Description: Total dissolvable iron (TDFe), particulate iron (PFe) and hydrogen peroxide (H2O2 measurements were performed along a N-S transect in the upper 250 m in the Southern Ocean (62°00E/66°42S - 49°00S, ANTARES II cruise, February 1994). TDFe was organically extracted (APDC/DDDC-chloroform) and analysed by Graphite Furnace Atomic Absorption Spectrometry (GFAAS), PFe was analysed by GFAAS following a strong mixed-acid leach, and H2O2 was analysed on board by fluorometry. The respective detection limits are equal to 0.13 nmol/kg, 0.02 nmol/kg, and 3.0 nmol/kg. TDFe concentrations vary from 0.4 to 6.2 nmol/kg and profiles are not completely depleted in the surface. PFe concentrations vary from 0.02 to 0.2 nmol/kg. Iron/carbon (Fe/C) uptake ratios for phytoplankton were calculated either from seawater or particle measurements. They are variable along the transect but are consistent when they could be compared. All the observed ratios are within the range of values proposed for the Fe/C uptake ratios by phytoplankton. Using our uptake ratio calculated in the Permanent Open Ocean Zone (4 x 10**?6 mol/mol), we estimate that the primary production which can be supported by the iron input flux into the surface waters is two times higher than the measured primary production in the same area. In the surface waters, H2O2 concentrations vary from 5.0 to 19.7 nmol/kg. Such low concentrations are due to strong vertical mixing, low dissolved organic matter concentrations and the latitude of the site.

Description: 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.

Description: A multidisciplinary approach is proposed here to compare toxicity mechanisms of methylmercury (MeHg) and inorganic mercury (iHg) in muscle, liver, and brain from zebrafish (Danio rerio). Animals were dietary exposed to (1) 50 ng Hg g–1, 80% as MeHg; (2) diet enriched in MeHg 10000 ng Hg g–1, 95% as MeHg; (3) diet enriched in iHg 10000 ng Hg g–1, 99% as iHg, for two months. Hg species specific bioaccumulation pathways were highlighted, with a preferential bioaccumulation of MeHg in brain and iHg in liver. In the same way, differences in genetic pattern were observed for both Hg species, (an early genetic response (7 days) for both species in the three organs and a late genetic response (62 days) for iHg) and revealed a dissimilar metabolization of both Hg species. Among the 18 studied genes involved in key metabolic pathways of the cell, major genetic responses were observed in muscle. Electron microscopy revealed damage mainly because of MeHg in muscle and also in liver tissue. In brain, high MeHg and iHg concentrations induced metallothionein production. Finally, the importance of the fish origin in ecotoxicological studies, here the seventh descent of a zebrafish line, is discussed.

Description: This study reconstructs the history of multiple industrial and urban mercury (Hg) emissions recorded in the sediment archive of Lake Luitel (France) from AD similar to 1860 to AD 2011. For this purpose, we provide a well constrained short-lived radionuclides continuous age-depth relationship of the sediment sequence (mean accumulation rate of 5.18 +/- 0.28 mm.yr(-1)) with Hg accumulation rates (Hg AR), Hg isotopic composition and extensive historical data. Hg AR were stable around 45 mu g.m(-2).y(-1) from 1860 to WWI and rose to reach their maximum at the end of WWII (250 mu g m(-2) y(-1)) followed by a gradual decreased to reach about 90 mu g m(-2) y(-1) in the current period. Normalization to a terrigenous Hg proxy highlighted the dominance of atmospheric Hg inputs to the lake. The combination of Hg AR with isotopic signatures through the use of binary mixing (Delta Hg-199 vs 1/Hg AR) models and isotopic plots (and comparison to literature data) allowed us to identify the main industrial and urban historical inputs. The major outcome of this study is that the Hg mass independent fractionation (MIF) signature did not enable the identification of particular anthropogenic sources but reflected an integrated pool of industrial and urban emissions which tend to shift to less negative MIF values (mean: -0.15 +/- 0.04%) during their period of maximum emissions. Temporal MIF and Hg AR variations depict the rising Hg emissions from the industrial revolution (1860-1910) to the modern industrial and urban development period (1950-1980). Mass dependent fractionation (MDF) signatures enabled the identification of major contributors in relation to their relative intensities lying between two endmember pools: (i) the combustion activities (smelters, cement factories and urban heating) with more negative delta Hg-202 values, and (ii) the chemical and electrometallurgical activities (electrochemistry, chlor-alkali) with higher delta Hg-202 values. Unconformities of MIF and MDF signatures were observed during WWI, WWII and interwar period, and were attributed to drastic and rapid changes in regional industrial activities. Finally, recent laws regarding Hg emissions (1998-2011) prove their efficiency as Hg AR decreased with a return to more negative MIF and MDF signatures such as during the industrial revolution period. Our study highlights that the combination of Hg isotopic data with Hg AR in sediment archives is a useful tool for reconstructing the history of anthropogenic Hg emissions, and has the potential to identifiy their relative contributions.

Description: Methylmercury is a potent toxin threatening the global population mainly through the consumption of marine fish. Hydrothermal venting directly delivers natural mercury to the ocean, yet its global flux remains poorly constrained. To determine the extent to which anthropogenic inputs have increased oceanic mercury levels, it is crucial to estimate natural mercury levels. Here we combine observations of vent fluids, plume waters, seawater and rock samples to quantify the release of mercury from the Trans-Atlantic Geotraverse hydrothermal vent at the Mid-Atlantic Ridge. The majority (67–95%) of the mercury enriched in the vent fluids (4,966 ± 497 pmol l −1 ) is rapidly diluted to reach background seawater levels (0.80 pmol l −1 ). A small Hg fraction (2.6–10%) is scavenged to the Trans-Atlantic Geotraverse mound rocks. Scaling up our findings and previous work, we propose a mercury flux estimate of 1.5–64.7 t per year from mid-ocean ridges. This hydrothermal flux is small in comparison to anthropogenic inputs. This suggests that most of the mercury present in the ocean must be of anthropogenic origin and that the implementation of emissions reduction measures outlined in the Minamata Convention could effectively reduce mercury levels in the global ocean and subsequently in marine fish.