Document dDq1eRVzma4X1o1py361QVByB

oEFV environmental PROTECTION AGEN' fteoion V pi,tMl3llL i 1 TO: 1 REGIONAL ADMINISTRATOR r " Deputy Region*' Administrator nu SRA. f m SpOC>*l All4tn| . Suit Coo'd-naio'i t Rt9'pn*> Counsel Rtiti'Ch & Development Rtp Great late* National Program m |" " OFFICE OF INTERGOVERNMENTAL .__' IXTERAAL PROGRAMS - \ Oli^ce o* Congressional and Federal Relation* Office o' CxmI Rights St'nCC - ** # \ ! SRC < i i SRO SGLNP i M 1 !I t si | SXCF I i! SXCR . SXMS . 11 Office of Envirpnmente' Review Wo'fc>Cf De*iooment Stall Office of Pwb'c P#n*c*pjio^ SXER Sxwo 1 Sxpp Oll.CF of Pup^e Inlo'maiion Sxpi 1 5xliB ! ASSISTANT REGIONAL ADMINISTRATOR - FOR PLANNING & MANAGEMENT BRANCH SM < Ar.|WI>c Center 5MAC ; Dill Processing Branch SMDP Resource Management S'antn' SMRM Pt-rir->.:tl Branch SMP General Services Branch SMGS Graphic Arts SMGS AIR ( HAZARDOUS MATERIALS DIVISION Office ol Grant* Support Olfice of Tone Swpsiance* Aii Prog'im* Branch Watte Management Branch Pesticides Branch SAn SAhGS SAHTS SA*?S 5AHWM SAHP i | /I WATER DIVISION Afi*;m Option Drec^r fpr Construction Grant* Cice o< Policy & Evaluation Fn\"enmtn:*l Engineering Branch . Facilities Planning Branch Construction Management Branch Wi'f r SuopN 8ranch Waie* Quantv Management Branch //t<( ORCEMENT DIVISION A.r'Enfocement * ' Permit Branch : 1 Watt' and Hatardout Materia* Enforcement Branch SW SW SWPE 5 WEE SWFP 5WCM 5WNVS SWWOM SE ^ SEAE SEAE SEWHME ~ Surveillance & analysis division Owa:Hv Assurance Ollrca SS SSOA Tecnmcai Support Branch SSTS | ^ nifOAmeni*i Em*fper\cy Mna | Invt^t.Qjt.ocs Br*r%cK--^ SSEEl y arsapcnisnoEnEni mrtsee* Central Q.hki Qfl.i 5SCD itctm O-Jtr.ct OH-ee SScD. Info 2 P*r T<coa 3 Comminu Z Action > .US 35328 PCB-ARCH-EXT0371735 REFER TO: United States Department of the Interior FISH AND WILDLIFE SERVICE COLUMBIA NATIONAL FISHERIES RESEARCH LABORATORY _ ROUTE 1 COLUMBIA, MISSOURI 65201 December 21, 1981 Mr. Curtis Ross US EPA Central Regional Laboratory 536 S. Clark Chicago, IL 60605 Dear Mr. Ross: Attached is a report summarizing the analyses of two fish samples (EPA 81-NF00S48(s) and EPA 81-NF 00S49(s)) for the levels of PCDDs and PCDFs in addition to the non-ortho-oythio'chlorine substituted PCBs. ~ A draft copy of a report I presented at the 2nd International Conference on TCDD and Related Compounds is enclosed. I hope these data will be of help to you. Sincerely DLS:db David L. Stalling PhD Chief Chemist 5330 PCB-ARCH-EXT0371737 Laboratory Report Methods Section Columbia National Fisheries Research Laboratory Analysis of Fish Samples from the Harbor at Waukegan Illinois for PCDF and PCDD . Residues From: Lawrence M. Smith James L. Johnson . Nov. 25, 1981 . To: Chief Chemist,CNFRL Two samples of single,ground whole fish from the harbor at Waukegan, Illinois were received May 14, 1981 from William Sargent, Jr. (EPA Surveillance and Analysis Division", 536 S. Clark St., Chicago, IL, 60605, FTS #353r9083). The samples were processed and analyzed by established procedures employed at CNFRL for polychlorinated dibenzofurans (PCDFs), dioxins (PCDDs) and also PCBs isomers possess ing no ortho chlorine substituents. The results of these determinations are given in the following tables. 35331 PCB-ARCH-EXT0371738 Table 2. PCDFs, PCDDs and non-ortho PCBs Residue Levels in Fish, EPA 81-NFOOS49 (S) L.M. Bass, single fish PCDFs (pg/g) CI4 Cl5 CI5 CI7 68 2+7+19 2 ND [2,3,7,81(3 isomers] (2) (2) (2) (10) Clg ND (10) 98 f>f 7 PCDDs (pg/g) ci4 ci5 C16 ^7 ^8 5 ND ND 3 ND 34 37 (1) CD (2) (2) (2) non--ortho PCBs (pg/g) 3,4,3',A'-Cl4 3,4,5,3",4"-Cl5 400 200 3,4 ,5,3'4',5'-Cl6 300 US 35332 PCB-ARCH-EXT0371739 Kesidues of Polychlorintated Diberizo--dioxins (PCDDs) and Dibenzofurans (PCDFs) in Great Lakes Fish D. L. Stalling, L. M. Smith, J. D. Petty, J. W. Hogan *>/ J. L. Johnson, C. Kappe*. and H. H. buser** / * * Columbia National Fisheries Research Laboratory, U. S. Fish and Wildlife Service, Rt. 1, Columbia, t-iO 652U1 'University of Uniea, Umea, Sweden Switzerland i \ US 35333 PCB-ARCH-EXT0371740 I*- * t ' i ABSTRACT Fisn fron the Great. Lakes. related rivers, and lakes in t.ne area ; were examined for PCri, PCDF, and PCDb residues. Patterns cf PCDF residues were more complex than PCDD residues, and were dominated by isomers having 2,3,7,6-chlorine substitution. PGUP residues , were present in samples from all of the Great Lakes and exceeded i 100 pg/g in fish from Lakes Ontario, Michigan, and Huron, and ; Saginaw bay. A composite sample of fish from the Tittabawassee River contained 290 pg/g of.PCDFs and 223 pg/g of PCDDs. The ratio ` of PCDFs to PCbs ranged from 1 to 20 x 10 exp-6. Understanding the : relationship of these residues in biological samples to the [ original PCDF concentrations in. PCbs is complicated by an apparent ; preferential retention or . accumulation of 2,3,7, B-substituted .. congeners. PCDF concentrations in a fish from Lake Siskiwit were ; the lowest detected in this study (1*5 pg/g). Fish from Lakes Huron and Ontario contained 2,3,7,8-TCDD in excess of 20 pg/g. Fish \ fron these lakes, the Tittabawasee River and Saginaw bay contained the highest concentrations of 2,3,7,8-TCDD (greater than 50 pg/g). ; r/hole body samples fron Lake Hichiaan contained 5 pg/g 2,3,7,8-TCDD and 35 pg/g 2.3.7,8-TCDF. Harked differences in the composition of ! PCDF and PCDD residues were found to exist between fisn and seai :ent samples from anotner aeographical location, woods Pond, MA, on the Housatonic River. V us 35334 PCB-ARCH-EXT0371741 T Tne impetus for initiating a survey for PCDD and PCDF residues in fish (Dougherty et al. 1980) was the discovery that pyrolysis of Aroclors 1254 and 1260 produces many PCDF congeners of four or more chlorines that have 2,3,7.8-chlorine substitution (Rappe and Buser 1980). Heating of PCBs. can yield percent conversion to PCDFs (Buser et al. 1978). The potential magnitude of the impact of PCS pyrolysis to form PCDFs is indicated by the quantity of PCBs produced domestically. Total production.of PCBs (Aroclors) by Monsanto is estimated at 1,400 million pounds during the period 1930-1975 of which 1,253 million pounds were marketed domestically (Brinkman and DeKok 1980). k- . Tne recent detection of PCDFs, PCDDs, as well as chlorinated biphenylenes in soot formed from PCBS in an electrical fire demonstrates that environmental contamination by PCDFs occurrs when PCBs are pyrolyzed (Stalling 1981a). This fire originated in a primary electrical distribution panel that was located in the basement of tne wew York State Office Building in Binghamton, MY, and thermal pyrolysis to form PCDFs occurred upon leaxage of PCBs ..fro; i a transformer. The concentration of PCDFs was increased from approximately 5 ua/q-PCB to 7,500 ug/q-PCB as a consequence of tne fire. - * i . ` i'. : .. : .. . .. ; ! ' : . Because no data existed on the isomer distribution of PCDFs or total concentration of PCDD or PCDF residues in fish, an assessment ; of the environmental occurrence of these'chemicals was undertaken. . This effort was a preliminary step toward determining the impact of : these toxic chemicals on the Great Lakes fisheries. Tne primary objectives of this study were to determine the distribution and composition of residues of PCDDs and PCDFs in the aquatic biota of the Great Lakes and other freshwater lakes and rivers. We also sought to correlate the concentration of PCDFs to the levels of PCBs known to be present in Great Lakes fish (Schmidt et al. 1981). Residues of TCDD and other PCDDs were measured also in order to assess tne extent of dioxin contamination. . ; j " ! " Tne extent of knowledge about PCDD isomers present in aquatic ecosystems was derived from analyses for PCDFs in the fat of a snapping turtle from the Hudson River and in fat from a grey seal from the Baltic Sea revealed the presence of PCDFs having congeners . with 2,3,7.8-chlorine substituents. Tne snappinq turtle fat '^contained 3 ua/xq of total PCDFs (Rappe ec al. lydl) . Analyses for t'CDFs (Douqnerty et al. 19oD) in fish suogested tnat a close . association of PCDF residues with PCB residues existed. ; . i BXPFRIMEIJTAL : ' ` Samule sources ` ' . nerrina null tissue collected* from the Saginaw Bay, ml a,rea was provided oy or. uounlas Hallet. National wildlife Kesearcn*Center, Ottawa, Ontario, Canada. Carp samples from Saciinaw bay, and lake . US 35336 PCB-ARCH-EXT0371743  -iiVv Samples processed for quality control and recovery studies were prepared by grinding frozen whole fish (brook trout, and grass carp) that were reared at the Columbia National Fisheries Research Laboratory. Following preparation of the mixture (4:1 w/w)of anhydrous sodium sulfate and ground fish (Stalling et al. 1931) the samples were spiked with a solution of PCDF and PCDD congeners: 2.3.7.8- tetrachloro-, 1,2,4,7,8-pentachloro-, 1,2,4,6,7.,9- hexachloro-.. 1,2,3,4,6f7,9-heptachloro-, and octachloro- dibenzofurans and 2,3,7,8-tetrachloro- (TCDD), 1,2,3,4,7,8- hexacnloro-, 1,2,3,4,6,7,-hexachloro-, and octachloro-dibenzo-- dioxin (OCDD). Other samples were spiked only with the 13C- 2.3.7.8- TCDD. Toluene was the spiking solvent and the solution of standards was applied to the sample mixture with a syringe after the 'feodium sulfate-santple mixture was placed in the extraction column. In audition to the standards listed above, the spike I solution contained either 20 or 100 pq/'g 13C-labeled 2.3,7,8-TCDD. The 13C-labeled TCDD was provided by Dr. Ron Mitchum, National Center for Toxicology Research, Food ana Drug Administration, Jefferson, Ak. % .The results of analyses of quality control samples associated with tne Great Lakes samples are presented in Table 1. All quality control samples were spiked with 13C-TCDD as an internal standard. Recovery of the 13C-TCDD internal standard ranged from 60 ' - 90 percent at the 20 part-per-trillion fortification level and 80 percent at the 100 part-per-trillion level. The recovery of the 1`3C-TCDD in the procedural. blank was 43 percent. The procedural blank and the grass carp tissue blank contained extremely low levels of PCDDs and PCDFs. The contamination of the brook trout control sample was tentatively traced to a PCB contaminated feed which contained PCDF levels comparable to those found in the trout. Recovery of PCDFs was lower than the fortification level (50 to 75 percent'). In general, the results obtained with the samples in the present study should be considered minimal values. Further improvements in the precision of the PCDF determinations should result from use of a 13C-labeled dibenzofuran internal standard. However, at the time tnis study was conducted the 13C-standard was not available for our use. Analysis . Detection of PCDDs and PCDFs was accomplisned with a Finnigan 4023 GC-M5 system equipped with negative and positive ion chemical ionization options. An Incos Software System running on a Data General Nova 3/12 minicomputer was used to obtain specta and to quantitate PCDF and PCDD conqeners. Another Finnigan 4023 GC-i4S system equipped with a PRO:ill-; multiple ion monitoring unit was employed for isomer specific analyses. in tnese latter analyses isobutane was used as tne reagent gas. Two analytical approacnes were emloyed. For the general survey, tne majority of samples were analyzed usinn GC conditions that allowed 35338 J PCB-ARCH-EXT0371745 A * samples to be analyzed in approximately 30 min. and minimized the amount of disc storage required for each GC-MS analysis. After a general perspective of the PCDD and PCDF residues was obtained. aliquots of the prepared extracts were analyzed independently using conditions shown to separate all 22 TCDD isomers (!*.:.ser' 1981 ). These conditions were also suitable for survey analyses (Rappe and Buser 1980) of the tetrachloro- through octa-CDD and -CDF congeners isolated by the enrichmnent procedure described above. . . . ' The chromatographic and mass spectrometry conditions for the survey GCmS analysies were: . . Gas cllr. .omato"qrao~ hy parameters -- Chromatography column - 3U m x 0.25 ran i.a. column coated with DB-5 liquid phase (J and * fused silica capillary W Scientific).' * Carrier gas - Helium at 6 psiq, 22 cm/sec linear velocitv . ' 4 Temperature Program -The initial temperature was held at 180 C . for 5 nin, tnen programed to 255 C at 3 C/nin. The rate, was then changed to 12 C/min until the oven reached 291 C and the final temperature was held for 1U min. . } ; | - ! .V'_: * I I :* j .. j '< I . 1 1 ! !Il I I i I | I i Mass spectrometer parameters -- . . * . Electron multiplier voltage = 2200 volts Electron energy = 55.1 volts Source temperature = 250 .C for electron impact and 200 C for negative chemical ionization mode (NCI) Manifold temperature = 100 C Methane gas pressure = 5.5 x10 exp-5 torr (NCI). . The multiple ion detection parameters employed to analyze PCDDs by EI-i-lS permitted the detection of tetra- to octa-CDD congeners. Eight ions were monitored in various time windows corresponding to elution times for the PCDDs. Ions for tne chlorine clusters of tetra-, penta-, and hexachlorobipnenyls (the non-ort'no, ortho'- chlorine substituted isomers) and penta- and nexachloro di'oenzofurans were included to keep total ion dwell times in each MS . scan equal to that used for the NCI analyses for PCDFs. Full scan spectra were acquired by scanning mass to charge ratios (m/z) '^40 to 520 in 1.95 sec, allowing a 0.05 sec interscan interval. Four chlorine isotope ions were monitored in tne multiple ion detection ' mode (Mlu) of analysis for quantitating low concentrations of PCDF and PCDD residues. In all cases the first ion of the chlorine cluster corresponded to the ; 35Cl'-isotopic molecular weight of the compound. RESuLTS and DISCUSSION . , j ... II" i i ' . ! . > j ( \ ; : . 1 i : Oetecti > i of PCDr's and nigner cnlorinateu PCDus was .greatly ennanceu by the use of NCI witn metnane as tne reaaent aas (Rappe ana uuser lydu). This techniaue afforded an increase in |/S 35339 . 7 PCB-ARCH-EXT0371746 ^ * 1 sensitivity of approximately two orders of magnitude over detection by electron impact ionization (El) and the accompanying selectivity for PCDFs significantly decreased interferences from sample background. The limit of detection (3 to 1 signal to noise ratio) was approximately 0.5 pg/g for PCDFs based on 100 g tissue, 50 ul final sample volume, and an injection of 2 ul into the GC-MS. Electron impact (El) ionization-MS was required to measure tetraCDDs due to their insensitivity to NCI-MS detection. The limit of detection .for TCDD under EI-MS ranged from 1 to 3 pg/g, but was approximately 5 to 10 pg/g for OCDD. Residues of PCDFs were measured in composite whole fish samples from *,ach of the Great Lakes, and a limited number of rivers in tneir 'watersheds. Concentrations of PCDFs were lowest in a walleye sample from Lake St. Clair and lake trout from Lake Siskiwit, a lake on Isle Koyale in Lake Superior (Tables 2-4). Levels of PCDFs were qreater in fish from Lakes Erie, Ontario, Michigan, and Superior (concentration range 18-119 pg/g). The greatest--PGBFconcentrations were observed in fish from Saginaw Bay 'in Lake Huron (153 pg/g) ana the Tittabav^ssee River (290 pg/g). Tne composition of the PCDF residues were similar in most of the samples examineav however, the concentration and relative proportions of nexa- and hepta- CDF congeners were greatest in fish from Saginaw Bay (Table 4). This difference was reflected by a lower ratio of tetra-CDF to total PCDF concentration. In the Saginaw Bay and Tittabawassee River samples, this ratio was 0.1b and 0.13 and the total PCDF concentration was 153 pg/g and 290 pq/a, respectively. The tetra-CDF to total furan ratio ranged from 0.17 (in Bay Port) to 0.65 in samples from the Great Lakes. Because of the presence of PCDFs in PCBs as manufactured (Rappe and Buser 1980) we felt it was important to determine the ratio of PCDFs to PCBs in these samples. An increase in this ratio should reflect the conversion of PCBs to PCDFs during use, incineration, or aaing prior to entry of the PCBs into the environment. The ratio of PCDFs to PCBs was >Q^terinHi'ei for selected samples and these data are summarized in^Table 5.This ratio found in a : limited number of samples strongly suggests PCDF residues correlate with PCB content. PCDF concentrations range from 1 to 20 parts, per millaSK re'Tafi've to the PCB content of the sample. However, caution should be exercised in comparing the concentration of '<~PCdFs in Aroclors to environmental residues. Arociors contain more than 30 PCDF isomers (Rappe and Buser 19cs0; while samples of Diological materials have only a few isomers wnich are predominantly those having 2,3,7.,8-cnlorine substitution patterns. ; in these studies. confirmatory hign resolution glass capillary GC- lov resolution EI-MS analyses were made. Tncse analyses iaentified 1 tne major pCOu ami PCDF isomers as those having 2.3,7,ti-cnlcrine substitution ITaoles 6 and 7). * Tne residues in many of tne. samples , nee isomer aistriuutions similar to PCDFs present in numah liver samples from .Yusno patients (Rappe et ai. 1B7Ba) anu seal and ,, US 35310 PCB-ARCH-EXT0371747 turtle fat (Rappe et al. 1981). Fish from Lake Superior and Lake Siskiwit did not contain measurable levels of TCDD or other PCDDs (Table 8). Samples from ! Lake Michigan and Lake Ontario contained 2,3*7,.8-TCDD at 5 and 33 j pg/g. Uo other PCDD isomers were detected. Fish and herring gulls ; from Saginaw Bay and fish from Lake Huron, contained high concentrations of 2,3,7,8-TCDD and more complex mixtures of other PCDD congeners (Tables 7 and 9 and Figure 1). These isomer specific \ analysis confirm that the tetrachloroaioxins residues are composed , of predominantly, or more often exclusively, the 2,3,7,8-tetra CDD i isomer. . ' **.* . . : The ratio of tetra-CDD to total PCDD residues ranged from 0.24 to 0.80 in samples from Lake Huron. Samples from Saginaw Bay and the . Tittabawassee River (Table 5), contained the most complex mixture I of PCDD congeners as was the case with the composition of PCDF residues. Total concentrations of PCDDs in herring gull samples was . 199 and 186 pq/g and the concentration of PCDFs in these . samples ; was somewhat lower, 121 and 117 pq/g (Tables 9 and h). Tnese : .residue data suggest a somewhat different congeners distribution exists between samples from Saginaw Bay, Lake Huron and samples from the other Great Lake's. Pollution with PCDDs is minimal in the other Great Lakes, except for Lake Ontario and Lake Huron. However, PCDFs were detected in all of the Great Lakes fish. Tne occurrence . of traces of methylated chlorop'nenoxy phenols (Figure 1) suggests that commercial clorophenols may contribute to the environmental pollution by PCDDs and PCDFs in Lake Ontario and Lake Superior. The occurrence of low levels of PCDFs in fish from Lake Siskiwitt is suggestive of atmospheric transport and rainout of PCDFs along with PCUs into Lake Siskiwit (Swain 1980). The ratio of tetra-CDFs to total PCDF residues is similar for the samples from Lake Superior and Lake Siskiwit, 0.65 and 0.48 vs 0.67 respectively (Table 2). ' In view of the occurrence of PCDDs in material from various combustion sources (Burnb et al. 1930 and Raooe et al. 1979b), the absence of PG&Us In Lake Siskiwit and Lake Superior fish sample raises questions abouut pur understanding of sources of these contaminants. These residue data suggest that the presence of PCDDs in fish from other areas is strongly influenced by point source discharges. Data from another geographical area was included to illustrate the ''complexity of the PCDD and PCD? distrioution in tne aquatic environment. Major differences between PCDF and PCDD residues in fish and sediment samples were detected in samples from Woods Pond, HA, a part of the Housatonic River. The extent, of PCB pollution at this location is comparaole to that in the Hudson River. PCB pollution resulted from the electrical manufacturing operations near Albany, I'JY (Horn et al. 1979). .-leaiiuurenent of tne residues in fish and sediment samples uy electron capture GC revealed the presence of Aroclor 120D in both sample types. A fish sample from Woods Pone contained 9 . VS 35341 PCB-ARCH-EXT0371748 approximately 170 ug/g of Aroclor 1260 (Table 10) and a sediment sample from the same location contained approximately 60 ug/g of PCBs. While these samples contained nearly the same level of PCDF residues, 2.2 ng/g in fish and 1.4 ng/g in the sediment, the sediment also contained 2.8 ng/g PCDD residues. These sediments also contained octa-CDD, a frequent contaminant in commercial pentachlorophenol formulations. . Tne PCDF. isonier distribution present in the : fish and sediment samples from Woods Pon^ differ markedly and were not similar to tne distribution of PCDFs in a sample of Aroclor 1260 (Table 10). A similarly disproportioned residue pattern in fish and sediment was observed also for the PCDD congener present in these samples, i.e. the 2,3,7,6-tetra-CDD (10 pg/g) was the dominant isomer in fish and octa-CDD was the dominant isomer in the sediment. . A limited but preliminary assessment of the composition of PCDFs in samples in relation to those PCDFs present in Aroclor 1260 was possible. We previously had obtained ami analyzed the PCDFs in a samoie from one of the lots of this Aroclor that the___ General Electric Company had used in their electrical manufacturing operation. However, the composition of PCDFs in other various Aroclors used during the period of PCD use in tne manufacturing operations at this site is unknown. CONCLUSIONS The presence of the lower chlorinated PCDF isomers in fish samples, particularly those., having a 2,3,7,8-c'nlorine substitution pattern is suggestive of greater biological retention, of these isomers. This situation could result from decreased excretion of these isomers or a diminished ability to metabolize PCDFs with this pattern of chlorine substitution. A similar PCDF residue pattern was present in samples of liver from Yusno patients (Rappe et al. 1979b). Alternatively, the lower concentrations of the more highly cnlorinatea congeners in the fish could result trara their lower water solubility and subsequent affinity fox. organic surfaces in aquatic systems. Tnis could reduce their bioavailability. However, such large differences among isomers of similar chlorine content seems unlikely. The observed residues in sediment might also reflect accumulation from fly ash particulates contaminated with PCDFs and PCDDs. These compounds would oe tightly bound to carbonaceous moeities in the ash. Additional study of the environmental significance of PCDFs is warranted because the observed composition of PCDF residues in fisn are primarily tetrachloro- and pentachloro-dibenzofuran congeners substituted in the 2,3,7,8-positions. Considering the mammalian toxicity of tnese cnlorinatea isomers, it- seems prudent to Determine tne factors responsible for tneir occurrence and retention in fish ana to assess tne nazarn these resiuues nay nose to ornanisms niqner in the food cnain. Ir^adaition. tne potential adverse effects on renrouuction and survival of lireat Lak.es fish arm other aouatic organisms remains unknown. US 35342 PCB-ARCH-EXT0371749 Table 1. Quality control data for analysis of Great Lakes fish samples. Recovery and level of laboratory contamination in blanks. >s l(pg/g) * Samples lSc- rCl-4 5_ 6 7 8 sum Recv. 1 5 Fs (]?s/g ) 6 7 8 sum eastern brook trout . spiked at 20 ppt !13C--TCDD 'fid nd nd nd nd nd 90% procedural solvent blank spiked -with 100 ppt 13C -TCDD 1.6 nd. nd nd ioa 12 45% 'lab-reared brook . . trout spiked at 20 ppt-.13C-TCDD and 20 ppt standard mixture 26 nd 31 nd 33 -- 60% ns ns `lab-reared . . trout (replicate) 30 nd 35 nd 67 ns ns lab reared grass carp spiked at 20 ppt 13C-TCDD -- .. 60% ` t nd nd nd nd 5 5 80% solvent blank (repeat) spiked at 100 ppt 13C-TCDD :" 1.6 nd nd nd 11 13 43% * nd nd 5 21 4 30 ; nd nd nd nd 1.4 1.4 8.6 8.8 nd 10.2 8.3 --' ns . : 8 9 nd 13 6.9 -- _ ns > 0.5 0.4 0.2 1.3 1.4 3.8 nd nd nd nd 1.4 1.4 s signal to noise =2 nd = not detected (s/n <= 3) ns = not spiked in congener group -- = not totaled US 35343 PCB-ARCH-EXT0371750 Table 3. DIBENZOFURAN RESIDUES IN COMPOSITE SAMPLES FROM LAKES ERIE AND MICHIGAN Site Sanple > CedaT Point, OH, L. Erie Walleye Port Clinton, L. Erie Carp Saugatuck, L. Michigan Lake Trout.01 'Saugatuck, L. Micigan Lake Trout 02 Dibenzofurans, ng/kg 4C1 501 6C1 7 Cl 8C1 Total 18 9 6 5 2 40 : . 5 5 2 4 2 18 Ratio . 4Cl/Total 1 18/40-0.45- j , 11 ! 5/18-0.28 S 1 . i *i 35 41 8 33 61 10 1' 1 35/86=0.41 t 4 2 /lit) / 33/110=0.30 i ! US 35345 PCB-ARCH-EXT0371752 Table 5. PCDF/PCB RATIOS IN COMPOSITE SAMPLES PROM THE GREAT LAKES Site and Sanple L. Huron (Saginav Bay) Carp .. . Herring Gull 01 Herring Gull 02 (PCDPs/PCBs) I 106) : ^ c (153/37.1) X10 - 4.1 (121/45.3) X106 - 2.6 <117/51.8) X106 - 2.2 '| i i i . i ! i i Tittabavasee River (Midland) Carp (290/103.7) X 106 - 2.8 L. Superior (Isle Royale, L. Siskivit) Lake Trout (15/4.3) X 106 - 3.5 L. Ontario (Roosevelt Beach) Brook Trout . IIiI i (32/5/2) X 106 - 6.2 L. Michigan (Saugatuck) Lake Trout * ; % (86/7.1) X 106 - 12.1 ^**, ' ; .. ; i . US 35347 PCB-ARCH-EXT0371754 .'-*** . ' . .' "able 2. RESIDUES OF DIBEKZO--DIOXINS IN COMPOSITE SAMPLES (Buser) . . Herring Gull Cl Isomer^ * L. Huron h Tetra-Clo / 2.3.7.8- 165(0.5)--7 1.3.6.8- other . Herring Gull C2 * _ . Carp Carp Grass. . Carp v: I L. Huron L. Huron ' L. Erie Residues in parts per trillion, ng/kg . CNFRL Control ' 1 . . 1 . i 75(1) 28 0.8(0.5) 3 2(1) 0.4 j ii Penta-Cl 1,2,3,7,8other 20(2) 18(2) 11(1) 2(1)' <2 Hexa-Cl 1,2,3,6,7,8other 11(2) 17(2) . 5(2) Hepta-Cl 1.2.3.4.6.7.8- <4 <4 1.2.3.4.6.7.9- Octa-Cl <4 <4 IPCDD . . 196 110 --^Measured by GC-EI-MS --^Detection licit in ( ) . 4(2) 3(3) 52 3(2) 3(2) <3 <2 5(5) 17 i 5(3) 5.4 US 35349 PCB-ARCH-EXT0371756 Table 8. DIBENZO -p-EXKINS RESIDUES IN COMPOSITE SAMPLES FROM LAKES ERIE, SUPERIOR, AND ONTARIO ` . $ Site and Sample L. Erie, Port Clinton, Carp L. Michigan, Saugatuck, Lake Trout L. Superior, Keweenaw, . Bloater Chub L. Superior, Isle.Royale, L. Siskiwit, Lake Trout L. Ontario, Roosevelt Beach, Brown Trout '. Dlbenro-p-dioxlns, ng/kg \ 4 Cl 5C1 6C1 7C1 8C1 Total Ratio 4Cl/Total ND '9 ND 'll 30 50 -- . 5 ND ND ND ' ND 5 1 ND ND ND `'ND ND ND . -- ND : ND ND. ND Trace Trace -- 33 ; ND ND ND ND 33 , 1, US 35350 PCB-ARCH-EXT0371757 Table 9. DIBENZO--DIOXIN RESIDUES IN COMPOSITE SAMPLES FROM LAKE HURON Site jahd Sarnie 'U ` " Saginaw Bay, Carp Dibenzo-p-dioxins, ng/kg 4 Cl SCI 6C1 7C1 94 157 122 12 8C1 Total ND 385 Ratio 4Cl/Total ! ii 94/385*0.24 Saginaw Bay, Herring Gull tfl 160 ND 20 ND 19 199 160/199^0.8 -- 00 <r> Saginaw Bay, Herring Gull $2 Bay Port, Carp 70 ND 88 ND 27 21 ND .31 28 32 111 70/186*0.38j \ 27/111*0.24 Tittabawasee River, Carp 81 31 44 S3 14 223 81/223=0.3( US 35351 PCB-ARCH-EXT0371758 4 References [ . Albro. P. W. and Parker, C. E., Comparison of the compositions of Aroclor 1242 and Aroclor 1016. J. Chromatoqr:, 169: 161-166, 197 9. ` ; . . . - . . r * * i- . l3owes, G. W., Mulvihill, M. J., Simoneit, B. R. T., Burlingame, A. i L. , and Risebrouah; R. W., Identification of chlorinated diDenzofurans in American polychlorinated biphenyls. Nature, 256(5515) :\305-307, 1975. *. ` Brinkman, U. A. Th., and DeKok, A., Production, properties and useagt. In: Kimbrough, R. D., ed. rtalogenatea Biphenyls; ' Terphehyls; Naphthalenes; Dibenzoaioxins; and Kelated Products: Amsterdam, NYl Elsevier/North-Holand Biomedical Press, 1980. pp. 1- : 4 0. ; Brunley, w. C., Roach, J. A. G.. Spnon, J. A., Dreifuss, P. A., Andrzejewski, D., Neiuan, K. A., and Firestone, D., J., Low resolution . multiple ion detection gas chromatoqraphic-mass spectrometrie comparison of six extraction-cleanup methods for determining 2,3,7,8-tetrachlorodibenzo-p-dioxin in fish. Agric. Food Chen;! 29(5):.1040-1046, 1931. ' Bumo. k. R. , Crummett, w. B., Cutie, S. S., Glednill, J. n., Kummel, R. H., Kaqel, K. O., Lamparski, L.L., Luoma, E. V., i-liller, D. L. , Kestrick, T. J., Snadoff, :L. A., Stehl, R. H. , and Woods, J. S., Trace chemistries of fire: a source of j chlorinated dioxins. Science 210(4468): 335-390, 1980. ; Buser, H.. R. and Bosshardt, H. P., Determination of polychlorinated ; dioenzo--dioxins and dibenzofurans in commercial pentachloro- ; phenols by combined gas chromatography-mass spectrometry. Assoc: Offic: Anal: Cnem:, 59(3): 562-569, 1976. I . Buser, H. R. , Bosshardt, H. P., and Rappe, C., formation of poly- ; cnlorinated dibenzofurans (PCDFs) from the pyrolysis of PCBs, Cnemosphere 7, 109-119, 1978. Buser, H. R., ana Rappe, C., High resolution gas chromatoaraphy of the 22 tetracnlorodibenzo--dioxin isomers. Anal: Cnem. 52:2257 2262, 1980. , ;i ^Dounnertv, R. C.. wnitaker, ?i. J., Smith, L. M., Stalling, D. L. and Kuehl, D. w., Negative cnemical ionization studies of human and food chain contamination with xenobiotic chemicals. Environ: Healtn Persp:, 36: 103-117, 1980. heloer. T. . Effects of 2,3,7,8-tetrachlorodioenzo-n-ciioxin (VCDD) on early life stages of the pike (so>: luciuus ' L.}. Sci. rotal environ. , 1**: 255-26*. 19du. US 35354 PCB-ARCH-EXT0371761 Horn'. * E: S., Hetling, L*. J., arid Tofflenire, T. J., The problem o_PCBs in the Hudspn R.'.ver'.system. Ann; N:Y: Acad; Sci:, 320: 591- 629. 1979. . Huff, J, E. , Moore, J. A., Saracci. R. . and Tomatis. L. , Long- term hazards* of polychlorinated dibenzodioxins and polychlorinated dibenzofurans. Env; Health Perspec:, 36: 221-240, 1930. . \ ' 1 K'i ; v - - : .. . Isensee, A. R., and Jones, G. E., Distribution of2,3,7,3- tetrachloro-r-dioxin (TCDD) in aquatic model ecosystems. Environ; Sci. Technoit 9(7):668-672, 1975. . ' " ---------- . Isensee, A.R.. bioacumulation of 2,3,7,,8-tetrachlorodibenzo-o- dioxija.' C. Kamel,, ed.. In Chlorinated Pnenoxy Acids and Their Dioxins.(Ecol. Bull. No. 27, Stocknolm: Swedish Natural Science Research Council, 1978, pp. 255-262. j . ( j \| . . ' . ' McConnell. . E., Acute and chronic toxicity, carcinogenesis, reproduction,_ teratogenesis and mutagenesis in animals. In: Kimbrough. R. D., ed. rialoaenated biphenyls; Terphenyls; Naphtha lenes;Dibenzodioxins; and Related Products;Amsterdam, NY: Elsevier/hortn-rioiand biomedical Press, 1980. pp. 109-150. Moore. J. A., McConnell-, E. E. . Dalaara. D. W., and Harris, i-l. W. , Comparative toxicity of three haloaenated dibenzofurans in guinea oiqs, mice and rhesus monkeys. Ann: New York Acad; Sci;, 32U: 151 163. 1979. ` . Rappe, C. and Buser, H. R. , Chemical properties and analytical methods. Kimbrough, R. D., ed. in Halogenated Biphenyls; Terphenyls; Naphthalenes; Dibenzodioxins; and Related Products: Amsterdam. NY, Elsevier/North-Holand Biomedical Press, 1980, pp. 47-76. ; j '. \ j Rappe, C. , Buser, H. R. ; Kuroki, H. and Masuuda, Y. Identification ' of polychlorinated dibenzofurans (PfJDFs) retained in patients with Yusno. Chemosphere, 8: 259-266, 1979a. Rappe, C.. Buser, H. k. . and Boss'nardt. H. P., Dioxins, dioenzo- * furans and other polyhalogenated aromatics: production, use, form ation. and destruction. Ann: N:Y: Acad: Sci:, 320: 1-18, 1979d. Kappa, C.. Buser, H. R.. Stalling, D. L., Smith. L. M. and . Dougherty, R. C., Identification of polvcnlorinated dibenzofurans in environmental samples. Na tur e, 292: 524-526. 1931 . Rappe, C., Gara, A.. and Buser. H. R., Identification of . polychlorinated dibenzofurans (PCDFs) in commercial chloropnenol forpiulations. Cnemospnere, 7(12): 981-931 , 1978. > ` ' Kanpe, C., Marxluna. S., Buser. rl. R. . ana Bossnardt. H.P.. Form ation of polvcnlorinated dibenzo-o-dioxins (PCuos) and dibenzofurans (PGDFs) by ourning chlorophenolics. Cnemospnere, 1(3): 269- 2oi. i978. US 35355 PCB-ARCH-EXT0371762 Schmidt, C., Ludke, L.*. J., and Walsh, D. F., Organochlorine residues in fish: National Pesticide Monitoring Program, 1970-74. Pest: Monitoring J:. 14(4): 136-206,' 1931. Stalling, D. L. , March 31,' 1931, " Preliminary Report, March 31, Chlorinated Dibenzofurans and Related Compounds in Soot Formed in a Transformer Fire in Binghamton, NY," to State of New York, Departmenmt of Health, Office of Public Health, Albany, NY. Columbia, MO: Columbia National Fisheries Research Laooratory> 1981a. \ ; ; Stalling, D. L., Personal communication: Report to Director, Fish and wildlife Service, on the occurrence of PCDFs in fish and sedi ments'.- from Woods Pond, MA. Columbia, MO: Columbia National Fisheries Research laboratory, 1931b. Stalling, D. L., Petty, J. D., Smith, L. M. , and Dubay, G. R., Contaminant enrichment modules, approaches to automation of sample extract cleanup. In: McKinney, J. D., ed. .Environmental Health Chemistry, Ann Arbor: Ann ArDor Science Puolishers, 1931. pp. 177- .19T: " Swain. .7. R. , Chlorinated orqanic residues in fish. water, and precipitation from the vicinity of Isle Royale, Lake Superior. J: Great Lakes Res: , 4(3-4): 398-4U7, 1930. i iI i US 35356 PCB-ARCH-EXT0371763