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Increasing Levels and Biomagnification of Persistent Organic Pollutants Marine Pollution Bulletin 48 (2004) 295–302 www.elsevier.com/locate/marpolbul Increasing levels and biomagnification of persistent organic pollutants (POPs) in Antarctic biota Helmut Goerke *, Kurt Weber, Horst Bornemann, Sven Ramdohr, Joachim Plotz€ Alfred-Wegener-Institut f €ur Polar- und Meeresforschung, Postfach 120161, D-27515 Bremerhaven, Germany Abstract Representatives of the Antarctic food web (krill, cephalopod, fish, penguin, seal) of the area around Elephant Island and from the Weddell Sea were analysed for the most recalcitrant organochlorine compounds. Due to sorption of the compounds to sinking particles and accumulation in sediments, two benthic fish species (Gobionotothen gibberifrons, Chaenocephalus aceratus) feeding on benthos invertebrates and fish reflected significantly increasing concentrations within a decade (1987–1996), while a benthopelagic species (Champsocephalus gunnari) feeding on krill did not. In the pelagic food chain, lipid normalised concentrations of all com- pounds increased from Antarctic krill to fish proving that biomagnification of highly lipophilic pollutants (log octanol–water partition coefficient > 5) occurs in water-breathing animals. As top predators Weddell and southern elephant seals (Leptonychotes weddellii, Mirounga leonina) biomagnified the persistent organic pollutants relative to krill 30–160 fold with the exception of hexachlorobenzene, the levels of which were lower than in fish indicating its intense specific elimination. Ó 2003 Elsevier Ltd. All rights reserved. Keywords: Halogenated hydrocarbons; POPs; Long-range transport; Temporal trend; Food webs; Bioaccumulation; Biomagnification; Antarctic 1. Introduction nants are biomagnified to humans obtaining nutrition on Arctic third-level predators. In view of future moni- Persistent organic pollutants (POPs) comprising or- toring studies in the Southern Ocean, changes of POP ganochlorines used for pest control and industrial pur- concentrations in Antarctic fish in roughly a decade and poses are globally distributed via the atmosphere and biomagnification in the most representative species of transferred to polar regions due to cold condensation the pelagic Antarctic food chain were determined, which (Bidleman et al., 1993; Wania and Mackay, 1996). An- is a basis for proper species selections in large-scale in- alyses of contaminants in biota of the remote Antarctic vestigations. This study covers only the most recalcitrant prove their persistence, long-range transport and bio- compounds in order to avoid interference of metaboli- accumulation. Owing to the absence of point emissions sation. and of riverine input in the Southern Ocean, POP con- centrations in Antarctic fauna reflect global pollution, including redistribution and recent usage of pollutants 2. Materials and methods in the southern hemisphere. While in the Arctic changes of POP levels over time by multiple year samples and Samples of Antarctic animals from various trophic data on biomagnification have been evaluated (de levels were collected from the Weddell Sea and the wa- March et al., 1998), no time series on organochlorine ters around Elephant Island and the South Shetland levels in any Antarctic biota except for minke whale Islands between 1986 and 2000 (Table 1). Blubber (Aono et al., 1997) have been obtained. This is attrib- samples were obtained from immobilised Weddell and utable to the facts that the Arctic is much nearer to main southern elephant seals after dermal incision. Pressure source areas for POPs than the Antarctic and contami- on the preen gland of Adelie penguins allowed pipetting drops of preen gland oil. Six fish species, glacial squid * Corresponding author. Tel.: +49-471-4831-1453; fax: +49-471- and Antarctic krill were collected during several cruises 4831-1425. of RV ‘‘Polarstern’’ by bottom and midwater trawls E-mail address: [email protected] (H. Goerke). respectively. All samples were stored at )30 °C. Samples 0025-326X/$ - see front matter Ó 2003 Elsevier Ltd. All rights reserved. doi:10.1016/j.marpolbul.2003.08.004 296 Table 1 Data of investigated species Species Position Depth (m) Date Length (cm) Wet weight (g) Tissue No.a EOMc;d weightb (g) (%) Range Meanc Range Meanc E. superba (Euphausiacea) 60°500S 6.86 3.9–4.4 4.2 (0.2) 0.24–0.57 0.38 (0.10) Total animal 6, 111 7.7 (1.2) 55°340W 7 P. glacialis (Cephalopoda) 63°020S 670 4.00 36, 37 291, 328 Digestive gland 4, 2 60, 54 0 59°10 W 2 H. Goerke et al. / Marine Pollution Bulletin 48 (2004) 295–302 C. gunnari (Pisces) 61°070S 306 10.87 27–32 30 (1) 119–172 143 (16) Liver 4, 18 4.9 (0.8) 56°080W 4 61°140–210S 87–300 11.96 25–42 32 (4) 89–446 208 (104) Liver 5, 35 3.3 (0.3) 54°530–55°560W 4 G. gibberifrons (Pisces) 60°540–590S 143–251 12.87 26–41 32 (3) 169–708 310 (115) Liver 8, 27 4.3(1.6) 55°080–400W 4 61°140–210S 87–300 11.96 27–41 32 (4) 179–535 287 (112) Liver 5, 32 2.9 (1.1) 54°530–55°560W 4 C. aceratus (Pisces) 61°000S 186 12.87 60–62 61 (1) 1376–2025 1736 (330) Liver 5, 3 6.5 (3.0) 55°030W 4 61°140–210S 87–300 11.96 48–62 57 (4) 995–1810 1363 (273) Liver 3, 16 5.8 (2.0) 54°530–55°560W 4 P. antarcticum (Pisces) 71°170S 630 3.00 16–23e 20(2) 30–102 73(22) Muscle 3, 9 2.7 (0.7) 13°470W 6 T. eulepidotus (Pisces) 71°120S 314 4.00 17–24 21(2) 44–134 88(26) Liver 4, 23 6.0 (0.7) 12°190W 4 G. nicholsi (Pisces) 61°470S 400–450 12.96 13–16e 14 (0.7) 19–32 27 (3) Muscle 4, 36 12 (1.3) 59°340W 6 P. adeliae (Aves) 72°520S 2.95 45–55 4 kg Preen gland 4, 4 100 19°260W oil 0.07 L. weddellii (Pinnipedia) 72°520S 2.95 230–320 kg 274 (34) Blubber 6, 6 89 (2) 19°260W 0.7 M. leonina (Pinnipedia) 62°140S 11.96 300–700 kg 442 (133) Blubber 7, 7 86 (3) 58°400W 0.8 a Number of samples, number of specimens. b Wet weight of sample. c Standard deviations in brackets. d Extractable organic matter. e Standard length. H. Goerke et al. / Marine Pollution Bulletin 48 (2004) 295–302 297 reanalysed for the 1987/1996 comparison did not reveal any storage losses (Weber and Goerke, 2003). Specimens of comparable weight ranges and non-reproductive pe- riods were selected for making POP level comparisons in fish species of different years. Fish and krill samples were pooled in order to minimize effects of individual varia- tion. Prior to analyses, liver and muscle samples were dissected from frozen fish in a cryostat between )5 and )8 °C. By grinding the frozen samples with sodium sulfate and quartz sand in a mortar mill, a dry tissue powder was obtained, from which organochlorine compounds were eluted with n-hexane/acetone (2/1, v/v) by cold column extraction, as described in other studies (Weber and Goerke, 1996, 2003). After dissolving re- sidual compounds in n-hexane, polar lipids were re- moved by percolation through neutral aluminium oxide deactivated by 5% H2O. Eluted parts were separated on Florisilâ. Only the least retained compounds, which are generally the most persistent ones, are considered here. They were identified by gas chromatographic retention (separation column 25 m · 0.25 mm fused silica, sta- tionary phase HP-5MS, film 0.25 lm) and mass spectra (EI(+), 70 eV, sector field instrument, mass resolution M/DM 3000). Quantification was mostly achieved by electron capture detection using authentic compounds as external standards. Low values of HCB in seals were confirmed by additive spiking of respective samples with authentic HCB. Procedures were checked for blanks once per day. No corrections were necessary except for PCBs. Blanks for PCBs 153, 138 and 180 amounted to 30% (s.d. ¼ 10%) of the low values of krill on an average. Mean recovery of certified organochlorines in Standard Reference Material 1588a, Organics in Cod Liver Oil (NIST, Gaithersburg, MD, USA) was 85% (s.d. ¼ 14%). 3. Results and discussion All concentrations of organochlorines were norma- Fig. 1. Concentrations of organochlorine compounds in liver and skeletal muscle of T. eulepidotus of different mean wet weight. Number lised to lipid content, as determined by extractable or- of fish in pooled samples, EOM in liver, EOM in skeletal muscle for ganic matter (EOM), in order to take variation of body paired values are from left to right: 6, 6.8, 1.1; 6, 6.3, 0.6; 5, 5.7, 0.6; 6, and tissue concentration with lipid content into account 5.3, 1.3. (Gray, 2002). According to results from comparative analyses of POPs in adipose (Weber and Goerke, 1996) and muscle tissues (Fig. 1) of various Antarctic fish emissions (Bailey, 2001), from its persistence, its high species, liver analyses can be regarded as representative. mobility in the atmosphere and its preferential conden- Dependencies of POP levels on fish weight were not sation in cold regions (Wania and Mackay, 1996). p,p0- detected, except for Chaenocephalus aceratus because of DDE is the most persistent metabolite of p,p0-DDT, size-dependent diet changes (Weber and Goerke, 2003). which has been extensively used as an insecticide in Hence, for this species samples were restricted to the wet tropical Asia and the southern hemisphere (Iwata et al., weight range > 1000 g. 1994; Connell et al., 1999). The present and future use of Hexachlorobenzene (HCB), p,p0-DDE and mirex DDT for vector control against malaria in the lower were generally the predominant POPs in Antarctic ani- latitudes is evident, as 31 nations recently applied for mals analysed between 1986 and 2000 (Figs.
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