Structural and mineralogical variation upon reoxidation of reduced Fe-bearing clay minerals during thermal activation.

The hydroxyl radicals (OH) produced from Fe(II) oxidation upon reoxidation of reduced Fe-bearing clay minerals (RFC) have received increased attention and thermal activation was used to enhance Fe(II) oxidation to improve OH production. However, changes in mineral morphology and structure during thermally-activated RFC reoxidation are not yet clear. Herein, the Fe(II) oxidation extent was measured by chemical analysis during the reoxidation of model RFC (reduced nontronite (rNAu-2) at elevated temperatures. Mineralogical variation of rNAu-2 particles was observed by scanning electron microscopy (SEM), Mössbauer spectra, and X-ray photoelectron spectroscopy (XPS). The structural Fe(II) oxidation in rNAu-2 was accelerated with increasing temperature, accompanied by the transformation of structural entities and the dissolution of Fe and Si, while the overall structure of rNAu-2 minerals was relatively intact. The surface microstructure of particles showed the dissolved holes, net-shape flocs, and even large pore channels after Fe(II) oxidation by thermal activation. Moreover, the rearrangement of structural Fe(II) entities, the regeneration of edge Fe(II), and the electron transport from the interior to the edge were enhanced during rNAu-2 reoxidation by thermal activation. The increasing electron transfer at elevated temperatures could possibly be owing to the increasing number of reactive sites by increasing the internal disorder of rNAu-2. This work provides novel insights into the structural and mineralogical changes in promoting electron transfer upon RFC reoxidation.

Effect of Stoichiometry on Nanomagnetite Sulfidation.

Magnetite (Mt) has long been regarded as a stable phase with a low reactivity toward dissolved sulfide, but natural Mt with varying stoichiometries (the structural Fe(II)/Fe(III) ratio, xstru) might exhibit distinct reactivities in sulfidation. How Mt stoichiometry affects its sulfidation processes and products remains unknown. Here, we demonstrate that xstru is a master variable controlling the rates and extents of sulfide oxidation by magnetite nanoparticles (11 ± 2 nm). At pH = 7.0-8.0 and the initial Fe/S molar ratio of 10-50, the partially oxidized magnetite (xstru = 0.19-0.43) can oxidize dissolved sulfide to elemental sulfur (S0), but only surface adsorption of sulfide, without interfacial electron transfer (IET), occurs on the nearly stoichiometric magnetite (xstru = 0.47). The higher initial rate and extent of sulfide oxidation and S0 production are observed with the more oxidized magnetite that has the higher electron-accepting capability from surface-complexed sulfide (S(-II)(s)). The FeS clusters formed from magnetite sulfidation can be oxidized by the most oxidized magnetite with xstru = 0.19 but not by other magnetite particles. A linear relationship between the Gibbs free energy of reaction and the surface area-normalized initial rate of sulfide oxidation is observed in all experiments under the different conditions, suggesting the S(-II)(s)-magnetite IET dominates magnetite sulfidation at high Fe/S molar ratios and near-neutral pH.

Insights into the degradation process of phenol during in-situ thermal desorption: The overlooked oxidation of hydroxyl radicals from oxygenation of reduced Fe-bearing clay minerals.

In-situ thermal desorption (ISTD) has attracted increasing attention owing to the efficient removal of organic contaminants from contaminated sites. However, it is poorly understood that whether and to what extent contamination degradation occurs upon oxygenation of reduced Fe-bearing clay minerals (RFC) in the subsurface during ISTD. In this study, we evaluated the mechanism of contaminant degradation upon oxygenation of reduced clay minerals during the ISTD. Reduced nontronite (rNAu-2) and montmorillonite (rSWy-3) were selected as RFC models. Results showed that thermal treatment during ISTD could significantly enhance phenol degradation, which increased from 25.8 % at 10 °C to 74.4 % at 70 °C in rNAu-2 and from 17.7 % at 10 °C to 49.8 % at 70 °C in rSWy-3. Correspondingly, the cumulative •OH at steady-state ([•OH]ss) increased by 3.7 and 1.5 times, respectively. The acceleration of Fe(II) oxidation with increasing temperature could be mainly responsible for [•OH]ss generation, which degrades phenol. Moreover, thermal treatment improved the fast oxidation of trioctahedral entities Fe(II)Fe(II)Fe(II) (TOF) and the slow oxidation of dioctahedral entities Fe(II)Fe(II) (DTF1), AlFe(II) (DAF1), and Fe(II)Fe(III) (DTF2). Our study suggests that the overlooked degradation progress of phenol by oxygenation of RFC during ISTD, and it could be favorable for contaminant degradation during remediation.

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.

Sequestration of free and chelated Ni(II) by structural Fe(II): Performance and mechanisms.

Ni(II) and chelated Ni(II) in wastewater are of environmental concern. This study explores the sequestration potential of structural Fe(II) in solid phase (≡Fe(II)) on Ni(II) and EDTA-Ni(II) using freshly prepared ferrous hydroxyl complex (FHC) as the Fe(II)-bearing mineral. The 1 mM Ni(II) could be completely sequestrated in 20 min by 3 mM FHC, although the sequestrated Ni(II) was partially released after 20 min. It is calculated that up to 156 mg Ni(II)/g Fe(II) can be sequestrated by ≡Fe(II) under neutral pH and anaerobic condition. According to the characterizations of the solid products, the large surface area for Ni(II) adsorption and the high ≡Fe(II) reduction capacity for Ni(II) reduction are the main contributors to the Ni(II) sequestration. After the reaction, the FHC is transformed to stable Fe-Ni layered double hydroxides. The concomitant ions can be either promotional or inhibitory to the sequestration performance depending on the ion type. The combination of FHC and Fe(III) can effectively sequestrate EDTA-Ni(II), whereas FHC alone has a low efficiency. Fe(III) substitutes Ni(II) from the EDTA-Ni(II), benefiting the subsequent Ni(II) sequestration by ≡Fe(II). This study demonstrates that ≡Fe(II) suspension is an cost-effective option for remediating Ni(II)-containing wastewater.

Sequestration of chelated copper by structural Fe(II): Reductive decomplexation and transformation of Cu(II)-EDTA.

Chelated coppers, such as Cu(II)-EDTA, are characteristically refractory and difficult to break down because of their high stability and solubility. Cu(II)-EDTA sequestration by structural Fe(II) (Fe(II)) was investigated intensively in this study. Up to 101.21mgCu(II)/gFe(II) was obtained by Fe(II) in chelated copper sequestration under near neutral pH condition (pH 7.70). The mechanism of Cu(II)-EDTA sequestration by Fe(II) was concluded as follows: 3Cu(II)-EDTA+7Fe(II)+9H2O → Cu(0)↓+ Cu2O↓(the major product)+2Fe2O3·H2O↓+3Fe(II)-EDTA +14H(+) Novel results strongly indicate that Cu(II) reductive transformation induced by surface Fe(II) was mainly responsible for chelated copper sequestration. Cu(0) generation was initially facilitated, and subsequent reduction of Cu(II) into Cu(I) was closely combined with the gradual increase of ORP (Oxidation-Reduction Potential). Cu-containing products were inherently stable, but Cu2O would be reoxidized to Cu(II) with extra-aeration, resulting in the release of copper, which was beneficial to Cu reclamation. Concentration diminution of Cu(II)-EDTA within the electric double layer and competitive adsorption were responsible for the negative effects of Ca(2+), Mg(2+). By generating vivianite, PO4(3-) was found to decrease surface Fe(II) content. This study is among the first ones to identify the indispensible role of reductive decomplexation in chelated copper sequestration. Given the high feasibility and reactivity, Fe(II) may provide a potential alternative in chelated metals pollution controlling.