Environ. Sci. Technol. 1093, 27, 1364- 1374
Polychlorinated Biphenyls and Polychlorinated Naphthalenes in Swedish Sediment and Biota: Levels, Patterns, and Time Trends Ulf Jarnberg,’lll Llllemor Asplund 11 Cynthla de Wlt,ll Anna-Karin Grafstrom,ll Peter Hagiund,t Bo JanssOn,ll Karin Lex6n,ll Michael Strandoll,/ Mats OIsson,s and BJ6rnJonssons
Laboratory for Analytical Environmental Chemlstry, Institute of Applied Environmental Research, Stockholm Unlverstty, S-171 85 Solna, Sweden, Institute of Environmental Chemlstry, University of Umei, S-001 87 Umei, Sweden, Environmental Monitoring Program, Swedlsh Museum of Natural History, S- 104 05 Stockholm, Sweden, and Physical Geography Department, University of Umei, S-901 87 Umei, Sweden Levels of non-ortho-polychlorinatedbiphenyls (PCB), some mono-ortho-PCB, and resolved peaks of tetra- to heptachloronaphthalenes are reported in biological and sediment samples from the Swedish environment. The results show that levels of individual PCB congeners, and especially PCB 126, may pose a greater threat to the environment than the 2,3,7,8-chlorinated dioxins and furans when expressed as 2,3,7,8-tetrachlorodibenzodioxin (TCDD)toxic equivalents. Polychlorinated naphthalenes are as widespread pollutants as PCB, and a t some locations the pollution situation indicates a specificsource, leading to a bioaccumulating hexachloronaphthalene contributing considerably to the total TCDD-like toxicity. A time trend study of guillemot eggs from the Baltic Proper seems to indicate that levels of non-ortho-PCB and -PCN have decreased since the 1970s. Introduction The toxic effects of 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) have been extensively documented (for reviews, see refs 1and 21, and this congener is recognized as one of the most toxic anthropogenic organic compounds known so far. Much attention has been drawn to the elucidation of the problem of polychlorinated dibenzop-dioxins (PCDD) and dibenzofurans (PCDF) and their potential threat to the ecosystem. More recently however, research on other substances with similar toxic properties as 2,3,7,8-TCDD has increased. Recent studies indicate that the levels of individual polychlorinated biphenyls (PCB) expressed as 2,3,7,8-TCDD toxic equivalents equals or precedes that of PCDD/PCDF (3-7). Among the PCB, the congeners with no chlorine substituents in the orthopositions show high toxicity, e.g., 3,3’4,4’-tetrachlorobiphenyl (PCB 77), 3,3’4,4’5-pentachlorobiphenyl(PCB 1261, and 3,3’4,4‘5,5‘-hexachlorobiphenyl(PCB 169). Several congeners substituted in one of the ortho-positions, although less potent, also have TCDD-like toxicity: 2,3,3’4,4’-pentachlorobiphenyl(PCB 105), 2,3‘4,4’5-pentachlorobiphenyl (PCB 118), 2,3,3’4,4’5-hexachlorobiphenyl (PCB 156), and 2,3,3’,4,4’5’-hexachlorobiphenyl (PCB 157). In addition to the PCB, several of the polychlorinated naphthalene (PCN)congeners also exhibit similar toxic properties as TCDD, i.e., chloracne, liver and damage, and EROD (7-ethoxyresorufin-o-deethylase) AHH (aryl hydrocarbon hydroxylase) enzyme induction. EROD and AHH induction by selected PCN is, however, about 2-3 orders less than for 2,3,7,8-TCDD (8). 11 Stockholm University.
t Institute of Environmental Chemistry, University of UmeH. t Swedish Museum of Natural History. Physical Geography Department, University of UmeH. 1364
Envlron. Sci. Technol., Vol. 27, No. 7, 1993
While total levels of PCB in Swedish environmental samples have been extensively investigated (9, IO),less is known about relative levels of individual non-ortho- and mono-ortho-PCB compared to total PCB content. Studies of PCNlevels in environmentalsamples are uncommon in the literature, although PCN was first described in the 1890s. Technical PCN formulations have been manufactured since the beginning of this century and have been reported in materials still in use (11). Apart from the distribution of technical PCN formulations to the environment, PCN are also released through the use of PCB due to its presence as a contaminant in PCB formulations (12).PCN are also formed and released to the environment through processes in which chlorine is present such as chlorine production (131, municipal waste incineration, and copper roasting (14). Extensive reports on the toxicity of PCN and cases of PCN intoxication were published already in the 1930s (15) (for review see ref 161, and production and use was subject to precautions as to handling and personal safety. Production never rose to the same levels as for PCB, but due to the versatility in technical application and careless use, combined with their lipophilic properties and persistency, PCN are now as widespread a pullutant as PCB. PCN are now even found in biological samples from remote areas like Spitzbergen in the Arctic (17). In the autumn of 1988, an investigation was initiated as part of the Swedish Dioxin Survey administered by the Swedish Environmental Protection Agency. The aim of this part of the survey was to study the occurrence and distribution of coplanar PCB and PCN in the Swedish environment and to establish background levels. The initial intentions were to analyze and quantify three of the non-ortho-PCB, PCB 77, PCB 126, PCB 169, and the tetra- to heptachlorinated PCN. In order to test the cleanup method the mono-ortho-PCB,PCB 105 and PCB 118,were also quantified in some samples. Severalsamples were also analyzed for either the sum of seven PCB congeners (PCB nos. 28,52,101,118,138,153, and 180) using capillary column gas chromatography or the total amount of PCB, as determined by packed column gas chromatography. This paper outlines the results of all the samples analyzed within this part of the survey and summarizes the conclusions made. Experimental Section
Chemicals. n-Hexane, 2,2,4-trimethylpentane, and acetone were all glass-distilled until pure enough to give no interferences in the analytical method. Cyclohexane, diethyl ether, dichloromethane, tetrahydrofuran (all HPLC, Lab Scan Ltd.) and sulfuric acid (98% w/w, BDH) could be used without any further purification. lsC12-labeled 0013-936X/93/0927-1364$04.00/0
0 1993 American Chemical Soclety
Table I. Sample Description sample nr Bil Bi2 Bi3 Bi4 Bi5 Bi6 Bi7 Bi8 Bi9 BilO Bill Bi12 Bi13 Bi14 Bi15 Bi16 Bi17 Bil8 Bi19 Bi20 Bi21 Bi22 Bi23 Bi24 Bi25 Bi26 Bi27 Bi28 Bi29 Bi30 Bi31 Bi32 Bi33 Sel Se2 Se3 Se4 Se5 Se6 Se7 Se8 Se9 SelO Sell Se12 Se13 Se14 Wal Prl
SEPA id4 002s001 002s004 0028024 002~005 002s006 0028025 002~014 006~001 006~004 006~002 006s006 006s003 006~006
001~003 001~004 001~007 001~008 001s009 00lsOlO 003~001 003~002 031~001 031~002 031~003 031~004 A885217
31Os001 310~002 310~003 310~004 320~001 320~002 320~003 320~004 320~021 3208023 320~024 3208025 320~011 4OOs002
description pike muscle pike muscle pike liver pike muscle pike muscle pike liver pike muscle pike muscle pike muscle burbot liver burbot muscle burbot liver burbot muscle burbot liver burbot muscle Baltic herring, spring 6 yr Baltic herring, spring 6 yr Baltic herring, fall 4 yr Baltic herring, fall 4 yr Baltic herring, fall 6 yr Baltic herring, fall 6 yr cod muscle cod liver common porpoise, 1yr, male common porpoise, 1yr, male common porpoise, 1yr, male common porpoise, 1yr, male grey seal guillemot, pooled 10 ind. 1974 guillemot, 10 ind. 1976 guillemot, pooled 10 ind. 1978 guillemot, pooled 10 ind. 1982 guillemot, pooled 10 ind. 1987 sediment, 0 - 2 cm depth sediment, 0 - 1cm depth sediment, 9 - 10 cm depth sediment, 0 - 1cm depth sediment, 0 - 2 cm depth sediment, 0 - 2 cm depth sediment, 0 - 2 cm depth sediment, 0 - 2 cm depth sediment, 0 - 2 cm depth sediment, 0 - 2 cm depth sediment, 0 - 2 cm depth sediment, 0 - 2 cm depth sediment, 0 - 2 cm depth sediment, 0 - 2 cm depth percolating water, city dump site self-copyingpaper, 1979
location
Latin name
Esox lucius Esox lucius Esox lucius Esox lucius Esox lucius Esox lucius Esox lucius Esox lucius Esox lucius Lota lota Lota lota Lota lota Lota lota Lota lota Lota lota Clupea harengus Clupea harengus Clupea harengus Clupea harengus Clupea harengus Clupea harengus Gadua morhua Gadua morhua Phocaena phocaena Phocaena phocaena Phocaena phocaena Phocaena phocaena Halichoerus grypus Uria aalge Uria aalge Uria aalge Uria aalge Uria aalge
Lake J h s j B n , River E m h Lake Viinern, Kattfjorden Lake Viinern, Kattfjorden Lake Viinern, Sandviken Lake Viinern, Vassbotten Lake Viinern, Vaesbotten Lake Storvindeln Lake KyrksjBn Lake KyrksjBn Bothnian Bay, Etukrunni Bothnian Bay, Etukrunni Torne River, Pajala Torne River, Pajala Bothnian Bay, SeskarB Bothnian Bay, SeskarB Karlskrona Archipelago Karlskrona Archipelago Karlskrona Archipelago Karlekrona Archipelago Karlskrona Archipelago Karlskrona Archipelago Utklippan Utklippan Kattegatt, Varberg Kattegatt, Leso Kattegatt, Kungsbackafjorden Kattegatt, BalgB Baltic Sea, Hudiksvall Gotland, Stora Karla6 Gotland, Stora Karla6 Gotland, Stora Karla6 Gotland, Stora KarlsB Gotland, Stora Karla6 River Em&, GrBnskogssj6n River E m h , Lake Jirnej6n River EmAn, Lake JirnsjBn River E m h , Lake Sjunnen River Daliilven, Lake GrBvelejBn River Daliilven, Lake Siljan River Daliilven, Lake Hovran River Daliilven, Hedesundafjiirden River G6ta Alv, RivBfjorden River G6ta Alv, Gothenburg Harbor River GBta h v , Gothenburg Harbor River GBta h v , Gothenburg Harbor Lake Viinern, Kattfjorden Lake Viinern, Anholmsviken Stockholm, Vaxholm
SEPA id is the systematic numbering of samples within the Swedish dioxin survey, also appearing in the dioxin database that is kept by the Swedish EPA.
standards were purchased from Cambridge Isotope Laboratories Inc. PCB standards were obtained from Bureau Centrale de Reference (BCR), EEC. Clophen A50 and Aroclor 1254 were obtained through the U.S. Federal Drug Administration (FDA). Polychlorinated naphthalene standards were generous gifts either from Prof. Udo A. Th. Brinkmann, Free Reformed University, Amsterdam, or from Eva Jakobsson and Ake Bergman, Wallenberg Laboratory, Stockholm University, Stockholm. Halowax technical mixtures were obtained from Koppers Co. Inc., Bridgeville, PA. Samplesand SamplingSites. Sampleswere collected either by local authorities or by the Swedish Museum of Natural History, Stockholm. Table I lists all samples and sampling sites covered by this investigation. Fish samples were analyzed to identify "hot spots" and sources as well asto study biological differences. Muscle and liver samples taken from the same individuals of pike, burbot, and cod have been analyzed to determine if these substances
partition differently between these two tissues. Pike were analyzed since these are stationary fish high in the food web and, thus, are good indicators of local pollution situations in freshwater lakes. Baltic herring were analyzed to study differences due to age and season of collection since these variables affect levels of other organochlorines (IO). Except for Bil, all fish samples were homogenates containing several individuals. Samplesfrom common porpoise, grey seal, and guillemot were analyzed to study biomagnification since these three species feed mainly on herring. To study time trends, guillemot eggs from several years were analyzed. Guillemot eggs have previously been shown to be a good matrix for time trend studies of organochlorines in the Baltic Sea (10).
Sediment samples are well-suited for studies of patterns of PCB and PCN distributed to the environment, since they reflect the original composition of these substances to a greater extent than biological samples. Sediment Envlron. Scl. Technol., Vol. 27, No. 7, 1993 1865
Figure 1. Map of Scandinavia showing sampling locations in Sweden.
samples were selected both from areas with a known pollution situation and from rather undisturbed areas. One water sample was analyzed to represent leachate from waste materials in a city dump outside Stockholm. The locations of the sampling sites are shown in Figure 1. Lake Storvindeln (Bi7) and Pajala (Bi12,13) can be regarded as background locations having no local source of pollution, thus reflecting airborne pollution. River Daldven begins a t Lake Grovelsjon (Se5), which is also a background location, then passes through Lake Siljan (Se6), Lake Hovran (Se7), and Hedesundafjbden (Sea) before emptying into the Baltic Sea. A number of smaller cities and various industries including metallurgical plants are located along the lower half of the river. The Baltic Sea (Bi16-23,28,29-33) is an enclosed sea with a very slow turnover time (more than 20 years) and receives effluents from pulp and paper mill industries, sawmills,metallurgical industries, and several large cities. The sampling sites in Lake Vlinern (Bi2-6,Se13,14) and the River Gota &v (Se9-12) are of specific interest since two chloralkali plants are located beside the water system, one at the northern shore of Lake Vlinern and the other at the lower half of River Gota dilv. These plants have produced chlorine gas and chlorinated products since 1917 and 1924, respectively, and have been found to be important sources of PCDD/F emitted into Lake Viinern and River G o t a k v (18). In addition to these sources, the combined water system is affected by waste water from several pulp and paper mills, sawmills, and urban waste water. The Kattegatt (Bi24-27) is a small sea between Sweden and Denmark. Water turnover is relatively slow, and the sea collects waste water from several large cities. 1366 Envlron. Sci. Technol., Vol. 27, No. 7, 1993
Lake Jlirnsjon (Bil,Se2,3), along the River E m h , and Lake Kyrksjon (Bi8,9) are small lakes with a specific pollution situation. Both have received effluents from paper mills processing recycled paper contaminated with PCB. Extraction. All biological samples were extracted using the same method, which can briefly be described as homogenization, n-hexanelacetone extraction, and liquid/ liquid partition between diethyl etherln-hexane and a water phase containing 0.9% sodium chloride in 0.1 M phosphoric acid. The n-hexane extract was then evaporated at 62 "C on a waterbath until dryness, and the lipid weight was determined. The lipid residue was then redissolved in n-hexane containing l,l-dichloro-2,2-diphenylethene (qj-DDE) and PCB 53, and recovery standards (Table 11) were added. A detailed description of the extraction procedure has been published previously (19).Sediment samples were extracted in a liquid/liquid extraction, and sulfur was removed according to a previously published method (20).Recovery standards (Table 11) were added prior to extraction. Dry weight and organic content was determined as follows. A subsample was heated to 110 "C for 24 h and then allowed to cool to ambient temperature in a desiccator. The sample was weighed, and ignition loss was determined at 550 "C for 24 h. The water sample was extracted in an extraction funnel with n-hexane. Recovery standards (Table 11)were then added to the n-hexane extract. Cleanup. The cleanup procedure involved two highpressure liquid chromatography (HPLC) systems. Prior to chromatographic cleanup, all extracts, except Bi29-33, were treated with sulfuric acid (98%1, eliminating most of the interfering lipids. The guillemot samples (Bi29-33) were preseparated on an open silica column (3% H20 deactivation, Merck). This separation method is described elsewhere (21). The following description of the HPLC fractionation applies to samples Bi24-Bi33 and Se9-Se12, Samples Bi29-33 and P r l were not fractionated on the first HPLC system. Other samples were fractionated according to the methods listed in Table 111, with complete descriptions found in the references given. Extracts were preseparated from the remaining lipid content on two HPLC gel permeation columns (PL-GEL, 5 pm, 50 A, 300 mm X 7.5 mm, Polymer Laboratories) coupled in series. The eluent was dichloromethane: cyclohexane, 1:1,at a flow of 1.0 mL/min. The retention time window for PCB and PCN was determined by injecting a mixture of Clophen A50 and Halowax 1014. PCB and PCN were normally collected between 14.5 and 19min. This fraction was injected onto two a-(l-pyrenyl)ethyldimethylsilylated silica HPLC columns (Cosmosil PYE 5 pm, 150 mm X 4.6 mm, Nacalai Tesque) coupled in series. The eluent was n-hexane, saturated with water, at a flow rate of 0.5 mL/min. Flow was reversed at 15.4 min and increased to 1.2 mL/min. Retention time windows for mono-ortho-PCB, non-ortho-PCB, and PCN were defined by injecting a mixture of PCB 118, PCB 77, and 1,3,5,7-TeCN. Mono-ortho-PCB were normally recovered between 12.2 and 15 min and non-ortho-PCB and PCN between 19 and 23 min. The HPLC systems used UV detection at 254 and 260 nm, respectively. Analysis. Total PCB as determined by packed column gas chromatography and levels of the seven congeners with PCB nos. 28,52,101,118,138,153, and 180were analyzed
Table 11. Standards Used standard
0
tYPe
analyte
2,2’5,6-tetrachlorobiphenyl,PCB 53 l,l-dichloro-2,2-diphenylethene, @-DDE Aroclor 1254 2,3,3’4,5,5’-hexachlorobiphenyl, PCB 159 2,2’5,6’-tetrachlorobiphenyl,PCB 53 2,4,4’-trichlorobiphenyl,PCB 28 2,2’5,5’-tetrachlorobiphenyl,PCB 52 2,2’4,5,5’-pentachlorobiphenyl,PCB 101 2,3,3’4,4’-pentachlorobiphenyl, PCB 105 2,3’4,4’5-pentachlorobiphenyl,PCB 118 2,2’3,4,4’5‘-hexachlorobiphenyl,PCB 138 2,2’4,4’5,5’-hexachlorobiphenyl, PCB 153 2,2’3,4,4‘5,5’-heptachlorobiphenyl, PCB 180 13C12-PCB77 13C1z-PCB126 ‘3C12-PCB 169 2,3,3’4,4’5,5’-heptachlorobiphenyl,PCB 189
recovery recovery quantitation recovery injection quantitation quantitation quantitation quantitation quantitation quantitation quantitation quantitation recovery recovery recovery injection
2,2‘3,3’4,5,6’-heptachlorobiphenyl,PCB 174
injection
3,3’4,4’-tetrachlorobiphenyl,WWPCB 77 3,3’4,4’5-pentachlorobiphenyl,l2C12-PCB126 3,3’4,4’5,5’-hexachlorobiphenyl, l2C1z-PCB169 1,3,5,7-tetra~hloronaphthalene(a)~ 1,2,3,5,7-pentachloronaphthalene( a)” 1,2,3,5,6,7- and 1,2,3,4,6,7-he~achloronaphthalene(a)~~~ hexachloronaphthalene(d)” 1,2,3,4,5,6,7-hepta~hloronaphthalene(a)~
quantitation quantitation quantitation quantitation quantitation quantitation quantitation quantitation
total PCB total PCB total PCB, packed column mono-ortho-PCB mono-ortho-PCB PCB 28 PCB 52 PCB 101 PCB 105 PCB 118 PCB 138 PCB 153 PCB 180 PCB 77 and 4-7PCN PCB 126 PCB 169 non-ortho-PCB and PCN, samples Bil-23, Sel-8, and Wal non-ortho-PCB and PCN, samples Bi24-33, Se9-14, and P r l PCB 77 PCB 126 PCB 169 tetrachlorinated naphthalenes pentachlorinated naphthalenes hexachlorinated naphthalenes hexachloronaphthelene(d) heptachloronaphthalenes
See explanation on labeling of PCN peaks in Figure 2. * Mixture of two coeluting congeners.
Table 111. HPLC Parameters column
eluent
charcoal/chromosorb Bio Beads S-X3
(1)n-hexane-CHzClz (2) toluene n-hexane
PL-GEL, 5 pm PL-GEL, 5 Fm Cosmosil5 PYE Cosmosil5 PYE
instrument
Scientific Systems Inc. Model 300 pump Scientific Systems Inc. Model 300 pump Hitachi L-6200 Hitachi L-6200
flow, mL/min
samples
ref
Wal
19
1.5
Bil-15,Sel-8
22
CHzClz/cyclohexane tetrahydro-furan
1.0 1.0
Bi24-28,Se9-12 Se13,14
this paper
n-hexane n-hexane
0.5/1.2
Bil-23,Sel-8 Bi24-33, Se9-14,Prl
22, 7 this paper
12
Table IV. Instrument Parameters instrument
column
carrier gas flow/head pres.
make up gas
HP 5890/5970B HP Ultra 2,25 m X 0.20 mm, helium 99.995%, 0.33-pm film, 5% 14 psi (95 kPa) phenylmethylsilicone HP 5890/ECD HP Ultra 2,50 m X 0.20 mm, Helium 99.995%, Ar/CH4(10%), 0.33-pm film, 5 % 0.3 mL/min 99.95% pheny lmethylsilicone
according to a previously published method (19). These methods are used for routine analysis and include extensive quality assurance and quality control measures. Mono-ortho-PCB were analyzed on a Hewlett Packard 5890A gas chromatograph equipped with an electron capture detector (cf. Table IV). Analytes were quantified against the mono-ortho standards listed in Table 11,using the internal standard method. Non-ortho-PCBand PCN were analyzed on a Hewlett Packard 5890A gas chromatograph using a Hewlett Packard 5970B mass selective detector operated in the SIM mode (cf. Table IV). Each congener was monitored using five masses ranging from M - 0.2 mass units to M + 0.2 mass units plus one mass for the M + 2 ion in order to verify isotope ratios.
inj. temp, det. temp, OC “C
program deg (time)/rate deg
280
290
9OU.5)-200(0)/20-280(15)/3.1
280
290
70(4)-180(2)/30-300(10)/2.0
A complete list of ions monitored and time intervals is found in Table V. Analytes were quantified against a multilevel calibration curve using the internal standard method. PCN peaks were quantified against the first eluting congener in a substitution level, with the exception of hexachloronaphthalene(d) [for labeling of PCN peaks, see Figure 2, panel dl, assuming the same response for all congenerswithin a substitution level. Standard substances and type of standards used are listed in Table 11. The analytical procedure for non- and mono-ortho-PCB has recently been evaluated in an intercalibration exercise conducted by the Swedish EPA. Nineteen laboratories took part in the analysis of one unspiked and two spiked herring oils. The relative standard deviation for five Environ. Sci. Technol., Voi. 27, No. 7, 1993
1367
Table V. Ions Monitored in MS Analysis ions (amu)
analyte
tetrachloronaphthalenes tetrachlorobiphenyls 12C tetrachlorobiphenyls pentachloronaphthalenes pentachlorobiphenyls 12C pentachlorobiphenyls hexachloronaphthalenes hexachlorobiphenyls IZC hexachlorobiphenyls 13C heptachloronaphthalenes heptachlorobiphenyls octachloronaphthalene
263.9 290.0 301.9 299.7 323.9 331.9 335.9 359.7 371.7 367.7 393.7 401.9
265.7 291.7 303.7 299.8 325.7 333.7 337.7 359.8 371.8 367.8 393.8 403.7
265.8 291.8 303.8 299.9 326.8 333.8 337.8 369.9 371.9 367.9 393.9 403.8
265.9 291.9 303.9 300.0 325.9 333.9 337.9 360.0 372.0 368.0 394.0 403.9
time interval, min
266.0 292.0 304.0 300.1 326.0 334.0 338.0 360.1 372.1 368.1 394.1 404.0
266.1 292.1 304.1 301.9 326.1 334.1 338.1 361.9 373.9 369.9 396.9 404.1
10-16 10-21 10-21 16-21 21-24.8 21-24.8 21-24.8 24.8-29.5 24.8-29.5 24.8-29.5 29.6-47 29.5-47 Sell copying paper
replicate samples for each oil analyzed by our laboratory was less than 4% for all five PCB congeners measured. The percentage deviation from the overall means was less than 15%for all congeners at all three spiking levels (23). Results and Discussion During the investigation, the method applied has undergone continuous development and, thus, changed slightly though this has not affected the absolute levels but merely added to the number of compounds quantified. The total amount of PCN is thus not fully comparable between some of the individual samples. Comparisons are, therefore, best performed on the basis of reported levels of individual peaks. All results are corrected for recovery. Recoveries for non-ortho-PCB and PCN, calculated as the mean (& standard deviation) of 45 of the samples were 66% (1251, 76% (&30), and 72% (f27) for PCB 77, 126, and 169, respectively. The overall method recovery for the monoortho-PCB is stated in ref 22. Results of PCN analysis are reported as the levels of the major resolved peaks according to their elution order on a 5 % phenylmethylsilylated gas chromatography column (Figures 2a-d and 3a-c). This labeling is consistent with previously reported results from this laboratory (24)(25). Results for all samples analyzed are presented in Tables VI and VII. Results for biological samples are reported on a lipid weight basis, and lipid content in percent is included in the tables. In the porpoise and seal samples (Bi24-28) analysis of PCN was difficult due to a large number of interfering peaks. The levels are, however, remarkably low in these samples with concentrations of 0nlyO.003~~01 ng/g of tetrachloronaphthalene(a)(the only quantifiable peak). These samples have been excluded from Table VII. Sediment data are reported on a dry weight basis, and ignition loss in percent is included with the tables. No PCN were detected in samples from the upper part of River Daliilven (Se5-7), and these have been excluded from Table VII. PCB 77 is found in all samples, except the two samples from Lake V h e r n (Se13 and 14), and PCB 126 is found in all biological samples and in some sediment samples. For both non-ortho-PCB and PCN there are large spatial and interspecies differences. Figures 4 and 5 give an overview of the data in this investigation and illustrate the variance in absolute levels between background samples such as pike from Lake Storvindeln (Bi7), burbot from River Torne iilv (Bi13), sediment from Lake Grovelsj6n (Se5), and samples from polluted areas such as the 1888 Environ. Sci. Technol., Vol. 27. No. 7, 1993
a
II
--r"--
28
Flgure 2. GC-LRMS chromatograms of selected sedlment samples and the self-copying paper. Chromatograms are composltes of lon traces for tetra- to heptachlorlnated naphthalenes Le., 286,300,334, and 868 amu. Peaks are labeled according to thelr elution order on a 5 % phenylmethylsllylatedcolumn as shown for the technicalmlxture Halowax 1014 (panel d). Instrument parameters are listed in Tables I V and V.
pike and sediments from Lake J h j o n (Bil,Se2,3). Levels of total non-ortho-PCB (pPCBsum) and total PCN (PCNsum) in pike samples from polluted areas are more than 2 orders of magnitude higher than in background samples (Figure 5). Some of the samples show evidence of specific pollution sources, for example, the pike (Bill and sediment (Se2,3) samples from Lake Jbnsjon and
~
_
_
-
-
-
P ~ k eL Vanern, Kottlprdan
a , 2Ecl
I
2,0E*5
1.6Et5
I . 6EC5
I 1.4E-5 I,ZE+5 C 4
l
I.OEt5 B.0Ec4 6.0E-4
-
L .0E*4
2.0Ei4
Guillemot egg
f
1
i 1 I ~
J iA
I0000 12
sOBOB 70000 60000
i
14
16
16
Tlms
20
22
Jh-A
24
26
. 20
I
C F
-4CN-
h
,J i
Holowax 1014
F
bi
1”
-i
- -5CN -
i
I1
Figure 3. OCLRMS chromatograms of selected biological samples. Chromatograms are composites of ion traces for tetra- to heptachlorinated naphthalenes Le., 266, 300, 334, and 368 amu. Peaks are labeledaccording to their elution order on a 5 % phenyimethylsllylated column as shown for the technical mlxture Halowax 1014 (panel c). Instrument parameters are listed in Tables I V and V.
Lake Kyrksjon (Bi8,9),where the levels are clearly elevated due to contamination by effluents from paper mills collecting PCB-contaminated recycled paper. The occurrence of PCB 77 in the samples from remote areas with no industrial activity and low population density such as the pike from Lake Storvindeln (Bi7), the burbot sample from Pajala (Bi13), and the sediment sample from Lake Grovelsjon (Se5) shows that this compound is transported by air (Table VI). The difference in the relative levels of the three nonortho-PCB is considerable when comparing the pike samples from Lake Jlirnsjon (Bil) and Lake Kyrksjon (Bi8,9),where PCB 77 dominates,with the pike from Lake Storvindeln (Bi7) and Lake Viinern (Bi2-61, where PCB 77 levels are lower and comparable to PCB 126levels (Table VI). This difference is most probably due to the exposure to PCB mixtures with a lower chlorination degree (like Clophen A30 or Aroclor 1242) originating from the selfcopying paper processed by the paper mills at these sites (27). This has resulted in a higher level of PCB 77 in pike from the two first mentioned lakes. The ratio of PCB 77 to PCB 126 in sediment samples from Lake Jlirnsjon is of the same order as that reported for Aroclor 1242by Kannan et al. (28). The same ratio in the pike sample from this lake is lower by 1order of magnitude, indicating that PCB 77 is more readily metabolized than PCB 126 and/or that PCB 126 bioaccumulates to a much higher extent. Concentrations of non-ortho- and total PCB as well as most PCN are approximately twice as high in the spring herring than those caught in the fall. This phenomenon has been described for other organochlorines and is linked to seasonal differences in lipid content (10). There were
no differences seen in fall herring due to age however. Levels of non-ortho-PCB and PCN are low both in Baltic seal (Bi28) and common porpoise (Bi24-271, and the levels are muchlower than in the Baltic herring (Bi1621) they feed on, suggesting that these substances do not biomagnify in these marine mammals. These results agree with other investigations (17,29,30)and may be due to adifferent uptake and/or metabolism as compared to other PCB congeners. The guillemot (Bi29-33), on the other hand, have remarkably high levels of all three non-orthoPCB and also hexachloronaphthalene(a). It can be clearly seen from Figure 6 that these four components as well as the tetrachloronaphthalenes(b)and -(d) and heptachloronaphthalene(a) biomagnify in Baltic guillemot. Tetrachloronaphthalene(a) was not analyzed in the Baltic herring and is, therefore, absent in this figure. The data from the muscle and liver samples from the same individuals of pike and burbot (Figure 7) reveal a difference in the relative occurrence of the five non- and mono-ortho-PCB measured. There is no difference in PCB composition between muscle and liver in pike from two sites in Lake Vinern. However the burbot from three locations in northern Sweden do have a different PCB composition in liver than in muscle. The PCB composition in burbot muscle is similar to that of the pike, but the liver samples have lower relative levels of PCB 77 and higher relative levels of PCB 118 compared to the muscle. This difference between pike and burbot indicates that PCB 77 and PCB 126are more readily metabolized in the burbot liver than in the pike liver. In most samples, levels of PCN follow the levels of nonortho-PCB, Le., where there is PCB contamination, levels of PCN are also elevated (Figures 4 and 5, Tables VI and VII). This finding may be explained by the occurrence of PCN as contaminants in commercial PCB, as reported by several authors (31,121. However in the pike (Bi2) and sediment (Se13,14) samples from northern Lake Viinern, levels of PCN alone are clearly elevated, indicating a different source. Among the sediment samples, those from Lake Jbnsjiin on River E m h (Figure 2b) show a tendency toward a lower chlorination pattern of PCN, resembling the pattern of PCN in self-copying paper (Figure 2a), whereas in the samples from Lake Vinern the pattern is displaced toward a higher chlorination degree (Figure 2c). Though the samples from Lake Vinern clearly resemble the peak pattern of technical Halowax, there is no single Halowax mixture with this composition (1001, 1099, 1013, 1014, 1051). There is, however, a chloralkali plant situated at this site that produced chlorine through reduction of sodium chloride using graphite electrodes, and PCN may arise from this procedure. Lutz et al. (13)reported on the presence of PCN in graphite electrode sludge from one chloralkali industry, and the use of highly chlorinated PCN mixtures (Halowax 1013 and 1014) as binding agents for carbonaceus electrodes has been reported in the literature (16).
Although levels of both non-ortho-PCB and PCN are low in the percolate water sample (Wall, the estimated annual runnoff for this site is more than lo6 m3, making this an important pollution source. The PCN pattern points to technical PCN or PCB as a possible source. Figure 3, parts a and b, clearly shows that the early eluting components at each substitution level, tetrachloronaphthalene(a1, pentachloronaphthalenes(a), and (c) Environ. Sci. Technol., Vol. 27, No. 7, 1993 1389
Table VI. Levels of Selected PCB Congeners in All Samples8 sample
sample type
location
Bil Bi2 Bi3 Bi4 Bi5 Bi6 Bi7 Bi8 Bi9 BilO Bill Bi12 Bi13 Bi14 Bi15 Bi16 Bi17 Bi18 Bi19 Bi20 Bi21 Bi22 Bi23 Bi24 Bi25 Bi26 Bi27 Bi28 Bi29 Bi30 Bi31 Bi32 Bi33 Sel Se2 Se3 Se4 Se5 Se6 Se7 Se8 Se9 SelO Sell Se12 Se13 Se14 Wal Pr 1
pike muscle pike muscle pike liver pike muscle pike muscle pike liver pike muscle pike muscle pike muscle burbot liver burbot muscle burbot liver burbot muscle burbot liver burbot muscle herring 8.6 yr herring 8.6 yr herring f. 4 yr herring f. 4 yr herring f. 6 yr herring f. 6 yr cod muscle cod liver com. porpoise com. porpoise com. porpoise com. porpoise grey seal guillem. '74 guillem. '76 guillem. '78 guillem. '82 guillem. '87 sedim. E m h sedim. E m h sedim. E m b sedim. E m h sedim. Daltilv. sedim. Daltilv. aedim. DalUv. sedim. Daltilv. sedim. Gdta Alv sedim. Gdta &v sedim. Gdta Alv sedim. Gdta Alv sedim. Vhern sedim. Vhern percol.water self copy pap.
JEVnsj Kattfj. Kattfj. Sandv. Vassb. Vassb. Storv. Kyrksj. Kyrksj. Etukr. Etukr. Pajal. Pajal. Seskar. Seskar. Karlskr. Karlskr. Karlskr. Karlskr. Karlskr. Karlskr. Utklipp. Utklipp. Katteg. Katteg. Katteg. Katteg. Hudiksv. St. Karlso St. Karlsd St. Karl86 St. Karlsd St. Karlsd Grdnsk.sj. Jirnsjdn JhnsjBn Sjunnen Grdv.sjdn Siljan Hovran Hedes.fj. Riv6fjord. Gothenb. Gothenb. Gothenb. Kattfjord. Anh.fjord. Vaxholm
lipid %/ign loss 96 PCB77 0.42 0.53 9.0 0.60 0.48 4.4 0.58 0.65 0.68 49 0.63 21 0.49 52 0.71 3.3 3.5 10 10 11 10 0.92 72 87 92 89 49 87 13 15 11 12 12 15 17 27 65 21 7 6 12 11 3.2 14 13 10 12 0.5 L
240 6.7 16 1.6 4.2 8.5 1.1 77 55 0.43 1.0 0.89 0.88 0.28 0.96 4.2 4.1 2.2 2.1 2.1 2.4 2.6 3.3 0.15 0.12 0.15 0.38 0.67 32 38 27 20 15 6.4 72 110 0.54 0.21 0.20 0.29 0.25 0.057 0.038 0.14 0.092 nd nd 0.85 1.6 x 103
PCB126 PCB169 PCBlO5 PCBll8 66 6.7 17 1.2 5.5 8.2 0.64 6.5 3.1 0.33 0.59 0.69 0.54 0.19 0.52 3.1 3.5 0.81 0.84 0.99 1.1 1.3 1.8 0.078 0.10 0.25 0.35 1.3 110 130 82 62 48 0.26 0.58 0.95 0.24 nd nd nd nd nd nd 0.015 nd nd nd na 330
0.78 0.34 1.1 0.10 0.29 0.30 0.22 0.42 nd nd nd nd ad nd nd 0.40 0.50 0.080 0.085 0.11 0.12 0.14 0.17 0.075 0.0063 0.0073 0.017 0.038 39 47 41 34 21 nd nd nd nd nd nd nd nd 0.0069 nd nd nd nd nd 0.68 nd
na 100 420 na 100 160 10 780 300 7.9 6.3 24 9.0 5.1 7.0 na na na na na na na na na na na na na na na na na na na na na na na na na na na na na na na na na na
na 330 860 na 350 530 21 2.1 x lo3 720 65 40 160 36 42 50 na na na na na na na na 1.3 x 103 1.0x 103 2.2 x 103 2.6 x 103 na na na na na na na na na na na na na na 2.9 x 103 2.1 x 103 8.8 x 103 5.6 x 103 na na na na
PCB153 PCBsum7* totPCBc na na na na na na na na na na na na na na na na na na na na na na na 2.0 x 108 2.0 x 103 3.3 x 103 3.0 x 103 na na na na na na na na na na na na na na 2.6 x 103 1.9 x 103 8.7 x 103 4.4 x 103 ne na na
na na na na na na na na na na na na na na na na na na na na na na na 6.4 x 103 5.8 x 103 11x 109 12 x 108 na na na na na na na na na na na na na na 14 x 103 9.9 x 108 42 x 103 27 X 108 na na na na
na na na na na na na na na na na na na na na 9.4 x 103 11 x 108
4.0 x 103 2.7 X 108 3.1 x 103 3.6 X 108 4.5 x 108 4.7 x 108 11x 108 10 x 108 22 x 108 23 X 108 66 X losd 270 X 108 300 X 108 170 X 108 130 X 108 67 X 108 na na na na na na na na 32 x 103 25 x 103 120 x 10x3 59 X 108 na na na 38 X 108
a Figures are given in ng/g of lipid weight and dry weight, respectively, or ng/L (Wal). PCBsum7 is the sum of seven PCB congeners with numbers 28,52,101,118,138,153, and 180, determined by GC-ECD accordingto a previously published method (19). totPCB was determined with packed column chromatography according to a previously published method (26). Value supported by Gun Blomberg, Swedish Environmental Monitoring Program, Swedish Museum of Natural History, S-104 05 Stockholm,Sweden.
and hexachloronaphthalene(a)are persistent in pike and guillemot. It has been shown previouslythat two congeners and 1,2,3,5,6,7coeluting as the HXCN(a) (1,2,3,4,6,7hexachloronaphthalene) predominated in rat adipose tissue and liver after exposure to technical Halowax 1014 (25,32). The results of the present investigation support earlier studies indicating differences in bioaccumulation mechanisms between different species (24). Levels of both non-ortho-PCB and predominant PCN in guillemot eggs are lower in the pooled sample from 1987 than the average of the 10 individual samples from 1976 (Tables VI and VII). Since this declining trend coincides with the results of a more detailed study of total PCB in guillemot eggs from the same population as in the present investigation (33) (Figure 8), there is reason to believe that PCN levels are decreasing in the Baltic Proper. 1370 Envlron. Scl. Technol., Vol. 27, No. 7, 1993
When comparing the ratios (R) of hexachloronaphthalene(a) to non-ortho-PCB (Table VIII), some interesting features become visible. In the sediment samples from Lake Jlirnsjon, in which the PCN content is due mostly to impurities of PCN in PCB from self-copying paper (Figure 2a), the ratio of HXCN(a) to PCB 77 is about 0.006 (loglo R = -2.2) [as compared to 0.005 (loglo R = -2.3) in self-copying paper]. On the other hand, one sediment sample from River Gbta Alv (SelO)shows a ratio above one (loglo R = 0.48) and apparently indicates a specific source for PCN. The pike samples from the northern part of Lake V h e r n also show a higher ratio than the ones from the southern part of Lake Viinern and Lake Storvindeln, Lake Jhnsjon, and Lake Kyrksjbn indicating a specific PCN source.
Environ. Scl. Technol., Vol. 27, No. 7. 1993
1371
M
L
M
L
M
L
M
L
M
L
100
90
80 70
8
60 0 5
50
D
=
40
30 20 lo
7....---. .
.
Bi2 Bi3 Bi5 Bi6 B i l l BilOBil3Bi12Bil5Bil4
Fbure 4. Levels of total n o n - e P C B (pPCBsum) and total PCN (PCNsum) with four to seven chlorine atoms for all sediment samples. Note that pPCBsum is off-scale for samples 2 and 3 and PCNsum Is off-scale fw samples 3 and 14. Actual levels are shown wfthin or beside individual bars for these samples.
[-...Pike samples][-
4
...-Burbot samples ...
Figure7. Relative levels of analyzed non- and r r m n ~ m b P C B In plke from Lake Vinern (B12,3.5,6) and burbot from EtukNnnl (BllO,ll), Pajala (8112,13). and Seskari, (8114.15). M and L denote muscle and llversamples,respectively. PCB 105and 118levelshavebeendklded by 10 before calculating relative contrlbullon.
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.
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.
.
. '
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250 PCN(rumj B(S"rn)
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2
,
, ,
p Z q ~ ! E + ~ ' & r
F w r e 5. Levels of total non-oriWFCB (pPCBsum) and total P C N (PCNsum) wim four to seven chlorine atoms for a selection of the biological samples. Note that tetrachloronaphthalene(a)is not Included in PCNsum for the spring and fall (sp.fa) herring, cod (22).and plke (7. 4 samples.
s200. :
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5
too.. 50 0
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.
.
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4
72
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00
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04
06
aa
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Fbura 8. Time trend series of hexachioronaphthaWa)in gulllernot egg. The 10 individual samples from 1978 and the pwled samples of Um oUmr years are plotted with stars. Fw the year 1976, the average (0)and 95% confidence interval (solld bar) Is glven. FW reference.total FCB in comparable samples (33)Is shown wim fllled triangles. Y-axls range Is 0-350 ppm for total PCB.
PCN peak 1ab.l
Figure6.
PCB congener
Ratio of lipid weight levels of IndMdual compounds in Baltic
guillerrmt egg (1987) to levels in Bank herring (fall 1988. 6 year old) indicating biomagnification. Tetrachloronaphthalene(a) was not an-
alyzed In Baklc herring. Another interesting feature is the difference in the HXCN(a) to non-ortho-PCB ratio between herring samples and samples of the herring consumer guillemot. This differenceclearly indicates a different metabolism and/or uptake in guillemot as compared to the herring and cod examined. 1372
Envlron. SCI. Techml.. VOl.
27.
No. 7. 1993
It has been shown hy other workers that in many caaes the level of PCB 126,when expressed as TCDD toxic equivalents (TEQ), precedes that of total PCDD/PCDF. The relative Contribution of each substance group to the totalTEQ is shown in Figure 9, illustrating three different situations. The pike from Lake Jiunsj6n was exposed to a PCB-contaminated sediment, the pike from Lake Vinern, Kattfjorden, were exposed to a PCDD/F- and PCN-contaminated sediment, and the guillemot from the Baltic Proper were exposed to a more diffuse pollution situation representative of nonpoint-source pollution. A similar distribution to that in guillemot is seen in pike from Lake Storvindeln. This picture shows that although PCB 126leads to the highest contribution in most samples, HXCN(a) may contribute considerably to the total TEQ in biological samples from sites where there is PCN contamination.
Table VIII. Ratio of H X C N ( a ) t o Nan-ortho-PCB
HXCN(a)/PCB 77 sample type
sample
R
pike muscle pike muscle pike muscle pike muscle pike muscle burbot muscle burbot muscle burbot muscle herring, 6 yr, spring, av herring, 6 yr. fall, av cod muscle guillem '87 surf. aedim. surf. sedim. deep sedim. surf. sedim. surf. sedim. surf. sedim. surf. sedim. self-copy paper
Bil Bi2 Bi4 Bi5 Bi7 Bill Bi13 Bi15
0.040 13 2.5 0.62 0.35 0.60 0.24 0.58 1.7 0.94 0.91 3.83 0.050 0.0046 0.0068
a
Bi22 Bi33 Sel Se2 Se3 Se9 SelO Sell Se12 Prl
0.80
3.0079 0.44 0.56 0.0051
HXCNWPCB 126
R
log10
sample location
0.14 13 3.2 0.47
(4.85)
L. JHmsj6n L. Vhern, Kattfjorden L.Vhern, Sandnken L. Vhern, Vaaabotten L. Storvindeln Bothnian Bay, EtuLruMi River Tornei, Pajala Bothnian Bay, Seskar6 Baltic Sea, Karlekrona Archipelago Baltic Sea, Karlskrona Archipelago Baltic Sea, Utklippan Gotland, Stora Karla6 River Emin, L. Gr6nskogwjdn River Emin, L. J-sjan River E m h , L. J-sjdn River G6ta h v , Riv6fjorden River G6ta &v, Gothenburg Harbor River G6ta A h , Gothenburg Harbor River G6ta Alv, Gothenburg Harbor self-copying paper
log10 (-1.4) (1.1)
(0.40) (4.21) (-0.46) (4.22) (4.62) (-0.24) (0.23) (4,027) (4.041) (0.58) (-1.3) (-2.3) (-2.2) (4.097) (0.48) (4.36) (4.25) (-2.3)
(1.1) (0.51)
(-0.33) (4.21)
0.61
1.0 0.39
(0)
(-0.41) (0.041) (0.32) (0.34) (0.26) (0.079) (0.079) (4.24) (4.086)
1.1
2.1 2.2 1.8 1.2 1.2 0.57 0.82 (P
LQ
4.2
(0.62)
LQ
0.027
(-1.6)
PCR 12fi was not detected.
HXCNI.)
pcDDE
(41 7%)
pcs 128
Pike L. Jarnsjon
Pike L. Vinern Kattfjorden
Guillemot egg 1987 Baltic proper
Fbure 8. Comparison of contribution lo TCDD loxlcny in samples from dmerem locatbns. TCDD equivalenl factors for nowampPCB and FCN are based on EROD enzyme Induction. as repwed by Hanbarg et ai. (a). TOXICequlvalents for PCDDIF are based on toxk equivalent faclors (TEF) according to th3 Nordic model
Conclusions Non-ortho-PCB and PCN were found in most of the investigated samples. PCN thus seem to he as widespread as PCB in the Swedish environment at levels equal to non-ortho-PCB. PCN found in sediment and biological samples may originate from impurities in technical PCB, in which case the ratio of HXCN(a) to PCB 77 is below loglo R = -0.5 or it may have specific PCN sources when the ratio is above loglo R = 1. The ratio may he used as a quick tool for tracing sources of PCN pollution. In the case of specific PCN pollution, HXCN(a) may contribute considerably to the total TCDD-like toxicity, and in the fish predator guillemot from the Baltic Sea,the HXCN(a) . . contribution exceeds that of PCB 77 and PCB 169. In several of the investigated samples, PCB 126 is to the total TEQ among the a major tigatedTCDD-like substances. Birds feeding on fish from the Baltic Sea are subject to a heavy pollution burden from hothPCBandPCN. Grey seal and common porpoise,
on the other hand, do not seem to biomagnify PCN or non-ortho-PCB. Levels of bothnon-ortho-PCB and PCN in the time trend series of guillemot from the Baltic Proper seem to follow levels of total PCB in this population in general, indicating a small decrease since the 1970s. More data are needed for an extended period of time in order to verify this finding. Acknowledgments The authors wish to thank Renate Andersson, UllaBritt Uvemo, and Anders Olsson for invaluable technical assistance and Kerstin L i t z h for supporting this investigation with generous advice and information on PCB analysis. Literature Cited (1)Safe, S. In Halogenated biphenyls, terphenyls, nnphtholenes, dibenzodiozins and related products: Kimbrough. R. D., Ed.; Elsevier Science Publishers: Amsterdam, 1989; p p 131-159. EWM.
sd. ~echnoi..vol. 27. NO.7, 1803 1573
McConnel, E. E. In Halogenated biphenyls, terphenyls, naphthalenes, dibenzodioxins and related products; Kimbrough, R. D., Ed.; Elsevier Science Publishers: Amsterdam, 1989;pp 161-193. Safe, S. CRC Crit. Rev. Toxicol. 1985, 13,319-395. Tanabe, S.;Kannan, N.; Subramanian, A.; Watanabe, S.; Tataukawa, R. Environ. Pollut. 1987,47, 147-163. Tarhanen, J.; Koistinen, J.; Paasivirta, J.; Vuorinen, P. J.; Koivusaari, J.; Nuuja, I.; Kannan, N.; Tataukawa, R. Chemosphere 1989,18,1067-1077. Kubiak, T.; Harris, H.; Smith, L.; Schwartz, T.; Stalling, D.; Trick, J.; Sileo, L.; Docherty, D.; Erdman, T. Arch.Environ. Contam. Toxicol. 1989,18,706-727. Jknberg, U.; Haglund, P.; Grafstrom, A,-K.; Asplund, L.; LexBn, K.; de Wit, C.; Strandell, M.; Jansson, B.; Olsson, M.; Jonsson, B. Extended abstract, Dioxin '90,Bayreuth, Germany, Sep 10-14, 1990. Hanberg, A,; Waern, F.; Asplund, L.; Haglund, E.; Safe, S. Chemosphere 1990,20,1161-1164. Reutergtdh, L. Ph.D. Thesis, National Environmental Protection Board Report 3465, Stockholm, 1988. Olsson, M.; Reutergtdh, L. Ambio 1986, 15, 103-109. Weistrand, C.; NorBn, K.; LundBn, A. Chemosphere 1992, 24,1197-1206. Haglund, P.; Jakobsson, E.; Asplund; Athanasiadou, M.; Bergman, A. J. Chromatogr. 1993,634,79-86. Lutz, G.; Otto, W.; Schonberger, H. Report, Regierungsprbidium Freiburg, Abt. Wasserwirtachaft; Freiburg, Germany, 1990. Wiedmann, T.; Ballschmitter, K. Personal communication. Greenburg, L.; Mayers, M. R.; Smith, A. R. J. Znd. Hyg. Toxicol. 1939,21, 29-38. Kover, F.Environmental hazard assessment report: Chlorinated naphthalenes. U.S. Environmental Protection Agency Report 560/8-75-001; US. E P A Washington, DC, 1975. Asplund, L.; Jansson, B.; Bergek, S.; Hjelt, M.; Rappe, C.; Odsjb, T.; Olsson, M. Extended abstract, Dioxin '90, Bayreuth, Germany, Sep 10-14, 1990. (18)Kjeller, L.-0.; Kulp, S.-E.; Bergek, S.; Bostrom, M.; Bergquist, P.-A,; Rappe, C.; Jonsson, B.; de Wit, C.; Jansson, B.; Olsson, M. Chemosphere 1990,20,1489-1496.
1874 Environ. Sci. Technoi., Vol. 27, No. 7, 1993
(19) Jansson, B.;et al. Fresenius J. Anal. Chem. 1991,340,439445. (20) Jensen, S.;Renberg, L.; Reutergtdh, L. Anal. Chem. 1977, 49,316-318. (21) Wideqvist, U.;Jansson, B.; Reutergtdh, L.; Sundstrom, G. Chemosphere 1984,13,367-379. (22) Haglund, P.; Asplund, L.; Jbnberg, U.; Jansson, B. Chemosphere 1990,20,887-894. (23) de Voogt, P.; de Wit, C. Report, Universiteit van Amsterdam, Vakgroep Milieu- en Toxicologische Chemie, Amsterdam, The Netherlands, 1992. (24) Jansson, B.; Asplund, L.; Olsson, M. Chemosphere 1984, 13,33-41. (25) Asplund, L.; Jansson, B.; Sundstrom, G.; Brandt, I.; Brinkman, U. A. Th. Chemosphere 1986,15,61!3-628. (26) Jensen, S.;Reutergtdh, L.; Jansson, B. FA0 Fish Tech. Pap. 1983,NO.212,21-33. (27) Jensen, S.; Renberg, L. PCB in self copying paper. National Environmental Protection Board report 73-01;National Environmental Protection Board Stockholm, 1973;7 pp (in Swedish). (28) Kannan, N.; Tanabe, S.; Wakimoto, T.; Tataukawa, R. J . Assoc. Off. Anal. Chem. 1987,70,451-454. (29) Koistinen, J. Chemosphere 1990,20,1043-1048. (30) Storr-Hansen, E. Ph.D. Thesis. National Environmental Research Institute, Roskilde, Denmark, 1992. (31) Vos, J. G.; Koeman, J. H.; Van Der Maas, H. L.; Ten Noever De Brauw, M. C.; De Vos, R. H. Food Cosmet. Toxicol. 1970,8,625-633. (32) Jakobsson, E.; Asplund, L.; Haglund, P.; Bergman, A. Extended abstract, Dioxin '90, Bayreuth, Germany, Sep 10-14, 1990. (33) Bignert, A.; Gothberg, A,; Jensen, S.; LitzBn, K.; Odsjo, T.; Olsson, M.; Reutergtdh, L. Sci. Total Environ. 1993,128, 121-139.
Received for review October 5, 1992.Revised manuscript received February 12, 1993.Accepted March 24, 1993.
