Identification of 19 Polybrominated Diphenyl Ethers (PBDEs) in Long ...

Arch. Environ. Contam. Toxicol. 36, 355–363 (1999)

A R C H I V E S O F

Environmental Contamination a n d Toxicology r 1999 Springer-Verlag New York Inc.

Identification of 19 Polybrominated Diphenyl Ethers (PBDEs) in Long-Finned Pilot Whale (Globicephala melas) from the Atlantic G. Lindstro¨m,1 H. Wingfors,1 M. Dam,2 B. v. Bavel1 1

Institute of Environmental Chemistry, Umea˚ University, SE-901 87 Umea˚, Sweden

2

Food and Environmental Agency, Debesartrod, FR-100 Torshavn, Faroe Islands

Received: 11 June 1998/Accepted: 6 October 1998

Abstract. Nineteen tetra- to hexabrominated diphenyl ethers were identified at ppb concentration in the blubber of pilot whale caught off the coast of the Faroe Islands in 1994 and 1996. Higher total concentrations were found in the pooled samples of young males (3,160 ng/g lipid) and females (3,038 ng/g lipid) compared to adult females (843 ng/g and 1,048 ng/g lipid) and males (1,610 ng/g lipids). The predominant isomers in all samples were 2,28,4,48-TeBDE (PBDE #47) and 2,28,4,48,5-PeBDE (PBDE #99) accounting for some 70% of the sum of the 19 isomers.

Polybrominated diphenyl ethers (PBDEs) have been used as flame retardants in a variety of consumer products. This includes their accelerated use in electronic boards in computers, radios, and television sets. In 1992 the world annual production was 40,000 t (WHO 1994). The consumption of flame retardants in the United States is expected to rise to $926 million in 2000. About 30% of this market is expected to consist of bromine-based flame retardants (Reish 1997). The PBDEs are mainly used as two formulations, deca-BDE and Bromokal 70-5DE, a mixture of tetra-, penta-, and hexa-BDE. The use of Bromkal 70-5DE has recently been reduced in several countries because of its bioaccumulation potential and toxicity (WHO 1994). The PBDEs were first discovered in the environment in Sweden in pike, eel, and sea trout samples from ViskanKlosterfjorden south of Gothenborg in 1981 (Andersson and Blomkvist 1981). These first findings have been confirmed by several others (Jansson et al. 1987; Wantanabe et al. 1987; de Boer 1989, 1990; Kuehl et al. 1991; Loganathan et al. 1995). Reported concentrations vary from 8–110,000 ng/g depending on the species or sampling site. Mainly the tetra- and pentabrominated isomers were recently found (Haglund et al. 1997; Asplund et al. 1997). PBDEs have also been detected in sediment, sewage sludge (Sellstro¨m et al. 1996; Hartonen et al. 1997), birds, and bird eggs (Sellstro¨m et al. 1993a, 1993b;

Correspondence to: G. Lindstro¨m; e-mail: gunilla.lindstrom@chem. umu.sc

Peterman et al. 1997). Recently, methoxylated bromodiphenyl ethers have been reported in herring and seal samples from the Baltic (Haglund et al. 1997). In humans, higher brominated PBDEs were first reported in the early 1990s (Remmers et al. 1990; Stanley et al. 1991). This is in contrast to the lower brominated congeners found in biota where tetra, penta, and hexa congeners were most abundant. Also recent publications of human concentrations show higher concentrations of the lower brominated congeners (Lindstro¨m et al. 1997; Haglund et al. 1997; Klasson Wehler et al. 1997). Although food is considered the main exposure route for humans, the influence from contaminated indoor air and dermal exposure are additional sources (Bergman et al. 1997). The PBDE concentrations in marine mammals are only known for a number of different seal species from the Baltic, the Arctic, and the North Sea. Total concentrations of 90 ng/g, 10–40 ng/g were reported for harbor and ringed seal (Jansson et al. 1987), respectively, from the Kattegat and the Baltic. Higher concentrations were measured in juvenile harbor seals (250– 650 ng/g), adult male harbor, ringed, and grey seals (230–320 ng/g) and adult female grey seals (280–1,500 ng/g) collected in 1988 (Andersson and Wartanien 1992). The first congenerspecific concentrations in a composite ringed seal sample from Svalbard in 1981 and a composite grey seal sample (1979–85) from the Baltic were reported by Jansson et al. (1993). Of the three congeners measured, 2,28,4,48 TeBDE was clearly the most dominant compound with concentrations of 47 to 650 ng/g reported in ringed seal and grey seal, respectively. The other congeners found were 2,28,4,48,5-PeBDE and an unidentified PeBDE congener. The concentrations of the two pentabrominated congeners were comparable in both ringed seal (1.7–2.3 ng/g) and grey seal, (38–40 ng/g). Recently, Haglund et al. (1997), in addition to these penta congeners, detected three hexabrominated diphenyl ethers, of which one was identified as 2,28,4,48,5,58 HxBDE (3–27 ng/g). Consistent with the previously reported high concentrations of chlorinated organic contaminants in marine mammals, brominated organic pollutants were expected to be found in pilot whale blubber. High concentrations of organochlorine contaminants have already been reported in Atlantic pilot whale (Simmonds et al. 1994; Abraham et al. 1995; Mo¨ssner and Ballschmitter 1997). There have been no determinations of

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Fig. 1. The sampling sites in Vestmanna and Hvannasund, Faroe Islands, in 1994 and 1996

PBDEs reported for pilot whale in these studies. In the present study the occurrence of PBDE in long-finned pilot whale was investigated both by full scan (SCAN) and selective ion recording (SIR) mass spectrometry to identify and quantify PBDEs.

of the blubber that had been in contact with the polyethylene bags. Thus the core of the blubber layer, which was in all approximately 5 cm thick, was used. Subsamples of similar weight were taken from each individual to make up the pooled samples to approximately 40 g. Five pooled fat samples of pilot whale, caught in Vestmanna and Hvannasund, Faroe Islands, in 1994 and 1996, were analyzed (Table 1).

Materials and Methods Sample Extraction and Cleanup Sampling Samples of blubber from long-finned pilot whales were collected from two separate schools taken in the traditional drive fishery (Bloch et al. 1990). Samples were taken after the whales were opened for cooling. Blubber samples were taken from the ventral side, in the posterial end of the incision already made by the skilled assistants on the quay. The first sampling took place on June 30, 1994, in Hvannasund (Figure 1). Samples were taken from 20 animals, and sex and lengths were determined by local authorities. With length and sex of the individuals known, the approximate age, or rather the degree of sexual maturity, could be inferred (Bloch et al. 1993a). The sampling was random from the pod containing a total of 119 whales. From this catch only the adult females were analyzed; they were nine in number and their mean body length was 4.30 m (range 3.95–5.12 m). The second sampling was on June 26, 1996, in Vestmanna from a pod of 192 whales. Samples were taken from 50 individuals randomly chosen. In the case of the Hvannasund samples, the whales were subdivided according to sex and maturity. The four subsamples represented were immature females (n 5 4, mean body length 5 2.97 m, range 2.55–3.5 m) and males (n 5 13, mean body length 5 3.59 m, range 2.73–4.75 m), mature females (n 5 19, mean body length 5 4.39 m, range 4.00–4.65 m), and males (n 5 8, mean body length 5 5.41 m, range 5.11–5.63 m). The average number of mature and immature females and males in an average pilot-whale school was 40% mature females, 20% immature females, 13% mature males, and 26% immature males (Bloch et al. 1993b). The sampling from Vestmanna June 26, 1994, was thus biased toward adult males, so fewer immature females than average were represented. The samples were frozen individually in polyethylene bags, and kept at approximately 220°C until preparation of pooled samples prior to analysis. When subsampling from the individual blubber samples, care was taken to cut away and thus exclude from the subsamples the parts

The pooled fat samples were homogenized in a mortar with sodium sulfate (1:4). An internal standard consisting of 13 13C-labeled polychlorinated biphenyls (PCBs), di- through deca-substituted (#15, #28, #47, #52, #101, #105, #118, #138, #153, #156, #180, #194, and #209) was added before the lipid extraction. The homogenates were applied on columns (4.7 cm ID) and the lipids were quantitatively extracted with methylene chloride and hexane (1:1) and gravimetrically determined. Further cleanup was performed on a multilayer silica column, consisting of sulfuric acid on silica, neutral activated silica, and potassium hydroxide on silica, using hexane as eluting solvent. A method blank was cleaned up simultaneously using the same procedure and amounts of solvents as for the samples. After concentration in a rotary evaporator a recovery spike, three 13C-labeled PCBs, tetra through hepta (#80, #128, and #178) dissolved in tetradecane, was added.

Instrumentation, HRGC/MS Analyses Full-scan HRGC/MS spectra were recorded using a Fisons GC 8000 gas chromatograph coupled to a MD800 mass spectrometer (Micromass, Manchester, UK) scanning from m/z 100 to m/z 700 in 1 s and operating in the electron impact mode (EI). Chromatographic separation was achieved by splitless injection of 2 µl on a nonpolar DB-5 column (J&W, Folsom, CA) using helium as the carrier gas. The GC oven was programmed as follows: 180°C initial hold for 2 min, increase at a rate of 15°C/min to 205°C, followed by an increase of 3.7°C/min to 300°C, final hold at 300°C for 20 min. The same chromatographic conditions were used for selected ion recording SIR MS. When using SIR the two most intense ions of the molecular ion cluster were monitored for TeBDE (m/z 483.7, 485.7), PeBDE (m/z 563.6, 565.6), and HxBDE (m/z 641.5, 643.5) in addition to two

Nineteen PBDEs in Pilot Whale

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Table 1. Concentrations of the 19 PBDEs in ng/g lipid in five pools of adult male, adult female, juvenile male, and juvenile female pilot whale samples from the Faroe Islands Vestmanna, June 1996 19 Females 79% Lipids (ng/g) Te-BDE (a) Te-BDE (b) Te-BDE (c) Te-BDE (d) Te-BDE #47 Te-BDE (e) Te-BDE (f) Pe-BDE (a) Pe-BDE (b) Pe-BDE (c) Pe-BDE (d) Pe-BDE (e) Pe-BDE (f) Pe-BDE #99 Pe-BDE (g) Hx-BDE (a) Hx-BDE (b) Hx-BDE (c) Hx-BDE #153 Sum BDE

Vestmanna, June 1996 8 Males 66% Lipids (ng/g)

Vestmanna, June 1996 13 Young Males 76% Lipids (ng/g)

Vestmanna, June 1996 4 Young Females 72% Lipids (ng/g)

Hvannasund June 1994 9 Females 82% Lipids (ng/g)

2.9 0.8 2.4 7.5 529.4 2.9 21.9

3.9 0.8 3.5 8.7 862.4 3.9 28.2

5.8 1.0 7.8 6.1 1782.1 8.1 40.2

8.5 1.4 7.9 11.2 1727.4 8.5 61.5

2.3 0.7 1.5 4.7 411.9 2.2 13.4

4.6 1.9 104.4 2.4 ND 209.0 4.8

6.8 0.2 2.8 153.6 3.4 1.7 292.0 12.4

13.1 0.5 6.4 280.5 6.4 3.6 603.6 25.2

12.1 0.4 6.3 281.1 6.3 3.3 562.2 19.1

3.5 ND 1.5 87.1 2.0 0.8 164.1 6.3

29.2 85.1 3.4 35.2

43.9 123.3 5.8 53.2

67.2 203.7 9.0 90.0

54.6 178.6 10.4 77.4

27.8 77.9 3.5 32.0

1,047.9

1,610.3

3,160.3

3,038.2

843.2

ND

ND 5 not detected

Fig. 2. The total ion current chromatogram of the male whale sample from Vestmanna during a full scan (m/z 100–m/z 700) between 19 and 30 min; indicated on the chromatogram are the retention times and location for TeBDE (19.8 min), PeBDE (24.8 min), and HeBDE (28.1 min)

masses for the 13C-labeled internal standard Deca-PCB (m/z 509.7, 511.7) at a dwell time of 40 ms and an interchannel delay of 1 ms. Quantification was achieved by comparing the relative responses of the target compounds against the internal standard (13C PCB #209) in both

the samples and a standard solution. The standard solution contained known amounts of 2,28,4,48-TeBDE (BDE #47), 2,28,4,48,5-PeBDE (BDE #99), 2,28,3,4,48-PeBDE (BDE #85), 2,28,4,48,5,58HxBDE (BDE #153), 2,28,3,4,48,5-HxBDE (BDE #138), and IS 13C PCB #209.

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Fig. 3. The mass spectrum of TeDBE eluting at 19.8 min. The molecular ion bromine cluster at mass 481.7 (M1) indicates the presence of four bromine atoms. The most abundant fragment showing a bromine cluster can be seen at mass 321.9, indicating the loss of two bromine atoms

Quality Assurance and Quality Control

Results and Discussion

Quality assurance and quality control concerning the analysis of PDBE is extensively discussed elsewhere (Haglund et al. 1997; Lindstro¨m 1997). In short, positive quantification of PBDE was reported when (1) S/N . 3 for the quantification ion in the SIR GC/MS mode; (2) the ratio of the two most abundant ions in the bromine cluster was within 10% of the theoretical ratio; and (3) concentration of the target compound in a laboratory blank sample, treated the same way as a real sample, was below 10% of the reported concentration in the samples. In this study the laboratory blank samples did not contain PBDE concentration above the detection limit (0.1–0.5 ng/g). The detection limit for the whale samples was 0.1–1.0 ng/g lipids, depending on the sample size (1.9–2.2 g wet weight) and the different responses of the PBDE congeners. All bromine isotope ratios were well within 10% of the theoretical ratio for all PBDE congeners reported in Table 1. Because no 13C-labeled PBDEs are available as internal standard, 13C-labeled PCB was used as an internal standard and added before the sample cleanup. PCBs and PBDE are structurally similar and have been shown to have a similar chemical behavior during extraction and cleanup of biological samples (Haglund et al. 1997). Therefore, in this study 13C-labeled PCB was used as an internal standard. The recovery of all internal standards was within acceptable limits, 50–90%. Quantification was performed using a PBDEs mixture containing five PBDE isomers at a concentration of 10 ng/µl (99% purity, Wallenberg Laboratory, Stockholm) and the internal 13C-labeled PCB congeners. For the PBDE isomers not present in the quantification mixture, a relative response factor, similar to the closest eluting PBDE, was assumed.

Identification A total ion chromatogram of the male whale sample from Vestmanna is given in Figure 2. Indicated on this chromatogram are the retention times for the brominated diphenyl ethers. The TeBDE is eluting around 19.8 min, PeBDE at around 24.8 min, and HxBDE at 28.1 min. Due to several other co-eluting compounds the PBDEs do not result in significant peaks in the full-scan chromatogram and are located on the ‘‘shoulder’’ of other more dominating peaks. This is especially the case for both the PeBDEs and HxBDEs, as can be clearly seen in Figure 2. The corresponding mass spectra’s generated at 19.8, 24.8, and 28.1 min are given in Figures 3, 4, and 5. Figure 3 shows the mass spectrum of TeDBE eluting at 19.8 min, the molecular ion bromine cluster at mass 481.7 (M1) indicating four bromine atoms and a very intense bromine cluster at mass 321.9 (M-Br2)1, indicating the loss of two bromine atoms. This spectrum of TeBDE is identical to the spectra of TeBDE published in the literature (Andersson and Blomkvist 1981; Buser 1986; Wantanabe et al. 1987). The mass spectrum of the compound eluting at 24.8 min is shown in Figure 4. The bromine cluster at mass 559.6 (M1) indicates the presence of five bromine atoms. Again the typical loss of two bromine atoms creates a base peak fragment at mass 401.8 (M-Br2)1. This spectrum is identical to EI spectra of PeBDE in the


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Fig. 4. The mass spectrum of the compound eluting at 24.8 min. The bromine cluster at mass 559.6 (M1) indicates the presence of five bromine atoms. The most abundant fragment showing a bromine cluster can be seen at mass 401.8, indicating the loss of two bromine atoms

literature by Buser (1986) and Watanabe et al. (1987). In Figure 5 the spectra of the shoulder peak at 28.1 min is presented. The molecular ion cluster at mass 641.6 (M1) and the typical base peak fragment of two bromine losses at 481.7 (M-Br2)1 are present, indicating that this compound is HxBDE.

Quantification After identification of the TeBDE, PeBDE, and HxBDE in the whale tissue, the samples were rerun in the SIR mode. Running a sample in the SIR mode strongly reduces noise and thus enhances the detection limit of the target compounds. In Figure 6 the chromatogram of the most abundant mass 485.7 in the bromine cluster is shown. In total, seven TeBDE congeners were found to comply with the theoretical bromine ratio between (M-2)1/(M-4)1. The largest peak in the chromatogram was identified as 2,28,4,48-BDE (BDE #47), showing the same retention time as for BDE #47 in the standard solution. BDE #47 was also identified as a major component in Bromkal 70-5 DE (Sundstro¨m and Hutzinger 1976; Sjo¨din et al. 1997). The structures of the other TeBDEs denoted as a, b, c, d, e, and f could not be verified, but it can be assumed that congener f is 2,38,4,48-BDE (BDE #66). In Figure 7 the chromatogram of the most abundant mass of the molecular cluster of PeBDE (563.6) is shown, and eight isomers were positively confirmed as PeBDEs by the theoretical bromine ratio. From these eight isomers the largest peak was

verified as 2,28,4,48,5-PeBDE (BDE #99), having the same relative retention time as BDE #99 in the standard solution. Tentatively, isomer d in Figure 7 was identified as 2,28,4,48,6-BDE (BDE #100). Both BDE #99 and BDE #100 are major peaks in Bromkal 70-5 DE. Four HxBDEs were found in pilot whale. In Figure 8 the ions corresponding to mass 643.5 are displayed. Again one isomer was found also in the standard solution, the last eluting HxBDE was positively identified as 2,28,4,48,5,58-HxBDE (BDE #153). The structure of other HxBDEs could not with certainty be determined. Although BDE #153 is the major peak in a Bromkal 70-5 DE mixture, in whale this is for all five samples the peak denoted with b and peak a is almost of the same intensity as BDE #153. This indicates that the PBDE pattern in whale is significantly different from Bromkal 70-5 DE, implying that Bromkal is not the only source of exposure. Metabolism of PBDEs by whales can also be a reason for the difference in congener pattern. In Table 1 the concentrations of the 19 PBDEs are given in ng/g lipid for the five pools of adult male and female and juvenile male and female samples. In all sample pools TeBDE #47 was found to be present in the highest concentrations, followed by two PeBDEs, one of which was identified as BDE #99 and one HxBDE.

Considerations Total concentrations of PBDEs in the five pooled pilot whale samples were significantly higher than the concentrations

Fig. 5. The spectra of the shoulder peak at 28.1 min. The molecular ion cluster at mass 641.6 (M1) indicates six bromine atoms present and the typical base peak fragment of two bromine losses at 481.7 (M-Br2)1

Fig. 6. The chromatogram of the SIR GC/MS run showing the most abundant mass 485.7 in the bromine cluster; a total of seven TeBDE congeners comply with the theoretical bromine ratio of (M-2)1/(M-4)1 and a S/N larger than 3. Between 17.5 and 19.5 min this trace is magnified by a factor of two

Fig. 7. The chromatogram of the SIR GC/MS run showing the most abundant mass of the molecular cluster of PeBDE (563.6); eight isomers were confirmed as PeBDEs. Between 22.5 and 23.5 and 19.5 min this trace is magnified by a factor of five

Fig. 8. The ions corresponding to mass 643.5 of the SIR GC/MS run, the last eluting HxBDE was identified as 2,28,4,48,5,58-HxBDE (BDE #153)

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previously reported in seals. The PBDE concentrations presented here are among the highest measured in biological samples so far. Also of interest was the fact that for the pooled samples of female pilot whales the concentrations in the samples from 1996 were somewhat higher than the concentrations found in samples from 1994. This is in agreement with other studies, where an increase in PBDE concentrations in the environment are reported and contradicting the observed decrease in concentrations of banned organochlorine compounds such as DDT/DDE and PCB (Sellstro¨m et al. 1993b; de Boer 1989). But these findings have to be confirmed because there are usually large between-school variations. High concentrations of PBDEs in young animals can be explained by a considerable lactational transfer of these compounds from the females to the offspring. In a recent study on PBDEs in human tissue we have found several of the 19 congeners reported in pilot whale to be present also in the general Swedish population (Lindstro¨m et al. 1998). On the basis of these findings we strongly recommend further monitoring of PBDEs in human tissue and in biota. Acknowledgments. Drs. Åke Bergman, Eva Jakobsson, and Peter Haglund of the Departments of Environmental Chemistry Stockholm University and Umeå University are gratefully acknowledged for PBDE reference compounds.

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