Inputs, amplification and sinks of perfluoroalkyl substances at coastal Antarctica.

The sources, biogeochemical controls and sinks of perfluoroalkyl substances, such as perfluoroalkyl acids (PFAAs), in polar coastal regions are largely unknown. These were evaluated by measuring a large multi-compartment dataset of PFAAs concentrations at coastal Livingston and Deception Islands (maritime Antarctica) during three austral summers. PFAAs were abundant in atmospheric-derived samples (aerosols, rain, snow), consistent with the importance of atmospheric deposition as an input of PFAAs to Antarctica. Such PFAAs deposition was unequivocally demonstrated by the occurrence of PFAAs in small Antarctic lakes. Several lines of evidence supported the relevant amplification of PFAAs concentrations in surface waters driven by snow scavenging of sea-spray aerosol-bound PFAAs followed by snow-melting. For example, vertical profiles showed higher PFAAs concentrations at lower-salinity surface seawaters, and PFAAs concentrations in snow were significantly higher than in seawater. The higher levels of PFAAs at Deception Island than at Livingston Island are consistent with the semi-enclosed nature of the bay. Concentrations of PFOS decreased from 2014 to 2018, consistent with observations in other oceans. The sink of PFAAs due to the biological pump, transfer to the food web, and losses due to sea-spray aerosols alone are unlikely to have driven the decrease in PFOS concentrations. An exploratory assessment of the potential sinks of PFAAs suggests that microbial degradation of perfluoroalkyl sulfonates should be a research priority for the evaluation of PFAAs persistence in the coming decade.

First evidence of legacy chlorinated POPs bioaccumulation in Antarctic sponges from the Ross sea and the South Shetland Islands.

Antarctica is no longer pristine due to the confirmed presence of anthropogenic contaminants like Persistent Organic Pollutants (POPs). Benthic organisms are poorly represented in contamination studies in Antarctica although they are known to bioaccumulate contaminants. Sponges (Phylum Porifera) are dominant members in Antarctic benthos, both in terms of abundance and biomass, and are an important feeding source for other organisms, playing key functional roles in benthic communities. To the best of our knowledge, legacy chlorinated POPs such as polychlorinated biphenyls (PCBs), hexachlorobenzene (HCB), and dichlorodiphenyltrichloroethane (DDT) and their metabolites have never been investigated in this Phylum in Antarctica. The aim of this work was to evaluate the bioaccumulation of PCBs, HCB, o,p'- and p,p'-DDT and their DDE and DDD isomers in 35 sponge samples, belonging to 17 different species, collected along the coast of Terra Nova Bay (Adèlie Cove and Tethys Bay, Ross Sea), and at Whalers Bay (Deception Island, South Shetland Islands) in Antarctica. Lipid content showed a significant correlation with the three pollutant classes. The overall observed pattern in the three study sites was ΣPCBs>ΣDDTs>HCB and it was found in almost every species. The ΣPCBs, ΣDDTs, and HCB ranged from 54.2 to 133.7 ng/g lipid weight (lw), from 17.5 to 38.6 ng/g lw and from 4.8 to 8.5 ng/g lw, respectively. Sponges showed contamination levels comparable to other Antarctic benthic organisms from previous studies. The comparison among sponges of the same species from different sites showed diverse patterns for PCBs only in one out of four cases. The concentration of POPs did not vary significantly among the three sites. The predominance of lower chlorinated organochlorines in the samples suggested that long-range atmospheric transportation (LRAT) could be the major driver of contamination as molecules with a high long range transport potential (e.g. low chlorinated PCBs, HCB) prevails on heavier ones.

Levels and trends of perfluoroalkyl acids (PFAAs) in water (2013-2020) and fish from selected riverine basins in Spain.

The aim of the present study was to assess the presence of perfluoroalkyl acids (PFAAs), namely perfluoroalkane sulfonates and perfluoroalkyl carboxylic acids, in Spanish river basins in order to: identify potential spatiotemporal variations; evaluate the effectiveness of the measures implemented for the reduction/elimination of these pollutants; verify the fulfillment of the Environmental Quality Standards (EQSs) in the European Union. PFOS and PFOA were determined in 116 water samples from four sites in the Duero basin, the largest in the Iberian Peninsula, collected seasonally from 2013 to 2020. In addition, 30 fish sample composites from the sample banks of Duero, Tagus, Ebro, Eastern Cantabrian and Catalonian basins were analyzed for 15 PFAAs. Median PFOS and PFOA concentrations were 0.72 and 0.42 ng/L, ranging from values below the limit of quantification (LOQ) to 81 and 22 ng/L, respectively. During the studied period, 51% of water samples were above the EQS of 0.65 ng/L for PFOS. In the case of fish, the PFOS range was

Evaluation of PCDD/Fs, PCBs and PBDEs in two penguin species from Antarctica.

Persistent Organic Pollutants (POPs) are a global threat, but impacts of these chemicals upon remote areas such as Antarctica remain unclear. Penguins can be useful species to assess the occurrence of POPs in Antarctic food webs. This work's aim was the evaluation of polychlorodibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in eggs of two penguin species, chinstrap (Pygoscelis antarticus) and gentoo penguins (Pygoscelis papua), breeding in the South Shetland Islands. Results showed a common pattern in POP levels regardless of the species, characterized by a major abundance of PCBs (98 %), followed by PBDEs (1-2%) and PCDD/Fs (<1 %). Concentrations of POPs in chinstrap and gentoo penguin eggs were 482 and 3250 pg/g l.w., respectively. PCBs, PBDEs and PCDD/Fs were found at higher concentrations in chinstrap penguin eggs, being these differences significant for PBDEs. Interspecies differences in POP levels agree well with potential trophic position differences among species due to changes in prey composition and foraging areas. POP profiles were dominated by congeners with a low degree of halogenation. Our results therefore suggest similar sources of POPs in the food webs exploited by both species and in both cases attributable to the long-range transportation rather than to the presence of local sources of POPs. TEQs were found between 1.38 and 7.33 pg/g l.w. and followed the pattern non-ortho dl-PCBs > PCDFs > PCDDs > mono-ortho dl-PCBs. TEQ values were lower than the threshold level for harmful effects in birds of 210 pg/g WHO-TEQ/g l.w.

Legacy and novel flame retardants from indoor dust in Antarctica: Sources and human exposure.

The air humidity in Antarctica is very low and this peculiar weather parameter make the use of flame retardants in research facilities highly needed for safety reasons, as fires are a major risk. Legacy and novel flame retardants (nFRs) including polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), Dechlorane Plus (DP), and other nFRs were measured in indoor dust samples collected at research Stations in Antarctica: Gabriel de Castilla, Spain (GCS), Julio Escudero, Chile (JES), and onboard the RRS James Clark Ross, United Kingdom (RRS JCR). The GC-HRMS and LC-MS-MS analyses of dust samples revealed ∑7PBDEs of 41.5 ± 43.8 ng/g in rooms at GCS, 18.7 ± 11.6 ng/g at JES, and 27.2 ± 37.9 ng/g onboard the RRS JCR. PBDE pattern was different between the sites and most abundant congeners were BDE-183 (40%) at GCS, BDE-99 (50%) at JES, and BDE-153 (37%) onboard the RRS JCR. The ∑(4)HBCDs were 257 ± 407 ng/g, 14.9 ± 14.5 ng/g, and 761 ± 1043 ng/g in indoor dust collected in rooms at GCS, JES, and RRS JCR, respectively. The ∑9nFRs were 224 ± 178 ng/g at GCS, 14.1 ± 13.8 ng/g at JES, and 194 ± 392 ng/g on the RRS JCR. Syn- and anti-DP were detected in most of the samples and both isomers showed the highest concentrations at GCS: 163 ± 93.6 and 48.5 ± 61.1 ng/g, respectively. The laboratory and living room showed the highest concentration of HBCDs, DPs, BTBPE. The wide variations in FR levels in dust from the three research facilities and between differently used rooms reflect the different origin of furnishing, building materials and equipment. The potential health risk associated to a daily exposure via dust ingestion was assessed for selected FRs: BDEs 47, 99, and 153, α-, ß-, and γ-HBCD, BTBPE, syn- and anti-DP. Although the estimated exposures are below the available reference doses, caution is needed given the expected increasing use of novel chemicals without a comprehensive toxicological profile.

Enrichment of perfluoroalkyl substances in the sea-surface microlayer and sea-spray aerosols in the Southern Ocean.

Sea-spray (or sea-salt) aerosol (SSA) formation and their subsequent atmospheric transport and deposition have been suggested to play a prominent role in the occurrence of ionizable perfluoroalkyl substances (PFAS) in the maritime Antarctica and other remote regions. However, field studies on SSA's role as vector of transport of PFAS are lacking. Following a multiphase approach, seawater (SW), the sea-surface microlayer (SML) and SSA were sampled simultaneously at South Bay (Livingston Island, Antarctica). Average PFAS concentrations were 313 pg L-1, 447 pg L-1, and 0.67 pg m-3 in SW, the SML and SSA, respectively. The enrichment factors of PFAS in the SML and SSA ranged between 1.2 and 5, and between 522 and 4690, respectively. This amplification of concentrations in the SML is consistent with the surfactant properties of PFAS, while the large enrichment of PFAS in atmospheric SSA may be facilitated by the large surface area of SSA and the sorption of PFAS to aerosol organic matter. This is the first field work assessing the simultaneous occurrence of PFAS in SW, the SML and SSA. The large measured amplification of concentrations in marine aerosols supports the role of SSA as a relevant vector for long-range atmospheric transport of PFAS.

Microbial responses to perfluoroalkyl substances and perfluorooctanesulfonate (PFOS) desulfurization in the Antarctic marine environment.

Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) acids are ubiquitous in the oceans, including remote regions, and are toxic to fish and mammals. The impact to the lowest trophic levels of the food web, however, remains unknown. We challenged natural bacterial communities inhabiting Antarctic coastal waters (Deception Island) with PFOS and PFOA concentrations ranging from 2 ng/L to 600 ng/L that selected for tolerant taxa. After 48 h, concentrations of PFOS decreased by more than 50% and sulfur metabolism-related transcripts were significantly enriched in the treatments suggesting desulfurization of PFOS. Conversely, no significant differences were found between initial and final PFOA concentrations. Gammaproteobacteria and Roseobacter, two abundant groups of marine bacteria, increased their relative activity after 24 h of incubation, whereas Flavobacteriia became the main contributor in the treatments after 6 days. Community activities (extracellular enzyme activity and absolute number of transcripts) were higher in the treatments than in the controls, while bacterial abundances were lower in the treatments, suggesting a selection of PFOS and PFOA tolerant community in the exposed treatments. Our results show a direct effect of PFOS and PFOA exposure on the composition and functionality of natural Antarctic marine microbial communities. While no evidence of defluorination of PFOS or PFOA was detected, probable desulfurization of PFOS depicts a direct link with the sulfur biogeochemistry of the ocean.

Spatial and Interspecies Heterogeneity in Concentrations of Perfluoroalkyl Substances (PFASs) in Seabirds of the Southern Ocean.

In this study, we evaluate the main factors driving the exposure of Southern Ocean seabirds to perfluoroalkyl substances (PFASs) across a wide geographic range. Five perfluoroalkane sulfonates (PFSAs, C4-12), 10 perfluoroalkyl carboxylic acids (PFCAs, C4-13), and perfluorooctane sulfonamide (FOSA) were analyzed in plasma (n = 128) from eight species, including penguins, giant petrels, skuas, albatrosses, and shearwaters, breeding at four sites in the Antarctic, sub-Antarctic, and adjacent cool-temperate regions. Mean ∑PFAS concentrations ranged from 0.53 to 53 ng/g wet weight from black-browed albatross to giant petrels, respectively. As expected due to biomagnification, greater concentrations of most PFASs were found in species near the top of marine food webs such as giant petrels. However, our results suggest that other factors, i.e., metabolic capabilities and spatial movements, can mask interspecies differences in PFASs, especially PFCAs, expected from trophic structure. For instance, trans-equatorial migratory seabirds exhibited PFAS levels and profiles that are consistent with northern hemisphere exposure, reflecting their potential biovector role in the global transport of these pollutants. Among resident species, greater concentrations of PFASs, especially long-chain PFCAs, were found in seabirds breeding or foraging north of the Antarctic Circumpolar Current (ACC) than in those restricted to Antarctic/sub-Antarctic distributions. Moreover, composition profiles of PFAS in Antarctic seabirds agree well with those expected from long-range transport. Our results confirm the importance of the ACC in protecting Antarctic food webs from water-phase-transported PFASs.

Assessment of POPs in air from Spain using passive sampling from 2008 to 2015. Part II: Spatial and temporal observations of PCDD/Fs and dl-PCBs.

Time series (2008-2015) of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in ambient air from the Spanish Monitoring Program were analyzed. A total of 321 samples were collected seasonally each year in 5 urban and 7 background sites by means of passive air sampling. Air concentrations were higher at urban than background sites (urban vs. background concentration ranges): PCDD/Fs (26.9-1010 vs. 20.0-357 fg/m3), non-ortho PCBs (0.113-3.14 vs. 0.042-2.00 pg/m3) and mono-ortho PCBs (0.644-41.3 vs. 0.500-32.8 pg/m3). Results showed significant decreases from 2009 for non-ortho PCBs and PCDD/Fs as well as for WHO2006-TEQs. These declines were sharper, and sometimes only significant, in urban places resulting in converging levels at urban and background sites for these pollutants at the end of the study period. In contrast, mono-ortho PCBs did not show any significant variation but a steady flat temporal behavior in their concentrations, suggesting the existence of different sources between mono-ortho and non-ortho PCBs. Seasonality was observed for air burdens of all these POPs. PCDD/Fs were mostly measured at higher concentrations in colder than in hot seasons, and the opposite was true for dl-PCBs. Seasonal variations for PCDD/Fs appeared to be related to changes in their sources (e.g. domestic heating, open burning) rather than to temperature per se. In contrast, environmental temperature dependent factors (e.g. increased partitioning into the gas phase) drove seasonal variations in dl-PCBs instead of seasonal changes in their sources. Regarding spatial patterns, significant greater levels of PCDD/Fs and dl-PCBs were generally found in cities compared to background areas, pointing out the role of densely populated areas as sources for these pollutants in Spain. As proven by our results, long-term monitoring activities are essential to assess and understand temporal behaviors for these POPs, as well as to evaluate the achievement of Stockholm Convention objectives.

Assessment of POPs in air from Spain using passive sampling from 2008 to 2015. Part I: Spatial and temporal observations of PBDEs.

The Stockholm Convention (SC) on Persistent Organic Pollutants (POPs) calls for the Parties' effectiveness evaluation of those measures taken to meet the reduction and eventual elimination of POPs from the environment. With that goal, air concentrations of different POP families have been measured uninterruptedly since 2008 under the Spanish Monitoring Program (SMP) by means of passive air sampling. This work focuses on data for polybrominated diphenyl ethers (PBDEs) determined in a total of 321 samples collected seasonally each year in 5 urban and 7 background sites. Neither significant temporal trends nor significant seasonal variations for total PBDE air burdens were detected. In contrast, significant variations were found among PBDE congeners. Those related to the octa-PBDE formulation significantly decreased in the study period. However, PBDEs related to the penta-formulation showed steady concentrations while PBDE-209, the congener found at the greatest levels, showed increasing or steady levels in most sampling sites. Seasonal variations were also markedly different among congeners. Concentrations of the lightest PBDEs (tri- to penta-substituted) were highly influenced by ambient temperature (T), showing maximum values in summer probably due to higher volatilization rates compared to those of heavier PBDEs. Contrarily, no clear seasonal trends were found for hexa- to deca-PBDEs, which were negatively related to precipitation; thereby, indicating an efficient atmospheric wash out by wet deposition episodes. Regarding spatial patterns, overall significant greater PBDE levels were found in cities compared to background areas, pointing out the role of highly populated areas as sources for these pollutants in Spain. Yet and especially in the case of PBDE-209, our results suggested the presence of significant unknown sources of PBDEs in some background sites. Further monitoring efforts are needed to assess potential unknown sources in the sampling network as well as to ensure temporal trends of these pollutants in Spain.

Miniaturised sample preparation method for the multiresidual determination of regulated organohalogenated pollutants and related compounds in wild bird eggs.

A simplified, miniaturised matrix solid-phase dispersion (MSPD)-based method allowing the simultaneous extraction and purification of contaminants belonging to selected families of regulated persistent organic pollutants (POPs), i.e. polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and penta- to octa-polybrominated diphenyl ethers (PBDEs), and related contaminants of emerging concern, such as deca-BDE and Dechlorane Plus (DP), has been proposed. Wild bird eggs were used as biotic fat-containing model matrices. Once optimised, the procedure allowed sample preparation to be accomplished within 30 min, in a single step, and with minimal sample and reagent consumption and waste generation. These features contributed to speeding up and greening the analytical process as compared to the large-scale multistep procedures for these types of analyses. The method was combined with gas chromatography-quadrupole mass spectrometry (GC-qMS) for PCB and OCP analysis and with GC-negative ion chemical ionisation-quadrupole mass spectrometry (NCI-qMS) for PBDE and DP determination. The complete analytical method provided satisfactory recoveries of the target compounds (above 83% for all analytes, except for PBDE 209, 63%), although as small an amount of sample as 0.300 g was used. The repeatability of the complete procedure was less than 16% (with the only exception for PCB 153, which looked to be affected by an interference). The limits of detection were in all cases lower than 34 pg g-1 dry weight (as calculated for real samples), demonstrating the feasibility of the proposed procedure for accurate determination of the target compounds in biological samples. The proposed procedure was applied to the analysis of the target POPs in unhatched eggs of wild bird species. Graphical abstract Scheme of the miniaturised methodology proposed for environmental monitoring of POPs and related compounds in wild bird eggs.

Relationship between legacy and emerging organic pollutants in Antarctic seabirds and their foraging ecology as shown by δ13C and δ15N.

Foraging ecology and the marine regions exploited by Antarctic seabirds outside of breeding strongly influence their exposure to persistent organic pollutants (POPs). However, relationships between them are largely unknown, an important knowledge gap given that many species are capital breeders and POPs may be deleterious to seabirds. This study investigates the relationship between Antarctic seabird foraging ecology (measured by δ13C and δ15N) and POPs accumulated in their eggs prior to breeding. Organochlorinated pesticides, polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and dechlorane plus (DP) were measured in eggs of chinstrap, Adélie, and gentoo penguins (Pygoscelis antarctica, P. adeliae, P. papua), as well as south polar skua (Catharacta maccormicki), sampled on King George Island. Total POP levels were as follows: skua (3210±3330ng/g lipid weight)>chinstrap (338±128ng/g)>Adélie (287±43.3ng/g)>gentoo (252±49.4ng/g). Trophic position and pre-breeding foraging sites were important in explaining POP accumulation patterns across species. The most recalcitrant compounds were preferentially accumulated in skuas, occupying one trophic level above penguins. In contrast, their Antarctic endemism, coupled with influence from cold condensation of pollutants, likely contributed to penguins exhibiting higher concentrations of more volatile compounds (e.g., hexachlorobenzene, PCB-28 and -52) than skuas. Regional differences in penguin pre-breeding foraging areas did not significantly affect their POP burdens, whereas the trans-equatorial migration and foraging sites of skuas were strongly reflected in their pollutant profiles, especially for PBDEs and DPs. Overall, our results provide new insights on migratory birds as biovectors of POPs, including non-globally regulated compounds such as DP, from northern regions to Antarctica.

Latitudinal exposure to DDTs, HCB, PCBs, PBDEs and DP in giant petrels (Macronectes spp.) across the Southern Ocean.

Studies on Persistent Organic Pollutants (POPs) in Antarctic wildlife are scarce, and usually limited to a single locality. As a result, wildlife exposure to POPs across the Southern Ocean is poorly understood. In this study, we report the differential exposure of the major southern ocean scavengers, the giant petrels, to POPs across a wide latitudinal gradient. Selected POPs (PCBs, HCB, DDTs, PBDEs) and related compounds, such as Dechlorane Plus (DP), were analyzed in plasma of southern giant petrels (Macronectes giganteus) breeding on Livingston (62°S 61°W, Antarctica), Marion (46°S 37°E, sub-Antarctic), and Gough (40°S 10°W, cool temperate) islands. Northern giant petrels (Macronectes halli) from Marion Island were also studied. Stable isotope ratios of C and N (δ(13)C and δ(15)N) were used as dietary tracers of the marine habitat and trophic level, respectively. Breeding locality was a major factor explaining petrel exposure to POPs compared with species and sex. Significant relationships between δ(13)C values and POP burdens, at both inter- and intra-population levels, support latitudinal variations in feeding grounds as a key factor in explaining petrel pollutant burdens. Overall, pollutant levels in giant petrels decreased significantly with latitude, but the relative abundance (%) of the more volatile POPs increased towards Antarctica. DP was found at negligible levels compared with legacy POPs in Antarctic seabirds. Spatial POP patterns found in giant petrels match those predicted by global distribution models, and reinforce the hypothesis of atmospheric long-range transport as the main source of POPs in Antarctica. Our results confirm that wildlife movements out of the polar region markedly increase their exposure to POPs. Therefore, strategies for Antarctic wildlife conservation should consider spatial heterogeneity in exposure to marine pollution. Of particular relevance is the need to clarify the exposure of Antarctic predators to emerging contaminants that are not yet globally regulated.

Towards the implementation of the Stockholm Convention in Spain: Five-year monitoring (2008-2013) of POPs in air based on passive sampling.

Within the framework of the Spanish monitoring program, this study reports on air concentration of DDTs, HCB, HCHs, NDL-PCBs, DL-PCBs, PCDD/Fs and PBDEs measured during the five-year sampling period 2008-2013. Spanish coastal remote and urban locations were studied using PUF disk passive air samplers which were deployed and collected every three months. Despite the wide range of concentrations measured for most contaminants, a common pattern of relative abundance (median values): NDL-PCBs (36.6 pg/m(3)) > HCB (24.8 pg/m(3)) ≈ HCHs (17.9 pg/m(3)) ≈ DDTs (16.6 pg/m(3)) > PBDEs (3.65 pg/m(3)) > DL-PCBs (2.99 pg/m(3)) >> PCDD/Fs (0.060 pg/m(3)) was found fairly consistent across most seasons and locations. Nevertheless, important variations in yearly concentrations were measured for different POPs. In general, higher levels of DDTs, HCHs, NDL-PCBs, DL-PCBs and PCDD/Fs were found in urban sites highlighting important differences between remote and urban sampling locations for most target contaminants. Greater concentrations of the banned organochlorine pesticides in urban locations suggested the existence of unexpected pointed sources that need to be further investigated and characterized. The limited dataset collected thus far rendered no clear temporal trends for most study target compounds, which emphasizes the necessity of the Spanish monitoring program future maintenance in time.

Influence of trophic ecology on the accumulation of dioxins and furans (PCDD/Fs), non-ortho polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in Mediterranean gulls (Larus michahellis and L. audouinii): A three-isotope approach.

The impact of pollution caused by severe anthropogenic pressure in the Mediterranean Sea, an important biodiversity hotspot, requires continuous research efforts. Sources of highly toxic chemicals such as Persistent Organic Pollutants (POPs) are misunderstood in representative Mediterranean species, which limits our capability to establish proper conservation strategies. In the present study, eggs of Audouin's and yellow-legged gulls (Larus audouinii and L. michahellis) were used to investigate the trophic sources, as measured by δ(13)C, δ(15)N, and δ(34)S, of legacy POPs, in particular, polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and non-ortho polychlorinated biphenyls (no-PCBs), as well as recently-regulated POPs, e.g., polybrominated diphenyl ethers (PBDEs). Special attention was paid to the usefulness of rarely-explored δ(34)S ratios in explaining POP exposure in wildlife, and δ(34)S was the isotopic ratio that best explained POP variations among gulls in most cases, thus demonstrating its usefulness for understanding POP exposure in wildlife. Significant relationships between stable isotope signatures and POP concentrations revealed increasing levels of no-PCBs and low halogenated PCDD/Fs and PBDEs in Mediterranean gulls as the consumption of marine resources increases. In contrast, highly chlorinated and brominated congeners appeared to preferentially accumulate in gulls feeding primarily on refuse from dump sites and terrestrial food webs. The use of suitable dietary tracers in the study of POPs in yellow-legged gulls revealed the importance of dump sites as a source of POPs in Mediterranean seabirds, which has not previously been reported. In contrast, the preferential accumulation through marine food webs of low chlorinated PCCD/Fs and no-PCBs, which show the highest toxic equivalents factors (TEFs), led to a significantly greater toxicological concern in Audouin's as compared to yellow-legged gulls. Audouin's gull exposure to POPs appears primarily related to the pelagic food webs commonly exploited by fisheries, highlighting the need for further research given the potential impact on human consumption.

Perfluoroalkylated substances in the global tropical and subtropical surface oceans.

In this study, perfluoroalkylated substances (PFASs) were analyzed in 92 surface seawater samples taken during the Malaspina 2010 expedition which covered all the tropical and subtropical Atlantic, Pacific and Indian oceans. Nine ionic PFASs including C6-C10 perfluoroalkyl carboxylic acids (PFCAs), C4 and C6-C8 perfluoroalkyl sulfonic acids (PFSAs) and two neutral precursors perfluoroalkyl sulfonamides (PFASAs), were identified and quantified. The Atlantic Ocean presented the broader range in concentrations of total PFASs (131-10900 pg/L, median 645 pg/L, n = 45) compared to the other oceanic basins, probably due to a better spatial coverage. Total concentrations in the Pacific ranged from 344 to 2500 pg/L (median = 527 pg/L, n = 27) and in the Indian Ocean from 176 to 1976 pg/L (median = 329, n = 18). Perfluorooctanesulfonic acid (PFOS) was the most abundant compound, accounting for 33% of the total PFASs globally, followed by perfluorodecanoic acid (PFDA, 22%) and perfluorohexanoic acid (PFHxA, 12%), being the rest of the individual congeners under 10% of total PFASs, even for perfluorooctane carboxylic acid (PFOA, 6%). PFASAs accounted for less than 1% of the total PFASs concentration. This study reports the ubiquitous occurrence of PFCAs, PFSAs, and PFASAs in the global ocean, being the first attempt, to our knowledge, to show a comprehensive assessment in surface water samples collected in a single oceanic expedition covering tropical and subtropical oceans. The potential factors affecting their distribution patterns were assessed including the distance to coastal regions, oceanic subtropical gyres, currents and biogeochemical processes. Field evidence of biogeochemical controls on the occurrence of PFASs was tentatively assessed considering environmental variables (solar radiation, temperature, chlorophyll a concentrations among others), and these showed significant correlations with some PFASs, but explaining small to moderate percentages of variability. This suggests that a number of physical and biogeochemical processes collectively drive the oceanic occurrence and fate of PFASs in a complex manner.

Geographic and trophic patterns of OCs in pelagic seabirds from the NE Atlantic and the Mediterranean: a multi-species/multi-locality approach.

Trophic ecology and geographic location are crucial factors explaining OC levels in marine vertebrates, but these factors are often difficult to disentangle. To examine their relative influence, we analyzed PCBs, DDTs and stable-nitrogen isotope signatures (δ15N) in the blood of 10 pelagic seabird species across 7 breeding localities from the northeast Atlantic and western Mediterranean. Large scale geographic patterns emerged due to the confined character and greater historical OC inputs in the Mediterranean compared to the Atlantic basin. Spatial patterns also emerged at the regional scale within the Atlantic basin, probably associated with long-range pollutant transport. Trophic ecology, however, was also a major factor explaining OC levels. We found clear and consistent OC differences among species regardless of the sampled locality. However, species δ15N and blood OC levels were not correlated within most breeding localities. Petrel species showed significantly greater OC burdens than most shearwater species but similar trophic positions, as indicated by their similar δ15N signatures. This pattern probably results from Petrel species feeding on mesopelagic fish and squid that migrate close to the sea surface at night, whereas shearwater species mainly feed on epipelagic diurnal prey. In sum, this study illustrates the lasting and unequal influence of past human activities such as PCB and DDT usage across different marine regions. In addition, our results suggest that multi-species designs are powerful tools to monitor geographic patterns of OCs and potentially useful to assess their vertical dynamics in the marine environment.

Interspecies and spatial trends in polycyclic aromatic hydrocarbons (PAHs) in Atlantic and Mediterranean pelagic seabirds.

PAHs were analyzed in the liver of 5 species of pelagic seabirds (Procellariiformes) from the northeast Atlantic and the Mediterranean. The main objective was to assess the trophic and geographic trends of PAHs in seabirds to evaluate their suitability as bioindicators of chronic marine pollution by these compounds. Although higher levels of PAHs have been described in the Mediterranean compared to other oceanic regions, we did not find significant spatial patterns and observed only minor effects of the geographic origin on seabird PAHs. However, we found significant higher PAH levels in petrel compared to shearwater species, which could be related to differences in their exploitation of mesopelagic and epipelagic resources, respectively, and the vertical dynamic of PAHs in the water column. Overall, although this study enhances the need of multi-species approaches to show a more comprehensive evaluation of marine pollution, seabirds emerged as poor indicators of pelagic chronic PAH levels.

Geographical PCB and DDT patterns in shearwaters (Calonectris sp.) breeding across the NE Atlantic and the Mediterranean archipelagos.

Although seabirds have been proposed as useful biomonitors for organochlorine contaminants (OCs) in marine environments, their suitability is still unclear. To understand the geographic variability and the influence of seabird trophic ecology in OC levels, we analyzed PCBs, DDTs, delta(13)C, and delta(15)N in the blood of adult Calonectris shearwaters throughout a vast geographic range within the northeast Atlantic Ocean (from Cape Verde to Azores) and the Mediterranean Sea (from the Alboran Sea to Crete). OC concentrations were greater in birds from the Mediterranean than in those from the Atlantic colonies, showing higher and lower chlorinated PCB profiles, respectively. This large-scale pattern may reflect the influence of historical European runoffs in the Mediterranean basin and diffused sources for OCs in remote Atlantic islands. Spatial patterns also emerged within the Atlantic basin, probably associated with pollutant long-range transport and recent inputs of DDT in the food webs of shearwaters from Cape Verde and the Canary islands. Moreover, a positive association of OC concentrations with delta(15)N within each locality points out diet specialization as a major factor explaining differences in OCs at the intraspecific level. Overall, this study highlights wide range breeding seabirds, such as Calonectris shearwaters, as suitable organisms for biomonitoring large geographic trends of organochlorine contamination in the marine environment.