Multi-element effects on arsenate accumulation in a geochemical matrix determined using µ-XRF, µ-XANES and spatial statistics.

Soils regulate the environmental impacts of trace elements, but direct measurements of reaction mechanisms in these complex, multi-component systems can be challenging. The objective of this work was to develop approaches for assessing effects of co-localized geochemical matrix elements on the accumulation and chemical speciation of arsenate applied to a soil matrix. Synchrotron X-ray fluorescence microprobe (mu-XRF) images collected across 100 mu m x 100 mu m and 10 mu m x 10 mu m regions of a naturally weathered soil sand-grain coating before and after treatment with As(V) solution showed strong positive partial correlations (r ' = 0.77 and 0.64, respectively) between accumulated As and soil Fe, with weaker partial correlations (r ' > 0.1) between As and Ca, and As and Zn in the larger image. Spatial and non-spatial regression models revealed a dominant contribution of Fe and minor contributions of Ca and Ti in predicting accumulated As, depending on the size of the sample area analyzed. Time-of-flight secondary ion mass spectrometry analysis of an area of the sand grain showed a significant correlation (r = 0.51) between Fe and Al, so effects of Fe versus Al (hydr)oxides on accumulated As could not be separated. Fitting results from 25 As K-edge microscale X-ray absorption near-edge structure (mu-XANES) spectra collected across a separate 10 mu m x 10 mu m region showed similar to 60% variation in proportions of Fe(III) and Al(III)-bound As(V) standards, and fits to mu-XANES spectra collected across the 100 mu m x 100 mu m region were more variable. Consistent with insights from studies on model systems, the results obtained here indicate a dominance of Fe and possibly Al (hydr)oxides in controlling As(V) accumulation within microsites of the soil matrix analyzed, but the analyses inferred minor augmentation from co-localized Ti, Ca and possibly Zn.