Julien Barre

Specific Pathways of Dietary Methylmercury and Inorganic Mercury Determined by Mercury Speciation and Isotopic Composition in Zebrafish (Danio rerio).

An original approach is proposed to investigate inorganic (iHg) and methylmercury (MeHg) trophic transfer and fate in a model fish, Danio rerio, by combining natural isotopic fractionation and speciation. Animals were exposed to three different dietary conditions: (1) 50 ng Hg g(-1), 80% as MeHg; (2) diet enriched in MeHg 10,000 ng Hg g(-1), 95% as MeHg, and (3) diet enriched in iHg 10,000 ng Hg g(-1), 99% as iHg. Harvesting was carried out after 0, 7, 25, and 62 days. Time-dependent Hg species distribution and isotopic fractionation in fish organs (muscle, brain, liver) and feces, exhibited different patterns, as a consequence of their dissimilar metabolization. The rapid isotopic re-equilibration to the new MeHg-food source reflects its high bioaccumulation rate. Relevant aspects related to Hg excretion are also described. This study confirms Hg isotopic fractionation as a powerful tool to investigate biological processes, although its deconvolution and fully understanding is still a challenge.

Sources and fate of mercury pollution in Almadén mining district (Spain): Evidences from mercury isotopic compositions in sediments and lichens.

Variations in mercury (Hg) isotopic compositions have been scarcely investigated until now in the Almadén mining district (Spain), which is one of the most impacted Hg areas worldwide. In this work, we explore and compare Hg isotopic signatures in sediments and lichens from Almadén mining district and its surroundings in order to identify and trace Hg aquatic and atmospheric contamination sources. No statistically significant mass independent fractionation was observed in sediments, while negative Δ(201)Hg values from -0.12 to -0.21‰ (2SD = 0.06‰) were found in lichens. A large range of δ(202)Hg values were reported in sediments, from -1.86 ± 0.21‰ in La Serena Reservoir sites far away from the pollution sources to δ(202)Hg values close to zero in sediments directly influenced by Almadén mining district, whereas lichens presented δ(202)Hg values from -1.95 to -0.40‰ (2SD = 0.15‰). A dilution or mixing trend in Hg isotope signatures versus the distance to the mine was found in sediments along the Valdeazogues River-La Serena Reservoir system and in lichens. This suggests that Hg isotope fingerprints in these samples are providing a direct assessment of Hg inputs and exposure from the mining district, and potential information on diffuse atmospheric contamination and/or geochemical alteration processes in less contaminated sites over the entire hydrosystem. This study confirms the applicability of Hg isotope signatures in lichens and sediments as an effective and complementary tool for tracing aquatic and atmospheric Hg contamination sources and a better constraint of the spatial and temporal fate of Hg released by recent or ancient mining activities.

Approach to spatialize local to long-range atmospheric metal input (Cd, Cu, Hg, Pb) in epiphytic lichens over a meso-scale area (Pyrénées-Atlantiques, southwestern France)

Geographically based investigations into atmospheric bio-monitoring usually provide information on concentration or occurrence data and spatial trends of specific contaminants over a specified study area. In this work, an original approach based on geographic information system (GIS) was used to establish metal contents (Hg, Cu, Pb, and Cd) in epiphytic lichens from 90 locations as atmospheric bio-monitors over a meso-scale area (Pyrénées-Atlantiques, southwestern France). This approach allows the integration of the heterogeneity of the territory and optimization of the sampling sites based on both socioeconomical and geophysical parameters (hereafter defined as urban, industrial, agricultural, and forested areas). The sampling strategy was first evaluated in several sites (nu2009=u200915) over different seasons and years in order to follow the temporal variability of the atmospheric metal input in lichens. The results demonstrate that concentration ranges remain constant over different sampling periods in “rural” areas (agricultural and forested). Higher variability is observed in the “anthropized” urban and industrial areas in relation to local atmospheric inputs. In this context, metal concentrations in lichens over the whole study show that (1) Hg and Cd are homogeneous over the whole territory (0.14u2009±u20090.04 and 0.38u2009±u20090.26xa0mg/kg, respectively), whereas (2) Cu and Pb are more concentrated in “anthropized” areas (9.3 and 11.9xa0mg/kg, respectively) than in “rural” ones (6.8 and 6.0xa0mg/kg, respectively) (Kruskall-Wallis, K(Cu)u2009=u200913.7 and K(Pb)u2009=u20099.7, pu2009<u20090.00001). They also showed a significant local enrichment for all metals in many locations in the Pays Basque (West) mainly due to metal and steel industrial activities. This confirms the local contribution of this contamination source over a wider geographic scale. A multiple linear regression model was applied to give an integrated spatialization of the data. This showed significant relationships for Pb and Cu (adjusted r2 of 0.39 and 0.45, respectively), especially with regards to variables such as industry and road densities (source factors) and elevation or water balance (remote factors). These results show that an integrated GIS-based sampling strategy can improve biomonitoring data distribution and allows better differentiation of local and long-range contamination.

Determination of total Hg isotopic composition at ultra-trace levels by on line cold vapor generation and dual gold-amalgamation coupled to MC-ICP-MS

An online pre-concentration method was developed to directly determine Hg isotopic compositions at the ng L−1 level in liquid samples. It is based on the hyphenation of a commercially available cold vapor generation dual gold amalgamation system to a multi-collector ICP-MS. This automated method supports a rapid throughput and consumes less than 100 mL of sample (20–90 mL), representing a decrease of the sample size of more than two orders of magnitude in comparison to existing off-line pre-concentration strategies. The accuracy and the precision were evaluated by the analysis of a secondary standard (UM Almaden) and results for a Hg concentration of 5 ng L−1 were δ202Hg = −0.55 ± 0.26‰ and Δ199Hg = −0.02 ± 0.15‰ (±2SD, n = 14). The method has been compared to the actual reference technique with the analysis of 6 environmental reference materials. Direct on line cold vapor generation and dual gold-amalgamation coupled to MC-ICP-MS demonstrates its relevant applicability for low Hg concentrated environmental samples (undersized biological samples, natural waters).

Mercury Stable Isotopes Discriminate Different Populations of European Seabass and Trace Potential Hg Sources around Europe

Our study reports the first data on mercury (Hg) isotope composition in marine European fish, for seven distinct populations of the European seabass, Dicentrarchus labrax. The use of δ202Hg and Δ199Hg values in SIBER enabled us to estimate Hg isotopic niches, successfully discriminating several populations. Recursive-partitioning analyses demonstrated the relevance of Hg stable isotopes as discriminating tools. Hg isotopic values also provided insight on Hg contamination sources for biota in coastal environment. The overall narrow range of δ202Hg around Europe was suggested to be related to a global atmospheric contamination while δ202Hg at some sites was linked either to background contamination, or with local contamination sources. Δ199Hg was related to Hg levels of fish but we also suggest a relation with ecological conditions. Throughout this study, results from the Black Sea population stood out, displaying a Hg cycling similar to fresh water lakes. Our findings bring out the possibility to use Hg isotopes in order to discriminate distinct populations, to explore the Hg cycle on a large scale (Europe) and to distinguish sites contaminated by global versus local Hg source. The interest of using Hg sable isotopes to investigate the whole European Hg cycle is clearly highlighted.

Mercury Isotopic Fractionation during Pedogenesis in a Tropical Forest Soil Catena (French Guiana): Deciphering the Impact of Historical Gold Mining

We used natural mercury (Hg) stable isotopes to investigate the Hg cycle in a rainforest soil catena (French Guiana) partially gold-mined during the early 1950s. Litterfall showed homogeneous Δ199Hg values [-0.18 ± 0.05‰, i.e., a modern gaseous elemental Hg (GEM) isotopic signature]. After litter decomposition, Hg bound to organic matter (OM) is mixed with Hg from pristine (-0.55 ± 0.22‰) or gold-mined (-0.09 ± 0.16‰) mineral materials. Negative Δ199Hg values in deep pristine mineral horizons (-0.60 ± 0.16‰) suggest the transfer of Hg bound to dissolved OM depleted in odd isotopes due to mass-independent fractionation during Hg abiotic reduction. Perennial palm tree leaves collected above gold-mined and pristine soil recorded contrasting Δ199Hg signatures likely resulting from GEM re-emission processes from soils and leaf surfaces. Upslope, soil δ202Hg signatures showed a negative shift (ε ∼ -1‰) with depth attributed to mass-dependent fractionation during Hg sorption and complexation onto iron oxides and dissolved OM. Downslope, higher δ202Hg values in soils resulted from hydromorphy [lower humification, greater Hg(II) reduction, etc.]. The unique Hg isotopic signatures of Amazonian soils probably result in multistep fractionation processes during pedogenesis (millions of years) and in a potentially different Hg isotopic signature of preanthropogenic background GEM.

Seabird Tissues As Efficient Biomonitoring Tools for Hg Isotopic Investigations: Implications of Using Blood and Feathers from Chicks and Adults

Blood and feathers are the two most targeted avian tissues for environmental biomonitoring studies, with mercury (Hg) concentration in blood and body feathers reflecting short and long-term Hg exposure, respectively. In this work, we investigated how Hg isotopic composition (e.g., δ202Hg and Δ199Hg) of blood and feathers from either seabird chicks (skuas, n = 40) or adults (penguins, n = 62) can accurately provide information on exposure to Hg in marine ecosystems. Our results indicate a strong correlation between blood and feather Hg isotopic values for skua chicks, with similar δ202Hg and Δ199Hg values in the two tissues (mean difference: -0.01 ± 0.25 ‰ and -0.05 ± 0.12 ‰, respectively). Since blood and body feathers of chicks integrate the same temporal window of Hg exposure, this suggests that δ202Hg and Δ199Hg values can be directly compared without any correction factors within and between avian groups. Conversely, penguin adults show higher δ202Hg and Δ199Hg values in feathers than in blood (mean differences: 0.28 ± 0.19‰ and 0.25 ± 0.13‰), most likely due to tissue-specific Hg temporal integration. Since feathers integrate long-term (i.e., the intermoult period) Hg accumulation, whereas blood reflects short-term (i.e., seasonal) Hg exposure in adult birds, the two tissues provide complementary information on trophic ecology at different time scales.

Origins and discrimination between local and regional atmospheric pollution in Haiphong (Vietnam), based on metal(loid) concentrations and lead isotopic ratios in PM 10

Southeast Asia is a hotspot of anthropogenic emissions where episodes of recurrent and prolonged atmospheric pollution can lead to the formation of large haze events, giving rise to wide plumes which spread over adjacent oceans and neighbouring countries. Trace metal concentrations and Pb isotopic ratios in atmospheric particulate matter <u200910xa0μm (PM10) were used to track the origins and the transport pathways of atmospheric pollutants. This approach was used for fortnightly PM10 collections over a complete annual cycle in Haiphong, northern Vietnam. Distinct seasonal patterns were observed for the trace metal concentration in PM10, with a maximum during the Northeast (NE) monsoon and a minimum during the Southeast (SE) monsoon. Some elements (As, Cd, Mn) were found in excess according to the World Health Organization guidelines. Coal combustion was highlighted with enrichment factors of As, Cd, Se, and Sb, but these inputs were outdistanced by other anthropogenic activities. V/Ni and Cu/Sb ratios were found to be markers of oil combustion, while Pb/Cd and Zn/Pb ratios were found to be markers of industrial activities. Pb isotopic composition in PM10 revealed an important contribution of soil dusts (45–60%). In PM10, the Pb fraction due to oil combustion was correlated with dominant airflow pathways (31% during the north-easterlies and 20% during the south-easterlies), and the Pb fraction resulting from industrial emissions was stable (around 28%) throughout the year. During the SE monsoon, Pb inputs were mainly attributed to resuspension of local soil dusts (about 90%), and during the NE monsoon, the increase of Pb inPM10 was due to the mixing of local and regional inputs.

Multi-element isotopic signature (C, N, Pb, Hg) in epiphytic lichens to discriminate atmospheric contamination as a function of land-use characteristics (Pyrénées-Atlantiques, SW France)

Multi-elemental isotopic approach associated with a land-use characteristic sampling strategy may be relevant for conducting biomonitoring studies to determine the spatial extent of atmospheric contamination sources. In this work, we investigated how the combined isotopic signatures in epiphytic lichens of two major metallic pollutants, lead (206Pb/207Pb) and mercury (δ202Hg, Δ199Hg), together with the isotopic composition of nitrogen and carbon (δ15N, δ13C), can be used to better constrain atmospheric contamination inputs. To this end, an intensive and integrated sampling strategy based on land-use characteristics (Geographic information system, GIS) over a meso-scale area (Pyrénées-Atlantiques, SW France) was applied to more than 90 sampling stations. To depict potential relationships between such multi-elemental isotopic fingerprint and land-use characteristics, multivariate analysis was carried out. Combined Pb and Hg isotopic signatures resolved spatially the contribution of background atmospheric inputs from long range transport, from local legacy contamination (i.e. Pb) or actual industrial inputs (i.e. Pb and Hg from steel industry). Application of clustering multivariate analysis to all studied isotopes provided a new assessment of the region in accordance with the land-use characteristics and anthropogenic pressures.