Local Structure and Crystallization Transformation of Hydrous Ferric Arsenate in Acidic H2O-Fe(III)-As(V)-SO42- Systems: Implications for Acid Mine Drainage and Arsenic Geochemical Cycling.

Hydrous ferric arsenate (HFA) is a common thermodynamically metastable phase in acid mine drainage (AMD). However, little is known regarding the structural forms and transformation mechanism of HFA. We investigated the local atomic structures and the crystallization transformation of HFA at various Fe(III)/As(V) ratios (2, 1, 0.5, 0.33, and 0.25) in acidic solutions (pH 1.2 and 1.8). The results show that the Fe(III)/As(V) in HFA decreases with decreasing initial Fe(III)/As(V) at acidic pHs. The degree of protonation of As(V) in HFA increases with increasing As(V) concentrations. The Fe K-edge extended X-ray absorption fine structure and X-ray absorption near-edge structure results reveal that each FeO6 is linked to more than two AsO4 in HFA precipitated at Fe(III)/As(V) < 1. Furthermore, the formation of scorodite (FeAsO4·2H2O) is greatly accelerated by decreasing the initial Fe(III)/As(V). The release of As(V) from HFA is observed during its crystallization transformation process to scorodite at Fe(III)/As(V) < 1, which is different from that at Fe(III)/As(V) ≥ 1. Scanning electron microscopy results show that Oswald ripening is responsible for the coarsening of scorodite regardless of the initial Fe(III)/As(V) or pH. Moreover, the formation of crystalline ferric dihydrogen arsenate as an intermediate phase at Fe(III)/As(V) < 1 is responsible for the enhanced transformation rate from HFA to scorodite. This work provides new insights into the local atomic structure of HFA and its crystallization transformation that may occur in AMD and has important implications for arsenic geochemical cycling.

Direct immobilization of Se(IV) from acidic Se(IV)-rich wastewater via ferric selenite Co-precipitation.

The attenuation of acidic Se(IV)-rich wastewater, including those associated with acid mine drainage (AMD) and nonferrous metallurgical wastewater (NMW), presents a serious environmental challenge. This study investigates the effects of diverse factors from pH values to Se(IV)/Fe(III) molar ratios, initial Se(IV) concentrations, and alkali neutralization agents on the direct co-precipitation of ferric selenites in AMD and NMW systems involving different orders of Fe(III) and alkali addition. Our results show that amorphous sulfate-substituted ferric (hydrogen) selenite and Se(IV)-bearing ferrihydrite-schwertmannite are the major Se(IV)-attenuation solids except that gypsum is an additional phase in the NMW system with Ca(OH)2 neutralization. Produced ferric selenites achieve 98-99.8% of Se(IV) immobilization under optimal conditions of pH 4.5, Se(IV)/Fe(III) molar ratios of 0.0625-0.5, and initial Se(IV) concentrations of 0.15-1.3 mmol·L-1. Moreover, completing FeSO4+ and FeHSeO32+/FeSeO3+ complexes as well as different ferric selenite co-precipitates are shown to collectively control aqueous Se(IV) remaining. Specifically, three distinct trends of aqueous Se(IV) concentrations separately correspond to changes in the four factors. The co-precipitation in the NMW system via pH adjustment followed by Fe(III) addition is more efficient for Se(IV) fixation than that in the AMD system because of minimal complexation, concurrent Fe(III) hydrolysis, and enhanced ferric selenite co-precipitation in the former.

Iron(II)-activated phase transformation of Cd-bearing ferrihydrite: Implications for cadmium mobility and fate under anaerobic conditions.

The factors and mechanisms affecting the fate of the associated Cd during the Fe(II)-activated Cd-bearing ferrihydrite transformation remain poorly understood. Herein we have conducted a series of batch reactions containing ferrihydrite with diverse pH values and initial Fe(II) and Cd concentrations coupled with chemical analyses and spectroscopic examination on the transformation products to probe the mechanisms of the Cd partitioning and the processes of Fe(II)-activated Cd-bearing ferrihydrite transformation under anaerobic conditions. Chemical analyses, Fourier transform infrared spectroscopy (FTIR), and powder X-ray diffraction (PXRD) results show that the initial Fe(II) and Cd concentrations as well as pH values all have significant effects on the rates and pathways of ferrihydrite transformation. Increasing Cd loading enhances the inhibition of the Fe(II)-activated ferrihydrite transformation rates. High Cd loading alters the Fe(II)-activated ferrihydrite transformation pathways by hindering the recrystallization of both ferrihydrite to more stable iron minerals and the newly formed lepidocrocite to goethite. Chemical analyses show that the release of Cd to solutions during ferrihydrite transformation is accompanied by a reduction in the 0.4 M HCl extractable Cd fraction and that a significant amount of the released Cd is transformed to a 0.4 M HCl unextractable form. Moreover, enhanced Cd release during the Fe(II)-activated ferrihydrite transformation is observed by reducing the pH value or increasing the initial Cd concentration. Results from synchrotron X-ray absorption spectroscopy (XAS) confirm that the majority of the 0.4 M HCl unextractable Cd form is associated with structural incorporation into the recrystallized iron (hydr)oxides via isomorphous substitution for Fe(III). These findings not only provide molecular-level understanding on the behavior of Cd under natural anoxic environments, but also are useful in predicting the geochemical cycling of Cd and developing long-term Cd contaminant management strategies.