Ellen M. Moon

Arsenic Mobilization Is Enhanced by Thermal Transformation of Schwertmannite

Fires in iron-rich seasonal wetlands can thermally transform Fe(III) minerals and alter their crystallinity. However, the fate of As associated with thermally transformed Fe(III) minerals is unclear, as are the consequences for As mobilization during subsequent reflooding and reductive cycles. Here, we subject As(V)-coprecipitated schwertmannite to thermal transformation (200, 400, 600 and 800 °C) followed by biotic reductive incubation (150 d) and examine aqueous- and solid-phase speciation of As, Fe and S. Heating to >400 °C caused transformation of schwertmannite to a nanocrystalline hematite with greater surface area and smaller particle size. Higher temperatures also caused the initially structurally incorporated As to become progressively more exchangeable, increasing surface-complexed As (AsEx) by up to 60-fold, thereby triggering enhanced As mobilization during incubation (∼70-fold in the 800 °C treatment). Although more As was mobilized in biotic treatments than controls (∼3-20×), in both cases it was directly proportional to initial AsEx and mainly due to abiotic desorption. Higher transformation temperatures also drove divergent pathways of Fe and S biomineralization and led to more As(V) and SO4 reduction relative to Fe(III) reduction. This study reveals thermal transformation of schwertmannite can greatly increase As mobility and has major consequences for As/Fe/S speciation under reducing conditions. Further research is warranted to unravel the wider implications for water quality in natural wetlands.

Dissolution and redistribution of trace elements and nutrients during dredging of iron monosulfide enriched sediments

The increased use of estuarine waters for commercial and recreational activities is one consequence of urbanisation. Western Australias Peel-Harvey Estuary highlights the impacts of urbanisation, with a rapidly developing boating industry and periodic dredging activity. The aim of this research is to evaluate the potential mobility of nutrients and trace elements during dredging, and the influence of flocculation on iron and sulfur partitioning in iron monosulfide enriched sediments. Our findings indicate a short-term increase in nitrate, phosphate and ammonium, during dredging through the resuspension of sediments. However, no increase in metal mobilisation during dredging was observed except copper (Cu) and zinc (Zn). Flocculant addition increased the release of nutrients, zinc (Zn) and arsenic (As) from sediments, had no effect on acid volatile sulfides and pyritic sulfur, but corresponded with an initial sharp rise in elemental sulfur concentrations. The run-off water from geofabric bags should be treated to decrease the concentrations of Zn and As to their background levels before releases into the estuary. Long-term impact of dredging on organic matter mineralisation and its subsequent effect on nutrients and trace elements dynamics needs further investigation.