Effects of the ZrO2 Crystalline Phase and Morphology on the Thermocatalytic Decomposition of Dimethyl Methylphosphonate.

Thermocatalytic decomposition is an efficient purification technology that is potentially applicable to degrading chemical warfare agents and industrial toxic gases. In particular, ZrO2 has attracted attention as a catalyst for the thermocatalytic decomposition of dimethyl methylphosphonate (DMMP), which is a simulant of the nerve gas sarin. However, the influence of the crystal phase and morphology on the catalytic performance of ZrO2 requires further exploration. In this study, monoclinic- and tetragonal-phase ZrO2 (m- and t-ZrO2, respectively) with nanoparticle, flower-like shape and hollow microsphere morphologies were prepared via hydrothermal and solvothermal methods, and their thermocatalytic decomposition of DMMP was systematically investigated. For a given morphology, m-ZrO2 performed better than t-ZrO2. For a given crystalline phase, the morphology of hollow microspheres resulted in the longest protection time. The exhaust gases generated by the thermocatalytic decomposition of DMMP mainly comprised H2, CO2, H2O and CH3OH, and the by-products were phosphorus oxide species. Thus, the deactivation of ZrO2 was attributed to the deposition of these phosphorous oxide species on the catalyst surface. These results are expected to help guide the development of catalysts for the safe disposal of chemical warfare agents.

A Review on Cyanide Gas Elimination Methods and Materials.

Cyanide gas is highly toxic and volatile and is among the most typical toxic and harmful pollutants to human health and the environment found in industrial waste gas. In the military context, cyanide gas has been used as a systemic toxic agent. In this paper, we review cyanide gas elimination methods, focusing on adsorption and catalysis approaches. The research progress on materials capable of affecting cyanide gas adsorption and catalytic degradation is discussed in depth, and the advantages and disadvantages of various materials are summarized. Finally, suggestions are provided for future research directions with respect to cyanide gas elimination materials.

Propagation and Diffusion of Fluorescent Substances with Footprints in Indoor Environments.

Some studies have shown that contaminants can be transferred between floors and the soles, and there are few studies on pollutant propagation caused by human walking in real-life situations. This study explored the propagation and diffusion law of ground pollutants from rubber soles to poly vinyl chloride (PVC) floor during indoor walking through employing a fluorescent solution as a simulant. The footprint decay (D) and transfer efficiency (τ) of the fluorescent solution transferred from the sole to the indoor floor during walking were analyzed based on the fluorescent footprint imaging. The effects of namely body weight (50-75 kg), walking frequency (80-120 steps/min), and solution viscosity (oil and water) were also investigated. It was found that the total fluorescence gray value on the ground decreased exponentially as the number of walking steps (i) increased. The relationship between the normalized gray value of the fluorescent solution (D) on each floor panel i was Di=aebi,2.1≤a≤3.8,-1.4≤b≤-0.7, and τ was distributed in the range of 0.51-0.72. All influencing factors had a significant effect on a, and a greater body weight resulted in a smaller a value, while only the body weight had a significant effect on b and τ, and a greater body weight led to larger b and lower τ values.

Oxidation of bioreduced iron-bearing clay mineral triggers arsenic immobilization.

Iron-bearing clay minerals and arsenic commonly coexist in soils and sediments. Redox oscillation from anoxic to oxic conditions can result in structural Fe(II) oxidation in clay minerals. However, the role of structural Fe(II) oxidation in clay minerals on arsenic immobilization is still unclear. In this study, we found that oxidation of structural Fe(II) in bioreduced clay mineral nontronite (NAu-2) triggered As(III) adsorption onto NAu-2. As(III) was adsorbed onto NAu-2 through ligand exchange with hydroxyl groups which were generated by the oxidation of structural Fe(II) in NAu-2. In addition, oxidation of structural Fe(II) led to the oxidation of As(III) to As(V), which further enhanced the adsorption of dissolved As(III) on NAu-2. Therefore, the adsorption capacity of As(III) onto oxidized NAu-2 was 1.6 times higher than that of native NAu-2. Oxidation of structural Fe(II) was a two-stage process that proceeded from exterior sites to interior sites, and the immobilization and oxidation of As(III) occurred predominantly at the rapid exterior structural Fe(II) oxidation stage. Our findings highlight that the oxidation of structural Fe(II) in iron-bearing clay minerals may play an important role in arsenic immobilization and transformation in the subsurface environment.

Sustainable enhancement of Cr(VI) bioreduction by the isolated Cr(VI)-resistant bacteria.

Bioreduction of mobile Cr(VI) to sparingly soluble Cr(III) is an effective strategy for in situ remediations of Cr contaminated sites. The key of this technology is to screen Cr(VI)-resistant bacteria and further explore the sustainable enhancement approaches towards their Cr(VI) reduction performance. In this study, a total of ten Cr(VI)-resistant bacteria were isolated from a Cr(VI) contaminated site. All of them could reduce Cr(VI), and the greatest extent of Cr(VI) reduction (98%) was obtained by the isolated CRB6 strain. The isolated CRB6 was able to reduce structural Fe(III) in Nontronite NAu-2 to structural Fe(II). Compared with the slow bioreduction process, the produced structural Fe(II) can rapidly enhance Cr(VI) reduction. The resist dissolution characteristics of NAu-2 in the redox cycling may provide sustainable enhancement of Cr(VI) reduction. However, no enhancement on Cr(VI) bioreduction by the isolated CRB6 was observed in the presence of NAu-2, which was attributed to the inhibition of Cr(VI) on the electron transfer between the isolated CRB6 and NAu-2. AQDS can accelerate the electron transfer between the isolated CRB6 and NAu-2 as an electron shuttle in the presence of Cr(VI). Therefore, the combination of NAu-2 and AQDS generated a synergistic enhancement on Cr(VI) bioreduction compared with the enhancement obtained by NAu-2 and AQDS individually. Our results highlight that structural Fe(III) and electron shuttle can provide a sustainable enhancement of Cr(VI) reduction by Cr(VI)-reducing bacteria, which has great potential for the effective Cr(VI) in-situ remediation.

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.

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.

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.