Total mercury and methylmercury in high altitude surface snow from the French Alps

Surface snow samples were collected weekly from the 31st of December 2008 to the 21st of June 2009 from Lake Bramant in the French Alps. Total mercury (THg), total dissolved mercury (THgD), methylmercury (MeHg) and particle distributions in surface snow were analyzed. Results showed that THg concentrations, MeHg concentrations and particle load increased with snow surface temperature, which is an indicator of rising temperatures as the season progresses. Significant correlations between MeHg and snow surface temperature and MeHg and total particles greater than 10 μm were observed. This suggests that the MeHg found in the snow originates from atmospheric deposition processes rather than in situ snowpack sources. This study suggests that an important post-winter atmospheric deposition of MeHg and THg occurs on summital zones of the French Alps and it is likely that this contamination originates from the surrounding valleys.     

Mercury distribution in fish organs and food regimes: Significant relationships from twelve species collected in French Guiana (Amazonian basin)

Within a multidisciplinary research programme set up in French Guiana (Amazonian basin), twelve fish species from six food regimes were collected from the upper part of the Maroni River in order to analyze mercury (Hg) distribution in six organs (gills, liver, kidneys, skeletal muscle, stomach, and intestine) and to look for a relationship between Hg organotropism and food regimes. As many studies have shown, mercury biomagnification leads to extremely marked differences in muscle accumulation levels: the average ratio between extreme concentrations measured in piscivorous and herbivorous species was almost 500. A first principal component analysis on primary Hg concentration variables showed that biomagnification had a marked effect, masking differences between Hg distribution in the organs according to fish species and their food regimes. In order to avoid this, we determined ratios between Hg concentrations measured in the different organs and in the skeletal muscle, considered as the reference tissue for biomagnification effects. A new principal component analysis using these normalized values, in conjunction with a Ward's hierarchical clustering method, revealed that there is a link between Hg organotropism and the food regimes, with comparatively high [Hg]gills/[Hg]muscle ratios for the herbivorous species; high [Hg]intestine-liver-kidneys/[Hg]muscle ratios for the benthivorous and periphytophagous species, and, in contrast, ratios of less than 1 in the different organs for the piscivorous and omnivorous species. Our determinations of methylmercury (MMHg) percentages in the food consumed by the fish (aquatic macrophytes, terrestrial material from the river banks, biofilms, benthic invertebrates, fish muscle tissues), according to the different food regimes (herbivorous, periphytophagous, benthivorous, omnivorous, carnivorous, piscivorous), showed that this criterion can account for the differences in Hg distribution in the fish organs. For instance, the periphytophagous and benthivorous fish species ingest biofilms and small benthic invertebrates with quite low MMHg burdens (18% and 35 to 52% of Hgtotal, respectively). The highest [Hg]organs/[Hg]muscle ratios were observed for the liver and kidneys, the two principal target organs for inorganic Hg in fish. On the other hand, the piscivorous species ingest a large amount of fish of varying size, with high MMHg percentages in their muscle tissue (nearly 80%); Hg organotropism is characterized by high MMHg concentrations in the skeletal muscle and comparatively low [Hg]organs/[Hg]muscle ratios.     

Atmospheric inputs of Ag and Tl to the Arctic: comparison of a high resolution snow pit (AD 1994-2004) with a firn (AD 1860-1996) and an ice core (previous 16,000 yr)

Applying strict clean room techniques and sector field ICP-MS, a total of 567 ice and snow samples from Devon Ice Cap, Arctic Canada, have been analysed for silver (Ag) and thallium (Tl), providing a continuous record of atmospheric deposition of both elements for the past approximately 16,000 yr. Concentrations of Ag and Tl ranged from 0.02 to 5.84 pg/g and from 0.03 to 3.40 pg/g, respectively. The natural Tl/Sc background ratio established with ice samples dating between 10,590 and 15,010 yr BP, amounted to 0.11+/-0.03 which is in good agreement with the corresponding value of 0.107 reported for the Upper Continental Crust (UCC). The Ag/Sc background ratio in ice (0.09+/-0.06), in turn, is much more variable and approximately 10-times higher than UCC values. The high temporal resolution provided by 45 samples from the 5 m snow pit representing the period AD 1994 to 2004, revealed the greatest elemental concentrations as well as accumulation rates during the winter months when air masses reach the Arctic predominantly from Eurasia. The greatest Sc concentrations, however, are also found during winter months which clearly reflect strong seasonal variations in atmospheric dust inputs. Enrichment factors calculated for both elements (Ag, Tl) using Sc show contrasting behaviours, with the maximum EF for Tl (up to 48) during summer when air masses arriving to the Arctic are predominantly from North America, probably reflecting coal burning, base metal mining and smelting. The greatest enrichments of Ag (up to 17), on the other hand, tend generally to be found in winter, although some enrichment maxima corresponding to summer months are also seen. While modern Ag EF are comparable to those corresponding to ancient (back to ca. 3 k yr) anthropogenic activities, modern Tl EF clearly exceed the impact of Medieval, Roman and Greek/Phoenician civilization. Accumulation rates during the past decade have been variable (mean 36 and 130 ng/m(2)/yr for Ag and Tl, respectively), but the trend is clearly in decline. Based on the best estimate of natural inputs, more than 80% of the Ag and 90% of the Tl supplied to the Arctic today (AD 1994-2004) are derived from anthropogenic sources.     

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.     

Long-term changes of mercury levels in ringed seal (Phoca hispida) from Amundsen Gulf, and beluga (Delphinapterus leucas) from the Beaufort Sea, western Canadian Arctic

Mercury (Hg) concentrations were determined in the canine teeth of ringed seals (Phoca hispida) harvested during the 13th–14th, late 19th and early 21st Centuries in Amundsen Gulf, Northwest Territories, Canada. Most historical and pre-industrial teeth contained undetectable Hg levels (i.e. < 1.0 ng/g DW), whereas samples from 2001–03 contained up to 12 ng/g DW in an age-dependent pattern. Assuming a median [Hg] value in 13th–14th Century teeth of half the detection limit (i.e. 0.5 ng/g DW), geometric means of Hg in modern teeth were 9–17 times those of seals in the 14th Century, equivalent to an anthropogenic input of 89–94% of total Hg in modern seals. These results corroborate a previous study of beluga (Delphinapterus leucas) in the nearby Beaufort Sea. While the seals' trophic position (inferred from δ¹⁵N values) did not change over time, modern δ¹³C values were lower by about 2‰ than in the 14th and 19th Centuries. This could be due to increased dissolution of anthropogenically derived CO₂ in the ocean from the atmosphere, but could also indicate more offshore pelagic feeding by modern seals, which might be a factor in their Hg exposure. New tooth [Hg] data are also presented for the Beaufort Sea beluga, using recently-discovered museum samples collected in 1960/61, which showed that most of the anthropogenic contribution to beluga Hg had already taken effect by 1960 (reaching  75% of total Hg). Taken together, the long-term seal and beluga data indicate that whereas Hg levels in the marine ecosystems of the western Canadian Arctic were probably unchanged from pre-industrial times up to the late 19th Century, there was a significant, many-fold increase in the early to mid-20th Century, but little or no change after about the early 1960s.     

Mass balance for polycyclic aromatic hydrocarbons in the urban watershed of Le Havre (France): transport and fate of PAHs from the atmosphere to the outlet

Polycyclic aromatic hydrocarbon (PAH) concentrations have been monitored simultaneously in ambient air, bulk atmospheric deposition and runoff waters during one year in a small urban watershed of the Seine river basin (France). PAH fluxes from the atmosphere to the outlet of the urban watershed have been calculated to establish a mass balance for PAHs. PAH flux in runoff waters was 5.2 kg km(-2) yr(-1) while PAH atmospheric deposition was 0.21 kg km(-2) yr(-1). The comparison between atmospheric input and output by runoff has shown the importance of street deposits that appeared to be the most important source of PAHs for surface waters in urban areas. PAH profiles in the various compartments showed the fate of PAHs in the air-water system: proportion of carcinogenic PAHs was more important in runoff waters (35%) than in bulk atmospheric deposition (22%) and air (6%).