (ref. 3) read similarly to that in the published document: "A quatic life should be protected where the maxi mum concentration o f total PCB in unfiltered water does not exceed 0.002 pg/l at any time or place, and the residues in the general body tissues of any aquatic organism do n ot exceed 0.5 pg/g." The National Academy report concluded that water quality levels alone were insufficient to predict what body burdens could result and therefore combined a body burden recommendation. If the body burden exceeded the recommendation, then obviously the water concentration was too high and should be further re stricted. In the four years since EPA received that recom mendation from the National Academy o f Sciences, sufficient data have been developed so that the recom mendation o f the Water Quality Objectives Subcom mittee to the International Joint Commission made in June 1975 (ref. 4) could read: The concentration o f total polychlorinated bi phenyls in fish tissues (whole fish, calculated on a wet weight basis), should not exceed 0.1 micro grams per gram fo r the protection o f fish consum ing birds and animals. NOTE: The Subcommittee expresses concern that a water concentration objective fo r this ubiqui tous contaminant is unavailable. Based upon poor ly defined bioconcentration factors it may be con cluded that PCB's n water should not exceed 0.001 micrograms per litre (1 ppt). However, this level may not be adequate to provide protection to certain predators, and could presently not be enforced because of insufficiently sensitive quanti fication limits. This was a reduction to 0.1 pg/g body burden in whole fish from the NAS recommendation o f 0.5 pg/g and a reduction in water level concentration from the 0.002 pg/l of the Blue Book to stating that 0.001 pg/l may be inadequate. I am pleased that EPA is currently releasing fo r re view their proposed Quality Criteria fo r Water. Remem ber yesterday Tom Kopp showed us the recommenda tion fo r PCB's, "0.001 pg/l fo r freshwater and marine aquatic life and fo r consumers thereof." Wastes go into systems, different systems have different capacities of response to PCB's. Is a blanket nationwide water level fair to industry, the environment, and the people? Will this water concentration alone do the job? Apparently there is no accompanying body burden recommendation. This is disturbing to me. I d id n 't know EPA was so confident that bioaccumulation from 0.001 pg/l w o n 't be a problem. Remember I to ld you .that 0.64 pg/g Aroclor 1254 in the diet o f ranch m ink eliminated reproduction? A modest safety factor o f 0.2 provided a recommended residue in fish o f 0.1 pg/g used to feed mink. You heard several speakers mention bioconcentra tio n factors greater than 100,000, some as high as 270,000. Two hundred thousand m ultiplied by a water concentration o f 0,001 pg/l yields a body burden of 0.2 pg/g, double the recommended residue if you're in the business o f selling fish to m ink ranchers. I d on 't believe the concentration o f PCB In the waters o f Lake Superior is known accurately enough that i t appears in the refereed literature. It is generally believed to be 0.001 pg/I, the concentration recom mended in EPA's proposed Q uality Criteria fo r Water. An analytical chemist of EPA's National Water Quality Laboratory at Duluth on the shores o f Lake Superior estimates the PCB concentration in Lake Superior water at 0.0004 pg/l, 0.4 parts per trillio n . The to ta l PCB body burden o f whole Lake Superior adult ciscoes is 5 pg/g and greater. Depending on which water concentration one chooses, we have a bioconcentration factor o f at least 500,000 times. I d o n 't believe the proposed EPA water concentration is going to do the jo b necessary so that Great Lakes fishery resources can be fu lly used, Canada shares the Great Lakes w ith us. The November 17, 1975, announcement by its Department o f Health and Welfare, lowering its PCB regulatory level to 2 pg/g riFNP 005900 346 774548 in edible tissue is going to further, restrict the fu ll use of Great Lakes fishery resources. You heard Dr. Munson say this morning that 99 percent of the PCB content in upper Chesapeake Bay water is associated w ith suspended sediment. Obviously it's going to affect analytical results if you measure water concentrations unfiltered settled, or filtered. I was surprised EPA's proposed recommendation fo r PCB did not include a mention o f whether suspended mate rials should be included in the analysis. By the way, are PCB's adsorbed to suspended materials biologically important? If not, perhaps the water should be filtered before analysis. Do regulatory agencies know the an swers to questions so critical to our environment and economic welfare? There are several avenues o f problem solution open to EPA. There are tough choices, and fortunately it is not my responsibility to make a recommendation. A ll I ask is that something be done, and that what is done w ill permit fu ll use o f the Great Lakes fishery resource. REFERENCES 1. R. K. Ringer, R. J. Aulerich,-and M. Zabik, "E ffe ct o f Dietary Polychlorinated Biphenyls on Growth and Reproduction o f M in k," Am er. Chem. Soc. N ational M eeting Preprints o f Papers, Vol. 12 (1972), pp. 149-154. 2. N. S. Platonow and L. H. Karstad, "D ietary Effects - o f Polychlorinated Biphenyls on M in k," Can. J. Comp. M ed., Vol. 37 (1973), pp. 391-400. 3. Water Q uality C riteria 1972, National Academy o f Sciences, National Academy o f Engineering, U.S. E n v iro n m e n ta l P rotection Agency Ecological Research Series, EPA-R3-73-C33, Superintendent of Documents, Washington, D.C., pp. 595. 4. Great Lakes Water Q uality Board, th ird annual re p ort to the International J o in t Commission, 1975, IJC Regional Office, Windsor, Canada. DR. WILBUR P. M CNULTY (Oregon Regional Primate Research Center, Beaverton, Oregon): I w ill sum marize briefly a series o f experiments on the toxic ity of polychlorinated biphenyls (PCB's) in rhesus monkeys. Three preliminary conclusions can be drawn from the results. First, PCB's produce a unique and reproducible constellation of pathologic changes in monkeys over a wide range o f doses. These changes are different from those reported fo r other laboratory animals. F urtherm ore, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) causes exactly the same constellation. Second, rhesus monkeys are lethally poisoned by very low levels of intake o f PCB's in the diet, roughly 100 times less than the levels which cause serious illness in rats. Third, some individual PCB components are quite toxic fo r monkeys and some are not. Contami nating chlorodibenzodioxins or -furans probably cannot account for the to xicity of commercial Aroclor 1242 in monkeys. Figure t shows extensive downgrowth of mu cous glands in to the submucosa o f the stomach o f a monkey which died after 8 months consumption o f regular monkey chow to which Aroclor 1242 was added at 3 ppm. The development o f this gastric lesion was studied by m onthly biopsies in monkeys fed Aroclor 1242 at 3 to 10 ppm, and the results w ill be discussed by my colleague Dr. Bell. An early clinical sign o f PCB poisoning in rhesus monkeys is thickening and reddening o f the eyelids. The Meibomian (sebaceous) glands were completely converted to squamous cysts (figure 2). Sebaceous glands associated w ith hair follicles in the face, end and scalp similarly underwent squamous metaplasia, w ith atrophy o f the gland or, occasion ally, cyst formation (figure 3). The thymus became markedly atrophic (figure 4); the thym ocytic cortex disappeared entirely, and the corpuscles formed small cysts. Exactly the same pattern o f changes was found In monkeys accidentally poisoned w ith what subse q u e n t chromatographic analysis o f the .tissues showed was probably Aroclor 1260, presumably used in construction materials in the pens. And finally, the same pattern followed experimental poisoning w ith TCDD--in only 12 days at an intake of 20 ppb in the diet. The spectrum was the same at exposure o f from 3 to 800 ppm o f Aroclor 1242, though of course 347 774549 GENP 00590] Figure 1a. Normal gastric mucosa of young male rhesus monkey. H&E, 30x. Figure 1b. Gastric mucosa of young male rhesus monkey fed diet containing 3 ppm Aroclor 1242 for 8 months. Extensive mucous epithelial invasion of submucosa. H&E, 30x. Figure 2a. Normal eyelid of young male rhesus monkey. Transverse section, con junctival surface below. H&E, 30x. Figure 2b. Eyelid of young male rhesus monkey fed diet containing 3 ppm Aroclor 1242 for 8 months. Squamous metaplasia and cystic dilation of Meibo mian glands. H&E, 30x. 348 774550 Figure 3a. Normal vibrissae or sinus hairs in lip of young male rhesus monkey. A garland of sebaceous glands encircles the hair follicle at the upper end of the blood sinus. H&E, 30x. Figure 3b. Sinus hair of lip of young male rhesus monkey fed diet containing 3 ppm Aroclor 1242 for 8 months. Garland of sebaceous glands is absent. H&E, 30x. GENP 005903 Figure 4a. Normal thymus of young male rhesus monkey. H&E, 30x. Figure 4b. Thymus of young male rhesus monkey fed diet containing 3 ppm Aro clor 1242 for 8 months. Severe atrophy and cyst formation in corpuscles. H&E, 30x. 349 774551 (limns ;ind 'death came sooner at higher doses. A riiiitary level of 3 ppm corresponds to an intake of 150 pnAfj/day, or about 40 times the level that Dr. Nisbet calculated might be the intake of a fisherman or a nursing baby today. A t least w ith respect to the effects on seba ceous glands, the disease in monkeys resembles that reported in the victims o f Yiisho, an accidental poisoning of Japanese people. I have tested three pure PCB compounds at 10 ppm; this is a reference level which, in the case o f Aroclor 1242, causes barely discernible histologic changes in 30 days, slight clinical illness in 45 days, and outspoken disease in 60 days. A t th is level, 2,4,4'-trichiorobiphenyl and 2,4,5,2',5'-pentachlorobiphenyl, both major compo nents of Aroclor 1242, caused no clinical or histo logical changes in rhesus monkeys experimentally fed fo r 80 days. On the other hand, 3,4,3',4'-tetrachlorobiphenyl, which is not significantly present in Aroclor 1242 killed a monkey and caused the usual pathologic changes in 34 days. This finding invites the speculation that the metabolites o f some PCB's may be the actual toxins. For example, 2.3,7,8-tetrachlorodibenzofuran (TCDF), which is known to be quite toxic fo r laboratory rodents but has yet to be tested in monkeys, could conceivably be formed from the 3,4,3',4'-tetrachloro-biphenyl by hydroxylation and condensation. But this lo t o f tetrachlorobiphenyl has yet to be analyzed fo r possible preexisting contaminants. However, it is not likely that contaminating dioxins or furans can account fo r the to x ic ity of commercial PCB's. Pilot experiments have indicated that TCDD is about 10,000 times as to xic as Aro clor 1242 on a per gram basis. TCDF can be expected to be somewhat less active. Since our analysis o f Aroclor 1242 has shown contamination to be not more than 1 ppm, there is n ot enough dioxin or furan present to account fo r the effects of the Aroclor. ULTRASTRUCTURAL FEATURES OF GASTRIC MUCOSA AND SEBACEOUS GLANDS AFTER INGESTION OF AROCLOR 1242 BY RHESUS'MON KEYS Mary Bell, Ph.D. The effects o f PCB's on the stomach, skin, and liver o f rhesus monkeys have previously been described by Allen and his associates (refs. 1-5) and some o f these effects by McNulty (ref. 6). O f these organs, the liver has been the only one on which any electron microscopic observations have been made. In the liver, PCB adminis tration results in a proliferation o f the smooth endo plasmic reticulum and, in some cases, the accumulation o f fa t droplets w ithin the hepatocyte. Because the cytological features o f these organs are extremely diverse, it is im portant to document the effects o f PCB's o f alt of them. M cNulty (ref. 6) has described a series o f rhesus monkeys that were fed either 3 ,1 0 ,3 0 , or 100 parts per m illion (ppm) Aroclor 1242 until they became m ori bund. The stomach and lip o f each animal were serially bropsied at m onthly intervals beginning 2 weeks after first ingestion o f these compounds. The tissues were 'Assistant Professor of Environmental Health, University of Cincinnati, Department of Environmental Health, Kettering Lab oratory, 3223 Eden Avenue, Cincinnati, Ohio 45267. processed according to routine procedures fo r light and electron microscopic observation. This report describes die effects o f ingestion o f Aroclor 1242 on the cellular components o f the stomach and o f the sebaceous glands associated w ith the large tactile, facial hairs, vibrissas, o f these animals. Figures 1 and 2 demonstrate the changes seen w ith the light microscope in the gastric epithelium o f an animal fed 100 ppm Aroclor 1242. A fte r 2 weeks inges tio n, the stomach was still essentially normal (figure 1). The mucus-secreting surface and the gastric glands th at contain parietal cells (hydrochloric add secretors) and zymogenic cells (enzyme secretors) showed no patho logic changes. A fte r ingestion o f 100 ppm PCB's fo r 2 m onths, however, the mucus-secreting surface had become hyperplastic (figure 2); the parietal and zymo genic cells o f the gastric glands had to ta lly disappeared and had been replaced by mucus-secreting cells. These effects, though demonstrable at varying times after onset o f PCB administration, were identical in all animals at any o f the dose levels used. Figures 3 and 4 show the 350 7 7 4 5 5 2 GENP 005904 Figure 1. A light micrograph of the gastric mucosa of a rhesus monkey fed 100 ppm Aroclor 1242 for 2 weeks. The mucussecreting surface mucosa and the gastric glands containing parietal and zymogenic cells are of essentially normal appearance (x140). Figure 2. An oblique section of gastric mucosa from a rhesus monkey fed 100 ppm Aroclor 1242 for 2 % months. Most of the gastric glands have been replaced by mucus-secret ing cells (x140). effects after 5-Vi months on the stomach o f an animal fed 3 ppm Aroclor 1242. A t this time, most o f the gas tric glands had been replaced by mucus-secreting epithe lium. A t the electron microscope level, the first PCBrelated changes were seen in the parietal cells o f the gastric glands, and some o f these changes were observed at the higher dosage levels shortly after the onset of PCB ingestion. These cells normally have a distinctive cyto logy, which includes intracellular canaliculi through which the hydrochloric acid is secreted, many small cytoplasmic vesicles, Bnd large numbers of mitochondria. A fter PCB ingestion, the intracellular canaliculi became somewhat distended, the cytoplasmic vesicles became less discrete and tended to break down, and small dense bodies, presumably containing hydrolytic enzymes, accumulated {figure 5). In the bases of the gastric glands, mucus-secreting cells were interspersed among zymogenic cells after ingestion of PCB's. Zymogenic cells normally contain extensive concentrations o f granular endoplasmic reticu lum located basally in the cells; this reticulum is respon sible fo r the production o f enzymes. A fter PCB inges tion, however, mucus-secreting cells w ith typically little endoplasmic reticulum began to appear adjacent to the zymogen-secreting cells (figure 6). In some cells still recognizable as zymogenic, the endoplasmic reticulum was dilated and the cells contained large autophagic vacuoles (figure 7). The latter usually occur in cells that are undergoing degradation. Figures 8 and 9 show the changes seen at the light microscope level in the sebaceous glands associated w ith the tactile hairs of the face after PCB ingestion. Nor mally, lipid production by the sebaceous glands begins close to the peripheral portions of the glandular alveoli and continues to the more central portions where the 351 O Va o. o 774553 Figure 3. Gastric mucosa ot a rhesus mon Key fed 3 ppm Aroclor 1242 for 5 7a months. Most of the gastric glands have been replaced by mucus-secreting cells. The effects are similar to those shown in figure 2 (x140). Figure 4. A higher magnification of a portion of figure 3. The gastric glands are almost completely composed of mucus-secreting cells.. Only one gland (at the left center of the field) contains zymogenic cells (x560). lipid is secreted onto the hairs. A fte r ingestion o f A ro clor 1242, lipid synthesis and accumulation became increasingly limited to the central zones o f the alveoli; ultimately, only small buds of cells no longer secreting lipid droplets were found adjacent to the hair follicles in the sites normally occupied by sebaceous glands. These effects were identical in all animals fed PCB's, but they occurred most rapidly at 100 ppm, least rapidly at 3 ppm Aroclor 1242. As observed at the electron microscope level, sebaceous cells normally contain large Golgi zones that are the site o f synthesis of the lipid droplets and many profiles o f agranular endoplasmic reticulum, which are considered to participate actively in the production o f lipid (figure 10). A fter PCB ingestion, these membranes acquired a softened appearance during stages when they w ere s till prominent. Many small electron-opaque bodies, probably indicative o f the presence o f hydrolytic enzymes, also occurred in these cells after PCB ingestion. When no lipid droplets were detectable after PCB inges tion ('v 2' Va months at 100 ppm, ^ 4-% months at 3' ppm), filaments usually associated with epidermal-type cells (from which sebaceous glands are embryologically derived) often increased in abundance in the sebaceous cells, they continued to contain a few profiles of granu lar endoplasmic reticulum, but smooth membranes could no longer be detected (figure 11). Ultimately, the seba ceous cells no longer even resembled the epidermal cell type, and they no longer appeared capable of producing lipid. These studies do not enable us to determine wheth er cells can change their direction o f differentiation under the influence o f PCB's or whether they merely differentiate in the only direction available to them when PCB's are present. They do tell us, however, that cells, depending on their location and function in the body, respond in very different ways to PCB's, 352 774554 ; Figure 5. An electron micrograph of a parietal cell from the stomach of a rhesus monkey fed 30 ppm Aroclor 1242 for 2 weeks. Many small perinuclear cytoplasmic vesicles (v) are disrupted and a portion of an intracellular canaliculus is distended (arrow) (x6300). 353 774555 GEttP OO5 9 0 7 Figure 6. An electron micrograph of a portion of a gastric gland from a rhesus monkey fed 10 ppm Aroclor 1242 for 4 Va months. Mucussecreting cells (M) have become interspersed with zymogenic cells (Z) in this location (x3400). KJ\ 354 774556 GENP 005909 Figure 7. Portions of two zymogenic cells containing large autophagic vacuoles (av) and dilated granular endoplasmic reticulum (er). The animal from which the tissue was biopsied had been fed 3 ppm Aro* clor 1242 for 5 % months (x 13,150). 355 774557 Figure 8. An oblique section through a tactile hair with associated sebaceous glands. Though the glands are small, cell differentiation, evi denced by sebum droplets, is still occurring close to the periphery of the alveoli (arrows). This tissue was taken from an animal fed 3 ppm Aroclor 1242 for 3 % months (x140). Figure 9. A light micrograph of a comparable site as that shown in figure 7 but after 3 ppm Aroclor 1242 for 4 1/a months. No sebum droplets or differentiating cells are visible in the sites (arrows) normally oc cupied by the sebaceous glands (x140). O t-T \0 >O 356 7 745S8 Figure 10. An electron micrograph of cells with essentially normal features in a sebaceous gland associated with a large tactile hair. The animal from which the tissue was biopsied had been fed 30 ppm Aroclor 1242 for 2 months. Although these cells are close to the periphery of an alveolus, they are producing abundant lipid droplets (Id) (x5600). 357 774559 GENP 00591J Figure 11. An electron micrograph of cells from a site similar to that shown in figure 10, but from an animal fed 3 ppm Aroclor 1242 for 4 14 months. The cells contain no lipid droplets, and their cytoplasm appears largely amorphous (x7200). ACKNOWLEDGMENT All o f the specimens and much o f the data fo r this study were collected at the Oregon Regional Primate Research Center. Work was supported in part by Grants AM08445 and RR00163 o f the National Institutes of Health and ES-00159-10 o f the National Institute of Environmental Health Sciences. REFERENCES 1. D. H. Norback and J. R. Allen, "Pathobiological Responses o f Primates to Polychlorinated Biphenyl Compounds," this conference. 2. D. H. Norback and J. R. Allen, "Chlorinated Aro matic Hydrocarbon Induced Modifications of the Hepatic Endoplasmic Reticulum: Concentric Mem brane Arrays," Environ. Health Perspec., Vol. 1 (1972), p.137. 3. L. J. Abrahamson and J. R. Allen, 'T h e Biological Response of Infant Nonhuman Primates to a Poly chlorinated Biphenyl," Environ. Health Perzpec., Vol. 4 (1973), p. 81. 4. J. R. Allen and D. H. Norback, "Polychlorinated Biphenyl and Triphenyl Induced Gastric Mucosal Hyperplasia in Primates," Science, V ol. 179 (1973), p. 498. 5. J. R. Allen, L. A. Carstens, and D. A. Barsotti, "Residual Effects of Short-Term, Low-Level Expo sure o f Nonhuman Primates to Polychlorinated Bi p h e n y ls ," Toxicol. A pp. Pharm acol., Vol. 30 (1974), p. 440. 6. W. P. M cNulty, Jr., this volume. 358 774560 16500 ENVIRTHOTENHMVEIEEONWCTCOAUFNRDTRHETENHCPEEANPOEEFERDPICNFBDO'SURSINRTERTGYHUEOLNATION Paul E. Trout* My name is Paul E. Trout. I am Director of Environ mental Control for Container Corporation of America and am presenting the follow ing comments on behalf o f my company and the American Paper Institute. The American Paper Institute is a national organiza tion composed of manufacturers of pulp paper, and paperboard. Members utilize both virgin and recycled fiber in the manufacture o f paper products. In 1973, the American paper industry and its wastepaper suppliers recycled nearly 15 m illion tons o f wastepaper (ref. 1) an all time high. In the same year, approximately 41 per cent o f the fiber used by Container Corporation of America's 13 paperboard mills was derived from wastepaper. This recycling of wastepaper unw ittingly plunged my company and similar recyclers into the morass o f the PCB problem in late 1970. I. THE PAPER INDUSTRY DOES NOT USE OR IN TRODUCE PCB'S INTO THE ENVIRONMENT B U T R A T H E R RECIRCULATES PCB'S A L READY PRESENT, WHICH ARE UNAVOIDABLY INCLUDED IN ITS M ANUFACTURING INPUT PCB's are not a part of the paper manufacturing process. Consequently the paper industry does not add new PCB's to the environment. PCB's are, however, unavoidably included in certain inputs into the paper manufacturing process. In particular, the water supply used in paper making contains PCB's,.from other unre lated sources. The paper manufacturing process is n o t' designed to remove PCB's and consequently effluents do contain low levels o f this chemical which have entered the mills in the intake waters. The other PCB input to the paper manufacturing process is the raw material used by recycling mills as a fiber source. Until early 1971, NCR paper (carbonless copy paper) used A ro d o r 1242 enclosed in microcapsules coated on the paper. Thus business forms made with carbonless copy paper have'been a component of office waste paper, a portion of which is recycled in the papermaking process. Inevitably the PCB's present in the office waste have been introduced' "into the paper recycling process. Again, no new PCB's are added to jh e environment D irector of Environmental Control, Container Corporation of America, Carol Stream, Illinois. by paper mills but, rather, existing PCB's are simply recirculated. If the paper mills could not recylce the office waste containing PCB-bearing paper, the paper would just as surely enter the environment either through leaching in landfills or volatilization in incinera tors which are unable to destroy the PCB's. In either of those events, municipal solid waste systems would have a very substantial new burden added to their normal operating loads and the important national recycling would be significantly injured. Moreover, the PCB present in the old NCR paper still occasionally finding its way into the waste stream is Arocior 1242, the one not accumulating in the environment. It is this PCB that is found both in the paper products and in the effluent o f paper mills. Since 1971, when the use of PCB in the manufac ture o f carbonless carbon paper was halted, PCB levels in recycled-fiber paperboard used fo r food packaging have continued to decline; The industry m onitoring program showed that, in the third quarter o f 1975, 99.63`percent o f such paperboard had a PCB content less than 10 ppm and 91.3 percent had a PCB content less than 2.5 ppm. These* results have been achieved through the most careful selection o f the wastepaper used in the recycling process w ith rejection o f all types of wastepaper sus pected to contain PCB's. II. THE PCB RECIRCULATED BY THE PAPER INDUSTRY, AROCLOR 1242, IS NOT FOUND TO ACCUMULATE IN AN IM ALS, MAN, OR IN THE ENVIRONMENT The PCB occasionally detected in paper products and in the effluent o f paper manufacturing plants is Arocior 1242. For the years 1960 through 1971, Arocior 1242 represented from 48.15 to 68.9 percent o f the total domestic PCB production, reaching this maxi mum percentage in 1967 and 1968 and decreasing there after. Accordingly, it would necessarily be the PCB most widespread in the environment if all PCB's were all equally degradeable. In fact, however, A ro do r 1242 is neither found in the tissues o f man or animal nor in the aquatic environment generally. This indicates that the lower chlorinated PCB's such as A ro do r 1242 are either metabolized, decomposed in aqueous environments, or degraded by photolysis. If accumulation o f PCB in aqua tic environments, and thereby in the food chain and GENP 005913 359 774561 man, is perceived to be a potential threat to^human health, it is a threat unrelated to Aroclor 1242. Any PCB regulation based on environmental needs must accomo date this fact. III. THE CURRENT LEVELS OF DIETARY INTAKE IS M ANY ORDERS OF MAGNITUDE LOWER THAN THE ALLOWABLE D AILY INTAKE AS FOUND BY THE FOOD AND DRUG ADM INI STRATION Evaluation o f the need fo r regulatory controls of the source and distribution o f PCB's must begin w ith the threat PCB's pose to the health o f man or other parts of the living environment. In the case o f PCB's, the possible threat to human health is through the food supply. Accordingly, that evaluation should start w ith the levels o f dietary intake o f PCB's w ith reference to the levels posing a threat to man. As a distinguished committee of the National Academy of Sciences, National Research Council stated, "F o r every chemical there is some fin ite level sometimes called the 'safe' level, at or below which it can be present in food w itho ut prejudicing safety (ref. 2 )." Conversely, as three other NAS committees have recently noted, "There is no substance which under certain circum stances, could not be dangerous and unsafe (ref. 3 )." The possible need fo r regulatory controls o f PCB's there fore must be assessed in terms not of the conceivable danger posed by some amount o f a substance but rather in terms o f the available margin o f safety between con ceivably harmful dosages and actual consumption. According to the Food and Drug Adm inistration's Director of the Office o f Science, Dr. Albert C. Kolbye, Jr., the allowable daily intake o f PCB's in the adult human diet is 200 pg/g/day. This conclusion is based upon Dr. Kolbye's analysis of available animal to xicity studies including the recent investigations of Dr. Kim brough as well as upon anajysis o f human to xicity data arising from the "Y ush o" incident in Japan involving massive intoxication by PCB's. The Food and Drug Administration's "Total Diet Studies" demonstrate that PCB average dietary intake, levels have never been remotely near this 200 pg/adtilt/day figure. On March 18, 1972, F D A stated in a Federal Register notice that its total diet studies indi cated an average daily intake o f 7/pg/day/adult or 4.7 ppb in the total diet. This is 3.5 percent o f the amount Dr. Kolbye concluded was plainly safe. Those data re flected the period of August 1969 through March 1972 when PCB exposure must have been at its peak since the steps taken by Monsanto Company in early 1971 to confine the sate o f PCB's to closed systems had not yet had tim e to be reflected in the data base. Fifteen months later, on July 6, 1973, FDA an nounced that die quantitatively measurable residue of PCB's were equivalent to an average dietary intake of 4.2 pg/day/adult. This corresponds to a dietary intake of 2.8 ppb or about 2 percent of the level Dr. Kolbye identified as safe. According to FDA's to^al diet studies fo r fiscal year 1973, the dietary intake of PCB's was 1 pg/day/adult or .67 ppb. This is less than % percent of the sa'e amount calculated by Dr. Kolbye. According to these studies fo r the period o f October 1972 to January 1975, the average dietary intake was .178 /tg/day/adult or .118 ppb (118 ppt), or below 1/10 of 1 percent o f Kolbye's safe level. An examination o f the total dietary intake as shown by FDA's total diet studies from January 1, 1974, through June 1S175 shows PCB intake has been zero: th at is, not a single quantifiable residue o f PCB has been detected in the total diet study which would allow any quantitative estimate whatsoever.* In short, dietary intake o f PCB has been declining rapidly since approximately the time Monsanto imple mented its voluntary controls on the distribution of PCB's to its customers. Even during the maximum expo sure period, the average dietary intake was nowhere near what the Food and Drug Administration states to be an allowable daily intake. A t the present tim e, there is an even vaster gulf--many orders o f magnitude-between the aliowable daily intake and the amount o f PCB posing any conceivable hazard to man. IV. ANY ADDITIONAL CONTROLS MUST ACHIEVE M A X IM U M ENVIRONMENTAL COST-EFFEC TIVENESS The paper recycling industry has been a participant in the PCB drama through circumstance, n o t by choice, and our industry is not alone in this. We thus appreciate the need fo r procedures to prevent similar happenings in the future as well as to correct remaining PCB problems. Our industry approves the principle o f restricting the use of hazardous substances. We do not, however, support far-reaching regulation o f the nature o f Senate Bill S776. Such legislation simply would amount to the "Biological and Analytical Chemist's Relief A ct o f 1975" and would, in addition, open a new Pandora's box of legal mischief. We believe duplication o f existing legislation should be avoided and that deficiencies in existing legislation be corrected by specific amendment in order to maximize environmental benefit at minimum cost to the public. I t Is also significant that for FY 1975 tha total diet studies did no t detect a single trace of Aroclor 1242, the PCB associated w ith the recycled paper manufacturing process. 360 774S62 We particularly urge States now considering new regulations to combat the PCB problem to develop ra tional rather than simplistic solutions. Destruction of the wastepaper recycling industry w ill benefit neither the public health nor the public purse. We commend the Environmental Protection Agency for establishing a task group to investigate PCB imports. We urge that they continue to track down specific uses of these materials in the United States and publish this information so that further unknowing use o f PCB's can be avoided. We urge EPA to publicize abroad the self-regulatory action taken by Monsanto Co. to minimize further PCB contamination of the environment. Hopefully, such enlightened action may spread worldwide. And, finally, we urge the Environmental Protection Agency to implement a program whereby PCB-containing wastepapers issuing from Federal agencies are dis posed of by incineration at a temperature sufficient to destroy PCB. If Aroclor 1242 is an environmental hazard, this procedure would prevent the reservoir of this material now residing in the files o f the world's greatest recordkeeper from contaminating the environ ment. A ll of these control actions can be initiated immedi ately, w ithout need fo r additional legislation and w ith immediate positive results. To conclude, I would like to summarize these points: I. The paper industry does n ot use or introduce PCB's into the environment but rather recirculates PCB's already present which are unavoidably included in its manufacturing input. II. The PCB recirculated by the paper industry, Aroclor 1242, is not found to accumulate in animals, man, or in the environment. III. The current levels o f dietary intake is many orders o f magnitude lower than the allowable daily intake as found by the Food and Drug Administration. IV . Any additional controls must achieve maximum environmental cost-effectiveness. REFERENCES 1. F. L. Smith, Jr., "Wastepaper Recycling: Review of Recent Market Demand and Supply," Pulp and Paper, September 1975, p. 148. 2. "Guidelines fo r Estimating Toxicologically Insignifi cant Levels of Chemicals in Food," Food Protection Committee, Food and N utrition Board, National Academy o f Sciences, National Research Council, Washington, D.C., p. 1. 3. "Principles fo r Evaluating Chemicals in the Environ m ent," a jo in t report o f three NAS committees: Committee fo r the Working Conference on Princi ples o f Protocols fo r Evaluating Chemicals in the Environment; Environmental Study Board, NAS, National 'Academy o f Engineering; and Committee on Toxicology, National Research Council, Washing ton, D.C., p. 83. MR. BERNARD A. KERNS (Westinghouse Electric C o rp o ra tio n , Pittsburgh, Pennsylvania): I very much appreciate the opportunity to make these comments at this conference. It is the hope of Westinghouse th at this conference w ill bring to gether all o f the scientific and technical information that -is available to identify the positive aspects of the current mixtures that are being used by the elec trical industry. The Westinghouse Transformer Divisions and the Westinghouse Distribution Apparatus Division are users o f a substantial quantity o f polychlori nated biphenyls in the production o f transformers and capacitors. A t this point I should point out that Westinghouse uses a term inerteen fo r the mixtures o f PCB's it uses as a dielectric, and th at the generic term used in die electrical industry isaskarel. These terms are really not interchangeable w ith the term PCB's. While there are 209 isomers o f PCB's; the electrical industry uses only several mixtures of PCB isomers as dielectric. O f these, Westinghouse utilizes primarily only tw o askarels, Aroclor 1242 fo r transformers and Aroclor 1016 fo r capacitors as inerteen. Since the early 1970's, when scientific studies indicated that PCB mixtures presented some hazard in the environ ment, Westinghouse has expended considerable money and e ffo rt to reduce the amount that might escape into the environment. Measures th at have been employed are: The sealing of drains in manufacturing areas where iner teen is used; utilizing specially designed incineration facilities fo r the destruction of scrap inerteen and special scientific landfills fo r the disposal of inerteen-contamnated materials; instructing operation personnel anr. our customers regarding the need for 774563 GENP 005915 care and that special waste disposal is required; and reducing the number of pounds of inerteen per K V A in transformers and capacitors. Most o f these measures were implemented prior to the enactment of the Federal Water Pollution Control Act amend ments of 1972. It is significant to note that France has just enacted regulations on the use o f PCB's which require actions that have been taken by West inghouse since 1972. Westinghouse recognized that these measures could not prevent the total elimination o f inerteen escaping into the environment. Therefore, concur rent w ith the above measures, we have conducted extensive evaluation programs designed to utijize those mixtures of PCB's having low persistence and high biodegradibility in the environment. By February 1968, Westinghouse determined that a- mixture o f PCB's sold by Monsanto as Aro* clor 1242 would be satisfactory as inerteen fo r transformers. A ro d o r 1242 contains about 91 per cent o f the lower isomers, containing fo u r chlorines or less that more readily biodegrade in the environ ment. This material has been used by Westinghouse since that time, w ith the understanding that over 90 percent of the small amount that did enter into the environment would have relatively low persistence. Monsanto subsequently developed a new material from A ro d o r 1242 which contains more of the lower chlorinated isomers and marketed this mate rial as A ro do r 1016. By the first quarter of 1972, this material was introduced by Westinghouse into the manufacture of all capacitors. This material contains 99 percent of the lower biodegradible isomers, four chlorines or less, so that less than 1 percent o f this material that might escape into the environment might be more resistant to biodegradation. The industry, Monsanto, our own research, scientific literature, and most o f the papers presented at this conference have indicated that the lower chlorinated mixtures of polychlori nated biphenyls are more biodegradible and do not present the same long-term to xic environmental problems as those which contain the higher chlori nated isomers. It is interesting to note, in this regard, that EPA researchers have found a significant difference be tween the effects o f A ro d o r 1242 and A ro d o r 1016 on rats, confirming our position. But they published this information in Great Britain and did not make the information available during the toxic hearings o f 1974. We believe the U.S. scientific comm unity should determine the benefits and the environ mental impact o f the tw o or three askarels used by the electrical industry on a scientific basis and not let the desire to see a toxic substance bill passed stampede us into a selection o f an alternate flu id which is more potentially dangerous to man and to his environment. Thank you. 916^00 dN.tJ STATEMENT RELATING TO POLYCHLORINATED BIPHENYLS ON BEHALF OF THE WISCONSIN PAPER COUNCIL James S. Haney* The Paper and Paper Recycling Industries in Wisconsin I appear today on behalf of the Wisconsin Paper Council, the trade association fo r the pulp and paper industry w ithin Wisconsin. I am chairman o f the Wiscon sin Paper Council's Government Relations Committee. There are 49 pulp and paper mills in Wisconsin employing 46,000 people who produce in excess o f 5 m illion tons o f pulp and paper products annually. Wisconsin manufactures more than 11 percent of the 'P u b lic Affairs Director, Bergstrom Paper Company, Neenah, Wisconsin. total production o f pulp and paper products in the United States and is the number one paper-producing State in the country. Not only do we lead the nation in papermaking, but we are also the number one State in paper recycling. A t least 19 Wisconsin paper firms recycle fibers to some extent and several firms make a specialty o f it. A fifth of Wisconsin's annual paper production, about 780,000 tons, is made from recycled, post-consumer wastes. Some Wisconsin papermakers, like my own company, hve been producing recycled paper and paperboard since the turn o f the century. 362 7 7 4 5 6 4 What Has The Wisconsin Paper Industry Done F or The E nvironm ent? Manufacturing any product is not a clean, tidy process. Generally, it is noisy, usually it is dirty, and often it involves work with large machinery. It normally takes skilled labor, of which Wisconsin is fortunate to have an ample and sufficient supply. The point being, however, that in the manufacturing process certain natural resources are consumed and related byproducts are discharged or emitted as a part o f the process itself. Recognizing this impact on the environment upon which our industry depends, the Wisconsin paper indus try had expended approximately $126 m illion on water pollution abatement equipment prior to 1975. It is esti mated by the industry that w ithin the next 5 years an additional $153 m illion, at a minimum, w ill be expended fo r a total investment of approximately $280 m illion for water pollution abatement equipment alone, not one cent of which is attributable to new production equip ment. As to air pollution, prior to 1975, the Wisconsin paper industry had invested approximately $34 m illion in air pollution abatement equipment and anticipates that between 1975 and 1980 it w ill invest minimally an additional sum in excess o f $60 m illion. In rough figures, therefore, the paper industry in Wisconsin alone w ill have spent approximately $375 m illion by 1980 fo r air and water pollution abatement equipment--approxi mately $8,200 per employee-on what is very environ mentally necessary, but absolutely unproductive, equip ment. The Issue o f Polychlorinated Biphenyls In light of previous comments at this conference, I th ink I need spendr little time in identifying polychlo rinated biphenyls (PCB's) or their historical uses. One of the many varied uses of PCB's prior to 1971 had been in carbonless copy paper, which has accumulated in the* files o f many businesses and numerous governmental agencies. From time to time, some of this paper is dis carded and becomes part o f the solid waste chain. A t this time I wish to make one point very clear. Wastepaper collectors and recyclers do n o t manufacture PCB's nor do they use them in th eir m anufacturing process. To the extent that recyclable wastepaper does contain traces of PCB's, this contaminant is introduced into the industrial system and becomes part of the in dustrial waste discharge o f recycling facilities. The only other known PCB's on a paper mill's premises might be PCB-containing transformers or capacitors. The Wisconsin Paper Council is vitally concerned that overly restrictive regulations of PCB's, both in fin ished paper or paperboard products or in effluent dis charges, could destroy the Nation's recycling efforts. We strongly urge that those who are drafting regulations concerning PCB's more fu lly analyze the impact of such regulations on recycling industries. ' You must understand, fo r example, that a very small portion of the total amount of PCB-'s manufac tured domestically by Monsanto Company were used for carbonless paper, which is the chief assumed source by which wastepaper contains the PCB contaminant. Aroclor 1242, by weight containing relatively lower amounts o f chlorine than other domestically produced and'sold PCB's, was used in the production of carbonless paper. Between 1958 and 1971, at which time the use o f PCB's in the manufacture o f carbonless paper was ceased, approximately 48 percent of Monsanto's PCB production was of Aroclor 1242. However, o f its entire domestically sold production during those years, only about 22 percent was used fo r "plasticizer applications." Plasticizer applications include not only use fo r carbon less paper, but also fo r adhesives, textile and other sur face coatings, inks, investment casting wax, and sealants. Therefore, we know that something considerably less than 10 percent o f Monsanto's total PCB production between 1958 and 1971 was used in the manufacture of carbonless paper, all of it being of the Aroclor 1242 variety. Aroclor 1242 has significantly different structural constituent characteristics, whereby its stability and persistence are less and its degradeability appears to be significantly higher than its comparatively more highly chlorinated Aroclor relatives. A t least 1,500 reports in scientific literature have been w ritten relating to PCB's and, whereas most o f these deal w ith only the question o f reporting the presence o f PCB's in the environment, invariably these reports describe and relate to Aroclor 1254 and 1260, the more highly chlorinated PCB's produced by Monsanto. In fact, a Monsanto spokesman has indicated that it was his opinion that " if we could just turn the clock back" and have produced only Aroclors 1221, 1232, 1242, and no others, we probably w ouldn't be holding hearings today. We are told that the principal Aroclors being found in Wisconsin fish are Aroclor 1254 (Mississippi River) and Aroclor 1248 (lower Green Bay). Predominantly it is Aroclor 1254 that is found in the environment. In terms of degrada tion and degradeability, there is a definite difference between Aroclors 1242 and 1254. On the issue o f bioconcentration, the EPA has stated that Aroclor 1242 bioaccumulates on the order of 8 times less than the more highly chlorinated Aroclors. On the issue o f removal from effluent, the EPA has predicted that we can .look forward to significant reduc tions in discharge concentrations as the program and GENP 005917 363 774 56 5 projected treatment systems required by the NPOES program become effectively operational. A ll of the above can be restated concisely as fo l lows. Only a small portion of total PCB's domestically produced were utilized for purposes of manufacturing carbonless paper and, as to those particular Aroclors, they are relatively less stable and persistent, appear to be more degradeable, and are less susceptible to accumula tion in fish than are their related, more highly chlori nated Aroclors. As a result, the im pact o f the waste paper recycling industry on the issue o f PCB's m ust be p u t in to a more proper and positive perspective. Concluding Remarks I think the time has come fo r us to recognize that we all know less than we would like to know about PCB's. Because o f th eir persistence and because of uncertainties about their impact, the new production o f this substance has all but been eliminated and is now used for only very specific purposes. A n inventory m ust be made o f where PCB's are com ing from ; the type o f A roclors th a t are being discharged, em itted, and landfille d ; the best methods o f decreasing these discharges, emissions, and la n d fillin g ; and to p u t some proper per spective on dte existence o f this substance in o ur envi ronm ent. We know of no current practical method by which to separate out o f the wastepaper mass that por tion of paper that contains PC 8's-particularly since PCB's have been recycled into paper products other than carbonless paper. PCB's cannot be legislated o u t o f the recycled paper system. The whole concept o f recycling wastepaper is at stake in considering the promulgatiqn of regulations particularly at a tim e when, as a national industry, the pulp and paper industry is expanding its papermaking capacity at a faster rate than i t is expand ing its ability to produce pulp. It simply must be a na-` tional p riority to encourage recycling. The Wisconsin Paper Council recognizes that there is a potential problem w ith the introduction of PCB's into the environment. We strongly support strict controls on the manufacture, distribution, and use o f PCB's and we favor a national ban on the importation o f PCB's. But' the paper industry has not created this problem, it does not use PCB's in its processes, and it finds itself caught in the middle of this controversy merely because of its recycling efforts, which would be halted by the adoption of overly restrictive regulations, For example, proposed regulations in Wisconsin place an incredible burden on our industry, requiring removal o f PCB's to levels 1,000 times smaller than the Food & Drug Adm inistration's temporary tolerances as applied to food. Our industry has a history o f cooperation w ith gov ernment agencies to reduce PCB levels in our finished products. We w ilt continue to cooperate w ith the Food & Drug Administration, w ith the EPA, and w ith our own DNR to fin d solutions to the PCB problem in effluent. We concurred w ith Mr. Schweitzer when he testified in Wisconsin that ''it is important to clarify the portion of the PCB contamination problem which can be attributed to specific discharges and the practical fe a sib ility o f reducing die discharges." We hope that his Department recognizes th at there is a difference in terms o f environ mental acceptance o f various forms o f PCB's and that this should be taken into account when dealing w ith any proposed regulations. But we continue to appeal to you fo r reason. Let us admit together that we do not know enough, at least at this point, to promulgate reasonable regulations and that ill-conceived rules could mean economic cata strophe fo r a significant portion o f Wisconsin's paper industry. The commitment o f this industry is to Wiscon sin and to its environmentally pure future. It has invest ed and w ill invest over $300 m illion prior to 1980 to accomplish that goal. We only hope th at realistic, reason able, feasible, and responsible regulations w ill be pro posed by the EPA which w ill bolster its reputation as a defender o f the environment while at the same time not place it in a position o f ridicule because it has suggested regulations so badly researched that they are either unenforceable or that they destroy recycling--one o f the this country's most environmentally considerate indus tries. 8t6SW i CHAIRMAN TIM M: Now fo r another change o f pace, y David Kotelchuck, followed by Lee Botts, j DR. D A V ID KOTELCHUCK (United Electrical Workers Union, New York, New York): A t present, several States are proposing new PCB standards while EPA is actively considering such a standard. New stand- ards fo r PCB's are clearly in process. I would like to discuss a matter that is o f great importance to elec trical workers, the people firs t affected by PCB's in the environment and the people whose lives are most immediately affected by the changes In the standards, both in terms o f the health and jobs. 364 774566 We want to point out that attempts to regulate PCB's use State by State leaves workers in existing plants subject to job loss through plants moving. United Electrical Workers represents over 1,000 workers at GE Capacitor plants at Fort Edwards and Hudson Falls, New York. Presently a New York State law is being considered phasing out PCB by next year. If the New York State laws pass in the absence of a Federal standard, then workers in New York and other States w ith stringent standards face possible plant moves and subsequent job loss. Local GE plant officials have already publicly threatened to move if proposed New York State standards pass. We recognize the need fo r change in PCB standards to protect the health o f workers and the general public. BUt we insist that this must be done by promulgating a Federal standard so as not to subject workers to this threat and not prejudice their job security relative to workers in other States.. It is incumbent upon EPA to set a new Federal, standard. We want to point out that this is also the most effective way to regulate PCB in the environ* ment. One further point. We commend scientists who have examined health and environmental hazards of PCB. But a report of the results in medical and scientific literature does not end the scientist's responsiblility in our opinion. We believe that scientists also have a responsibility to inform elec trical workers, those most directly affected by any PCB health hazard, o f their results. In the past several years neither workers at the Fort Edward and Hudson Falls plants nor their national Union were informed by scientists or government officials o f their findings or proposals. One cannot claim to be helping mankind by researching PCB hazards and regulating its use while ignoring precisely those individuals most intimately affected by PCB. We request that as new scientific studies are conducted the authors please inform us o f their results. Our address: Research Department, United Electrical Workers, 11 East 51st Street, New York, New York 10022. Thank you. BETTER LATE THAN NEVER: THE CASE FOR TREATING PCB'S AS TO X IC SUBSTANCES NOW Lee Botts* My name is Lee Botts, and I represent the Lake Michigan Federation, a .coalition of citizen groups and in d iv id u a ls w ith members in Wisconsin, Illinois, Michigan, and Indiana. Our affilitates include organiza tions o f conservationists, of sports fishermen, o f orga nized labor, of school children, and of people who could be classified under many other labels but share. a common concern fo r protection of Lake Michigan from manmade pollution. Today T am here to express `die dismay of our organization over the failure of the Gov ernment o f the United States to protect the lake and those o f us who depend on it for drinking water, fo r food, and fo r the quality o f our lives in the future against contamination by polychlorinated biphenyls (PCB's). The fact that such contimaination exists is not news. Attention was called to PCB's as a potential dan ger in a Lake Michigan Enforcement Conference in 1971. We worked fo r and celebrated the passage o f the Executiva Director, Lake Michigan Federation, Chicago, . ' IH no ii. Water Pollution Control Act amendments in 1972. We have asked for and waited fo r regulatory action on toxic substances that would include PCB's as provided fo r under Section 307. In the past year we have become increasingly alarmed over the failure o f EPA to make use o f its powers under Section 504. Under this section, the administrator may bring suit on behalf of the United States to stop pollution that threatens either the public health or the means o f liveli hood o f people. PCB's d o to th , and yet what has EPA done? EPA ACTIONS TO DATE Since 1972, EPA officials have been assuring them selves, If n ot the rest o f us, that, In the words o f John Buckley, chairman o f this conference, 'T h e PCB prob lem is fairly well in hand." This statement was attributed to him in a Science magazine discussion of PCB's In October, 1972 (page 388, Vol. 178). Just how EPA reached this conclusion is a mystery, since it was not 365 774567 GENP 005919 confirmed by the monitoring efforts being made by agencies here in Region V, including the National Water Quality Laboratory in Duluth and the Great Lakes Fishery Laboratory in Ann Arbor. When confronted with the rising levels of PCB's found by monitoring in the Great Lakes, Washington EPA officials dismissed the problem as a regional one. Now this is a fairly large region, and it might have seemed reasonable to investigate whether PCB's were present in other waterways when their existence in the largest fresh water system in the world was so wide* spread. But evidently the thought was that if you do not look fo r a problem, you w ill not have to deal w ith it. Unfortunately, the problem was not only present else where; research confirmed that it was growing worse. NATURE OF THE PCB PROBLEMS In various research efforts, the nature of the prob lem wa: becoming clear. First, there is the fact that PCB's have high concentration factors, considerably higher than those of the chlorinated hydrocarbon pesti cides. Evidence suggests that PCB's may not be as solu ble in water, but there is no doubt now that biomagnifi cation of PCB's in the food chain is very great. Second, a number o f the 190 different PCB com pounds degrade very slowly. The U.S. Department of Agriculture found in experiments reported in a 1972 conference that the isomers in the intermediate range of chlorine content were more to xic to chickens than those w ith either very small or very h ttji chlorine content. Third, it was learned that, like DDT and other pesti cides, PC8*s are stored in fa tty tissues o f animals and man, ready to be released w ith metabolism o f the t i t . One 1974 report on this phenomenon in the Bulletin of Environmental Control and Technology found that normal persons seem to have small blood level concen trations of both DDT and PCB's even if they have higher levels in stored fat. But nine persons w ith cancer were found to have extremely high levels o f both the degraded form o f DDT and PCB's in their blood, suggest ing that the to xic chemicals had been released into the bloodstream during an illness that causes weight loss* through fat metabolism. The authors of this report speculate that this mechanism may offer a much more serious long-term threat to health than was previously realized, since it would affect people already sick, or growing old, or even those trying to improve their health by dieting to lose weight. The point is that fo r several years many investi gators have been trying to find out not only whether PCB's are toxic but how they cause trouble. That is. many investigators outside EPA were studying the prob lem. . WHAT EPA HAS NOT DONE In this connection, let us consider what EPA has not done that might have reasonably been expected of the agency that has the charge of protecting the environ ment and public health in general but has the power to regulate specific toxic substances. The major action to determine sources o f PCB's was to request information from industries that might have occasion to discharge wastes containing PCB's into waterways, that is, to be point sources o f PCB's. Since Section 308 applies only to owners and operators o f such sources, this inquiry was not adequate to disclose all the industrial users of PCB's nor means o f distribu tion from manufacturers through middlemen to actual users. Strictly speaking, an industry that did n ot dis charge PCB's directiy would not have to provide infor mation under Section 308 letters about whether it made and sold products containing the chemicals that might ultim ately reach the environment by other means. Conceivably, EPA might have been trying to find out fo r itself just how the PCB's were being scattered so widely. But EPA did not, fo r example, investigate whether PCB's are finding their way into rivers and lakes from sanitary landfills. Nor did it obtain information about possible atmospheric transfer, even though the fact that other substances are carried into bodies of water tike Lake Michigan by rainfall is stimulating atten tion to this mechanism. Having failed to take advantage o f PL 92-500, it might have been supposed that EPA would turn to other means o f regulation. Again, not so. PCB's are not regu lated under the Safe Drinking Water Act, either. CONCLUSION I spoke in the beginning of the failure o f the Federal Government to deal adequately w ith the PCB problem, but in truth some agencies have already taken some initiative. The Food, and Drug Adm inistration is amend ing its food packaging regulations to prevent contamina tion by plastic wrappings. The Department o f Defense and the General Service Adm inistration have indicated willingness to restrict purchase and use o f items contain ing or using PCB's. Some States have acted, at least to protect the public even though such actions can do little to prevent continuing environmental contamination. Wisconsin and Michigan have issued warnings to the public about eating GENP 005920 366 774568 fish caught in Lake Michigan more than once a week. This warning, of course, is cold com fort indeed to the fishermen, whether fo r sport or fo r a living. Present at this meeting are representatives of both groups who will speak to their own interests in this matter. In calling fo r decisive regulatory action by the Envi* ronmental Protection Agency now, I would like to submit to you several petitions signed by individual members of one o f the member organizations of the Lake Michigan Federation, the National Council of Jewish Women. This is tangible evidence of their con cern, but I can assert w ith confidence that it is shared not only by o th e r. members o f the Lake Michigan Federation but almost everyone who understands the nature of this problem. EPA must understand that its leadership is needed to deal w ith this national problem now. A FAILURE OF GOVERNMENT Richard R. Knabel* Representing: The Hudson River Fisherman's Association The Hudson River Sloop Restoration The Federated Conservationists o f Westchester County The Hudson River Fisherman's Association, the Sloop Restoration, and the Federated Conservationists o f Westchester County together represent the major ele ments of the environmental movement in the Hudson Valley. They have collectively helped to define many of the environmental safeguards, such as they are, that have come into being since public awareness o f ecological problems came into its own during the past 10 or 12 years. My comments today, on behalf o f these groups, are intended to raise the "decibel level," as Administrator Train commented yesterday, but not intended to c riti cize the efforts of this conference or its participants. What we in the Hudson Valley have experienced over the past 3 months, and all that I have heard since arriving in Chicago, indicates that the decibel level has n ot yet reached the pain threshold in government offices. We are astonished e t the delays. We cannot understand why it has taken so long fo r the PCB menace to surface, and we are horrified that so little action seems to be contem plated. We wonder what would have happened If the expose begun by Commissioner of Environmental Con servation, Ogden Reid, in New Y ork State had not occurred. As many o f you may know, this conference owes its genesis, in part, to the almost unbelievable revelations in the Hudson Valley last August. On August 8, 1975, Commissioner Reid dropped a bombshell on the public Director, Hudson River Fishermen' Association, Yorktown Heights, New York. by warning them not to eat striped bass from both the Hudson River and Lake Ontario because data given him by the EPA indicated levels o f PCB's exceeding 5 ppm were found in the fish taken from both waterbodies. He identified the culprit in the case o f the Hudson River as primarily the tw o General Electric facilities at Fort Edward and Hudson Falls, New York, whose massive capacitor plants there were dumping an average o f 30 lb. per day o f PCB. The river is apparently contaminated fo r a distance exceeding 100 miles, and the entire fishery is in question. As one might imagine, the reaction to this stunning announcement was one o f shock, frustration, disgust, dismay and confusion. The reasonably successful clean up of sewage and industrial waste in the Hudson Valley, while far from complete, was making visible progress. The water was not only cleaner to the eye, but the increased variety o f fish returning to the river in num bers not seen by commercial fishermen fo r over 20 years inspired confidence and pride. Since 1972, the Sloop Restoration had been sponsoring an annual shad sail in which thousands o f people had participated by eating freshly caught shad. Eating fish from a cleaner Hudson was a natural outgrowth o f the cleaner water we all thought existed. Imagine the concern, and frig h t o f all these people on the morning o f August 8th. When the shock wore o ff somewhat, many o f us asked; was this a new discovery? Was this just another layer o f contamination that no one had looked fo r before? Did new analytical techniques, or a fortuitous 367 774569 GENP 005921 ihnovrersotri,gactoionnsteprrnoadtuiocne,thanisddaanmgearg,inwghiantfworemfaotuionnd?, iTnoNoeuwr York State anyway, was an Environmental Watergate that knows no parallel. The confusion rapidly changed to an angry feeling of betrayal. As early as February 17. 1971, we discovered, ef forts were rtroantmede.natanld made by Mr. Robert Boyle perhaps others, to alert New Yoof rSkpSotrattse Iellnuvsi officials, notably Mr. Carl Parker, chief of the Bureau of Fisheries, to the presence of dangerously high PCB levels in striped bass eggs, and levels approaching the cutoff of 5.0 ppm in fish tissue. Mr. Boyle describes the response he got as "derisive." Not only was no ac tion taken by State officials, but considerable evidence exists that active efforts to suppress any information about PCB contamination persisted within the depart ment for several years. All of this despite reports of the problem written by A u d uInb oJnunMea, g1a9zi7n1e, Boyle in in 1970. the New both York Sports State andIllu s tr a t e d Department of Health certified that the water quality of the discharge from the two enormous General Electric plants met its criteria. In spite of the fact that 5.7 million lb of PCB's are used at these plants each year, no mention of PCB's was made by the health department. In July and through September 1972 (1% years aufntedrerBtoooykle PfiCrsBt sainganlaylseeds tirnouthbelem),id-NHeuwdsonYaorreka anSdtadties covered concentrations exceeding FDA limits of 5.0 ppm in fish. This information never saw the light of day. The then Commissioner, Henry Diamond, recently dis claimed any knowledge of the study or its damaging results. His successor, James Biggane, also denies knowl edge, and the new Commissioner claims he found out from Federal sources, not from within his own depart ment. Reid said in Savero, "There has baeNenewa faYiolurkre Toifmgeosvsetornrym,ebnyt Richard here...," referring to the suppression of information within his newly aquired department. That was a masterful exam ple of understatement. Subsequent further investigation revealed that between 1970 and 1975, 99 analyses of Hudson River fish were conducted by State officials, and in 52 cases the PCB levels were greater than the maximum allowable level of 5.0 ppm. A largemouth bass caught at the mouth of Esopus Creek, about 80 miles north of New York City, in 1970, but not analyzed until 1972, contained 53.8 ppm, or more than 10 times the maximum allow able limit. Subsequently, levels were detected in several species that ranged to over 100 ppm, with levels gener ally decreasing as distance from the GE discharges increased. On September 8, 1975, GE was ordered by the State to stop dumping its average of 30 lb per day by September 30, 1976, and to immediately curtail its dis crehqaurgireesdtoGE2 ltbo ppeorsdtaay $a2s omfilSlieopntepmerbfeorrm30an, c1e97b5o.nRdetiod back up his order. GE's response was to contest the order, as it did the provisions of its NPDES permit, wcrehhdaiurcgcheesd,altsahonedrdeitqsocuhircaelradgiemaletvmheaalsjtotroit cuhunarddtaeirlam2lreelbnadtpyeorfvdoaPlyuC.nBtHarodiwilsy ever, in the course of hearings, going on at this moment in Albany, it has been revealed that in the 24-hour period between October 17 and 18, 1975, 75 lb of PCB's were dumped at the Fort Edward Plant, by virtue of "heavy rain during sewer line repair." On September 13-14, 1975, a horrendous 116 lbs of PCB's were dstuamtepde.dBobtyh pthieecesHoufdsdoanta Fcaalmlse fprloamnt GwEi'tshownno wreriatstoenn responses to questions raised by State environmental mlaweeyteinrsg., BbaostehdoufptohnesdeaotacctuhreanEcePsArehparsespernestemntaejdorastptihlliss. I wonder if the EPA is aware of them, and what they will do about them. In any case, it is clear that GE has not curtailed its discharges, and it seems probable that this random and manadssivjeeopdaorsdinizge ofthtehe hHeauldthso, n swafielltyc,onatninduewteolfaproeisoonf ereassitderenntssenaobtoaorndl,ywihnertehecovmalmleeyr,cbiaultfiasllhearlmonegn tchaetcnhofritshh bornWanhdileratihseedreincotrhde oHfuSdtsaotne Eosfftiucairayls. is both shamefui and scandalous, the EPA has not acted with openness, or alacrity either. I should say that Region It's behavior has tdlheefestirmifnuuglclthhdetoemtab,ielosud,reswiinrhveiedcshtiingItahtiwiosinlmls aogtftleatdhr.leyWRidetohgiooufnot rpIIrooavnffiyidcoienn'ges actions indicate that it too had knowledge of the sever ity and extent of the PCB problem in the Hudson long before it forwarded the data to Albany or made it public themselves. An internal EPA memo dated May 31, 1974, reveals a request from Sandra Kunsberg, attorney in the Water SEunrfvoericlleamnceentanBdraAncnha,lystois DDirv.isRioinc,hatordcoSnpedaurcst, sCahmiepflinogf at the GE plants and in the Hudson River, to "Deter tmheinemwehaneitnhger oofr nSoetcttihoenre 5e0x4istosfa thheealtWh ahtearzarPdolwluitthioinn Control Act." This request was occasioned by testimony at the May 1974 EPA hearings on toxic substances scthaanrdgaesrdisntwo hthereeHGuEdsorenveRailveedr.the extent of its PCB dis The EPA lab report on this investigation, dated October 1974, concluded "that the biotic component of the river ecology are heavily contaminated with PCB's, r,F N P 005922 368 774570 grazing populations as well as carnivorous piscine popu lations," and notes that certain areas around Fort Edward and Hudson Falls "are fished primarily by the youngsters of Fort Edward. Ingestion of these fish by the populus would certainly lead to contamination of specific tissues in their bodies...." There was no health alert. No news release. There was nothing. Almost 1 year went by before this information finally reached the new environmental commissioner of New York. The question again is why? We must ask, how can so-called public servants walk around w ith the knowledge that commercial and sports fishermen up and down the North Atlantic as well as on the Hudson were catching Hudson River striped bass, shad, small mouth bass, and eels fo r human consumption, knowing full well that the likelihood of their contamination was great, that the fish posed a health hazard, and that their oaths o f office required action. That this situation could per sist for literally years is unforgiveabte. A failure of gov ernment? No. Indictable criminal offenses more suited to investigation by a grand ju ry than discussion at a conference such as this one. As far as action to end the problem nationwide is concerned, we decry the procrastination, fear, or what ever, that seems to underlie the apparent lack of direc tion and assertiveness thus far displayed. There still appears to be a question about what comes first, the national health or the business interests of the electrical and other industries that rely upon PCB's fo r their profits. We fail to see how a proposed standard o f 1 part per trillio n ambient in the Nation's waterways w ill solve the problem. Is it low enough? Can it be enforced? How was it arrived at? Can we live w ith PCB's at all? What w ill happen, or rather what should happen to the more than 100 m illion lb o f PCB still available-to be degraded or released into the environment? How w ill we deal with this problem? It is equally alarming to note that the FDA has not stated here one syllable about any proposed change in the permissible PCB levels in food or fish. We wonder why fish have highest permissible PCB level in the first place. The suggestion that PCB levels are decreasing in all foods except fish seems to contradict the ubiquitous nature of PCB's, and creates a false sense of security. Our Canadian neighbors have announced a new lower standard o f 2.0 ppm in food, and Commissioner Ogden Reid has taken the position, to his credit again, that a standard o f 1,0 ppm seems to be desirable. When w ill the FDA take some action? Getting back to the Hudson Valley, which we hope is riot the average situation around the country, the fledgling Hudson River fishery, thanks to GE, is dead for all intents and purposes. Commercial fishermen who had hoped to go back to fishing fu ll time have scrapped their plans. Even if their catches were n ot contaminated, fish markets w on't buy them or pay such low prices that no p ro fit is possible. The public is now convinced that Hudson fish are tainted, and w ill continue to think so fo r many years regardless of cleanup requirements or measurable improvements that may or may not take place. The implications fo r the North Atlantic fishery have yet to be explored or defined, but the. potential economic impact o f the August 8th revelation, an envi ronmental Pearl Harbour, fo r fishermen everywhere is devastating. Confidence in government and in die Hudson's recovery is at a new low. In conclusion, the time to act is now. Administrator Train said yesterday that he hopes this w ill be his last PCB conference. Well, we also hope that no more confer ences on PCB's w ill be necessary. How much data does it take before action can be justified? Must we suffer an outbreak of Yusho disease before the problem assumes real proportions? We must have more than conferences. And we expect more than talk. Thank you fo r your attention, and fo r this opportu n ity to speak. GENP 005923 MS. EILEEN JOHNSTON (Concerned citizen): Thank you, Chris. Well, I would like to thank die U.S. Environmental Protection Agency for putting on this stimulating meeting. I felt privileged to be in the room with so many fantastic research members and I was a little encouraged and discouraged. I happen to live in the Lake Michigan basin. I was wondering, too, where are all the concerned c iti zens. I really saw very few people from Illinois that I fe lt should have been here if they were concerned about PCB's. I also want to congratulate the State o f Wiscon sin fo r the hearings that they have held, and I'll be very anxious to see what comes from those, and also to congratulate the State o f Michigan fo r the fine presentation that John Hesse made. I w ill be inter ested to follow House Bill 5619 in Michigan. My own great concern fo r PCB's in the environ- 369 774571 ment is due to my own Illinois Environmental Pro tection Agency. Last February the agency was asked to host the February meeting for the Governor's five-State Interdisciplinary Council on Pesticides. Jim Frank, a very capable young man from EPA, put on an all-day meeting on PCB's. I was the only citizen at this meeting and it was so stimulating that I started out to do what an individual citizen can do. I talked to a few citizen groups that I am associ ated with and we decided to put on a meeting to help warn the Lake Michigan fishermen about this and we held the meeting in March or April. I urged more citizen groups to do this sort of thing--to take positive action. Citizens need more education. I hope that USEPA and everybody else concerned with PCB's will really listen to Carlos Fetterholf, who really socked it to people tonight. Getting back to Illinois, I've talked to 225 citi zens quite recently and explained to them the perils of PCB's and they signed petitions for me to take to the Illinois Pollution Control Board to ask it to hold informational hearings on PCB's, to get them in formed, and to get our own Illinois EPA and inter ested citizens to be better informed. They decided to wait until after these meetings to decide whether to hold hearings. Another thing I heard today that the research ers mentioned is that we ought to get together and get some standardized analytical methods. Remem ber when we were concerned about DDT? I attend ed a 2-day seminar out on Pershing Road at EPA headquarters. Everybody was analyzing whole fish, half fish, and it seems to me from what I heard that they really should get together and develop uniform procedures. I think it was a great conference but I really want to know what EPA is going to do. What are you guys going to do? I have great faith in the U.S. Environmental Protection Agency. I know so many people in Region V--but what are you going to do? Are you going to Congress? Are you going to take action? Are you going to answer the questions tonight, Chris? Thank you. Session continued on next page. GENP 005924 27 7 4 5 7 370 MR. RAY OLTMANNS (Illinois W ildlife Federation, Blue Island, Illinois): I am a delegate from the Illinois W ildlife Federation. 1 am going to read a letter (figure 1) that is going to go to Mr. Train; it is from Frank Goetschel, our president. Thank you. IL L IN O B iO jJ M M e , e r a t i o n II inos L WtsniN AVI. hue iuano, * o mIllinois K o. EOI II* PHONE 111-IM.im November 18 1975 Hr. Bussell B. Train Adsinlstritor 0. S* Environmental Protection Agency Washington, 0. C. 20460 Dear Hr. Tralnt Tba Illinois wildlife rederation concurs with the need for Mediate and strict regulations of production, distribution and use of the industrial chemicals called polychlorinated biphenyls (PCS). Failure of the Envlromental Protection'Agency to have restricted these ^i>-- as toxic substances under the Federal Water Pollution Control Act of 1972 eannot be excused. Their widespread distribution in the environment and the threat they pose to public health has been fully documented and are well known to your agency. Tet to date EFA has contented itself with requests for voluntary action by industry even while PCS'a have continued to ecemulate In ever higher levels in all vatar wastes, and while research evidence hes continued to confirm their toxicity. a The chance to taka preventive action was Dieted when EPA delayed and delayed its regulations of FCBs as a toxic substance. We feel action is now nandatory to ban the use of PCBa. Sincerely yours, FC Isa cci Acs Extra, Exec. Sec Frank Goetschel' President n a t i o n a l wildlife federation a f h u a t e puniSHiuoP ILLIHOI Figure 1. Letter. 371 774573 GENP 005925 MR. BURNETT BAUER (State Senator from South Bend, Indiana): First of all, I want to congratulate the EPA fo r holding a meeting at which it can't really win. I've heard in this meeting that they've done too much and then I've heard them damned for doing too little . And they d o n 't have to do that; we in politics every election have to stand up and take it, but they really don't have to . But they did call this meeting and I think it's been very beneficial and the fact that we've had discussions is a real step toward solving what all of us recognize is a real problem. Now the reason I want to talk here is because 1 want to make one suggestion fo r those who want the government to take some action. That was sug gested a number o f times. It'll also maybe warn those who don't want the government to do a dam thing. What I'm suggesting is this, that you not wait fo r the Federal Government to start action on PCB's but you start it in the States. I know that's contrary to most o f the procedure and most o f the thoughts that people have, particularly those in State Govern ment. But the historical fact is most o f the social changes in our country started in States first. The women's sufferage movement was not suddenly brought on by the Federal Government; the States first started allowing women to vote. We know that most o f the environmental actions were started in a locality and in the State. It's just a fact th a t once the Federal Govern*' ment sees States acting that this indicates to them seriousness, and then they go in and invest the time and money that they have. Now there are several reasons why we want the States to do this. First of all, most o f the legislatures are citizen legislatures. In one sense, we're n ot as vulnerable to lobbyists. Most o f us are serving there because we want to better our State. We want to give our children a better place in which to live, and we are doing what we th in k prim arily would be best in the long run. Second, we are closer to specific problems and when we p ut a solution in there, it is probably a lo t closer to a genuine solution. It's much harder for people in Washington to try to legislate something that applies over the 50 States. If you start-w ith your actions at home--and God bless these women out here who have these groups, they'll bring you specific instances y o u 'll start legislating laws that w ill work. I'll give you just .one instance and then I'll sit down. In Indiana we have pollution o f a lot o f our fine lakes and we heard it was because of phosphates. Indiana passed the firs t statewide ban against phos phates in detergents. I'm the grandfather o f that bill because it was my son, who just happened to be in the House, who got it passed. He had more energy than I did. The real fact was that I was out for 2 years and the lobbyists went out of the State. They did n't think the bill would be brought up. By the tim e they found out, the Governor had already signed it. So there's something in passing the w ork onto the next generation. We have found as a result o f that ban that our State's lakes^are clearing up fantastically. That law works. New York now has it. We hope other States o f the Great Lakes w ill adopt it. One reason I'm here is I have met w ith groups that are around the Great Lakes and the Great Lakes are in danger of many things. And I just want to urge you people w ho are in favor o f having something done to go home and start working on your State legislatures. I know I'll get some letters from some o f those guys saying, " why d on 't you shut up, Bauer, we've got enough w ork to d o ." But do that if you really are genuine in your interest o f getting some action toward cleaning up our environment, and in passing on to the next generation an atmosphere and envi ronment that can make us happy, and can make us really enjoy the greatest country in the world. I want to congratulate again EPA and every one of you who came here from industry. I've learned a heck o f a lo t here, and I th in k that all those who participated in this meeting are really leaders and genuine pioneers in this country. I salute you. a vU ? 005926 372 774574 MR. BARRY SCHADE (Minnesota Pollution Control Agency, Roseville, Minnesota): The Minnesota Pol lution Control Agency is a member of a task force made up of 11 agencies which represent the various interests of two States and the Federal Government. This task force was formed to investigate the PCB pollution problem in the upper Mississippi River and its tributaries. In response to preliminary information provided by this task force and by vari ous other studies, the Minnesota Pollution Control Agency board passed a resolution related to PCB's on June 24th, 1975. This resolution, which supports a Federal ban on the sale and use o f PCB's, is sub m itted as figure 1. CERTIFICATE OF MINNESOTA POLLUTION CONTROL AGENCY'S AUTHORIZING RESOLUTION I, Peter L. Gove, do hereby certify that I in Executive Director of the Minnesota Pollution Control Agency, and that the attached is a true, complete and correct copy of a resolution adopted at a meeting of the Board of the Minnesota Pollution Control Agency duly and properly called and held on the 24th day of June, 1975, that a quorum was present at said meeting, that those present unanimously voted for the resolution and that said resolution is set forth in the minutes of said meeting and has not been rescinded or modified. IN WITNESS WHEREOF, I have hereunto subscribed my name this 25th day of June, 19751 Executive Director Subscribed and sworn to before MKnAuRrYrnEm. uWeY- AuTiTknqsta Ur_tt_mDwAKAOeTuAChOeUjNtiTyY, m i Figure 1. Resolution of Minnesota Pollution Control Board. 373 774575 GENP 005927 STATE OF MINNESOTA MINNESOTA POLLUTION CONTROL AGENCY June 24, 1975 RESOLUTION WHEREAS, th e A gency i s c h a r g e d w ith th e a d m in is t r a t io n and e n fo r c e m e n t o f a l l la w s r e l a t i n g to the pollution o f any w a te r s o f t h e s t a t e a s g iv e n i n M in n eso ta s t a t u t e s o f 1 9 7 1 , chapter 1 1 5 . 0 3 , and; WHEREAS, no sew a g e, i n d u s t r i a l w a ste o r o t h e r w a s te s s h a l l b e d is c h a r g e d into any o f th e I n t e r s t a t e o r in tr a s ta te w aters c l a s s i f i e d as f i s h e r i e s and r e c r e a t i o n s o a s to cause any m a te r ia l change i n any o t h e r s u b s ta n c e s o r c h a r a c t e r is t ic s which may Im pair th e quality o f Interstate or Intrastate raters or the a q u a t i c b i o t a i n any manner r e n d e r them u n s u i t a b l e o r ob jectionable f o r f i s h i n g , f i s h c u l t u r e o r recreational uses as per Minne sota Pollution Control A gen cy r e g u l a t i o n s WPC 1 4 and I S , (1 9 7 3 S u p p le m e n t), and; WHEREAS, s i g n i f i c a n t c o n c e n t r a t io n s o f p e r s i s t e n t o r g a n ic compounds known a s p o ly c h lo r in a te d b ip h e n y ls (PCBs) have been i d e n t i f i e d w ith in th e M is s i s s i p p i R iv e r n e a r t h e b o r d e r a r e a s o f M in n e s o ta -N is c o n s in known as Lake P e p in , and/ WHEREAS, t h e U n ite d s t a t e s Food and D rug A d m in is t r a t io n h a s e n f o r c e d t h e mA c t io n L i m i t m o f f i v e (5 ) p a r t s p e r million total PCfis on s e v e r a l s h ip m e n ts o f c o m e r c i a l l y cauyht rough f i s h fro m the L ake P e p in a re a resulting i n v o lu n ta r y d is p o s a l o f the f i s h b y the industry, and; WHEREAS, a s a result o f the a b o v e , coamercial f i s h i n g o p e r a t io n s fhave te m p o r a r ily b e e n ceased in the Lake P e p in a r e a , and/ Figure 1. Resolution of Minnesota Pollution Control Board (con,). 374 77457S GENP 005928 WHEREAS, on May 2 7 , 19 7 5 D r. Warren R . Law son, M in n eso ta C o m m issio n er o f H e a lth a d v is e d t h e public to limit consumption to no more than qne meal per week o f f i s h taken from th e M is s is s ip p i R iv er from th e M in n ea p o lis-S t. Paul metropolitan area and lover L ake P e p i n , and/ WHEREAS, a major study co m p le te d by D r. J .R . A ll e n o f t h e U n iv e r s it y o f W isco n sin (19 74 ) indicated short-term toricity to a low-level exposure to PCBs i n nonhuman primates, and this study and o t h e r s s u g g e s t s t h a t t h e r e e x i s t s a significant potential for harmful effects to humans, and; WHEREAS, and a s a r e s u l t o f the above actions s i g n i f i c a n t environmental effects on the a q u a tic life and economics of com m ercia l and s p o r t s f i s h e r i e s as w ell as tourism have o ccu rred , and; WHEREAS, the Great Lakes Environmental Contaminant Survey (CLECS) conducted yearly by Michigan's Departments of Natural Resources and Agriculture, the U . S . fo o d and Drug A d m in is tr a tio n - D e t r o it R e g io n , and the Great Lakes F is h e r y L a b o ra to ry h a s d e te rm in e d that Lake Superior lake trout collected near Isle Royale a re show ing a pattern of elevated PCS residues s im ila r t o Lake M ichig a n . NOW THEREFORE BE IT RESOLVED, Chat the Minnesota Pollution Control Agency Board h ereb y supports a F e d e r a l ban on the s a l e and u se o f PCBs. Figure 1. Resolution of Minnesota Pollution Control Board (con.). 375 774577 GENP 005929 MR. RICHARD T. FERRY (Bio-International, Inc., W oods H o le , Massachusetts): Bio-International, I nc., is principally located in Ft. Lauderdale, Florida, and holds four U.S. patents covering its processes for the microbial degradation of petro leum and petroleum byproducts. Bio-International holds one United States patent fo r a microbial degradation facility; that is, a mechanical facility comprising an interconnected initial and final de gradation system, each containing an inlet and out let and a conveying means together w ith aeration or stirring devices and a drainage means. This patent was issued only 3 months ago, on August 11, 1975. Of particular interest to the group here today is a patent held by the company relating to the microbial degradation o f polychlorinated biphenyls that was issued on December 18, 1973 (see figure 1). Bio-International is currently engaged in the optimization o f its processes at three leading univer sities in the Southeast. The purpose of this ongoing work is to further increase the efficiency o f the inte grated system and to broaden the scope o f field applications. In the process, a significant amount o f scientific and technical data is being electronically stored fo r quick retrieval when circumstances demand. This information is also being synthesized in order to prepare an affirmative response to the revised Annex Ten of the National Contingency Plan rela tive to the introduction of microbial additives to the environment. A d d itio n a lly , Bio-International maintains a staff of internationally recognized scientific authori ties whose main thrust is in the area of environ mental consulting. The company is now analyzing the effluent of major industries who recognize their own obligation to solve their own effluent prob lems, particularly where PCB contamination is involved. Upon the completion of these analyses, it is envisioned that the -company's integrated proc esses w ill be brought to bear on the problem e fflu ents. I would be remiss if I did not note in closing that our ongoing studies relative to the problems of PCB's in the environment would be much more d if fic u lt were it not fo r -the cooperation o f Mr. Papageorge and his colleagues at Monsanto as well as other representatives of government and industry, particularly the fishing and marine-related indus tries. For those o f you who may be interested in the biodegradation approach to environmental prob lems, you're invited to contact me here or by letter and we'll be happy to provide you w ith more specif ic data. Thank you very much. Figure 1 on following'page. GBTP 005930 376 7?4578 UNITED STATES PATENT 3,899,376 August 12, 197S MICROBIAL DEGRADATION FACILITY ABSTRACT A facility for the microbial- degradation of petroleum and oil wastes, as contained in, e.g., industrial effluent discharge materials, comprising an interconnected initial and final degradation system, each of which contains at least one tank means, associate! inlet and outlet means, conveying means, aeration ot stirring means and drainage means. The effluent to be degraded is introduced into the initial degradation system together with the microorganisms imployed and nutrients therefore, and degradation proceeds with aeration or stirring with the formation of a protein-containing cell mass. The sub stantially degraded effluent is conveyed to the final degradation system where addi tional microorganisms are added to obtain the final degradation or polishing. The resulting effluent, after filtering, is clean and clear and may be discharged safely into the environment.* UNITED STATES PATENT 3,779,866 ________________________________________________________ Dec. 18, 1973 MICROBIAL DEGRADATION OF POLYCHLORINATED BIPHENYLS ABSTRACT A process for the microbial degradation of polychlorinated, biphenyls (PCBs) which comprises treating the PCBs with certain non-pathogenic, hydrocarbon-utilizing strains of Cladosporium cladosporiodes, Candida lipolytica, Nocardia glaberula, Nocardia rubra and/or Saccharomyces cerevisiae until the PCBs have been substantially degraded. The process is applicable degrading PCBs as they may b e present as pollutants or contami nants in water, in industrial effluents, in various land arias such as industrial sites and the like or in varied laboratory or commercial installations. The process may also be used to d e a n up and degrade mixtures of PCBs and various hydrocarbon oils or petro chemicals whenever their presence constitutes a deleterious pollution. Figure 1. Abstract of patent relating to the microbial degradation of polychlorinated biphenyls. GENP 005931 MAJOR GORDON GOFF (U S . Arm y Materiel Com mand, Alexandria, Virginia): The follow ing descrip tion o f the spill o f 265 gallons of PCB's into the Duwamish Waterway in Seattle is presented here as an ongoing practical problem that we're facing in the recovery and disposal o f contaminated bottom sediments from a busy waterway in this industrial area. The spill itself occurred on September 13, 1974, when a large electrical transformer fu lly sheath-crated fo r open-deck shipment to Alaska was being sling-loaded aboard a barge. As the slung crate was about 2 feet o ff the dock the bottom members gave way, the transformer felt to the dock, and the outboard cooling fins struck the bull rail, rupturing them and leaking approximately 265 gallons of PCB material in the transformer onto the dock and into the waterway. A t that point in time, because of a lack o f awareness o f the people on the scene as to exactly what was in the transformer and the lack o f labeling or warning on the crating itself, the normal oil spill procedures used at th at dock were instituted. W ith in . 2 or 3 days, however, the possibility that PCB's were implicated in the spill appeared. Subsequent investigations bore out the fact that the spill was indeed PCB's. EPA and the State o f Washington Department of Ecology instituted an emergency cleanup procedure. Handheld dredges manned by divers recovered the visible pools of PCB's which were lying on the bottom o f the waterway. A filtratio n u n it was then moved into the area 774579 and the recovered material was run through this f il tration u nit and the sludge that resulted was drum med and was subsequently disposed o f by a com mercial contractor. In this emergency operation, approximately 80 gallons of visible pools of PCB's were recovered. The remaining PCB's are now in the bottom sediments and subsequent sampling has established an area of relatively high PCB contamination in the area of the spill. To cover the proposed procedures fo r the re covery o f this I 'd like to ask Mr. Jack Thompson, who ts a fisheries biologist w ith the Seattle District Corps o f Engineers, to cover the details of it. MR. JOHN S. THOMPSON {Seattle District, U S. Army Corps o f Engineers, Seattle, Washington): The pre vious speaker described events leading up to the accidental loss o f PCB's into the Duwaniish Water way, Seattle, Washington, and partial removal o f the PCB's by EPA and Washington Department of Ecology. There remains about 185 gallons o f Aroclor 1242 in the immediate area where the spill occurred. About 2 months ago the Corps was re quested by the Department o f Defense to remove the contaminated sediments. This decision is sup ported by EPA and the State o f Washington. The Duwamish Waterway is a dredged channel in the Duwamish River. It is dredged a distance o f 5 miles from salt water w ith one-half o f the channel dredged to 30 feet below mean lower low water (MLLW). The spill occurred at about river mile 2, where the dredged channel is 30 feet below mean* lower low water. Background levels o f PCB's in bottom sedi ments run from 0.16 ppm to about 2.5 ppm. Levels o f PCB's in the area of spill range from about 5.4 ppm up to 390 ppm in the sediments. We propose to remove the contaminated sediments, which w ill require dredging up to 40,000 cubic yards. We plan to use a dredge called Pneuma pump, which is manufactured in Italy and represented in the United States by a Chicago firm . This type of dredge has never been used in Puget Sound country and it is a little experimental fo r us. The advantage of this particular dredge is that small amounts o f water are used fo r the pipeline dredging; in other wofds, about 60 percent o f the material that w ill enter the pipeline is sediments and about 40 percent water. Also, this dredge is excellent fo r controlling *0 tu rb id ity and has excellent control of dredging depth. We plan on including predredging and post dredging m onitoring1sampling, which w ill be per formed by EPA. There w ill be sampling during the actual dredging. We have looked at a number of disposal sites and methods and we have selected one. A ll o f the areas have one thing in common and that is that no one wants the stuff. The proposed disposal method is as follows: (1) We w ill pump, using the pneumadredge, into a watertight 4,000-yd3 barge; (2) When fu ll, the barge w ill be hauled 2 miles upstream to the disposal area; (3) The pneumadredge w ill then be placed into the barge and sediments w ill then be pumped into a disposal area. The disposal area w ill be prepared beforehand and w ill be roughly 300 feet from the waterway. In the Seattle area, we have a tide drain from about plus 12 feet down to about minus 2 feet below MLLW. The disposal area bottom w ill be at 0 feet MLLW elevation. Consequently, this material w ill be placed in the water table. The disposal area w ill be filled to about the plus 14 fo o t level. The disposal area w ill be covered w ith 2-3 feet o f clean dredged materials after dredging is .completed and material has solidified. A ll effluents leaving the disposal area w ill be run through a sand filte r to remove sus pended sediments. The cost o f this operation w ill be between $300*,000 and $500,000. This is about $2,500 per gallon o f PCB's removed. This case study has been presented to you to show one removal operation and illustrate the problems involved in removal and disposal o f hazardous materials. Thank y o u .. X6SO O 378 774580 CHLORINATION OF WATERS FOR DISIN FEC TIO N -A STUDY OF THE PRODUCTION OF UNDESIRABLE CHLORINATED PRODUCTS Richard Johnsen, Ph.D.* The current emphasis on environmental preservation and human health is resulting in an increased use of chlorine fo r disinfection and waste treatment. Few ef forts, if any, are being made by those proposing such procedures to determine the possible adverse impact of increased usage. The use o f chlorine fo r water treatment falls into two categories: protection of public health, and indus trial use fo r antifouling and fo r waste treatment. In the United States, chlorination o f municiple water supplies and wastewater treatment plant effluents is the most common procedure fo r disinfection. Most biologists who have maintained aquatic animals in laboratories are aware of the to x ic ity o f chlorinated tap water. Brungs (ref. 1) thoroughly reviewed the current knowledge of the effects o f residual chlorine on aquatic life. However, this paper is n ot concerned directly; per se, w ith chlorine toxicity but rather its reaction with other constituents o f waste waters to produce unwanted chlorinated prod ucts. The u tility o f chlorine in water treatment Is at tributable to its toxicological characteristics and its oxidative capacity. Chlorine is employed to destroy pathogenic and nuisance bacteria and other microorgan isms, to modify the chemical constituents o f the water being treated (e.g., reduction of tastes and odors), or both. In Fort Collins, as well as in most other Colorado cities, chlorination is used not only fo r disinfection of community water supplies, but also in the disinfection of effluent waters from the two sewage treatment plants. This latter water is released, usually directly, into the Cache La Poudre River, which is part of the South Platte River system. There are tw o sewage treatment plants in Fort Col lins, w ith the most recent one (onstream in 1969) cur rently undergoing a large expansion. The newer plant currently 'handles about 5.5 m illion gallons per day of waste waters w ith a near tripling in capacity nearing completion. Terminal chlorination at this plant site is carried o ut on the effluent stream from the clarifying tanks and just before the effluent enters the chlorination holding basin from which the water is released to the river. * A sso cia te Professor, Pesticide Research Laboratory, Department of Zoology and -Entomology, Colorado State Univarsity, Fort Collins, Colorado 80523. The question that arises is whether this terminal chlorination treatment, w ith a desired disinfection as its goal, can give rise to undesired chlorinated products. Recently considerable concern was voiced in the na tional wire services over the findings by regulatory agencies o f certain chlorinated compounds in the drink ing waters of numerous communities (e.g., New Orleans) which are potentially dangerous to human health. Most o f those cited to date include chlorinated alkanes (meth anes and ethanes, etc.) and chlorinated phenols. The sources of these compounds were not ascertained but were being attributed to industrial effluents. The high reactivity o f chlorine w ith many organic compounds may provide another answer. Since sewage effluent waters from one comm unity become the eventual drinking waters o f communities downriver, it is o f considerable importance that it be known that a disin fection process at one point does n ot contribute to the pollution burden at a second point. Another concern is the effect on aquatic fauna o f such chlorinated com pounds as may be formed by chlorination o f waste waters. Although tremendous amounts o f data are avail able on many chlorinated compounds having deleterious environmental effects (e.g.t the insecticide DDT and the herbicide 2,4,5-T), very little is known about chlorinated compounds that may emanate from chlorinated sewage effluent waters. Review o f the Literature A recent release of preliminary results o f an Envi ronmental Protection Agency (EPA) survey o f U.S. drinking waters suggest that chemical contamination is a national problem (ref. 2). The report states that all 79 cities surveyed contained some amount o f chloroform, ranging from 0.1 part per billion (ppb) to 311 ppb. This and other chemicals found were reported to be partially due to chlorination o f drinking waters, Delfino (ref. 3), in response to earlier related reports, doubted the forma tion. of chloroform in the chlorine disinfection process but called fo r more research in this area. Schwartz (ref. 4), in response to Delfino, cites the relative ease in which one may expect to fin d chlorinated compounds after chlorination considering all the possible organic com pounds found just in sewage effluents. Laubusch (ref. 5) stated that when chlorine is added to water, a mixture of hypochlorous (NOCI) and hydrochloric (HCI) acids is formed and that this reaction is complete in a few seconds. He points o ut that under some conditions. GENP 005933 379 774581 chlor-addition o r chlor-substitution products may be fo rm e d , b u t gives no fu rth e r data. G affney {ref. 6), in a le tte r in S cience, fo u n d p o ly c h lo rin a te d biph enyls (PCB's) in a sewage treatm e nt p la n t's tric k lin g filte r bed. These PCB's were the result o f a high biphenyl in flu x fro m a te x tile m ill coupled w ith waste w a ter prechlorinatio n . Our interests in this area were rekindled w ith the paper by Carlson et al. (ref. 7). They reported that not only were 10 organic compounds, ranging from phenol to benzene, chlorinated but also that biphenyl, used as a fungicide, was chlorinated under various conditions to varying extents. This.latter compound was of particular interest since we have been working w ith PCB's for several years as an industrial pollutant. Glaze et al. (ref. 8) found a number o f chlorinated compounds by gas chromatography (GC) after extracting wastewater efflu ents containing from 10 to 100 ppm chlorine. Only chloroform was identified although it was evident from their chromatograms that higher molecular weight chlo rinated compounds also were involved. Although levels o f chlorine can be quite variable in effluent waters, depending on the chlorine metering devices and operator control, there are known to be some treatment plants that discharge effluents containing as high as 15 ppm total chlorine residual (ref. 9, p. 456). The literature is replete w ith references to PCB's in aquatic animals, such as fish, crayfish, snails, shellfish, etc., in fish-eating birds, predatory birds, and other vertebrates, and the question that now arises is whether some o f these PCB's are industrial pollutants or those produced by chlorination o f waste waters. Background Experience We have studied and monitored PCB concentrations in digested sewage sludge, fish, and effluent waters for several years. We have shown that PCB levels have stabil ized in sewage sludge at about 4-6 ppm, that they are in the effluent discharges from the sewage plants, and that they are concentrating in the fish n*the Poudre River at levels often exceeding 5 ppm (refs. 10,11). Although we have tried, we have been unsuccessful in determining the source o f PCB's into the sewage treatment plants. In addition, the gas chromatograms of extracts from efflu ent waters and fish tissues are not the same as those from digested sludge. If this is not due to some meta bolic process, it may possibly be due to chlorination of the effluent water. This we would like to determine. The fact that PCB's have been reported in effluents from paper mills which use biphenyl in slime control and chlorine in bleaching processes, gives credence to the preliminary w ork we report below and that already cited. Prelim inary Work Recently we have conducted some prelim inar/ work using biphenyl in water (5 ppm) to which was added chlorinated water to give chlorine concentrations of 8, 83, and 830 ppm. Under ambient conditions and after aging fo r 24 hours and 1 week, the samples were analyzed, along w ith suitable controls, by gas chromato graphy. The chromatograms shown in figure 1 indicate at least 8 peaks attributed to PCB's. If the individual chromatograms o f A and C were superimposed over B, one would see striking overlaps although relative peak heights o f most o f the peaks aren't comparable. The standard (B) is Aroclor 1221, an industrial form ulation containing 21 percent chlorine by weight. This is just one o f eight formulations. It is evident that the higher level o f chlorine resulted in higher chlorine substitution levels, as indicated by the longer retention times. The above data have not yet been quantitated nor have PCB isomer assignments been made to the various peaks. However, we have on hand over 50 pure PCB standards ranging from several monochtoro to decachloro bi phenyls which w ill be used fo r identification. Present work has indicated that biphenyl is chlorinated readily under conditions similar to those in the local sewage treatment plants. Other w ork done has involved use of sodium and calcium hypochlorite as chlorine sources. Discussion o f these preliminary studies need not be included here since chlorine gas is used locally and we w ill coVifine our w ork to this source in itia lly . Work Pian Since we have on hand a very sizable supply o f chlo rinated PCB isomers, it is our intent to study the chlorin ation process in itia lly in the laboratory using biphenyl and later A ra d o r 1221, to determine the parameters necessary fo r chlorination. Some o f these parameters would be pH, concentration o f reactants, reaction tim e and lastly, chlorine source. Since Fort Collins and most other communities use chlorine gas, and since that is what we have used prim arily in the preliminary work, we w ill continue using this form . A fte r this w ork has been completed, we plan on using effluent waters obtained from the sewage treatment plant and conduct timecourse studies to determine extent o f chlorination w ith time. Chlorine concentration would be the next factor studied. Probably o f utmost concern is the unequivocal identification o f the products formed. The fact that we have many o f the potential products is extremely bene ficial. The water samples w ill be routinely extracted w ith hexane and analyzed by GC using our Micotek MT-220 equipped w ith four columns and dual Ni 63 electronca p tu re detectors. An infrared spectrophotometer (Perkin-Elmer 337) is on hand fo r determination o f rvFNP 005934 380 774582 1 GENP 005935 Figure 1. Gas chromatograms of extract of biphenyl reacted with CI2-water (83 ppm Cl) for 1 day (A), 830 ppm Cl for 1 day (C) and comparison to to Aroclor 1221 (B). 3?| 774583 COLORADO i \1 A B Figure 2- Gas chromatograms of extract of biphenyl reacted with Clo"water (83 ppm Cl) for 1 week (A) and comparison with Aroclor 1221 (B)3 774584 GF.NP 005936 COLORADO Figure 3. Gas chromatograms of extract of biphenyl reacted with C ^ - w a t e r (830 ppm Cl) for 1 week (A) and comparison to Aroclor 1232 (B). o w 3 *3 774585 U) infrared spectra o f products isolated by thin-layer chromatography. Confirmation of identities is planned using a mass spectrometer coupled w ith a GC. Figure 2 illustrates the sim ilarity of the extract (A) (the reaction of 83 ppm Cl2 water w ith 5 ppm biphenyl incubated 1 week] with that of Aroclor 1221 but not in the same proportions. Using a light table, the peaks are superimposable on one another. This is true also of figure 3, where the chromatograms show the results of 830 ppm Cl and 5 ppm biphenyl incubated fo r 1 week in comparison to Aroclor 1232. It is evident that increasing chlorine dosages, result in greater degrees o f chlorination. The chromatograms in both figure 2 and figure 3 were very similar also after 1 day in incubation w ith the exception that the later eluting peaks are more pro nounced. In figure 3 as in 2 above, all the peaks in the extract are in the Aroclor 1232. It was surprising to us that biphenyl was so readily chlorinated in light of its assumed unreactivity. Further work is planned along these lines using shorter reaction'tim e spans (hours), utilization o f th io sulfate to terminate the reaction, use o f CCI4 or CHCI3 instead of hexane as extracting solvent, and use of glassdistilled water (rather than from Bamstead still) distilled over basic K M n04 . We have used reagent-grade Cl? gas and have ,not noticed any problem w ith bromine as an im purity. We would like to get access to a MS to check our peaks fo r chlorine content. We have checked the pH of the saturated Cl?-water and found it to be 2.4 and after bubbling air through it, via a fritte d disc, to be 2.45. So apparently the HOCI and HCI formed by the reaction of Cl? gas w ith water is quite stable. Some early peaks showing up in our blanks, especially the Cl? -water blanks, are due possibly to the chlorination of hexane. This is the main reason we want to terminate the chlo rination reaction with thiosulfate prior to extraction. REFERENCES 1. W. A. Brungs, "Effects of Residual Chlorine on Aquatic Life," J. Water Po/fut. Contr. Fed,, Vol. 45 (1973), pp. 2180-93. 2. Anonym ous, "Water Contaminated Throughout U.S.," Chem. Eng. News, April 28, 1975, pp. 18-19. 3. J. J. Delfino, "D rinking Water S tudy," Chem. Eng. News, December 23, 1974. 4. H. Schwartz, "Chlorine in Water," Chem. Eng. News, January 20, 1975, p. 5. 5. E. J. Laubusch, "Water C hlorination," J. S. Sconce, ed., Chlorine, its Manufacture, Properties and Uses, Reinhold, New York, (1962), pp. 457-84. 6. P. E. Gaffney, "PCB's: Another Source," Science, Vol. 183 (1974), pp. 367-8. 7. R. M. Carlson, R. E*. Carlson, H. L. Kopperman, and R. Caple, "Facile Incorporation of Chlorine Into Aromatic Systems During Aqueous Chlorination Processes," Envir. Sci. Techno!., Vol. 9 (1975), pp. 674-5., 8. W. H. Glaze, J. E. Henderson, IV, J. E. Bell, and V. A . Wheeler; "Analysis of Organic Materials in Wastew a te r Effluents A fter Chlorination," J. Chrom atogr., Vol. II (1973), pp. 580-4. 9. G. C. White, "Handbook o f C hlorination," Van Nostrand Reinhold Company, New York, (1972), p. 744. 10. R. E. Johnsen, "Polychlorinated Biphenyls: An Industrial Pollutant," E n viro n m e n t/ ChemicalsHuman and A nim al Health, Proc., F o rt Collins, Colorado, August 7-11, 1972, Environmental Pro tection Agency, 1973, pp. 213-20. 11. R. E. Johnsen, and L. Y. Munsell. "PCB's Their Origin and Fate in A River Ecosystem." Environ m ental Chemicals- Human and A nim al Health, Pro ceedings F o rt C ollins, Colorado, 3 rd A nnual Confer ence, July 15-19, 1974, Environmental Protection Agency, 1975, pp. 273-92. oo'-s O HERBERT GILNER (Tivian Laboratories, Providence, Rhode Island): I would like to address myself brief ly to the methods used to gather information about polychlorinated biphenyls as environmental con taminants. I do not argue w ith the need, only w ith the methods. It has been claimed both in the press and at this conference that of the 84 firms to whom letters were sent in August concerning the use of PCB's, only one has refused to respond. That company has been named in the press. That company is Tivian. However, to our knowledge, there is at least one other company which has also refused. There are tw o distinct principles involved in this refusal. The first is that Tivian Laboratories does not use PCB's. O n hearing this, the Environ mental Protection Agency demanded information concerning Tivian's use o f polychlorinated ter* phenyls, a series of compounds qualitatively d iffer ent from PCB's. There has been, to our knowledge. 384 774586 no evidence that the PCT's accumulate in human tissues. Moreover, we state and have stated in the past that Tivian Laboratories do not pollute the environment. Furthermore, and this gets us to the second principle, Tivian feels that the information demand ed is proprietary and that EPA, having been set up by executive order, has no constitutional or statu to ry right to demand such information or to make . threats concerning penalties fo r noncompliance. The company I represent feels that the harassing activi ties of the EPA, including trial by the press, are totally illegal. EPA has sought to v ilify the name of Tivian by passing its name to the press, claiming that Tivian has contaminated the environment with PCS's, which our company does n ot use. Tivian Laboratories has filed a $20 m illion dam age suit against EPA fo r this release o f false informa- tion to the public. Tivian has further requested the U.S. Marshall's Office in Providence, Rhode Island, to issue a warrant fo r the arrest o f EPA personnel fo r the violation o f Constitutional laws and con gressional statutes in its dealings w ith Tivian. It is ironic that the company most responsible fo r the manufacture and distribution of PCB's in this .country continues to do so, but a small company which does not handle PCB's is harassed. A t our request, the EPA supplied us w ith a list of companies to whom questionnaires were sent. However, the names of certain firms, as we heard again yesterday, were excized from the list. Is it hot strange that the name o f one company is pejora tively released to the press while the identity of others is concealed? Why? Is it not capricious that under our unelected administration in Washington, these names as well as those o f the companies dealing with the Arabs and cooperating w ith the Arab boycott of Israel are kept secret? The objectives o f EPA are w ithout a doubt useful, necessary, and w orthy, and we still support them, but we w ill not submit to an agency which is so blatantly being used as a tool of an unethical policy. Figure 1, literature handed out by Tivian Laboratories, is on the following pages. GENP 005939 385 774587 November 1 8 , 1 9 7 5 PROVIDENCE COMPANY HITS BACK AT EPA FOR IMMEDIATE RELEASE Tivian Laboratories of Providence R.I, today announced that it has initiated actions against the Evlromental Protection Agency end Hr Michael Deland for allegedly ruining the Company's reputation and its business relations with what the President of the Company described as unfounded, hysterical harrassment, which resulted in a newpaper story instigated fay the EPA. Specifically, a $20,000,000.00 claim has been filed against the Environmental Protection Agency for damages. The newspaper story was released to the Providence Journal Bulletin alleging that the Company contaminated the environment with PCB's, which, incidentally the Company does not deal with. Tivian described the story as highly exageratad. Furthermore, the Company has requested that tha-U 3. Marshall's offlea, and particularly Marshall Vfyatt, 305 Federal Building, Providence, R.I. issue a warrant for the arrest of certain Environmental Proteotion Agency Personnel such as Michael Deland New England Enforcement Officer for violating various sections of title 18 of the U. S. Code, namely Section 242, "Whoever, under color of law, statute or ordinance, regulation, or custom, wilfully subjects any inhabitants of any state to the deprivation of any rights, privileges, or immunities secured or protected by the Constitution or Laws of tho United States. shall be fined no more than $1000 or imprisoned on# year or both," Section 2hl, "If two or more persons conspire to injure, opress, threaten or intimidate any citizen in the free exercise or enjoyment of ar.y right or privilege secured to him by ths Constitution or laws of the United States ...they shall be fined no more than $5000 or imprisoned not more than ten years or both." Andrew J. Mole chin sky, constitutional attorney for Tivian Laboratories stated that the EPA harrased the Company with registered letters which were Figure 1. Tivian Laboratories handout. 386 774588 (2) refused by Tivian. When Tivian requested the exact contents of these letters and their nature , they were not given a definite answer as to their content. After Tivian had refused these letters, a letter was served upon Tirian by all.S. Marshall, which contained a very lengthy questlon&lre fora. Melechlnsky charges the EPA with several Constitutional violations In sending out the fora particularly Amendment XXII of the U.S. Constitution, which states "Neither slavery nor involuntary servitude.... shall exist within the United S t a t e s . A n y involuntary response to the subject letter would constitute involuntary servitude. Meleehinslcy further maintains that it is beoonlng s disgusting praetics for many states snd federal agencies to harreso businessmen with lengthy fo r . He asks 1. Do not such fora adl to a tax bill which is already fantastica lly high? 2. Who pays companies for the time and effort required for filling them out? 3* If such funds are available, isn't that a further unwarranted expenditure of tax monies? h, How can governments Justify adding another nuisance load to the many which various governmental agencies are already seeking to impose on businesses? 5* Isn't this an inv asion of privacy? 6. What Constitutional authority la there for such forms? The claim against EPA has bssn filed fay Tivian's Vice-President of Legal Affairs, Paul Wallins. Marvin Antelman the President of the Corporation, hss stated that he believes that the Agency harrassed him because of his constant criticism, In his capacity as an officer of the National Leadership Conference for The Security of Israel of Kissinger and Ford for their hard line against the State of Israel and Commerce Secretary's Mortton's support of the Arab Bo ycott. Antelman stated that the Company will attempt in its litigation to document this. In a terse reply to Michael Deland Antelman stated' "This most recant incident smacks very much like that of a medieval antiaamitie libel Figrel. (con.). 387 774589 GENP 005941 O) cuch as1the Jens poisoned the wells.** Antolman further has stated that he views EPA oxtromism as following in the spirit of Karl Marx who wrote MA V-rld without Jews", and Marx equated Jews with capitalism and urged their destruction. Acusing EPA of adopting, a atdlev&l scenario in which the capitalist replaces the Jewi Antelman stated "This is one Jew who does not pollute the wells and who refuses to be intlni- ti dated by an nti-serdtic EPA blood libel* and accused EPA of attempting to dishonor responsible businessmen and to portray them before the public as poll uters. Furthermore, Antelman stated It would be a good idea for Congress to investigate Intensively the backgrounds of some EPA people, as he has found that there are members of the EPA today who havo had past left wing associa tions with radical militant anti-business groups such as the filaok Panthers and S.D.S as well as strong Communistic leanings or who have worked for various foundations whose main programs and goals appear to be the destruction of American business end the substitution of a Socialist or Communist state hers In the ti.S. end who fund radical organisations Antelman feels that while it is true that there era irresponsible Individuals who have polluted the environment and, that measures should be taken to improve the environment, the EPA smacks of too much hsrrsssment end too much hysteria and has substituted realistic objectives with Impossible and technologically unfeasible goals 'Above ell. If ther are polluters that muat be dealt with they should not be denied their Constitutional rights in our society. Instead! EPA Intimidation has resulted In vast destruction of the Industrial capacity of the United States and has weakened our economy. Melechinsky in his reply to Marshall Wyatt eccused S>A of practicing a vicious form of extortion churacti.ristic of a totalitarian government Figure 1. (con.). 388 774590 IMOtlnvnWv/1J,ru). il--.rl-TV- Iwt J. Vj>'L P r o v id e n c e i'ir m given ultim atim i on data request ' Y ROBERT FRII1ER1KSEN- \ *r* consenting, or complying, with the cements. PROVIDENCE - Tivian La boratories. Inc. 33(1 Silver Sp ring St., was idrnlifird yrstre*. day as the only firm in the' nstimi that has ignored govern* mem requests lor data on h ig h ly to x ic PCBs -- polychlorinated biphenyls. As a result, the Envi ronmental Protection Agrney has formally ordered officers of the firm, said to be a "major PCD user," to supply the data, or face penalties of up to I2S.000 a day, a year in jail, or both. Marvin S. Antrlman of New* ton. Mass., president- of the tix<year-old chemical manulae* taring firm, said It does not use PCBs in Its business of making plating solutions for the jewelry tnd ekttronics industries. He confirmed that two cer tified EPA data request letters were ignored because of company policy against acsepting certified, or registered, tellers on grounds (hat Hus night be interpreted legally u Antdman also confirmed that a IIS marshal had served the formal EPA order, but said, "It was not properly served be* cause It was not placed in my hands, as Is required. I read It and w ill respond, however." He accused .EPA and the federal Occupations! Safety and Health Adm inistration of "harrassini and bugging" him hreause of his past criticism of them and of President Ford and Secretary of State Henry Kissinger for ihetr'hzrd treat;' ment of line). The stale Health Department, which was notified by EPA, but has taken no action (n the case, said the firm appears to be on a city sanitary-storm sewer that overflows Into the Moshassock River alter heavy rains. Antrim said, bowrvrr. that only domestic waste from twotoilets and two sinks goes into the sewer. Laboratory wastes are haulrd away. "We don't use any PCBs. We dont put any Ip the sewer." he said. Blake Bit. of EPA'l Wash ington office, said Tivian La boratories, was one of 81 firms, including eight in New England, that were sent letters in August, requesting PCBuse and disposal data for use in developing controls because ot growing concern over effects oo public health. . Figure 1. (con.). Tivian was the only one of. the 84 firms that Ignored the letters, dri^ile sevrral followup phone cills by EPA's Wash ington and Barton offices before the lonm l order w u Issued, be said. The firms' names were taken from customer lists ot the Monsanto Chemical Co. the nation's largest PCB manufac turer.'U.5. Customs and EPA hazardous materials .-data. Biles said. PCBs are chlorinated hydro carbons resembling DDT, which EPA banned in 1073, the same year it limited PCBuse to closed electrical systems to reduce wa ter and fish contamination, ac* cordiny, to recent news release fay John A. S. McGlennea. EPA regional director in Boston. Health effects associated with PCBs Include eye discharge, acne, ulcers ot the uterus, ab normal akin pigmentation and reproductive failures. New York recently urged the public not' to tat Striped bass and certain other fish from the Hudson River and Lake Ontario because of dangerously high PCB levels, McGlesnoo noted. Because eoma striped bass spawned In the Hudson Rivermigrate to New England waten. extensive tests have ben started to determine PCB levels b food fUh here, be said.' *r "Final results of the testing w ill not lie available for a few* months, but preliminary data Indicate that PCB levels are well below the fire parts per m illion tolerance level es tablished in 1972 by the US. Food and Drug Administration," McGlennon said. "Three Is no need for New Englanders to atop eating striped bass or any other fish because of possible PCB cortamiiutioo." he raid, but added that It b crucial to continue existing controls and may be oecrm ry to extend them as a result o( current Budics and tests. GENP 389 774591 O o VO -P Z 6S fr W 6S00 IV IA N UIIAIOUIIS WC. 14011 4 2 1 -1 3 0 * ' November 1,1975 United States iarshal ATX1I: Marshal Wyatt 305 Federal Building Providence, Abode Island 02901 Jeer S i n I a m in receipt of your Certified envelope No. 155215, containing a lcttor from the United States Environmental Protection Agency to Tivlan Laboratories, Inc., dated October 16, 1975 end a four page brochure entitled POLYCHLORINATED BIFHSilL (PCB) COMPOUMJS O A MIXTURES. As you s:y now realize, after our phone conversation of 10-27-75, the E.P.A. letter has* no validity or authority under the United States Constitution. In referring to a non-existent "authority" contained In the unconstitutional Veter Pollu tion Control Act and the equally illegal Clean Air Act and in demanding that certain (private) information "mist be provided" within certain time limits, the Environmental Protection Agency is practicing a vltflous form of extortion, charecterlatic of a totali tarian government. By its unsupported attack on chlorinated terphenyls and its unwarranted demands for con fidential information and trade secrots, the Environmental Protection Agency ie break ing numerous lows, some of which follow! The Constitution of the United States of Americai 1. Amendment IV, "The right of the people to be secure in their persons, houses, papery and effects, against unreasonable searches and seizures, shall not be violated, .... " The demands in the E.P.A. letter constitute on a t t e s t e d search of Tivlan Laboratories, Inc4, and seizure of our trade secrete. Figure 1. (con.). u(O \ -2- sa IVIAM lAiOBAioans inc PROVt4ID0iNt C-Cla, iM-.isI.oOa il 2. Amendment IV, ''no Warrant shall Issue, bit upon probable cause, supported by Cath or affirmation, and particularly describing the place to bo searched, and the persons or things to be seized." The E.P.A. letter is not a warrant and has no claim to legality. 3. Amendment V, "No person shall b e .... compelled in any criminal case to be a wit ness against himself, .... " Tivian Laboratories, Inc. is made up of people who enjoy the same rights collectively as we do individually. Any possible adverse information might be used agclnst Tivian Laboretorlea, Inc. Ve would be violating the Constitution end our own bast Interests if we answered the E.P.A. letter. A. Amendment V, "No person shall be ..... deprived of liberty, .... without due pro cess .... n Inis includes the liberty to Ignore the illegal demands of the E.P.A. letter. 5. Amendment IX, "The enumeration In the Constitution, of certain rights, shell not be construed to deny or disparage others retained by the people." This law guarantees the right of Tivian Laboratories, Inc. to do as we please without government Interference of the kind represented by the E.P.A. letter, unless ve clearly do harm to others. The E.P.A. letter contains no claims that Tivian Laboratories, Inc. has harmed anyone. We cb not have to prove our innocence. The Intent of the E.P.A. letter is to coerce us into producing such proof. 6. Amendment X, "The powers not delegated to tho United States by the Constitution :.... ere reserved .... to the people." This means that the government cannot demand infor mation from Tivian Laborntorlee, Inc. unleaa it haa the backing of exact wording in the Constitution. There is no wording in the Constitution which backs or authorizes the Freedom-destroying provisions of the Federal Water Pollution Control Act and Clean Air Act. 7. Amendment XIII, "Neither slavery nor Involuntary servitude, .... shall exist within the United States, .... " An y involuntary reaponae to the subject letter would consti tute involuntary servitude. Figure 1. (con.). 774593 SH5S00dN30 774594 9V6900 gM -> eg c rv j a a i ^ T ^ l l V I A N LABORATORIES INC pmovioincc. m. i. 01104 MOII 421.1300 Title 18, U. S. Codei 8. Section 242, "Whoever, under color of lew, etatutu, or ordinance, regulation, or cus tom, wilfully subjects any Inhabitants of any state to the deprivation of any rights, privileges, or 1m u n i t i e s secured or protected by the Constitution or Laws of the United S t a t e s .... shall be fined no more than $1000 or imprisoned one year or both." 9* Section 241, "If two or core persons conspire to Injure, oppress, threojben or intimi date any citizen in the freo exercise or enjoyment of any right or privilege secured to him by the Constitution or lavs of the United S t a t e s .... .they shall be fined no more than $5,000 or Imprisoned not more than ten years or both." Also, consider the nuisance, Inconvenience and additional expense which a conscientious response would entail. As Tivlan Laboratories1 Chief Executlvo for Federal Affairs, I am assuming responsibility for declining to respond to the latter of the Zhvironmental Protection Agency. As stated previously, the "laws" quoted ty the E.P.A. are illegal. "An unconstitutional law, ..... is as inoperative as if it had never been paseed .... imposes no duties, con fers no rights, creates no office, bestows no power or authority on anyone, affords no protection, and Justifies no seto performed under i t .... " ' (l6 A m Jur 2d See. 177) The Constitution provides that (as stated in 16 A m Jur 2d Sec. 177) "Ho one is bound to obey an unconstitutional l a v .... 1 The Constitution la the lav which ve will obey, and that lew guarantees the right of Tivlan laboratories, Inc. to stand up against the kind of tyranny represented by the E.P.A. letter. Figure 1. (con.). IVIAM LAIOIAtOXItS INC. PHOwiHDInC I. n4. I. 01*104 ii440iiii oaaii-.iiaaooaa has broken cany leva, rather than assist In the peraecutlon of llvlan Laboratories, Inc., which has not broken any valid laws and which has not done ,hara to anyone. 1 will be plocsed to sign the cocplalnt. -Constitutionally Tours, Info tot Ur. Robort IhoEpson Environmental Protection Agency John F. Kennedy Federal Building Boston, Massachusetts 02203 Hr. Jeffry 0. Killer. Acting Assistant Administrator for Ehforcement U. S. Ehvlrowaeotal Protection Agency Washingtoc, D. C. 20^60 Figure 1. (con.). 1^6500dN30 774595 THE NEED FOR COST-BENEFIT ANALYSIS IN TOXIC SUBSTANCE USAGE A. Eatock* INTRODUCTION Yesterday, mercury had the limelight; today, it is PCB's; tom orrow--what? We face a recurrent problem in dealing with toxic substances in the national-social context. Thus, this paper discusses the overall problem o f toxic substances rather than just PCB'-s. The purpose o f this paper is threefold: a. to show the absolute necessity o f cost-benefit analysis in achieving an equitable balance be tween private and social costs and benefits; b. to illustrate the need in cost-benefit analysis fo r researchers to be specific in delineating the chain of consequences together w ith the risks involved in toxic substances; and c. to illustrate the elements of a simplified costbenefit analysis based on PCB's. Conceptually, cost-benefit analysis is quite simple in that one places a value on the costs o f an action or program and a value on the benefits resulting therefrom, If the dollar benefits exceed the dollar cost, then one proceeds w ith the action or program. However, simple ideas do tend to get complicated in practice and cost-benefit analysis is no exception. One im plication, which w ill be ignored hereafter, is what interest rate to use in finding the present value o f future benefits such that they can be compared to the costs. Another complication is how to value intangibles (such as good health and aesthetics) that do not have an established price from being traded on the open market. There is no easy, or even commonly accepted, method fo r valuing the unintended effects o f toxic substances resulting in social costs. This results in considerable conflict due to the judgmental valuing in estimating social costs and, frequently, th ignoring o f the whole issue of intangibles. MAGNITUDE OF THE PCB PROBLEM To illustrate one aspect of the magnitude o f the PCB problem and to lay the groundwork fo r a cost-benefit analysis, a hypothetical case on the accumulated PCB loading to the Lower Great Lakes from U.S. sources is worked out. There are three categories of inputs as follows: "Social Science* D ivision, Inland Waters DrectorataO ntario Region, B urlington, O ntario, Canary L7R 4A6. 1. Uncontrolled Imports; a. Estimate (ref. 1) o f uncontrolled imports of PCB's as part o f other products in 1972 s 375,000 lb. b. 1971 U.S. population in the Lower Great Lakes Basin (ref. 2) 13 X 10* a 6.3 percent of total population. c. Lower Great Lakes water volume converted to weight a 4,575 X 1012 lb. Assumptions: a. The PCB distribution is similar to the population distribution (ref. 2). b. The continuing flo w o f im port products results in a continuing equivalent amount going into the environment. c. T hirty percent o f PCB's are o f the persistent (nonbiodegradable) types (ref. 4). Then, 375,000 lb o f uncontrolled imports result in an equivalent lake water PCB load o f 1.5 ppt. Please note the word "equivalent/' in actual fact, the lake water has a very much lower level since PCB's tend to accumulate in the biota and sediment. 2. Existing Pool: It is reported (ref. 3) that the U.S. consumption was approximately 1 billion lb o f PCB's during the 40-year period from 1930 to 1970. The majority o f this PCB consumption must now be in the environment, prim arily in garbage dumps and sediment. If 0.1 percent of this pool is released annually from the various sources, then the equivalent lake load is 4 ppt PCB's in the water. 3. Continuing Use: The third category is continuing authorized use fo r transfqrmers and power factor capacitors, which con stitute a consumption of more than 50 X 10* Ib/yr (ref. 4). An assumption o f a 0.1 percent leakage rate to the environment results in an equivalent lake load o f 0.2 ppt in the water. This is the U.S. loading on the Lower Great Lakes, to which the Canadian contribution must be added. Keeping in mind that these figures are based on unsupported assumptions, it is still interesting to compare them w ith the proposed water quality target of 1 ppt. It does indicate that, since PCB's are so persistent, the problem w ill have to be lived w ith fo r a long time. How fa r to go in rectifying the problem is where CtRNP 005948 394 774596 A COST-BENEFIT FORMAT Benefits The chief benefit of PCB's is their nonflammability in the liquid phase. This has resulted in onfy PCB-cooled transformers and power factor capacitors being allowed in the upper floors of tall buildings. On similar safety grounds, it is the only fluid permissible for use in electrostatic precipitators that keep the particulate pollution from going up the stack of most industries. No estimates for the value of these benefits, and others which are not considered, are readily available, but they must be substantial or the OECD (ref. 8) group would not have recommended continuing these uses. While not ignoring the necessity of confirming these benefits, the cost-benefit analysis may be simplified to the tradeoffs between direct costs o f controlled usage and the cost of damage to the natural and human environment. A t this point, the three sources o f contamination can be incorporated in the cost-benefit analysis, as shown in table 1. These figures give some indication of the most cost-effective tradeoffs between various control methods and damages to the natural and human environment. COST OF CONTROLLING USAGE The cost of controlling the authorized usages o f PCB's consists of the direct and indirect costs (table 2). The direct costs include containment devices to avoid leakages and losses; the handling o f contaminated containers, cloths, etc.; the decontamination of equip ment; the incineration of contaminated cleaning solvents, clothes, etc.; and the cost of m onitoring and policing these activities to minimize leakages to the environment. Indirect costs could include the m in itoring and policing required to reduce unauthorized imports of PCB's as part of other products, and sewage incineration to reduce the environmental levels o f PCB's. This latter indirect cost is o f , considerable interest since hightemperature incineration appears to be the only practical method of destroying PCB's, and sewage sludge incinera tion has the potential to break the continuing cycle of PCB through the environment. In Ontario, approxi mately 40 percent of the sewage sludge is incinerated, principally by the larger centers that are the main sources of PCB's. Unfortunately, temperatures well in excess of 860 C are required to destroy PCB's and the normal incinerator operation is just at or below this temperature. Further, since considerable energy is required to burn the wet sludge, optimization of sewage p la n t operations dictates operating at even lower operating temperatures as the cost of fuel increases. Obviously, there is a need to optimize sewage plant incinerator operations w ith the destruction of PCB's included in the criteria. The higher cost of fuel can possibly be alleviated by exhaust gas heat recovery to dry the incoming sludge, which apparently is not common practice at present. SOCIAL COSTS Social costs, including damage to the environment, as shown in table 3, are again split into direct and in direct costs. The direct costs include loss of commercial fishing and loss o f recreational industry business due to the contamination by PCB's o f the larger predatory fish which are at the top o f the bioaccumulation chain (ref. 5). Another direct cost is the loss o f foodstuffs due to contamination during production and packaging. Should PCB's continue to be dispersed to the environment from sewage incineration stacks, and sewage sludge utilized as fertilizer, there 5 a good possibility that the level of PCB's in m ilk, presently as high as 0.1 ppm near indus trial centers in southern Ontario, w ill continue to rise and result in value lost when the m ilk is not f i t for consumption. The occasional poisoning o f industrial workers working w ith PCB's, or the poisoning of individ uals in the general population due to accidental spills, gives rise to costs from lost work time and medical atten tion. Indirect costs (table 4) include such things as fish-eating birds that have all but disappeared from the lower lakes; these include osprey, bald eagle, cormorant, bittern, herons, and loons (ref. 6): The herring gulls would also disappear except fo r the influx from the East Coast and the Upper Great Lakes (refs. 6,7). There are tw o aspects related to the loss o f these birds. One is that, if the predator fish population declines, the alewife population w ill increase, and if the gull population declines, who is going to clean up, and at what cost, the mess resulting from massive alewife dieoffs such as we had a few years ago. This is what can happen if the balance o f nature is disturbed. However, the main interest at the moment is the social cost aspect. How does one cost the aesthetic value o f the bird population? This problem is typical o f the m ultitude o f social costs that must be considered, and there is no easy answer or agreement on methods. EXAMPLE OF SOCIAL COST ANALYSIS One approach taken to illustrate the problem is as follows. According to the Federation o f Ontario Naturalists, there are approximately 750 bird watchers 395 GENP 005949 774597 T a ble 1. Fu nctio n a l organizational model B e n e fits Due e x is tin g pool Due continuing usage Due u n c o n tro lle d im p o rts T ransform er and power fa c to r capacitators safety Reduction in p roperty loss Reduction in loss o f l i f e Reduction in mdeical costs Reduction in employment loss Reduction in p o llu tio n (e le c tro s ta tic p re cip itato rs) Reduction in cost o f c o n tro llin g p o llu tio n Table 2. Costs of controlling the authorized usages of PCB*s Risk (c o s t) due existin g pool Risk (c o s t) due continuing usage Risk (c o s t) due u n c o n tro lle d im p o rts Cost o f c o n tr o llin g usage . D ire c t costs C ontainm ent Contaminated a r tic le s disposal D e c o n ta m in a tio n In cin eratio n M o n ito rin g and p o lic in g In d ire c t costs M o n ito rin g and p o licin g (im ports) Sewage sludge in cin eratio n 396 774598 Table 3. Social costs of PCB's Risk (c o s t) due e x is tin g pool Risk (co st) due continuing usage Risk (c o s t)due u n c o n tro lle d im p o rts Cost o f c o n tro llin g usage Social costs (en viro n mental damage c o s ts ) D ire c t costs Commerci a l fish eries R e c re a tio n in d u s try Contami nated food Worker lo s t tim e Worker medical costs N o n re c y c lin g of paper in Ontario who report on migratory birds and spend approximately 500 hours a year observing; there are another 15,000 bird watchers who pay $12,00 per year to belong to the organization, and it may be arbitrarily assumed that they spend 10 days a year watching birds, fo r a total of 60 h r/yr. Assuming this Is an exponential function tailing o ff to the 8 m illionth person in Ontario, who never looks at birds, it can be calculated that 125,000 hours are spent in bird watching. Again being arbitrary, it could be assumed that 10 percent o f the pleasure in bird watching fo r Ontario residents is lost with die loss of the previously mentioned birds. The loss is then 12,500 hours o f enjoyment, and there is still the problem o f putting a value on it. In the past, economists have attempted to value recreation on the basis o f travel costs, money spent on equipment, die leisure hours tradeoff against employment income, and many other methods. The potential loss o f employment income probably sets the upper lim it, while the casual obsemc, at no cost, sets the lower lim it. A t this stage, no attempt to put a value on leisure hours wit) be made. The point to be made here is that the researchers have to provide risk data on the consequences of varying levels of toxic substances in the environment. W ithout the probabilities o f resultant consequences being specified, no cost-benefit analysis can be performed a~d resource allocation cannot be optimized. Note that the incremental increases in social costs in the Legal Usage columns and the Uncontrolled Imports columns in the figures can be balanced against the same columns in the Cost of Controlling Usage subsection. Alternatively, the cost and effectiveness of sewage sludge incineration may result in a considerable reduction in the Social (Risk) Costs such that other Controlling Usage Costs may be reduced. The combinations and permutations are manifold, but operational research methods are available to find the optim um least-cost arrangement. STRUCTURE OF TOXIC SUBSTANCE RESEARCH In conclusion, it w ill be indicated how cost-benefit analysis relates to the overall scheme o f things, along with a few comments about the organizational structure. The follow ing (figure 1) shows a conical structure w ith the research disciplines at the base, leading up through Economic and Social Cost and Social Goals Policy to Legislation and Regulation at the apex. It may be observed that, at present, the research 397 774599 GENP 005951 Table 4. Indirect costs of PCB's Risk (c o s t) due existin g pool Risk (c o st) due continuing usage Risk (c o s t) due u n c o n tro lle d im p o rts Cost o f c o n tro llin g usage Social costs (environ m ental damage c o s ts ) In d ire c t costs Aesthetics - loss o f osprey, bald eag le, cormorant, b itte r n , heron, loon R ecreati onal fish in g R e c re a tio n a l hunting Cleanup .o f alew ife d ie o ff Human - lo ss o f physical w ell-being (in c lu d in g a b o rtio n s ) Loss o f mental w ell-being Loss o f s o c ia l w ell-being tpeonrdtastitoon bmeofdrealg.m{seenctoendd alenvdeluinnctohoerdcoinnaet)e,dw. hTichhe sthraonwss how a particular toxic substance cycles through the tniaetutroagl,etbhieorloaglilcatlh,eanvdareiocuosnodmisiccipelinnveisr.onTmheennt,extetnldesvetol, economic and social cost assessments, should also pro vide a unifying force among these disciplines, as well as linking the research with the social goals. Further, the ultimate unifying research objective may be stated as: To determine the tolerable level of specific toxic substances in the environment with a holistic approach that balances die direct and indirect, private and soda! costs and benefits relevant to the use, or nonuse of the substance. tcroaolirzdeCidnleabateroldyty,oxtiosicnmesueedbetestdathniincseeoarbecjsheeccatiorvcuehn, tasrmoymotonegifnottrhemegrvaoatfericaoenunds agencies and disdplines involved. These bodies would specify and insure the planning. Implementation, and cinodnutrdaoi.lngs:ttparhagretoeenjgecoyciretgssfa;oanrnizdaatcsihouinbeovbainjnegdctitavhleelsocraeamstieooannrcghothfoebrejvesacertaiiorvcuehs, b. .the identification and effective communica tion of available information and data; c. the periodic communication of the overall satnrdategy and progress in meeting objectives; .^ $ * % 398 % $$ 7 7 4 6 0 0 Legis lation & Regulation Social Goals Policy Economic & Z& Social Transportat ion Costs Zo --- ------------- Model Analytical u .^^Inventories /\ /Sew age ( Levels) \ M easu re-/^ m e n t s > ^ emjca| \ / Treatment \ y interaction \ Contributing Organizations >^(Synergism & \ -- Federal Gov't Dept's / Antaaonism) l -- Provincial Gov't Dept's \ &AV1 Toxicology N^Microbiological | \ Human .xy^Tox.i- BioKDegradation logicar^Accumu - / \ cology Degrad - \J a t io n / -- Educational Institutes Industry Private Groups >/ / Aquatic & ation & x. y ^^Terrestrial Accumu- y S lation 774601 6S00 dNHO Figure 1. Toxic substances simplified function organization. d. the formulation of recommendations based on the research findings, and their communica tion to policy and decisionmakers. Clearly, to meet this objective, some form of centralized body is needed in each country to integrate and coordinate toxic substance research among the various agencies and disciplines involved. These bodies would specify and insure the planning, implementation, and control strategy fo r achieving the research objective, including: (a) the organization and allocation of research projects and subobjectives among the various agencies; (b) the identification and effective communication of available information and data; (c) the periodic communication of the overall strategy and progress in meeting objectives; and (d) the form ulation of recommendations based on the research findings, and their communication to policy and decisionmakers. A il the elements fo r the lead agencies, the Depart ment o f Environment and the Environmental Protection Agency, appear to be present, such that they could grasp the authority and carry out the above objectives. It is suggested, as a first step, that each o f these lead agencies appoint a Toxic Substances Research Coordination Com mittee. Both these national committees should be endowed w ith the power, through interdepartmental agreements, to carry out their objectives effectively. If we can proceed in this direction and if everyone pro motes these objectives, an effective solution to the toxic substances problem w ill be realized. REFERENCES 1. Statement by G. E. Schweitzer, Director, Office of Toxic Substances, Environmental Protection Agency, during hearings on PCB's by Wisconsin Department of Natural Resources, August 29,1975. 2. Population Estimates fo r the Great Lakes Basins and Their M ajor Tributaries, Social Science Series No. 1, Inland Waters Directorate, Canada Centre fo r Inland Waters, 1973. 3. Kevin P. Shea, "PC B," Environm ent, Vol. 15, No. 9 (November 1973). 4. I. C. T. Nisbet and A. F. Sarofim, "Rates and Routes of Transport of PCB's in the Environment," Environm ental Health Perspectives, Experimental Issue No. 1 (April 1972). 5. Great Lakes Water Q uality, Third A nnual R eport to the International J o in t Commission, Great Lakes Water Quality Board, July 1975, p. 641. 6. Glen Agnew, Federation o f Ontario Naturalists, Toronto, personal communication, November 1975; 7. D. P. Peakail, "PCB's and Their Environmental Effects," CRC C ritical Reviews in Environm ental C ontrols, Vol. 5, No. 4 (September 1975). 8. OECD Council Takes M ajor Decision w ith Regard to the C ontrol o f Certain Toxic Chemicals, Organiza tion o f Economic Cooperation and Development, Press/A(73)3, Paris, February 14,1973. CHAIRMAN TIM M : I have just a few comments on what kind o f comes through to me, about three things really. Hopefully it came through to you on the various types o f presentations we've had. Ob viously we are dealing w ith a very real problem that impacts the livelihood of people in this country, other countries, etc. Another big thing to come through was that the technical people and the sci entific people have got to improve our communica tion o f the scientific facts that we know to the people that are affected. I th ink this is probably the biggest frustration on the part o f the average c iti zen--he just doesn't understand what we're doing or what we find out or maybe does not know what it means. But I think we've got to continue to try. Finally, no matter what action is taken, it w ill have an adverse effect on some people, which of course is an impact on the environment. I th in k like the Senator says, EPA is in a "n o w in " situation as far as everybody is concerned. But I th ink we've learned some things tonight and gained some com ments'good and bad that are going to help us to go forward. Carlos wants to have some additional com ments and then w e'll open to the floor. MR. CARLOS FETTEROLF: I am very disturbed by an item in the statement o f the man from the Hud son Valley representing the Sloop Restoration Society. He told us that Ogden Reid, Commissioner o f the New York State Department o f Environ mental Conservation, applauded the Canada Depart ment o f Health and Welfare fo r establishing its fish O O KJ\ v> 400 774602 .7 PCB regulation at 2 ppm and that Reid felt the numlIxiramshoaulsldo lxd:is1tuprpbmed. by the Indiana Senator urging that wr; all go home and pound on our legis lators tor action on PCB's. There may not be one immediately correct solution to the PCB problem, but there is a best solution. The best solution is one which recognizes all phases of the problem; weighs the advantages, disadvantages, and costs; evaluates the impacts on the environment, the industry, and the people. I don't think Ogden Reid can do that o ff the top of his head, nor do I think a State legislature can do it w ithout great thought and the wisest technical guidance. I'm worried. I don't want to see a panic situation. I hope USFDA does not panic. Once regu lators deviate from scientifically defensible environ mental actions, everyone loses. We waste resources, we -trade one problem fo r another, and we create unnecessary costs and limitations on important seg ments of society. EPA must take some action. Hopefully, it w ill be scientifically defensible and not emotionally or politically motivated. MR. JOHN CHASTAM (Lake Erie Cleanup Committee, Toledo, Ohio): I represent the Lake Erie Clean Up Committee, Michigan United Conservation Clubs, and the Associated Yacht Clubs o f Toledo, Ohio. I wasn't going to get up to make any statement what soever, but after what I've heard here tonight, I feel very much like Carlos. Several years ago, you remember taconite was a big issue after the mercury scare. Everybody was under the impression that everything was all settled and all o f a sudden we had taconite. We got asbestos and that worried me. I contacted as many of the Governors and as many of the State officials as I possibly could around the Great Lakes fo r the simple reason that you people out there as well as me own a part of our Great Lakes. Industry doesn't own them, indivi duals don't own them, they're a collective thing that we all have to enjoy. I just want you people to know that the fight is ours. Industry should realize what its doing to the very people they need for help, the people that they employ. GENERAL CHAIRMAN BUCKLEY: I want to say about three words and they really are that I deeply appreciate your being here. Obviously I can't agree w ith each comment because there have been some mutually exclusive ones, but I certainly found it informative and really appreciate this. And tire other thing I have is a personal observation. I think you're an enormously courteous audience and you've sat, you've listened to views that were entire ly different from your own. I really enjoyed it, and thanks again. MR. TIM M : Good night. I got roasted literally as well as physically. OENp W)S9ss 401 774603 C O M M U N IC A T IO N S TO THE CONFERENCE 403 Preceding pageblank 774604 gBTP 005956 SOME A D D IT IO N A L COMMENTS W ITH RESPECTTO A M B IENT A IR SAMPLING FOR PCB'S .Gordon H. Thomas* The ORF, under contract to the A ir Resources 8ranch o f the Ontario Ministry o f the Environment, has conducted ambient air sampling fo r PCB's. The a m b ie n t a ir was sampled fo r gaseous constituents by metering the air through impingers containing ethylene glycol. In addition, sampling o f the ambient air fo r suspended particulates was performed concurrently w ith the mpinger sampling. For this purpose, a Hi-VoI suspended particulate sampler using a ' Senior Research Scientist, Ontario Research Foundation,Sheridan Park, Mississauga, Ontario, Canada, L5K 1B3. glass fiber filte r was employed. Standard analytical procedures for the extraction, cleanup, and separation of PCB's from interfering com ponents were followed. Final extracts were analyzed by gas chromatography using electron capture detection. Confirmation o f the presence o f PCB's in some of the extracts was obtained w ith the aid o f gas chromato- igraphy-mass spectrometry. PCB's were detected in both gaseous and particulate sample extracts. Levels found were as follows: Gaseous 0.9 2.6 ng/m3 Particulate 0.14*0.61 ng/m3 JACK TAY LO R : Gedcor Corporation markets a solvent swellable polymer manufactured by Dow Chemi cal Company that possesses the unique ability to absorb or imbibe a broad range o f hydrocarbons, including chlorinated ones such as askarels. The polymer, sold under the name "D ow Imbiber Bead," draws the hydrocarbon flu id into it's mole cular structure, thereby capturing and containing the hazardous substance. The sealoff attribute o f the bead allows valves to be manufactured that w ill allow water to pass and prevent free hydrocarbon escape into the environment. MS. DORCAS THOMPSON {private citizen): I would like to speak on citizen involvement awareness and communication. It is not enough to have hearings on toxic substances, pollution problems, energy problems, transportation. Ordinary citizens feel they have much to do. They w ill not get interested in any problems they should be concerned about, because they are not at all aware of the problems. If a problem such as PCB's is identified, EPA must issue "educational" public releases before hearings regularly to inform people of this threat to our health. Of registered attendees at the conference th e re are fe w Chicago suburban citizens--all . attendees connected w ith companies or agencies such as EPA. N ot one suburban environmentalist or health person is registered. Several citizens such as L W. Van Audobon are present. If dangers are identified, we need to be edu ca ted b y "decree,*" signs must be posted on all areas o f known PCB traces or presence--such as in air, parks, streets, buildings, beaches, water, mar kets, and fish and other foods. (We need to treat this similarly to the warning signs on cigarettes.) The knowledge of the presence o f PCB's in breast m ilk must also be imparted to hospitals and new mothers--if all of these warnings were posted w ith addresses of persons to w rite, people would be con cerned and would know their opinions and concerns are important. I disagree w ith Dr. Muir's concern over industry--he is compromising by his "p h ilo sophical" remarks. As we see Dow, Corning, and Shell have a new product (we are not so entrenched that we must consider economic factors o f comp anies). Relocate company personnel, reeducate per sonnel to new job, retread personnel, computerize information, and compare notes industry to indus try . A fter all, none o f our businesses were in busi ness 100 years ago (in the same States they are in today) so let us gear fo r change and not allow any in d u s trie s dangerous ecologically or environ mentally. Preceding page blank 405 774605 GENP 005957 LETTER TO CONFERENCE ON POLYCHLORINATED BIPHENYLS Susan E. Caswell Friends of the Earth, Madison, Wisconsin November 19,1975 I am sending this statem ent to the Environmental Protection Agency technical conference on polychlorinated biphenyls for the 200 members of the Madison, Wisconsin, branch of Friends of the Earth. We are deeply concerned about the growing PCB contam ination of rivers and lakes in the Midwest and throughout the country. We are particularly disturbed by the apparent high levels of these chemicals in fish and fowl taken from Lake Michigan and from the Upper Mississippi River. ( Both of these great bodies of water have been major sources for recreational and commercial fishing in the Midwest and provide the municipal water supplies for many communities. It seems to us that Irreparable harm has already been done to the sport and commercial fishing industries which utilize these water resources and that a very real threat exists to the health of persons ingesting PCB contaminated fish and fowl or drinking from PCB contam inated waters. We feel that scientific studies have proven the toxicity of PCBs to a wide variety o f wildlife including prim ates even at levels below the standards set by the Federal Drug Administration. That they are also toxic to man has been shown by the tragic Japanese experience. The fact that polychlorinated biphenyls are virtually indestructible by ordinary chemical or microbial processes means that they will persist in the environm ent for all tim e, and since their uses In industry axe so diverse and widespread, the possibility for environmental contamination seems to us to be even more serious in the long run than the analogous situation with DDT. Indeed, there is evidence that PCBs are already ubiquitous in the environ m ent-having been detected in the sewage o f all m ajor cities, in snow melts, In organisms from the A tlantic Ocean, as well as in fish and sediments of m any lakes and rivets. Therefore, we feel that the time to take effective action on this grave pollution problem is long past due. We favor an outright Congressional ban on production and use of PCB's, but in the m eantim e, we call on the Environ mental Protection Agency to develop a comprehensive monitoring program for Identifying sources o f PCB pollution of Lake Michigan and the Upper Mississippi River as well is other lakes and rivers and imm ediately begin to exercise its authority under the W ater Pollution Control Act of 1972 to regulate or eliminate PCB discharges. Thank you. /s/ Susan E. Caswell Friends of the Earth Madison, Wisconsin 406 774606 GETSFP 005958 LETTER TO THE ADMINISTRATOR OF THE ENVIRONMENTAL PROTECTION AGENCY Mrs. Meredith C. Tucker September 8,1975 Russell Train, Administrator U.S. Environmental Protection Agency Waterside Mall Washington, D.C. - - Dear Mr. Train: We are m ost concerned with the lack o f action the EFA is taking w ith regard to FCB pollution in Lake Michigan and other waterways. The seriousness of PCB pollution has been well known since 1972, yet nothing has been done to control th e release o f PCB's into th e environm ent. It seems clear that M onsanto Company is n ot going to voluntarily withdraw the chemical from the m arket; nor are im ports o f PCB's going to cease through inform ing industrial users ab o u t chem ical concentrations in o u r w ater. Much stronger enforcement measures are needed. Banning the use o f PCB's clearly seems to be the only real solution to the problem . Since substitute chemicals are available fo r all uses o f polychlorinated biphenyls, banning PCB's should present no real hardship. As a first step tow ard eliminating PCB's from Lake Michigan and other w ater sources, we advocate participation in the N ational Conference on PCB's. Industrial users should be alerted to th e dangers o f PCB's and to alternative chemicals they could use. In addition, the public should be aware o f the dangers the chemical poses In use or through human consumption of fish and water. We urge y o u to take strong an d im m ediate action to elim inate the environm ental pollution o f PCB's. T hank you for your attention to this m atter. Sincerely, x : Senator Percy Senator Stevenson Lake Mich. Fed. /s/ M eredith C. Tucker (Mrs.) Pesticide Control Committee Chicagoland Chapter Friends of the Earth 498 N. Inverway Road Inverness, Palatine nUnois 80067 GENP 005959 407 774607 G EN P 005960 LETTER TO LAKE MICHIGAN FEDERATION Chairperson, Pesticide Committee Knob & Valley Audobon Society of Southern Indiana November 17, 1975 Lake Michigan Federation 53 W .Jackson Chicago. Illinois 60604 Dear Sirs, By unanimous decision the Knob & Valley Audobon Society of Southern Indiana voted to advocate the ban of PCB's or the severe restriction of their use. This recom m endation is based on several factors: 1. The perm anent nature of PCB'S. They are not biodegradable and are stable to heat making them very difficult to be destroyed. 2. The high levels of PCB's already found in fish in the Hudson River, Lake Michigan, and other bodies of water. 3. The toxic nature of PCB's to hum an life. If possible please have our position presented at the EPA conference in Chicago. Sincerely, // Chairperson, Pesticide Committee Box 237 Linesville, Indiana 47136 LETTER TC THE ENVIRONM ENTAL PROTECTION AGENCY, REGION V Douglas V. Whitesides, Jr. November 16,1975 U.S. - EPA, Rgion V Chicago, Illinois Re. PCB Problem Confrence November 19-20-21,1975, Chicago, Dlinois G entlem en: Due to the buildup of PCB's (polychlorinated biphenyls) in the environm ent and the serious problem s caused by this material, I believe that its manufacture and use should be completely banned immediately. Surely the world will be a much better place w ithout this extrem ely environmentally degrading substance. TTiank y o u , /*/ Douglas V. Whitesides Rt. 1, Box 296 Lanesvllle, Indiana 47136 408 7 7 4 6 0 8 **