Removal of Arsenic (III) from groundwater applying a reusable Mg-Fe-Cl layered double hydroxide

BACKGROUND: Layered double hydroxide compounds (LDHs) have been applied for the removal of oxyanions including arsenate (As(V)). However, the aim of this present research is to develop a LDH to treat arsenite (As(III)). Both batch and column sorption studies were conducted to assess the effect of LDH dosage, contact time, solution pH and initial As(III) concentrations on the As(III) removal performance. The potential re-use of this sorbent was also investigated.<p></p> RESULTS: For 2 g L−1 of Mg-Fe-Cl LDH, As(III) in test solution can be reduced from 400 µg L−1 to <10 µg L−1 after a contact time of 2 h. High As(III) concentration in Bangladesh groundwater can be reduced to meet the national drinking water standards (<50 µg L−1). The maximum adsorption capacity of As(III) by Mg-Fe-Cl LDH is 14.6 mg g−1-LDH. Further, reusability of this sorbent was at least 20 cycles of regeneration with effective As(III) removal between 93.0 and 98.5%. Moreover, As(III) removal was unaffected by the solution pH but affected by the co-existing competing anions and concentration of As(III). Finally, the main mechanism of As(III) removal by Mg-Fe-Cl LDH was suggested to be chemical sorption together with anion and ligand exchange with interlayer Cl− and OH− ions.<p></p> CONCLUSION: High efficiency of sorption of As(III) by the developed Mg-Fe-Cl LDH was demonstrated in this study which is generally not the case for most other sorbent materials. Pilot-scale trials are needed to explore the suitability of full application of the developed Mg-Fe-Cl LDH for the removal of As(III).<p></p&gt

Natural attenuation of arsenic by sediment sorption and oxidation

Arsenic sorption onto aquifer sediments was investigated in anaerobic laboratory batch and column uptake experiments and characterized by As, Fe, and Mn X-ray absorption spectroscopy (XAS) to estimate the extent and mechanism of abiotic sorption and oxidation of As(III). Batch experiments at pH 6 showed that the amount of As(III) or As(V) sorption from synthetic background porewater to sediments was similar as a function of total As concentration, but slightly more As(V) was sorbed than As(III) with increasing As concentrations. Column experiments with As(III) solutions in the absence and presence of dissolved Fe^2+ showed more As uptake in the presence of Fe but also more Fe desorption during flushout with As-free solutions such that net As uptake was similar to, or less than that of, the Fe-free experiment. Fits to bulk Fe X-ray absorption near-edge spectroscopy (XANES) spectra showed no change between unreacted and reacted sediments. Manganese XANES revealed small increases in absorption in the spectral region associated with Mn(II) after reaction, indicating sediment Mn reduction. However, XANES spectra showed that Mn is not present as Mn^(IV)O_2(s) but is probably substituted into other sediment minerals as a mixture of Mn(II,III). Quantitative analyses of As XANES spectra, which indicated mixtures of As(III) and As(V) after reaction with As(III) solutions, were used to estimate a fraction of As(V) in excess of native As(V) in the sediment (0.2 mmol kg^−1) that corresponds to sorbed As(III) oxidized to As(V). The spectroscopic and solution data indicate that the aquifer sediments have a limited abiotic capacity to oxidize As(III), which did not exceed 30% of the total amount of As sorbed and was estimated in the range of 0.025−0.4 mmol kg^−1 sediment. In the presence of dissolved Fe^2+, the precipitation of Fe(III) hydrous oxide phases will be an effective mechanism for As scavenging only if there exists sufficient dissolved oxygen in groundwater to oxidize Fe. Once the aqueous oxidative capacity is exhausted, dissolved Fe^2+ may compete with As(III) for the limited abiotic oxidation supplied by sediment Mn-bearing phases

Arsenic(III) remediation from contaminated water by oxidation and Fe/Al co-precipitation

Battery grade γ-MnO2 powder was investigated as an oxidant and an adsorbent in combination with Fe/Al coagulants for removal of arsenic from contaminated water. Simultaneous oxidation of As(III) and removal by coprecipitation/adsorption (one step process) was compared with pre-oxidation and subsequent removal by coprecipitation/adsorption (two step process). The rate of As(III) oxidation with MnO2 is completed in two stages: rapid initially followed by a first order reaction. As(III) is oxidised to As(V) by the MnO2 with a release of approximately 1:1 molar Mn(II) into the solution. No significant pH effect on oxidation of As(III) was observed in the pH range 4 - 6. The rate showed a decreasing trend above pH 6. The removal of As(V) by adsorption on the MnO2 decreased significantly with increasing pH from 4 to 8. The adsorption capacity of the γ-MnO2 with particle size 90% passing 10 µm was determined to be 1.5 mg/g at pH 7. MnO2 was found to be more effective as an oxidant for As(III) in the two step process than in the one step process

Preparation of graphene oxide/titanium dioxide nanocomposites and its adsorption for AS(III) ions

Arsenic is a naturally occurring element, which is found in both in natural waters and industrial waters. Graphene oxide/Titanium dioxide (GO/TiO2) nanocomposites were prepared by using hydrothermal technique, their structure was observed and their adsorption performance for As(III) in water was evaluated. X-ray diffraction and Raman spectroscopy spectra confirmed the anatase structure of the TiO2 nanoparticles. The adsorption system is mainly depended on the As(III) concentration and follows a pseudo second-order kinetic model. The initial adsorption was rapid and reached equilibrium after 20 min. The overall equilibrium data were well fitted to Langmuir model for the nanocomposites. The adsorption results indicated that the GO/TiO2 nanocomposites can be a good adsorbent material to treat water that contaminated with As(III)

Arsenite sorption and co-precipitation with calcite

Sorption of As(III) by calcite was investigated as a function of As(III) concentration, time and pH. The sorption isotherm, i.e. the log As(III) vs. log [As(OH)3 degrees / Assat] plot is S-shaped and has been modelled on an extended version of the surface precipitation model. At low concentrations, As(OH)3 degrees is adsorbed by complexation to surface Ca surface sites, as previously described by the X-ray standing wave technique. The inflexion point of the isotherm, where As(OH)3 degrees is limited by the amount of surface sites (ST), yields 6 sites nm-2 in good agreement with crystallographic data. Beyond this value, the amount of sorbed arsenic increases linearly with solution concentration, up to the saturation of arsenic with respect to the precipitation of CaHAsO3(s). The solid solutions formed in this concentration range were examined by X-ray and neutron diffraction. The doped calcite lattice parameters increase with arsenic content while c/a ratio remains constant. Our results made on bulk calcite on the atomic displacement of As atoms along [0001] direction extend those published by Cheng et al., (1999) on calcite surface. This study provides a molecular-level explanation for why As(III) is trapped by calcite in industrial treatments.Comment: 9 page

A parametric evaluation of the removal as(III) and as(V) from aqueous water by red mud

In the present study, removal of arsenide (As(III)) and arsenate As(V) ions from water/wastewater by adsorption on red mud is investigated. Laboratory experiments were carried out to analyze removal capacity of the adsorbents, to achieve adsorption isotherms and kinetic parameters. Optimum doses of adsorbents, pH dependence of solutions, and contact time have been discussed. This study proposes the potential adsorbent material for water/wastewater which is contaminated with As species

Pathway of human AS3MT arsenic methylation

A synthetic gene encoding human As(III) S-adenosylmethionine (SAM) methyltransferase (hAS3MT) was expressed, and the purified enzyme was characterized. The synthetic enzyme is considerably more active than a cDNA-expressed enzyme using endogenous reductants thioredoxin (Trx), thioredoxin reductase (TR), NADPH, and reduced glutathione (GSH). Each of the seven cysteines (the four conserved residues, Cys32, Cys61, Cys156, and Cys206, and nonconserved, Cys72, Cys85, and Cys250) was individually changed to serine. The nonconserved cysteine derivates were still active. None of the individual C32S, C61S, C156S, and C206S derivates were able to methylate As(III). However, the C32S and C61S enzymes retained the ability to methylate MAs(III). These observations suggest that Cys156 and Cys206 play a different role in catalysis than that of Cys32 and Cys61. A homology model built on the structure of a thermophilic orthologue indicates that Cys156 and Cys206 form the As(III) binding site, whereas Cys32 and Cys61 form a disulfide bond. Two observations shed light on the pathway of methylation. First, binding assays using the fluorescence of a single-tryptophan derivative indicate that As(GS)3 binds to the enzyme much faster than inorganic As(III). Second, the major product of the first round of methylation is MAs(III), not MAs(V), and remains enzyme-bound until it is methylated a second time. We propose a new pathway for hAS3MT catalysis that reconciles the hypothesis of Challenger ((1947) Sci. Prog., 35, 396-416) with the pathway proposed by Hayakawa et al. ((2005) Arch. Toxicol., 79, 183-191). The products are the more toxic and more carcinogenic trivalent methylarsenicals, but arsenic undergoes oxidation and reduction as enzyme-bound intermediates

Rapid and Efficient Arsenic Removal by Iron Electrocoagulation Enabled with in Situ Generation of Hydrogen Peroxide.

Millions of people are exposed to toxic levels of dissolved arsenic in groundwater used for drinking. Iron electrocoagulation (FeEC) has been demonstrated as an effective technology to remove arsenic at an affordable price. However, FeEC requires long operating times (∼hours) to remove dissolved arsenic due to inherent kinetics limitations. Air cathode Assisted Iron Electrocoagulation (ACAIE) overcomes this limitation by cathodically generating H2O2 in situ. In ACAIE operation, rapid oxidation of Fe(II) and complete oxidation and removal of As(III) are achieved. We compare FeEC and ACAIE for removing As(III) from an initial concentration of 1464 μg/L, aiming for a final concentration of less than 4 μg/L. We demonstrate that at short electrolysis times (0.5 min), i.e., high charge dosage rates (1200 C/L/min), ACAIE consistently outperformed FeEC in bringing arsenic levels to less than WHO-MCL of 10 μg/L. Using XRD and XAS data, we conclusively show that poor arsenic removal in FeEC arises from incomplete As(III) oxidation, ineffective Fe(II) oxidation and the formation of Fe(II-III) (hydr)oxides at short electrolysis times (<20 min). Finally, we report successful ACAIE performance (retention time 19 s) in removing dissolved arsenic from contaminated groundwater in rural California

Microbial communities and arsenic biogeochemistry at the outflow of an alkaline sulfide-rich hot spring.

Alkaline sulfide-rich hot springs provide a unique environment for microbial community and arsenic (As) biogeochemistry. In this study, a representative alkaline sulfide-rich hot spring, Zimeiquan in the Tengchong geothermal area, was chosen to study arsenic geochemistry and microbial community using Illumina MiSeq sequencing. Over 0.26 million 16S rRNA sequence reads were obtained from 5-paired parallel water and sediment samples along the hot spring's outflow channel. High ratios of As(V)/AsSum (total combined arsenate and arsenite concentrations) (0.59-0.78), coupled with high sulfide (up to 5.87 mg/L), were present in the hot spring's pools, which suggested As(III) oxidation occurred. Along the outflow channel, AsSum increased from 5.45 to 13.86 μmol/L, and the combined sulfide and sulfate concentrations increased from 292.02 to 364.28 μmol/L. These increases were primarily attributed to thioarsenic transformation. Temperature, sulfide, As and dissolved oxygen significantly shaped the microbial communities between not only the pools and downstream samples, but also water and sediment samples. Results implied that the upstream Thermocrinis was responsible for the transformation of thioarsenic to As(III) and the downstream Thermus contributed to derived As(III) oxidation. This study improves our understanding of microbially-mediated As transformation in alkaline sulfide-rich hot springs