A comparative assessment of fatty acids in Antarctic organisms from the Ross Sea: Occurrence and distribution.

Lipids are important energy source and structural component for cellular membranes and tissues, involved in the osmoregulation and immune response, and are very important in the bioaccumulation of lipophilic chemicals too. Among lipids, fatty acids (FAs) give information on diet of organisms, since FA of consumer lipids can be related to those of diet; plants and animals vary in their FA signature because of differences in the synthesis of lipids. In this study, lipid content and FA composition in tissues of Antarctic organisms from the Ross Sea (Odontaster validus, Sterechinus neumayeri, Chionodraco hamatus, Trematomus bernacchii, Pygoscelis adèliae) were assessed. Differences in lipid characterisation were found between both species and tissues. The lipid content was highest in C. hamatus liver (3.51%), and lowest in T. bernacchii muscle (0.16%). The polyunsaturated fatty acids (PUFAs) prevailed in the C. hamatus muscle, and among FAs, the docosahexaenoic acid (DHA; C22:6n3) was the most abundant (20.93%). The C22:6n3 accumulated more in fish and penguin tissues than in invertebrate species. The high contribution of unsaturated fatty acids (>74%) in fish tissues wats related to the low environmental temperature. The fatty acid profile and the essential fatty acids occurrence were also discussed in the light of physiological adaptations and feeding habits of organisms; the relationships with contaminant bioaccumulation were also assessed. To the best of our knowledge, this is the first report of fatty acid composition and fingerprint in a Ross Sea trophic web and their correlation with contaminant concentration.

Chlorinated biphenyls and pesticides in migrating and resident seabirds from East and West Antarctica.

The unhatched eggs of the following seabirds were analyzed to quantify PCBs, hexachlorobenzene (HCB), α-, ß-, γ-, δ-hexachlorocyclohexanes (HCHs), o,p' and p,p' isomers of DDT, DDD and DDE: resident Adèlie (Pygoscelis adèliae, ADPE) and Emperor (Aptenodytes forsteri, EMPE) penguins, migrating snow petrel (Pagodroma nivea, SNPT) and South Polar skua (Catharacta maccormicki, SPSK) from the Ross Sea (East Antarctica); and migrating Brown skua (Catharacta antartica, BRSK) and resident ADPE from the Brainsfield Strait (West Antarctica). The general aims were to evaluate the contaminant accumulation in eggs of migrating and resident species in the two study areas, and to compare levels in penguins and skuas nesting in East and West Antarctica. PCB congener and HCH and DDT isomer profiles were also assessed. Comparisons were evaluated using seven PCB congeners (IUPAC nos. 28, 52, 101, 118+149, 138, 153, and 180), p,p'-DDE, ΣDDTs, and ΣHCHs. Higher contaminant concentrations were detected in migrating seabirds (South polar skua and brown skua)>sub-Antarctic species (snow petrel)>Antarctic species (penguins) from both the sampling sites, suggesting contamination events at lower latitudes for those birds migrating northward. HCHs showed the lowest concentrations in all species (from 0.03±0.03 ng/g wet wt in SPSK to 1.81±1.23 ng/g wet wt in ADPE from West Antarctica), and PCBs were the most abundant contaminants (from 4.34±2.15 ng/g wet wt. in EMPE to 53.41±19.61 ng/g wet wt. in brown skua). Among pesticides, it is relevant the detection of p,p'-DDT in Adèlie penguin from West Antarctica and in both species of skua; the detection of this pesticide can confirm its actual use in certain malaria-endemic countries from where it is transferred through the long range transport to the polar regions. Contaminants did not show any significant temporal trend during a ten year time span, from 1994/95 to 2004/05, in organisms collected in East Antarctica and they did not indicate any latitudinal gradient along the Ross Sea coasts.

Polybrominated diphenyl ether contamination levels in fish from the Antarctic and the Mediterranean Sea.

Polybrominated diphenyl ethers (PBDEs) concentrations and congener profiles were evaluated in four species of Antarctic fish (Chionodraco hamatus, Chaempsocephalus gunnari, Gymnoscopelus nicholsi,Trematomus eulepidotes) and in one Mediterranean species (Tuna, Thunnus thynnus). The GC/MS-ECNI analysis revealed that average sigmaPBDE concentrations in Antarctic fish species ranged from 0.09 ng g(-1)wet weight (wet wt) in G. nicholsi to 0.44 ng g(-1)wet wt in C. gunnari. In Mediterranean tuna they were two or three orders of magnitude higher (15 ng g(-1)wet wt). The PBDE congener profiles differed between species; low brominated congeners prevailed in Antarctic species while in tuna tetra- and pentabromodiphenyl ethers were the most abundant congener groups (41% and 44%, respectively). These results showed that PBDE levels significantly correlated with the length of the fishes (r(2)=0.85, p<0.01) in C. hamatus, but not with the weight of the fish. Moreover, mean sigmaPBDE concentrations in tuna were statistically higher in females than in males (18 and 13 ng g(-1)wet wt, respectively; p<0.05), which was explained by the lower fat contents of the males that just had entered the spawning period. The results of this study confirm that PBDE contamination of the marine environment now occurs on a global scale.

Anthropogenic and naturally-produced organobrominated compounds in bluefin tuna from the Mediterranean Sea.

Anthropogenic compounds, such as polybrominated diphenyl ethers (PBDEs), together with naturally-produced organobromines, such as methoxylated PBDEs (MeO-PBDEs), polybrominated hexahydroxanthene derivatives (PBHDs), 2,4,6-tribromoanisole (TBA) and a mixed halogenated monoterpene (MHC-1), were measured in muscle from 26 farmed and wild bluefin tuna (Thunnus thynnus) caught in the Mediterranean Sea. This species is ecological attractive because of the changes of geographic habitat throughout its long lifespan which affect its feeding. PBDE concentrations were similar between tuna samples of different groups (17-149 ng g(-1) lipid weight - lw in farmed tuna, 25-219 ng g(-1)lw in longline fished tuna and 26-126 ng g(-1)lw in net-fished tuna). However, higher concentrations of naturally-produced MeO-PBDEs and PBHDs were observed in the two types of wild tuna (longline fished and net-fished) compared to farmed tuna suggesting that wild tunas come easily in contact with sources of these compounds. In all cases PBHDs presented the highest contribution to the sum of organobromines (50% in farmed tuna and >90% in wild tuna). TBA was detected at low concentrations (<6 ng g(-1)lw), while MHC-1 was found at higher concentrations (up to 42 ng g(-1)lw) in farmed tuna. The estimated daily ingestion of PBDEs from tuna was 830 ng PBDEs day(-1), regardless of the origin of the tuna. While this value is approximately 600 times lower than the minimum risk level set by the US Department of Health and Human Services, it is approximately eight times higher than the total intake of PBDEs via diet, suggesting that consumption of tuna can add considerably to the total daily intake of PBDEs.

Contamination profiles of selected PCB congeners, chlorinated pesticides, PCDD/Fs in Antarctic fur seal pups and penguin eggs.

The aim of this study was to investigate levels of some major environmental contaminants, such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and organochlorine pesticides in Antarctic samples. Concentrations of some persistent organic pollutants (POPs) were investigated in Antarctic fur seal pups and eggs of three species of penguins. Dichloro-diphenyl-trichloroethane (DDT) was the main pollutant, followed by PCBs; other organochlorine compounds such as hexachlorobenzene (HCB) and PCDD/Fs were usually found only in minor quantities. Adélie penguin eggs had significantly higher mean PCB concentrations (p<0.05) compared to the other two penguin species, but there was no difference in DDT levels (p>0.05). TEQ values in fur seal blubber in our study were one order of magnitude lower than those considered to elicit physiological effects in aquatic mammals. In general, POP concentrations in our samples suggested that likely the study populations were not currently at risk for adverse health effects, but indicated a clear need for further monitoring to assess the presence and time trend of a broad range of contaminants, mainly emerging POPs thought to be increasing in polar regions.

Organochlorine pesticide air-water exchange and bioconcentration in krill in the Ross Sea.

Mean hexachlorobenzene (HCB) and hexachlorocyclohexane (HCH) concentrations, measured in seawater and air samples, confirmed the decline in levels of these compounds in Antarctic air and water. However, low alpha/gamma-HCH ratios in air at the beginning of the sampling period suggest a predominance of fresh lindane entering the Antarctic atmosphere during the Austral spring probably due to current use in the Southern Hemisphere. Water-air fugacity ratios demonstrate the potential for HCH gas deposition to coastal Antarctic seas, while the water-air fugacity ratios for HCB imply that volatilization does not account for the observed decrease of HCB in surface seawater. HCH concentrations found in krill samples were correlated with seawater concentrations indicative of bioconcentration of HCHs from seawater.

Levels of polybrominated diphenyl ethers (PBDEs) and organochlorine pollutants in two species of Antarctic fish (Chionodraco hamatus and Trematomus bernacchii).

In the late 1960s the first scientific studies on contamination in Antarctica demonstrated the presence of pollutants in Antarctic ecosystems. Many Persistent Organic Pollutants (POPs) are transported globally from the areas in which they are produced and released into the environment in remote areas, including Antarctica. Here we report results obtained concerning the accumulation of polybrominated diphenyl ethers (PBDEs), mono- and non-ortho-polychlorobiphenyls (PCBs), polychlorodibenzodioxins (PCDDs) and polychlorodibenzofurans (PCDFs) in the tissues of two species of Antarctic fish (Chionodraco hamatus and Trematomus bernacchii). The 2,3,7,8-TCDD toxic equivalents (TEQs) were also calculated to evaluate the potential risk of these compounds for the two species. In general, POP levels were higher in the tissues of T. bernacchii than in C. hamatus and the highest concentrations were found in the liver of both species. The PBDE levels varied from 160.5 pg g(-1) wet wt in C. hamatus muscle to 789.9 pg g(-1) wet wt in T. bernacchii liver and were lower than the levels of PCBs. PCBs were the main organochlorine compounds detected and their concentrations ranged from 0.3 ng g(-1) wet wt in C. hamatus muscle to 15.1 ng g(-1) wet wt in T. bernacchii liver. TEQ concentrations resulted higher in C. hamatus than in T. bernacchii and were due mainly to PCDDs. The presence of PBDEs and organochlorine pollutants in the tissues of Antarctic organisms confirms their global transport and distribution.

Polybrominated diphenyl ethers, polychlorinated dibenzo-dioxins, -furans, and -biphenyls in three species of Antarctic penguins.

BACKGROUND, AIMS AND SCOPE: Fish-eating seabirds are recognized to be at risk of accumulating toxic contaminants due to their high position in the trophic web and to their low ability to metabolize xenobiotic compounds. Penguins are widely distributed in Antarctica and represent an important fraction of the Antarctic biomass. They feed mainly on krill and, depending on krill availability, also on fish. It has been reported that predators may be a sink for volatile and toxic chemicals and this may pose a serious environmental problem. Polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo-dioxins (PCDDs), -furans (PCDFs), and -biphenyls (PCBs), including non-ortho congeners, hexachlorobenzene (HCB) and p,p'-DDE, were quantified in three species of Antarctic Pygoscelids in order to evaluate their accumulation patterns. The potential toxicity of twenty-two dioxin-like congeners was assessed and expressed as 2,3,7,8-tetraCDD equivalents (TEQs). Differences between males and females were investigated. METHODS: Blood samples of the Adélie penguin Pygoscelis adeliae, Chinstrap penguin Pygoscelis antarctica and Gentoo penguin Pygoscelis papua were collected at Admiralty Bay, King George Is (62 degrees 10'39" S, 58 degrees 26'46" W) in February 2004. Halogenated hydrocarbons were identified and quantified using gas chromatography coupled with gas chromatography mass spectrometry analyses. Results are expressed on a wet weight basis. RESULTS AND DISCUSSION: HCB, p,p'-DDE and sigmaPCBs were higher in Adélie penguins (6.7 +/- 6.1, 8.2 +/- 3.3 and 9.8 +/- 3.8 ng/g, respectively) than in Chinstrap and Gentoo penguins, both of which showed values in the same order of magnitude, but approximately 40% lower than Adélie penguins. Hexa-CBs ranged 35-45% of the residue. Low-chlorinated PCBs (nos. 70+76+95+ 56+60+101) accounted for 40-60% in the three species. PCB101 made up 15% of the residue in Adélie penguins. PBDEs were 291 +/- 477, 107 +/- 104 and 116 +/- 108 pg/g in Adélie, Chinstrap and Gentoo penguins, respectively; the most abundant congeners were BDE47 in Adélie and Chinstrap penguins and BDE17 in Gentoo penguins. PCDDs were 22 +/- 32, 6.5 +/- 7.4 and 18 +/- 23 pg/g in Adélie, Chinstrap and Gentoo penguins, respectively. PCDFs were higher in Adélie penguins and lower in Chinstrap penguins. PCDDs/Fs and PBDEs were higher in males than in females of Gentoo and Chinstrap penguins; differences in concentrations were likely related to the partial detoxification that occurs in females during egg formation. Of the four non-ortho PCBs measured, PCB126 occurred at the highest concentrations and contributed the majority of the non-ortho PCB-TEQ in Gentoo and Chinstrap penguins. The highest TEQs were found in the Gentoo penguin and due mainly to PCDDs and non-ortho PCBs. CONCLUSIONS: POP concentrations in penguins were lower than those found in seabird species from other areas of the world. Different chemical accumulation patterns were observed in relation to species and sex; the Adélie penguin showed the highest POP levels. Dissimilar ecological or metabolic features may be involved; the diverse timing of reproduction steps can be responsible for those differences; moreover, Adélie penguins feed on krill (a fatty resource) more abundantly than the other two species during the rearing period. RECOMMENDATION AND OUTLOOK: The South Shetland Islands might be subjected to a higher chemical impact with respect to the rest of Antarctica, due to their being near South America. Because penguins are fish-eating birds showing low detoxifying capacities and key-species in Antarctic ecosystems, further studies on their xenobiotic metabolism should be carried out.

HCB, p,p'-DDE and PCB ontogenetic transfer and magnification in bluefin tuna (Thunnus thynnus) from the Mediterranean Sea.

The bluefin tuna, Thunnus thynnus (Linnaeus 1758), is biologically and economically important in the Atlantic--Mediterranean ecosystems. Bluefin tuna feed on diverse food items depending on their age, thus they occupy different trophic levels during their lifespan. Hexachlorobenzene (HCB), p,p'-DDE and polychlorinated biphenyls (PCBs) are well-known persistent organic pollutants (POPs) in the Mediterranean basin. The relationship between stable isotopes of nitrogen (N) and the POP residue levels in tissues has recently increased knowledge on the link between the trophic levels and the contaminant accumulation. Trophic levels were estimated by using 15N/14N ratio (delta15N) and HCB, p,p'-DDE, and forty-three PCBs were quantified in bluefin tuna from the southern Tyrrhenian Sea. Results showed that changes in PCB and p,p'-DDE concentrations were a function of size and trophic level, while no correlations were observed for HCB. Apart from HCB and PCB nos. 101, 207, 95, 158, and 60 + 56, which did not show any significant increase per trophic level, the other PCBs and the p,p'-DDE increased significantly. The ontogenetic magnification factor of PCBs was 6.6 +/- 0.5, which was significantly (12 times) higher (p < 0.05) than the values found for p,p'-DDE (1.4) and HCB (1.4).