Arsenate Adsorption Structures on Aluminum Oxide and Phyllosilicate Mineral Surfaces in Smelter-Impacted Soils

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Abstract
A clearer understanding of arsenic (As) retention and transport in forest soils impacted by copper smelter emissions may reduce risks to human health and provide insight into As behavior in the vadose zone. On Vashon-Maury Island in Puget Sound, As is predominantly associated with the fine (<63 μm) fraction of surficial soils. X-ray diffraction of oriented samples from the <2-μm size fraction indicate that clinochlore is the dominant phyllosilicate. X-ray absorption spectroscopy (XAS) was employed to examine As oxidation state and local coordination environment in impacted soil samples. Arsenic is present as As(V) in tetrahedral coordination with oxygen, associated with aluminum (Al) octahedra in bidentate binuclear (bridging) structures with As−Al distances of 3.15−3.16 Å. Including multiple scattering (MS) paths derived from the arsenate tetrahedron in esperanzaite significantly improved the match between XAS fine structure (EXAFS) data and models generated from theoretical phase and amplitude functions. The data are interpreted to indicate arsenate adsorption onto poorly crystalline aluminum oxyhydroxides and/or the edges of clinochlore interlayer hydroxyl sheets with constrained geometries causing MS to be important. This implies that As initially released from the smelter as particulate As(III) and As(V) oxides was oxidized, dissolved, and adsorbed onto soil minerals and colloids; no evidence for relic arsenic oxide was observed. Physical transport of arsenic oxide particles and As adsorbed on soil colloids may account for limited downward migration of As within the soil column. The oxidizing and mildly acidic pH conditions in the upper vadose zone promote stable sorption complexes; barring substantial changes in soil chemistry, As is not expected to experience significant mobilization.

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