Electrocatalytic Removal of Low-Concentration Uranium Using TiO2 Nanotube Arrays/Ti Mesh Electrodes.

Groundwater containing naturally occurring uranium is a conventional drinking water source in many countries. Removal of low concentrations of uranium complexes in groundwater is a challenging task. Here, we demonstrated that the TiO2 nanotube arrays/Ti (TNTAs/Ti) mesh electrode could break through the concentration limit and efficiently remove low concentrations of uranium complexes from both simulated and real groundwater. U(VI) complexes in groundwater were electro-reduced to UO2 and deposited on the TNTAs/Ti mesh electrode surface. The adsorption rate and electron transfer rate of the anatase TNTAs/Ti mesh electrode were twice that of the rutile TNTAs/Ti mesh electrode. Therefore, the anatase TNTAs/Ti mesh electrode exhibited excellent electrocatalytic activity toward the electrochemical removal of U(VI), which could work at a higher potential and significantly reduce the energy consumption of U(VI) removal. The U(VI) adsorption capacity on the anatase TNTAs/Ti mesh electrode was limited due to the low U(VI) concentration. However, the anatase TNTAs/Ti mesh electrode displayed a huge U(VI) removal capacity using the electroreduction method, where adsorption and reduction of U(VI) were mutually promoted and induced continuous accumulation of UO2 on the electrode. The accumulated UO2 can be easily recovered in dilute HNO3, and the electrode can be used repeatedly.

Anaerobic oxidation of arsenite by bioreduced nontronite.

The redox state of arsenic controls its toxicity and mobility in the subsurface environment. Understanding the redox reactions of arsenic is particularly important for addressing its environmental behavior. Clay minerals are commonly found in soils and sediments, which are an important host for arsenic. However, limited information is known about the redox reactions between arsenic and structural Fe in clay minerals. In this study, the redox reactions between As(III)/As(V) and structural Fe in nontronite NAu-2 were investigated in anaerobic batch experiments. No oxidation of As(III) was observed by the native Fe(III)-NAu-2. Interestingly, anaerobic oxidation of As(III) to As(V) occurred after Fe(III)-NAu-2 was bioreduced. Furthermore, anaerobic oxidization of As(III) by bioreduced NAu-2 was significantly promoted by increasing Fe(III)-NAu-2 reduction extent and initial As(III) concentrations. Bioreduction of Fe(III)-NAu-2 generated reactive Fe(III)-O-Fe(II) moieties at clay mineral edge sites. Anaerobic oxidation of As(III) was attributed to the strong oxidation activity of the structural Fe(III) within the Fe(III)-O-Fe(II) moieties. Our results provide a potential explanation for the presence of As(V) in the anaerobic subsurface environment. Our findings also highlight that clay minerals can play an important role in controlling the redox state of arsenic in the natural environment.

Removal and Recovery of Uranium from Groundwater Using Direct Electrochemical Reduction Method: Performance and Implications.

Removal of uranium from groundwater is of great significance as compared to in situ bioimmobilization technology. In this study, a novel direct electro-reductive method has been developed to efficiently remove and recover uranium from carbonate-containing groundwater, where U(VI)O2(CO3)34- and Ca2U(VI)O2(CO3)3 are the dominant U species. The transferred electron calculations and XPS, XRD analyses confirmed that U(VI) was reduced to U(IV)O2 and accumulated on the surface of the Ti electrode (defined as Ti@U(IV)O2 electrode) with high current efficiencies (over 90.0%). Moreover, over 98.0% of the accumulated U(IV)O2 could be recovered by soaking the Ti@U(IV)O2 electrode in the dilute nitric acid. Results demonstrated that the accumulated U(IV)O2 on the surface of the Ti electrode played a key role in the removal of U(VI), which can promote the electro-reduction of U(VI). Therefore, the electrode could be used repeatedly and has a high removal capacity of U(VI) due to the continuous accumulation of active U(IV)O2 on the surface of the electrode. Significantly, the uranium in both real and high salinity groundwater can be efficiently removed. This study implies that the proposed direct electro-reductive method has great potential for the removal and recovery of uranium from groundwater and uranium-containing wastewater.

Microbial mobilization of arsenic from iron-bearing clay mineral through iron, arsenate, and simultaneous iron-arsenate reduction pathways.

Clay minerals are an important host for arsenic in many arsenic-affected areas. The role of bioreduction of structural Fe(III) in clay minerals in the mobilization of arsenic from clay minerals, however, still remains unclear. In this study, Fe(III) reducing bacterium, As(V) reducing bacterium, and Fe(III)-As(V) reducing bacterium were employed to investigate the possible bioreduction pathways for arsenic release from Nontronite NAu-2. Results demonstrated that microbial reduction controlled arsenic mobilization from NAu-2 through Fe(III), As(V), and simultaneous Fe(III)-As(V) reduction pathways. Although the bioreduction of structural Fe(III) led to a negligible dissolution of NAu-2, it triggered a significant release of arsenic from NAu-2. The bioreduction of tetrahedral Fe(III) initiated the release of As(V), and the further bioreduction of octahedral Fe(III) induced the release of As(III) in NAu-2. In addition, bioreduction of As(V) resulted in the desorption and transformation of As(V) from NAu-2. Simultaneous bioreduction of Fe(III) and As(V) led to an almost complete release of As(V) from NAu-2. These findings suggest that simultaneous Fe(III)-As(V) reduction was the dominant pathway governing As(V) release from NAu-2, while structural Fe(III) reduction controlled As(III) release from NAu-2. Therefore, the bioreduction of iron-bearing clay minerals has a great potential for arsenic mobilization in the subsurface environment.

Pre-aggregation of Al13 in optimizing coagulation for removal of humic acid.

The effective removal of humic acid (HA) by coagulation has been extensively investigated for water treatments. However, the limitations of pH variation and excessive residual aluminum issues were still factors needed to be considered. In this study, to investigate the coagulation mechanism for removing HA by Al13 and optimize Al13 operation for removing HA, Al13 and preformed Al13 aggregates (Al13agg) were applied to remove HA at different pH conditions. The results showed that preformed Al13agg exhibited superior HA removal performance than Al13 due to its wide pH range and low residual Al level. During coagulation, Al13 and Al13agg interacted with HA in their original status, but the DSlope325-375 difference implied that the complexation capacity between HA and Al13agg was stronger than Al13. The new peaks of HPSEC representing larger molecular weight substances were formed under acidic and neutral conditions, which indicated that HA firstly aggregated into larger complexed molecules by interacting with Al13 or its hydrolysates and was subsequently removed by forming large flocs which was completely different from Al13agg situation. Therefore, the different coagulation mechanisms played the roles in HA removal for Al13 and Al13agg which were studied in this paper. It was believed that the complexation and charge neutralization effects dominated coagulation process for Al13 while sweep flocculation and adsorption coagulation were main driving force for Al13agg in HA removing. This work provides significant understanding of HA removal by Al13 and Al13agg coagulation, which can help to design and optimize the high efficiency coagulant based on Al polycations.

Iron(III) minerals and anthraquinone-2,6-disulfonate (AQDS) synergistically enhance bioreduction of hexavalent chromium by Shewanella oneidensis MR-1.

Bioreduction of hexavalent chromium (Cr(VI)) to sparingly soluble trivalent chromium (Cr(III)) is a strategy for the remediation of Cr(VI) contaminated sites. However, its application is limited due to the slow bioreduction process. Here we explored the potential synergistic enhancement of iron(III) minerals (nontronite NAu-2, ferrihydrite, and goethite) and electron shuttle anthraquinone-2,6-disulfonate (AQDS) on the bioreduction of Cr(VI) by Shewanella oneidensis MR-1. AQDS alone increased the bioreduction rate of Cr(VI) by accelerating electron transfer from MR-1 to Cr(VI). Iron minerals alone did not increase the bioreduction rate of Cr(VI), where the electron transfer from MR-1 to Fe(III) minerals was inhibited due to the toxicity of Cr(VI) to MR-1. AQDS plus NAu-2 or ferrihydrite significantly enhanced the bioreduction rate of Cr(VI) as compared to AQDS or NAu-2/ferrihydrite alone, demonstrating that AQDS plus NAu-2/ferrihydrite had the synergistic effect on bioreduction of Cr(VI). Synergy factor (kcells+Fe+AQDS/(kcells+Fe + kcells+AQDS)) was used to quantify the synergistic effect of AQDS and iron minerals on the bioreduction of Cr(VI). The synergy factors of AQDS plus NAu-2 were 2.09-4.63 (three Cr(VI) spikes), and the synergy factors of AQDS plus ferrihydrite were 1.89-4.61 (two Cr(VI) spikes). In the presence of Cr(VI), AQDS served as the electron shuttle between MR-1 and iron minerals, facilitating the reduction of Fe(III) minerals to Fe(II). The synergistic enhancement of AQDS and NAu-2/ferrihydrite was attributed to the generated Fe(II), which could quickly reduce Cr(VI) to Cr(III). Our results provide an attractive strategy to strengthen the bio-immobilization of Cr(VI) at iron-rich contaminated sites through the synergistic enhancement of iron(III) minerals and electron shuttle.