Transformation Of Arsenite Research Articles

As(III)-Oxidizing Bacteria Alleviate Arsenite Toxicity via Reducing As Accumulation, Elevating Antioxidative Activities and Modulating Ionome in Rice (Oryza sativa L.).

Paddy rice trends to accumulate more arsenic (As) from soils than other terrestrial crops. The toxicity and mobility of As mainly depend on its chemical species. Transformation of arsenite [As(III)] into arsenate [As(V)] would be a promising method to mitigate As toxicity. In the current study, As(III)-oxidizing strain SMS11 isolated from As-contaminated soils was employed for As remediation. Co-cultured with SMS11 alleviated As(III) stress to the rice plants by increasing the length and biomass of rice shoots up to 10% and 15%, respectively. Evaluation of oxidative stress indices showed that the activity of catalase in the rice shoots was weakened when exposed to As(III), increasing the risk of hydroxyl radical (·OH) formation. When co-cultivated with the bacteria, ·OH formation was significantly inhibited in the rice shoots. The ionomes of the rice plants were impacted by the external conditions. As(III) stress significantly disturbed ionome homeostasis in the rice plants. Uptake of As simultaneously elevated the levels of macro and nutrient elements such as Mg, P, K, Ca, and Zn in the rice shoots. The ionomic variation in the rice plants under As(III) stress was mitigated by inoculated with SMS11. The results represented that the As(III)-oxidizing bacteria alleviated external As(III) stress to the rice plants through elevating antioxidative activities and modulating ionome homeostasis.

Ultrahigh resolution MS1/MS2-based reconstruction of metabolic networks in mammalian cells reveals changes for selenite and arsenite action

Metabolic networks are complex, intersecting, and composed of numerous enzyme-catalyzed biochemical reactions that transfer various molecular moieties among metabolites. Thus, robust reconstruction of metabolic networks requires metabolite moieties to be tracked, which cannot be readily achieved with mass spectrometry (MS) alone. We previously developed an Ion Chromatography-ultrahigh resolution-MS1/data independent-MS2 method to track the simultaneous incorporation of the heavy isotopes 13C and 15N into the moieties of purine/pyrimidine nucleotides in mammalian cells. Ultrahigh resolution-MS1 resolves and counts multiple tracer atoms in intact metabolites, while data independent-tandem MS (MS2) determines isotopic enrichment in their moieties without concern for the numerous mass isotopologue source ions to be fragmented. Together, they enabled rigorous MS-based reconstruction of metabolic networks at specific enzyme levels. We have expanded this approach to trace the labeled atom fate of [13C6]-glucose in 3D A549 spheroids in response to the anticancer agent selenite and that of [13C5,15N2]-glutamine in 2D BEAS-2B cells in response to arsenite transformation. We deduced altered activities of specific enzymes in the Krebs cycle, pentose phosphate pathway, gluconeogenesis, and UDP-GlcNAc synthesis pathways elicited by the stressors. These metabolic details help elucidate the resistance mechanism of 3D versus 2D A549 cultures to selenite and metabolic reprogramming that can mediate the transformation of BEAS-2B cells by arsenite.

Selenite and selenate showed contrasting impacts on the fate of arsenic in rice (Oryza sativa L.) regardless of the formation of iron plaque

The different effects of selenite and selenate on the fate of As and the function of iron plaque in the interaction between Se and As are poorly understood. Rice seedlings (Oryza sativa L.) were selected as experimental plants in this study, the hydroponic experiments were conducted to investigate the possible regulatory roles of selenite and selenate on the uptake, translocation, and transformation of arsenite or arsenate accompanied by iron plaque. In arsenite- and arsenate-treated rice, the Fe30 treatments stimulated root uptake by 12.4–39.8% and 18.6–37.0%, respectively, but inhibited the movement of As from iron plaque to the roots, resulting in the absorption of a considerable amount of As on iron plaque. Regardless of the iron plaque formation, selenite (selenate) significantly increased (decreased) the root uptake of arsenite and arsenate by 28.1–53.0% and 40.0%–61.7%, respectively (45.6–56.3% and 42.5–47.7%, respectively). Interestingly, the supply of selenite significantly reduced root-to-shoot As translocation by 71.9–77.3% and 66.2–67.7%, respectively, in arsenite- and arsenate-treated rice seedlings; however, a significant increase (90.5–122.9%) was induced by selenate was found only in the arsenate-treated plants. Furthermore, the translocation of As from iron plaque to the roots was significantly increased (decreased) by selenite (selenate). As and Fe in iron plaque were significantly positively correlated in all As-treated rice plants, and this correlation was more profound than that in the shoots and roots. However, neither Fe treatments nor inorganic Se addition affected the interconversion between As(III) and As(V) obviously; and As(III) was the dominant species in both shoots (68.3–84.9%) and roots (90.7–98.2%). Our results indicate selenite and selenate are effective in reducing the As accumulation in an opposite way, and the presence of iron plaque had no obvious impact on the interaction between Se and As in rice plants.

Impacts of ammonium ion on triclinic birnessites towards the transformation of As(III)

Triclinic birnessite (TB), a typical layered Mn oxide which is abundant naturally occurring minerals with a vital impact on the transformation of arsenite (As(III)) by adsorption and oxidation. As one of the most common critical metalloids, ammonium ion (NH4+) universally coexists with birnessite in marine, sediments or groundwater where are contaminated with As(III). In this study, we investigated the impacts of NH4+ on TB towards the transformation of As(III). Compared with the original TB (40.1%), the As(III) removal efficiencies of three different concentration (0.5 M, 1 M and 2 M) NH4+ impressed triclinic birnessite (TB-0.5 N, TB-1N and TB-2N) are increased rapidly in the order of: TB-2N (80.4%) > TB-1N (75.8%) > TB-0.5 N (71.5%). In addition, TB-2N exhibited the highest initial oxidation rate of 0.0031 min−1 which exceeds twice as much as this of TB (0.0014 min−1). And TB-2N could reach the max oxidation efficiency when the As concentration is 0.08 mM. Due to two different mechanisms of As(III) oxidation on birnessites under acidic and alkaline conditions, TB-2N showed a higher removal efficiency than TB at pH 3.0, 5.0, 7.0 and 9.0. Hence, there are two main reasons for the advanced As(III) oxidation capacity of TB-2N. One is the improvement of the average oxidation state of Mn, the other is the increase of oxygen vacancy with the coexistence of NH4+. Moreover, the larger specific surface area of TB-2N also contribute to enhancing As(III) oxidation capacity. This study holds a fundamental understanding of the behavior of triclinic birnessite which is coexisted with ammonium ion towards the transformation of As(III) in the environment.

Electron shuttle-induced oxidative transformation of arsenite on the surface of goethite and underlying mechanisms

The redox process of electron shuttles like cysteine on iron minerals under aerobic conditions may largely determine the fate of arsenic (As) in soils, while the interfacial processes and underlying mechanisms are barely explored. This work systematically investigates the interfacial oxidation processes of As(III) on goethite induced by cysteine. Results show that the addition of cysteine significantly enhances the oxidation efficiency (~ 40%) of As(III) (C0: 10 mg/L) by goethite at pH 7 under aerobic conditions, which is 19.5 times of that without cysteine. cysteine induces Fe(III) reduction on the surface of goethite, and the generation absorbed Fe(II) species play an important role in As(III) oxidation. In particular, the further complexation of Fe(II) with cysteine is thermodynamically favorable for electron transfer, leading to an enhanced As(III) oxidation efficiency. The oxidation efficiency of As(III) in the goethite/cysteine system increases by increasing cysteine concentration and decreases by elevating pH conditions. In addition, evidence indicates that •O2- radicals account for approximately 80% of total oxidized As(III). Meanwhile, only 16% of As(III) oxidation can be attributed to the formed •OH radicals. This work provides new insight into the role of organic electron shuttling compounds in determining As cycling in soils.

An Ion Chromatography-Ultrahigh-Resolution-MS1/Data-Independent High-Resolution MS2 Method for Stable Isotope-Resolved Metabolomics Reconstruction of Central Metabolic Networks.

The metabolome comprises a complex network of interconnecting enzyme-catalyzed reactions that involve transfers of numerous molecular subunits. Thus, the reconstruction of metabolic networks requires metabolite substructures to be tracked. Subunit tracking can be achieved by tracing stable isotopes through metabolic transformations using NMR and ultrahigh -resolution (UHR)-mass spectrometry (MS). UHR-MS1 readily resolves and counts isotopic labels in metabolites but requires tandem MS to help identify isotopic enrichment in substructures. However, it is challenging to perform chromatography-based UHR-MS1 with its long acquisition time, while acquiring MS2 data on many coeluting labeled isotopologues for each metabolite. We have developed an ion chromatography (IC)-UHR-MS1/data-independent(DI)-HR-MS2 method to trace the fate of 13C atoms from [13C6]-glucose ([13C6]-Glc) in 3D A549 spheroids in response to anticancer selenite and simultaneously 13C/15N atoms from [13C5,15N2]-glutamine ([13C5,15N2]-Gln) in 2D BEAS-2B cells in response to arsenite transformation. This method retains the complete isotopologue distributions of metabolites via UHR-MS1 while simultaneously acquiring substructure label information via DI-MS2. These details in metabolite labeling patterns greatly facilitate rigorous reconstruction of multiple, intersecting metabolic pathways of central metabolism, which are illustrated here for the purine/pyrimidine nucleotide biosynthesis. The pathways reconstructed based on subunit-level isotopologue analysis further reveal specific enzyme-catalyzed reactions that are impacted by selenite or arsenite treatments.

The fate of arsenic in rice plants (Oryza sativa L.): Influence of different forms of selenium

As contamination of rice plants has aroused worldwide concern because of the threats posed to human health through its accumulation in the food chain. However, no data are currently available on the effect of Se nanoparticles (SeNPs) on the fate of As in higher plants, and previously reported relationships between As and Se are inconsistent. Therefore, in this study, the possible mediating roles of SeNPs or selenite on the uptake, translocation, subcellular distribution, and transformation of arsenite and arsenate in rice seedlings (Oryza sativa L.) were investigated through hydroponic experiments. The results showed that, when supplied as arsenite and arsenate, selenite significantly increased root As uptake by 71.7% and 45.9% but decreased shoot As content by 48.9% and 52.4%, respectively. In comparison, the reducing effect of SeNPs on shoot As content (37.1%) was only significant in arsenite-treated rice plants. Furthermore, selenite significantly reduced and increased the As content of different shoot and root subcellular fractions, respectively; and SeNPs also led to a dramatic decrease in the As content of the different shoot subcellular fractions of arsenite-treated rice plants. Moreover, As(III) and As(V) content was reduced in rice shoots while enhanced in rice roots by selenite. Generally, neither As(III) nor As(V) content in rice tissues was dramatically changed by SeNPs. Our results indicate that both SeNPs and selenite are effective in mitigating As toxicity in rice plants, although selenite showed a stronger inhibiting effect on As translocation.

A two-step approach for arsenic removal by exploiting an autochthonous Delftia sp. BAs29 and neutralized red mud.

Groundwater arsenic contamination represents a global threat to human health. Among the proposed bioremediation applications, microbial transformation of arsenite (As (III)) seems to be the most favorable approach as it can be easily coupled with several adsorption techniques, without producing lethal by-products or demanding chemical addition. This study highlights the potential contribution of a highly efficient As (III) transforming bacteria Delftia sp. BAs29 followed by the adsorption of transformed arsenate (As (V)) using neutralized red mud under suitable treatment conditions. Diverse experimental conditions elucidated (inflow As (III) concentrations, flow rate) the rate and oxidation efficiency to mediate the process. Red mud is a waste by-product from the Bayer's process of the alumina industry, which when neutralized aids the removal of As (V). The neutralized red mud was characterized using X-ray diffraction (XRD) microanalysis, Scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDX) and Fourier-transform infrared spectroscopy (FTIR). Arsenate adsorption using neutralized red mud was also studied as a function of pH and time, adsorbent dosage, and initial As (V) concentration. The adsorption process was significantly affected by the solution pH, which on decreasing gradually increased the adsorption efficiency. The maximum monolayer capacity for adsorption of 274.1mg/g As (V) was found at optimum conditions of pH4.0 and a contact time of 30min at a temperature of 30°C, respectively. Furthermore, this process significantly contributed in fabricating a two-step bio-filter column for the removal of total arsenic from groundwater. Graphical abstract.

Influence of environmental factors on arsenite transformation and fate in the Hydrilla verticillata (L.f.) royle - Medium system

Hydrilla verticillata (L.f.) Royle has a great ability to accumulate large amounts of arsenic (As). We studied the influence of phosphorus (P), nitrogen (N), pH, and arsenite (As(III)) on As transformation and fate in the H. verticillata - medium system via orthogonal experimental design. The results showed highest plant growth was under intermediate As(III) in the medium, with Chlorophyll a and Chlorophyll b contents in plant diminishing after 96 h treatment. Exposure to high N, high As(III), intermediate P, and low pH in the medium, the highest total arsenic uptake by plants were 169.1 ± 5.5 μg g−1 dry weight, with As(III) as the predominant speciation (49.1 ± 4.8% to 88.5 ± 0.2%) in plants. Meanwhile, trace As (mainly arsenate (As(V))) was adsorbed on the surface of H. verticillata, and the adsorption amounts of As(V) increased with increasing As(III) concentrations in the medium. The dominant As species was As(V) in the medium although plant was supplied with As(III), and highest As(III) oxidation proportion in the medium would occur when low N and pH associated with high P and As(III). Collectively, As(III) uptake and transformation by H. verticillata cannot be overlooked in the biogeochemical cycling of As in aquatic environment.

Arsenite malignantly transforms human prostate epithelial cells in vitro by gene amplification of mutated KRAS.

Inorganic arsenic is an environmental human carcinogen of several organs including the urinary tract. RWPE-1 cells are immortalized, non-tumorigenic, human prostate epithelia that become malignantly transformed into the CAsE-PE line after continuous in vitro exposure to 5μM arsenite over a period of months. For insight into in vitro arsenite transformation, we performed RNA-seq for differential gene expression and targeted sequencing of KRAS. We report >7,000 differentially expressed transcripts in CAsE-PE cells compared to RWPE-1 cells at >2-fold change, q<0.05 by RNA-seq. Notably, KRAS expression was highly elevated in CAsE-PE cells, with pathway analysis supporting increased cell proliferation, cell motility, survival and cancer pathways. Targeted DNA sequencing of KRAS revealed a mutant specific allelic imbalance, ‘MASI’, frequently found in primary clinical tumors. We found high expression of a mutated KRAS transcript carrying oncogenic mutations at codons 12 and 59 and many silent mutations, accompanied by lower expression of a wild-type allele. Parallel cultures of RWPE-1 cells retained a wild-type KRAS genotype. Copy number analysis and sequencing showed amplification of the mutant KRAS allele. KRAS is expressed as two splice variants, KRAS4a and KRAS4b, where variant 4b is more prevalent in normal cells compared to greater levels of variant 4a seen in tumor cells. 454 Roche sequencing measured KRAS variants in each cell type. We found KRAS4a as the predominant transcript variant in CAsE-PE cells compared to KRAS4b, the variant expressed primarily in RWPE-1 cells and in normal prostate, early passage, primary epithelial cells. Overall, gene expression data were consistent with KRAS-driven proliferation pathways found in spontaneous tumors and malignantly transformed cell lines. Arsenite is recognized as an important environmental carcinogen, but it is not a direct mutagen. Further investigations into this in vitro transformation model will focus on genomic events that cause arsenite-mediated mutation and overexpression of KRAS in CAsE-PE cells.

Inactivation of Laccase by the Attack of As (III) Reaction in Water.

Laccase is a multicopper oxidase containing four coppers as reaction sites, including one type 1, one type 2, and two type 3. We here provide the first experimental data showing that As (III) can be effectively removed from water and transformed to As (V) through reactions mediated by laccase with the presence of oxygen. To this end, the As (III) removal, As (V) yields, total protein, active laccase, and copper concentrations in the aqueous phase were determined, respectively. Additionally, electron paramagnetic resonance spectra and UV-vis spectra were applied to probe possible structural changes of the laccase during the reaction. The data offer the first evidence that laccase can be inactivated by As (III) attack thus leading to the release of type 2 copper. The released copper has no reactivity with the As (III). These findings provide new ideas into a significant pathway likely to master the environmental transformation of arsenite, and advance the understanding of laccase inactivation mechanisms, thus providing a foundation for optimization of enzyme-based processes and potential development for removal and remediation of arsenite contamination in the environment.

Adaptive responses and arsenic transformation potential of diazotrophic Cyanobacteria isolated from rice fields of arsenic affected Bengal Delta Plain

In the Bengal Delta Plains (BDP) of South Asia, there is an increased report of bioaccumulation of arsenic (As) in rice grains and plants which can ultimately result in health hazards in human population consuming rice as a primary staple food. Five abundant cyanobacteria were isolated from the rice fields of BDP and maintained in vitro. The characterized isolates resembled Leptolyngbya sp. (isolate LBK), Nostoc spp. (isolates NOC and NOK) and Westiellopsis spp. (isolates WEC and WEK) based on polyphasic taxonomy. All the five isolates were assessed for biotransformation potential of As vis-a-vis adaptability and survivality under different levels of arsenite compared to control set of experiments. Adaptive changes of cyanobacterial photosynthetic pigments in terms of autofluorescence emission along with nitrogenase activity and exopolysaccharide production were measured for all isolates. The inorganic As absorption in terms of bioconcentration factor (BCF) in dry biomass was found to be highest in NOC (0.201–0.220), followed by NOK (0.147–0.150), WEK (0.071–0.074), WEC (0.051) and LBK (0.014) when exposed in presence of higher (200–400 μM) to lower (100 μM) arsenite concentrations respectively for 7 days. The transformation of arsenite to relatively less toxic arsenate was detected in varying efficiency in all the studied isolates. When treated with 100–400 μM arsenite, 9.58–78.4 % arsenate was detected in growth medium whereas 33–100 % in dry biomass of cyanobacterial isolates. The cyanobacterial isolates of this study could be potentially applied to reduce bioavailability of As in rice fields of South Asia based on further field trials, thereby ultimately rendering rice grains safe for human consumption.

Microbial contributions to coupled arsenic and sulfur cycling in the acid-sulfide hot spring Champagne Pool, New Zealand.

Acid-sulfide hot springs are analogs of early Earth geothermal systems where microbial metal(loid) resistance likely first evolved. Arsenic is a metalloid enriched in the acid-sulfide hot spring Champagne Pool (Waiotapu, New Zealand). Arsenic speciation in Champagne Pool follows reaction paths not yet fully understood with respect to biotic contributions and coupling to biogeochemical sulfur cycling. Here we present quantitative arsenic speciation from Champagne Pool, finding arsenite dominant in the pool, rim and outflow channel (55–75% total arsenic), and dithio- and trithioarsenates ubiquitously present as 18–25% total arsenic. In the outflow channel, dimethylmonothioarsenate comprised ≤9% total arsenic, while on the outflow terrace thioarsenates were present at 55% total arsenic. We also quantified sulfide, thiosulfate, sulfate and elemental sulfur, finding sulfide and sulfate as major species in the pool and outflow terrace, respectively. Elemental sulfur concentration reached a maximum at the terrace. Phylogenetic analysis of 16S rRNA genes from metagenomic sequencing revealed the dominance of Sulfurihydrogenibium at all sites and an increased archaeal population at the rim and outflow channel. Several phylotypes were found closely related to known sulfur- and sulfide-oxidizers, as well as sulfur- and sulfate-reducers. Bioinformatic analysis revealed genes underpinning sulfur redox transformations, consistent with sulfur speciation data, and illustrating a microbial role in sulfur-dependent transformation of arsenite to thioarsenate. Metagenomic analysis also revealed genes encoding for arsenate reductase at all sites, reflecting the ubiquity of thioarsenate and a need for microbial arsenate resistance despite anoxic conditions. Absence of the arsenite oxidase gene, aio, at all sites suggests prioritization of arsenite detoxification over coupling to energy conservation. Finally, detection of methyl arsenic in the outflow channel, in conjunction with increased sequences from Aquificaceae, supports a role for methyltransferase in thermophilic arsenic resistance. Our study highlights microbial contributions to coupled arsenic and sulfur cycling at Champagne Pool, with implications for understanding the evolution of microbial arsenic resistance in sulfidic geothermal systems.

Arsenic speciation transformation and arsenite influx and efflux across the cell membrane of fungi investigated using HPLC–HG–AFS and in-situ XANES

Microorganisms dominated speciation of arsenic (As) play an important role in the biogeochemical cycling of As. In the study, species transformation of arsenite [As(III)] and As(III) influx and efflux across the cell membranes of Trichoderma asperellum SM-12F1, Penicillium janthinellum SM-12F4, and Fusarium oxysporum CZ-8F1 cells were studied using a cellular lysis plus chromatographic separation method and further the in-situ X-ray absorption near edge structure (XANES) analysis. The results indicated that As(III) can enter into fungal cells and that a portion of the As(III) can be exuded out of cells. For both As sequestrated into fungal cytoplasm and As adsorbtion onto cell walls, As(III) was found to be the dominated form of As. XANES analysis showed that As(III) accounted for 58.4%, 59.5%, and 73.0% of the total As in the cells of T. asperellum SM-12F1, P. janthinellum SM-12F4, and F. oxysporum CZ-8F1, respectively. Among these fungal strains, however, there were obvious differences in the relative proportions of arsenate [As(V)], monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA). For T. asperellum SM-12F1, the proportion (%) of MMA was 31.1%, and no As(V) or DMA was detected. For F. oxysporum CZ-8F1, the proportions of As(V) and MMA were 15.8% and 8.8%, respectively, but no DMA was observed. As(V), MMA, and DMA accounted for 4.2%, 29.5%, and 8.1%, respectively, of the P. janthinellum SM-12F4 cells. Some of the intracellular As(III) can be oxidated and methylated by these fungal strains and yield As(V), MMA, and DMA as products.

The role of rainwater-borne hydrogen peroxide in the release of arsenic from arsenopyrite

A microcosm experiment was conducted to examine the effects of hydrogen peroxide (at a concentration range of 5–50μM) on the release of arsenic from the dissolution of arsenopyrite, a dominant arsenic-bearing mineral occurring in natural environments. This was to simulate the reaction between rainwater-borne hydrogen peroxide and arsenopyrite grains exposed on the land surfaces during rainfall events. The results showed that the release of arsenic from arsenopyrite was enhanced by the H2O2 at this concentration range. It was also evident that H2O2 played an indirect role in the transformation of arsenite into arsenate in the solutions, which might affect the fate of the liberated arsenic species due to the formation of FeAsO4 precipitates. The preliminary study sheds some light on the possible role of rainwater-borne H2O2 in the weathering of arsenopyrite, which could complicate the geochemical processes governing the release, transport and fate of arsenopyrite-derived arsenic in natural environments. This provides a rationale for conducting additional laboratory-based investigations to obtain further insights into the chemical mechanisms and kinetics, and the subsequent field-scale study to validate the research findings.

Arsenite sorption and oxidation by synthetic birnessite

Research Article| June 01 2013 Arsenite sorption and oxidation by synthetic birnessite N. Wang; N. Wang 1Department of Environmental Science and Engineering, Liaoning Technical University, Fuxin 123000, China2Department of Soil and Environment, Shenyang Agricultural University, Shenyang 110866, China E-mail: wnnan83@163.com Search for other works by this author on: This Site PubMed Google Scholar C. Liang; C. Liang 2Department of Soil and Environment, Shenyang Agricultural University, Shenyang 110866, China Search for other works by this author on: This Site PubMed Google Scholar L. Du; L. Du 2Department of Soil and Environment, Shenyang Agricultural University, Shenyang 110866, China Search for other works by this author on: This Site PubMed Google Scholar H. Cui H. Cui 2Department of Soil and Environment, Shenyang Agricultural University, Shenyang 110866, China Search for other works by this author on: This Site PubMed Google Scholar Journal of Water Supply: Research and Technology-Aqua (2013) 62 (4): 245–253. https://doi.org/10.2166/aqua.2013.099 Article history Received: July 10 2012 Accepted: March 31 2013 Views Icon Views Article contents Figures & tables Video Audio Supplementary Data Share Icon Share Facebook Twitter LinkedIn MailTo Tools Icon Tools Cite Icon Cite Permissions Search Site Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentAll JournalsThis Journal Search Advanced Search Citation N. Wang, C. Liang, L. Du, H. Cui; Arsenite sorption and oxidation by synthetic birnessite. Journal of Water Supply: Research and Technology-Aqua 1 June 2013; 62 (4): 245–253. doi: https://doi.org/10.2166/aqua.2013.099 Download citation file: Ris (Zotero) Reference Manager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex Arsenite (As(III)) is a more toxic form of inorganic arsenic and its removal from drinking water is less effective compared with arsenate (As(V)). In the present study, synthetic birnessite (δ-MnO2) was used to investigate the oxidative transformation of arsenite into arsenate using batch experiments under different reaction conditions. Results showed that arsenite transformation occurred and was accompanied by the sorption and fixation of both As(III) and As(V) on δ-MnO2. Approximately 90% of the arsenite (1.0 mg/L) was transformed by δ-MnO2 at 25 °C and pH 6.0, 49% of which was sorbed and 10% fixed by δ-MnO2. Increased δ-MnO2 dosages promoted the transformation rate of As(III) and sorption of As species. As pH increased from a very low value (pH 2.0), the amount of As(III) oxidized by the tested δ-MnO2 initially decreased, then negatively peaked at pH 4.0, and eventually increased remarkably. At the same time, the oxidation of As(III) by δ-MnO2 had a buffering effect on the pH variation in the solution; the oxidation rate decreased and sorbed As(III) and As(V) increased with the increase in initial arsenite concentration. These findings are of great significance in improving our understanding of As geochemical cycling and in controlling As contamination. As(III), As(V), birnessite, manganese oxide, oxidation, sorption This content is only available as a PDF. © IWA Publishing 2013 You do not currently have access to this content.

The oxidative transformation of sodium arsenite at the interface of α-MnO2 and water

Arsenite is acute contaminant to human health in soil and water environment. In this study, Pyrolusite (alpha-MnO(2)) was used to investigate the oxidative transformation of arsenite into arsenate with batch experiments under different reaction conditions. The results showed that arsenite transformation occurred and was accompanied by the adsorption and fixation of both As(III) and As(V) on alpha-MnO(2). About 90% of sodium arsenite (10mg/L) were transformed by alpha-MnO(2) under the conditions of 25 degrees C and pH 6.0, 36.6% of which was adsorbed and 28.9% fixed by alpha-MnO(2). Increased alpha-MnO(2) dosages promoted As (III) transformation rate and adsorption of arsenic species. The transformation rate and adsorption of arsenic species raised with increasing pH values of reaction solution from 4.7 to 8.0. The oxidation rate decreased and adsorbed As(III) and As(V) increased with increasing initial arsenite concentration. The enhancement on oxidative transformation of sodium arsenite may result from abundant active sites of alpha-MnO(2). Along with adsorption and fixation of arsenic species during the reaction, the crystal structure of alpha-MnO(2) did not change, but the surface turned petty and loosen. Our results demonstrated that alpha-MnO(2) has important potential in arsenic transformation and removal as the environmentally friendly natural oxidant in soil and surface water.

Sorption and Redox Transformation of Arsenite and Arsenate in Two Flooded Soils

AbstractThe fate of As in soils is regulated mostly by its participation is sorption reactions and redox transformations. Few studies have examined the rate of arsenite and arsenate reduction or the extent to which these redox transformations may be affected by sorption reactions. The objective of this study was to examine changes in solution concentrations of H3AsO03 and H2AsO−4 in two soils subjected to prolonged flooding. The soils, which differed in H3AsO03 and H2AsO−4 sorption capacities, were flooded by suspending 1 g of soil in 25 mL of a solution containing 0.01 M CaCl2 and 1 g d‐glucose kg−1. The suspensions were amended with NaAsO2 or Na2HAsO4·7H2O and were incubated for 0.5 h to 20 d. Changes in solution chemistry (electrode potential [Eh], pH, and dissolved Fe, Mn, H3AsO03, and H2AsO−4) were observed with time. Sorption processes controlled the dissolved concentrations of H3AsO03 and H2AsO−4 during initial stages of flooding. When anaerobic conditions were achieved, dissolution of Fe and Mn oxyhydroxides occurred, causing desorption of H3AsO03 and H2AsO−4. In NaAsO2‐amended suspensions, desorbed H3AsO03 disappeared from solution within 10 d. In Na2HaSO−4‐amended suspensions, desorbed H2AsO−4 also disappeared within 10 d. Concurrent with the disappearance of H2AsO−4 was the appearance of H3AsO03, indicating that H2AsO−4 was rapidly reduced to H3AsO03. First‐order plots of H3AsO03 and H2AsO−4 disappearance had a linear relationship. Rates of desorption and disappearance of H3AsO03 and H2AsO−4 were slower in the soil with higher adsorption capacity, suggesting that sorption processes may influence redox transformations of As oxyanions.