Legacy and emerging organic contaminants: Levels and profiles in top predator fish from the western Indian Ocean in relation to their trophic ecology.

Tuna and billfish are large pelagic fish of ecological importance in open oceans. As top predators with a long lifespan, they are prone to exposure to various contaminants such as persistent organic pollutants (POPs) and contaminants of emerging concern. In this study, three pollutant families were investigated, including polychlorinated biphenyls (PCBs), organochlorinated pesticides (OCPs) and perfluoroalkyl substances (PFASs), including perfluorooctane sulfonate (PFOS) and perfluorocarboxylic acids (PFCAs). Contamination was investigated in individuals from three tropical tuna species, namely bigeye (Thunnus obesus), skipjack (Katsuwonus pelamis) and yellowfin (Thunnusalbacares) tunas and the billfish swordfish (Xiphias gladius), collected from various areas of the western Indian Ocean (WIO) in 2013-2014. Contamination levels and profiles were examined in fish muscle, together with biological parameters (fish length / age, sex, lipid content) and ecological tracers (carbon and nitrogen stable isotopes). POP levels were low in all species in comparison to other locations worldwide, revealing a low impact of anthropogenic organic contaminants in the WIO. A predominance of OCPs (especially DDTs) versus PCBs was highlighted in all species; PFASs were predominant over chlorinated POPs in tunas. Among the studied PFASs, long-chain PFCAs were found to prevail over PFOS in all species. Organic contaminant profiles differed across species according to their foraging habitat; swordfish and bigeye tuna, which both feed in deep oceanic layers, showed similarities in their contaminant profiles. Geographically, the distinct DDT profiles of fish from the Mozambique Channel suggested an exposure to different DDT sources, in line with regional use of this insecticide and coupled with an extended residence time of fish in the Channel. To our knowledge, the data presented here are among the first obtained for legacy and emerging organic contaminants in various species of large pelagic predators from the WIO.

Tissue-specific distribution and maternal transfer of polybrominated diphenyl ethers (PBDEs) and their metabolites in adult common sole (Solea solea L.) over an entire reproduction cycle.

Tissue-specific accumulation and distribution of polybrominated diphenyl ethers (PBDEs) and their debrominated metabolites were studied in common sole (Solea solea) over an entire reproduction cycle. The fish were dietary-exposed to selected PBDEs in laboratory-controlled conditions for one year. Fish of both sexes were sampled throughout the reproduction cycle and their muscle, liver, viscera, carcass, skin and gonads (female) were analysed for total lipid content, PBDEs and their debrominated metabolites. On a wet weight basis, the concentrations of most spiked congeners showed an increase at the end of the exposure time in the whole body of fish of both sexes. Conversely, BDE-99 and BDE-209 - the two most highly metabolized congeners - did not show a similar increase, while their debrominated metabolites exhibited a linear increase over time. Biomagnification factors (BMFs) calculated in whole body were > 1 for all PBDEs except BDE-99 (0.89 ± 0.22) and BDE-209 (0.013 ± 0.006). BMFs were strongly correlated to apparent assimilation efficiencies, which ranged from 1.6% ± 0.7% (BDE-209) to 88% ± 11% (BDE-100). Fish carcass was the most predominant storage compartment for all PBDEs except BDE-209 in both male and female fish, followed by skin, muscle, female gonads, liver and visceral tissue. BDE-209 showed a different distribution and was stored more predominantly in the liver, viscera and female gonads than other congeners, probably due to its transport with lipoproteins. All PBDEs except BDE-209 showed equilibrium partitioning between the liver and other studied compartments, while BDE-209 showed a higher affinity with blood-enriched tissues, leading to higher liver / carcass, skin and muscle concentration ratios. Visceral tissue and liver exhibited the most pronounced differences in terms of concentration variations between sexes and over time. In females, both tissues showed a significant decrease in most PBDE concentrations (ww) and TLC in March during the spawning season, with low inter-individual variability, reflecting the striking utilisation of lipids by females for reproduction at this time. In males, no differences were found in concentrations in these compartments over time and a high inter-individual variability was observed. Maternal transfer of PBDEs from gonad to eggs was constant, regardless of spawn rank in the spawning season. Egg / gonad PBDE concentration ratios (in lw) were 1.3 ± 0.7 for all congeners and 2.6 ± 0.3 for BDE-209, suggesting a higher transfer of this congener from gonads to eggs.

Persistent Organic Pollutants in albacore tuna (Thunnus alalunga) from Reunion Island (Southwest Indian Ocean) and South Africa in relation to biological and trophic characteristics.

The contamination of albacore tuna (Thunnus alalunga) by Persistent Organic Pollutants (POPs), namely polychlorinated biphenyls (PCBs) and dichlorodiphenyl-trichloroethane (DDT), was investigated in individuals collected from Reunion Island (RI) and South Africa's (SA) southern coastlines in 2013, in relation to biological parameters and feeding ecology. The results showed lower PCB and DDT concentrations than those previously reported in various tuna species worldwide. A predominance of DDTs over PCBs was revealed, reflecting continuing inputs of DDT. Tuna collected from SA exhibited higher contamination levels than those from RI, related to higher dietary inputs and higher total lipid content. Greater variability in contamination levels and profiles was identified in tuna from RI, explained by a higher diversity of prey and more individualistic foraging behaviour. PCB and DDT contamination levels and profiles varied significantly in tuna from the two investigated areas, probably reflecting exposure to different sources of contamination.

A large diversity of organohalogen contaminants reach the meso- and bathypelagic organisms in the Bay of Biscay (northeast Atlantic).

Deep-sea ecosystems play a key role in the cycling and vertical transfer of matter and energy in oceans. Although the contamination of deep-sea demersal and benthic organisms by persistent organic pollutants has been proven, deep pelagic species have been far less studied. To fill these gaps, we studied the occurrence of a large variety of hydrophobic organic contaminants including polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), legacy and alternative brominated flame retardants (BFRs) and per- and polyfluoroalkyl substances (PFASs) in crustaceans and fish species collected in the Bay of Biscay, northeast Atlantic. The results highlighted the global predominance of PCBs in fish, followed by OCPs, PFASs and PBDEs, with highly variable concentrations among species. Most of the chlorinated or brominated contaminants showed increasing concentrations with increasing δ15N values, while most PFASs showed inverse trends. The contaminant profiles and diagnostic ratios revealed species-specific metabolic capacities and peculiar contribution of highly-brominated BFRs.

Legacy and emerging organic contaminants in two sympatric shark species from Reunion Island (Southwest Indian Ocean): Levels, profiles and maternal transfer.

The contamination of tiger sharks (Galeocerdo cuvier) and bull sharks (Carcharhinus leucas) by legacy persistent organic pollutants (POPs) and emerging organic contaminants was investigated in specimens from Reunion Island (Southwest Indian Ocean) in 2018 and 2019. Contamination levels were determined in the muscle of adult individuals of both sexes in relation to biological and trophic parameters. Maternal transfer was additionally investigated in one set of embryos in each species. Polychlorinated biphenyl (PCB), organochlorinated pesticide (OCP) and perfluoroalkylated substance (PFAS) concentrations were 2597 ± 2969, 785 ± 966 and 267 ± 194 pg g-1 ww, respectively, in bull sharks, and 339 ± 270, 1025 ± 946 and 144 ± 53 pg g-1 ww in tiger sharks. The results highlighted higher PCB contamination, and by the heavier congeners, in adult bull sharks versus tiger sharks. The significant differences found in PCB profiles and concentrations suggest that the two species are exposed to different contamination sources. As bull sharks rely on a more coastal habitat for feeding, their higher contamination by PCBs suggests the occurrence of local PCB sources. DDT concentrations were similar in both species, suggesting a more homogeneous contamination on the scale of the Southwest Indian Ocean. Female bull sharks showed lower OCP and PCB concentrations than males, while this trend was not observed in tiger sharks. The ratio of chlorinated contaminants in muscle between the mother and her embryos was related to molecule hydrophobicity in bull shark but not in tiger shark, suggesting that shark mode of gestation, known to be different in the two species, is a key driver of organic contaminant maternal transfer. Finally, the results show that organic contaminant levels in the studied species were lower than those of other shark species in the Southern Hemisphere, related to the limited urbanization and industrialization of Reunion Island.

Tissue-specific bioaccumulation of a wide range of legacy and emerging persistent organic contaminants in swordfish (Xiphias gladius) from Seychelles, Western Indian Ocean.

Swordfish (Xiphias gladius) is a major marine resource of high economic value to industrial and artisanal fisheries. As a top predator with a long lifespan, it is prone to accumulate high levels of contaminants. The bioaccumulation of a wide range of both legacy and emerging persistent organic contaminants was investigated in the muscle, liver and gonads of swordfish collected from the Seychelles, western Indian Ocean. The detection of all target contaminants, some at frequencies above 80%, highlights their widespread occurrence, albeit at low levels. Mean concentrations in muscle were 5637, 491 and 331 pg g-1 ww for organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and perfluoroalkyl substances (PFASs), respectively. ∑BFR mean concentrations were far below, i.e. 47 pg g-1 ww. The data are among the first obtained for such a high diversity of contaminants in an oceanic top predator worldwide and constitute a benchmark of the contamination of Indian Ocean ecosystems.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in marine mussels from French coasts: levels, patterns and temporal trends from 1981 to 2005.

The levels and temporal trends of toxic polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in archived marine mussels collected between 1981 and 2005 from selected sites along French coasts. The geographical distribution and levels of PCDD/Fs generally reflect regional inputs of these contaminants: the highest concentrations were determined in samples from the Seine river estuary (English Channel) and Toulon area (Mediterranean coast); the lowest levels were determined in Corsica (Mediterranean Sea). PCDD/F isomeric composition showed a fairly homogeneous distribution pattern throughout the various sampling sites. This pattern, dominated by 2,3,7,8-TCDF and OCDD, can be considered as typical for the study species. However, on a more local scale, some differences in isomeric composition in mussels were identified in relation to local source characteristics. The time trend study showed a pronounced decrease in PCDD/F concentrations over the 24-year period at most sites, except Toulon on the Mediterranean Sea, where the decrease was not significant. This overall decrease probably reflects the general drop in PCDD/F emissions in Europe since 1980. However, high concentrations were determined in mussels collected in recent years (1999, 2001 and 2005) from the mouth of the Seine river. These concentrations are related to particular hydrological conditions, and intensive sediment dredging due to a new port construction at the mouth of the estuary. The results presented in this paper provide reference data on the contamination of shellfish by persistent organic pollutants in the marine environment.

Classic and novel brominated flame retardants (BFRs) in common sole (Solea solea L.) from main nursery zones along the French coasts.

Brominated flame retardants (BFRs) were investigated in juvenile common sole from nursery zones situated along the French coast in 2007, 2008 and 2009. Extensive identification was performed with regard to PBDEs, novel BFRs 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE), and other non-PBDE BFRs, namely, hexabromobenzene (HBB) and 2,2',4,4',5,5'-hexabromobiphenyl (BB-153). Polybrominated diphenyl ether (PBDE) concentrations (Σ 14 congeners) ranged from 0.01 ng/g to 0.16 ng/g wet weight (ww) in muscle, and 0.07 ng/g to 2.8 ng/g ww in liver. Concentrations were in the lower range of those reported in the literature in other European locations. Lower PBDE concentrations, condition indices and lipid contents were observed in the Seine estuary in 2009, possibly in relation to a lower water flow. The PBDE patterns and ratios we observed suggested that juvenile sole have a relative high metabolic degradation capacity. Non-PBDE BFRs were detected at lower levels than PBDEs, i.e., within the < method detection limit - 0.005 ng/g ww range in muscle, and < method detection limit - 0.2 ng/g ww range in liver. The data obtained is of particular interest for the future monitoring of these compounds in the environment.

Dietary exposure of juvenile common sole (Solea solea L.) to polybrominated diphenyl ethers (PBDEs): Part 1. Bioaccumulation and elimination kinetics of individual congeners and their debrominated metabolites.

The uptake and elimination of six PBDE congeners (BDE-28, -47, -99, -100, -153, -209) were studied in juvenile common sole (Solea solea L.) exposed to spiked contaminated food over a three-month period, then depurated over a five-month period. The results show that all of the studied PBDEs accumulate in fish tissues, including the higher brominated congener BDE-209. Several additional PBDE congeners were identified in the tissues of exposed fish, revealing PBDE transformation, mainly via debromination. The identified congeners originating from PBDE debromination include BDE-49 and BDE-202 and a series of unidentified tetra-, penta-, and hepta- BDEs. Contaminant assimilation efficiencies (AEs) were related to their hydrophobicity (log Kow) and influenced by PBDE biotransformation. Metabolism via debromination appears to be a major degradation route of PBDEs in juvenile sole in comparison to biotransformation into hydroxylated metabolites.

Dietary exposure of juvenile common sole (Solea solea L.) to polybrominated diphenyl ethers (PBDEs): Part 2. Formation, bioaccumulation and elimination of hydroxylated metabolites.

The uptake, elimination and transformation of six PBDE congeners (BDE-28, -47, -99, -100, -153, -209) were studied in juvenile common sole (Solea solea L.) exposed to spiked contaminated food over a three-month period, and then depurated over a five-month period. Methoxylated (MeO-) and hydroxylated (OH-) PBDEs were determined in fish plasma exposed to PBDEs and compared to those obtained in control fish. While all MeO- and some OH- congeners identified in fish plasma were found to originate from non-metabolic sources, several OH- congeners, i.e., OH-tetraBDEs and OH-pentaBDEs, were found to originate from fish metabolism. Among these, 4'-OH-BDE-49 was identified as a BDE-47 metabolite. Congener 4'-OH-BDE-101, identified here for the first time, may be the result of BDE-99 metabolic transformation. Our results unequivocally showed that PBDEs are metabolised in juvenile sole via the formation of OH- metabolites. However, this was not a major biotransformation route compared to biotransformation through debromination.

PCDD/F and PCB multi-media ambient concentrations, congener patterns and occurrence in a Mediterranean coastal lagoon (Etang de Thau, France).

Ambient concentrations, congener patterns and multi-media distribution of PCDD/Fs and PCBs were determined in air, water, sediment and mussels in a semi-enclosed marine ecosystem (Thau lagoon, France). Sigma2,3,7,8-PCDD/F and sigma7ICES PCB air concentrations (0.2-1.4 and 31-57 pg m(-3), respectively) were typical of rural areas. Concentrations in the water column were very low for PCDD/Fs (163-476 fg L(-1)) and low for PCBs (138-708 pg L(-1)). PCDD/F and PCB concentrations found in surface sediment (0.15-1.6 and 2.5-33 ng g(-1) d.w., respectively) and mussel (13-21 pg g(-1) d.w. and 10-39 ng g(-1) d.w., respectively) were medium levels. PCDD/F congener patterns observed in air, water particulate phase and sediments were similar suggesting direct coupling among these compartments and atmospheric inputs of PCDD/Fs into the lagoon. Conversely, for the same set of samples, similar patterns were not observed for PCBs in the mentioned compartments.