International audience | Seabirds integrate bioaccumulative contaminants via food intake and have revealed geographical trends of contamination in a variety of ecosystems. Pre-fledging seabird chicks are particularly interesting as bioindicators of chemical contamination, because concentrations in their tissues reflect primarily dietary sources from the local environment. Here we measured 14 trace elements and 18 persistent organic pollutants (POPs) in blood of chicks of skuas that breed in four sites encompassing a large latitudinal range within the southern Indian Ocean, from Antarctica (Adélie Land, south polar skua Catharacta maccormicki), through subantarctic areas (Crozet and Kerguelen Islands, brown skua C. lonnbergi), to the subtropics (Amsterdam Island, C. lonnbergi). Stables isotopes of carbon (δ13C, feeding habitat) and nitrogen (δ15N, trophic position) were also measured to control for the influence of feeding habits on contaminant burdens. Concentrations of mercury (Hg) and selenium (Se) were very high at all the four sites, with Amsterdam birds having the highest concentrations ever reported in chicks worldwide (4.0 ± 0.8 and 646 ± 123 µg g-1 dry weight, respectively). Blood Hg concentrations showed a clear latitudinal pattern, increasing from chicks in Antarctica to chicks in the subantarctic and subtropical islands. Interestingly, blood Se concentrations showed similar between-population differences to Hg, suggesting its involvement in protective mechanisms against Hg toxicity. Chicks’ POPs pattern was largely dominated by organochlorine pesticides, in particular DDT metabolites and hexachlorobenzene (HCB). Skua chicks from subantarctic islands presented high concentrations and diversity of POPs. By contrast, chicks from the Antarctic site overall had the lowest concentrations and diversity of both metallic and organic contaminants, with the exception of HCB and arsenic. Skua populations from these sites, being naturally exposed to different quantities of contaminants, are potentially good models for testing toxic effects in developing chicks in the wild.

International audience | To support environmental management programs, there is an urgent need to know about the presence and understand the dynamics of major contaminants in seabird communities of key marine ecosystems. In this study, we investigated the concentrations and trophodynamics of trace elements in six seabird species and persistent organic pollutants (POPs) in three seabird species breeding on Grand Connétable Island (French Guiana), an area where the increase in human population and mining activities has raised concerns in recent years. Red blood cell Hg concentrations in adults were the highest in Magnificent frigatebirds Fregata magnificens (median: 5.6 μg g−1 dw; range: 3.8-7.8 μg g−1 dw) and lowest in Sooty terns Onychoprion fuscatus (median: 0.9 μg g−1 dw; range: 0.6-1.1 μg g−1 dw). Among POPs, dichlorodiphenyldichloroethylene (p,p’-DDE) was the most abundant compound in plasma of Cayenne terns Thalasseus sandvicensis (median: 1100 pg g−1 ww; range: 160±5100 pg g−1 ww), while polychlorinated biphenyls (PCBs) were the most abundant compound class in plasma of Magnificent frigatebirds (median: 640 pg g−1 ww; range 330±2700 pg g−1 ww). While low intensity of POP exposure does not appear to pose a health threat to this seabird community, Hg concentration in several adults Laughing gulls Leucophaeus atricilla and Royal terns Thalasseus maximus, and in all Magnificent frigatebirds was similar or higher than that of high contaminated seabird populations. Furthermore, nestling red blood cells also contained Hg concentrations of concern, and further studies should investigate its potential health impact in this seabird community. Differences in adult trophic ecology of the six species explained interspecific variation in exposure to trace element and POPs, while nestling trophic ecology provides indications about the diverse feeding strategies adopted by the six species, with the consequent variation in exposure to contaminants.

Widespread use of insecticides for the control of urban pests such as ants, termites, and spiders has resulted in contamination and toxicity in urban aquatic ecosystems in different regions of the world. Passive samplers are a convenient and integrative tool for in situ monitoring of trace contaminants in surface water. However, the performance of a passive sampler depends closely on its affinity for the target analytes, making passive samplers highly specific to the types of contaminants being monitored. The goal of this study was to develop a passive sampler compatible with a wide range of insecticides, including the strongly hydrophobic pyrethroids and the weakly hydrophobic fipronil and organophosphates. Of six candidate polymeric thin films, polyurethane film (PU) was identified to be the best at enriching the test compounds. The inclusion of stable isotope labeled analogs as performance reference compounds (PRCs) further allowed the use of PU film for pyrethroids under non-equilibrium conditions. The PU sampler was tested in a large aquarium with circulatory water flow, and also deployed at multiple sites in surface streams in southern California. The concentrations of pesticides derived from the PU sampler ranged from 0.5 to 18.5 ng/L, which were generally lower than the total chemical concentration measured by grab samples, suggesting that suspended particles and dissolved organic matter in water rendered them less available. The influence of suspended particles and dissolved organic matter on bioavailability was more pronounced for pyrethroids than for fipronils. The results show that the developed PU film sampler, when coupled with PRCs, may be used for rapid and sensitive in-situ monitoring of a wide range of insecticides in surface water.

The effects of salinity on metal toxicity are complex: not only affecting metal bioaccumulation, but also altering the physiology and sensitivity of organisms. In this study, we used a toxicokinetic-toxicodynamic (TK-TD) model to separate and quantify the dual effects of salinity on copper (Cu) toxicity in a euryhaline clam Potamocorbula laevis. The toxicokinetics of Cu was determined using the stable isotope 65Cu as a tracer at concentrations (10–500 μg L−1) realistic to contaminated environments and at salinities ranging from 5 to 30. At low Cu concentrations (ca. 10 μg L−1), Cu bioaccumulation decreased monotonically with salinity, and the uptake rate constant (ku, 0.546 L g−1 h−1 to 0.213 L g−1 h−1) fitted well with an empirical equation, ku = 1/(1.35 + 0.116·Salinity), by treating salinity as a pseudo-competitor. The median lethal concentrations (LC50s) of Cu were 269, 224, and 192 μg L−1 at salinity 5, 15, and 30, respectively. At high Cu concentrations (ca. 500 μg L−1), elevating salinity were much less effective in decreasing Cu bioaccumulation; whereas Cu toxicity increased with salinity. The increased toxicity could be explained by the increases in Cu killing rates (kks), which were estimated to be 0.44–2.08 mg μg−1 h−1 and were presumably due to the osmotic stress caused by the deviation from the optimal salinity of the clams. The other toxicodynamic parameter, internal threshold concentration (CIT), ranged from 79 to 133 μg−1 g−1 and showed no clear trend with salinity.

The use of Ni and Cu isotopes for tracing contamination sources in the environment remains a challenging task due to the limited information about the influence of various biogeochemical processes influencing stable isotope fractionation. This work focuses on a relatively simple system in north-east Norway with two possible endmembers (smelter-bedrock) and various environmental samples (snow, soil, lichens, PM10). In general, the whole area is enriched in heavy Ni and Cu isotopes highlighting the impact of the smelting activity. However, the environmental samples exhibit a large range of δ⁶⁰Ni (−0.01 ± 0.03‰ to 1.71 ± 0.02‰) and δ⁶⁵Cu (−0.06 ± 0.06‰ to −3.94 ± 0.3‰) values which exceeds the range of δ⁶⁰Ni and δ⁶⁵Cu values determined in the smelter, i.e. in feeding material and slag (δ⁶⁰Ni from 0.56 ± 0.06‰ to 1.00 ± 0.06‰ and δ⁶⁵Cu from −1.67 ± 0.04‰ to −1.68 ± 0.15‰). The shift toward heavier Ni and Cu δ values was the most significant in organic rich topsoil samples in the case of Ni (δ⁶⁰Ni up to 1.71 ± 0.02‰) and in lichens and snow in the case of Cu (δ⁶⁵Cu up to −0.06 ± 0.06‰ and −0.24 ± 0.04‰, respectively). These data suggest an important biological and biochemical fractionation (microorganisms and/or metal uptake by higher plants, organo-complexation etc.) of Ni and Cu isotopes, which should be quantified separately for each process and taken into account when using the stable isotopes for tracing contamination in the environment.

Understanding the binding characteristics of copper (Cu) to different functional groups in soil dissolved organic matter (DOM) is important to explore Cu toxicity, bioavailability and ultimate fate in the environment. However, the methods used to explore such binding characteristics are still limited. Here, two-dimensional correlation spectroscopy (2DCOS) integrated with Fourier transform infrared (FTIR), 29Si nuclear magnetic resonance (NMR), 27Al NMR, and synchrotron-radiation-based FTIR spectromicroscopy were used to explore the binding characteristics of Cu to soil DOM as part of a long-term (23 years) fertilization experiment. Compared with no fertilization and inorganic fertilization (NPK), long-term pig manure fertilization (M) treatment significantly increased the concentration of total and bioavailable Cu in soils. Furthermore, hetero-spectral 2DCOS analyses demonstrated that the binding characteristics of Cu onto functional groups in soil DOM were modified by fertilization regimes. In the NPK treatment, Cu was bound to aliphatic C, whereas in the manure treatment SiO groups had higher affinity toward Cu than aliphatic C. Also, the sequence of binding of functional groups to Cu was modified by the fertilization treatments. Moreover, synchrotron-radiation-based FTIR spectromicroscopy showed that Cu, clay minerals and sesquioxides, and C functional groups were heterogeneously distributed at the micro-scale. Specifically, clay-OH as well as mineral elements had a distribution pattern similar to Cu, but certain (but not all) C forms showed a distribution pattern inconsistent with that of Cu. The combination of synchrotron radiation spectromicroscopy and 2DCOS is a useful tool in exploring the interactions among heavy metals, minerals and organic components in soils.

Humpback whales, Megaptera novaeangliae, breeding off la Reunion Island (Indian Ocean) undergo large-scale seasonal migrations between summer feeding grounds near Antarctica and their reproductive winter grounds in the Indian Ocean. The main scope of the current study was to investigate chemical exposure of humpback whales breeding in the Indian Ocean by providing the first published data on this breeding stock concerning persistent organic pollutants (POPs), namely polychlorinated biphenyls (PCBs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), DDT and its metabolites (DDTs), chlordane compounds (CHLs), polybrominated diphenyl ethers (PBDEs), and methoxylated PBDEs (MeO-PBDEs). Analyses of stable isotopes δ13C and δ15N in skin resulted in further insight in their feeding ecology, which was in agreement with a diet focused mainly on low trophic level prey species, such as krill from Antarctica. POPs were measured in all humpback whales in the order of HCB > DDTs > CHLs > HCHs > PCBs > PBDEs > MeO-BDEs. HCB (median: 24 ng g−1 lw) and DDTs (median: 7.7 ng g−1 lw) were the predominant compounds in all whale biopsies. Among DDT compounds, p,p′-DDE was the major organohalogenated pollutant, reflecting its long-term accumulation in humpback whales. Significantly lower concentrations of HCB and DDTs were found in females than in males (p < 0.001). Other compounds were similar between the two genders (p > 0.05). Differences in the HCB and DDTs suggested gender-specific transfer of some compounds to the offspring. POP concentrations were lower than previously reported results for humpback whales sampled near the Antarctic Peninsula, suggesting potential influence of their nutritional status and may indicate different exposures of the whales according to their feeding zones. Further investigations are required to assess exposure of southern humpback whales throughout their feeding zones.

Total mercury (T-Hg) and cadmium (Cd) were measured in twenty species of fish to study their bioaccumulation patterns and trophodynamics in the Augusta Bay food web. Adult and juvenile fish were caught in 2012 in Priolo Bay, south of the Augusta harbour (Central Mediterranean Sea), which is known for the high trace element and polycyclic aromatic hydrocarbon contamination level. T-Hg concentration was found to significantly increase along δ15N and from pelagic to benthic sedentary fish, revealing a marked influence of trophic position and habitat use (sensu Harmelin 1987) on T-Hg accumulation within ichthyofauna. Cd showed the opposite pattern, in line with the higher trace element (TE) excretion rates of high trophic level fish and the lower level of Cd environmental contamination.Trophic pathways were first characterised in the Priolo Bay food web using carbon and nitrogen stable isotopes (δ13C, δ15N) and a single main trophic pathway characterised the Priolo Bay food web. Biomagnification was then assessed, including basal sources (surface sediment, macroalgae), zooplankton, benthic invertebrates and fish. T-Hg and Cd were found to biomagnify and biodilute respectively based on the significant linear regressions between log[T-Hg] and log[Cd] vs. δ15N of sources and consumers and the trophic magnification factors (TMFs) of 1.22 and 0.83 respectively. Interestingly, different Cd behaviour was found considering only the benthic pathway which leads to the predatory gastropod Hexaplex trunculus. The positive slope and the higher TMF indicated active biomagnification in this benthic food web due to the high bioaccumulation efficiency of this benthic predator. Our findings provide new evidences about the role of Priolo sediments as a sources of pollutants for the food web, representing a threat to fish and, by domino effect, to humans.

Reservoirs typically have elevated fish mercury (Hg) levels compared to natural lakes and rivers. A unique feature of reservoirs is water-level management which can result in sediment exposure to the air. The objective of this study is to identify how reservoir water-level fluctuations impact Hg cycling, particularly the formation of the more toxic and bioaccumulative methylmercury (MeHg). Total-Hg (THg), MeHg, stable isotope methylation rates and several ancillary parameters were measured in reservoir sediments (including some in porewater and overlying water) that are seasonally and permanently inundated. The results showed that sediment and porewater MeHg concentrations were over 3-times higher in areas experiencing water-level fluctuations compared to permanently inundated sediments. Analysis of the data suggest that the enhanced breakdown of organic matter in sediments experiencing water-level fluctuations has a two-fold effect on stimulating Hg methylation: 1) it increases the partitioning of inorganic Hg from the solid phase into the porewater phase (lower log Kd values) where it is more bioavailable for methylation; and 2) it increases dissolved organic carbon (DOC) in the porewater which can stimulate the microbial community that can methylate Hg. Sulfate concentrations and cycling were enhanced in the seasonally inundated sediments and may have also contributed to increased MeHg production. Overall, our results suggest that reservoir management actions can have an impact on the sediment-porewater characteristics that affect MeHg production. Such findings are also relevant to natural water systems that experience wetting and drying cycles, such as floodplains and ombrotrophic wetlands.

Quantitative identification of nitrate (NO3−-N) sources is critical to the control of nonpoint source nitrogen pollution in an agricultural watershed. Combined with water quality monitoring, we adopted the environmental isotope (δD-H2O, δ18O-H2O, δ15N-NO3−, and δ18O-NO3−) analysis and the Markov Chain Monte Carlo (MCMC) mixing model to determine the proportions of riverine NO3−-N inputs from four potential NO3−-N sources, namely, atmospheric deposition (AD), chemical nitrogen fertilizer (NF), soil nitrogen (SN), and manure and sewage (M&S), in the ChangLe River watershed of eastern China. Results showed that NO3−-N was the main form of nitrogen in this watershed, accounting for approximately 74% of the total nitrogen concentration. A strong hydraulic interaction existed between the surface and groundwater for NO3−-N pollution. The variations of the isotopic composition in NO3−-N suggested that microbial nitrification was the dominant nitrogen transformation process in surface water, whereas significant denitrification was observed in groundwater. MCMC mixing model outputs revealed that M&S was the predominant contributor to riverine NO3−-N pollution (contributing 41.8% on average), followed by SN (34.0%), NF (21.9%), and AD (2.3%) sources. Finally, we constructed an uncertainty index, UI90, to quantitatively characterize the uncertainties inherent in NO3−-N source apportionment and discussed the reasons behind the uncertainties.