Document 2RzeJr94DM5owqZzzr33rn2BL

Progress Report I Lake Michigan Pesticide Investigations WARE Institute, Inc. January 1970 MGNS 067963 I [ 1 D 0 B 0 1 I s\ 3 a !l I i i i Table of Contents Introduction and Summary Section I - Samples Collected Section II - MethodB of Preparation and Analysis Section III - Results A. Sediment, stream water, stream plankton, offshore water and offshore plankton. B. Fish C. Investigative Samples - Racine and Kenosha D. Miscellaneous Samples Section IV - Discussion HONS 067964 Jf- - Lake Michigan Pesticide Investigations The WARF Institute study was designed to support other monitoring work being conducted or planned by various State and Federal agencies. It included one-time mid-summer sampling of stream water (IW), stream sediment (SCO), stream plankton (IP) , off-shore water (OW) and off-shore plankton (OP) at over 60 sites along the Lake Michigan shoreline. Fish samples were collected at IB locations and water and sediment samples were obtained at sites of obvious municipal and industrial outfalls. In addition* 25 samples of water were collected at siteB of industrial input into stream water and sewers in the cities of Racine and Kenosha. Other miscellaneous water samples were obtained and analyzed. All samples were analyzed by the electron capture gas chromatographic method (FDA Pesticide Analytical Manual, 1968). Modifications were employed as required for each type of sample: sample size, method of preparation, method of extraction and deemup. A number of samples were also analyzed after hydrolysis (dehydro chlorination). All injections were made into gas chromatographs with columns packed with 5% DC-200 on Cromport XXX, B0-90 mesh. The results of the analyses of these samples will be compared to the results of fish water, invertebrate, clam and soil analyses by the State and Federal agencies. Some conclusions can than, perhaps, be drawn concerning the value of each of the different types of sampling and the degree to which Lake Michigan is being or has been possible contaminated with chlorinated hydrocarbon insecticide residues. MOWS 067965 I From the results reported to date by various agencies and our own findings, it would appear that any possible contamination consists of low levels of apparent DDT and metabolites, very low levels of apparent dieldrin and very little occurrence of any other chlorinated hydrocarbon insecticide. Of great concern to us, however, is the finding of apparent polychlorinated biphenyls in many samples of water, plankton, sediment and fish, particularly at locations in the southern end of the lake. Also of great concern to us is the occurrence in many samples of other G. C. peaks which may not be insecticides but could easily be considered to be such. These peaks, as in the case of the apparent PCB type compounds, interfere with the interpretation of results for DDT, DDD and DDE. The identity, toxic potential, and metabolic fate in fiBh of these interfering compounds is not yet known. We are recommending extensive analytical and biological Btudies to determine these facts. HONS 067966 k I B B r" a I B I a s 'i i ! SECTION I SAMPLES COLLECTED : MOWS 067967 ( July, 1969 Sampling of Lake Michigan Basin A. Samples Related to Clam and Major Tributary Monitoring of Lake Michigan Interstate Pesticides Committee SED IW IP OW OP Fish b July B r 1 East River 1 X Little Sturgeon Bay 2 >X GB Dumping Ground 3 JX Fox River 0 4 )X Northern Paper Outfield 1July 9 0 2 Big Suamico River 3 Little Suamico River -4_^Pensaukee River li 5 Oconto River 6 Peshtigo River 7 Menominee River '*0 July 10 X X X X X X X X X X XX X XX X XX X X X XX X XX XXX XXX XXX XXX E. Shore Green Bay W. Shore Green Bay B Mud Lake Creek 9 Clark Lake Creek 10 N. Jacksonport Creek a 11 Kangaroo Lake Creek 12 Moonlight Bay iJuly 11 13 Stony Creek * 14 Ahnapee River u 15 Kewaunee River 6 X Molash Creek 16 East Twin River 17 West Twin River 0 7 X Outfall at Two Rivers Sewage Disposal 1 July 12 IB Manitowoc River 19 Silver Creek i 20 Calvin Creek 21 Pine Creek , 22 Point Creek 23 Fisher Creek 24 Centerville Creek X XXX X XXX X XXX X XXX XX X XXX X XXX X XXX X XX X XX XX X XXX X XXX X XXX X XXX X XXX X X XX XXX E. Shore Door Peninsula Sturgeon Bay to l-.-o Rivers Two Rivers to Port Washington ronii i *0NS 067968 t ASwnim ive^tfUfch Foundation * Madison, Wisconsin July 12 (continued) | 25 Seven Mile Creek 26 Pigeon River 127 Sheboygan River 28 Black River July 13 k 29 Sauk Creek j 30 Milwaukee m 9 X Kinn. R. Effluent , July 15 030 Kinnickinnic River 31 Menominee River 32 Oak Creek |j 33 Root Creek July 16 II 10 X So. of Racine 11 X No. of Kenosha 34 Pike River 0 35 Barnes Creek 12 X Dead River 13 X Waukegan Harbor 14 X willmette July 17 B 15 X No. Branch of Chicago River 16 X So. Chicago L 17 X Outfall Calumet City IB X Calumet River at East Chicago 0 36 Calumet River at Calumet City 19 X Gary Harbor 0 20 X Outfall No. G.H. 21 X Outfall in G.H. 37 Burns Ditch 38 Trail Creek |uljj_ SED 1W IP OW OP Fish X XXX X XX X X X XX X X X XXX X Two Rivers to X Port Washington X X XXX X Port Washington XX to Milwaukee X XXX XX X XX X XXXX Milwaukee to Racine XXX XXX X XXXX XX X XXX XX X Racine to Chicago X XX Chicago to Michigan itX X XXX X X XXX X XX X X X X XXX X X XXX X x X P39 Galien River 40 Drain at Sawyer 41 St. Joseph River 42 Paw Paw River 143 Black River 44 Kalamazoo River XX XX X XX XX XX XXX XX XXX XXX XX X Michigan City to Sauqatuck X X X 0biqb* > roi*M t Wisconsin Alumni Research Foundation Madivm, WUcmuin July 19 X 22 Pine Creek 45 Black River 46 Pigeon River 4? Grand River b 48 Muskegon River at mouth into Musk. Lake X 23 Muskegon River at Lake Michigan I 49 WhiteRiver July 20 Q 50 Pentwater River 51 Pere Marquette River a 52 Manistee River 21_ r S^^tfetsie River 54 Platte River 55 Crystal River 56 Leelanan Lake n uly 22 57 Boardman River SED IW IP OW OP Fish X XX X XXX X X XXX X X XXX Saugatuck to Whitehal X X XXX XX X X XXX X XXXX Whitehall to Manistee X XXXX X XXXX X X X XXX Manistee to Leland XX XX XX Xx XX X -X X X X x Leland to Traverse City tul 23 58 Elk River , 59 Lake Charlevoix Outlet ^ 60 Bear River,Petoskey July 24 X X X XX X X X XX X X X XX Traverse City to Harbor Springs Harbor Springs to LeJ and J uly 25 24 Mid Lake Michigan T I 1 ! P Leland, Michigan to Sturgeon Bay, wis. on< HONS 067970 f Wisconsin Alumni Research Foundation MadUon, wimntin July 28 and 29 61 Millecoquins Creek 62 Manistique River 63 Sturgeon River 64 Whitefish River 65 Escanaba River I 66 Ford River t Totalst Regular Extra X Total SED IW IP OW OP Fish X XXXX X XXXX X XXXX X XX X XXX X X. X X Upper Michigan Peninsula Shore 60 62 56 60 40 17 13 ie 9 6 4 3 73 BO 65 66 44 20 295 53 34B B. Investigative X 25 B a i 8 0 B B HONS 067971 SECTION II Methods of Preparation and Analysis 1. Stream water and outfall samples. 2. Offshore water samples. 3. Stream and offshore plankton samples. 4. Sediment samples. 5. Fish samples. 6. Hydrolysis {dehydro chlorination) MONS 062972 1. Stream water and outfall samples The sample was mixed well before sampling. 1,B00 mis. was measured into a graduate. The sample was placed in a clean empty nanograde solvent bottle. 100 mis. of ethyl ether and 200 mis. of hexane was added and the sample placed on a magnetic stirrer for 3 hours at medium to high speed. The sample was transferred to a 2 liter separatory funnel and allowed to separate. 3tie lower layer was drained back into the extraction bottle. The hexane layer was rinsed twice with 100 mis. of de-ionized water, discarding the wash layer each time. The hexane layer was dried with 10-15 grams of NaSO* and transferred to a 1 liter flask using 50-60 mis. of hexane to transfer with. The sample was placed on a steam bath and evaporated to 2-3 mis. Bie hexane was transferred to a florisil coluim (1.5 em. x 10 inches) packed with 3.5 grams of pre-standardized florisil and eluted with 15 mis. of 5% etherpet ether and then 15 mis. of 15* ether - pet ether. The resulting solutions were concentrated under nitrogen to dryness and taken back up in 2 ml. of hexane. The sample was injected into gas chromatograph. HONS 067973 2. Offshore water samples. The sample was mixed well before sampling. Four 2,000 ml. portions were measured and placed in four clean nanograde solvent bottles. 200 mis, of hexane was added to each bottle. The bottles were placed in a case and put on a shaker for 5 minutes. The bottles were removed from the case and shaken by hand for three minutes. The bottles were allowed to stand for four hours and the above method of shaking was repeated. The samples were then transferred to 2,000 ml. separatory funnels and the layers allowed to separate. After separation the lower layer was drained back into the extractor bottleB. The hexane layers were combined, and dried with Na^SOj. The hexane was transferred to a 2 liter flask. The hexane was concentrated to 2-3 ml. on a steam bath and then transferred to a florisil column and eluted the same as the I.W. samples. The elutions were evaporated and made to 2 ml. and injected into a gas chromatograph. HONS 067924 3. Stream and offshore plankton samples. The samples were filtered through a Buchner funnel using a glass fiber filter pad. The pad was weighed and then the sample was filtered. The pad was placed in an oven at 40C and re-weighed and the dry weight obtained. The samples were ground with 10-20 grams of Na2SO* and extracted on Goldfisch extractor for 4 hours using 50 mis. of ethyl ether. The ether was evaporated and the sample run through a small florisil column as with the I. W. Blanks showed little or no interfering peaks. The samples were made to 2 mlB. and injected on a gas chromatograph after florisil. MGN5 067975 4. Sediment samples. The samples were mixed and two 25 gram samples were weighed into two 150 ml. beakers. One beaker was placed in an air oven at 100C and dried for 2-3 days and the moisture was determined. The other sample was transferred to a Waring blender jar (1 gt.) and blended for 2 minutes with 200 ml. of acetonitrile. The acetonitrile was filtered through a plug of glass wool into a 1 liter separatory funnel containing about 500 ml. of top water. The sample was then blended for about minute with an additional 50 ml. of acetonitrile and then filtered into the separatory funnel. 200 ml. of petroleum ether was added to the separatory funnel and shaken for 2 minutes. The layers were allowed to separate and the bottom layer was drawn off. The petroleum ether extract was washed two more times with about 600 mis. of tap water, discording the water layer both times. 10 grams of NB2S04 was added to the petroleum ether extract and the sample was filtered into a 300 ml. erlenmeyer flask (rinse separatory funnel with about 70 ml. of petroleum ether). The sample was then taken down to about 5 ml. on a steam bath. The sample was then run through a Florisil column using 20 grams, of florisil and 150 ml. of 5% ether in petroleum ether and 250 ml. of 15% ether in petroleum ethei-. The column elutions were made up to 25 mis. with hexane. 10 microliters or less of the cleaned up extract was injected into a gas chromatograph. MONS 06 79 76 S. Fish samples. The total weight of the fish was obtained and each fish was measured. The average weight and average length were reported. The fish was then ground in a model B41B1D Hobart until homogeneous. A portion of the sample was placed in an B ounce bottle and frozen until analysis was preformed. Extraction and Cleanup. 1. The samples are removed from freezer and thawed and mixed. 2. 20 grains of sample were weighed into a 150 ml. beaker. 3. The sample is transferred to a Haring blendor jar (1 qt.) and blended for 2 minutes with acetonitrile. 4. The acetonitrile is filtered through a plug of glass wool into a 1 liter sep. funnel containing about 500 ml. of tap H20. 5. The sample is then blended for about 1/2 minute with 50 additional mis. of acetonitrile and then filtered into the sep funnel. 6. 200 mis of Pet-Ether is added to the sep funnel and then shaken for 2 minutes. 7. The layers are allowed to separate and the bottom layer is drawn off. B. The Pet-Ether extract is washed an additional two times with about 600 mis of tap H20 (discarding H20 layer both times). 9. 10 grains NaS04 is added to the Pet-Ether extract and the sample is filtered into a 300 ml erlenmeyer flask. (Rinse ` sep. funnel with about 70 mis of Pet-Ether). 10. The sample is then taken down to about 5 mis. on a steam bath and made to 25 mis. with Pet-Ether. 11. A 51 ml. aliquot is taken and an acetonitrile partition run. (equivalent to 12.0 grams). Pesticide Manual Vol. 1, p. 2-3 section 2.21A. 12. The sample is then run through a florsil column (Pesticide Manual Vol. 1, p. 3 section 2.21A). 13. The elutions are made to 25 mis. with Hexane. Injection. 10 ml or less of the cleaned up extract is injected into Gas Chromatograph and the peaks measured and the ppm, recorded. Cas Chromatograph conditions. A. Column: 1/4" x 4' glass *QNS 067977 I I I l 6 0 Q I D 0 Q D I [ I I I B. Packed with 5* D.C. 200 on cromport XXX {60-90 mesh) C. Column Temp.: 195C. D. Injector Temp.: 250C. E. Deetector Temp.: 240C. p. Carrier gas: - 100 ml. per minute or so that prp' - DDT has retention time of 8-10 minutes. Gas chromatograph-Barber Coleman Pesticide-Analyzer Model 5360 equipped with a Sr-90 detector. HONS 0679^8 6. Hydrolysis. A 10 ml aliquot of the first elution from the florsil is placed in a 125 ml erlenmeyer. Evaporate to small volume {2-5 mis) on a steam bath and then to just dryness using nitrogen. 20 mis of 2% alcoholic KoH is added. The sample allowed to reflux for 30 minutes using a water conclensor. The sample is transferred to a 125 ml separatory funnel by rinsing flask with 3-10 ml portions of Petroleum Ether. 20 ml of distilled water is added. Shake vigorously for 1 minute. The aqueous layer is drained into a second 125 ml separatory funnel containing 20 mis of Petroleum Ether. Shake vigorously for 1 minute. The H2O layer is discarded and the Petroleum Ether layer is added to the first separatory funnel. The Petroleum ether extracts are washed with 3 x 20 mis portions of distilled water. The extract is dried with about 10 grams of Na2SOj and transferred to a 125 ml erlenmeyer using 15-20 mis to rinse separatory funnel. The sample is concentrated to 2-3 mis on a steam bath and made to 10 mis with Hexane and injected intc the gas chromatograph. Discussion of Hydrolysis. Hydrolysis will dehydrochlorinate p,p'-DDT to p,p'-DDE and p,p'-DDD to p,p'-DDD olefine. PCB's will not be affected by the Hydrolysis. To determine the amount of p,p'-DDD and p,p'-DDT present in a sample in which there are apparent PCB's would be accomplished in the following manner. The original extract would be injected, DDE, DDD, and DDT calculated. The hydrolized extract would be injected and the DDE, DDD, and DDT values calculated. The Est. PCB's are also calculated. HChS 067979 using the peaks between ODD and DDT and the peak at DDT. The value obtained from DDD original minus the value obtained from the DDD for the hydrolysis would equal the P.P.M. of the actual DDD present. The same is true for DDT. The total DDT and metabolites present in the sample can therefore be calculated two ways: (1) DDE (original non hydrolized) plus the actual DDD, plus the actual DDT, or (2) the DDE (hydrolized) plus the actual DDD. MOHS 067960 Wisconsin Alumni Research Foundation Marfnon, wfston*in I i D Q 0 1- 0 I 0 0 0 0 '[ I I ' rofftt f , SECTION HI RESULTS . HONS 067961 WHcvidih ASomiia Research Foundation * MadHan, Wncsmln LAKE MICHIGAN STUDY! Results Definitions s x.xxL = X.XXE " N.C. = Block I Retention time late Retention time early Not calculated Peak is masked by some othe: time or unknown time making r Off scale = Peak was off scale of std. SED " Sediment IW - Inshore water D OW - Outshore water IP - Inshore Plankton OP Outshore Plankton PPM = Parts per million 0 PPT * Parts per trillion Calculation: Section TIT ^ Eat. PCb. on all samples except fish PCb is est. from peak that falls between DDD t DDT on a DC-200. The fish Est. PCb are taken from Hydrolized amples and the peak between DDD fc DDT and the peak at DDT are measured and Compared to a standard. Results: O.P. t I.P. on a dry basis, SED on a wet basis, Fish - as is basis (wet) I L 0 6 |l I I t MOMS 067982 ^ fOUn I jh r S 0 sti 1 s I B B I I I ' A. Stream Water, Stream Plankton, Sediment, Offshore Water and Offshore Plankton. . HONS 0679B3 Wisconsin Alumni Research Foundation Madison, Wisconsin ;ample Type Values No. in % h2o DDE DDD DDT Dieldrin BHC Est PCb 1 2 B3 B 4 r B 5 I Q6 '0 B7 08 < E 'p 9 10 SED IW IP SED IW IP OW OP SED IW IP OW SED IW IP OW Fish SED IW IP OW OP SED IW IP OW SED IW IP OW SED IW IP OW SED IW IP OW OP SED IW IP OW PPM PPT PPM PPM PPT wet PPM PPM PPT PPM PPM PPT PPM PPM PPM PPT PPM PPT PPM PPM PPT PPM PPM PPT PPM PPM PPT PPM PPM PPT PPM PPT PPM PPM PPT PPM 68.0 Wet 0.018 <10.0 0.010 44.00 <0.001 <10.0 0.042 Dry 0.32 19.44 0.001 <10.0 Dry 0.17 21.55 0.010 <10.0 Dry 1.00 as is 2.60 18.90 Dry Dry <0.001 <10.0 0.060 4.8 0.11 17.53 <0.001 /10.0 _ Dry 0.096 18.04 <0.001 <10.0 Dry 0.049 9.24 Dry <0.001 <10.0 0.079 14.99 Dry Dry 0.003 300E 0.098 <1.0 0.017 27.29 0.001 <10.0 Dry 0.10 0.048E <10.0 0.057 0.041L <10.0T . 0.023L <0.001 <10.0 -- <0.001 <10.0 0.069 0.12 <0.001 <10.0 "0.0611' I. 0.21 <0.001 -- ---- 0.080 0.002 <10.0 0.099 O-OOS1* <10.2. o. iSL <0.001 -- 0.049 0.007 <10.0 0.34 o.oo6L <10.0 "Block 0.51 0.60 <0.001 <10.0 0.030 2.3 0.060 <0.002 <10.0 Block 5.6 0.20 0.001 <10.0 0.032 0.001L <10.0 0.088" <0.001 <10.0 0.025 0.12 <0.001 <10.0 0.015 1.3 0.040 <0.001 <10.0 0.010 N.C. -- 0.50 N.C. N.C. N.C. N.C. <0.01 N.C. N.C. 0.014 0.79 N.C. 0.099 0.02 N.C. 0.37 ... N.C. Block 0.05 N.C. 0f scale 0.030 1.98 -- N.C. 0.058 50.3 -- <0.01 N.C. Off scale 0.46 -- 73.5 0.051 0.01 N.C. 0.20 0.001 <10.0 0.060 <0.002 <10.0T 0.13L <0.001 <10.0 0.006 -- <0.01 128.0 N.C. 0.22 0.63 <0.001 <10.0 0.047 0.001L <10.0T 0.16" *-0.001 -- 0.007 -16.0 0.12 <0.01 N.C. 0.28 0.003 300E 0.063 1.1 0.006 0.002 <10.0 0.040 0.005L '10.0T 0. 17l 2.4 0.036" <0,002L <10.0 0.10L -<10.0 0.008 1.5 0.001 <0.001 "- 0.020 -- 17.8 0.092 13.7 0.033 0.028 N.C. 0.65 9.0 -- <0.01 43.3 N.C 0.050 0.21 HOhS 067984 Wisconsin Alumni Research Foundation Moditon, wiontln Sample Type Values % DDE | No. in h2o DDD DDT Cieldrin BI1C Kst rcb 11 11 1 [r12 IUI13 n B 14 Bam m 0 15 |I 6ft 16 L1 n 17 0y 118 A1 1 19 SED IW IP OW OP SED IW IP SED IW IP OW SED IW IP OW OP Fish SED IW IP OW Fish PPM PPT PPM PPT PPM PPT PPM PPM PPT PPM PPM PPT PPM PPT PPM PPM PPM PPT PPM PPT PPM SED IW IP OW OP SED IW PPM PPT PPM PPT PPM PPM PPT 20.45 Dry Dry 0.003 <10.0 0.060 <1.0 0.049 0.009 ao.o 0.055 <1.0 0.033 0.003L 14.4L Block Block O.llL No data <10.0 <10.0 <10.0 Dry 0.092 0.063 0.14l 18.01 0.005 <10.0 Dry 0.12 0.007 <10.0 0.070 0.007** <10.0 0.20l <0.001 <10.0 0.011 1.7 0.008 <10.0 0.017 <0.001 <10.0 0.030 52.2 0.000 8.0 0.051 0.01 N.C. Off sea Off sea 0.24 27.2 0.11 N.C. 0.48 35.3 0.040 0.03 N.C. 3.09 75.74 Dry Dry as is 0.074 180 0.20 1.9 0.27 0.78 72.68 Dry as is (Chub) 0.008 <10.0 0.13 '1.0 2.08 50.49 Dry Dry 0.023 <10.0 0.22 1.5 0.059 56.47 0.00 8 4.8 0.12E 180e 0.28 5.6 0.091 0.27 0.0161* <10.0T 0.38L 8.9L 0.22l 0.70 0.010 <10.0 0.12 <1.0 0.35 0.015l <10.0. 0.15" <1.0 1.07 0.028e <10.0 0.13 2.8 0.047 0-028L <10.0 Block 4.5 0.14l 0.012 10.0 0.015l 12.8 0.001 <10.0 0.056 1.0 0.009 0.11 <0.001 <10.0 0.040 1.1 0.12 <0.001 <10.0 0.030 2.2 -- 0.001 <10.0 72.2 0.22 23.3 0.44 0.015 1. 10 N.C. 2.79 50.8 0.73 1. 50 -- 13.3 0.080 8. 5 0.021 0.03S N.C. 6.40 1.35 -- 0.21 50.0 N.C. 0.18 >7.25 20.0 19.5 0.070 0.32 -14.4 0.052 SED IW IP OW OP Fish SED IW IP ow PPM PPT PPM PPM PPM PPT PPM 62.05 Dry 0.00 8 <10.0 0.20 0.013 0.016L <10.0 0.15 <io. oT 0.27l as is (Chub) No data 2.34 0.51 14.23 0.006 <10.0 Dry 0.050 0.005 <10.0 0.036 1.31 0.005L 10.8 . 0.093L 0.001 <10.0 0.16 0.17 -- <10.0 0.005 __ _ 66.7 0.060 0.12 N.C. 0.97 0.021 0.87 0.01 34.4 N.C. 0.020 0.20 HONS 067985 Wisconsin Alumni Research Foundation MorfUon, Wnconiin jSn'.iplo Typo Values % DDE No. in il20 DDD DDT nleldrin DUC K:t rcb . 20 1 21 I L 622 n D mIk,i2 3 B 24 1l fp L1 Hu26 ya 1 1 1 SED IW IP OW Fish SED IW IP OW OP SED IW IP OW SED IW IP OW OP SED IW IP OW SED IW IP OW Fish SED IW IP OW OP FiBh SED IW PPM PPT PPM PPM PPM PPT PPM PPT PPM PPM PPT PPM PPM PPT PPM PPM PPT PPM PPM PPT PPM PPM PPM PPT PPM PPM PPM PPM PPT 48.53 Dry 0.060 <10,0 0.11 as is 0.93 15.28 Dry Dry 0.002 280e 0.058 5,3 0.098 44.54 Dry 0.008 <10.0 0.080 0.11 <10.0 0.060 0,11 <10.0 0,12L 0.57 0.002 280e 0.055 25,9 0.040 0.004** 14.OL 0.13l Block 0.11B 0.011 <10.0 0.050 0.0071* <10.0 T 0.090l 0.001 <10,0 0.030 0,030 w <10.0 -- 2.6 0.011 <0.001 <10.0 0.020 -- <10.0 0.020 0.01 N.C. 0.77 0,031 2.34 <10.0 0.020 7.5 0.049 0.033 N.C. 0.52 8^8scale -- <10.0 0.037 0,015 N.C. 0,17 51.88 0.012 <10.0 Dry 0.14 Dry 0.52 0.015 <10.0 0.081 0.15 0.015L <10.0 0.13l 0.37L Dry No data <10.0 <10.0 0.15 0.10 <10.0 0.21l <0.001 <10.0 0.074 1.73 -- 0.021 <10,0 N.C. 0.017 0.47 0.030 10,4 <10.0 0.016 174.0 N.C. 0,030 0.55 30.31 0.020 20.0L 0.0 30 94.0E 0.017 116.0L Dry 0.43 0.25 Block as is 42.04 Dry Dry as is 64.87 0.40 0.013 <10.0 0.36 0.18 1.75 0.55L 100.o1- 0.057 0.028 <10.0 0.10 0.080 0.18 0,80 120e 0.14 0.0121* <10.oL 0.24 0.16L 0.49 0.38L 40,0B <0.001 <10.0 -- 20.8 -- 0.35 0.18 Off scale 0.040 -- <10.0 0.032 0.015 -- <10.0 0,060 0.77 0.036 N.C. 0.80 0.040 0.049 0,050 0.42 0,023 3.05 <0,001 <10.0 -- 5.2 7.2 Very pos- IP OW OP Fish PPM PPT PPM PPM Dry Dry as is 2.00 -- 0.20 3.63 3.63 -- 0.27 1.25 Block 0.2 3L 1,73 0.035 <1.0 1.37 0.13 0.61 Off scale 0.020 1. 36 0.060 i, 31 HONS 067966 Wisconsin Alumni Research Foundation Marfnen, Saiple Typo Values % DDE 1 Ho. in u2o DDD DDT Dieldrin DJC Est rci> 11 28 k "29 1 n^30 un p i 31 n 32 ] 33 f! a^34 nLi L r *36 1 1 SED IW IP OW SED IW IP OW Fish PPM PPT PPM PPM PPT PPM PPM SED IW IP OW OP SED IW OW OW OP SED IW IP OW OP SED IW IP OW OP SED IW OW SED IW IP OW OP Fish PPM PPT PPM PPT PPM PPM PPT PPT PPT PPM PPM PPT PPM PPT PPM PPM PPT PPM PPT PPM PPM PPT PPT PPM PPT PPM PPT PPM PPM 17.42 Dry 0.002L 15.5 0.27 0.003 43.2e 0.41 0.006L 38.7l 0.28l 23.97 Dry 0.035 <10.0 0.28 0.13 10.2 0.16 0.19?* 19.6?* 0.47" as is (Chuh) 55.08 2.99 0.17L 8.8 0.52 0.41 18.0 2.14 0.24L 16.0L Dry Dry 69.28 0.93 1.1 0.62 0.35** 17.6l 2.2 1.63 1.4 0.35 0.52 22.0 3.6 1.44l 3.0 y 0.711* 0.27L 14.2l 6.2 Dry 70.24 Dry Dry 54.73 Dry Dry 1.1 0.23 0.012 <10.0 0.24 1.7 0.38 0.028L 10.0E 0.27 <1.0 0.45 2.6 0.23 0.035 10.0 0.21 1.5 0.19 0.078 19.1E 0.19 <1.0 0.090 7.1 L 0.33l 0.022L <10.0. 0.41l 2.7 L 0.48L 0.031L 20.0?* 0.281* 2 1 T 0.35l 18.07 41.03 0.003l 16.2e 2.2 0.038L 7.2 0.00 4l 2B. 2e 1.0 0.003l 31.1L 1.8 0.13E 14.8 0.12l 28.0L Dry Dry as is 0.25 1.1 0.20 1.43 0.70 1.6 0.15 1.43 0.79l 1.4 T 0.26L 0.23 <10.0 0.054 0.052 18. 4 V.Pos.Pres 0.061 2.00 <0.001 <10.0 0.040 0.26 _ 19.5 0.090 0.065 Possibly 1.02 0.065 2.60 0.040 28.8 -- 44.0 3.20 Possible 0.050 2.2 0.050 0.040 14.0 1.1 -- 8.0 0.24 -84.0 20.2 7.04 9.5 4.58 4.4 Possible 15.0 3. 3 0.050 22.8 27.2 0.022 1.55 0.004 <10.0 1.30 4.5 0.060 64.0 0.13 110.0 0.11 0.075 Possible 1.30 5.5 1.33 0.002 <10.0 0.090 3.1 0.060 -- 10.4 0.020 27.8 0.090 0.20 Possible 1.19 0.47 -- <.10.0 1.9 0.004 <10.0 <10.0 9.0 -40.4 0.013 Possiblc "" 1.25 0.050 2.1 0.040 0.18 Block 7.8 0.080 0.065 6.67 55.9 1.72 2.02 MCNS 06798? I Sample | No. Type Wisconsin Alumni Research Foundation Values in % 2 DDE DDD DDT Medium. w;>con><n Dieldrin BHC Est PCb |1 37 I1 38 r0t n39 n u r 40 RB i 41 h *'42 nV p i. 43 Dn i P SED IW IP OW OP Pish SED IW IP OW OP SED IW IP OW OP SED IW OW OP SED IW Fish SED IW IP OW OP SED IW IP OW OP Fish Fish PPM 23.64 0.00 4 PPT <10.0 PPM Dry 0.14 PPT 1.4 PPM Dry 0.25 PPM as is 1.56 PPM PPT PPM PPT PPM 63.96 Dry Dry 0.075 24.4e 0.71 <1.0 0.33 PPM PPT PPM PPT PPM 46.49 Dry Dry 0.007 15.1E 0.23 2.1 0.37 PPM PPT 18.88 0.002 4.0 PPT PPM Dry <1.0 0.39 PPM 20.72 0.008 1-* t rf PPM as is 1.42 PPM PPT 29'.63 0.012 12.0 PPM PPT PPM Dry Dry 0.10 5.6 0.32 PPM PPT PPM 73.43 Dry 0.011 40.0E 0.46 PPM PPM PPM Dry as is (chub) as is (trout) 0.30 2.41 1.93 0.007 <10.0 0.11 1.5 0.18 1.64 0.38 27.4e 2.16 1.5 0.27 0.011 19.6S 0.13 2.0 0.20 0.006L <10.0 Block 1.8 L 0.38L 0.13 0.03pL 41.8" 0.84L 2.0 0.84" 0.006L 22.2l 0.41l 6.0 0.511* 0.004 0.003l 6.0 6.0 <1.0 0.19 1.5 _ 0.52" 0.011 0.010L 0.97 0.06 0.011 6.0 0.0I2L 18.0" 0.19 2.5 0.25 0.30l 3.0" 0.50l 0.023 30.5s 0.31 0.010L 11.7l 0.52l 0.18 0.54 0.44" 0.92 1.20 1.13 <0.001 <10.0 0.050 2.3 0.050 0.14 0.002 <10.0 0.070 2.1 0.040 0.002 <10.0 0.10 3.4 0.050 __ <10.0 0.021 17.9 N.C. 0.10 >22.7 8.3 9.3 0.040 1. 82 0.0 30 2.33 47.0 0.15 1.5 0.10 -- Possible 4.47 6.5 2.00 ,, 14.0 0.11 4.5 0.11 0.060 Possible 0.77 15.0 3.33 40.0 0.037 1.9 0.070 <0.001 7.4 0.080 -- 1.82 0.032 0.13 0.001 45.2 0.046 -- 7.2 1.67 0.08 0.030 3.0 0.14 0.0 80 0.93 34.3 28.3 0.073 1.50 0.005 <10.0 0.050 -- 0.11 <10.0 N.C. 0.16 >9.26 0.003 0.17 0.012 0.80 0.046 3.96 0.21 0.034 4.02 I HONS 06 798fl Wisconsin Alumni Research Foundation Madison, Wisconsin JE D"np lo Typo Values No. in % n2o DDK DDD DDT Dield\ rin DFIC Cst PCb 11 44 1, 1 I1 45 1 nLJ p46 u 8 47 D i * 48 FuI L49 nu Injso I _I i 51 P SED IW IP OW OP Fish SED IW IP OW OP SED IW IP OW OP SED IW IP OW OP SED IW IP OW OP SfiD IW IP OW OP SED IW IP OW OP SED IW IP OW OP PPM ppT PPM PPM PPM PPT PPM PPM PPM PPT PPM PPM PPM PPT PPM PPM PPM PPT PPM PPM PPM PPT PPM PPM PPM PPT PPM PPT PPM PPM PPT PPM PPM 23.55 Dry 0.017 <10.0 0.19 0.018 <10.0 0.30 0.018L <10.0, 0.25" Dry as is 0.21 1.56 0.12 0.47 0.32l 0.01 No data <10.0 <10.0 <10.0 Dry 0.47 0.47 0.45L Dry 0.24 0.22 0.42L 84.64 Dry 0.008 <10.0 0.40 0.013 <10.0 0.14 0.009l <10.0 0.31l Dry 0.18 69.64 Dry 0.010 <10.0 0.53 0.13 0.026 <10.0 0.37 0.26l 0.025L 11. 4, 0.30" Dry 0.22 0.32 0.53 85.68 0.002 <10.0 Dry 0.12 0.004 <0.001 <10.0 <10.0, 0.12 0.24" Dry 0.33 0.32 0.49l 74.21 Dry 0.002 <10.0 0.30 Dry 0.27 0.004 <10.0 0.20 0.16 0.002l <10.0 0.2Bl 0.30L 20.27 Dry Dry 0.001 <10.0 0.54 <1.0 0.29 58.91 Dry 0.002 <10.0 0.65 <0.001 <10.0 0.20 1. 5 0.080 <0.001 <10.0, 0.33" 3.5 . 0.27" 0.003 <10.0 0.15 0.002l <10.0 0.36l Dry 0.11 0 .050 0.10L <0.001 <10.0 0.030 0.010 0.090 33.0 0.12 0.043 N.C. 1.79 0.0 30 0.45 0.044 2.66 <10.0 <10.0 <10.0 0.050 0.060 2.40 0.020 0.050 1.34 <0.001 <10.0 0.053 0.018 10.0 N.C. 0.050 1.23 0.033 0.002 <10.0 0.080 <0.005 -<10.0 0.14 0.77 0. 17 Possible 1.83 0.0 30 0.050 2.22 <0.001 <10.0 0.030 0.056 <10.0 0.13 0.01 N.C. 0.73 0.050 0.003 <10.0 0.10 0.050 2.06 -- <10.0 0.012 0.02 N.C. 2.35 0.045 0.070 0.89 <0.001 <10.0 0.050 2. 7 0.040 <0.001 <10.0 0.060 <10.0 0.20 5.8 0.090 <0.01 <10.0 2.04 12.5 0.42 -- 0.01 20.0 N.C 0.020 1.55 0.020 0.012 0.29 HONS 067*58 9 Wisconsin Alumni Research Foundation Madison, Wisconsin Rnnple Type Values NO. in t h2o DDE DDD DDT Dieldrin niic ! Tt PCb I 52 1 1 1" n u fj54 "55 0s6 1 / BM s7 fL [j59 u 60 1 61 I1 ' 1 SED IW IP OW OP Fish SED IW IP OW OP SED IW OW OP OW OP SED IW IP OW OP Fish SED IW IP OW OP SED IW IP OW OP SED IW IP OW OP SED IW IP OW OP PPM PPT PPM 22.98 Dry <0.001 <10.0 0.070 PPM Dry 0.83 PPM LH as is 2.90 PPM PPT PPM PPT PPM 78.71 Dry Dry 0.004 <10.0 0.67 <1.0 0.23 PPM PPT 17.74 0.003 <10.0 PPM Dry 0.21 <0.001 13.3 0.020 <0.001 U.1lt 0.040l 0.30 1.17 0.005 <10.0 0.47 <1.0 0.18 0.70l 1.31 0.003L <10.0 1.19L 1.3 L 0.31L 0.003 <10.0 0.11 0.005l <10.0 T. 0.35^ <0.001 <10.0 0.00 8 <0.01 <10.0 Possible 0.070 0.13 0.090 0.14 0.12 2.33 0.034 4.37 <0.001 <10.0 0.066 1.2 0.025 ____ <10.0 0.090 6.2 0.040 <0.01 N.C. 4.76 -- 0.51 <0.001 -- <10.0 ao.o 0.01 N.C. 0.040 0.10 0.77 PPM Dry 0.32 T. 0.070 0.27" pPM 35 .60 PPT 0.001 0.002 <10.0 <-10.0 No data 0.002l <10.0 PPM Dry 0.37 PPM as is 3.59 0.13 0.15 0.35L 0.25 PPM PPT PPM 24.12 Dry 0.002 <10.0 0.70 0.004 <10.0 0.20 0.002L <10.0 0.6 3l PPM Dry 0.64 0.090 0.25l PPM PPT PPM 36.99 0.002 ^30 0E Dry 0.12 0.003 >300E 0.060 0.003l N.C. 0.15l PPM PPM PPT PPM PPT PPM Dry 0 .20 17.01 Dry Dry 0.001 <10.0 1.00 <1.0 0.50 0.060 0.002 <10.0 0.20 <1.0 0.12 0.16l 0.00 3L <10.0 0.57l 1.5 0.30l PPM PPT PPM PPM 24.91 0.001 <10.0 Dry 0.38 Dry 0.58 0.001 <10.0 0.11 <0.002l <10.0 0.19l 0.21 0.35l 0.070 0.040 0.27 <0.001 -- <10.0 <10.0 0.01 NC 0.055 0.21 0.080 0.51 0.054 1.91 <0.001 -- 0.01 <10.0 Interfer. N.C. 0.080 0.14 2.00 0.12 0.15 0.55 <0.001 <10.0 0.022 -- <10.0 0.034 0.01 N.C 0.31 0.040 0.020 0.35 <0.001 <10.0 0.13 1.3 0.080 __ N.C. 0.28 2.1 0.23 0.01 N.C. 1.33 1.00 <0.001 <10.0 0.050 -- N.C. 0.12 0.01 N.C. 4.79 0.090 0.13 2.08 HONS 067990 1 Wisconsin Alu mni Research Foundation Malison, Wisconsin Scv'ipla Typo Values i in % 1J20 DDC ODD DDT Dieldrin u:;c Lst 1Tb 162 1 63 1 n "64 B 65 r1 fl66 SED IW IP OW OP SED IW IP OW OP SED IW IP SED IW IP OW SED IW IP PPM PPT PPM PPT PPM PPM PPT PPM PPM PPM PPT PPM PPM PPT PPM PPM PPT PPM 48.99 Dry Dry 0.036 <.10.0 0.44 3.0 0.83 0.053 <10.0 0.28 3.2 0.18 0.025L <10.0 0.54L 4.9 0.38l 19.44 Dry <0.001 <10.0 0.13 0.001 <10.0 0.070 0.002** <10.0T 0.40" Dry 0.58 0.14 0.29l 26.39 Dry 0.002 1.110E 0.13 0.0Q3E 0.002** 945 29.01* 0.12 Block 49.73 0.037 <10.0 Dry 1.63 0.14 <10.0 0.40 0.18** <10.0 1. 33** <0.001 <10.0 0.060 1.6 0.080 <10.0 0.16 6.5 0.11 0.80 N.C. 2.22 1. 25 <0.001 <10.0 0.020 0.01 <10.0 N.C. 0.030 0.42 0.32 0.0. <10.0 0.011 0.001 <10.0 0.16 0.060 N.C, 0.006 _ <10.0 0.67 0.89 0.04 N.C. Off scale 1.46 N.C. 2.67 20.82 0.001 <10.0 Dry 0.51 0.003 <10.0 0.13 0.003L <10.0 0.41** <0.001 <10.0 0.10 40.0 0.16 0.03 N.C, 0.77 D 0 E 0 l i P MG*S 067991 Wisconsin Alumni Research Foundation Maditon, VViicaniin Sample Type Values | No. in % h2o DDE DDD DDT Dieldrin BHC Est PCb 1 X1 1 k1 nx2 11 f]x3 U r0ix4 X6 0x7 | X9 0rXl Xll h rxi2 u[I n 4l3 |ml4 i15 *xi6 j1 ! IB SED PPM IW PPT IP PPM ow OP PPM SED PPM OW OP PPM SED PPM IW IP PPM IW SED PPM SED IW IP PPM PPT PPM SED IW PPM PPT IW PPT SED PPM IW SED IW IP PPM PPM SED IW IP Fish PPM PPT PPM PPM OW OP PPM OW IW PPT OWSED OP Fish PPM PPM PPM IW 44.25 Dry 0.002** <10.0 0.11 0.002 <10.0 0.0 80 0.002L *10.0 0.22** Dry 0.097 0.077 0.097** 65.91 0.009 0.008 0.007l Dry 0.13 0.16 0.080** 36.95 0.024 0.029 0.010L Dry 0.19 0.25 0.13** 15.68 0.001 17.61 Dry 0.002 <10.0 0.080 26.02 0.002 <10.0 43.0 76.06 0.25 0.002 0.002*' 0.003 <10.0 0.030 0.003** <10.0 0.099** 0.003 0.005** <10.0 <10.0 32.0 0.069 50.0** 0.09 8** 19.87 0.012** 0.014** 0.016** Dry 0.21 0.22 0.22** 20.26 asDry is 0.001 <10.0 0.13 4.73 0.002 <10.0 0.11 0.57 0.002** *J0.0 0.23** 1.02 Dry 0.52 1.00 0.76** <20.0 24.20 0.002 Dry as is 0.24 0.94 <20.0 <20.0 0.005 0.30 0.74 0.040 0.41** 0.27 <0.001 10.0 -- 0.037 0.001 0.020 <0.001 0.016 <0.001 <0.001 <10.0 0.007 <0.001 <10.0 <20.0 0.007 0.002 0.040 <0.001 <10.0 0.024 0.18 0.060 30.0 <0.001 0.060 0.12 83.0 0.0 49 -- 0.13 0.048 0.01 N . C. 0.50 0. 42 0.11 0.87 0.25 1.43 <0.01 <10.0 0.040 0.020 N.C . 0.092 10.0 0.0 30 N.C. 46.7 150 0.84 0.040 <10.0 0.029 0.060 0.060 0.39 0.0 20 0.56 4.87 0.30 5.17 64.0 0.0 80 0.03 220 0.070 >4 6 3 1 45 HONS 067992 Wisconsin Alumni Research Foundation Madiwn, wbcemin Sample Type Values j No. In 1I20 DDE DDD DDT Dieldrin BHC rst PCb 11 ^ X18 IW SED IW IP Fish PPT PPM PPT PPM 46.6 58.45 Dry 0.060 <10.0 0.73 132.0E 150L 0.095 12.1 1.01 0.23L <10.0 1.01L 10.0 0.018 <10.0 0.098 69.0 <10.0 0.45 1,222.0 0.73 N.C. 6.70 iL 19 n x20 SED IW IP Fish IW PPM PPT PPM PPM 31.68 Dry as is 0.002 <10.0 0.15 0.77 0.003 <10.0 0.14 0.30 0.003L <10.0 0.43** 0.02 0.001 16.5 0.020 0.050 <10 0.15 0.013 0.02 20.0 0.77 1.20 D21 X22 DB y,23 u X24 IW SED IW IP IW IP 0W PPT PPM PPT PPM PPT PPM PPT <10.0 77.42 Dry 0.003 <10.0 0.48 Dry <10.0 0.10 3.0 <10.0 <10.0 0.010 <10.0 0.48 0.007k 12.2l 0.45l <10.0 <10.0 0.050 0.090k <10.0 <0.001 <10.0 0.050 <10.0 0.020 3.5 1.0 3.2 <10.0 21.0 0.090 <10.0 0.050 1.5 0.050 N.C. 2.99 N.C. O.31 29.0 El L P y ;i i rOMt f MOWS 067993 Wi^cr>rin Alumni Rp?parch Foundation * Madiion, Wuconiin I .w. Ranges (P.P.T.) DDE, DDD, DDT: h I e Dieldrin i L = 0.00 - 10.0 M - 10 - 50 N.C. H = 50 i up O = odd peaks Early peak MOO B - Blocked X Probable presence of L <10 M >10 E BHC L = 0 - 10 M - 10 - 50 c H - 50 & up N.C. Not calculated I I Interference Section -I-II Not calculated c G E R 0 ecu i HONS 0679S4 Wisconsin Alumni Research Foundation Madin, Wiicemin Sample IWSampleI_W No. DDE DDD DDT Diel. BHC PCb No. DDE DDD DDT Diel. nuc PCb 1 bLL 2 LLL 3 LLL 4 bLL 5 LLL LLL 7 LLb 8 LLL 9 00L 10 L L L 11 L L M 12 L L L 13 L b b 14 0 0 b 15 L L b 16 17* bLb LLM 17 0 0 L 18 L L L 19 L L M 20 L L L 21 0 0 M 22 L L L 23 L L b 24 L L L 25* 25 MHH 0 0M 26 L L L 27* H H M 27 M H M 28 M M M 29* L 29 L M M 30* L M M 30 H H N 31 M M M 32 33 L M L L N.C L N.C L N.C b N.C * L N.C bH LH L M io LH LM LH LH bM LH LM LM L b M M X bH bM b L e jo bL bL bL bH bM b MX bL b bX b MX b MX b MX M MX L MX M HX b HX 34 M M M L M X 35 M M M L L X 36 L M M L M X 36 0 0 H b M X 37 L L L b M 38 H M M b M X 39 M M M b M X 40 b b L b M 40 0 0 M b L 41 NO data 42 M L M M L 42 0 0 M M M X 43 H M M L L 44 L L b L M 45 L L b L L 46 L L b L L 47 b L M b b X 48 b b L b b 49 b b L b L 50 b b L b L 51 b b L b M 52 b M M b L X 53 b b L b L 54 L b b ' b L 55 56 b b b b L 57 b b b b I 58 59 0 0 N.C . L L 60 L L L L N.C 61 b I. L L N.C 62 b L b L L 63 b b b L L 64 0 0 M L N.C 65 b b b L L 66 L L b b L HCNS 067S95 Wisconsin Alumni Research Foundation Moditon, witonin Sample IW No. DDE DDD DDT Diel. BHC ESt. PCB XI DLL L H X2 X3 X4 X5 X6 L L L L L X7 L L L L L XS X9 M M M L M X xio Xll X12 L L L L L N.C. X13 X14 X15 H M M M H X X16 X17 M H H L H X X1B X19 L ML L L L LL M L X20 X21 L L L L L X22 X23 L LM L LL LH LL X24 flQNS 067996 Wi$COnr In Aliimni Rpvnrch Foundation MadUon, WItomln SED Ranges: (P.P.M.) DDE , DDDi DDT: L <0.001 - 0.020 M = 0.020 - 0.10 H = 0.10 6 up Dieldrin: L - <0.001 - 0.005 M - 0.005 - 0.010 H - 0.010 /it up PCB L <0.01 1- 0.10 M - 0.10 - 0.70 H * 0.70 up HONS 067^97 Wisconsin Alumni Research Foundation Modiion. witcomin Sample ___________ SEP________ ________ No. DDE DDD DDT Diel. BHC Est. ____ PCB Sample No. ______ __ SED DDE DDD DDT Di'eT. Bile' Est. PCB 1 2 I3 4 5 I6 7 8 9 D 10 11 12 G 13 14 15 16 G 19 E 20 21 22 23 24 25 26 0 27 28 29 S 30 31 32 33 0 LM M LL L LL L LL L LL L LL L LL L LL L LL L LL L LL L No data LL L MH L LL L MM M DLL LL L LL L NH H LL L LL L LL L No data MM L L M' L HH H LL L MH H H H. H HH H No data LM N L L L L L L L L L L L L L L L L L L L L L L L L L L L H H L M 34 M M M L - M L 35 L L L L - L L 36 MHH L -H I 37 LL L L-L L 38 MHM L-L L 39 LL L L- L L 40 LL L L-L L 41 LL L L-L L 42 DLL L-L L 43 L M M M - M L 44 LL L L-L 45 No data L 46 LL L L-L H 47 LM M L-M L 48 L L L I* - L M 49 LL L L-L L 50 LL L L- L M 51 LL L L-L L 52 LL L L- L L S3 LL L L- L L 54 LL L L- L L 55 L 56 LL L L L 57 LL L L L L 58 L 59 LL L L- L H 60 LL L L- L L 61 LL L L- L L 62 MM M L- H H 63 DLL L- L H 64 LL L L-L 65 MH H L H L 66 LL L L- L D F I HONS 067998 Wisconsin Alumni Research Foundation Modlton. w;ontin Sample SEP_______________ No. DDE DDD DDT Dlel. BHC Est. PCB XI X2 X3 X4 X5 X6 X7 XB X9 X10 Xll X12 X13 X14 X15 X16 X17 X18 X19 X20 X21 X22 X23 X24 LL LL MM LL LL LL HM LL LL L L L L L L M L L L L L L L L M L L L LM MH H LLL LL L L H L L L M M L L L H L L L H L L HCNS 0679S9 Wisconsin Alumni Research Foundation Madison, Wisconsin IP, i O.P. Range (P.P.M.) DDE, DDD, DDT, Dieldrin, BHC L *= 0.0 = 0.10 M * 0.11 - 0.40 H e 0.40 t up B Block O.S. = Off scale PCB L * 0.00 - 0.50 M - 0.50 - 2.00 H B 2.00 ( up O.S. * Off scale HONS 066000 Wisconsin Alumni Research Foundation Madison, Wisconsin Sample O.P. No. DDE DDD DDT Diel. BHC PCB 1 2 3 k4 5 6 r7 8 9 10 c 11 12 13 y 14 15 16 17 IB "M9 20 B 21 22 23 24 25 ' 26 27 28 L. 29 30 i 31 32 M MM M LM L LL L LM M LH L LM L LM H MM M LM M MM H MH M M *M L LM L LL L LL L LL L HM L LL L LL H LH L LL H LM L MH L LM L E I I I. | O.P. No. DDF. DDD DDT Diel. BHC PCB 33 M M H L M M 34 H L M L L L 35 36 M M M L L M 37 M M M L L M 38 M M H L L H 39 M M H L M H 40 M M H L L M 41 42 M H H M L M 43 M M H L L M 44 M M M L L L 45 M M H L L M 46 M M M L L' M 47 M M H I. L H 48 M M H L L H 49 M M M L L M 50 M L M L L L 51 M L L L L L 52 H M H L L H 53 M H M L L M 54 M M M L L M 55 M L M L L L 56 M M M L L M 57 H L M M M M 58 59 N L M L L L 60 H M M L M M 61 H M M L M H 62 H M M L M M 63 H M M M L M 64 65 66 HONS 068001 Wisconsin AJ-mni Research Foundation Maditen. Wwontin Sample ____________IP ____________ NO. DDE DDD DDT Diel. B11C PCB 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 vlB 19 20 21 22 23 24 25 26 27 28 29 30 31 32 r 33 M L N L Is L H M B L B O.S. L L B Is L O.S. LLL L LL L LM L MH L L M L M Is Is L M L Is M Is L L L L Is BIs Is L L O.S. Is Is M L M Is M LM L LH MMM L NH MMM L LH MMB L MH M N H M Is M L L L Is Is Is M Is N Is Is M L L M Is Is H L L Is L Is L H Is N Is Is L H L M Is Is M H M B N N O.S. M L H L Is H H H B L H O.S. MHM L LH HMH L LH H HH L LH M M H H MM E c I I I Sample IIP No. DDE DDD DDT Diel. BUC PCB 34 M M M L L M 35 36 M H H L B H 37 M M B Is L H 38 H H H Is M H 39 M M H Is M M 40 41 42 M M M Is L M 43 H M H Is M H 44 M M M Is M M 45 H H H Is L H 46 M M M Is L M 47 H M M Is M M 48 M M M Is M M 49 M M M Is L H 50 H M M Is H H 51 H H M Is L H 52 L L L Is Is Is 53 H H H Is Is II 54 55 56 57 H M H I. I H 58 59 M L M Is L M 60 H M H M M M 61 H M H L M H 62 H M H L M H 63 M L H L Is L 64 N M B L L O.S 65 H M H N H H 66 H H H Is M M HONS 068002 ronu Wisconsin Alumni Research Foundation Madison, Wisconsin Sample IP No. DDE" BDD'UDT" Diel. BIIC Est PCB xi M LM L LL X2 K X3 X4 X5 M MM L LM X6 I X7 XS L LL L LL X9 D X10 Xll M MM L L L X12 M M M L L M I XI3 X14 X15 AXX16 rsxl 8 HHH L HH X19 MMH L MM !l X20 X21 X22 HHH L LH X23 ` L L L L L L X24 SampleO.P_. No. DDE DDD DDT'Diel."bHC XI X2 X3 X4 X5 X6 X7 X8 X9 X10 Xll X12 X13 X14 X15 X16 X17 X18 X19 X20 X21 X22 X23 X24 LL L L L L M M L L MM HH H MM H L MH L LH cn O W P. F: t: '[ ) R OM| < HCNS 068003 c SECTION V B. FISH B l 0 0 I R i t HONS 066004 Wisconsin Alumni Research Foundation Modison, wucomin I Lake Michigan Study || Fish Data: r DDE DDE from non hydrolyzed I ODD (DDD from non hydrolyzed) - (DDD from hydrolyzed) DDT * (DDT from non hydrolyzed) - (DDT from hydrolyzed) Est PCB - Peaks between DDD t DDT and peaks at DDT from |j hydrolyzed sample t I' 1 l E c i i } | Ot'fct I MCNS 068005 Wisconsin Alumni Research Foundation Modisen, wion!n Sample No.s Location: Type: Pensaukee River Alewife Ave. Weight: 38.25 grams Ave. Length: 6.58 inches No. of fish: 20 . Pesticide Corrected P.P.M. BHC 0.030 , Dieldrin 0.12 DDE 2.60 DDD 0.51 DDT 0.60 Est PCB 1.98 Total DDE, DDD, DDT P.P.M. 3.71 Not Corrected P.P.M. 0.030 0.12 2.60 0.76 0.84 -- P.P.M. 4.20 % of Total: DDE DDD DDT 70.1% 13.7% 16.2% Total of DDE hydrolyzed 6 actual DDD in P.P.M. 3.20 i ) rmri MONS 066006 Wisconsin Alumni Research Foundalion Madison, Wisconsin Sample No.i 14 Location: Ahnopee River Type: Alewife Ave. Weight: 26.75 grains Ave. Length: 5.39 inches No. of fish: 4 Pesticide BHC Dieldrin DDE DDD DOT Est PCB Corrected P.P.M. 0.015 0.11 0.78 0.27 0.70 1.50 Not Corrected P.P.M. 0.015 0.11 0.78 0.47 0.90 -- Total DDE, DDD, DDT P.P.M. 1.75 P.P.M. 2.15 % of Total: DDE DDD DDT 44.6% 15.4 40.0% Total of DDE hydrolyzed 6 actual DDD in P.P.M. 1.90 NGNS 060007 Wisconsin Alumni Rescorch Foundation Mndi*on, whcomi, Sample No. 15 Location: Kewaunee River Typer Chubs (cleaned) Ave. Weights 143.3 grams Ave. Lengths 9.6 inches No. of fish: 5 . Pesticide Corrected P.P.M. BHC Dieldrin DDE DDD DDT Est PCS 0.021 0.12 2.08 0.35 1.07 1.35 Not Corrected P.P.M. 0.021 0.12 2.08 0.48 1.23 -- Total DDE, DDD, DOT P.P.M. 3.50 P.P.M. 3.79 % of Total: DDE DDD DDT 59.4 10.0% 30.6% Total of DDE hydrolyzed i actual DDD in P.P.M. 2.88 MQNS 068008 Wisconsin Alumni Research Foundation Madison, Wisconsin Sample No.: 18 Location: Manitowoc River Type: Chubs Ave. Weight: 142.2 grams Ave. Length: 8.41 inches No. of fish: 6 Pesticide BHC Dieldrin DDE DDD DOT Est PCB Corrected P.P.M. 0.021 0.17 2.34 0.51 1.31 0.87 Total DDE, DDD, DDT P.P.M. 4.16 Not Corrected P.P.M. 0.021 0.17 2.34 0.60 1.41 -- P.P.M. 4.35 % of Total: DDE DDD DDT 56.3% 12.3% 31.5% Total of DDE hydrolyzed & actual DDD in P.P.M, 3.48 MONS 068009 Wisconsin Alumni Research Foundalion Mod!on, iviiconsin Sample No.: 25 Location: Seven Mile Creek Type: Alewife Ave. Weight: 19.42 grams Ave. Length: 5.05 inches No. of fish: 5 Pesticide Corrected P.P.M. Not Corrected P.P.M. BHC 0.015 0.015 Oieldrin -- DDE 0.040 0.40 0.040 0.40 DDD 0.057 0.13 DOT 0.14 . 0.23 Est PCB 0.77 -- Total DDE, DDD, DDT P.P.M. 0.63 P.P.M. 0.76 % of Total: DDE DDD DDT 63.5% 14.3% 22.2% Total of DDE hydrolyzed t actual ODD in P.P.M. 0.92 M0*S 068010 Wisconsin Alumni Research Foundation Madison. Wisconsin Sample No.: 26 Location: Pigeon River Type: Alewife Ave. Height: 30.23 grams Ave. Length: 6.38 inches No. of fish: 4 Pesticide BHC Dieldrin t ' DDE DDD DDT Eat PCB Corrected P.P.M. 0.023 0.049 1.75 0.18 0.49 3.05 Not Corrected P.P.M. 0.023 0.049 1.75 0.59 0.83 -- Total DDE, DDD, DDT P.P.M. 2.42 P.P.M. 3.17 % of Total: DDE DDD DDT 72.3% 7.4% 20.2% Total of DDE hydrolyzed t actual DDD in P.P.M. 2.90 HONS 068011 Wisconsin Alumni Research Foundation Madison, Wisconsin Sample No. 27 Location: Sheboygan River Type: Alewife 1 Ave. Height* 15.76 grams Ave. Length* 4.85 inches I No. of fish* 7 l Pesticide Corrected P.P.M. Not Corrected P.P.M. BHC 0.060 0.060 D^ejldrin 0.13 0.13 r DDE 3.63 3.63 DDD 1.25 1.69 [ DDT 1.73 2.10 Eat PCB 3.32 -- i Total DDE, DDD, DDT P.P.M. P.P.M. E 6.61 7.42 L % of Total: r- DDE DDD 54.9% 18.9% i DDT 26.2* Total of DDE hydrolyzed 6 actual DDD in P.P.M. i 6.57 i i HONS 068012 Wisconsin Alumni Research Foundation Motion, wuiomin Sample No.: 29 Location: Sauk Creek Type: Chubs (cleaned) Ave. Weight: 214.8 grams Ave. Length: 10.7 inches No. of fish: 5 . Pesticide Corrected P.P.M. BBC 0.065 Dieldrin DDE 0.26 2.99 DDD DDT 0.52 2.14 Bst PCB 2.60 Not Corrected P.P.M. 0.065 0.26 2.99 0.91 2.41 -- Total DDE, DDD, DDT P.P.M. 5.65 P.P.M. 6.31 % of Total: DDE DDD ' DDT 52.9% 9.2t 37.9% Total of DDE hydrolyzed & actual DDD in P.P.M. 5.48 rci.t t HONS 068013 Wisconsin Aiunml Research Foundation Madison, Wisconsin Sample No.: 37 Location: Burns Ditch Type: Alewife t Perch (?) Ave. Weight: 127.55 grams Ave. Length: 7.50 inches No. of fish: 2 Pesticide BHC Dieldrin DDE DDD DDT Bst PCB Corrected P.P.M. 0.030 0.14 1.56 1.64 0.13 2.33 Not Corrected P.P.M. 0.030 0.14 1.56 1.95 0.48 -- Total DDE, DDD, DDT P.P.M. 3.33 P.P.M. 3.99 % of Totals DDE DDD DDT 46.8% 49.2% 3.9% Total of DDE hydrolyzed t actual DDD in P.P.W 3.07 MONS 068014 Wisconsin Alumni Research Foundcilion MoJiien, w;nin Sample No.t 41 Location: st. Joseph River Type? Alewife Ave. Weight: 35.3 grams Ave. Length: 6.50 inches No. of fish: 2 Pesticide BHC Dieldrin -- DDE DDD DDT Est PCB Corrected Not Corrected P.P.M. P.P.M. 0.046 0.046 0.13 0.13 1.42 1.42 0.97 1.15 0.06 0.44 1.67 -- Total DDE, DDD, DDT P.P.M. 2.45 P.P.M. 3.01 % of Total: DDE DDD DDT 58.0% 39.6% 2.4% Total of DDE hydrolyzed t actual DDD in P.P.M, 2.58 MGNS 068015 Wisconsin Alumni Research Foundation Macfoon, wijcemin Sample No.: 43 Location: BlacJc River Type: Chubs Ave. Weight: 177.9 grams Ave. Length: 10.33 inches No. of fish: 6 * Pesticide ^ BHC Dieldrin DDE DDD DDT Est PCB Corrected P.P.M. 0.046 0.17 2.41 0.54 0.92 3.96 Total DDE, DDD, DOT P.P.M. 3.87 Not Corrected P.P.M. 0.046 0.17 2.41 0.94 1.37 -- P.P.M. 4.72 . % of Total: DDE DDD DDT 62.3% 13.9% 23.8% Total of DDE hydrolyzed t actual DDD in P.P.M. 4.14 MONS 068016 Wisconsin Alumni Research Foundation Madijen, Wisconsin Sample No.: Location: 43 Black River Types Trout Ave. Weight: 405.8 grams Ave..Length: 12.5 inches No. of fish: 2 . Pesticide BHC Dieldrin DDE DDD DDT Eat PCB Corrected P.P.M. 0.034 0.21 1.93 1.20 1.13 4.02 Not Corrected P.P.M. 0.034 0.21 1.93 1.60 1.63 -- Total DDE, DDD, DDT P.P.M. 4.26 P.P.M. 5.16 % of Total: DDE . DDD DDT 45.34 28.2% 26.54 Total of DDE hydrolyzed t actual DDD in P.P.M. 3.84 oira HONS 068017 Wisconsin Alumni Research Foundation Madison, Wisconsin Sample No.: 44 Location: Kalamazoo River Type: Alewife Ave. Weight: 38.7 grains Ave. Length: 6.20 inches No. of fish: 5 Pesticide BHC Dieldrin DDE DDD DDT Eat PCB Corrected P.P.M. 0.044 0.090 1.56 0.47 0.01 2.66 Not Corrected P.P.M. 0.044 0.090 1.56 0.90 0.32 -- Total DDE, DDD, DDT % of Total: DDE DDD DDT P.P.M. 2.04 76.5 23.0% 0.5% P.P.M. 2.78 Total of DDE hvdrolvzed S actual ' 2.03 MQNS 068018 Wis>c<jniii Alumni Research Foundation Moduon, Wmonjin Sample Ho. > 52 Location: Manistee River Manistee Mich. 5VPes Lake Herring Ave. Weight: 394.6 grams Ave. Length: 12.6 inches No. of fish: 4 Pesticide BHC Dieldrin DDE DDD DDT Bst PCB Corrected P.P.M. 0.034 . 0.14 2.90 1.17 1.31 4.37 Not Corrected P.P.M 0.034 0.14 2.90 1.65 1.83 -- Total DDE, DDD, DDT P.P.M. 5.38 P.P.M. 6.38 % of Total: DDE DDD DDT 53.9% 21.7* 24.3* Total of DDE hydrolyzed t actual DDD in P.P.M. 4.22 MCNS 068019 Wia.w<i>io A'uniiii Hcecncli Foundation Mndi*on, Witonin Sample No.: X12 Location: Dead River Type s Alewife Ave. Weight: 21.3 grams Ave. Length: 5.70 inches No. of fish: 5 Pesticide BHC Dieldrin DDE DDD DDT Est PCB C?rpeCMted 0.060 0.18 4.73 0.57 1,02 4.87 Not Corrected P.P.M ____ 0.060 0.18 4,73 1.26 1.56 -- Total DDE, DDD, DDT P.P.M. 6.32 P.P.M. 7.55 % of Total: DDE DDD DDT 74.8 9.0% 16.1% Total of DDE hydrolyzed & actual DDD in P.P. 5.95 HONS 066020 Wisconsin Alumni Research Foundation Modiion, wion*tn Sample No. X16 Location: Off South Chicago Type: Alewife Ave. Weights 14.9 grams Ave. Length: 4.30 inches No. of fish: 3 Pesticide Corrected P.P.M. BHC 0.031 Dieldrin 0.12 DDE 0.94 DDD 0.74 DDT 0.27 Eat PCB 1.46 Not Corrected P.P.M 0.031 0.12 0.94 0.87 0.46 -- Total DDE, DDD, DOT P.P.M. 1.95 P.P.M. 2.27 % of Total: DDE DDD DDT 48.2% 37.9% 13.8* Total of DDE hydrolyzed S actual DDD in P.P.M. 1.68 MONS 068021 Wisconsin Alumni Research Foundation Modiwn. wiicemin Sample Mo.: X19 Location: Gary Harbor Types Alewife Ave. Weights 25.2 grains Ave. Length: 5.50 inches No. of fish: 5 Pesticide BHC Dieldrin ---- DDE DDD DDT Est PCB Corrected P.P.M. 0.013 0.050 0.77 0.30 0.02 1.20 Mot Corrected P.P.M. 0.013 0.050 0.77 0.50 0.18 -- Total DDE, DDD, DDT P.P.M. 1.09 P.P.M. 1.45 % of Total: DDE DDD DDT 70.6% 27.5% 1.8% Total of DDE hydrolyzed t actual DDD in P.P.M. 1.17 MONS 068022 Wisconsin Alumni Research Foundation Moditon, wc*ntio Sample No.s 20 Location: Gary Type: Ave. Weight: Alewife 36.14 grams Ave. Length: 5.85 inches No. of fish: 7 Pesticide BHC Dieldrin DDE ODD DDT Est PCB Corrected P.P.M. 0.031 0.030 0.93 0.57 -- 2.34 o 00 1/1 Not Corrected P.P.M. 0.031 0.030 0.93 0.26 Total DDE, DDD, DDT % of Total: DDE DDD DDT P.P.M. 1.50 62.0 38.0 0.0% P.P.M. 2.04 Total of DDE hydrolyzed actual DDD in P.P.M. 1.45 MONS 068023 Wisconsin Alumni Research Foundation Ma<inl w.*<w*in Sample No.: 36 Location s Grand Calumet River Type: Alewife Ave. Weight: 33.68 grams Ave. Length: 6.33 inches No. of fish: 9 Pesticide Corrected P.P.M. BHC Dieldrin DDE DDD DDT Est PCB 0.065 0.18 3.02 1.43 0.23 2.02 Not Corrected P.P.M. 0.065 0.18 3.02 1.69 0.48 -- Total DDE, DDD, DDT P.P.M. 4.68 P.P.M. 5.19 % of Total: DDE DDD DDT 64.5 30.6% 4.9% Total of DDE hydrolyzed 6 actual DDD in P.P.M, 3.81 HONS 068024 Alumal Research Foundation Mod;on, wconin Sample No.: 56 Location: Lerlanua Lake, Leland Mich. Type: Chubs Ave. Weight: 160.3 grams Ave. Length: 10.0 inches No. of fish: 3 Pesticide Corrected P.P.M. BHC Dieldrin DDE ODD 0.054 0.21 3.59 0.15 DDT 0.25 Est PCS 1.91 Not Corn P.P.M. 0.054 0.21 3.59 0.29 0.44 -- Total DDE, DDD, DDT P.P.M. 3.94 P.P.M. 4.32 t of Total: DDE DDD DDT 88.81 4.8* 6..41 Total of DDE hydrolyzed fc actual DDD in P.P. 3.78 HONS 068025 ' WJ>imii!ii Aluifltii Rewarch Foundation Madison, Wisconsin Fish DDE DDD DDT 4) 2.60 H 14) 0.78 L 15) 2.08 H 18) 2.34 H 25) 0.40 L 26) 1.75 M 27) 3.63 H 29 2.99 H 37 1.56 M 41) 1.42 M 43) 2.41 H 43) 1.93 M 44) 1.56 M 52 2.90 H 0.51 M 0.27 L 0.35 L 0.51 M 0.057 L 0.18 L 1.25 H 0.52 M 1.64 H 0.97 M 0.54 M 1.20 H 0.47 L 1.17 H 0.60 M 0.70 M 1.07 H 1,31 H 0.14 L 0.49 L 1.73 H 2.14 K 0.13 L 0.06 L 0.92 M 1.13 H 0.01 L 1.31 a Ranges (P.P.M.) 0 1 Of 1.00-L 1. 00-2.00M 0-0.50=1. 500 o.so-:L.00=M o.so-;1.00 2. OOtup-H 1.00tUp=H l.OObup 0 1o Dieldrin BHC 0.12 M 0.11 M 0.12 M 0.17 M 0.040i L 0.049i L 0.13 M 0.26 H 0.14 M 0.13 M 0.17 M 0.21 H 0.090 M 0.14 M 0.030 L 0.015 L 0.021 L 0.021 L 0.015 L 0.023 L 0.060 M 0.065 M 0.030 L 0.046 L 0.046 L 0.034 X. 0.044 L 0.034 L 05 0.0-0.005 0.05-C1.20 0.05-0 .10 0.20iup X12) X16) X19) 20) 56) 36) > 4.73 H 0.94 L 0.77 L 0.93 L 3.59 H 1.43 M 0.57 M 0.74 M 0.30 X. 0.57 M 0.15 L 0.43 M 1.02 H 0.27 L 0-.02 L L 0.25 L 0.23 L 0.18 M 0.12 M 0.0S0 L 0.030 I> 0.21 H 0.18 M 0.060 M 0.03 3 0.013 L 0.031 L 0.054 M 0.065 M Est PCS 1.98 1 1.50 M 1.35 M 0.87 L 0.77 L 3.05 H 3.32 H 2.60 H 2.33 H 1.67 M 3.96 H 4.02 H 2.66 H 4.37 H 0-1.00 l.oo-;2.00 2.00- 4.87 H 1.46 M 1.20 M 2.34 M 1.91 M 2.02 H 066026 MO NS C. Investigative Samples Racine and Kenosha HONS 068027 I Wisconsin Alumni Research Foundation Motion, winomin I Sample Description of Sample PPb Pesticide No. DDE DDD DDT Dieldrin Est SHC : An1alysis Dfroy r:Cleaning -Pesticide Residue I i De2scriptionWOneoerfnHeSorau'smr pMClelae: artnininKizgeinnogsha,<00W..12i00s00e. S<0a4m..71p50l00eEs <0.100 0.250l <0.100 0.700 i S13ubmittIendAdpubyysa:tniaRl ug CoG.. E. Schm<o0le.1s0ki0 0.170 0.100 <0.100 I b2 * Snap On TooWlsaCrfoIrpn.stitu<0te.10I0nc. <4.100 <0.100 <<0.100 Anaconda Copper <0.100 t0.100 <0.100 <0.100 3 Forest Park Auto Wash <0.100 40.100 <0.100 <0.100 PCB <0.100 0.160 25.0 Blocked 0.300 Blocked <0.100 <0.100 0.100 0.600 0.120 0.218 4 Kelsey Welding i LaBlanc Mfg. <0.100 <0.100 <0.100 `0.100 <0.100 0.400 5 AMC Paint fc Body PI. <0.100 <0.100 <0.100 <0.100 0.120 0.470 6 Mac Whyte Mfg. <0.100 <0.100 <0.100 <0.100 <4.100 1.310 F7 1 Eaton Mfg. Overflow Sewer Maina <0.100 <0.100 <0.100 <0.550 0.100 0.440 Outflow Anaconda, etc. Masked Masked Masked <0.100 Masked Masked i2 Overflow (AMC. etc.) <0.100 <0.100 <0.100 <0.100 0.100 0.385 3 Storm Sewer CO.100 <0.100 <0.100 <0.100 <0.100 <0.100 1 Municipal Dump B2 Drainage ditch From pond at above <0.100 <0.100 <0.100 <0.100 <0.100 <0.100 ' dump <0.100 <0.100 <0.100 <0.100 <0.100 <0.100 BV PCB est. on peak between DDD & DDT 0 y i p i ^ RONS 066028 I Wisconsin Alumni Research Foundation Ma<Jitn, Wi>cn>in j i Analysis for: Pesticide Residue \ Description of Sample: Racine, Wise. Samples Submitted by: : G.E. Schmoleski Warf Institue Inc. Sample Description of Sample NO. ________________PPb Pesticide DDE DDD DDT Dieldrin Est pea B>1L Dry Cleaning 1 2 One Hour Martinizing Paris Royal *J).100 <0.100 <0.100 <0.100 tO.100 <0.100 0.135 0.237 0.100 0.9 30 3 Independent Cleaners Courtesy Cleaners Industrial i Walker Mfg. 2 S.c. Johnson a0.100 0.375 0.725L 0.405 0.175 0.250 0.295l 6.25 0. 320 2.80 <0.100 Gordon Mfg., Case Trans Masked Masked 0.300 1,771.0 P.D.I., Inc. 0.250 Printing t Devel.Co. Overflow Sewer Main - CO. 100 <0.100 <0.100 0.463 <0.100 1 Storm Sewer <0.100 CO.100 <0.100 <0.100 <0.100 <0.100 2 English St. (from resident.) North Shore beach into lake <0.100 <0.100 0.107 <0.100 <0.100 <0.100 3 From West Racine residential into Root River s then lake Masked Masked Masked 0.250 drainage ditch on Oaks Masked Masked Rd. . 1 Municipal Dump - leading from dump area. <0.100 <0.100 <0.100 0.312 0.100 <0.100 I PCB est. on peak between DDD 6 DDT r- i: r p HONS 068029 I [ p D. Miscellaneous Samples r i i e i f L I HONS 068030 tI WISCONSIN ALUMNI RESEARCH FOUNDATION LABORATORIES Modhon, Wisconsin Reports ore submitted to clients on a confidential botis. No roferonco to the work, the results or to the Foundolion in ony form ol advertising, newt release r Iher public announcement moy be mode without written authorisation from the foundation ASSAY REPORT Annlysii for Pesticide Residue I Description of Sample Additional samples from Ahnapee River Date Received 9-5-69 Control Number I Submitted by John J. Birdsall WARF Institute Inc. Claimed Content Location At river mouth DDE 140.0 14-2X ^4-3X 4-4X 14-SX At sewage disposal plant outlet <20 100 yds. dnstrm. from major ind. at fork of N. i W. branches 40 West branch upstream from major industries <20 North Branch 80 DDD <20.0 PPT Pesticide DDT Dieldrin BHC Eat.PCB <20.0 <20.0 Interfer 280 Blocked Blocked <20.0 <20 Blocked <20.0 <20.0 Blocked Blocked <20.0 <20.0 <20.0 Blocked 140.0 <20.0 Blocked Blocked <20.0 Blocked 200 L Remarks t I I. ___ Signed by and for the WISCONSIN ALUMNI RESEARCH FOUNDATION Date W. A. R. F. No. HONS 068031 Analysis for Pesticide Residue Sample Description - Fish Pellets Date Received - May 12, 1969 WARF No. 9051223 DDE 0.055 PPM Insecticide DDD DDT 0.029 0.054 Dieldrin <0.005 HONS 068032 WISCONSIN ALUMNI RESEARCH FOUNDATION LABORATORIES Modiion, WUcn4n Rcporli are submilled 10 clients on a confidential bout. No reference to the work, the remits or to the Foundation in any form of advertising, now* release or other public announcement moy be mode without written authorization from the Foundation ASSAY REPORT Analyst* for Pesticide residue Description of Semple Water (Berrien County) Dsto Received 11-6-69 Control Number Submitted by State of Michigan Dept, of Natural Resources Lansing, Michigan Carlos Fetterolf Claimed Content Results DDE PPT DDD PPT Station 3 Station 5 Station 3 Station 5 10-22-69 10-22-69 11-3-69 11-3-69 Blocked Blocked Blocked Blocked <20 <20 <20 <20 DDT Dieldrin PPT PTT <20 20.0 <20 <20 200.0 62.7 150.0 243.0 BHC ESt. PCB PPT PPT 194.0 23.1 20 83.8 ----- Method { E r Remarks ( f l ; rones i Signed_____________ by and for the WISCONSIN ALUMNI RESEARCH FOUNDATION Date W. A, R. F. No. HONS 068033 WISCONSIN ALUMNI RESEARCH FOUNDATION lABORATORtES Modtsen, Wisconsin Report* are submitted to client* on o eonfidonliol baii*. No reference to the work, the result* or to the Foundation in any (arm ol advertising, news leicota or other public announcement maybe made without written authorization fiom the Foundation ASSAY REPORT Analysis for Pesticide Residue Description of Sample Water I Date Received 10-21-69 Control Number t Submitted by Gary Sanitary District Gary, Indiana E E Claimed Content Results L E DDE 97.0 , PPT Pesticide DDD DDT Dieldrin 194.0 117.0 V10 BHC 140 I Method [ S Remarks c [ 4 I Signed I by and for the WISCONSIN ALUMNI RESEARCH FOUNDATION D,t* W. A. R. F. No. HONS 06803<t WISCONSIN ALUMNI RESEARCH FOUNDATION LABORATORIES Mudliwi, Wisconsin Reports ore submillod to clients on a confidentiol botis No reference to the work, the results or to the Foundotion tn ony form of advertising, newt release or othor public announcement may be mode without written authorization from the Foundation ASSAY REPORT Analysis for Pesticide Residue Description of Sample Water-Black River-So. Haven,Mich. I Date Received 10-8-69 Control Number I Submitted by 0 Board of Public Utilities 529 Phoenix St. Box 152 South Haven, Midi. 49090 e Claimed Content Results K Sample No. 3 ' ' V' V XPPT .Pesticide DDE '" DDD t)DT Dieldrin BHC Est. PCB <10 <10 <10 <10 351 j Method B l e Remarks g i i Signed by end for tlie WISCONSIN ALUMNI RESEARCH F0UNDA1 ION Date W. A R. F No HONS 066035 ' WISCONSIN ALUMNI RESEARCH FOUNDATION UBOKATOtffiS Mocfnon, Wisconsin Reports ore submitted to cllonts on a confidential basis. No reference to the work, the results or to the Foundation in ony form of odvcriising, news release or other public announcement maybe made without written authorization from the Foundation. ASSAY REPORT Analysis for Pesticide Residue I Description of Sample Water Date Received 10-10 69 I Submitted by Control Number L t Claimed Content Results I -ample No. * I* 2 lb | DDE Grand River -Oct. B, 1969 8:30 A.M. Railroad Bridget Right t Left <10 Banks downstream from Grand Rapids waste treat- merit plant. Method E PPT Pesticide DDD DDT Dieldrin BHC ESt. PCB <10 0.0 <10 26.9 -- l ^ Remarks [ l Signed__________________ ___ _____________________ ___________ I by and for the WISCONSIN ALUMNI RESEARCH FOUNDATION Date W. A. R. F No. MONS 068036 WISCONSIN ALUMNI RESEARCH FOUNDATION LABORATORIES Mod?***, V/tc*n*fo Reports ore submitted 10 ettonts 00 a confidential basts. No reference to th* work, the resells or to the Foundation in any form of advertising, news roleos* or other public announcement may bo made without written authorization from tho Foundation ASSAY REPORT Analyst* for Description of Sample * Date Received C Submitted by E Claimed Content E Result! B C Method Pesticide Residue Water 9-15-69 Control Number Mr, James B. Gifford, Supt. Sewage Treatment Plant 532 Franklin St. Michigan City, Indiana 46360 PPT Pesticide DDE <10 DDD <10 DDT <10 Dieldrin 34.0 Est.PCB Blocked BHC 19.2 P Remarks E E [ I Signed by and for tba WISCONSIN ALUMNI RESEARCH F0UNDAT10 Date W. A. R. P. No. HONS 060037 SECTION IV Discussion i HONS 068038 Figure 1 has been prepared to graphically portray the interference caused by apparent polychlorinated biphenylo and other other unknown hexane soluble electron capturing compounds. Other workers have encountered similar interference recently (References 1-9). The presence of these non-pesticide interfering compounds causes extreme difficulty in interpreting results. If, because of peak similarities, it is suspected that there may be PCB's present, hydrolysis of the sample is necessary to enable a calculation to estimate the amounts and to thereby adjust downward the amounts of DDT and its metabolites. Estimates may be made without hydrolysis, but they are not very accurate. All fish samples and many of the other samples contained apparent PCB's. More frequent incidence was in samples from the southern part of the lake and in samples from cleaning establishment outlets. The average of five chub samples for DDT and metabolites was 4.70 ppm without adjustment for apparent P,,CB.'s. The only chub sample in excess of 5 ppm was from the southern part of the lake (Sauk Creek, 6.31 ppm). The average for 13 alewive samples for DDT and metabolites was 3.54 ppm without adjustment for apparent PCB's. The two alewive samples in excess of five ppm were from the southern part of the lake (Sheboygan River, 7.42 and Dead River, 7.55). Adjustment of the DDT and metabolite results for apparent PCB's would result in a 4 to 27% reduction. MON3 068039 pattern is evident, indicating that plankton may circulate widely around the lake. This may relate to the ish results discussed previously. The presence of apparent BHC in many samples is difficult to understand since so little BHC and lindane have been in use in recent years. It is likely that this is also an artifact. Many additional analyses are needed to determine the identity of the artifacts found. Meanwhile, care must be exercised so as not to confuse them with actual pesticide chemicals. 0680110 M0*s The other unknown hexane-soluble electron-capturing compounds are perhaps more disconcerting than the apparent PCB's. Since the identity of these compounds is not as yet known, no adjustments can be made. Yet they occur as early and late peaks near the retention times of DDT, DDD and DDE. They may or may not be eliminated from contention by the use of second or third G. C. columns or by use of thin layer chromatography. Although they do not occur to any extent in fish samples, their extensive occurrence in water, sediment and plankton samples is cause for concerni (a) they may be part of peaks being identified and quantified as pesticides and (b) they may have toxic properties of presently unknown significance. If the apparent PCB's and other unknown hexane soluble electron-capturing compounds can be ignored, the occurrence of chlorinated hydrocarbon insecticides in Lake Michigan is at low levels. Most stream waters contained less than 10 ppt of DDT, DDD, DDE and Dieldrin. Higher levels of apparent BHC were found in stream waters (10-50 ppt) but it is extremely doubtful that this is truly BHC. Stream sediments follow a similar pattern as stream waters but no BHC was detected. Levels of DDT, DDD, DDE and Dieldrin were generally less than 0.02 ppm except in the southern part of the lake. Stream and off-shore plankton varied widely but contained low levels of Dieldrin (0.10 ppm or less) and somewhat higher levels of DDT, DDD, DDE and BHC (o.11-0.40 ppm). No geographical MONS 068041 1 I I c E r i i i e i 4 iT Ip References 1. Holmes, D. C. , J. H. Simmons and J. 0. G. Tatton. 1967. Nature 216, 227. 2. Jensen, S. 1966. New Scientist 32,, 612. 3. Harrison, R. B. 1966. J. Sci. Fd. Agric. 17, 10. 4. Holden, A. V. and Marsden, K.r 1967. Nature 216, 1274. 5. Widmark, G., 1967. J.A.O.A.C., 50, 1069. 6. Koeman, J. H., et al. 1967. Med. Rijksfaculteit. Landbouwwetenschappen Gent. 32^, 3. 7. Risebrough, R. W., et al. 1968. Nature 220, 1098. 8. Koeman, J. H., M. C. Ten Noever de Brauw and L. H. deVos 1969. Nature 221, 1126. 9. S. Jensen, A. G. Johnels, M. Olsson and G. Otterlind. 1969. Nature 224, 247. MQNS 0680*3