Department Water Resources and Drinking Water

The sorption of thallium (Tl) onto manganese (Mn) oxides critically influences its environmental fate and geochemical cycling and is also of interest in water treatment. Combined quantitative and mechanistic understanding of Tl sorption onto Mn oxides, however, is limited. We investigated the uptake of dissolved Tl(I) by environmentally relevant phyllo- and tectomanganates and used X-ray absorption spectroscopy to determine the oxidation state and local coordination of sorbed Tl. We show that extremely strong sorption of Tl onto vacancy-containing layered δ-MnO₂ at low dissolved Tl(I) concentrations (log K_d ≥ 7.4 for ≤10^-8 M Tl(I); K_d in (L/kg)) is due to oxidative uptake of Tl and that less specific nonoxidative Tl uptake only becomes dominant at very high Tl(I) concentrations (>10^-6 M). Partial reduction of δ-MnO₂ induces phase changes that result in inhibited oxidative Tl uptake and lower Tl sorption affinity (log K_d 6.2-6.4 at 10^-8 M Tl(I)) and capacity. Triclinic birnessite, which features no vacancy sites, and todorokite, a 3 × 3 tectomanganate, bind Tl with lower sorption affinity than δ-MnO₂, mainly as hydrated Tl⁺ in interlayers (triclinic birnessite; log K_d 5.5 at 10^-8 M Tl(I)) or tunnels (todorokite). In cryptomelane, a 2 × 2 tectomanganate, dehydrated Tl⁺ replaces structural K⁺. The new quantitative and mechanistic insights from this study contribute to an improved understanding of the uptake of Tl by key Mn oxides and its relevance in natural and engineered systems.

The speciation of highly-diluted elements by X-ray absorption spectroscopy in a diverse range of materials is extremely challenging, especially in biological matrices such as articular cartilage. Here we show that using a high energy resolution fluorescence detected X-ray absorption spectroscopy (HERFD-XAS) technique coupled to an array of crystal analyzers, selenium speciation down to 400 ppb (μg kg^–1) within articular cartilage can be demonstrated. This is a major advance in the speciation of highly-diluted elements through X-ray absorption spectroscopy and opens new possibilities to study the metabolic role of selenium and other elements in biological samples.

Streambed morphology, streamflow dynamics, and the heterogeneity of streambed sediments critically controls the interaction between surface water and groundwater. The present study investigated the impact of different flow regimes on hyporheic exchange in a boreal stream in northern Sweden using experimental and numerical approaches. Low-, base-, and high-flow discharges were simulated by regulating the streamflow upstream in the study area, and temperature was used as the natural tracer to monitor the impact of the different flow discharges on hyporheic exchange fluxes in stretches of stream featuring gaining and losing conditions. A numerical model was developed using geomorphological and hydrological properties of the stream and was then used to perform a detailed analysis of the subsurface water flow. Additionally, the impact of heterogeneity in sediment permeability on hyporheic exchange fluxes was investigated. Both the experimental and modelling results show that temporally increasing flow resulted in a larger (deeper) extent of the hyporheic zone as well as longer hyporheic flow residence times. However, the result of the numerical analysis is strongly controlled by heterogeneity in sediment permeability. In particular, for homogeneous sediments, the fragmentation of upwelling length substantially varies with streamflow dynamics due to the contribution of deeper fluxes.