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H\iur Kftfitrch PcrgAmon Press 1971. Vol. 5, pp. 1107-1115. Printed in Great Britain CMLOROmmENYLS (PCBs) IN THE MILWAUKEE RIVER Gilman D. Vkitii and O. Fred Lee W.ucr Chemistry Laboratory, University of Wisconsin, Madison, Wisconsin 537QC, U.S.A. (Received 14 April 1911) | AhMrncb-Thc nnnlyxcs of water from the Milwaukee River indicated that isomers of chlorinbiphenyl similar to those used in industry were present in Ihc river from West Dcnd to. I ,t.e MaUiy.nn. Analyses of municipal sewage treatment plant effluents, industrial discharges, and the Milwaukee River water near covnbiued sewer outfalls presented evidence that chloro* hi:*'u'n>U (I'l'UO were discharged to noHital waters through municipal and industrial wastes. I't its concentration at the ng I '1 level suggested that PCBs in large ecosystems such as Lake Mu lligan have resulted, in part, through water transport from metropolitan areas. i INTRODUCTION Tm: cut orinati o biphenyls (PCBs) arc a class of chlorinated hydrocarbons which have industrial importance ns plasticizers, dielectrics, lubricants, and flame retardants (lit imAitn, 1964; Monsanto Co., undated). The PCBs arc produced commercially bj Monsanto Company under the trade name, Arodor,and exist as mixtures of isomers vitlt chlorine contents of 21, 32, 42, 48, 54, 60 and 62 per cent by weight, in general, the chemical stability of the mixture increases with increasing chlorine content while the aolatility decreases in the more highly chlorinated mixtures. Many of the industrial applications of PCBs depend largely on the chemical stab ility of Ihc mixtures. Their uses as dielectrics in transformers and capacitors and as addi'r.cs to lijdraulic fluids restrict the chlorinated biphenyls to dosed systems. However, possible uses of PCBs in paints, varnishes, waxes, synthetic polymers, inks, duM-inhibitors, and pesticide formulations may lead to direct contamination of natuul waters through industrial and sanitary waste dischargers. Also, the stability of the more highly chlorinated mixtures to low temperature flames may result in aerial transport of the PCBs from industrial and municipal solid waste incinerators to natiiial waters. ' Th: presence of PCBs in the environment has been detected only recently and reviews of th current knowledge of PCBs have been presented (Huudard, 1964; Veith and Lrr, 1970a; Piakall and Lincer, 1970). In general,PCBs have been found in organisms associaied with natural waters which'receive wastes from urban centers. Concentra tions of PCBs (as Aroclor, 1254) in excess of 250 j/g 1"' have been reported (Dukb <*r i:l., 1970; Hut di n, 1970) in industrial discharges while those in municipal sewage irc.itr rent plant effluents and receiving streams typically range from the low ngl-1 to tlu low /ig I*1 levels where detectable. The PCBs arc similar to many chtorinatcd pesticides in that higher concentrations arc frund in oiganisins representative of the higher trophic levds. Concentrations of the PCBs in the predator food chain range from at or near the determinable limit in water lo 75 100 /ig g"` in fish-eating birds. Consequently, the chronic effects of the PCIR in higher organisms and the levels of PCBs in water supplies are of concern and irqtiiic evaluation- The presence of PCBs in fish from th*. Milwaukee River at con centrations cxc^ding 100 />g g"1 on a whole fish basis ini icated that this tributary of Lake Michigan receives comparatively large quantities of PCBs. This paper presents the results of a study of PCD sources in the Milwaukee River drainage basin. 1107 . HONS 084516 NO* Gilman l>. Vmtm and G. FatD Lee The Milwaukee River originates in the Kettle Moraine area of southern Fond du lac and Sheboygan counties, Wisconsin, and Hows in a southerly direction for appioximatcly 95 stream miles into Lake Michigan al Milwaukee. Ficimn 1 presents the Milwaukee River watershed and the major industrial and sewage treatment plant (STB) outfalls into the river. The major municipalities along the river include West Bend. Saukvillc, Grafton, Cedarburg, Thiensvillc and Milwaukee, all of which dis charge municipal and industrial wastes to the river, The major physical alterations of the natural river have been the construction of a total of 22 dams and spillways for l-ir,. |. Milwaukee river watershed (Milwaukee river study committee, 1968)--Municipal Sir Outfall. 1-WcM Rend 2-Frcdonia 3-Snukvilte 4-Grafton 5-Ccdarburg 6-Thicnsvilte 7-Milwaukec Combined Sewer Outfalls STP--Sewage Treatment Plant. CMm power (Martin, 1965), th* North Avenue dam, and I Avenue dam to flush the w Field sampling e; The collection of water interaction of the sample w were collected from the rir of 0.2 m in the center of I were sampled by submerge were not added, a$ sample Extraction Water samples (20 I.) w Hexane (400 ml) was plat introduced into the first 1 layers were drained into d 20-1. sample was cxtroctet anhydrous Na^SO*. andc Liquid chromatography The cleanup of extras! liquid chromatography or ct at. (1970). The media (X 24 hwith an azeotrope af The azeotrope was evapost to 650C for 2.5 h for ad! The Florisil column Am Florisil into a 25 mm o.d. stopcock. The column wa deactivation of the Florinl on the column and eluted toxaphene, strobane, ami column was eluted with 2 DDD, dicldnn, hcptachk particularly those from ST eluate from the 25 mm o.d . to isolate the PCBs from arated from the DDT gn (Armour et at, 1970; Rcr | I Instrumentation ( The analyses of water chromatograph equipped ! mCi) and a 50:50 effluent MONS 084517 Chlorol'ipUcnyls (PCBs) in ihc Milwaukee River 1109 power l%5), Clio dredging of the river from the mouth to the Milwaukee Noith Aumuc dam, and the construction of a flushing tunnel just below the North Avenue dam to Hush the wastes from the lower river with water from Lake Michigan. /> U uimpfing EXPERIMENTAL PROCEDURES The collection of water was conducted with ailglass systems to preclude possible interaction of the sample with rubber, plastic, or polyvinyl chloride surfaces. Samples weie collected from the river by submerging a weighted, glass carboy (20 I.) at a depth of 0.2 m in the center of the main channel. Sewage treatment plants (STP) effluents wcic '.impled by submerging a glass bottle (4 I.) directly into the effluent. Preservatives swic not added, as samples were cooled and extracted within 24 h of collection. f.virucfWM . Water samples (20 1.) were batch-extracted with hexane in 2 I. separatory funnels. Hexane (400 ml) was placed in 6 funnels and 1600 ml portions of the sample were introduced into the first 3 funnels. After repeated shaking and settling, the aqueous layers were drained into the 3 remaining funnels. The process was repeated until the 20-1. sample was extracted twice. The hexane portions were combined, dried with anhydrous NaiS04, nnd concentrated to 15 ml for cleanup in a gentle air stream. Liquid chromatography The cleanup of extracts for gas chromatographic analysis was conducted with liquid chromatography on Florisil as described by Reynolds (1969) nnd Hughes cl al. (1970). Tim media (Kensington Scientific) was extracted in a Soxhlct extractor for 24 hwith an A2cotropc of hexane and acetone (41:59) to remove organic impurities. The a.cotropc was evaporated from the Florisil at I05C, and the FJorisil was heated to f*50'C for 2.5 h for activation. Ihc Florisil column for preliminary cleanup was prepared by vibrating 19 g of Florisil into a 25 mm o.d. glass column which was fitted with a glass frit and Teflon stopcock. The column was topped with 10 g anhydrous sodium sulfate to prevent deactivation of the Florisil by traces of water in the extract. The extracts were placed on the column and eluted with hexane (200 ml) to recover DDE, hcptachlor, aldrin, lox.iphenc. strohanc, and PCBs, if present. After changing the receiving flask, the column was eluted with 20 per cent ethyl ether in hexane (200 ml) to obtain DDT, DPI), dicldrin, hcptachlor epoxide, and lindane, if present. With some samples, panictH.illy those from STPefllucnts, it was necessary to rechromatograph the hexane ciuatc from the 25 mm o.d. Florisil on a smaller diameter Florisil column (9 mm i.d.) to isolate the PCBs from organic interferences. If necessary, the PCBs may be sep arated from the DDT group of pesticides through chromatography on silicic acid (Armour cl al., 1970; Rlincft, 1970). Instrumentation Ihc analyses of water extracts were conducted on an Aerograph 1745-20 gas chromatograph '.quipped with concentric tube electron capture detectors (3H, 250 mCi) and a 50:5') effluent splitter for simultaneous analysis with electron capture and HONS 084518 1110 . Gilman P. Vcith and O. Fxec Lu name ionization detectors. Analytical GLC columns consisted of 2.0 m X 1.8 mm glass coils which were packed with either OV-IOI (3 per cent), OV-IOI/XE-60 (3:3 per cent), or OV-IOI/QIM (3:4.5 per cent) coated onto Gas Chrom Q (720/140 mesh). The carrier gas (purified N2) wns maintained at 21 ml min" `; and the injector, column, and detector temperatures were 250C, I8CPC, and 220aC, respectively. Analysis ^ The commercially prepared PCBs in the u.S.A. (Monsanto Company, St. Louis, Mo.) exist as seven complex mixtures under the name "Aroclor", which range in chkuinc content from 21 to 62 per cent. When the PCB mixtures are chromatographed with GLC, the mixtures of isomers produce both resolved and superimposed peaks and arc somewhat characterized by the GL fingerprint presented as relative peak heights and retention times. Because of the complexity of the mixtures, determinations have been quantitatively defined by comparing the area of a sample chromatogram to the area of a known quantity of the commercial mixture which most closely resembles that of the sample. However, some of the samples contained PCBs which appeared to be mixtures of the Aroclor mixtures and were not representative of a single commcrdaily prepared mixture. Estimates of PCDs in these samples were made by visually comparing the chromatograms to mixtures of standards prepared from the Aroclor mixtures. Explicit chemical confirmations for the presence of PCBs in each sample were not possible in (his study. PCBs with similar retention volumes and relative peak heights were confirmed in the fish from the Milwaukee River using i.r. and mass spectrometry. Thus, from the i.r. and mass data, GLC refention data under multiple column con ditions, and the stability of the extract mixti res to dehydrohatogenation and nitration, the components in the chromatograms were presumed to be PCB isomers. However, the analysis do not preclude (he possible presence of other chemicals which may have similar chemical properties such ns the chJoronaphthalcnes. The analytical procedures for PCBs in n.atural waters were evaluated using Aroclor 1260 which contains 60 per cent chlorine. Six replicates of unfiltercd Lake Mendota water (4.0 I.) were "spiked" with 4.0 /*g of Aroclor 1260 as a 50 ml acetone solution. The water was aerated for 5 min and incubated at room temperature for 2 days. The recovery of PCBs from water at the 1.0 ftg l-3 level was found to vary with the degree of chlorination of PCB components. If the major component of Aroclor 1260 which eluted at 12.8 min on the OV-10I/QF-1 column was used as a reference, 82.3 6.3 percent of the Aroclor 1260 mixture was removed. If the major component of Aroclor 1260 which eluted at 6.4 min was used, the recovery was 80.0 8.2 per cent of the quantity added. When the component eluting at 4.1 min which is a major component of Ardor 1242 was used as a reference, only 69.0 6.5 per cent of the mixture was recovered. The recovery of the minor component of Aroclor 1242 eluting at 1.3 min was slightly less than 50 per cent, and the minor component eluting at 0.7 min could not be detected in any of the 6 replicates. Since the "spiking" procedure may be of questionable reliability when applied to nonclcctrolytes, the recovery data must be regarded as climates which indicate that the precision a>:d accuracy of the analytical procedures ar* satisfactory for the analysis of natural waisrs. The data also indicate that the com- CM position of the PCB mix minimize loss of the mor Sections of the Milwa determine the levels of 1 municipal sewage (realm sampled on March 26, IS The water quality chat arc presented in Tabu I impoundments and less f (DO), pH, and suspended lower river within the citj water contained 10.0 mg contrast, (he water at th l'1 DO, 14.7 mg l_l sus and conductivity from 19r dam to U 8 mg 1"1 and 41 water below the dam thre The estimates of PC! The GLC analyses indie, inatcly the latef-eluting K mately 0.05 /ig l-1. Tribn firm, was not a source m Thus, a PCB source(s) up Possible sources upstrt selected outfalls to the m STP at West Bend, Fred, highest concentration obe a chemical plant effluent: The river downstream fr of the isomers correspond (GLC) which closely fese* in the concentration of A PCB isomers suggested a is Cedar Creek in which oi a problem in the past (Sen The PCBs were found Riverside Park region of t associated with the water i February, 1970, respectiv* likely to be the Milwauk cooling waters which diat Estabrook Park. The presence of pg I*1 natural waters may genera for PCBs in drinkingwatet WATV* J/JI-- "|WW MGNS 084519 Chlorobipltcnyls (PCBs) in the Milwaukee River 1111 pOMti.'ii of I lie PCII mixtures may be altered durintr analysis if care is not taken to minimise l'1'* of the more volatile PCIJ components. RESULTS AND DISCUSSION Sections of the Milwaukee River were sampled on August 23 and 2S, 1969, to dctvi mine the lewis of PCBs in (he river system. In addition, selected tributaries, municipal sewage treatment plants (STP) effluents, and industrial discharges were sampled on March 2(, 1970. 1 he water quality characteristics of the river on the August, 1969, sampling dates are presented in Taju.c I. In general, because of photosynthesis of plankton in the impoundments and less pollutional loading in the upper river, the dissolved oxygen tPO). pi I. ami suspended solids w ere higher in the upper river above dams than in the lower river within the city of Milwaukee. For example, above the dam at Grafton the water contained 10.0 mg l"1 DO, 60.5 mg!-1 suspended solids, and a pH of8.7. In contrast, the water at the Buffalo Avenue bridge in Milwaukee contained 4.2 mg I"' DO. 1*1.7 mg l"1 suspended solids, and a pH of 7.7. The decreases in alkalinity and conductivity from J96 mg I*1 and 642 jifi cm respectively, at the North Avenue dam to 118 mg l"1 and 420/<Ocm~l at the harbor reflect the input of Lake Michigan water below the dam through the flushing tunnel. I he estimates of PCBs in the Milwaukee River water are presented in Tablb 2. The CiI.C analyses indicated that PCB mixtures similar to Aroclor 1260 (predora- inately the blcr-cluting PCBs) were present above the dam at Grafton at approxi mately 0.05 /*g 1_l. Tributary "O'*, the receiving stream for a plastics manufacturing firm, was not a source since PCBs could not be detected in the water near the firm. Thus . PCH sourrc(s) upstream from Grafton was indicated. Possible sources upstream from Grafton were examined through the analyses of selected outfalls to the ri\cr. The data, which arc presented in Table 3, show that the SIP at West Hend, I'rcdouia, Saukville, and Graftpn were discharging PCBs. The highest concentration observed in effluents was 2.5 /tg I"1 Aroclor 1242 observed in a chemical plant effluent several miles upstream from Grafton. The river downstream from Graflonand Thicnsvillc contained higherconccntrations of the isomers corresponding to Aroclor 1260 as well as many early-eluting isomers (Gl C) which closely resembled those in Aroclor 1248 or Aroclor 1242. The increase in the concentration of Aroclor 1260 to 0.26 ng I'1 and the introduction of other PCH isomers suggested a sourcc(s) between Grafton and Thicnsvilte. The likely source is Cedar Creek in w hich oil films, petroleum odors, and water discoloration have been a prob'em in the past (Schkauenagel ef ai., 1968; McKersie et ai, 1969). The PCIls "ere found nt greatest concentrations in the Estabrook Park-East Riv ers dc Park region of the river in Milwaukee. The concentrations of Aroclor 1242 assoei; ted w ith (he water in this region were 2.07 and 2.80/ig I-1 in August, 1969, and Febru; iy, 1970, respectively. The sources of the contamination in this region are likely .o be the Milwaukee combined sewer outfalls and contaminated industrial coolmy. waters which discharge to Lincoln Creek and the Milwaukee River near Lsialu >ok Park. The presence of fig 1"' quantities of chlorinated materials such as the PCBs in natural waters may generate concern in regard to public health. Although standards for PC IN in drinking water supplies have not been established due, in part, to a lack of WAIIft .'/I I--I . T mr MONS 084520 G ilm a n D. V m n and G . Fbf.d L eb MONS 0 8 4 5 ^ 1 i A Table 1. Chajuctejusticj oe Milwaukee River surface water (August 25,1969) Location Depth of Secchi Water Depth (m) (m) Temp. rp DO (mg l*`) pH Alkalinity (mgl-`CaCOj) Tributary "O", Grafton 200 m above dam, Grafton 100 m above dam, Thiensville Highway 167, (below dam), Th.msville 200 m above dam, Glendale 100 m above dam, Estabrook Park 100 m below North Avenue Dam Milwaukee River Mouth (Buffalo Avenue) Menomonee River Mouth Kinnickinnic River Mouth Harbor Breakwater 0.3 1.7 2.1 0.5 0.8 2.4 5.4 7.0 9.6 10.0 10.4 _ 24.5 10.1 Q.4 26.0 100 0.6 27.5 13.6 _ 27.2 10.2 -- 27.0 15.4 0.3 30.0 15.6 0.8 26.0 8.5 1.0 28 1.1 27 0.7 23 1.7 19 4.2 3.4 4.1 8.7 8.8 ' 8.7 8.9 9.2 -- 9.0 8.6 7.7 12 7.3 8.0 242 257 24$ 251 -- 232 196 14S 131 127 118 Conductivity 0*ncm-1 20'C) 670 720 720 740 -- 745 642 505 565 478 420 Suspended solids (mg l*1) 12.2 60.5 30.0 24.0 __ 50.0 14.6 14.7 10.6 5.0 5.6 o* * > : =r-3 S 3 .H g. 3 5 2,S^ S' U 2 * i? * a 3 ? 3 5 a- 2 * Q g- C OHIJ ill I Hu tHrt Srt; T--. <n* *3* M** 3o a * a -3 I i1f*?1*1 Is ?f;8 "3 ??: = ?2 D-8SHf 3S=! |B.||J|2|33f?33E sliH llffll??5. = R 3 > JJ 5?S?' z *g a. = a. c. : i'-3-! If-is i OdorobiphcnyU (PCBs) in (he Milwaukee River Tabix 2. Concentrations or PCRs in the Milwaukee River August 23-25,1909 Location Tributary "O", Grafton 21K) m above dam, Grafton 100 m above dam, Thicnsville Highway K>7 (below dam), 1 hiensMile 200 m above dam. Glendale 100 in above dam. l*vta brook Park J00 m Mow North Avenue . Dam Milwaukee Hlver Mouth (flulValo Avenue) Mcm'inonoe River Mouth Kinniikiiinic River Moulh Milwaukee Harbor Lntrance Estimate of corresponding Aroclorts) (Mt l"`>* Aroclor 1260 Aroclor 1242 t o.os 0.26 0.13 0.1) 0.10 0.05 0.05 0.03 0.03 0.02 \ it t 1 0.08 i 0.03 Jt ( 2.07 0.26 , 0.13 0.13 0.12 0.10 * The 1200 series of Aroclors are mixtures of PCBs. The last two numbers pertain to (lie percent chlorine of the mixture, t Itclow determinable limit of approximately 0.02 pg l*1 for A-1242 to 0.01 t<g I'1 for A-1260, depending on foil condition. , Tam r 3. OoNrrNNunoNS or PCD* in outfama rmo W Milwauxes Rover ON March 26, 1970 Location Estimate of PCD concentration G*g l-*1) Corresponding Aroclor mixture iin West Bend STP* effluent f redonia STP effluent Tributary "D" at Frcdonla Saukville STP effluent C hemical plant effluent, Suukvrllc Grafton SI P effluent 0.25 0.12 0.04 0.13 2.50 0.04 Aroclor 1254 , Aroclor 1254 Aroclor 1260 Aroclor 1260 Aroclor 1242 Aroclor J254 * STP-- Sewage Treatment Plant. toxicological data, reviews by Veith and Lee (1970a) and Peakall and Lincer (1970) luxe concluded that the PCBs appear to be less toxic to many organisms on an acuto lusi. Iltan ispp'DDT. Since the permissible limit for pp'DDT in public water supplies in the U.S.A. has been established at 42 ftgl-1 (Federal Water Pollution Control Ap'hnisiration, 1968), it is unlikely that the observer* levels of PCBs in the Mil waukee River system pose an immediate health hazard. This conclusion is substantiated by the fact that much of the PCBs found in the water t re associated with suspended solids in the water and are removed during the water treaxment and filtration processes. r MONS 0B4522 1114 Oilman D. Vr.mi and O. Fred Lei However, Hie presence of PCD* nt the fig l"` level In natural waters iray pose 4 lhro.il to nqunlic organisms and the food chains sustained by them. Kismuougm ct at.. (l%S).iml Andi'rson etui. (1969) have demonstrated and discussed the induction of hepatic hydroxylaling enzymes by PCBs which is similar to that observed from chlorinated pesticides. This enzyme induction cITcct has been proposed as the factor leading to egg shell thinning and reproductive failures in avian communities. More specifically, Dcki (1970) found that I /ig l_t of Aroclor 1254 killed juvenile shrimp in the laboratory. Also, Stalling (1970) found that 1 /*g l"1 of PCBs caused adverso physiological efTecis to blucgills, channel catfish, and trout, and that 10 /ig I-1 caused 50 per cent mortalilics. Vijth and Lnn (1970b) reported that the goldfish in the Psiahrook Park region of the Milwaukee River contained as great as 405 /ig l'1 of PCHs (as Aroclor 1242) on a whole fish basis. This evidence indicates that the 1 /eg I"1 concentration of PCHs may endanger aquatic communities either by direct exposure to the water or by feeding on high-lipid organisms which partition the PCBs from the water at concentration factors of approximately 100,000. Of particular interest were the relative variations of PCB isomers within the river system. The results of the analyses of water repeatedly indicated a more rapid decrease in the concentrations of the Icsscr-chlorinntcd biphenyl isomers with respect to the more highly chlorinated isomers. For example, in Table 2 the apparent Aroclor 1242 concentration in the lower river decreased from approximately 2 l"l at Estabrook Park to approximately 0.3 /ig I"1 just below the North Avenue dam. In the same reach of river the the more highly chlorinated components which are predominant in Aroclor 1260 decreased from 0.10 to 0.05 /ig l_l at the respective sampling sites. Similar results were obtained from the February sampling of the river. The relative variations of the composition of PCBs in the river suggest that the lesser-chlorinated isomers may be removed from the river water through preferential vaporization or co-distillation arising from their greater volatility than the heavier isomers (Monsanto Co., 1959) and/or through the more rapid degradation of the Icsscr-chlorinatcd isomers. The chemical stability of the PCB isomers toward nucleo philic and electrophilic substitution has been found to increase with increasing chlorine content (Vi;ith, 1970). Consequently, the environmental data reported in this paper may be viewed as an indication that similar trends exist toward microbial degradation whereby the lesser-chlorinated isomers in Aroclors 1232 and 1242 are selectively removed from natural waters. Experiments aimed at verifying these indica tions arc In progress. SUMMARY The PCBs present in Milwaukee River water were seldom comparable to a single Aroclor mixture. The data are reported as mixtures of Aroclor 1260 and Aroclor 1242, ond (he respective assignments imply the presence of components which elute later than those of Aroclors 1254 and 1248 in GLC analyses and the presence of com ponents which elute earlier than Aroclor 1248. The low-level PCB concentrations in all sampling regions and in the STP of small communities suggest that PCBs may be discharged in municipal wastes in addition to industrial wastes. The introduction of PCBs into the Milwaukee River by both large and small municipalities throughout the river basin may reflect the widespread use of the PCBs in products of advanced technology and indicates a need for the examination of PCD leva cological studies arc need* ment. Arknn*lrHt!tmrnt\ This tfudy of Natural Resources, by an N| Comm/tree. Additional suppor Station, Hie Department of Ch and the federal Water Quality . Anwrson D. W.. Hickey S. S i Significance of chlorinate ' Ftcld-Kotural. 8J, 92-112. - Armour i. A. and flcaxi J. A ami its analog. /. Ass. Duke T. W. (1970) Director, 1 Communication to G. Fre * Duke T. W., Lows J. I. and V water. sediment, and biota Feihral Water Pollution C i Government Printing 06% ; Holoin A. V. (1970) Source o l Nature 228, 1220 1221. Huboaro H. L. <I9M) Chlerii Chemical Technology, 2nd ffuouu R. A.. Viitu, G. D.. natural water, fish, and to Martin L. (1965) 7*# Phytk I Madison. McKrnsic J. R., Hansel G. t, . Pollution of the Mil<*auhfi 1 Resources. Madison. Wise Monsaniu Comi-a.nv (1939) 7, Monsanto Company (undated 1 Pcakai.l D. 8. and Likcc* 1 chemical in the enviromMt Ripcert R E. (1970) Fishery unpublished. Rivnolds L. M. (1969) PolycM analysis. Bull. Environ. Co> RtSCKROtCM R. W,, RllCMt F chlorinated biphenyls intt SCHRAUf NAGtL F. H., MONTO of the Pollution in the MU of Natural Resources, Ma Stalling D. L. (J970) Acting j Service. Personal Commor Vemi G. D. (1970) Environs*! thesis (Water Chemistry) l Vtmt G. D. and Lri G. F. (1*7 Water Hesearch 4, 263-26* Vemi G. D, and Lei G. F. 1 Report to the Wisconsin C *r HONS 084523 Chlorobiphenyls (PC!1s)i n the Milwaukee River IMS examination of PCIl levels in common consumer-products. Comprehensive toxicoloiuoal .studios arc needed to fully evaluate (he significance of PCBs in the environ ment. .1,1 Hi'iiVc/eiwwi - 7 his study was supported by a research contract from the Wisconsin Department of N.itm.il Kevnuecs. by an NDl A 1 itlc IV Fellowship, and by the University of Wisconsin Research (VinnnUiT. Additional support was given by the University of Wisconsin Engineering Experimental Sun-'ii. the Derailment of Civil Engineering, the University of Wisconsin Water Resources Center, ami the I cdcral XSatcr Quality Administration. REFERENCES V Ammikom I). W,, Hickiv J. J., Rtsumoucm R. W., Hughes D. L. and Christensen R. E. (1969) S< mtlVance of chlorinated hydrocarbon residues to breeding pelicans and cormorants. Ca/t, h.U.\,nwal. H.\ 92-112. Armoi h ). A. and Norm J. A. (1970) Methods of separating poly-chlorinatcd biphenyls from DDT and it* analogs. J. Ass. Official anulyt. Cheat, 53, 761-768. Dvm T. W.JI9T0) Director, Gulf Brccrc Laboratory, U.S. Fish and Wildlife Service, Personal (Vmimmication to G. Fred Lee, 1.1 October. Dim T. W., Low i J. I. and Wusun A. J. (1970) A polychlorinated biphenyl (Arocior 1254) in the w.ucr. sediment, and biota of Escambia Day, Florida. Dull. Environ. Contam. Toxicol. S, 171-180. |*ipin \i. Watir Pot i ution Conirol Aominisi ration (1968) Water Quality Criteria, 234 pp. U.S. (i<wcmmcnt Printing Office, Washington, D.C. I Ini ot \ A. V. (1970) Source of polychlorinated biphenyl contamination in the marine environment. N.iturr 23R, 12.70-1221. Hiihiishii M. L. (190-1) Chlorinated biphenyl and related compounds. Kirk-Olhmer Encyclopedia of ('hemicitl Mmolitsy, 2nd edn, Vol 5. pp. 289-297. Inlcrscicnce, New York. Hum s K. A., Stmt, G. D. and l.rr G. F. (1970) Gas chromatographic analysis of toxaphene in natural water, fish, and lake sediments. Water Research 4, 547-558. Martin L. (1965) Ihe Physical Geography of Wisconsin, 698 pp. University of Wisconsin Press, Vadison. Mr k, < mi J. It, HaMII. G. L., Kaouin T. and Conway 3. (1969) Report on an investigation of the I' llutian of/ V Milwaukee River, its Tributaries, and Oak Creek, 43 pp. Department of Natural K srwirecx, Madison. Wisconsin. Moss *.to Compass' (1959) Technical Bulletin PL-321, 4 pp. Moss mo Company (undated) Technical Bulletin O/P1.-306, St. Louis, Missouri, 20 pp. Pi as; a t. I). II. nnd ItsttR J. L. (1970) Polychlorinated biphenyls--another long-life widespread cl :mica! in the environment. Dio. Sci. 20, 958-964. Riisiit R. L. (1970) Fishery lliologist, U.S. Fish and Wildlife Service, Ann Arbor, Michigan, ui published. RttM-!.i>! |*. M. (1969) Polychlorinated biphenyls (PCDs) and their interference with pesticide residue ai alssis. Hull. Environ. Contam. Toxicol. 4, 128-143. Rtstm' non R. W., RirritR I'., Hsrman S. G.. Bcakall D. C. and Kirvin M. N. (1968) Poly* il.loi mated biphenyls in the global ecosystem. Nature, Lond. 220, 1098-1102. SritRA' tNsoti I- It., Moniie L. A.. Karl G. W. and Kroemn T. (1968) Report on on investigation of the 1'i`iln'i.in in the Milwaukee River Basin made during 1966 and 1967, 25 pp. Department of Natuial Resources, Madison, Wisconsin. Srai i tso l>. I.. (1970) Acting Director, Fish-Pesticide Research Laboratory, U.S. Fish and Wildlife Si 'Nice. I'civ'ii.il Communication to G. Fred Lee, November 17. - Vtitii Ci. I). (1970) Lnvironmcntal chemistry of chloroblphenyls in the Milwaukee River. Ph.D. thesis (Water Chemistry) University of Wisconsin, Madison, 180 pp. Vi tut G D. and I n C>. F. (1970a) A review of chlorinated biphenyl contamination io natural waters. It tier Research 4, 265-269. Vimi G. I). and Lie G. F. (1970b) Chlorinated organic contaminants In the Milwaukee River. Report to Use Wisconsin Department of Natural Resources, June, Mimeo., 40 pp. |W* MONS 084524