Suiling Wang

Speciation and surface structure of inorganic arsenic in solid phases: A review

Accurate determination of individual arsenic species is critical because the toxicology, mobility, and adsorptivity of arsenic vary substantially with its chemical forms and oxidation states. Separation techniques together with techniques for chemical identification make it possible to determine the combinational forms and oxidation states of arsenic in solid phases. Selective sequential extraction is often employed to determine operationally defined fractions, but it has a poor precision and selectivity. Direct methods, based on X-ray techniques and vibrational spectroscopy, have been developed to analyze the valence, local coordination, protonation, and other properties of arsenic in solid phases. Extensive research studies in the literature have been performed to elucidate the interfacial reactions between inorganic arsenic and solid surfaces of sulfides, and Fe, Al, and Mn (hydro)oxides. Outer-sphere and inner-sphere complex (monodentate mononuclear, bidentate mononuclear, and bidentate binuclear complex) models have been proposed to interpret the sorption mechanisms. The nature of the surface complexes has been inspected by spectroscopic methods but remains controversial. This paper focuses on the recent advancement in arsenic speciation in solid phases and covers relevant methodological, analytical and modeling aspects. The identification of arsenic species in natural materials, however, is complicated by the presence of multiple species, and the applications of instrumental methods are usually limited due to their comparatively high detection limits. Development of advanced in-situ methods with high sensitivity, therefore, is required.

Enhanced mobilization of arsenic and heavy metals from mine tailings by humic acid.

Arsenic and heavy metal mobilization from mine tailings is an issue of concern as it might pose potential groundwater or ecological risks. Increasing attention recently has been focused on the effects of natural organic matter on the mobility behavior of the toxicants in the environment. Column experiments were carried out in this research study to evaluate the feasibility of using humic acid (HA) to mobilize arsenic and heavy metals (i.e., Cu, Pb and Zn) from an oxidized Pb-Zn mine tailings sample collected from Bathurst, New Brunswick, Canada. Capillary electrophoresis analyses indicated that arsenate [As(V)] was the only extractable arsenic species in the mine tailings and the addition of HA at pH 11 did not incur the oxidation-reduction or methylation reactions of arsenic. A 0.1% HA solution with an initial pH adjusted to 11 was selected as the flushing solution, while distilled water (initial pH adjusted to 11) was used as the control to account for the mobilization of arsenic and the heavy metals by physical mixing and the effect of pH. It was found that the HA could significantly enhance the mobilization of arsenic and heavy metals simultaneously from the mine tailings. After a 70-pore-volume-flushing, the mobilization of arsenic, copper, lead and zinc reached 97, 35, 838 and 224 mg kg(-1), respectively. The mobilization of arsenic and the heavy metals was found to be positively correlated with the mobilization of Fe in the presence of the HA. Moreover, the mobilization of arsenic was also correlated well with that of the heavy metals. The mobilization of co-existing metals to some extent might enhance arsenic mobilization in the presence of the HA by helping incorporate it into soluble aqueous organic complexes through metal-bridging mechanisms. Use of HA in arsenic and heavy metal remediation may be developed as an environmentally benign and possible effective remedial option to reduce and avoid further contamination.

Effect of natural organic matter on arsenic mobilization from mine tailings

This research study was to elucidate the mechanisms of arsenic mobilization from mine tailings in the presence of natural organic matter (NOM). Humic acid (HA) was chosen as a model for NOM. The introduction of the HA at a low mass ratio (below 2mg added HA/g mine tailings) inhibited arsenic mobilization under acidic conditions. Arsenic mobilization increased with increasing mass ratio. When pH was above 7, the addition of HA enhanced arsenic mobilization significantly. A mobilization isotherm was developed to predict arsenic mobilization from the mine tailings in the presence of HA. It was indicated that HA sorption to the mine tailings was essential for arsenic mobilization. HA might enhance arsenic mobility through formation of aqueous complexes, competition for adsorption and electrostatic interactions. Capillary electrophoresis analyses indicated that arsenic redox reactions might not have a significant effect on arsenic mobilization in this study. The mobilization of co-existing metals could enhance arsenic mobilization by helping incorporating it into soluble complexes in the presence of HA.