Document baRQkx9nOwQdb4QXRg6mvzYao

- kv */ / * 4,j$*rtrid %rVf Polychlorinated biphenyl residues in silos in die United States v :. . . . . *y .-.. . . ; ; : L. B. WiLlett* and J. F. Hess, Jn.*^ " > Contents 1. luUwlurtton .. It. PCB-cootalnini (k> OOattng >..._.--____ 138 III. .The Contamination process*--------------------- ..--V.V...... 139 IV. Ciwi and PCD residin'*___ _....-------------------------- --------------------- 140 V. Regulation of PCB'a ............------ .. '142 ' VI. Impact of FCD-ctMrtatnfiwted dim___ '--......_____--------------------- 143 Summary ..............------------ -----------.................... 148 v Reference* ....----------------------------- ------- ...--.....-------- ....---------------- - 148 V. ..W 1. Introduction - . , . Polychlorinated biphenyls (PCB's) were described in the scientific literature In 1881 by Sciimiut and Shultz, and successful commercial production was achieved in 1030 (Huiihaiu) 1905). The manufacturer of these compounds was Swan and Company who recommended their use in commercial applications for proitectivu coatings, Waterproofing, fliuncproofinR, electrical Insulation, and adhesives along with multiple mistvUum'mis uses (Pknnino 1030), PCB's were marketed under the trade1 iiuiik* of Aroclors hy Swaii and Gnmnpny and then by Monsanto Cnmimny. Chemically the Arodore are relatively Inert; thus, they are not hydmty/cd hy water and tltey resist alkalies, acids, and other strong corrosive chemicals. They are not appreciably volatile at normal ambient temperatures and have boiling points which sire in excess of 275 C (Mon santo Company). They are stable to long periods of heating and can be disfityed at oidinuty pressure without any csttbonlzation oi* decompositfon. PCfls are insoluble in aqueous media and very soluble in hydrocarlKui solvents. Therefore, these chemical compound* have the chemical * Department of Datry Science, Qbto Agricultural Btutfdi and Development tenter, Wooster, Ohio 44091. Approved a* Journal Article no. 87-74, OhtoAgri* cultural Research and Development Center. Wooster, Ohio 44891. , American, Burt and Janet Co., L.P.A., Canton, Ohio 44702. V) 1978 by Springcr-Vcrlag New York Inc. . ''V-' . .* v``1A. ` *: ' * . . . .. ifSlf! IV QSW 032130  ',>'... :/'. **;f****"'%.;.,-. . ' ' yfr+ftr. : and physical characteristics to be persistent in the enVlraijlment and ac cumulate up the food chain (Pkakall. and Lincer 1970). . Nesarr and Samoam^ (197$) estimated that sale* of PCBV in North America between 1930 ana 1970 totaled 5 X 10* tons. This large talcs volume is indicative of tlte Industrial versatility of tin.11 PCB's, tlk'lr Imv cost, ami lack of concern for their toxicity. In fact. It was suggested In 1930 (Penning 1930) that PCBs might be substituted for chide In diewtng gum. Tiudon et eL (1956) investigated the effects, of the vaputs from hatred ArocloM242 and 1254 on small animals. The vapors of Aroclur 1242 were not shown to be toxic and the vapors of Arocror 1294 caused histopathologic injure only when sufficiently concentrated (5.4 ytg/L). However. lHtk) was known about the biological signlRditice tf the Aro- cion until after f*CB residues were found in fish from Swedish waters in 1988 (Jensen 1966). Since 1666, PCB's were found to have wide envinHiittuntul distribution ami wore found as tissue residues in many animat species. The occurrence of these residues have been reviewed (Depart* went of Commerce 1972, Eowaubs 1971, Jensen ct a!. 1909. Pkksst el til. 1970, RisEMOU<jtif of. 1968, Vtrnt and Lee 1970). t PCB residue* natter; tjte environment primarily through tlrevapori/n- tlon of 'yiwwsrfisaitfoiiV ' fluriijg open burning, lenlcs and dis posal of Industrial flnjds, and the Intentional spreading such as through the use af^pcMl^fdQ fpnmfluUom which contained KJflV (Nnuwrr and SAnbriM ' 107$}..'Afr these uses have led to detectable concentrations of FCB residues ln jjhe environment, these sources of residue* haw contrilr* iftcd only xt|usil (|wuitities of the PCB's consumed by hiunan beings. With the exception of fish positnuoptloi1, thematn sources of contamination for human beings .have Inyo 'injutftrlal acddiuit* which directly contaminate food sonroes a^l from PftjSVJn etaanufactured food or feed packaging from which the resldue'h^s feactaxl into B*e foodstuff. .' ' ' ` '* ' " ' ` ' * itaminajtpn dta food source ..." ' ajMK (CVHATStlNE uiui*TM](^ mw..ymgwpm jnddent more titan Wl# pttrsom i^ved a taodc dose of rCB'$ through rice oil that hod lieeii contaminated during its manufacture. It was festimnted from this Jncjdeitf that the average patient received approximately two g toodc cffr*ct was approximately Oj g (KuitATitJ^t et ah 1W3). Whereas Ho Significant spill such s the; :lw^..'jP00OcnHl In the United States, several Industrial accidents and/or mistakes have yielded contaminated food stuffs. The most costly Incident which occurred in the United States was in a fishmeal plutit oh the east coast where fishmeal was contaminated by n leaky beat transfer system ns the metd was being prepared for live Stock feed (Spaulding and Wesskl 1972). The r^Eal was subsequently fed to fish and poultry, resulting in extensive losses <bf fish, meat, and eggs which Were impounded and dcstroysd., Sevttll E4her episodes oc curred where poultry and turkeys were foun$ fo^^^gtoesslvely high `eOfr* '-isiwifc.il STLCOPCB4016093 41'- rth lex w in 411 '(f til . rs n- . l * 'v''- h <i f Ji r levels of PC!V. T1k`mi have occurred in Minnesota, Oklalioum, und Cali- fnmiit; however, the source of the PCB's nut l>o determined In tliese .. Incidents (Si'AUUiim; und YVksskl 19/2). PCllx from transformer fluid f*- '-^were used at o vehicle for herbicides sprayed glongthc highway rlght- v ~ of*\vuys in tlie Murtinsburg, West Virginia Urea. Through this route, ... ` _ PCB'x contaminated the duliy cattle graying urea, and PCB residues were \ -detected In the milk (Si*auu>ing ami Wgsskl 1972). . The iiw of recycled pajx'r products for packaging of fond nntl fiH.il hus also led to the contumlnutlnn of htmtrin foodstuffs with PCB's (Si'AUWUNO und VVkhni-:i. 1972). Ilie iiiu|Or ttniru' of FClix in recycled paper is carlxmlcKS self-duplicating paper (Tnoirr 1972). In March and April of 1970, the Ohio State department of Aprlcul- turn detected u chlorinnUHl bydrocnrlion residue, presumed to l>c n PCB, in the milk from several dairy farms. Initially, the milk from one of these ' farms was excluded from the market liy tlie Ohio Stute Pv/mrltneiU of ARrtcttlture for containing u DOT residue. Upon further investigation it was determined that this residue was a I*CB. Tlw source of the PCB Tcsldnewns determined to lie nn Ingredient iff the coating materials , inside tho silos. Since that time it has been determined from regulatory experience and information supplied by x|h ctonponlex that PCB's had lieen used in the coating materials in sillos located in Ohio, Indiana, v Kentucky, Tennessee, Michigan, Illinois, Atabuiim, Georgia, North Caro-' ... linn, South Carolina, Pennsylvania, Maryland; West Virginia, Virginia, I and New York (Willett 1973). -. - II. FCD-contuinlng silo coating , / The organic acids produced by the ensiled inuteriul in farm concrete silos cause considerable decomposition and erosion of Inside walls. Tberefore, coating materials have lieen used for many years to resist the oorrosivc action of tlie silage (nfccs and thus extend the useful life of the silo. Through the years, mail)' products have been used to coat the inside of silos including wax, mitkerul oil, epoxy rfeslus, and many other resinous routing. One such coating, Cuninr1, was the coating responsible for most, If not all, of the PCIkcrmtumiuuted silos. ' , Gumar was formulated in the summer of 1941 for the Concrete Silo Company of BloomRcld, Indiana (gan 1971). The formula for the Cnimir silo coating is kIhiwm in Tame I. It wus liused on formulations develo|X'd by SeaouL (1941) for the protection of concrete silos from the ' otgmiic acids produced (hiring the ensiling process. Aroclor 1254* was incorporated liecause of low cost, good ability to plasticize, and excellent .' 1 Hh1 silo cmtlnft calk'd Cotnar which oonUlni Arootor 1254 (Hon*onlo Com- ' pony) should hot bo confuted with Neville R-l<hA resin which has the same name. '.'h * Annlitr 1254 Is a mixture of chlorinated htphenyh containing ahoot 54% iiSMorine (Momente Company). ; , . ' V'-r r: i- - - DSW 032132 kiu STLCOPCB4016094 .'\ 4v, . . -V >. i . . . n v" vf: ' 138 \ r"-:';!.> Wuxairaad1. F. Ho*, .. "............. *tW* I. Permutation of Cumar oBo eoolhvt <Eoam1971). '' ' ' ' ' " Ingredient ' Amount , : in H`." If 'PaisdeoeNo. S(rlariclUked) . R-IO-A NcvlIU rain (flalcml) . ' ' Clay ' .' ' ; . ' tenon' 1 . - . -1 ;; :.< 1! v i-- : AmolorSMO ,`C r ' Aioolor 1854 . - ... ... . Xylol .... . . , , . 8.C. SolvM-lfl) '. ' , S.C. Solvetit-S J-*' ` . . ,- ,:,Sr y : i'Cr %?.*, ' 'V. ' . . 40 lb 40 lb 10 lb 88 B> *0 D> 70 lb 13 ftal 8 gal * *sl i? f r ' . , chemical resistance. Aroclor 'S460Y* polychlorinated terphetiyl (1*CT), was a resin fortifier. The application of Cumar varied with various silo . companies which were involved with its use. The wide distribution of this coating materia! ou silos in the eastern half of the United States was the result of various mergers and .disbursements of the silo companies involved. -i : : . .: Michigan Silo Compuuy, founded in 1909 and Incorporated in 1916. had initial production facilities located in Charlotte, Michigan, White Marsh, Maiylund, and Massillon, Ohio (Ecan 1971). Concrete Silo Com pany, with silo production facilities in Bloomfield, Indiana and Monteagle. Tennessee, was later acquired and was operated as a subsidiary of Mlchigan Silo Company. After acquisition of Concrete Silo Company, the head quarters for the entire operation were $n Bloomfield, Indiana. In 1906, a corporate reorganization split the company s assets; thus, the Massillon plant became the Michigan Silo Co., Inc., and likewise the Bloomfield Silo Co., Inc. wus formed in Bloomfield, Indiana and the Montiuglu Silo : Company, Inc. wns formed in Monteagle, Tennessee. , Personnel of the Michigan Silo Go., Inc. have stuted that the purpose f Cumar on new construction Wo* In provide a attthuit. to retain moisture ; In the joint mortar during caring ana to protect the mortar from silage add (Ecan 1971). On rocoatiug. tlie material %vu* applied to the faint mortar and in some instances oii the entire sntface of the silo. Ciunar had ' been used for reooatinu of silo interiors since 1948 throughout the entire 1' territories selVed by the eld Michigan Silo Company. Silos .constructed >; by the Monteugle Silo Company, Inc. and the southern division of Michi gan Silo wen* primarily of a warn) stave construction. Tliercforo. the use of Cuihar by these companies was limited to the mortar between Hie . Stave blocks as it would not bond to the waxed surface. ' it Is difficult to cstimnte the exact mtmlxrr of silos which hove been treated with the Cumur silo coating. Records of the company' which used this material prior to 1966 arc either nonexistent or unavailable. To ftir- * Arcelor 5400 h a mixture of chloriuntcil terphruyla eootahUnR about . 00% chlorine (Monsanto Company). i * i i i 0SW 032133 STLCOPCB4016095 titer complicate number estimates, many of the sHus which were coated with Cunmr have been torn down or are no longer in use. .The Michigan Silo Co., Inc.' reported 108 sales of Gumar during the ; period 1006 through the end of 1009 (Egan 1971). Record* for Monteagle or Bloomfield Silo Companies are not complete for theCumar sales or - We. The liest estimate to dnte as to the number of eilos constructed by the present or predecessor companies and to which the PCB-contalnlng Cmnur coating was applied U from 5,000 to 6,000 slhw { V. S. Detriment of Agriculture 1973). ' 1- , HI. The contamination process Cuinnr was fust one of many coating materials uliioh have been ap plied to silos in order to All tho pores of efctcrrto and reduce the surfaoe vulnerable to odd attack. When Cumor was applied to a silo wall, sol`vents in tlso coating material penetrated into the concrete, thus carrying tfie PGB's and PCTs into the silo wall. After the carrier solvents evapo rated, a firm coating material was left on and in the Inside walls of the sflo, Themechanisms by which the PCB's from this Afoclor-oontainlng coating were transferred to silage was originally thought to be only mechanical, as by Baking off of chips of tho coating. It is hot uncommon for these drips to contain 5,000 to SO,000 ppm of Arodor 1254. How ever, recent work has shown that this Aroclor is soluble in silage juices (Skrentny et at. 1971). The solutes may well be lactic and acetic odd, which are important organic adds formed when sllase ferments (Pratt et aL 1958). Aroclor 1254 has liecn shown to lie soluble in acetic add (Moneanto Company). After PCBs are dissolved by the silage Juices, they diffuse into the silage: tlierefore, the residue concentrations are slgniflcantly higher in the silage adjacent to the slio wall as compared to that in the central portion of the silage. Skaentny et of, (1971), Wojjbtt and Conrad (1973), and Wiixktt (1974) have shown that most of the Aroclor residue was within the first 15 cm from the silo wall. Residues ; were not delected lieyond 120 cm from the silo wall. One might expect /this to lie a typical distribution in most silos; however, the distribution ; will probably be influenced by time and temperature, Superimposed on the diffusion distribution of the ArGdOr tesMue'Irt 'ih4 silage was the confounding effect of precipitation and the downward migration of the silage juices. This effect tends to cause ail accumulation of the Arodor residue near the bnse of the silo (WnxETr 1974). ' Failure of the Cumar coating occurs with time, and flakes of the matertai fall into the silage. Theoretically, when animals consume these , contaminated chips of coating they oould receive substantial doses of tin* Aroclor residue. Through continued use of the silo all of the coating material will evcutuully flake off of the silo Avails. At this point, many ^ddr)-meu are uuawnre that they hnve a PCB residue prolJem, as there . no visible coating left on the silo wall. However, organic adds from : ' ' " , i < , DSW 032134 STLCOPCB4016096 it i iirw;.. V 140 nr. ... tlie itliige dissolved PCD'* which had penetrated Ihro the concrete. These residues rtbsequeurfyidilused Iwio rfw.jtilage. Silos last,coated with PGB Compounds 16 yean ago still emitted significant contamination of the silage long after traces of the coating had disappeared ( Willett 1,973 a). _ Reported levels of Aroclor liil from scrapings of contaminated silos have a range between 100 to greater than 20,000 ppm ( Skbkntny 1971, Willett 1974).;Ar6clor 1254 in silage adjacent to these contaminated wrface*Jia*re9l!^J[r^1 than one to greater than 7,000 ppm. Most ~ '1 * ' Wt levelsketween ien and 60 ppm. -Although the )fl|Fs w* fhe!litifie procedure lisctl for Aroclor 1254. rejw fluted at tW Maximum temperatures of the gus liquid olirwi>atoj^)V jt^X^) coliitnii used for routine analyse* of Aroclor 1954 <Fw.(Md,MARBOw lff72). FiUE* and Maanow (Wfe) were able to detect FCT residue* in silage and silo Wall ncrapiugx; liowever. methodology proMcms prevented their quantitation. The relative GLC peak areas for standard, Arodor 1254 and those extracted from silages were essentially tho same (Fries 1972 b, Skuentnv et of, 1971, Willett 1974). These results indicated that microorganisms and/or fuices in the siiage do not selectively alter nr extract tlie Aroclor component* (Ftm* 1972 b). Figures 1 A and 8 show typical chromatograms of Aroclor 1254 standard and silage extract (Willett 1973 c). v :: , IV. Cows and PCS residues When cows were fpd PCB's orally or consumed PCB-contamlnated Silage, restdues were detected in the ht% within six hours (Willett 1973 c). Whon constant levels of PCB's wore continually fed to cows the concentration In milk fat Increased rapidly for ihe Brat five to ten ! days. Tlie concentration in milk fgt continued to Increase and npnmnched a steady state in |0|o 69 days (Fiues 1972 a). Platonow et of. (1971) showed that the FCB's fed to,cpws.w<m deposited In fh4 fat portion of die milk. They also showed a strong predilection of the FOB residues for the lipid phase of various products produced from milk. '' : Upon GLC nnu!ysls,PCIi residues found ip milk after cow* had con- finned Aroclor 1254 wore quite different in appearance from, the standard Aroclor 1254 (Fig. 1C). Of/. (1973) ufwerved Hint ilK' Pcoks with shorter retcnitioii times did not occur in the milk templet, wliereas the Plater peaks i<tre more predominant. Bqsed on tin? work of Sissons and Welti (1971),FmES #fof. (1973) determined that the major components of tlie PCB residues which occur in milk were the pentuchloroblnhenyls and the hoMchlond>ipb0iyb< Those component* of the stamlnrd which did not appear In die milk os residues were theorised to be tetrachloro- biphenyls and tome of die ientachlorobiphetiyix. ^ v Fiura et at. (1973) estimated that cows that were continuously fed Aroclor 1254 excreted about 21% of the dully intake In the milk. How ever, these data were obtained wltcn cow* were fed 200 mg of Aroclor IfyjV+VAVI. asqisA ism*. OSW 032135 `TST! '1-' STLCOPCB4016097 032136 STLCOPCB4016098 142 - L. B. Willett oad J.F. Hess, J. - : ' ' 1254/dav for 00 days. This quantity of Aroclor was at least four Miik> higher than, would be expected from an average PCB-contamlnnted illo. Based oil the roKItt of Willett (1074), one can calculate that a more reasonable figurtfor dally intake of PCB s might be in the range of one to 20 ing/day. (hirmitly. research is underway to determine If similar excretion rates occur when cows are fed the lower levels of l'CU's (Wil lett 1873 c). - - Upon withdrawal at PCB residues from dairy cattle, there was a rapid decline in concentration of the residues in milk fat ( Fkjks el al. 1971. Fiues 1972 a). Fmes et at (1973) demonstrated with cows fed Aroclor 1254 that the decline iu concentration of PCB's in milk fat is adetiuulely descrlbod by a Two-conjponcnt, first-order system equation. The first or fast component in this system was about 15 days in length and the residue concentration declined about 50%. Tltc second component or slmv-ratc of decline was much slower, representing a daily decline of 1%. Ibis slow-component remalued linear throughout the duration of tlie afore mentioned experiments. The rates of decline for Aroclor 1254 concentra tions perform very similarly to those of DDE which is the most persistent degradation product of DDT when fed to cows (Fnns 1972 a, Fiues et ul. 1972 and 1973). in contrast, DDD and p,p'-DDT and o.p'-DDT were transferred to body fat and milk fat at much lower rates than DDE and PCB (FmtS 1972). Activated charcoal (Fiues et of. 1970, Wilson- et of. I960) and certain barbiturates (Fans et of. 1969) have been used to influence the rate of discretion of various orgnnochlorine compounds. However, the use of activated carbon and pheuobarbital were ineirective in reducing the final concentration of PCB's in milk fat (Fates 1972 a). As yet there is no known treatment which can increase the rate of excre tion of PCB residues from luctuting dairy cows. V. Regulation of PCB's At least toil Federal laws ore potentially relevant for regulation of PCB's (Davies 1972). The Federal Food, Drug, and Cosmetic Act (21 U.S.C. 391 et teq.) is applicable for regulating the movement in com merce of dal# and livestock products containing PCB residues from farm silos, and action has been taken by tbc U. S. Food ami Drug Ad ministration (FDA) under its rule-making authority provided in this Act . . .The FDA in 1909 first established an "internal guideline" or "work ing level" of ppm In whole inllk and declared that ivhole milk with PCB residues exceeding that level would lie excluded from commerce (Kolhye 1972). Regulations pursuant to the Food, Drug, and Cosmetic Act [21 U.S.C. 342(a), 346, 348, 3711 were published on fuly 6, 1973 (Department of Health, Education, and Welfare 1973) anti became ef fective after September 4, 1973, amending 21 Code of Federal Regula tions Parts 3,128, and 135 and adding new Part 122. These regulations are intended to limit "the sources by which PCB's STLCOPCB4016099 ;l PCB' in silos 143 muc* stlo. mure . . :.nir iilliir tVii- ; '*&& , rajiid W71. odor j*i*ly *t or 4dm* . -frat*!' V'IIiIh riore- irtru- isteiit i7 al. w ) and <7 rtf. id to miikIk. utlve 2 a), i-wro- uiay contaminate nniinnl fc^xl, food, and food-packaging materials during, manufacturing, handling, and storage^ and limit "levels of FCBVthat t may be present in animal feed, food, arid f6ftd-pnckaglng material* a a ;jenilt of unavoidable,* environmental contamination." The regulations set ."temporary tolerances" for rcslduesof PCfi'fc itrtnilk (fat basts) and in inimofariuivd dairy products (fnl lmxlx)at 2,5 ppm; in finished nnimnl feed or food producing nniinnts (except the following: finished aninml feeds, fix'd conccitlrutcs, fmi supplements, ami f^xi premlxc*) at 0.2 ppni; and in animal fetid components of animal origin, including fish meal and other by-product* of marine origin end in finished animal feed concentrates, supplements, and premlxe* Intended for food producing animals at two ppm. The regulations also provide that "coatings or paints for iwe on the contact surfaces of food ttorngo area* may not contain PCB's dr any other harmful or deleterious Substances likely to contaminate feed" (DcpuitmctU of Health, Education, anti Welfare 1273). . VI. Impaet of PCB-contaminated silos Surveys of milk produced in various mtlkshcds conducted ly the FDA (Kolbyk 1972) unu in our lulxiratory f Wuxctt 1973 c) indicated that 7% of the samples assayed contained detectable traces of PCB's. Many of the "positive** samples had levels l>cluw the current FDA-established . tolerance of SL5 ppm on o fat hosiif. This figure may lie ipiite variable as Frigs (1972) has shown that milk from a farm with a PCB-contaminated silo may be alxivc or l>clo\v the "temporary tolerance" level depending on the amount of contaminated silage fed. The amount of silage fed usu ally varies with the season of the year and the availability of alternative foodstuffs. Since producers haring PCB-oontumfndted silos are dispersed wit)i iu any mtlkshed. there is a natu{id dilution'of residue with the milk produced on other dairy furms. A ,*ecpf)dary dilution occurs when the milk is pooled at the various handler plants prior to'shipment to the con sumer, Tlicroforc, therivdocii imt appear to.be a.significant health haxanl lo the general public Wif. . Thera may lie a possible health husard (or Qirilt 'jth>harunses the milk produced on the fann. Assuming consumption of one quart/ person/day with an average contamination of 7.5 ppm of PCB's in the milk fat, an individual could consume as, much ns ten mg of PCB's/year ((/. S. De)Htrtment of Agriculture.1972). This level is. equivalent to about one-tenth of the minimum short-tenn dose required to produce dinical , ilefccts ns observed in the Japanese experience >rith Yusho poisoning ' (Ki'raisunk et at. 1971), Data are obt available to determine whether : the effects are the same for short-term or long-term exposure; however, the FDA has concluded that in ooccte4hould die dolly intake of PCB's v 'from all food sources exceed 1.4 mg {Dejpartment of Health, Education, and Welfare 1972 and 1673). Long-term exposure would seem less harm ful considering tliat PCB-contaminated silos have been on farms since ' `. . - t. - ` .Ol < v j. ; ' '' V; i DSW 032138 STLCOPCB4016100 144 ' . ,, . ...I* B. Willett and J. F. Hem, Jr. 1041 and farm families generally consume the milk produced on their (aim. There have not keen reports of wjrlous illnesses umoiig nildwestern and mideasteru United State* (aim families such as than* documented by the Japanese Yusho incident (Kvratsune 1972, Kuratsunk et at 1972). The greatest huraird from a silo that has residues of PCB's is a finan cial one to the dairyman Involved. If the milk market Is determined to contain PCBs by a regulatory agency, the producer suffers a loss ns the product must be impounded aha destroyed.. The producer mutt also re place the feedstuff stored in the contaminated silo. Tliese kisses muy well exceed $14,000 In a single year (Willett 1973). Frits (1973) found that when cows were, producing unmarketable milk due to PCB residues, the PCB concentrations in.their bpdy were also high. Therefore, a Ualryman cannot mlntmfre his losses by selling contaminated cows and replac ing them until sufficient tiino bus clupscd for decontamination, An additional cost is that of decontaminating or replacing the silo. ! Willett and OdsitAO (1973) and Willett (1974) have demonstrated that silos with POD residue# can Ik* decontaminated and returned to use hy carefully cleaning and recoatlug the silo surfaces with u protective barrier coating. Whereas tliese barrier coatings have not lieeu lOOCr effective, the small quantities of residue that can lie detected in the silage have not been sufficient to raise the concentration of PCB* in milk'of animals fed this silage to the .actionable level preserilicd hy the FDA. On silos that are in good repair the procedure of carefutly cleaning tlie silo surfaces mid recoating proved to he a practical approach as tin? cost was only ten to 1S% of the cost of replacing the slip. Willett (1973 b) has outlined recommendations for procedures to lie followed liefore n-coating . silos and lius dost-rilied the.important proiiertta of coating materials if they are to lie effective Iwririert. Some of the properties of a good Itarrier coating include aderjuato adliercuce to the 'concrete surface, Add resist- Alice, temperature resistance, durability, waterproof characteristics, and . .,410 opn]i>t .dtmpounds or toxic elu-mientx which can for kjoatfpg selection include environmental quality 4ikI*Qocupattib$iid Safety irtulHealth Act (Depart- went of Labor 1972) standards for the protection of the environment , and workers who may be applying or handling the materials. With careful . management dairymen should be able to get many additional years of - service from a dip thatijvns once contaminated with PCBs through care ful use of a Iniriier coating trod routine umiittcnunc-c. . The munlier of silos contributing PCB residues to human food is de* dining. Unfortunately, the rate pf decline is unknown. Several factors are responsible for fewer pf these problem silos. Companies previously formulating and using Q]p)ar discontinued the use of this coating as soon as silos were identified as spurocs of PCB residues in milk. Similarly, Mon* muto ConifHioij will no longer sell Arodors for use In surface coatings. Dairymen have been advised by regulatory agencies, the V, S. Depart ment of Agriculture, the Agricultural Extension Sendee, and field repre sent; they have rffei dim redo resit I to a Inert glob per wintaut sum oft silo StiO |NH* tin- lir gn him tin in firs e is. wit <U I ; del mi D> IX l>: 0SW 032139 V- V V STLCOPCB4016101 FCBrtatllo* 148 jeutatlves from cooperative* to have thdr Allege analyzed for residues If ^theysuspeot PCB problem. As a result, many of the contaminated silos ' bave lrcen dismantled, others haveltt&idlMtkfoitfed, and many have been jufrifoctively doeontamlirated with a barrier cutdhig. Efforts to locate and JSrWmhinto contaminated strurturW are <*mtlfniJng.Soch activities should reduce further the riumlter of farm si|os resptmiflMefor die entry of PCB residues into ihe human food chuin. ... / ; - . v:' \ v. ,, V.: ... -'oaft-a*-V* , V* ' Tr;': Summary. Polychlorinated htphonyi* (PCB's) haye lyeen wpplietl commercially 10 a wide range of products for over 40 years, Since PCOV are cliemieally inert they resist degradation and .Aire,, {jberefore, found throughout the glnlml ecosystem and ciui accumirlute up `the food 'chain, Many of the PCB's which are widely spnyd in our; iNiviroriirteiit mVe little importance when considering the accumulation of PCBs in man. The direct con tamination of food products with PCI) residue's is tiro main contamination source for human beings. One use of PCB's that led to the contamination of dairy products was a coating used on the inside of farm silos. 1 The coating responsible for nwwt, if not atl, of the PCB-contaminated silos was called Cumar and was used in the extent half of the United &tnlc* Icitvci'n UM1 and 1M70. TltcPCB (ArnooJor JiVl) that was a com ponent of this coating whs dissolved by organic add* produced during the ensiling process, llic PCD residues tlten diffused into the silugo. De tected residue concentrations in silage adjacent to silo walls have been greater than 7,000 ppni. ' When PCB-contiiniiontcd silage was fed to livestock the residues accu mulated in the Imdy fat and deposited in the fat portipn of milk. When the source of PCIVs was withdrawn from dairy cattle the concentration in milk fat declined rapidly and cqti Ik* descriltcd by a two-oomponent first-order system equation. jj(.,( ft has 1>een estimated that 5,000 to 0,000 siloj Jjave been treated with . !/ with barrier coatings. Surveys have indicated that PCB residues could be detected hi milk from aland 7% of the farinS.JnVesHgftted. hfany of the delcctnbh* residues were below the .FDA temporary tolerance of 2A ppm 011 U fat llttsis. ' : ' ' : ' 'A It:., . ; References .tv Davucs, T.s Rogulntaiy action on PCB'i. In U. S. Department of Commmat Poh- -chlorinated btpHenyb and the environment. Wat. ToOh. Information Service . Comm. Tt-lOttO, 173 (1072). . ? . '7^...v. rr itfefierfmml of Contnoro*> Polychlorinated btphenyiiand the environment. Nat Tech. *' , . Infiirimitiun Service Conmi. 70-10410,173 (1978). ' : Deportment of 11*0U/t, lUluoatlon, end Welfare, Food and Drug AdmtabtraHon: Final I OSW 032140 STLCOPCB4016102 4 IK'S, . . 'ui'V-' . 'iu::,. ...... 146 WnxttT and J. F, Hw, Jm. environmental do matdns 6? pntycbhtfirted'jttphet^ Dec. -------Myohlorbwtod typhroyl*. '.F><|,Register M (120), 16006 (1073). Department bit tjbor, Woiiptttioiul Safety aod Health Admluhtmtlan: .ONppnttutral . safety ml health Sl*wlIrds.Fed. Mbter 37 (202), 2*101 (1972). Edwami*, A.: Thu polytMorublplienyb, Qwlr eoovncnoo and algnifktmcci A review. Chem, & Ind. 47,1340(1071). , ,. Boast, R.: Personal comfnuntctttlon (1071). Funs, C. F.i Polychlorinated biphenyl naiduet in mflk ol environmentally and experi mentally contaminated cowi. Environ. Health Perspectives 1, 85 (1072 a). -ir+r . Dsgridation of chlorinated hydrocarbons under anaerobic condition*. Adv. iand 0. S.MAiwbWi PotychloriAt*d tarpbenyb u potential contaminant* o( aninuilproducts.!.AanOfl^^waLa^titalN^ IMS (1072). 'V ,A. MJIakAKW, tod L, of DDT aminos Vym rah TU Offer* 01 hesobarbital on the wtentlim Opotam. Toxicol. 4* 210 (1060). c. $. Maiwow, Jn,, C. n. COtooM,' L. r. DnrMN, and A. M. liauniAM; Efftri of activated carbon on elimination of offanochlortne pesticide* from rats and cows. J. Diary Sci. S3,1832 (1970). --------- - --Similarity to. betavtor ,,f DDE and polychlorinated biphenyl (Arodor 1254) residues in an environmentally contaminated herd of dairy cows. J. Dairy Sd. 84,798 (1971). _ ---------------Similarity.of a polychlorinated biphenyl (Arodor 1284) and DDE in rate of elimination tWO* ctoi. "Bnll. Environ. Contam, Toxicol. 7, 252 (1072). . Lmqptcthi studka of residue rtXiotion and cscrdlon by cows f1 a polychlorinated htpheinyl (Arodor 1254). /. Agr. Food Chom, |1. 117 (1973). HUMANA II. L. Chlorinated biphenyl and related compound*. Encyclopedia of Chemical Technology, 2nd eel* p. 280. New Yorlct Interscience (1985). . Jcmsxn, S.: Report of a now chemton hazard. Now Sci, 32, 612 (1066). . ____ , A. C. JoHNsaa, M. Ojlcson, and C. Oitoiland: DDT and PCB In marine animal)) from Swedish outers. Nature 224, 247 (1060). ' . KuHAunmK, M.i (MiAhatract T results of. laboratory examination of patents with 1 1 Yusho and of ttiilroul experiments. Environ. litwith Perspective* I, 120 (1072). ----, T, Yomumura, jb ffATsvxAXA, and A. Yamacvcih: Yusho, a poixoitfng caused by rioe oil umtamtnattd will) polychlorinated biphenyls. Pnlilio Health Reports 66.1083(1071). ; -- ---- .-- --- fvpidemlnlogk) study on Yusho, a poisoning entmd by Inge*. ttowa_nto_ Compenpi Aiow ^*tnd-iM*^l tAM-)(n'.\W3a.':Te;i.(s4.i.*<*lt*--d*l. '6/ri.^wA(ywWNiort). ; Nnwrr, 1. C. T.,amd A. P.'sXttbnMi Rutca and routes of tnuupdrt of Kills in (tie environment. Environ. Health Perspectives 1,21 (1072). Psakall, D, B., and J. L LtNoipu Polychlorinated biphenyls, anotlier kmg-llfe wide spread chemical in the envlroomort. BloScitmoe 20,058 (1070). Kcnnino, C. li.: Physical Characteristics and commerck! possibilities of chlorinated diphenyl. 1ml. Epg. Chem. 22^. W30). . Platonow, N. S., 11. s. FvnnkUv t). IL BdLutcg, D. R. Anuorr, P. \V. Sasctixu- aunniRn, ami D. C. CrutVa: Fate of potydilorinated biphenyls in dairy products ' procecscd from the milk of exposed cows. |. Dairy <h:i. 84, 1305 (1071). PtUTT, A. D., R. C. Wasuivun, and C. F. Roowt: Comparative palatabdltirs of Wphenybin wild : binu In Btttain and tlselr avian toxicity. Environ. Pollution 1, $ (1070). RixKiutoonn, R. W., P. Rincnu, D. B. Peakaill, S. C, Hxkuan. and M. N. Ktinvi! IVilyclilurinatud hiplanyh in tlw gtulml ecusystiiti. Nature KM, MW7 (1008). OSW 032141 Sr Si Si Si * Si. Tv Ta V. Vs U'r STLCOPCB4016103 At, 4r t` ' .* >.* Ifttod biphenyls. Dec. !\^5SwirwSwr<)?nil>ii(i<Kinl J), 22101 (MT2). V , ami *tHntftc*nan A review. 'H:i -- rt.y m' id expert* Mg*-t<(vf* t. 55 (1072 *1. ' et anaerobic condition*. Adv. f 1 \ , ' ' % m m potential contaminants of 4 10M (1070). jyheattbarbftal on the retention tmmmM. 4.820 <1080). ';!, j A. M. Hartman.' Effect |;tori*cp*rticide* from rat* and polychlorinated biphenyl ^ affmnfiurtcd herd of dairy cow*. *' toji (Arocfor 1284) and DDE totem. Toxicol, 7, 252 (1972). -f:r' n> and exertfkHv by cow* fed a . Food Chcm. tl, 117 (1973). i; 1 compounds. Encyclopedia of r< Vi Interaclemv (1965). . v^hiveu aw). Awn: DDT and PCS in marine IMN). tv examination of patients wHh iW IVnipcctlvr* I, 129 (1972). iTHii Yuiho, u poisoning caused ; dpltenyls. Public Health Reports At, ' iv'lwmiiiu caused tty (nget. Aerial brand of polychlorinated >72). ^4pdiUtrial Cbtm. Co. Tech. Bull. .t res', i. PCB's In ados 147 SctSMiOT, II., and C. Souin.Tei F.lnwidtung von Funffocb-chlorphosphor oof dsn a-Dtphepoi Ann. Qtctn. 207,838 (1881). . *- .... x ; .. SwaoAs, b.kfldJ>. 5MH9V 4dentt8catkm of, polychlorinated WpbenyV ttcdmmercial .. ,,,mixtures of RtslltfUd Chromatography, choicer roasonance end mo* apectroaeopy. . . . -L,. 4., SeAituMHo, |. and J. R.Waascu Occurrence awl touw* of PCS* hi <eod. In ; V. S. Department of Ccmmerotft PolyoMorlnated hlpbenyli and the environment. Wat. Teen. Infer. SanlceComm. 72-10419.107 < W72)* Sruem. t It.; Actd-rcelxtant concrete coatings. Agr. Eng. *2, 209 (1941). ; r Skwcntoy. ft, F., R. W. llgMWK, w- Itowwiis.Wto biiil m a aooroe of pofychlonAtiphcnyd (PCS) cofttandnatton af animal feed. Bull. Environ. Coo- `'''TlJfcWjS'fc SjtttiwA^* CAet^and R. W. Arcmaw: 7Veto^ of I J r.tr r* lilffnrnirAHIIs |e mj* VsliriMs, pins * n. assn ismenwy sm ly/'l J.p; Di1ee* vap*or* of A* ro.c<lur. t1n24s2n_a__n4d Arocfor I1f2tC84i. AAnmsjo>r. TInfudl. IHVymg. AAesaauolct. *Qnaureaor4t * 1*7m19,8--0- 4m g(1*9w66r). '. , T9W. p. E.1 FCB ; JPeropoctlvet 1,88 I -v' progress report. Environ. Health i'r'.{/ - V* . Deportment of Agrioiilturei reeponeibllity concerning paiyohlcri- na|ed biphenyl <1 - i and Education, Washingtoa, D. (X, No.t0250 (1072). Summary of Infopnattocn the pofychlortnated bmtmnyh (PCB) iBp problem. ' Report submitted to the Director of Science and Education, Washington, D. C, . V Jan. 12(1973). - .v': ..:, ' .' Vamt, C. D.. and C. F. Lass A review of chlorinated biphenyl contamination in nat- uml amten. WaterJ2e|.A> S^f WiLtirr, L. 1).: Duua your sflo'obntuln PCB tesidoei? Hoard's Diarymap 418, 810 . (1973). ' ^-- Evaluation of barrier coating* fn farm silo* which were FCB-oositamtnated. Ohio Agr. Res. A Dev. Center Rea. Summary 69,88 (1973 a). Decontamination of alWn oontamlnated with polyohloriostrd biphenyls (FCB's) --Some Important consideration*. Ohio Agr. Res. 4 Dev. Center Res. Summary 89,40 (1973 b). ^ UnpuUiihad nfdlts (1878 o), ^ : r-- Coating* as barrier* to prevent polychlorinated biphenyl contamination of adage. J. Dtlry 6oi. 87, In preee (1974). ; --, and H. R. Cokkaoi Coatings a* protective benteis to polycblorinated biphenyl residues in contaminated siloa (Abstract). J. Dairy Sci, 58, 889 (1973). , Wilson, JC. A., R. M. Cooc, and R. S. Emcav: Effect* of charcoal feeding on dhddrin excretion in ruminwnts. Fad. Fioc. t7,568 (1988). : Ivad April 4,1974; accepted May 20,1974. ;|^p,yb. another tongdlfe wide* r;.5#rw(t970). , ^ . ocrciul pnmlhilltle* of chloriiiatod Tl Ahnott, P, W. KAMsnmJgpeted biphenyls hi dairy products >fg.i HSJyScTH 1305 (1971). Oomporative palaubilities of "`'-.A., - itVdyehlminutod biphenyl* in wild 'Ifljno. Tuttutlmi I, 3 (170). ry.lB/flaPMAit, and M, N. Kinvan: ? torsti. Nature 829. |fl7 (1068). f- . ' ' '."/'.-i'lUjriiip *y lifif *. tj \. . DSW 032142 STLCOPCB4016104 /d Subject Index Aatram and Aatrex, see Atrozlne Abate, automated analyse* 67 ' ' r LC 51. Abwiptlimef v|mn JI17V. ' Adsorption of vapors Its If. '* " ' Aerosols, centrifuging 114 - electrostatic precipitation 112 filtration 106 . . Impingement 107 IT. tan\p1ing 105 ff. sedimentation 112 thermal prccipltfttlnn 114 ' Alston, we Uminm , ; ; : Air iimpki, analytical determination 127 sampling, alterations ol eonsttto- 101 : ; sampling, analytical limitation*, 101 . ' .'' ' .r-r- sampling, collection limitntinns . >' ,; . sampling, eoroblnifiHon system*. . I ; .. sampling-detection systems 121 sampling duration 40 saniptfng. 4Tn'tlvem>ss 100 - stapling, elemental (lastgu . sampling, froezMiut 121 sampling, grab aamplcn 121 . sampling, metering devices 103 sampling. Nylon Art* 123 :; sampling, packed absorption column* 110 ff. , '. sampling, paper strip* 124 -- sampling.pesliddes In (see also specific wnnpounds) 01 ff. -- sampling, quantity measurement devices 101 sampling, rah* and rsrta'measure- ment devices 07,104 sampling, samplers vs. detectors 102 - i. .-.I. sampling, sopunliat samplers 100-102 -- sampling, sloe of sample 00 -- -- sampling trains 123 - -- sampling, units of measure 07 -- sampling, vacuum sourves 102 Aldrin In air 107, 110,120,124, 125 Alfalfa 51 Alvit, see DleUlrin Ammonia analysers and autuinntal . analyses 10,65 Amoxonc, wv 2,1-D Anderson samplers 110, 111 Anilines, automated analyse* 11 Annfex. see DDT . .. Auti-ChK analyser* 3 . Antimony, automated analyses 30 Apbolutc, sntoimlcil analyse* 23 Aphoxidr, see Tepa . Apple* 13.90 Arodor*. see HCB n Aromntic amine*, auhxnnted analyse* 11 Arnnilfc add, automated analyse* 38 Arsenic anplyzers 30 --automated analyses 30 Asparagus 20 1 Ativan, see lamim-pam Atrnxlne. automated analyse* 63,64,66 ------ In soil, automated sample prepe- ration 38 .. _ Automated ammonia analyzers 10 . -- analyse*, advantages 2, 60 , - analyte*. future 00 ff. ---r~ analytical systems (see also specific compound*) 10 ff, ' ---- analyzer*, recognition T1 ff. ------- - *ntf-CbF. iml>7en 3............ arsenic anulyrers 30 - {iKitiiihtwiM'tiiyi analyzer* 10 i--------- azirktiac analyzers 22 - -----biphenyl analyser 25 ---- cartouy! auatyzcr 25 ' carlmn dhmlfitleanalyser 26 . ------ cyanide analysers 30 11 -" -- data handling 57 ff. ' ------ dlaroN/atUm ami coupling analyzer* U --------- diinwt analyzer 28 ------- dttniocaibamate analyzer 27 - element analyzers 30 IF. 'gas chromatography 15,40, 43 ff. -- 1R detection 56 V -- lead analyzer* 38 ' :- -- liquid chromatography 47 If. -- malaltilim anulyzor 28 -- iuervury analyzers 34 -- uaplitlml uimiyzcr 25 -- nicotine analyzer 28 -- orgw4>n>mlne analyzer* 17 -- argnnnchlorine analyzers 13 -- orgnnonKrogen analysers 17 orgoitophotplioruB analyzers 15 orgnnnsulfur analyzers 18 paraquut analyzer 28 > pstlrtle analyzers (tee alsq specific compounds) 1 ff. -- phenol* analyzer 30 ---- polarograpby 50 ---- sample preparation 38 if. DSW 032143 R n ,.i ^;V /\ STLCOPCB4016105