Enhanced nitrate removal using in situ reactive zone with reduced graphene oxide supported nanoscale zero-valent iron.

Nitrate pollution in groundwater is becoming more serious, which is harmful to human health. The reduced graphene oxide supported nanoscale zero-valent iron (nZVI/rGO) composite prepared in this paper can effectively remove nitrate in groundwater. In situ remediation of nitrate-contaminated aquifer was also studied. The results showed that NH4+-N was the main product of NO3--N reduction, and N2 and NH3 were also produced. When the dosage of rGO/nZVI was more than 0.2 g/L, there was no accumulation of intermediate NO2--N during the reaction process. NO3--N was removed by rGO/nZVI mainly through physical adsorption and reduction process with the maximum adsorbing ability of 37.44 mg NO3--N/g. After the slurry of rGO/nZVI was injected into the aquifer, a stable reaction zone could be formed. NO3--N could be removed continuously within 96 h at the simulated tank, and NH4+-N and NO2--N were as the main reduction products. Moreover, the concentration of TFe near the injection well increased rapidly after rGO/nZVI injection, and could be detected at the downstream end, indicating that the reaction range was large enough for NO3--N removal.

Highly efficient removal of Se(IV) using reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO): selenium removal mechanism.

Se(IV) removal using nanoscale zero-valent iron (nZVI) has been extensively studied. Still, the synergistic removal of Se(IV) by reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) has not been reported. In this study, nZVI/rGO was successfully synthesized for Se(IV) removal from wastewater. The effects of different environmental conditions (load ratio, dosage, initial pH) on Se(IV) removal by nZVI/rGO were investigated. When the load ratio is 10%, the dosage is 0.3 g/L, the initial pH is 3, and the removal rate is 99%. The adsorption isotherm and kinetics accorded with the Langmuir isotherm and first-order kinetics models (R2 > 0.99). The fitted maximum adsorption capacity reached up to 173.53 mg/g. NZVI/rGo and Se(IV) is a spontaneous endothermic reaction (△G < 0, △H > 0) and is characterized by EDS, XRD, and XPS before and after the reaction, to further clarify the reaction mechanism. The XPS narrow spectrum analysis suggested that Se(IV) was reduced to elemental selenium (Se(0)), while the intermediate Fe(II) was oxidized to form hydroxide precipitation. Therefore, nZVI/rGO was favored for Se-contaminated wastewater remediation.

Graphene oxide supported sulfidated nano zero-valent iron (S-nZVI@GO) for antimony removal: The role of active oxygen species and reaction mechanism.

Sulfidated nano zero-valent iron (S-nZVI) was used to remove various pollutants from wastewater. However, the instability, poor dispersibility, and low electron transfer efficiency of S-nZVI limit its application. Herein, graphene oxide supported sulfidated nano zero-valent iron (S-nZVI@GO) was successfully synthesized using graphene oxide (GO) as a carrier. The properties of S-nZVI@GO were characterized by scanning electron microscopy coupled to X-ray photoelectron spectroscopy (SEM-EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) concerning the surface morphology, crystalline structure, and elemental components. S-nZVI@GO displayed an excellent capacity for antimony (Sb) removal under aerobic conditions (96.7%), with a high adsorption capacity (Qmax = 311.75 mg/g). It maintained a high removal rate (over 90%) during a wide pH range (3-9). More importantly, S-nZVI@GO activated the molecular oxygen in water via a single-electron pathway to produce •O2－ and H2O2, and then oxidized trivalent antimony (Sb(III)) to pentavalent antimony (Sb(V)) and further separated it by synergistic adsorption and co-precipitation. Therefore, S-nZVI@GO shows excellent potential for Sb contamination remediation.

An in-situ bio-remediation of nitrobenzene in stimulated aquifer using emulsified vegetable oil.

Widespread nitrobenzene (NB) contamination in groundwater requires an economical and effective remediation technology. In situ microbial reactive zone enhanced by injecting emulsified vegetable oil (EVO) is an effective method for remediating NB-contaminated groundwater, which can be reduced to aniline (AN) effectively in the reactive zone. However, the bio-mechanism of NB remediation in a real contaminated site is still unclear. Thus, a 3-D tank was established to conduct a pilot-scale experiment and the bacterial communities in the tank were analyzed by 16S rDNA high-throughput sequencing. The results suggested that the injection of EVO can stimulate some certain microorganisms to grow, and reduce NB though biological and biochemical processes. There were three degradation pathways of NB: (1) direct oxidation by Pseudomonas; (2) direct mineralization by Clostridium sensu stricto; and (3) coupled reduction of NB through microbial dissimilatory iron reduction by Geobacter and Arthrobacter. Among these pathways, the coupled reduction process is the main degradation pathway.

Reduced graphene oxide-nano zero value iron (rGO-nZVI) micro-electrolysis accelerating Cr(VI) removal in aquifer.

Nanoscale zero-valent iron (nZVI) assembled on graphene oxide (GO) (rGO-nZVI) composites were synthesized by reduction of GO and ferrous ions with potassium borohydride, for use in Cr(VI) removal from aqueous solution. The results showed that the two-dimensional structure of GO could provide a skeleton support for Fe0, thus overcoming the bottleneck of aggregation for nZVI. Also, rGO-nZVI would form a ferric-carbon micro-electrolysis system in Cr(VI)-contaminated aquifers, enhancing and accelerating electron transfer, exhibiting high rate and capacity for Cr(VI) removal. The optimum dosage of the applied rGO-nZVI was linearly correlated with the initial Cr(VI) concentration. Characterization of rGO-nZVI before and after reaction with Cr(VI) revealed the process of Cr(VI) removal: rGO-nZVI firstly transferred electrons from Fe0 cores via their Fe(II)/Fe(III) shells to the GO sheet; there, negatively charged Cr(VI) received electrons and changed into positively charged Cr(III), which was adsorbed by the negatively charged GO sheet, avoiding the capping and passivating of nZVI. rGO-nZVI formed a good electrically conductive network, and thus had long-term electron releasing properties, which was important for groundwater remediation.

Mechanism on emulsified vegetable oil stimulating nitrobenzene degradation coupled with dissimilatory iron reduction in aquifer media.

Microbial dissimilatory iron reduction could remediate reducible pollutants in groundwater, such as nitrobenzene (NB). But the natural attenuation rate in aquifer is limited. To stimulate this process, emulsified vegetable oil (EVO) was injected as a remediation agent. The mechanism of this process was studied. Results showed that the addition of EVO made iron easier used by microorganisms and thus promoted dissimilatory iron reduction. The readily used Fe(III) served as electron acceptor and was reduced to Fe(II). Fe(II) supplied electrons to NB, with NB reduced to aniline. Sulphide in the aquifer media also donated electrons and oxidized to polysulfide, then forming precipitates with Fe(II) to the surface of aquifer media, and thus slowing down the electron supplying of EVO and forming permanent efficiency for NB remediation. The work helps to complete a systematic understanding of NB remediation process under stimulation of EVO.

Kinetics of nitrobenzene degradation coupled to indigenous microorganism dissimilatory iron reduction stimulated by emulsified vegetable oil.

Widespread contamination by nitrobenzene (NB) in sediments and groundwater requires better understanding of the biogeochemical removal process of the pollutant. NB degradation, coupled with dissimilatory iron reduction, is one of the most efficient pollutant removal methods. However, research on NB degradation coupled to indigenous microorganism dissimilatory iron reduction stimulated by electron donors is still experimental. A model for remediation in an actual polluted site does not currently exist. Therefore, in this study, the dynamics was derived from the Michaelis-Menten model (when the mass ratio of emulsified vegetable oil and NB reached the critical value 91:1). The effect of SO42-, NO3-, Ca2+/Mg2+, and the grain size of aquifer media on the dynamics were studied, and the NB degradation dynamic model was then modified based on the most significant factors. Utilizing the model, the remediation time could be calculated in a contaminated site.