No abstract

Sorption to iron (Fe) minerals determines the fate of the toxic metalloid arsenic (As) in many subsurface environments. Recently, thiolated As species have been shown to dominate aqueous As speciation under a range of environmentally relevant conditions, thus highlighting the need for a quantitative understanding of their sorption behavior. We conducted batch experiments to measure the time-dependent sorption of two S-substituted arsenate species, mono- and tetrathioarsenate, and compared it to the sorption of arsenite and arsenate, in suspensions containing 2-line ferrihydrite, goethite, mackinawite, or pyrite. All four As species strongly sorbed to ferrihydrite. For the other sorbents, binding of the thiolated As species was generally lower compared to arsenate and arsenite, with the exception of the near instantaneous and complete sorption of monothioarsenate to pyrite. Analysis of the X-ray absorption spectroscopy (XAS) spectra of sorbed complexes implied that monothioarsenate binds to Fe oxides as a monodentate, inner-sphere complex. In the presence of Fe sulfides, mono- and tetrathioarsenate were both unstable and partially reduced to arsenite. Adsorption of the thiolated As species to the Fe sulfide minerals also caused the substitution of surface sulfur (S) atoms by As and the formation of As-Fe bonds.

Boreal lakes are impacted by climate change, reduced acid deposition, and changing loads of dissolved organic carbon (DOC) from catchments. We explored, using the process-based lake model MyLake, how changes in these pressures modulate ice phenology and the dissolved oxygen concentrations (DO) of a small boreal humic lake. The model was parametrized against year-round time series of water temperature and DO from a lake buoy. Observed trends in air temperature (+0.045°C yr À1 ) and DOC concentration (0.11 mg C L À1 yr À1 , +1% annually) over the past 40 years were used as model forcings. A backcast of ice freezing and breakup dates revealed that ice breakup occurred on average 8 days earlier in 2014 than in 1974. The earlier ice breakup enhanced water column ventilation resulting in higher DO in the spring. Warmer water in late summer led to longer anoxic periods, as microbial DOC turnover increased. A long-term increase in DOC concentrations caused a decline in lake DO, leading to 15% more hypoxic days (<3 mg L À1 ) and 10% more anoxic days (<15 μg L À1 ) in 2014 than in 1974. We conclude that climate warming and increasing DOC loads are antagonistic with respect to their effect on DO availability. The model suggests that DOC is a stronger driver of DO consumption than temperature. The browning of lakes may thus cause reductions in the oxythermal habitat of fish and aquatic biota in boreal lakes.