Potential negative consequences of adding phosphorus-based fertilizers to immobilize lead in soil.

A study of the potential negative consequences of adding phosphate (P)-based fertilizers as amendments to immobilize lead (Pb) in contaminated soils was conducted. Lead-contaminated firing range soils also contained elevated concentrations of antimony (Sb), a common Pb hardening agent, and some arsenic (As) of unknown (possibly background) origin. After amending the soils with triple superphosphate, a relatively soluble P source, column leaching experiments revealed elevated concentrations of Sb, As, and Pb in the leachate, reflecting an initial spike in soluble Pb and a particularly dramatic increase in Sb and As mobility. Minimal As, Sb, and Pb leaching was observed during column tests performed on non-amended control soils. In vitro extractions tests were performed to assess changes in Pb, As, and Sb bioaccessibility on P amendment. Lead bioaccessibility was systematically lowered with increasing P dosage, but there was much less of an effect on As and Sb bioaccessibility than on mobility. Our results indicate that although P amendments may aid in lowering the bioaccessibility of soil-bound Pb, it may also produce an initial increase in Pb mobility and a significant release of Sb and As from the soil, dramatically increasing their mobility and to a lesser extent their bioavailability.

Immobilization of mercury by pyrite (FeS2).

Elemental mercury (Hg(0)) is a metal with a number of atypical properties, which has resulted in its use in myriad anthropogenic processes. However, these same properties have also led to severe local subsurface contamination at many places where it has been used. As such, we studied the influence of various parameters on Hg(II) sorption onto pyrite (pH, time, Hg(II) concentration), a potential subsurface reactive barrier. Batch sorption studies revealed that total Hg(II) removal increases with both pH and time. X-ray absorption spectroscopy analysis showed that a transformation in the coordination environment at low pH occurred during aging over 2 weeks, to form an ordered monolayer of monodentate Hg-Cl complexes on pyrite. In column studies packed with pure quartz sand, the transport of Hg(II) was significantly retarded by the presence of a thin pyrite-sand reactive barrier, although dissolved oxygen inhibited Hg(II) sorption onto pyrite in the column.

Arsenate adsorption structures on aluminum oxide and phyllosilicate mineral surfaces in smelter-impacted soils.

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 microm) fraction of surficial soils. X-ray diffraction of oriented samples from the < 2 microm size fraction indicate that clinochlore isthe 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 angstroms. 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.