Characterization of arsenite (As(III)) and arsenate (As(V)) sorption on synthetic siderite spherules under anoxic conditions: Different sorption behaviors with crystal size and arsenic species.

Arsenite (As(III)) and arsenate (As(V)) uptake by synthesized small- and large-sized siderites (S-siderite and l-siderite) and the effects of crystal size on arsenic sorption were investigated under extremely anoxic and neutral pH conditions. Both siderites exhibited spherical growth mechanism with an inverse relationship between crystal size and specific surface area (SSA). The maximum adsorption capacities normalized to SSA (qm,nor) of S-siderite and l-siderite were 0.161 and 0.174 mg/m2 for As(III), and 1.460 and 0.360 mg/m2 for As(V), respectively, indicating that the sorption affinity of S-siderite depends more on the arsenic species (III and V). Extended X-ray absorption fine structure (EXAFS) revealed that without oxidation change, As(V) adsorbed on both siderites forms inner-sphere complexes through bidentate-binuclear corner-sharing. In contrast, outer-sphere and inner-sphere complexes are formed for As(III) adsorbed on these siderites. In addition, the highest sorption affinity for As(V) uptake by S-siderite is attributed to the precipitation of symplesite (FeII3(AsVO4)2·8H2O), whereas the lowest sorption affinity for As(III) uptake by S-siderite was due to bicarbonates generated by the faster dissolution of S-siderite competing for sorption sites. Our findings suggest that arsenic sorption behaviors and mechanisms are strongly dependent on the arsenic species and the crystal size of siderite.

Enhanced Arsenic (III and V) Removal in Anoxic Environments by Hierarchically Structured Citrate/FeCO3 Nanocomposites.

Novel citrate/FeCO3 nanocomposites (CF-NCs) were synthesized for effective arsenic (III and V) sorption with constant addition of Fe2+ into HCO3- solution in the presence of citrate. This paper is the first report on the formation of CF-NCs, and in this study we investigate the mechanisms of arsenic uptake by the sorbent under anoxic conditions through various solid- and liquid-phase spectroscopic methods, including X-ray absorption spectroscopy. In CF-NCs, citrate was found to be incorporated into the structure of siderite (up to 17.94%) through (Fe2+citrate)- complexes. The crystal morphology of rhombohedral siderite was changed into hierarchically nanostructured spherical aggregates composed of several sheet-like crystals, which improved the surface reactivity in the presence of sufficient citrate. Compared to pure siderite (15.2%), enhanced removal of As(III) in the range of 19.3% to 88.2% was observed, depending on the amount of incorporated citrate. The maximum sorption capacities of CF-NCs for As(III) and As(V) were 188.97 and 290.22 mg/g, respectively, which are much higher than those of previously reported siderite-based adsorbents. It was found that arsenic (III and V) sorption on CF-NCs occurred via bidentate corner-sharing surface complexation, predominantly without changes in the arsenic oxidation states. These results suggest that arsenic (III and V) can be attenuated by siderite in anoxic environments, and this attenuation can be even more effective when siderite is modified by incorporation of organic compounds such as citrate.

Applicability of weathered coal waste as a reactive material to prevent the spread of inorganic contaminants in groundwater.

It is necessary to determine an environmentally friendly method of reusing the vast amount of coal waste that is generated during coal preparation. This study evaluates the applicability of using weathered coal waste in a permeable reactive barrier to prevent groundwater contamination. Coal waste, with different weathering degrees, was obtained from two coal mining sites in South Jeolla Province, Korea. The reactivities of the coal waste with inorganic contaminants, such as copper, cadmium, and arsenic, were examined in batch and column experiments. The batch experiment results indicate that the coal waste removal efficiencies of copper (99.8%) and cadmium (95.4%) were higher than those of arsenic (71.0%). The maximum adsorption capacities of coal waste for copper, cadmium, and arsenic calculated from the Langmuir isotherm model were 4.440 mg/g, 3.660 mg/g, and 0.718 mg/g, respectively. The equilibrium of adsorption was attained within 8 h. The column experiment results reveal that the coal waste effectively removed inorganic contaminants under flow-through conditions. Faster breakthrough times were observed in single solute system (As(V) = 19.3 PV, Cu(II) = 47.6 PV) compared with binary solute system (As(V) = 27.8 PV, Cu(II) = 65.4 PV). To confirm the applicability of using coal waste in a groundwater environment, its decontamination ability was analyzed at low concentrations and under various pH conditions. To examine the potential ecological risks in the subsurface environment, a test to determine acute toxicity to Daphnia magna and a toxic characteristic leaching procedure (TCLP) test were conducted. The coal waste was found to satisfy appropriate standards. The acute toxicity test also confirmed the ecological safety of using coal waste in a groundwater environment. The acceptably high capacity and fast kinetics of inorganic contaminant sorption by the coal waste indicate it could potentially be employed as a reactive material. The recycling and application of this abundant waste material will contribute to solving both coal waste disposal and water pollution problems.