Selenium distribution and speciation in waters of pristine alpine lakes from central-western Pyrenees (France-Spain).

The speciation of both redox reactive and volatile selenium (Se) compounds, barely reported in pristine aquatic environments, has never been investigated in remote alpine lakes, considered as sensitive ecosystems to detect the effect of global change. This work presents an integrated investigation on Se distribution and speciation conducted in 20 high altitude pristine lakes from the central-western Pyrenees. Five seasonal sampling campaigns were carried out after snowmelt (June/July) and in early fall (October) for the period 2017-2019. Concentrations of total dissolved Se (TDSe) ranged from 7 to 78 ng L-1, with selenate being ubiquitously observed in most cases (median of 61% of TDSe). Selenite was only occasionally detected up to 4 ng L-1, therefore a fraction of TDSe was presumably in the forms of elemental Se(0) and/or selenides. Depth profiles obtained in different lakes showed the occurrence of such Se(-II, 0) pools in bottom hypoxic to anoxic waters. The production of volatile Se compounds presented a low median total concentration (TVSe) of 33 pg L-1 (range 3-120 pg L-1), mainly in the form of dimethylselenide in subsurface samples (median of 82% of TVSe). The Se concentration in lake waters was significantly correlated with the sulphate concentration (ρ = 0.93, p < 0.0001), demonstrating that it is influenced by erosion and dissolution of Se and S-enriched parent bedrocks. In addition, for Se depleted alpine lake-bedrock systems, long-range transport and wet atmospheric depositions represent a major source of Se for lake waters.

Characterization of ferruginous cements related with weathering of slag in a temperate anthropogenic beachrock.

This work outlines a temperate latitude beachrock occurrence, which represents the legacy of heavy anthropogenic environmental disturbance. The units contain high amounts of slag and iron-rich wastes derived from metallurgical activities that attest the impact of the past industrial development on such coastal systems. The exposition of the anthropogenic wastes to weathering processes, such as the influence of marine aerosols and the chemical attack of acid gases like the SOx coming from the nearby urban-industrial atmosphere, gave rise to the formation of early diagenetic ferruginous cements. A new analytical methodology based on the combination of micro-Raman spectroscopy (MRS), Raman chemical imaging, SEM-EDS and the Structural and Chemical Analyzer (SCA, an emerging system that hyphenates micro-Raman and SEM-EDS), was applied for the first time to characterize the ferruginous cements. The MRS analyses revealed Fe2+/Fe3+ oxides and oxyhydroxides, CaCO3 polymorphs and less frequently silicates. The Fe mineral species detected were hydrated goethite, hematite, magnetite, magnesioferrite, lepidocrocite and goethite. Complementary Raman imaging, SEM-EDS and SCA analyses unraveled the preferential distribution of hydrated goethite. The identified iron mineral phases are weathering sub-products of hematite commonly derived from atmospheric/aqueous leaching processes triggered by the chemical attack of the acid gases. EDS showed the existence of other elements such as Si, Mg, Cl, Na, Al, K and sporadically S that indicated the importance of permeability, atmospheric deposition and the acid attack. Additionally, calcite and gypsum minerals also evidenced the action of meteoric waters, dry deposition processes or the attack of SOx acid gases. The presence of such compounds is modifying the cement stratigraphy and suggests that the dissolution of carbonates is currently taking place. Those facts influence the erosive susceptibility and the release of the anthropogenic materials trapped originally in the beachrocks, which could act as potential secondary sources of contaminants to the coastal environment.