Antimony speciation and mobility during Fe(II)-induced transformation of humic acid-antimony(V)-iron(III) coprecipitates

Antimony, as the Sb(V) species, often occurs in oxic soils and sediments as coprecipitates with poorly-crystalline Fe(III)-bearing minerals. It is common for these Sb(V)-Fe(III) coprecipitates to also contain varying quantities of co-occurring humic acid (HA). When exposed to reducing conditions, the production of Fe(II) may cause the initial metastable HA-Sb(V)-Fe(III) phases to undergo rapid transformations to more stable phases, thereby potentially influencing the geochemical behavior of coprecipitated Sb(V). However, little is known about the impacts of this transformation on the mobility and speciation of Sb. In this study, we reacted synthetic HA-Sb(V)-Fe(III) coprecipitates (Fe:Sb ratio = 4, and C:Fe molar ratios = 0, 0.3, 0.8 and 1.3) with 0, 1 or 10 mM Fe(II) under O-2-free conditions at pH 7.0 for 15 days. Fe K-edge EXAFS spectroscopy revealed that solid-phase Fe(III) in the initial coprecipitates contained a mixture of similar to 4/5 ferrihydrite (Fe10O14(OH)(2)) and similar to 1/5 tripuhyite (FeSbO4), regardless of the corresponding amount of coprecipitated HA. Tripuhyite persisted throughout the full experiment duration, while ferrihydrite was partially replaced by goethite (FeOOH) when either 1 or 10 mM Fe(II)(aq) was added to the coprecipitates. The greatest level of goethite formation (similar to 55% of solid-phase Fe) was observed in the HA-free/10 mM Fe(II)(aq) treatment, with ferrihydrite transformation being partially attenuated at higher levels of HA. Mobilisation of aqueous Sb was the greatest for 1 mM Fe(II) treatments at high HA:Fe ratios. Sb K-edge XANES spectroscopy showed that the largest reduction of Sb(V) to Sb(III) (similar to 37%) and the greatest repartitioning of Sb to the mineral surface (similar to 7.9-9.8%) occurred in the coprecipitates with the highest HA contents in the presence of 10 mM Fe(II). The results indicate that the amount of HA in HA-Sb(V)-Fe(III) coprecipitates can greatly influence mobility and speciation of Sb in Fe(II)-rich conditions. The results of this study provide new insights into alterations in Sb mobility and retention in response to Fe cycling under organic matter-rich reducing conditions. (C) 2019 Elsevier Ltd. All rights reserved.