Document 10DgbEOKX9NNojXgEGmm1R2wZ

I fc ft- di AMERICAN CHEMICAL SOCIETY DIVISION OF WATER, AIR, AND WASTE CHEMISTRY AagMl 26*5ep1emher |, 1972 164th ACS National Meeting He* York City, New York R. S.Baker,Chairmen J. I. TmiIc^, Secretary } , MUTIVS RATES OF WMlm Of OKSWIC COIPOWM FROM AQUtOUl BOlUTtCKS. Met tor D. Smith. and John W. Pvlnnerton, U.6. Naval Research Laboratory, Coda B330, Washington, D. C. 20390. Om ol el valor, previously equilibrated vlth ao organic coapound, was Injected Into a purging ohMSber, filled with a fixed volume of dlatlllod vator <9 ml). Hallua at a oonatant rata of 90 al/mln vaa paaaod through a frit In the bottoa of the ohaabar. The gaaaaua affluent floved dlractly to a flea* Ionisation detector via a short length of hatted tubing. The rise and fall in the algna) vaa followed on a recorder, the tie# re quired for the signal to fall to one-half a given value vaa taken to be the "purging half-tlae". The ratio of the "purging half-tlee" of a given organic to that of n - Cg, an arbitrary reference, vaa expressed aa the "relative purging half-tine". A plot of th* logarltha of the "relative purging helf-tiae" va the noler voluae geve a linear reletionehip for otch typo of organic atwdlod. Paraffine, olefine, cyeloolefine, cyclo paraffine and branehed-ohalrv paraffine gave etralght Uneo with positive elopea. Por e given noler voluae the "relative purging helf-tinee" were 1.0,*0.6, 0.3, 0.3 and 0,1 reepeetlrely. AronatJce, nethyl ketones and aloohole gave similar piote aave with oegatlve elopea. The "relative purging half-tinea" for the C-aton oonpounda of these types vers 1.6, 47.0 and 130,0 respectively. Purging vs* practical and etfeetive in the renoval of hydrocarbons, C3 - C,c fron solution, but vaa of little or no value Is the ronevel of the ware vetvr soluble organics. 2. RAPID OIL-IN-WATER ANALYSIS BY CAPILLARY TEST BOTTLE: A FIELD EVALUATION. Lcrmt Enabere Hearn, From Gorporallon/Induatriel Division, P.0, Box 50096, Tulsa, Oklahoma 74150, A rapid procedure for determining trace quantities (5 to 2000 ppm) of oily sub stances in water haa been developed and widely fteld-teeied. The method is baaed on sample emulsification followed by transfer to a specially designed trace oil analyais bottle and subsequent demulslttcatlon. The released oil is concentrated by centrifuga tion and then forced into the capillary neck of the bottle by further addition of demulsi fier to the aqueous phase. The height of the oil column thus formed la measured and converted to concentration using a calibration curve. The emulsifier is composed of a blend of anionic and non-ionic ourfaetanta. A 0. 62 Molar solution of sodium citrate Is the principal demulsifier. Tha effect# of additional water contaminants on the test is discussed, as is modification of the procedure to accomodate aoiuble and volatile otls. A comprehensive summary of the results obtained by different workers with widely varying oily-water systems, both in the laboratory and in the field, la presented together with evaluation of these result#. J. AN IMPROVED METHOD FOR REMOVAL OF ORGANIC POLLUTANTS FROM WATER. A. Vinson, Department of Chemistry, Washington and Jefferson College, Washington, Pennsylvania 15301. Organic pollutants era commonly rsvoved fron vasts or potable water by solvent extraction or activated carbon adeorptioo. These aethode suf fer fro* limitations due to the Ieoh of quantitative reaoval of the pol lutants, especially at trees levels. This work describes a new atthod of extraction using aecroretIcular polyaeric adsorbents. Aroaatlc hydrocsrboas, carboxylic acids, aalneo, phenols, pesticides, herbicides, monomere, polymers and plasticisers era quantitatively removed by passage of the water through a short eoluan of the raelo. The organics way be quantitatively eluted vlth ao organic solvent and anslycad by any con venient asans. Separations are accomplished by making use of the resins' HONS 079495 WATR preference for non-lonired noleculee. Poaalble application* of the realn* for industrial vaace water and aunlclpal watar traataent la dlacuaaed 4, COMPUTER-CONTROLLED MASS SPECTRAL CHARACTEnJ2AT1ONS OF INDUSTRIAL ' ORGANIC POLLUTANTS. L. H. Keith and J. M. McGuire, Environmental Protection Agency, Southeast Water Laboratory, Athena, Georgia 30601. A computer-controlled quadrupole mass spectrometer tentatively Iden tified about 25 compounds on re-examination of a treated petrochemical waste effluent. About 500 spectra can be automatically collected on magnetic tape (a 40 minute GC run) and then tranafered to an auxiliary disc for rapid manipulations. Limited mass reconstructed gas chromato grams using select mass ranges indicative of various molecular fragments revealed much about the compounds in this sample even before the naaa pectra were analysed. The computer subtracted background or interfering peaks from the spectra of interest and matched these spectra with a library of over 11,000 mass spectra. Plotting a typical mass spectrum takes only 3-4 minutes and spectral matching is completed within 2 minutes. Spectra of pesticides and other compounds being found in the environment are added to the computer library of mass spectra to enhance chemical characterization of environmental samples. $. SPECTROSCOPIC CHARACTERIZATION OF HUMIC ACID FRACTIONS IN AQUEOUS MEDIA by Alan ft.Honahsn and Allen F. Deluca. Xerox Rochester Research Center, Rochester, VoricNew 14603, and Robert l. Wershsw, ll.S. Geological Survey, Denver, Colorado 8022$. Analyses of the electronic absorption spectra of a series of fractionated sodium humete samples In aqueous media (pH-9) demonstrated the presence of monomer-dimer equilibria In the 10'M0~4M concentration range. The sodium humate samples In this study were extracted from a North Carolina soil and fractionated on a Sephadex G-50 chromatographic column,i Tha dimerization constants, X^Cd/Cn* were found to have a range of Ur to 10*M'' depending on the sample fraction. The absorption spectra of the pure monomer and the aggregate were measured for each fraction by a spectroscopiccomputer procedure. The aggregates were characterised by broad absorption maxim at ^OOmu and structureless absorption Into the green region of the visible. The resolved monomer spectra were found to have at least one absorption band In the ultra violet viz. 210, 270, 320 and/or 380mu. The number of bands appearing in the resolved monomer spectre and their relative Intensities were dependent on the sample fraction. Confirmation of the absorption measurements were obtained by fluorescence emission and excitation spectra as a function of sodium humate concentration. 1 R. 1. Wershew, S. J. Heller and D. J. Pinckney. Advan. X-Ray Anal., 1_3, 609 (1970), 2 A. R. Monahan and 0. F. Blossey, <1. Phys. Chem., 74, 4014 (1970). 6. ORGANIC COMPOUNDS IN CHARLES RIVER RASIM (BOSTON). Ronald A. Hltee end E. Itomam, Department of Chemiotry, Naaenchueette Inetltute of Technology, Cambridge, Niieiehir eette 02139, The eejor lipophilic organic compound* preoont in the voter of the Charlee River Satin (Roeton) hove been identified by |*o chromatography-maoo opoctromotry and by high proeaure liquid ehromatORraphy. They art alkane* (C^j to Cji), elkyl bonceoeo, alkyl naphthalene*, alkyl anthcaeenea or phananthranoa, pyrene, fluoranthene, dibutyl phthelate, and di-(2-#thyl-h#xyl) phtholete. Quantification of the eromotlc hydro carbon* w*o eerrlad out by liquid-oolid chromatography an Poreail T with heptane aa the eluant. On i weekly koala, there it * high correlation between the naphthalan* concen tration and the effective atom-water runoff content of tho rlvor. (The effective rtetoff, Eg, of weak j 1* doflnod net vhor* En.j i* the proelpitatlon in incha* of weak n-i.) Thle indicataa that tha aro matic hydrocarbon* are Veins washed off of the atreet* and bulldlnte by rainfall and finally Into tho rlvor. Tha type# of thae* compound* found In the rlvor or* vary tlnllar to thee* found in auto oxhauat. ThU, therefore, would atom to bo their ultimata eourc*. HONS 079496 MONDAY AFTERNOON - GENERAL - C. R. O'Mella, Presiding WATH 7. PROCESS CHANGES IN AN ORGANIC CHEMICALS PRODUCTION PLANT TO IMPROVE YIELDS AND DECREASE BYPRODUCTS. Robert C. Bailey. Thomas L. Kennedy, Richard T. Keller. R. A. Geske, The Dow Chemical Company."Ml <fland, Michigan 48640. The production of crufomale, the common name for 4-t-butyl-2-chlorophenyl methyl methylphosphoroamldate, U accompanied by the formation of slieable amounts of bypro ducts. In addition to tars, a large aqueous stream containing organics and NaC! had to be treated end disposed of. intensive laboratory work has led to the planned 1mplewnlettoft of * hydrolysis step In which the tars and aqueous wastes are hydrolyzed and converted to the starting feed compound, 4-t-butyl-2-chloropheno1. Instead of experiencing only a 56* yield, the process will now enjoy close to a 90* yield and avoid difficult waste disposal problems. The recovery and recycle of byproducts 1$ an economically attractive venture. Startup of the process additions was completed In March 1972 with excellent results. 8. FLOCCULATION OF RAW SEWAGE WITH FOLYELECTROLYTES. V. Srtakantham, Donald L. guea*an, Deportment of Civil 4 Environmental Engineering, University of Rhod* leland, Klngaton, Rhode ioland 02961. in the phyaicai-chemical treatment of raw sewage, tha initial atep la a clarification by using a precipitating agent with a floccolant. Thia study waa concerned with the uaa of a flocculant to remova turbidity and nutrients from raw sewage. Tha flocculanta uaad ware anionic, ca tionic and nonionic polyelactrolytae that are commercially available. Thoae polyelectrolyte# were used alone,and in the caae of anionic poly electrolytes, ion binding and complewing cation# were added to note the effect on the flocculetlon proceea. Raw sewage waa obtained at tha Unlvereity of Rhode leland eewage treatment plant at timea corresponding to peak loads. Yhi sewage waa characterised by tha COD, organic N, Nil3, total Pr turbidity and hardness. This study waa defined in terms Of the rete of flocculation, the final turbidity end removal of nutrienta from tha sowaga. 9. FLOCCULATION Of METAL PLATINO HASTES WITH POLYSLECTROLYTES, Edward C. Hang, and Donald L. Euaeman, Department of Civil and Environmental Engineering, University of Rhode island, Klngaton, Rhode Island 02181. Thia presentation describee tha studies on tha flocculation of metal plating wastes with eationio, anionio, and nonionio polyelactrolytae. Modal waetee ware prepared with CrgO?*, Hi*2, Cu+2, and day a* a aourca of turbidity. Actual waste sample# elec were aeed, Theee were taken as untreated affluents from metal plating and finishing plante. The effi ciency of tha treatment of thaaa wattes with polyalaotrolytaa waa defined In terms of tha flocculation kinetics. The parameters of interest were tha initial decrease in turbidity, di/dt and the turbidity after 1 hour. Other parameters that were evaluated in order to follow the flocculation process ware tha final particle else and the settled sludge resistivity to flow. Tha treatment of metal plating wastes by polyalaotrolyta floc culation is compared to the treatment by raduotion and precipitation methods. 10. CARBON JSOTOPF RATIOS AS REFLECTIONS OF CHANCES IN THE CARBON CYCLE John A. CiUtr and David J. Shulta, Dapt. Oceanography. FSU, Talla- haaaec, Florida 32306. The varloua natural reaervolra of carbon have e definite and often distinct rang* of C-13/C-12 valuea. In lnatancea where aodern civilisa tion haa altered the natural cycle of carbon, changes can often be observed In the C-13/C-12 ratio. Pulp alll wastes preaant an Interaatlng situation to tha geochealet, in that the Isotope ratio of these vaetes la identical to noreal terrestrial organic natter. Particulate organic carbon fro* pulp ellls la detectable in aarlne aedlventa up to 3 to 4 alias fro* short. Doeeetlc aewage wastes contain Inorganic carbon generated by oxidative processes during vaete treatnent which la about MQNS 079497 WATR 22 per mil enriched in C-12 compered to normel marine Inorganic carbon. Petrochemical operations release wastes which are enriched In C-12, Both of these types of waste can be traced in the marine environment by using C-13/C-12 measurements. The extent of organic waste clean-up operation* can ba determined by monitoring the C-13/C-12 ratio of the remaining organic matter In the final effluent. 11. INHIBITION Or OXIDATION Or SULFUR DIOXIDE DURING ALKALINE SCRUBBING. Paul Counterman and Elmar R. Altwlcker. Blo-Divironmental Engineering Division, Rensselaer Polytechnic Institute, Troy, New York 17181. The inhibition of the oxidation of sulfur dioxide during alkaline scrubbing la de sirable from the standpoint of pollution control and economics. The aim of this research la to study the oxidation in a system that may permit translation of the data to Indus trial absorption systems such ts packed columns. The experimental system used consisted of a continuously stirred batoh reactor into which gas stream consisting of 88.9% nitro gen, 9.8% oxygen and 1.3% sulfur dioxide was continuously diffused. Sulfite and sulfate concentrations and SO~ removal efficiency were measured as a function of time. The aystem parameters studied were: inhibitor-type. Inhibitor concentration, catalyst, pH, and time. Benzyl alcohol (2%), phenol (.005%), and hydroquinone (.001%) were all found to be effective Inhibitors for contact times as long as 30 minutes. Evidence would indicate that the inhibitor Is consumed during oxidation. TUESDAY HORNING - SYMPOSIUM ON PCB'S - STILL PREVALENT - STILL PERSISTENT Joint with Division of Pesticide Chemistry - C. 0. Cuatafeon, Presiding PCB'S I - EVIDENCE FOR UBIQUITY 12. POLYCHLORINATED BIPHENYL (PCB) IDENTIFICATION IN MARINE ARCTIC ANJ) SUBARCTIC FOOD CHAINS. CTTMTB W. Bowes (1) and Charles J. Jonkel (2). (1) Toxic Chemicals Section, Canadian Wildlife Service, 6 Boechwood Ave., Ottawa, Ontario; (2) Canadian Wildlife Service, Eastern Region, 2721 Highway 31, Ottawa, Ontario. Canada. Analysis of biological samples from Arctic and Subarctic marine food chains revealed gas chromatographic patterns similar to those of the polychlorinatod biphenyls (PCB). Samples were taken from polar boars, seals and fish. Zooplankton, and possibly phytoplankton, analyses also will be reported. Geographical locations represented by the data extend across North America from Alaska to Baffin Island, and down into Hudson Bay. Tissues analysed included brain, liver, moat, and fat. Samples were extracted with hexane after having been ground with sodium sulfate or digested in glacial acetic-perchloric acid. Column material employed for extract clean-up included both Florisil, deactivated 10%, and Celitefuming sulfuric acid. Quantitation was done on S% SP-2401(fluorosilicone) on 100-120 mesh Supelcoport. Confirmatory techniques included use of the GC alkalino pre-column, conversion of PCB to docachloroblphenyl, and silica gel column separation of the PCB and chlorinated pesticides. Electron-capture GC indicates the PCB concentration in polar bears to be greater than the combined DDT and DDE. A striking feature is that the GC PCB pattern in bears from all geographical locations sampled to date, is similar. 13. INSECTICIDES, FQLYCHLORINATEO BIPHENYLS AND MERCURY IN WILD CORMOR ANTS , PELICANS .""THEIR HOGS, food'AND ENVIRONMENT. Yvonne A. Crelchus. Alglrdss Crelchus, Royce j. EMerlek, Experiment Station Biochemistry Department and Entomology-Zoology Department, South Dakota State Uni versity. Brooking#, South Dakota 57008. A study of the level# and distribution of organochlorlne Insecticides, polychlorin ated biphenyls (PCB'a) aid mercury in water, bottom sedlmente, flah end (leh-eatlng blrda from -the Lake Poinaett, South Dakota ecosystem was conducted during the eumnera of 1970 td 1971. Levele of ail three compotsids increased In higher trophic levels with insactlcldes concentrating most rapidly and mercury least rapidly. Average levels In bodies of Doubla-creeted Cormorant* were 10.0, 4.6 end .64 parts per million and In bodies of White Pelicans were 12.3, 2.3 and .29 ppm for Insecticides, PCB'a and mercury respectively. Other tissues examined for these compounds Included brain, muscle, kidney, liver, fat and egRs. HONS 079498 WATK Procedure* used in the purification. Identification and quantitation of Insecticides and PCK'e Included column, ges-llquld and thin-layer chromatography and aaponlflcatlon and oxidation of samples. The presence of PCR'e In pelicans, cormorants and their eggs was confirmed with mass-epcctromctry. A procedure for the remove! of all insecticides fro* the PCS'# was employed prior to the maes-apectroiae try analysis. 14. HOVKMBNT OP PCB'S INROUCM THE CHESTER RIVER ESTUARY J. D. Taaler and T. 0, Munaon, Wcsllnghousf Vc^kn Research Laboratory, P.0. Box 1771, Annapolis, Marylanf 2lW4. As part of a molti-dl*clpllnary study (jointly funded by the State of Maryland and the Meetinghouse Electric Corforation} of the Chester River Estuary (pan of Upper Chesapeake Bay), the authors analysed bottow sediments, suspended sediments, water and biological tissue* for PCB'a end "hard" chlorinated pesticide residues, the level* of ptttJcldca observed were relatively low for moat of the year although aome "contaminent" peaks were efeaerveri which could easily be mistaken for pesticides or PCB'a. The PCB contamination (of the Aroclor 1232-42 type) waa low compared to the part-per-mllllon levels observed by others In the lower Chesapeake Bay but waa high enough to indicate Inputs other than genera) atmospheric fallout. In format loo from the hydrological, rteorloglr*), and geological parts of the program was ueed to estimate the possible rates and routes of the chlorinated hydrocarbons through the system. IS. PCB CONTAMINATION OP THE AQUATIC ENVIRONMENT IN ONTARIO, O.W.Berg, P.L'.'MoMdy rtd O.A.V.Reoa, Ministry of tbs Environment, Laboratory Branch, Bor 213, RexOale, Ontario, Canada. Sporadic analyses of eamplas from the aquatic environment have shown that PCB'a are universal pollutants. Almost without exception the contaminant was of the Aroclor 2254 type. The approximate levels were ee foil owei effluents from aewage treatment planta-0.001-0,1 ppm, river odimonta-up to 0.6 ppm, fish-up to 20 ppm end eeagulls-up to 1500 ppm in oil. in order to gain more systematic type of information, a large scale survey waa undertaken. Four different typee of aqueous systems ware studied) 1. industrialized "impounded system", 2. industrialised "dynamic system", 3. natural "impounded system" - a clean lake receiving no waste and 4, natural "dynamic system". Data concerned with the analysis of water, bottom sediments end fish are presented and discueaed. The analytical techniques - separation of PCB'a front other chlorinated materials and the determination of PCB'a in terms of the fully chlorinated derivetives-decachloro biphenyl are diacuaaed as well. 16. DISTRIBUTION OF RDLVCHIPRIWATEU BIPHENYLS IN THE AQUATIC ENVIRONMENT. Marvin L. Kerman R. Feits. and*Hana 7. fcrump-Meisnsr. U.S. Geological Survey, Water Resource* Division, Wasfiington, 20242, ---- Data fathered from llmlLtd monitoring activities and project studies in several Sisiaa indicate the ubiquitous occurrence and distribution of polychlorlnattd biphenyls In the aquatic environment. Residue* have been detected in samples collected in several States, Including Connecticut, New York, Pennsylvania, Virginia, South Carolina, Florida, Mississippi, Texas, Arkansas, and California. Data indicate concentrations ranging irom 0,1 pg/l to 4 pg/1 in unflltared water samples and 0.5 jig/kg to 3200 ^g/kg In bottom aeterlel. 8ome PCB residues war* found in fish and aquatic plants. Samples ware prepared by the same techniques used for general chlorinated insecticide detection, with spscls) attention to clean-up and separation of PCB'a from other compounds. Basic identification and quantlflcatlnn were mad* by duel-column electron-capture gas chromntograpliy. Confirmation was accomplished by gss chromatography-mass spectrometry whenever possible. The sampling program is expected to be broadened geographically In 1973, and increased in successive ycers in order to more adequetely assess the presence of PCB residues in major drainage basins of the contiguous United States, Hawaii, and Puerto Rico. MCNS 079*99 WATR 1 7 OHPOSITIONAL CHANGIB OP CHLOROBlPHiMYL MIXTVRIfiS IN ANAUtOBIC LAX* SfflllUflltS, Rlohard 0. TloUrd end ClIiRart DTTCXtrr, deter Chaeistry Program, University of Wisconsin, Mmdieon, Wisconsin 53706, Th* ooapositional ohengee of ohloroblphenyl mixture# In anaerobic eedimente hes bn inveetigeted by inaubeting Arcolor 125b In littoral sediments from Uko Michigan - Groan Bay* Replloate samples of 25 al **t sedlaant (lo gm dry weight) containing 100 ug of Aroolor IZfk vara sealed and incubated at U c* Dupllcata samples ara analysed parlediaally. The analysis of ohloroblphenyls in sadiaants has bean evaluated using exhaustive solvent extraction and staaa distillation aatnede* Because itau distillation raaovaa ohlocrobiphenyla froa asdiasnta aors rapidly than doss aolvsnt extraction and allatnates the need for liquid ehromat^raphlo olaamip procedures, a aodlflad Deane - Stark apparatus has been developed for the aediaent analyais* Re fluxing acidified eedlaents for four hours results in the transfer of approxlaately 85 percent of Aroelor froa the aediaenta to the cold hexane trap. The extract le dried with anhydrous Ne^SOt*, refluxed over clean, powdered oopper to remove eleaental sulfur, and analysed by electron oapture gae ohroaatography* This paper will dleoues the ohangea In the ohloroblphenyl oonoentratlone during the feur-aenth Lnoubatlon period* 18. WIYPM10RJ8ATEP BIPHENYL LEVELS IN HUMANS. A. R, Yobg. State Services Branch, fflv; of Pestfcf3e ComnunHy Studies, Off. of Pesticides Programs, EPA, Chamblee, Ga. 30341. Polychlorinated biphenyls (PCBs) have been reported In many different parti of the environment. Previous reports of PCBs In humans have been few In number and have aenerally been concerned primarily with analytical procedures, reporting findings In only 4 few Individuals. This report presents results from a human monitoring program In which samples have been routinely analyzed for these materials since April 1971. Case reports are presented In selected Instances. TUESDAY AFTERNOON - SYMPOSIUM ON PCB'S - STILL PREVALENT - STILL FRRSISTENT (Continued) - Joint with Dlvlelon of Pesticide Chemistry - C. C. Cuatefeon, P residing PCB'S II - ANALYSIS AND DEGRADATION 19. ANALYTICAL ASPECTS OP POLYCHLORINATED BIPHENYL DETERMINATIONS IN HUMAN AND ANIMAL ADIPOSE TISSUE. T, J. Biros1 rf. P. Enos, A.~C. W*lker, end J. F. Thompson, EPA, Pcrrlne Primate Lab., P.O. Box 490, Perrlne, Fla. 1)157. A. R. Yobe, EPA, Dlv. of Pest., Cotmunfty Studies, Oftlc. of Pesticides Programs, Chamblee, Ga. 30341. An analytical evaluation and comparative study have been performed to establish and Improve the efficacy of a method employed routinely for easi-quantitative determination of polychlorinated biphenyls (PCB) in tissue samples by thin layer chromatography (TIC). (Mulhern, B. et. el, Abstr. 84th ann. meeting, AOAC, Oct. 1970). Quantitative result# obtained at various stages of the TLC procedures to eliminate Interferences from organochlorlne pesticide residues, have been compared with those obtained by total area measurements of gas-liquid chromatogram# of the same tissue samples. These evaluations have resulted In modifications of the original procedure and recoaaendatfona concerning the choice of Aroelor standard used In the eeml-quantltatlva estimation of sample PCB concentration. Additional studle* have been performed to establish quantitative PCB levels in human and animal tissue sample# which would (a) escape detection, and (b) be expected to lead to ambiguities in the estimation of levels of certain orgsnochlorln# pesticide residues including DDT and Its Isomers, analogs, snd metabolites concurrent In the awple. A total of 140 general population adipose tissue samples hevs bsen sub jected to analysis by combined gae chroaetogrephy-masa spectrometry to eonflrm and Identify PCB components stored In human adipose tissue. Levels of total PCB ranged from 0.4 to 3.5 ppm. Representative chromatographic and mass spectral data will be presented in addition to Identification of eoonon PCB components encountered. 20. IDENTIFICATION OF PCB's IN THE PRESENCE OF DDT-TYPE COMPOUNDS USING LOW TEMPERATURE LUMINESCENCE. J. T. Brownrigg. j, Guilfoyle, and A. W. Hornig, Raird-Atomic, Inc. ,125 Middlesex Tpk. , Bedford, Maas. 0)730. Polychlorinated biphenyls (PCB't) interfere with gas chromatographic analyses of DDT and related compounds, necessitsting a simple independent method for PCB and MOMS 079500 WATH DDT determination. The purpoac of the preeertt study wee to determine the applica bility of low temperature (77* K) luminescence methods to this problem. Basic studies Included documentation of excitstlon/emlsslon spectra of 6 pestle Idas (p, p' - snd o, p' DDE, DDD and DDT), 7 PCB isomers, and 5 PCB mixtures (Aroclors). Although phosphorescence spectra of the DDD snd DDT compounds are very similar, possible differences In lifetime and polarisation measurements may aid in differentiation. Emission from DDE Is at least 100X less Intense than that of DDD or DDT, and ta therefore more difficult to determine with adequate sensitivity. Spectral differences among various Aroclors are sufficient to allow those studied to be differentiated, in our work, emission from solvent impurities limited detection sensitivities to shout 1 0 ppm for DDT/DDD and about 0. 01 ppm for Aroclors. By removing interference, detection sensitivities should be improved by two orders of magnitude. Low tem perature luminescence studies in various binary mixtures of Aroclor 1254 and p, p' DDT indicate Aroclor 1254 may be Identified and quantitated in the presence of DDT concentrations 100X greater. (Work supported by EPA Contract No. 68-01-0082) 2 1, QUANTITATIVE PCB STANDARDS FOR ELECTRON CAPTURE CAS CHROMATOCRAPIIY. Ronald G. Webb, Ann C. McCall, Southeaat Water Laboratory, College Station Aoad,~Athena, Georgia 30601. Solutions of Aroclors 1221 through 1260 have been prepared in which the weight of PCB present in each GC peak is known. These materials will ba proposad as quantitative PCB standards. Their composition was determined by elemental analysis, gas chromatography with a Coulson conductivity detector, GC-MS, and EC in both the pulsed and D. C. modes. They can be used for PCB analysis of water, sediments, fish, and other environmental samples. 22. A COMPUTER ASSISTED GC-MS EXAMINATION OF PISH EXTRACTS FOR PCB AND PESTICIM RESIDUES IN SILICIC ACID COLUMN FRACTIONS. David L. Stalling, Plah-Paatlddt Research Laboratory, Rout* 1, Columbia, Mfaaourl 65201. Extract* of 20.0 g of fiah froe selected araae In the environment were prepared for mass spectrometry using a combination of gal permeation (CPC) and column adsorption chromatography. Extracta after GPC (using cyclohexane-BloBeada S-X2) were asperated into 6 and 15X diethyl athar-pat ethar fractions using Florlsll*. The 61 fraction was resolved by GLC and concentrated ptlor to GC-MS examination. Ravarae-phaae TLC was also employed to examine the PCB fraction. The GC-MS computer system was a PDP-11 LDP computer inCer-facad CO a Parkin Elmer 270-9 GC-maaa apactromater. The MASH (Maas Spectrometer Handler) software system wa* used for data acquisition and preparation of aaa fragmentograma. Spectra ware acquired every 6-8 seconds for up to 33 minutes (up to 250 acana). A male range of 14-555 was scanned end each spectrum was scored on magnetic tape. Meat searches for up to five combined masses were made on each act of pectra. The distribution and incidence of paretn lone of the PCB honologuee were Indicative of PCB reelduee and mass fragmentograme greatly facilitate location of spectra for confirmation. Mixtures of PCB formulations residues In fleh era clearly Indicated The occurrence of Helowaxas* or chlorinated terphenyla have not yet been detected. The GC-MS computer system la one of the few available techniques for Identification of Cheat contaminants. 23. PHOTOCHEMICAL DEGRADATION OF ISOMI-RICAUY PURE D1-, TETRA-, HI-XA-. OCTA- AND PREACHI.OROBfPliENYLS. O. Hutzinger. W. D. Jamieson, S. Safe, National Research Counci1 of Canada, Atlantic Regional Laboratory, Halifax, N. S., and V. Zitko, Environment Canada, Fisheries Service Biological Station, St. Andrew's, N. &., CANADA. The photolnitiated degradation of 4,4-di*, 2 , 2 ' ,S,5'tetra-, 3,3',4,4 *-tetra-, 2,2',4,41,5,51-hexa-, 2,2',5,31 ,4,4 ',S,5'octa- and decachlorobiphenyls was investigated under natural and simulated natural (avoiding organic solvents, wavelength of irradiation >300 nm) conditions. In most experiments, thin films of sample wore phorolyzed in the presence of H*0. From the abovementioned chlorobiphenyls, major products were those resulting from dechlorination and/or polymerization as well as polar compounds which had retained little or no chlorine. Qualitative analyses HONS 079501 1 WATR of products were by usual techniques such as GLC-mac* spectrometry as well as oy high resolution mass spectrometry using photoplate detection. Structures of degradation products will be discussed as will be conditions for their formation, 2*. DEGRADATION OF FOB'S AS STUDIED BY OXIDATIVE ELECTROCHEMISTRY. Jamo* D, Smart. Richard R. Keenan, Robart J. Fenn, Department of Chemistry, and Robart G. Janatn, Walter J. Pudelklewlca, Pesticide Research Laboratory, University of Connecticut, Storrs, Connecticut 06266. Although very resistant to oxidation, FCB'a are oxldlced at very high anodic potantlala In moderately-dried acetonitrile solvent. The anodic voltanmtry at a glassy car bon end shiny platinum alcroelectrods of Arochlur sample* yielded sn Irreversible peak In the region of +2.2 Volts vs. (aqueous) SCE. A series of pure 2,S-chloro-aubstltuted biphenyls, with Increasing numbers of chlorine atoms ranging from one to ten, wee studied by fast sweep electrochemical technlqua*. Volismnetrlc date showed that their anodic pathway# involved the Irreversible remove 1 of one or more electrons followed by rapid chemical reactlona whose unstable products were, in turn, further oxldlied. ' Macro scale electrolyaea, keeping the anode et a constant potential with a carbon (etc or platinum mssh electrode, were used to produce eufflclent amount* of the oxidative product*. Couloaetry indicated a large irreproduclble electron count. After the Initial removal of electrons from tha v-aromatlc system, the Intermediate and final product* suggest pathways that Invulva (a) hydrolysis through hydroxy compounds that in turn suffer further oxidation, (b) solvolysl# of the cationic species, (c) lntre-molsculsr oxidative coupling, (d) intar-molecular dlmerltatlon, Fast follow-up chamlcal raactions between the unstable cationic apeclea with trace* of water invariably present as Impurities in the acstonltrlle solvent or between other nucleophiles added to the solu tion will be dlacueaed lending support to the anodic pathways suggested. 25. DETERMINATION OF FCB and PCT IN PAPERBOARD SAMPLES. G.H, Thomas and L.M. Reynold*, Ontario ResearchToundatIon, Sheridan Park, Ontario, Canada, PCBs ate now recognised as possible contaminants in paperboards,particularly those containing recycled material. During the course of snalysing paper and board samples for PCBs, analytical problems veie encountered due to the ptesence of components with very long retention times under GtC conditions that were used for the PCB analyses. This paper will describe our methods for PCB analysis in pulp samples, how the con taminants other than PCB were identified * polych)arot*rph*ny) (PCTs), methods of analysis for PCTs, and how PCTs are now routinely analysed in the presence of PCBs. The procedure involved soxhlet extraction of the paperboard sample with hexane, followed by cleanup and separation uaing Florlsil column chromatography. PCTs are quantitated using electron capturs (H3) and/or (Ni63) gas chromatography. Recovery data substantiating the reliability of the method will be presented. Son* discussion will relate to methods of confirmation involving CC-MS and porchlorlnatlon. WEDNESDAY MORNING - SECTION A - SYMPOSIUM ON FCB'S - STILL PREVALENT - STILL PERSISTENT - (Continued) - Joint with Division of Pastlelde Chemistry - J. 1. Tatsley, Presiding PCB`8 III - TOXICOLOCY AND PHYSIOLOGICAL ACTIVITY 26, PCB`S IN LAYING HENS. Helene C. Cecil. Joel 81tman, George F. Fries. 1. W. Smith, end R. J. liine. Animal Science Research Division, AgrlcultdflI"Research Service, U.S. Department of Agriculture, Beltsville. Maryland 20705. Polychlorinated biphenyls (Aroclors 1221, 1232, 1242, 1248, 1254, 1268), a poly chlorinated triphenyl (PCT-Aroclor 5442) and a polybrominated biphenyl (PBB) were administered to 12 groups of 35 laying white Leghorn chickens at a dietary level of 2 or 20 ppm. Egg production, eggshell characteristics, body weight, feed consumption, mortality, fertility, hatchabillty, end progeny performance were measured. The transfer of dietary PCB, PCT, and PBB Into eggs and carcass tissue of hens was determined. Rates of depletion (decontamination) of PCB residues In tissues were studied following with drawal of dietary PCB. The patterns and rates of PCB, PCT, and PBB excretion were followed in feces of hens fed these materials. In addition, the fate of these polyhalogenated bi- and trtphenyl compounds was studied during processing and recycling to rats and cows. MOWS 079502 WATH Z7. EVALUATION OF RESIDUES Of AROCHlOP 1254 IN POULTRY PRODUCTS - B, H Tlit; 8. H, Armbrecht, Bldg. 339-D, Agricultural Research Center, Beltsvine, Hd. 20705; and H. 0. Paulin, Blonetlcs Research Laboratories, Inc., Falls Church, Va. 22048. PCB residues occurring In tissues and eggs from White Leghorn chickens following feeding or Arochlor 1254 at graded dietary concentrations are reported. Broiler Phase: Chicks were Initiated on an 8-week feeding study employing diets containing irocfflor 1254 at graded concentrations up to 10 mg PCB/kg of feed. Tissue samples for PCB analysis were collected from birds sacrificed at termination of the feeding period (no withdrawal oerlod) and tissue residue depletion was followed for 3 weeks following termination of th* feeding period. Layer Phase: Chicks (Group A) were Initiated on diets containing graded concen trations of Arochlor 1254 and maintained until onset of eg9 production. A parallel group of birds (Group B) were maintained on control diet until onset of egg oroductlon at which time feeding of test diets was Initiated. Eggs from both PCB analysis and hatchablllty determinations were collected periodically. PCB residues and egg hatchability for Groups A and 6 were compared. 28. TOXICODYNAMICS OF AROCLOR(r> 1254 IN THE MALE RAT. D.U Crant, C.A. Hoodie, and W.E.J. Phillips, Research Laboratorisa, Health Pro tection Branch, Department of National Health and Welfare, Ottawa, Canada. Male wistar rats, 30 days old, were placed on a ground cube diet con taining one of four level* (0, 2, 20 or 100 ppm) of Aroclor*R) 1254, e polychlorinated biphenyl (PCB), for 8 months and then on the baeal diet containing no pcb's for a further S months. Five rata were Killed from each group after 2, 4, 6 and 8 months to study accumulation of residues as well aa biochemical, physiological and pathological change*. Rats were alao killed at 10, 12 and 14 months to determine the reversibility of the changes. The blood, brain, heart, liver and fat were analysed for residues of PCS'* and were found to be doee related. Consistently, the 20 ppm diet significantly (P <0.05) decreased the vitamin A stored in the liver and increased the hepatic analine hydroxylase activity. This microsomal enzyme activity was also significantly increased by th* 2 ppm diet after 4 and 6 months. Liver weight was significantly increased by the 100 ppm diet after 2, 4, 6 and 8 month* and by th* 2 and 20 ppm diet after 2 months. Rats ingesting the 2 ppm diet for 2 and 4 months were significantly heavier, while rate receiving the 100 ppm diet were lighter. Results of the pathological examination of the liver end kidney, the rate of depletion of body burdens of the PCS and reversibility of the physiol ogical and pathological changes will be presented. 29. INDUCTION OP RAT LIVER M0N00XYCENA6E ACTIVITY EY SELECTED PCS ISOMER*. J. C. *ttaat> R, D. Ccar2, 7. H. Urry1, 7. A. Balend2, and 5. E. Blau1. 'Department of Animal Science, Division of Blochomtetry, Utah State Unlvaraiey, Logan, Utah 84321. 2Dapartment of Chcmlatry, Montana State University, Bozeman, Montana 59715. Prevloua study In this laboratory established the rente of liver moneoxygansa* activity Induced by the Aroclor* PCB product*. Such entyme Induction was shown to be a direct function of ihe percentas* chlorine in thoaa product* end was highly correlated with thelT mean partition coefficient! (determined ae Ra values In reverted phea* TLC). We now report the enzyme induction obtained with a asrlaa of PCB laomera administered in the diet of female rate for IS days. Liver enlargement wee minimal (IX) with th* 2,5,2' ,5'-tetrachloroblph*nyl, fed at either SO or 100 ppm In the diet. Hepatomegaly gradually Increased to a maximum of 14 and 201 (reapectfvaly for thoeo doeagoe) through the aerlee 2,4,6,2',4*,6'-hexechloto- 2,5,2',4' .S'-pentachloro-, 3,5,3',5'-t*trachloro-, decachlore-, and 2,4,5,2',4',5'-he*achlorobiphenyl. Monooxygenaee activities measured In the 10,000 x g eupernatent of liver Homogena te* uelng EPN, p-nlcroanlaole, and aniline a* subetratee followed the earn* progression ae the liver enlargement. The 2,5,2',5'-ieoeer Increased th*#* activities slightly but only at the 100-ppa dietary level (120, 104, 11BX of control for th* three substrate*, respectively) while th* moat active laomer, 2,4,5,2' ,4' ,5'*-hexachloroblph*nyl, led to values of 413, 358, and 247X of control at th* 50-ppm dietary lavel. That* activities were found to be inconsistent with the Rg, values of the compounds. Similar Investiga tion vleh aeyxneerle PCB laomara (only one ring chlorinated) will be reported. HONS 07V5C3 WATR 30. ENZYMATIC CHANGES IN THE LIVER OP RATS PED CHLORINATED BIPHENYLS, TRIPHENYLS AND DDT. James R. Allen and Lola J. Abrahemeon, Depart ment of Pathology, University of Wisconsin, Madison, Wisconsin 53706. Similar morphological and biochemical changes occurred in the liver of rats receiving chlorinated biphenyls, triphenyle and dot in the diet with the major variation being in the time required for changes to deve lop. The most obvious gross alteration was hypertrophy of the liver which developed within the initial 24 hours and persisted throughout the 30 day examination period. This increase in size was attributed primari ly to proliferation of the smooth endoplasmic reticulum <srr) and to ths formation of numerous large cytoplasmic concentric membrane arrays (CMA) within the hepatic cells. Homogenates prepared from these livers had in creased levels of protein and RNA and decreased concentration# of dna. The microsomal fractions of the hepatocytes had a decided increase In Ndemethylaae and nitroreductase while esterase levels were not altered appreciably. Thera were reduced levels of glucose-6-phosphatass and aro matic hydroxylase when expressed as a ratio to microaotnal protein. These enzymatic changes were obvious within the Initial 24 hours reaching a maximum deviations from ths controls during the first week and leveling off thereafter. Animals that aurvived for 4 months showed a reduction in rate of gain, decreased hepatic SER, reduced number* of CMA and dscreassd enzyme activities of the liver. 31. PHOSPHOLIPID SELECTIVITY IN REVERSAL OF BEEF BRAIN (Na4+K+)ATPsse INHIBITION BY POLYCHLORINATED BIPHENYLS AND DDT. C. W. Sharp and W. f. Wilson. Anal. Syn. Cheelttry Branch. NIEHS, P. 0. Box 12233, Research Triangle Park, CTTT77C57 Since membranal (Na*+K*)ATPases may play several Important physiological roles, we have tried to ascertain th* mode of action of polychlorinated biphenyls (PC8) end 00T as inhibitors of the brain microsomal enzyme. In addition to chlorinated hydrocarbons (CHs), we Investigated enzyme responsiveness to oleate, dodecyl sulfate and deoxycholate (DOC). At Inhibitory concentrations, the CHs and detsrgents form oll-fn-water disper sions or micelles; thus, limiting conditions were determined for reversal of and pro tection against enzyme Inhibition by the CHs and the detergents. (Na4+K4)ATP*se responsiveness to the detergents exhibits a thermal dependence which Is not observed for CHs. Albumin or the phospholipids can protect against or reverse Inhibition by oleate or dodecyl sulfate. (Na4+K4}ATPase responsiveness to phosphatidyl serine (PS) end. to a lesser extent, to phosphatidyl Inositol (PI) contrasts wltn that to phosphatidyl choline or to phosphatidyl ethanol amine In two respects: (1) PS and PI can reverse enzyme In hibition by DOT and by PCBs. (2) PS and PI can protect the enzyme from severe Inhibition by DOC. PS and/or PI are also effective as activators of phospholipase-treated (K. Tanlguchl and Y. Tonomura, J. Blochem.. 69, 543, 1971) or OOC-solublllzed (K. P. Nheeler and ft. Whtttam, J. Physiol.7 20f, 303. 1?70) preparations of brain (Na*+K*)ATPise. Should each of the Various observations of phospholipid selectivity have a conrnon significance. It could be hypothesized that DOT and the PCBs may effect their Inhibitory action by Interfering with normal phospholipid stabilization of the brain (Na*+K4)ATPase. 32 . DYNAMICS AND METABOLISM OF POLYCHLORINATED BIPHENYLS (PCBs) IN COLD EXPOSED PIQCON6. A.S.W. deFreitas. R.J. Noratrom, National Research Council of Canada, Ottawa K1A 0R6: O. Hutzlnger. NRCC, Halifax. Nova Scotia, Canada. Metabolism of PCBs in oold oxposed White Camoau pigeons occurred most repidly Immediately after dosing, flowing down to a much lower rats after storage of the PCBs was oomplete. The relative rate of this initial metabolism of the various component peeks appeared to be similar over a fifty fold range in total dose. Movement from adipose tissue to muscle, brain and liver tissues occurred during starvation-induced utilization of half their lipid reserves. On subsequent refeeding the PCB content ot these tiseues returned to normal values. Similar studies with DDT have shown the same effect. The enzyme system* involved in PCS metabolism ore probably linked to glycolysis as a preferred energy source, since their metabolism was more pronounced during refeeding than during starvation-induced movement from adipose tissue. Essentially no metabolism of the hexachloro components was observed. However, preferential mobilization end/or metabolism of other Aroclor 1254 components suggested that the position of the ohlorlne atoms, as well as the degree of chlorination has an influence. HONS 079504 WEDNESDAY MORNING - SECTION B - GENERAL - J. L. Monkwan, Presiding WATH j5 ivwicw-ios'Nl s-iiojg acid: oocutoh-no;, ul cers and n-nwn-uiwriON mctuoos. Cyrin * Drwct, Swedish Water A Mr Rcsomdi Laboratory, S-400 40 Gotltenburg, Swocten. Stullcs oil the formation of strong acid cn particles have shown that this process is dcjoKipnt uiw tlte tint* of sunpesnsion of a particle In different air spaces as well as of POj- oonrvntrailon and htxddity of these air ajjaces. Particle-borne strong acid, but also tJiat formed as a result of Uk> ir^iact of SOj on different surfaces could be assoclaterl with two very severe effectsi Firstly, the acidification of lakes and of the ground.Sec ondly, Uir ImuWu) effect on huan )*ea)Ui arising wlim sulphuric acid Is deposited in t)ie lower renplihtro'y trart*. As already pointed out 1-y Mrsen (ATCA, 1070), tills could >< liilerpreU'd an u ayncrgintlr effect of PO2 an' particles. It is therefore of irportance that oonllnueun funsnura <ota of strong arid In resnlrnl.le dust are nadc in ocrr.vnities with clow stirvclllance of mortality oral morbidity an related to air pollution. Tliroc najor pnobloo are asnorlated with satisfactory rreanurerent rethodst 1) Adequate sorpllne ?) Pul tnLlr fiJtf.rn for crOl^ctim of portlcles and 3> Deterrlnatice of strong acid in tlip fKkilud smilo. to wv- on roar*ilng the Bolutlcn to 1) ant' 2), vhereas 3) car no.; -e IX'^aixIe*' nr. oolvoh. 34. THE APPLICATION OK SCALE FACTORS TO EMISSION STANDARDS. Mr. Robert D. Colewan and Professor Arthur C. Stern, Department of Environmental Science# and Engineering, School of Public Health, University of North Carolina, Chapel Hill, North Carolina, 27SH. A linear programming node] which producea a rational baaia for drteralnlng the rate of change of allowable emlaaion with change of aourca tire, capacity or throughput la derived. It la designed to mlnlmlr-e coat of control to achieve air quality atandarde subject (0 the constraint of available technology. It provide* a viable alternative lo standard* baaed solely on available technology, euch ae process weight atandarde, which do not directly consider coal or air quality considerations. 3 j A CASK STUDY IN TDK DF.VKJ.OFKENT OP AIR QUALITY MANAGEMENT STANDARDS-HYDROGEN CHLO' RIDE.. Dr. Cinseppo Fumarols and Professor Arthur C. Stern, Department of Environ mental Sciences and Engineering, School of Puhiic Health, University of North Carolina, Chapel IU11. North Carolina, 27514. Historically, hydrogen chloride waa one of the first industrial pollutants regula ted. Development of air quality management standards for it presents an illuminating case ntudy of the problem of the interpretations of data on air pollution effects and on control technology. Of particular current Interest is the evaluation of eennory and re activity data from diverse sources. 3(, , THE RELATION BETWEEN CONCENTRATIONS OK SULFATE AND AMMONIUM IN AIR SAMPLER. L. Duhola, 1.. Eagan, T. Tclchman, and J. L. Monkiuan. Air Pollution Control Dir., Environmental Health Centre, Tunney'a Pasture, Ottawa. Canada. Sulphate, a ubiquitous contaminant in a suspended particulate matter, has received aome attention on account of the relatively high concentration. There la also a suspicion that sulfates may be partly responsible for the irritating properties of smog. With the present availability of specific Ion electrodes for the amnonlum Ion, it becomes possible lo study the ammonium lo sulfate relationship on a large number of samples. At the same time, it has become feasible lo monitor the genesis of ammonium sulfate in polluted ait. Analytical comparison has also been made with ammonium ion levels obtained using other method*. 37. THE PHOTO-OXIDATION OF ISOPRFNF IN THE PRESENCE OF NITROGEN DIOXIDE, CAIUION MONOXIDE AND WATER VAPOR, by Daniel Lillian and Mark Antell. Dept, of Environmental Sciences, college of Agriculture & Environmental Science, Rutgers, tlte State University, New Brunswick, N.J. 06903. Isoprene is a biologically generated atmospheric constituent suggested by theory and aome experimental observations of undergoing tropospheric photo-oxidation similar to smog forming olefins. HONS 079505 WATR A such. It may play an Important rola in the formation of naturally occurring organic aaroaol and the behavior of other atmospheric trace constituents such as ozone, NO(x), and CO. A study was undertaken in our laboratory of the effects of simulated eolar irradiation on mixtures of isoprene. NOj. ozone, and other selected atmospheric constituents. The results of this study will be presented. Based on the kinetics date obtained during the controlled irradiation, possible mechanlsmsfor the photo-oxidation of isoprene will be discussed. AEROSOL FORMATION FROM THE PHOTO-OXIDATION OF NON-LEADED FUELS Daniel Lillian and David Hansen, Dept, of Environmental Sciences. College of Agriculture & Environmental Science, Rutgers, the 9tate University, New Brunswick, N.J, 08903. A study to characterize the formation of light scattering aerosol and condensation of non-leaded highly aromatic fuels is now in progress. Gaseous mixtures of nitrogen dioxide and fuel, or its individual constituents, are blended in 200 liter Teflon bags. The bags ars placed in # controlled temperature chamber and irradiated by a lOXw linear xenon lamp with suitable filtering for tropospheric solar simulation. Variables measured ae a function of time during the two irradia tions include! condensation, nuclei, ozone, light scattering aerosol, oxidants, NO,, and hydrocarbons. The effect of aromatic fuel content on these variable* will bo presented and the mechanistic implica tions will be discussed. WEDNESDAY AFTERNOON - SECTION A - SYMPOSIUM ON PCS'9 - STILL PREVALENT STILL PERSISTENT - (Concluded) - Joint with Division of Pesticide Chemistry C. C. Gustefson, Preeidin| PCB'S IV - TOXICOLOGY AND PHYSIOLOC1CAL ACTIVITY 39. METABOLISM OF ISOMERICALLY PURE MONO-, DI-, TETRA- AND HEXACHLOROBIPIIKNYLS BY MAMMAL, BIRD AND FISH. 0. Hu Winder, D. Nash, S. Safe, National Research Council of Canada, Atlantic Regional Laboratory, Halifax, N. S., A. S. W. DeFreitas, R. J. Norstrom, National Research Council of Canada, Division of Biology, Ottawa, D. J. Wildish and V. Zitko, Environment Canada, Fisheries Service Biological Station, St. AndroWs, N. B.CANADA. Commercial polychloroblphenyl preparations, because of their complex isomer composition are unsuitable for a study of the metabolic change of these important environmental pollutants. Several unlabelled, chemically defined chlorobiphcnyls have been administered to rats (SO mg/kg for 3 days) and comparative data for pigeons and brook trout are being obtained for 4-chloro-, 4,41-dichloro-, 2,2',S,S'-tetrachloro- and 2,2'4,4*5,S'hexachlorobiplvenyl. Excreta were hydrolyzed, to liberate phenolic compounds from the glucuronic and sulfate forms, and feces and urine from treated animals compared to controli by thin-layer and gas chromatography. Mass spcctromotry established that the main metabolite, in most cases, is a hydroxychlorobiphenyl which is formed by hydroxylatlon without replacement (loss) of chlorine. In each instance, the majority of the administered chlorobiphenyl appears unchanged in the feces. Attempts at establishing the structures of the metabolites by synthesis and 220 MHz NMR will be discussed. 40. ELIMINATION PATTIRN UF ARUCIOR I2b4 COWONbNIS IN IHt BObWHllt. Georqt t. Baqlfy. ERA, Pesticide Regulation Division, So. Agriculture Bldg., Rm 1159, 14th and Inde pendence Ave., $. W., Washington, 0. C. 20250; Eugene Cromartle, Patuxent Wildlife Re search Center, Laurel, Maryland 20B10. The elimination pattern of the components of Aroclor 1254 In the bobwhtte qua11(Co!f nus vlrglnlanus) was studies under laboratory conditions. Aroci -- was administered HONS 079506 WATR as a dietary component at the rate of 300 ppm for a period of 14 days. Birds were then placed on untreated food end sacrificed at 14 or 42 days thereafter. At the end of test, three birds from the control group were each given an oral capsule dose of Aroclor 1254 in com oil equivalent to 500 mg/kg body weight and were sacrificed after 1 hour. Analysis by combined gas chromatorgraphy - mass spectrometry was accomplished on several samples from each group of test birds. Chromatograms of the treated and untreated birds are presented. The chromatograms show that a dynamic system Is at work, slowly remov ing certain components while Increasing others. The GC profile for Arochlor 1254 did not maintain Its Integrity In bobwhlte quail fed Aroclor 1254 for 14 days and clean food 14 or 42 days thereafter. Absorption of all components occurred at essentially the same rate, as shown by analysis of birds sacrificed an hour after a single oral dost of Aroclor. Significant alterations of certain PCB Isomers appeared to take place. De chlorination was clearly apparent and Isomeric transformation was suggested. 41 . EFFECT Of DIETARY POLYCHLORINATED BIPHENYLS ON GROWTH AND REPRODUCTION OP HINK. R. K. Ringer. R. J. Aulerlch and M. 2ablk, Department* of Poultry Sclent* and Entomology, Michigan State University, East Lanalng, Michigan 48023. Reproductive failure or total early kit mortality has occurred In mink receiving diets that contain Lake Michigan coho salmon. Research Indicates that an environmental pollutant of industrial origin such aa Che chlorinated hydrocarbons may ba responsible. Feeding known dietary levels of DOT, ltd laomera and dleldrln far in exceaa of that found In coho aalmon failed to duplicate the results. Adult mink were divided into three groups (12 female* and 3 males) and fad aithar a basal ration, baaal ration ex cept for the substitution of 30% coho salmon for 30% ocean fish, or tha baaal ration supplemented with 30 ppn PCB'a (10 ppm each of Aroclor* 1242, 1248 and 1234). All mink receiving PCS'* died within 121 days. Six mink fed the coho eelmon died in thie erne period. Hlscopathologlcal examination and PCR residue analysis were conducted. PCB content of brain, Liver, kidney, spleen, lung, muscle and heart of mink that died whan fed coho aalmon or PCB supplementation was extremely similar. Brain content of PCB was about twice that of other tissues measured. Organ weights, expressed aa percent of brain weight, were not algnlflcently different. Peeding 10 ppm Aroclor 1734 signi ficantly reduced body weight gains during the growing period. Combination* of Aroclor 1254 with either 0.5 ppm dleldrln or 10 ppm DDT further reduced body weight galne. Date on effect of continuous low-level feeding of Aroclor 1254 alone and In combination with DDT end/or dleldrln on mortality and reproduction will be presented. 42. TOXICITY AND PHYSIOLOGICAL ACTIVITY OF AROCLOR 1254 TO SEVERAL ESTUARINE ORGANISMS, D, R, Nlttmo, D. J, Hansen, J, A, Couch, NRCooley, and P, R, Parrish, Environmental Protect Ion Agency, Culf Breese Laboratory, Sabine Island, Culf Breeze, Florida 32361 . The polychlorinated biphenyl, Aroclor 1254, wet detected in oyiter* from Eacarabla Ba Florida, for Che first time In April 1969, The latest survey, 26 Oct, 1971, llluatrste* the extent of contamination! residues in biota ranged from non-detectsble in plants eo 10,0 parts per million (whole body) in fish (Mcnidla berylline). Since 1969, much of our effort hat been to study the effects of thla chemical on species, populations, and ecosystems. Population density of test tube cultures of the dilate Tetrahymena pyrlformls W at 96 hours was reduced significantly by 1,0 part per billion. Chronic toxicides of Aroclor to seven specie* of estuarine organism* were determined in flowing-water bloasaeys. The minimum concentration that killed shrimp was 0,9 parts per billion. Fishes were killed and oyster growth was reduced at slightly higher con centrations, Residues In organs of shrimp (Penaeus duorsrum) were greatest in the hepatopancreas, least In the abdominal muscle or axoskeleton. Craas shrimp (Palaemonetea punlo) accumulated Aroclor 1254 from water that contained concentrations las* than 40 parts par trillion, Tiaeua alteration* were found In oysters, shrimp, and fish after chrontc laboratory exposure* to the chemical. Shrimp had the least detectable histological changer-nuclear damage in hepatopancreatic cells* Oysters had more generalized tissue responses with heavy Infiltration of leukocytes and atrophy of digestive diverticula. Pish had extreme vacuolization and necrosis of the liver. MCNS 079507 WATH 43. SOUitCiiS, UWALii, AiU 'I'0/.ICOLOOICAL MUi.l KlCAIvCei UK K1B IK HATCilliHYUtiXWi'b ATLANTIC SAIjIUK. V. Zltko and 0. Hutzinger, Biological bluUoii, St. Andrews, K.H., Canada, and Atlantic Hegional Laboratory, Natiotiai i<t-scarcii Council of Canada, Halifax, N.S., Canada. ICb rosiducB found in hatchery-roared juvenile Atlantic salmon (1.23*7 4C/C wot wolf,lit, whole fish) originate from an antifouling paint. coulaJuinc 6.5# of ArocJor^ I29i. Kish food (HCB level 0,3-0.? ^g/g) is a minor source of PCB, leading to an equilibrium kcb level of 0.19 ug/g in fish never exposed to other COB sources, and to a decrease from 1.97 to 0,76 yg/g lfl 1^0 days in fish removed from tanks painted with the entifoullng paJnt. No buildup of PCB residues occurred in fish fed dry food containing 1.0 yf./c of Aroclor1' 12?N. An equilibrium level of 3*5 Mg/g was roachod in fish fod dry food with PCD level of 10.3 ug/g. Feeding food with ICB at 100 mC/c results in significant KCB accumulation (28 g/g in 120 days), "normal" mortality of fish could not be related to their KJB levels. A study of the toxicological significance of found PCB residues Jr, under way. Tha PCB concentration in the antifouling paint docroaoos ?0St on irradiation in air and changes only slightly on Irradiation under water. Possible formation of chlorinated dibensofurans ujidor those conditions is investigated. *4, residuf dynamics and moi-ocicai. effects op rotYcwoRt sated biphenyis in aquatic ORGANISMS. P. L. MATER, Jr., P. M. Mehrle, Jr., H. 0. Sender*. Flsh-Pestlcide Research laboratory, Route 1, Columbia, Missouri 65201. Toxicity residue dynamic* end blolORlcsl effects of polychlorinated blphenylR (PCHa) were investigated in severs) frosbvater flahse and Invertebrates. Acute toxlelllrs (96-hr IXjq) of PCH* to fish ranged from 278 to 50,000 jtg/1 while those for quelle Invertebrates were 3.2 to 2,400 jig/]. The l-Cj0 values for fish continuously exposed for ?5 to 30 dsys vsried frow 3.4 to 433 jug/l and 5-to 10-day exposures of Invertebrates resulted in J.C30 values of 0.6 to SOjig/l. Biological magnification of Aroclors 1746 and 1254 by blueglll* won 26,300 to 71,400 times the levels In water after 60 days. Invertebrates sxposed to Aroclor 1254 showed e residue magnification up in 47,000 lime* greater than in water. Dietary doses from 1.45 to 14,500 pg Aroclor lJ34/kj* body wl. per day to coho salmon had no effect on growth, nor pioduced observable toxicosis until death occurred In the highest dosage group after 260 daye. Thyroid activity, a* measured by 72-hr thyroid*) 325] uptake, was increased algnlflcantly. Stimulated thyroid activity occurred In ealmon doaed with 1/lOOOth of that causing mortality. Dietary dosea of Aroclors 1232, 1248, 1254, and 1260 to channel catfish st concentration* of 68 and 480 pg/g caused no mortality nor had any effect on growth. Thyroid activity was altered only by Aroclor 1254. The low doee Increased thyroid activity by 56X, whereas a 9)X Increase was Induced by the high doee. Implications concerning PCIle in the aquatic environment are discussed. 45. EXTENDING TOXICOLOGICAL INVESTIGATIONS. Joseph C. Street, Department of Animal Science, Division of biochemistry, Utah State University, Logan, Utah 64321. blaruRNion on thr future of toxicological studies for the PCB's with both terrestrial end aqtinlic orgaitlnmfi. 46. PKOSPLCTS FOR THE FUTURE! FDA REGULATIONS AND TOLERANCE LIMITS. A. C. Colbye, Jr., U, S. Food and Drug Administration, Washington, P.C. 20000. The Fond and Drug AdmJnj*trm 1 on'e regulations and tolerance limits for the FCB'e will be diactiRBcd aa well an the prospects regarding future PCB tolerance limits. WEDNESDAY AFTERNOON - SECTION B - GENERAL - J. L. Monkman, Presiding 47. TWI ORGANIC CONTENT OF STANDARD REFERENCE SAMPLES OF ASBESTOS. A. Edrojewakl. J. HllHom, L. Dubois, and J. L. Monkman. Air Pollution Control Dir., Environmental Health Centre, Tunney's Pasture, Ottawa. Canada . Some studies on the totsl organic and polycyclic hydrocarbon content of asbeatoa have been made under conditions which could have led to significant losses. Indeed, in some of the nethods used complete evaporation of the solvent was made after extraction of the organic compounds. MQNS 079508 WATH Wlilt low boiling compounds such as the C-9 ate. aliphatic* and some aromatic*, complete elimination of the solvent should be avoided. Four standard asbestos samples, provided by the International Union sgalnsi Cancer, have been extracted with a low boiling solvent and the organic content measured by ultraviolet spectrophotometry end gaa chromatography inter alia. 40, AN INTERIM REPORT ON ANALYTICAL MJTHOUB UBEI) IN A COK* OVEN EFTLUENT STUDY, Donald J. Larsen and John V. Crabls, U.8. DHEV-PHR-HSMHA-JIstional Institute for Occupation al Safety and Health, 1011* Droadvay, Cincinnati, Ohio L5202. NIORII Is evaluating the applicability and efficiencies of sampling procedures and analytical methods In determining the potential hasards associated with coking and roof ing operations. Thla 1* an Interim report dlacuealng analytes obtained from seven ana lytical methods that vsrs applied to temples collected in e coke oven effluent study. The analytical methods Includsd: (1) bentene soluble extract; (9) the gas chromato graphic eeperatlon method for fluoranthene, pyrene, benx(e)anthracene, chrysene, bento(a)pyrene, bento(e)pyrens, bent(c)acrld]ne, beni(a)antnrone, Penso{b)fluorsnthee, beno{J)flooranthene, banto(k)fluoranthene, dlbena(a,h)anthracene, anthanthrene, and banao(g,h,lIparylene; (3) thin-layer chromatography for beno(a)pyrene; (k) the liquid column chromatographic separation for pyrane, fluoranthene, chrysene, bens(a)anthracene, bcnao{a)pyrsns, benio(e)pyrene, ben*o(k)fluorenthene, perylene, bento(g,h,lJperylene, and anthanthrene; (3) fluorlmetrlc index; (6) atomic absorption techniques for nickel, cobalt, chromium, manganeae, copper, and sine, (7) gas chromatographic procedures for samples of solvent vapors on charcoal tubes for bentene, toluene, xylene, and napthalene. 49, 1NSTRUHKNTAT10N. L. Dubois, R. S. Thomas, end J. L, Honkman. Air Pollution Control l>lr., Knvlrnnmrntal Health Centre, Tunncy'e Pssture, Ottswa, Canada. An snllvonrd public awareness about the environment hoe broadened the scope and diversity 0( ambient sir quality meaaurcmonts. Increasing demands are being placed on control agencies to provide date on both long term trend end transient pollution levels. An concentrations of permitted pollutants are lowered by legislation, the onfs falls on the analyst and lnatrmient manufacturers to provide techniques and instrument a which will produce data comparable and interrelatable from city to city and country to country. While new techniques are besoming available, much of the data publlahed In the literature suffers from Inconsistencies related to sampling problems, aamplo preparation, calibration standards, chemical Interfertncea and non reliable monitoring Instrumentation. As the emphasis toward network monitoring grows, en Increasing reliance will be placed on field or remote sensors feeding data to a central processing centre. A number of failures and pitfalls ere discussed and some solutions are offered In problem areas. 10. MONITORING REACTIVE AND NON-REACTIVE HYDROCARBONS IN AIR USING SELECTIVE ABSORPTION. Bernard E. Saltiman, William R, Burg, John E. Cuddeback, Kotterlng Laboratory, University of Cincinnati, Cincinnati, Ohio 45219. A convenient air monitoring system oapable of assessing concentra tions of hydrocarbons with the potential for producing photochemical smog is reported. A pump with appropriate flow controls continuously forces simple sir through an empty column and an absorbent column arranged in parallel. The air flow from each column is directed alternately by a switching valve to a flame ionisation detector. Quantitative measure ments of the concentrations of total hydrocarbons and of unreactive hydrooarbons are made directly. The concentration of reactive hydrocarbons removed in the packed oolumn is obtained by difference. Solid absorbents and the factors affecting their ability to absorb various classes of hydrocarbons ware studied. Column dimensions, flow rates and the tempera* ture were adjusted so that a maximum of the hydrocarbons participating in atmospheric photochemical reactions was absorbed, while allowing all re maining hydrocarbons to pass through the column unaltered. Monitoring data for Cincinnati is reported using this technique. HONS 079509 WATR 5! THE APPLICATION OP GAS-PHASE TITRATION IN THE SIMULTANEOUS CALIBRATION OP NO, NOj. ' NO*, AND Oj ATMOSPHERIC MONITORS. K. A. Rehme. B. B. Martin, and J. A. Hodgaaon, Environmental Protection Agency, National Environmental Reeearch Canter, Reeearch Tri angle Park, N. C. 27711. The fast reaction between nitric oxide and ozone has been used to compare Indepen dent method* for calibrating NO, NO2. NO*, and Qj monitors, and to provldt a routine calibration procadura for NO, N02 N0X, and O3 at a common manifold. A conatant flow of air containing NO at concentration* of 0 to 1 ppm la aetabllehed In a flow reactor. Up stream of the reactor, the air passes through an ozonizei capable of producing ozone concentration# of 0 to 1 ppm. Ozone Is added to the air stream In concentrations up to 50 percent of the initial NO concentration. The concentration of NO2 produced le equivalent to tha concentration of O3 added, whereas the N0X concentration remalne the aama. The decrease In NO, or the appearance of NO2 can be monitored by meant of specific Indicators (e.g., chemiluminescence) and related to the ozone added. The experimental apparatus and tha titration conditions will be described. This system permits routine calibration of monitors of oxides of nitrogen snd ozone at a common manifold, using a primary standard for only one of the gases. Tha primary standard can be known concen trations of MO2, NO or O3, as determined by uae of permeation tubes, precalibrated cylinders, or wet chemical methods. Absolute relatione among these standards, as determined by gas-phase titration, will be presented. 52 A COMPARISON OP SULFUR COMPOUNDS (H2$Oft, F.S.S. AND T.S.S.) POUND IN THE ATMOSPHERE OP MEXICO CITY, MEXICO, MONTREAL AND OTTAWA, CANADA. H. Bravo A.. Inetituto da Ceoflaica, Univereldsd Naclonal de Mexico, Mex ico, 2oT D.P., Mexico, L. Morkman, Department of the Environmental Air Pollution Control Division, Ottawa, Ontario, Canada, A. Lowe, Inetituto de Ceoflaica, Unlvaraldsd Naclonal de Mexico, Mexico, 20, D.P., Mexico. Sulfur compounds are found In urban atmospheres as gases and particu lar matter such as mecaptans. hydrogen sulfides, sulfur dioxide and sulfates of calci um or ammonium. One of the constituents of sulfur compounds found in the atmospiiic In sulfuric acid. in our sampling we used a High Volume Air Sampler with fiberglass free sulfate filter) which collected all the sulfur compounds discriminating the gaseous sul fur compounds. The sulfuric acid determination was carried on by the micro diffusion method described by Monkman. The polarographtc method of Mayer with some modifi cation was used to measure the sulfates. Samples from Mexico City 1968-1969, Mon treal and Ottawa are compared and are reported in this paper. The near values of sulfuric acid In Mexico City were to three times high er titan that found In Ottawa's air. The percentage of sulfuric orT. S. S. is higher than usual tn Mexico. The values In Montreal during the winter are near the value for sulfu rlc acid In Mexico City. The correlation coefficients found in Mexico City and Mon- " treal amoung particulate matter In relation to sulfuric acid and l7. S. S. and T.sA ran ged from 0.86 to 0.97. " S3. THE MEASUREMENT OF MERCURY IN AMBIENT AIR. G. L. Corte, J. L. Monkman, R. S, Thomas, and L. Dubois. Air Pollution Control Directorate, Environmental Health Centra, Tunney's Pasture, Ottawa, Ontario. K1A 0113, Canada. An air sampling device for air borne mercury waa developed and evaluated. The trapping element le silver In the form of gauze which la able to quantitatively absorb, retain and quantitatively desorb up to 100 nenogrema of elemental mercury from elr. Air is drawn through the absorber by aeane of a modified "personal" air tempter, which la Operated by a A,8 volt rechargeable nickel cadmium battery. The sampling time can be selected manually, by means of clock-work timers and by remote radio con trol. By varying sampling times and flow rates, one can measure a range of S to 100,000 nsnngramt of mercury per cubic metre of air sampled. The mercury collected la desorbed into a modified DuPont 400 mercury analyzer and measured by ultraviolet abeorptlon. A strip chart recorder end a Hewlett Packard C.C. Integrator provide total output measurement. The analyser was calibrated by liberating mercury from standard aqueous solutions by injecting known volumes of saturated mercury vapor and by means of a mercury permeation tube. HONS 079510 WATH A mull ipurpoao sampling manifold was constructed with provision for the continuous epoauremcnl o( mercury In air, tn compressed gases, In rock and ore samples, and In liquids, Some appllcstlono of the eieihod to organic mercurial compounds are given. 54. TIIK V0MT1L1TY OF P0LYCYL1C AROMATIC HYDROCARBONS AND RELATED PROBLEMS IN AIR POLLUTANT ANALYSIS. L. Dubois, A. Albagll, J. L. Monkmen and A. Zdrojewakl, Air Pollution Control Dir., Environmental Health Centre, Tunney'e Pasture, Ottowa. K1A 0)13, Canada. It has been observed In the paper chromatography of polycyclic aromatic hydrocarbons thal moat of an anthracene spot (as en example) would disappear from the paper In a few days. Knowing the volatility of the two and thras ring polyeycliee it seems appropriate to find out if some of the higher numbered ring hydrocarbons are also volatile In the conditions usually encountered during the measurement of these compounds. In evaluating thla property. It was found that the adsorption of the compounds on the surface of heakers and glass fibre sheets la much more Important if the solvent la coaipletely evaporated. Prom these results, It is indicated that In any mctltod for the measurement of such compounds, all steps involving the complete evaporation of the solvent should he eliminated and other methods of sampling and extraction should also be investigated. THURSDAY MORNING - SECTION A - SYMPOSIUM ON THE TRACB METAL INTERACTIONS HUM SKDIMKMTE - J. 0. Leekie. Presiding 55. TOR TOP. PATE OF HEAVY METALS IN SEDIMENT. Teh Fu Yen and Kanneth Y. Chen, Environmental Engineering Programs, Univ. of Southern Calif., Los Angeles, Calif. 90007. SuipKon, redo* reactions, precipitation and complex formation oo-detarmlne the fata of heavy metal* In natuial water* and sediments. Heavy metals art concentrated by metal oxides and hydroxide#, e.g. M^Og, Fc(0HU, AlgOj, up to several thousand times of solu tion concentrations and coproclpltate ln^aedlment. Supcraeturatlon with respect to metal carbonates could also lead to precipitation and accumulation In sediment. An exanqtle la the precipitation of COOO^ observed In eomc paTte of Southern California coaatai waters. In sodlmenla, reducing conditions ean lead to the dissolution of metal oxides end hydro xides with subsequent release of heavy metal*. However, under thla condition, metal sulfides are usually formed and further reduce the availability of hoavy metals to over lying water*. Availability of heavy metal* can be Increased through coaiplex formation. Many of lhr metal complexes and chelates found In sediment were actually present via template reactions. Organic ligands from biological debris and synthetic organic material* bind tightly to metal Ions In covalent linkage*. Frequently organic ligands, which appear as functlonel groups of hydroxyl, carboxyl, aldehyde, amino, amide, mercaptan, ate., are part of natural murromolecular ayatema. In this manner, micelle formation, association and dlaessoclation, characteristic# of water-sediment interface and other colloidal behav ior can he explained. Experiment*! roaulta and evidence using electron spin resonance, mate spectrometry, Infrared anectormetry, and atomic absorption methods will be discussed to substantiate these model*. 56. THE EXTRACTION OF BIO-D1AGF.NFT1CA1.LY AVAILABLE TRACE ELEMENTS FROM SEDIMENTS AND SOILS. B. A.Jcnnc and J. W. Bell, (I. S. Geological Survey, Weter Resources Division, 345 Middlcfleld Road, Menlo Park, California 94025. The Important short-range trace-element elnks tn eedlmenti end soils ere organic, hydrous oxide* of Iron and manganese, and carbonates. The trace elements In these sedi ment fraction* may be released to the biosphere under the combined action of biological and chemical dlagcnetlc processes. A method has baen developed for the extraction of trace element* from ssrth materials at 80C by the serial addition of reagents using a single container. Carbonates which may be present are dissolved with hydrogen-aodiutn citrate (pH 3), then hydrogen peroxide in dilute nitric acid la added to decompose readily oxldlaable organics and allowed to react overnight, finally sodium dlthlonlte Is added to reduce iron and manganese oxides. Following centrifugation and decantation the trace elements In thla extract ere analysed directly by atomic absorption or following solvent concentration aa appropriate. The trace elements presently analysed for Include Ag, Be, Cd, Co, Cu, No, Nl, Pb, end En. HONS 079511 WATK 57. TRACE METAL INTERACTIONS AT TOE MANCANE* DIOXIDE - SOLUTION INTERFACE. J.W, Hurray, Department of Chemistry, Woods Hole Oceanographic Institution, Woods Hole, Hast. 02543. Hnngsnsis Dioxide has long been known to be an efficient scavenger of trace metals. The two factors that are responsible for this phenomenon (Che surface charge and apoclfio adsorption) have been studied In detail. Electrophoresis, Na+ and K+ adsorption, and alkalimetrlc titration experiments have been used to locate the pH (EPC) of a suspension of 6Mn0g at approximately 2.25. As for other motal oxides, W+ and OH* have been found to be potential determining lone, however, below pH 3 the reduction of Mn02 by HgO releases rtf1-2 and It la possible that this Ion must also be considered to be potential determining. Because of the low pH (ZPC) the surface charge in the pH range of natural waters can reach valusa up to 100 w coul/cm2. In addition to the high surface charge, specific edsorptlon is en important factor in considering the adsorption of some trace metals. Alkalimetrlc experiments have bsen combined with direct messuremente of adsorption snd desorption for severs! metal lone. The results of these experiments indicate that the alkali earths adsorb reversibly on the (JKnO, surface Iti the order- - 2 Mg4"2 < Ca*2 < Sr+2 < Ba*2 and that the transition metals adsorb in a highly Irreversible manner In the order Cvo.+2 * h.,+2 . Cu >' mNl4^* 58. KINETICS OF SOME SILICATE REACTIONS IN SEDIMENTS. R. Slevet end J. B. Maynard, Department of Ceologtcal Sciences, Harvard University, Cambridge, Haas. 02138 . Dissolution of magnesium silicates and of potassium feldspar have been reported to follow parabolic klnatles. We have found that the dissolution of plagloctisa feldspars also obey* this rate law ss does a silicate reconstitution or ''reverse weathering" type reaction, that of kaollnlts sorption of H.SlOj and K4" from solution. We find rate con stants for the ilumlno-illlcate reactions of about 10*'' molcs/cm2. see*'2 liter 1 at 25 C, In agreement with the K- feldspar date but somewhat slower than the 10*11 reported for magnesium silicates. Except for a very rapid Initial portion of the reaction that seems to be essentially a surface phenomenon, the rates are largely Independent of solu tion co^>osltion so long ss the stability field of the reactant mineral Is not entered or at leeet closely approached. These observations Indicate that the reaction Is limi ted by diffusion within the solid either through a rind of some dletlnct product pheea or along continuous gradient of variable composition of the phase produced by altera tion of the original structure and composition. These rstee are sufficiently rapid tor equilibration of silicates with any surrounding waters over geological time scales as low as thousands of years. This may indeed be the case for sea water, at least at allies concentrations found In the pore epaces of may recent eediment*. The periltttnci of detrltal feldspars of sand grain site for 109 yeara may Imply long term equilibrium with ground water and clays. S9, THE ADSORPTION OP HYDROLYZABLE METAL IONS AT THE OXIDE-MATER INTERFACE. R. O.JAJg, Department of Applied Earth Sciences, Stanford University, Stanford, California 94305. The absorption behavior of hydrolyesble metal Iona ac the solid-water interface is strongly pH dependent and la characterised by a general egreenent between the hydroly sis of the aqueous metal Ions and their enhanced adsorption, charge reversal and coagu lant properties. Models which are used to describe the phenomena, Including the Ion exchange end specific adsorption of certain species are compared to a recent nodal pro posed by James and Healy. In this model all the species of hydrolyesble metal ion are considered ss potential adsorbates, but only (he lower charged, less strongly hydrstsd hydrolyesble complexos have favorable free energies for the adsorption process. THURSDAY MORNING - SECTION B - GENERAL - J. L. Monkman, Presiding 80. PHOTOFRAGMENT DETECTION OP N02 AT REDUCED PRESSURE. W. A. McClenny. J. P. Bell, snd J. A. Hodgeson. ENVIRONMENTAL PROTECTION AGENCY."National Environmental Research Center, Research Triangle Park, N. C. 27711, A low-pressure system for the separate detection of nitrogen dioxide (NOj) end ozone (O3) at ambient concentrations la described. A sample sir stream containing NO] and O3 la passed through an irradiation chamber In which NO] la photolyted to form oxygen atone (0) and nitric oxide (NO). After passing through * *'"ible Wood's horn HONS 079512 mm light trip, the air stream enters a reaction chamber Into which purr NO is also intro duced. Chcallumlnrscsnce occurs from the reactions: 0 NO NOJj ((11)) Oj 4 NO * N0$ (2) recorded continuously. Oaone la determined separately by turning off the Irradiation sourer and recording only the signal from reaction (2). This signal Is subtracted from the total algnal of reactions (1) and (2) to give that due to NO) alone. The sensitivity of this system depends upon several factors, which Include: (l)light source, (2)reactlon-chamhcr pressure, (3)pumplng speed, and (A)nlrric oxide flow rates. With a nitric oxide flow rale, of 10 ail/min., a 200 watt Xc - Kg arc source, a pumping speed of 4 1llern/min., and a reaction chamber pressure of 8 Torr, the sensitivity of the system is greater than 0.0> na/pph. Data showing signal dependence upon the different factors are given, and interference# are discussed. 61. AN ANALYTICAL TECHNIQUE FOR CASEOUS POLLUTANTS BASED ON PHOTOLYSIS AND DETECTION OF PRIMARY FRAGMENTS. J. A. Hodges on and W. A. HcClenny. ENVIRONMF.NTAt. PROTECTION AGENCY, National Environmental Research Center, Research Triangle Park, N. C. 27711. A new technique is proposed for the detection of a class of toxic air pollutantn which have the common property that each undergoes photolysis in the solar region or the near-ultraviolet. This class Includes pollutants such as nitrogen dioxide, nr.nnc, formaldehyde, halogens, hydrogsn halides, hydrogen peroxide, and organic peroxides. These molecules yield, upon photolysis, reactive atomic and molecular fragments, which may he important In atmospheric chemical processes. By a spectroscopic detection of the fragment, the photolyal* property may be used In the measurement scheme for the prltsary pollutant. The fragment will Inherently possess more Intense amission and absorption apoctra than the primary molecule. Detection schemes proposed include applications of chemiluminescence and resonance fluorescence. The primary fragments of interest are the oxygen atom, hydrogen atom, halogen atoms, and the hydroxyl radical. Related works on detection of these species arc reviewed. The experimental methods being employed In both chemiluminescence and fluorescence detection schemes are doscrlhod. 62. DETECTION OF NITRIC OXIDE BY CKEK1LUMINESCENCE AT ATMOSPHERIC PRESSURE. B. E. Msrtjn, J* A. Hodgsson, and R. K. Stevtns, Environmental Protection Agency, Envi ronmental Research Center, Research Triangle Park, N, C. 27711. A system for detecting ambient concentrations of nitric oxide (NO) la described. Tltls system Is similar to other chemiluminescence systems, except that it is operated at atmospht'ilc pressure. Ths system consists of a detector cell, a photomultiplier, a cut off filler, a sampling pump, and two low-pressure, mercury lamps. The detector cell is similar In design to the Nederhrsgt ozone-ethylene detector cell. A visible cut off filter Is added In front of the photomultiplier to make the system specific for NO. A small pump pulls the sample through the detector cell where it is mixed with an excess of otone. The total flow Into this system la 1600 cc/eiln., which includes 75 cc/min. of oconJzrd oxygen. The light emitted from the reaction between ozone and NO is monitored by a closely coupled, thermorlectrlcally cooled photomultiplier. With the current system, 0.006 ppm of NO can be detected with a 2:1 eignal-to-noise ratio when the re sponse tine Is 10 seconds. Data are given for signal versus concentration of NO for various sample and otone flow rates. Operating conditions for achieving optimum enaMfvJly and linearity will be given. Data will be shown for real-time ambient measurement. A list of compounds that produce chemiluminescence when reacted with ozone will be given. Also given will be data obtained with and without the cut off filter, which wns added to reduce the interference from such compounds. *3 APPLICATION OP SOLID ABSORBENTS IN AIR POLLUTION SAMPLING AND ANALYSIS. Bernard E. Salteman, j. e. Cuddeback, and William R. Burg, Department of Environmental Health, University of Cincinnati, Cincinnati, Ohio 45219' The u*e of eolid absorbent* for the sampling and analysis of NOx has beon studied. Several absorbents have been found suitable for use with highly sensitive detectors such as the couleon conductivity detector and the mloroooulometrlc detector. The absorbent# provide a versatile easily HONS 079513 WATR handled system for taking samples at a remote location with subsequent desorption and analysis done in the laboratory. Efficiency data, sampling rates, capacity and other data will be presented for a copper based absorbing system as well as the analytical procedure tor quantita tion of NO . The system is not subject to interferences from the commonly occurring air pollutants. 64, DEPOSITION OF RJBT ON A BODY IN A FLOW 3TORAH. 0. F. Morr anq 3. L. Soo. Depart ment of Mechanical and Industrial Engineering, University of Illinois, Urbana, Illinois 61001. Deposition of dust on a body in the form of an ellipsoid of revolution was studied to determine the ways of enhancing or reducing deposition of dust particles. In flow velocities up to 66 feet per second is a wind tunnel, deposition of 10 micron magnesia dust on an ellipsoid mads of brass was measured. The dust particles were charged as in the case of particle In nature; the Influence of electric potential on the ellipsoid was also studied. Deposition patterns showed effects of flow regimes over the body. 65. MEASUREMENT OF STATIONARY SOURCE GAS EMISSIONS: EXTRACTIVE MONITORING TECHNIQUES. John S. Nader, Environmental Protection Agency, National Environmental Research Center'/ feraarch triangle Park, North Carolina 27711* The extractive method of measuring gas emissions is presented as the approach utilized more extensively than the newer approaches under development. The whole measurement system is treated end includes both sampling and analyst*. Systems for sample transport end sample pretreatment, which vary, are described. Mechanical di lution and diffusion techniques are discussed. Analytical methods of both on-going systems and those under development or evaluation are presented. The techniques are reviewed in terms of physical and/or analytical principles that are categorized as electrical, nuclear, thermal, electromagnetic, chemi-electromagnetic, and magnetic. A summary is givon of the status of development of extractive monitoring systems that includes commercial systems, prototype systems, research instruments, and feasibility studies. 66. MORTALITY EXPERIENCES OF U. S. ROOKING WORKERS EXPOSED TO POLYCYCLIC HYDROCARBONS. Irving J. Selikoff, Mount Sinel School of Medicine of the City University of New York, Fifth Avenue and 100 Street, New York, N. Y. 10029. We have been following, prospectively, the mortality experience of al) 18,000 members of tha Roofers' Union In the U. B. and Canada on the Union's lista as of Jan. 1, 1959. Mora than 2,500 deaths occurred by Dec. 31, 1971. Age, year and specific expected death rates have been calculated and will be compared with the numbers observed, by specific ceuae. We have also measured the exposure of auch wuckere to benepyrene end other polycyclic hydrocarbons at Job sites, using personal (mask) samplers. Comparison of expected and observed deaths will thus provide information concerning cancer risk associated with occupational polycyclic hydrocarbon exposure derived from coal tar pitch and asphalt. 67. PREDICTION OF HEAVY METALS IN SETTLEARLE PARTICULATES. Rosa F. McCurdy and Harold J. Paulus, School of Public Health, University of Minnesota, Minneapolis, Minnesota 551*55- Dustfall samples have been collected for a one year period In Sydney, Nova Scotia, Canada, Tha main industry In this city consists of an intergrated Iron and steel manufacturing oomplax consisting of coks ovens, two blast fumacss, a sintering plant and five open haarth furnaces, Ths dustfall samples were analysed by the classical gravimetric prooedure. The iron, manganese, and sine oontents of each of ths samples were determined using a Beckman Atomic Absorption Spectrophotometer, Analysis of variance, linear and multiple regression techniques wars applied to the data. Seasonal trends appeared to be absent. The dustfall residue showed a high degree of correlation with the dustfall ash. Slndlarlly, the iron, manganese and slno were found to be slgnlfioantly correlated with the dustfall residue or ash. A working prob ability model for prediction of heavy metals in dustfall was estimated. HONS 07951* WATK Sever*) Important results oan be drawn from this study, fy knowing the statietlcel distribution of elr pollution variables, a prediction model may be Implemented to est imate will) accuracy the oonoentretlon of certain elr pollutants, with e limited amount of Information. 8ocondly, to avoid complicated or tedious laboratory analysis, the most easily determined constituent oan be analysed end other oonstltuente predicted. The awn hours and monoy saved could be projected in extending useful areas. THURSDAY AFTERNOON - SECTION A ~ SYMPOSIUM ON PHOSPHATB INTERACTIONS WITH SKMMKNTS - J. 0. tackle, Presiding 61. PHOSPHATES IN THE SEDIMENTS OT THE PAMLICO ESTUARY. Joseph B. Upchurch. Jawee X. Cdswald, Chariee R. O'Neils, Department of Environmental Sciences and Engineering, Sehoel of Publie Health, University of North Carolina, Chapel Hill* N. C. 2751k. The amount of "available" P extracted from sediment samples along the 30 mile length of the Pamlioo estuary was observed to decrease from l.S mg P/g sediment In fresh water to 0,9 ^ P/g in water with a salinity of IS ppt. Wet-eleve analyaaa indicated that ailt and clay-aiaed materials comprised DO peroent by weight of these aedimente. X-ray diffreetien measurements Indicated that tha clay mineral* were primarily kaolinite, llllte, ohlorite, and a chlorite-like lntergrade clay. The "available" P wee aeeeured by modification of the HC1~H2&0u (pH 1.1) acid extraction procedure of Oleen and Dean (Oleen, I.R., Dean, L.A., Methedt of 8oll Anelvsle. Part 2. C.A. Sleek, Ed., pp. 109Sat. Amer. Soo. Agron., Madison, Vie.. 19651. A highdegree of correlation (r o.M) between oxalate-extractable Pe and "available'' P was found in the upper reach of the oatuary (salinity 1 ppt). Correlation between re end P has else been reported in fresh waters for sediments collected from Wisconsin lakes (Williams, at el., Envlr. Set. 5 Teohnol. Ii 1119-20, (107D). Xn the lower part of the oatuary (salinity > 1 ppt) this re - f oorreleticn decreased (r 0.06). The decrease in the "available" P content ef the sediments and the reduction in the re - P correlation along the length of the estuary are consistent with the suggestion that P la held to suspended eleye and sedi ments by sons typs of Ts-lnorganlc P complex of limited stability. Clays entering the estuary In ths freshwater Inflow would then lose P as they are transported through waters of increasing salinity to the mouth of the estuary. KJNKTIC 8TUW OF PHOSPHATE REACTION WITH ALUMINUM OXIDE AND KAOLINITE. Y.8. Chen. J. N. Bullet, W. Slum, Division of Engineering end Applied Physics, Hsrverd Univer sity, Cambridge, Maes, 021JU. The kinetics of phosphate reaction witho-AlgOj end kaolinite Involves two steps (1) an Initial rapid step, (2) a following slower Step )efter 24 hours). In the rapid step, phosphate quickly adsorbs on -A)-0)1 surface sites or is precipitated by available posi tively charged aluminum Ions. In the slow step, phosphate resets with the aluminum which dissolves from aluminum oxide or kaolinite end forms a new aluminum pboaphste solid phase. Tiro formation of hexagonal crystals of e new solid phase wee verified by electron microscopy. The s-rsy diffraction pattarn showed lines which ere probably due to an aluminum phosphate. The heterogeneous resell one of phosphite wltha-AloOa and kaolinite In acid aolutlon af ter the initial rapid removal atep can be described By the first order form - i lP)/.t 5 K,,b, [P] where [P) la the total soluble phosphite end t is time. The observed specific rate con stant (K_h,,) is higher for lower pH, higher surface areas end higher Ceapereture*. At high pH (approx, pll>7,5) there is adsorption but essentially no aluminum phosphite pieclpUatlon. The slow step reaction rate for a second phosphaee addition was higher than for the first phosphate additions. For the a-AlgO* system, a fluoride Ion concsntrstlon ni 1 x 10** H decreases the degree of phosphate removal In the initial rapid etep, but does not decrease the rate In the following slower step. Successive additions of phosphate to the o-AlpOt-phoephete and kaollnite-phoephate systems how that the amount of phosphate removal in the initial rapid step decreases with each addition ot phosphate. Tills indicates the dogres of eurtace saturation by phosphate and the relative acarclty of exchangeable aluminum In solution. 70. SPECIFIC ADSORPTION OP PHOSPHATE AND SILICATE AT HYDROUS ALUMINUM OXIDB/KLECTROLYTE (O.lMNaCJ) INTERFACE. Chln-pao Nuent. (Department of Civil Engineering, Wayne State University, Detroit, Michigan 68202) end Werner Stum (1AWAG-ITH, Zurich, gwllscrlend). The sdeorption characteristics of ortho-phoephete end.mono-eil^cace species on hydrous y-AljO^ surface from dilute aqueous solutions (10 M to 10 M) st constant ionic HONS 079515 WATH trongth (O.iM NaCl) 1b reported. Phosphate and silicate lana art strongly adsorbed onto either poaltlvtly or negatively charged hydrous aluminum oxide surfaces, resulting In a raleaea of protona. The aaount adoorbed la apparently pH dependent with a maximum at 4.5 for phosphate and 9.0 for atllcAta. In general, the rata of adgorptlon la a function of auapanalon pH, total.aoluta.conceatratlana, and total solid aurfaca; the addition of divalent cat Iona (Be , Sr , Co , Mg , Ou(II), Zn(II), Co(II), Nl(Il)) haa little effect on aodlfylng the extent of adaorpdon at 1:10 level, bur enhanced adaorptlon la obaarved with Increaae cation concentration (1:1). The aechanlaa of adaorptlon can be primarily described by the Crahame-Stern model of Ionic doubla layer. 7J ,THR MECHANISM Or CRYSTAL CROWTH or CALCIUM PHOSPHATES. C.H. Nancollaa And J.S. Wefeli Chemistry Department, State University of New York at Buffalo, Buffalo, New York, 14714 . The precipitation and dlasolution of calcium phosphates frequently pea* Important problems in natural water systems. Their BOlutlon depends upon en understanding of the mechanisms of thess processes and the ways In which they can be controlled. Moat pre vious studies have bean concerned with spontaneous precipitation experiments which ara complicated by the fact that nucleation and crystal growth occur simultaneously. In our work, we have studied the kinetics of crystal growth of both dlcalctun phosphate dihydrete (OCPD) and hydroxyapatlte(HAP) under reproducible conditions of seeded crystal growth. The growth kinetica of DCPD has revealed e second order dependence of rate upon relative aupersaturetion whereas dissolution la first order with respect to aubeaturetlOft. The remarkable growth inhibiting effects of adsorbed additives such aa pyrophoaphata Iona can be interpreted in terms of a simple Langmuir type edeorptlon isotherm as an sffactlva blocking, by adsorption, of the active growth site* at the crystal aurfaca. Tha growth of HAP takes place through the formation of one or more precursors having a calciumiphoaphats mola ratio appraciably lower then that requirad for tha final crystalline produce. The effect* of additives such ss phosphonate, magnesium end other metal Iona upon tha cryatal growth will be discussed. 7 2 . THE EFFECT OP PHOSPHATES AND PHOSPHONATES ON NUCLEATION AND CRYSTAL GROWTH OP CAL CIUM CARBONATR. M.M. Reddy end G.H. Nancollaii Chemistry Department, State Univer- of New York at Buffalo, Buffalo, New York 14214. Characterisation of the rates and mechanism of caleiw* carbonate crystal growth have been performed using a highly reproducible seeded growth technique. Results of these investigation* indicate that the rate determining step in the growth or calcium car bonate, a ccsmnon sediment in natural water system*, is a surface controlled reaction, precipitation of calcium carbonate in the presence of certain phosphates and phos phonate* may play e role in phosphorus exchange between natural waters and sediments. Seeded crystal growth experiments have bean carried out in solution* with phosphorus containing ions. Results of thsse experiments show that both the nuclaatlon and crystal growth rates of calcitsn carbonate are markedly reduced by low concentrations (>10ppn| of several phosphonate or phosphate Iona. In addition, striking changes in calcita crystal morphology have boon observed during spontaneous precipitation of cslclun carbonate in the presence of these ions. These results have been interpreted In teime of an adsorption process involving blockage of crystal growth mites on the calclte surface by phosphonate and phosphate Ions. This adsorption mechanism nay be respon sible for both (1) the decreased rates of nucleation and cryatal growth of calcivs* and carbonate and (2) the removal of phosphorus containing ions, in natural waters super saturated with calcium carbonate. THURSDAY AFTERNOON - SECTION B - GENERAL - J. L. Monkman, Presiding 7J. AN AUTOMATED INSTRUMENT FOR THE SPECIFIC DETERMINATION OF AMBIENT H 50^ APH0S01.. S, C, Barton. H, G, McAdle, Department of Physical Chemistry, Ontario Research Foundation, Sheridan Park, Ontario, Canada. A sensitive and selective method for the automated measurement of ambient H.SQ, aerosol level* over one-hour Intervals with a detection limit of ~0.02 ppb ia des cribed. H-SO^ aerosol is collected, together with othor particulates, on an inert Nuclepore polycarbonate membrane filter, then selectively eluted with i-propsnol for analysis by the barium cidoraniltee method. After color development occurs in a stirred reactor, the excess reagent is removed by filtration and the absuihance is measured with a double-beam UV photometer. Experiments have shown a collection effi ciency of "95S in the ppb range for a synthetic H^SO^ aerosol with mass median dls- HONS 079516 VATU M'in of 0,7y. Oxidation of SO. on the filter Is not a problem, nor ore other gaseous l<c-Jhitti!* irlalru'rt by the ftHoi . Interference fro* other particulate material is eliminated by selective elution of the II SO from the total particulate sample and buffeting of Uk* colot isictt ic aystea. rfutlon with l-propanol has been shown to remove || g(> selectively fvofti filler* coniafnitii-. sulphaie salts in amounts several times f.fcalVi than amounts repot ted in typical atmospheric particulate samples. Four months ul field operation tn downtown Toronto have proven the basic concept of the method and llie design of the prototype inairumeut. Average M.50, ari'osol concentration* measured wnr slr.nlf leant ly lowet than tltose root led from other North American cities. The measured aerosol cenccnl rat ions sttow a al&ntf icant correlation of concurrent SO^ eonrenltallohfi, but do not bear any fixed relationship to the total aulphate content of hi pt,-volume su|>rnded particulate samples. 74. KMCTIVimS OF COMI'l.KX MIXTUHKS OF 1IYUKOCAKRON5 AMI NO . S. L. XopcaynakJ and R. j.. KuitU, El*A, NKRC, DOT, Research Triangle Park, NorthMCarollna, 27/11. kceauae of interactions between pollutants, results from photochemical studies of sixes of individual hydrocarbons with HO may not be generally valid for prrdlrling reactivities of complex mixtures. In orlrr to better predict the effects of vsrlous hydrocarbon and HO emission controls in the resl atmosphere, photochemical studies were carried out uBlng a simulated atmospheric hydrocarbon mix. Thr hydrocarbon mixes consisted of acetylene, 5 paraffins, 6 olefins, and b arnmnilrs in proportion# found in the bo# Angeles atmosphere. Thr complex mixtures of hydrocarbons and HO in air were reacted for 5 1/2 hours In a large irradiation chamber using u)traviolet"fluorescent lamp*. The hydro carbons wcic reacted at concentrations of 5, 10, and 20 ppmC in mixes containing 1/2 or 1 pp* NO . Kate of oxidation of nitric oxide, nitrogen dioxide dosage, hydrocarbon consumption? cyr irritation, and yields of pcroxyscctylnlcrate, formaldehyde, and oxidant were measured. The effect* of changes in hydrocarbon composition and hydrocarbon concentra tion on the varlnun measure* of photochemical reactivity were evaluated. 7 S . X-RAY FLUORESCENCE ANALYSIS OF AIR POLLUTION PARTICULATES. 3, V. GWrlch, P. C. Burkhalter, L, S. Birka, Naval Research Laboratory, Washington, P, C. 20390 and J, Wagman, Environmental Protection Agency, Research Triangle Park, N. C. 27111 X-ray fluorescence analysis is a very rapid and efficient tool for analysing the particulate matter filtered out of ambient air or from the effluent gases of pollution sources. The sample collected on filler paper can be used directly as the x-ray specimen because Ha mats is small and therefore the contribution to background by thr scattered primary radiation is minimised. Because the particulate sample is thin matrix effects are negligible, at least to a first approximation. Measurements have been made to establish sensitivity and detection limits for x-ray tube excitation and crystal spectrometer measurement, as well as for energy dispersion snalysi* using x-ray tubes, first (luorcscers, radioisotopes, and ions (protons and alpha-particles} to excite the samples. Detection limits were the best lor prolon excitation - one to a few ng/ent* Jit 100 sees - but required that the specimen be deposited on s thin nitrocellulose or carbon film which i not practical for routine analyst*. Detection limit for x-ray tube excitation la a few tens of ng/cm^ in 100 see*, using either a crystal spectrometer or a solid state detector, making the technique suitable for analysis of a wide variety of sample types and elements of interest. 7b s EFFECT OF pi) ON THR STOICHIOMETRY OF THE IODOMETRIC DETERMINATION OF OZONE, Russell N. Pleta. Jacob Pruaanaky, and James D. Smith, Brookhnven National Laboratory, Department of Applied Science. Upton, New York 11973. The reference technique for the determination of oxidants in the air is the neutral buffered potassium iodide procedure assuming a ll stoich iometry. A spcctrophotometric analyzer, which measured the absorbance HONS 079517 WATR_____________________ ___ due to ozone in the ultraviolet at 254 nm, was calibrated absolutely by measuring the increase in pressure resulting from decomposition of l to 3% ozone in oxygen mixtures: the ratio of spectrophometrieally measured O3 to absolute determination was 1.00 + 0.03. The analyzer was then used to determine the stoichiometry of the ozoneiodide reaction using 1 and 2% KI buffered solutions at pH from 4 to 14 for ozone concentrations ranging from 50 to 600 ppm. The stoichiometry (ratio of spectrophotometric to XI determined ozone) at various pH were: 0.80 0.10 at 14.0i 0.93 + 0.05 at 12.0; 1.00 + 0.02 at 9.18; .1.04 + 0,01 at 6.86; and 1.07 + 0.05 at 4.01. Using a midget impinger, a calibrated colorimetric proce dure based upon measurement of the lodinestarch color at 440 nm, and air containing 0.1 ppm Oi collected at 2.5 liters/ minute, the stoichiometry was confirmed to be 1:1 for neutral buffered Kl determination of ambient ozone. 77. AN ALIPHATIC ALDEHYDE COLORIMETRIC DETECTOR rOR CAS CHR0MAT0CRAPHY. John M. Cray am) Paul uroue, Environmental Engineering, University of Florida, Calneavllla Florida 32601. A flowing colorimetric detector for aliphatic aldehydaa haa been built uaing the 3*othyl-2*bentothlasolona method of Hauaer & Cuneeln* (Hauser. T. R.. Cumins, R. L., AWL CHEH 36, 679 (1964)) and 8awlckl at al. (Sawtckl, B.. Hauaer, T. A., Stanley. T. W.. Elbert, U.. AWL CHB< 33. 93 (1962)). This detector haa been coupled to a dual*channel gas chromatograph with flame lonieetlon detector. Uaing thia ayetem It hat bean possible to etmultaneoualy analyse aliphatic aldehydes In the presence of other oxygenated compounds and hydrocarbons without the need for previous derivet last Ion or extensive flow switching mechanism*. The flowing llqutd colorimetric detector haa been studied at varloua operating condition* and In various configuration* to determine the optimum response, sensitivity and detection limit. Sensitivity Is In the mlerogrem range with extension to submlcrogram quantities being possible. The combined gee chromatogrsph'flowing liquid colorimetric detector haa been used to study some reactions of aldehydes and hydrocarbon* with mixtures of NO^ and S0j in air. Attempt# have been made to determine rates of reaction for aldehydee*ln air and to correlate these with other studies. 78. MAINTAINING AIR QUALITY IN THE VICINITY OF THE SMELTER. f, Frentl*ak, 1NCO, Toronto-Domlnion Centre, P. 0. Box 44, Toronto 111, Ont- erlo, Ceneda. Three smelters in the Sudbury area, two owned by INCO, produce 60% of the free world's nickel. The smelters treat sulfide ore, releasing oulfur dioxide to the atmosphere. In 1956, a network of 10 SO] monitors was established within a 40 mile radius of Sudbury. This network has later expanded to include three fixed and one mobile station in Sudbury. Again later, INCO designed a warning system to detect deteriorating air conditions. In creating the API, which is based on SO? and suspended particulate matter, the Ontario Government assumed similar air aystema affected London, U.K., New York, Osaka, Detroit and the industrial cities of Ontario. At API of 50, the Government may request a production cut back. To hasten cut-back, time can be saved only in stack-to-detection, and this by eliminating from API the COH factor. Cut-back does not correspondingly reduce ground-level SO} concentration, since a cooler gas and lower plume rise is produced. Heating of stack gas is required. Incorporating this feature, INCO in March, 1971, inaugurated a warning system, and the record of Sudbury's air quality is now bettar than that of Toronto or Hamilton. 79. THE UTILIZATION OF AN URBAN AIR POLLUTION MODEL IN AIR MANAGEMENT. L. Shenfald, A. E. Boyar, Ontario Mlnlaery of the Envlronaant, Air Quality Branch, 880 lay Streat, Toronto, Ontario, Canada. A Mathematical simulation model has been completed for the urban atmosphere of Metropolitan Toronto and has been in usage by Ontario Ministry of The Environment, Air Quality Branch, for the past year. Emission data of five pollutants - sulphur dioxide, carbon monoxide, hydrocarbons, nitrogen oxides and suspended particulate matter - have been treated for three types of sources * point sources, area sourr** end Una sourees. HONS 079518 WATK A point source is s major source In terns of quantity of emission, normally large con* buatfon or industrial processing plane. The area aource sums s large number of small emissions, such as from home heating. Line sources are used to model emissions from major expraaeeays, The output of the model is a prediction of eir quality. Nomelly, titit output ia In the form of e contour mop with the Itopleths Joining points of equsl concentrations for s specific time of day. A number of these predictions will be pre sented and discussed. This paper Mill discuss the usage of tho etmospheric simulation model es s planning tool in an sir management programme. Planning strategies to best insure eir quality goals Include consideration of variable lend usage, urban development Industrial expansions, abatement programmes for point and mobile sources, locations of such sources as airport*, traffic arteries, incinerators, power stations, and degrees of control on the sulphur content of fuels. 90. H,UX fOKCl. SCRUBBLKS AN j:NGJNM;KJNG ANALYSIS. Jliuda Goldshmid, David Loith * APT Inc., P. 0. Box 71, Riverside, Ca. 92502 and Seymour Calvert > University of California, Riverside, Ca. 92507. Collection efficiency of particles in wot acrubbort reaches a minimum for the range O-l-lum in diameter. Particles in this size range are too small to be collected efficiently by Inertial forces, and too large to be collected efficiently by Brownian diffusion forces. One way to increase collection efficiency of particles in this range is to supplement inertia by additional forces which do not approach zero at the 0.1-ly* particle site range. Among such forces are the diffusiophorctic and thermophoretic forces, which arc part of the group called flux forces. The magnitude of these forces is directly proportional to the condensing vapor concentra tion and to the temperature gradient, respectively. Thus a detailed ana lysis of the magnitude of flux forces in scrubbers and their variation with residence time, requires the knowledge of change of temperature and vapor concent rat ion gradients with time and position inside the scrubber. The collection efficiency for basic geometrical configurations Isuch as bubbles, drops, or liquid sheets) was calculated for combinations of inertia, diffusion and flux forces. Predictions wore made for the in crease in collection efficiency of various scrubbers using bubbles, drops or liquid sheets. The effect of the system physical properties on collection due to flux forces was also shown. FRIDAY HORN!NC - GENERA). - J. L. Monkaan, Presiding Si , CAS CONTENT OP A1RRORNK PARTICULATE HATTKR. R. C. Uo, R. S. Thomas and L. Duboie. Air Pollution Control Dir., Environmental Health Centre, Tunney'e Pasture, Ottawa. Canada. Air pollutants emit ted to the atmosphere can react with other pollutants or with normal constituents oi the atmosphere. Consequently, their effect as polluting agent* can be completely different from what could be expected as originally emitted. Since particulate matter can act aa a catalyst for some of those reactions, it seems appropriate to Identify the presonce of gasea adeorbed and absorbed on the dust. Experimentally, four different eamplee of dust were pieced In a high vacuum system and the gasea were deaorhed at four temperaturea, room temperature, 50* C, ISO* C and 250* C. The desorbed gases were collected in liquid nitrogen traps and analyzed by anas spectrometry. 92- SAMPLE TREATMENT AND PREPARATION IN THE ACCURATE MEASUREMENT OK METALS IN THE ANALYSIS OK AIR POLLUTANTS. 1.. buhoia. J. C. Hi1born, end J. L. Honkman, Air Pollution Control Dir., Environmental Health Centre, Tunncy'e Pasture, Oitewe.Canada. Since the quantities of metals in olrbornf pollutants may be low, it can be difficult to obteln en acrureic measurement. When shorter then usuel templing times are uaeil, proportionately leae materia] may be captured, putting an additional strain On the analytical sensitivity. An example might be the change from 24 hour sampling by high volume Instrument to a 2 hour aample taken on paper tape. As the sample available decreases In amount, the car* or lack oi cere taken in aample preparation becomes increasingly important as docs the filter end/or reagent blank. The analyst swat be assured that the acts! is in s form which can be extracted or made available for measurement. The Impurities present In the sampling medium and in the reagents must be under control at all time*. Illustrations are given of the large scale accurst* analysis of such airborne metal* using atomic absorption and polarography. The sensitivity, accuracy and precision of such measurements are discussed. MENS 079519 WATR 83 AN EFFICIENT SEPARATION OF BENZO(a)PYRENE FROM DllNZO(k)FLUORANTHENE ' AND THEIR FLUOROMETRIC DETERMINATION IN AIR SAMPLES. E^.Jj._Adamok. Government of Ontario, Dept, of the Environment. 680 Bay St., Toronto, Ont. Canada . The suitability of various organic Solvents as extractants for poly nuclear hydrocarbons from particulate air samples was investigated by de termining extraction efficiencies and effects on fluorescence by these solvents. For the fluorometrlc determination of QaP in air sample ex tracts, its isolation from compounds of similar fluorescence is necessary, but difficulties ere invariably caused by the presence of BkF. separa tion of BkF from BaP was only possible by elaborate and time-consuming procedures which are unsuitable for large-scale analytical surveys. How ever, by a fluorometrlc approximation technique, the interference from the presence of BkF can be minimized, provided that BaP does not greatly exceod the amount of BkF. A generally more applicable method of determin ing BaP ia now reported. A chromatographic prooedure has been developed by which BaP and BkF can be separated from each other In a one-step opera tion directly from the sample extracts. Subsequent or simultaneous fluorometric analysis of these two compounds can be done without mutual interfer ence. After surveying these compounds in the air of eight urban communi ties in Ontario, attempts have been made to correlate differences and changes in their levels with a number of environmental conditions, such as sampling location, wind direction, amount of dust, seasonal variations, and others. 8. A DILUTION DEVICE FOR COUPLING MONITORS TO SOURCE EMISSIONS. James . HomoJ/a ft Robert J. Griffin, Environmental Protection Agency, National Environmcnttl"Research Center, Research Triangle Park, N. C., 27711 , The coupling of continuous gaseous source monitors to stacks or ducts usually re quires some degree of sample conditioning. Conventional techniques Involve extracting a stack gas sample via a probe and transporting the sample to analyzers through heated inert tubing to prevent moiature condensation and loss of sample. The tubing must be either steam-traced or electrically heated.Particulate matter is usually filterod at the probe inlet and moisture present in the sample line (often 10-12% H;0) is removed at the monitor by condensation. Such methods are costly and still suffer from varying degrees of sample lossos. A novel dovice has been designed and constructed to eliminate the prob lem of moisture condensation and particulate entrainment by diluting the gas sample imme diately within the stack environment. A rotating perforated-disc placed In the stack gas atmosphere is used to extract a small volime of gas which is mixed with a metered stroam of diluent. The mixture can then be analyzed directly by ambient air or source-level monitors without the need of heated sample lines particulate filter* or refrigerated driers. A prototype of the disc-dilutor has been designed to encompass a range of di lution ratios of from 10:1 through 1S00;1. The device can be readily inserted through any standard 3" sample port and requires minimal msintainance. The choice In using an ambient or source level monitor and the appropriate diluting ratio is depondent on the initial pollutant concentration at well as the moisture and particulate levels. Labora tory and field studies have been carried out using both ambient and source level SO; monitors. 85, AN IMPROVED METHOD FOR THE CONTINUOUS ANALYSIS OF ATMOSPHERIC ALIPHATIC ALDEHYDES. S.C. Barton. E. N, Turner, Department of Physical Chemistry, Ontario Research Foundation Sheridan Park, Ontario, Canada. Aldehydes end Ketones, although major and detrimental products of photochemical alt pollution prooeeiee, have not been etudled extensively. There are no latlsfartory continuous meeeurement method* for either total carbonyls or individual aldehydes or ketonee. A continuous adaptation of the 3-methyl-2-ben*o-thlazole hydtazone (H6T1I) method, the most widely used end recommended reference method for total carbonyls, is described. Air la sampled continuously through a submerged jet into a spherical, spraytype scrubber which provides essentially 100X collection efficiency. Long color de velopment time, bubble formation and solution tutl/ldicy were the major problems en countered In using the static MBTH method. In the continuous method, the use of in creased temperature results in the formaldehyde-HBTH reaction and subsequent color de velopment being completed in approximately 3 minutes, Rubble formation and turbidity have been eliminated by replacing the uauel oxidising solution, ferric chloride, with an acidic ceric ammohlum sulphate solution. This also provides a self-ctaanlne action which eliminates solid deposition in the spectrophotometer cells. A small multiple- HOMS 079520 HATH channel pcnataltic pump la used to meter the reagents and to maintain a smooth and con stant liquid flow through the system. With art air sampling rate of 2 l.mtn"! and an alr/llquld contact ratio of lOftOsl, the detection limit of the method Is Spe.m"* (as formaldehyde), compared with reported average concentrations ol 50 pg.nf3 in urban areas. 86. H0N1T0RINC CARBON MONOXIDE IN AMBIENT AIR. Robert S. Ajcmlnn, Crvat Lakes Steel Ecorse, Detroit, Michigan, 48229. Interest In ambient carbon monixide levels resulted from the concern over th> establishment of air quality standards. Due to this Interest, a method was developed utilising equipment available In moat laboratories engaged In an sir sampling program, the method does not require the purchaco of Infrared detection systems, will yield tellable data, and uses a sequential air sampler and plastic bags. Samples were collected In che plastic bags over a twenty-four hour period and returned to the laboratory for analysis. The concentration of carbon monoxide In the sampling bags was determined by the catalytic conversion to methane and analyzed using a gas chromatograph with a flame ioni2atlon detector. A comparison of amhlcru carbon monoxide levels obtained using this sampling technique and the Infrared analyzer will yield comparable results. Although the carbon monoxide concentration was determined by gas chromatography, the analysis could be made with infrared equipment if available. 87. COMPARISON OF ANALYTICAL MKTHODS TO MF.ASURK AMHIKNT CONCENTRATIONS OF NITROGEN DIOXIDE AND NITRIC OXIDES. R. X. Stevens, T. A. Clark, ft. Baumgardner, and J. A. Hodgcaon. ENVIRONMENTAL PROTF.CTlOti AGEffC'Tj National Environmental Research Center, Research Triangle Park, N. C. 27711. Recently, the Environmental Protection Agency has developed two chemiluminescent procedures that are capable of measuring sub-part-per-million concentrations of nitrogen dioxide (NO2) and nitric oxide (NO). Both procedures are based on che chrmtluinlncsccnt reaction of NO with ozone (0j), supported by the conversion of NO2 to NO. One technique is designed to operate at l to 5 Tore pressure, whereas the second method measures the luminescent reaction of NO and 0j at about 300 Torr. These two procedures are compared with the claaale colorimetric Saltcman and Jacob-Hochhelacr methods. Other principles evaluated during this study were based upon second-derivative spectroscopy in ihr visible region, (4480 X) and upon mlcrocoulometry. Correlation of measurement! between instruments, in addition to a detailed study of maintenance requirements, calibration stability, and typical response patterns, will be presented. 88. STANDARD Rl-R'.RLNCb MATERIALS TOR AIR POLLUTION ANU GAS ANALYSIS lirnest 13. Hughes and John K. Taylor, Microchcmic.il Analysis Section, Analytical Chemistry Division, National Bureau of Standards, Washington, t). C. 20234- The increasing importance of the analytical chemistry of the atmos phere and its natural and unnatural components has emphasized a ciitic,il shortage of gaseous standard reference materials. The National Bureau of Standards is engaged In a program to produce such reference materials for a number of major constituents and pollutants. A number of materials jio currently being Investigated and a smaller number have already been made available as NBS Standard Reference Materials. Oxides of nitrogen, high concentrations of sulfur dioxide, carbon monoxide in air and propane in air arc nearing completion while atmosphere concentration of oxygen and carbon dioxide, and methane in air are already available. Sulfur dioxide permeation tubes arc also available. The lack of extensive data concern ing the stability of gas mixtures and ihe need for development ol methods of sufficient accuracy for primary certification and methods of suffi cicnt speed and precision for final certification arc among the factors which results in a long delay between recognition of the need for such standards and the final distribut ion. in some cases special contuiners and devices arc required to produce satisfactory standards. An important part of the development of standards of this type is long term stability. The history of gas mixtures up to five years of age have been compiled. MONS 079521 WATK 9, EVALUATION OP NEW OZONE MONITORING INSTRUMENTS FOR MEASUREMENTS IN NONURBAN AIMOIPNItRKft. T. A. Clark. R. Baumgardner, K. Kroet, and R. R, Steven*. ENVIRONMENTAL PROTECTION AGENCY, National Environmental Raaearch Center, Reaearch Triangle Peril, N. C. 277] 1 The ehomllumlnsscent reaction between oeon* and ethylene la the reference method cited In the April 10, 1971, Federal Raglater for the aeaaureaent of aaiblant concen tration* of oaone. Three new analytical procedure* capable of measuring aub-part-perllllon concentration* of oaon* have recently bacoae comerclally available and arc being conaldrrod aa alternaie aethod*. The aeeeureaent principle* are beeed on: (1) measuring the attend derlvetlve of the abeorbence of oaon* with raapact to wavelangth at 2t)3 K{ (?) direct aeaaureaent of the attenuation of the 2567 1 band aacrlbabl* to otonei and (3) the decoapoaltlon of oaone on an alualnua aurlace, which produce* light energy proportional to th* cone concentration. Thl* report describee the general perioraanre eharacterletlca of each of theee new monitoring procedure* and cOTralatae (heir raapona* to aablanl concentration# of ocene to that of the reference aethod. Deecrlptlon* of aallbrailen procedure# and atabillty an well aa typical raaponae pattern# of Ilia livtlil Monitoring principle# are preaented. 10. FINE PARTICLE EMISSIONS FRCN AUTOMOTIVE BII8S10N8 CONTROL CATALYSTS - PRELIMINARY INVESTIGATION - ttflllam D. Baiaord. Research S Pevolopnont Unit, New York State Departoant of Environmental Conservation, Albany, New York 12201. High lumber concentrations (>10* partlclee/cc) of eondaneatlon nuclei have been Induced froth ggjfemgfg catalyete containing chromium, copper, and nlekel under condition# hlallar to that of automobile exhaust. Sasll temples of coamarclal formu lation# previously evaluated for NOj, reduction, a* well aa catalyete prepared in the New York State O.l.C. laboratory, have been Investigated end found to eeiit fine particle# under s range of controlled condition*! 190 to 800C, in 3K CO in N2 end In synthetic automobile exhaust (pulsed flits* combustor product strewn) at flow rates of approximately 600 cc/mlnut*. It 1# postulated that metal carbonyl formation way occur ot the lower temperature ranges. Metal carbonyl a, being unstable at moderately tie* vated tSMp#r*tur#*,d*eonpo#e leaving finely divided state! or aetel oxide particles depend tag an th# prevailing oxygen partial presaura. Th* fin* particles art detected with a condensation nuclei detector which count* ell submicron sired particles larger than bout 90s diameter. Subsequent experiment* with OE Research end Development Center using surface Ionisation Interfaced with magnetic sector mass spectra#*try demonstrated conclusively the emleeieo of the fine chromium containing particles from * commercial copper chromite and corroborated our Initial observation* suggesting potentially hefsrdou* particle emissions from certain catalysts bslng considered for use In automotive emissions control systems. It's Unique... 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