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There are many areas in the world where the ground water has been contaminated by arsenic. MnO2 is one of the most cheap materials which can both adsorb arsenic and oxide arsenite [As(III)]...

As solid waste posing a great threat to the environmental system, the disposal of arsenic-alkali slag has become the top priority in the development of the antimony industry. In this paper, a novel technological scheme combining the advantages of chemical precipitation and fractional crystallization is proposed for the safe disposal and resource utilization of arsenic-alkali slag. The scheme is mainly composed of three parts, namely, leaching of arsenic-alkali slag, selective removal of arsenic in the arsenic-alkali solution, and evaporation crystallization of alkali solution. In the leaching part, the optimum leaching parameters are determined by orthogonal tests. In the arsenic and alkali separation part, based on thermodynamic analysis, the selective removal of arsenic from arsenic-alkali solution is realized by forming ammonium magnesium arsenate (MgNH4AsO4) precipitation. In the evaporation crystallization part, the crystalline product with sodium carbonate (Na2CO3) content of 89.87% is obtained by the evaporation crystallization experiment. The whole process does not produce secondary pollution and realizes the reuse of wastewater. The final products are leaching residue, arsenic slag, and sodium carbonate with an arsenic content of 0.83%, 24.93%, and 0.18%, respectively.

In modern agricultural practice, heavy metal (HM) contamination is one of the main abiotic stress threatening sustainable agriculture, crop productivity, and disturb natural soil microbiota. Different reclamation techniques are used to restore the contaminated site; however, they are either costly or unable to remove contaminant when concentration is very low. In such circumstances, bioremediation is used as a novel technique involving microbes for soil restoration. In the current project, Aspergillus welwitschiae(Bk) efficiently endure metal stress (i.e., Cr-VI and As-V in the form of K2Cr2O7 and Na3AsO4) up to 1200 μg/mL and enhanced the production of phytohormones, i.e., 54.83 μg/mL of indole acetic acid (IAA) compared to control 15.56 μg/mL, solubilized inorganic phosphate, and produced stress-related metabolites. The isolate Bk was able to enhance growth of soybean by showing higher root shoot length and fresh/dry weight under stress (p

The distribution and chemical speciation of arsenic (As) in different sized atmospheric particulate matters (PMs), including total suspended particles (TSP), PM10, and PM2.5, collected from Baoding, China were analyzed. The average total mass concentrations of As in TSP, PM10, and PM2.5 were 31.5, 35.3, and 54.1 µg/g, respectively, with an order of PM2.5 >PM 10 > TSP, revealing that As is prone to accumulate on fine particles. Due to the divergent toxicities of different As species, speciation analysis of As in PMs is further conducted. Most of previous studies mainly focused on inorganic arsenite (iAsIII), inorganic arsenate (iAsV), monomethylarsonate (MMA), and dimethylarsinate (DMA) in PMs, while the identification and sensitive quantification of trimethylarsine oxide (TMAO) were rarely reported. In this study, a high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry system was optimized for As speciation including TMAO in PMs. An anion exchange column was used to separate MMA, DMA and iAsV, while a cation exchange column to separate TMAO and iAsIII. Results showed that iAsV was the dominate component in all the samples, corresponding to a portion of 79.2% ± 9.3% of the total extractable species, while iAsIII, TMAO and DMA made up the remaining 21%. Our study demonstrated that iAsIII accounted for about 14.4% ± 11.4% of the total extracted species, with an average concentration of 1.7 ± 1.6 ng/m3. It is worth noting that TMAO was widely present in the samples (84 out of 97 samples), which supported the assumption that TMAO was ubiquitous in atmospheric particles.

Environmental context Hematite nanoparticles are efficient adsorbents for proteins and pollutants in environmental and biological systems. Hematite and the protein bovine serum albumin (BSA) were used as models to investigate the surface chemistry and competitive role of BSA in arsenate adsorption. Results show that surface BSA inhibits arsenate adsorption, potentially altering its mobility and bioavailability. Abstract The surface chemistry of metal oxide nanomaterials controls their health impacts and fate in environmental and biological systems. These systems contain proteins capable of binding to nanoparticles, which forms a protein corona that modifies the surface properties of the nanoparticles and reactivity towards pollutants. Using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, we investigate the adsorption of bovine serum albumin (BSA) and quantify the competitive effect of BSA on the adsorption kinetics of arsenate, AsV, to hematite nanoparticles. Experiments were conducted in the flow mode at pH 7. BSA was first adsorbed on hematite, then AsV was allowed to flow over the BSA/hematite thin film. Adsorption kinetic and thermodynamic parameters were calculated using a modified Langmuir adsorption model for both BSA and AsV. The adsorption thermodynamic model showed that BSA binds through two active sites with a binding energy of –41 kJ mol−1, which corresponds to the spontaneous formation of chemisorbed and physisorbed species. When AsV flowed over the BSA/hematite film, only 11 % of surface BSA was desorbed by AsV. This result highlights the inhibitory effect of BSA for AsV adsorption. Structural analysis of BSA revealed changes to the local conformational geometry upon adsorption to and desorption from hematite nanoparticles. Molecular docking simulations showed that the binding free energy of a modelled hematite nanoparticle towards the BSA surface is –6.8 kcal mol−1 (−28.5 kJ mol−1) owing to the formation of various bonds, which agrees with the adsorption kinetics modelling. Overall, surface BSA inhibits arsenate adsorption and therefore increases its mobility and bioavailability.

This study aims to investigate the potentiality of selenium in modulating arsenic stress in rice seedlings. Arsenate accumulation along with its transformation to arsenite was enhanced in arsenate exposed seedlings. Arsenite induced oxidative stress and severely affected the growth of the seedlings. Arsenate exposure caused an elevation in ascorbate and glutathione levels along with the activities of their metabolizing enzymes viz., ascorbate peroxidase, glutathione reductase, glutathione-S-transferase, and glutathione peroxidase. Phytochelatins content was increased under arsenic stress to subdue the toxic effects in the test seedlings. Co-application of arsenate and selenate in rice seedlings manifested pronounced alteration of oxidative stress, antioxidant defense, and thiol metabolism as compared to arsenate treatment only. ANOVA analysis (Tukey's HSD test) demonstrated the relevance of using selenate along with arsenate to maintain the normal growth and development of rice seedlings. Thus, exogenous supplementation of selenium will be a beneficial approach to cultivate rice seedlings in arsenic polluted soil. Novelty Statement Arsenic toxicity in the environment is a global concern, causes chronic signs of poisoning to plants and humans, leads to ecological imbalance. Selenium is known for its antagonistic characteristics and has been found to be effective in combating the adversities of arsenic at low concentrations (5 µM). The present study was performed to explore the comparative responses of rice seedlings during the joint application of selenium and arsenic in terms of growth, generation of oxidative stress, antioxidant defense, and thiol metabolism. Although the molecular basis of arsenic-selenium interaction is widely known a small number of reports were listed about the physio-chemical role of selenium against arsenic stress. Thus, we investigated the influence of selenium to alleviate arsenic-induced toxic effects by modulating the activities of antioxidant enzymes and reducing the levels of oxidative stress markers. It has been noted that selenium regulates thiol metabolism which is known to play a key role in growth preservation by restriction of arsenic translocation. The outcome from the study would be useful in field trials for sustainable agriculture in arsenic-contaminated soil.

The soil and groundwater of Asanpara village (Bhagobangola I block) of Murshidabad district are contaminated with non-permissible limit of arsenic and other elements that co-exist with arsenic in various chemical compounds like arsenopyrite, ferrous arsenate, ferric arsenate, etc. Arsenic resistant bacteria (ARB) were isolated from arsenic contaminated soil of Asanpara and biochemically characterized. These bacteria were identified as Lysinibacillus sp. and Bacillus safensis by 16S rDNA sequencing and subsequent phylogenetic analysis. Isolated strains could grow in 76.98 mM and 88.53 mM of arsenite, and 560.88 mM and 721.13 mM of arsenate, respectively. ARB also show hypertolerance to other toxic metals like copper (Cu2+), cobalt (Co2+) and chromium (Cr3+). The level of arsenic and other heavy metal tolerance is unprecedented. Based on the inhibition of urease activity of isolated ARB by cadmium, the bacteria can be used to detect the presence of cadmium. These bacteria could biotransform arsenite into arsenate, which explains its uninhibited growth at very high arsenic concentration. The change in size of these bacteria depicted by scanning electron microscopy is a defence mechanism against arsenic stress Lysinibacillus sp. shows 32.33%, 31.29% and 31.20% bioremediation, whereas Bacillus safensis shows 37.54%, 35.26% and 35.24% bioremediation in the presence of 0.027 mM (2 ppm), 0.133 mM (10 ppm) and 0.667 mM (50 ppm) arsenic, respectively. Also, these bacteria could bioaccumulate or bioadsorb arsenic. The bioremediation potential of isolated ARB could be exploited for removal of arsenic from soil, groundwater and wastewater.

Arsenic pollution is a worldwide problem. In flooded arsenic-contaminated paddy soils, arsenic bioavailability to rice plants is elevated due to the reductive dissolution of arsenate (As(V)) contai...

Chromium (Cr) (VI) is a toxic, mutagenic, and carcinogenic water pollutant. The standard ion chromatography (IC) method for quantification of Cr (VI) in water samples is Environmental Protection Agency Method 218.7, which requires postcolumn derivatization with 1,5-diphenylcarbazide and UV-Vis spectroscopy detection. Method 218.7 is Cr (VI) specific; thus, it does not allow detection of co-occurring natural and anthropogenic anions in environmental media. In this study, we developed an isocratic IC method with suppressed conductivity detection, a Metrohm Metrosep A Supp 7 column, and sodium carbonate/acetonitrile as mobile phase for simultaneous quantification of Cr (VI), ClO4−, As (V) as arsenate, Se (VI) as selenate, and the common anions F–, Cl–, NO2−, NO3−, and SO42−. The determination coefficient for every analyte was >0.99 and the method showed good accuracy in quantification. Cr (VI), As (V), Se (VI), and ClO4− limit of detection and limit of quantification were 0.1–0.6 μg/L and 0.5–2.1 μg/L, respectively. Recovery of Cr (VI) in various aqueous samples (tap water, surface water, groundwater, and wastewater) was between 97.2% and 102.8%. Overall, most analytes showed acceptable recovery (80–120%) in the environmental samples tested. The IC method was applied to track Cr (VI) and other anion concentrations in laboratory batch microcosms experiments with soil, surface water, and anaerobic medium. The IC method developed in this study should prove useful to environmental practitioners, academic and research organizations, and industries for monitoring low concentrations of multiple anions in environmental media, helping to decrease the sample requirement, time, and cost of analysis.

Dimethylmonothioarsinic acid (DMMTA(V)) and dimethyldithioarsinic acid (DMDTA(V)), which are commonly found in landfill leachate and pore water of rice paddy soil, have attracted considerable attention for their high toxicity. This study aims to evaluate the behavior and potential risks of DMMTA(V) and DMDTA(V) in the environment by conducting an equilibrium sorption test using 2-line ferrihydrite and acute toxicity (immobilization) test using Daphnia magna. The overall maximum sorption capacity (qm) derived by the Langmuir isotherm model showed an increase in the order of inorganic arsenate (As(V)) > dimethylarsinic acid (DMA(V)) > DMMTA(V) > DMDTA(V), which was likely due to steric hindrance due to the presence of methyl and thiol groups. Moreover, DMMTA(V) and DMDTA(V) showed no or negligible change in qm with pH change, while qm decreased rapidly with increasing pH in As(V) and DMA(V). The 50% inhibition concentrations (IC50) for As(V), DMA(V), DMMTA(V), and DMDTA(V), which were measured after 48 h exposure to D. magna, were 9.5, > 30, 1.7, and 6.5 mg/L, respectively. Overall, the results demonstrated that DMMTA(V) and DMDTA(V) have high mobility and eco-toxicity in the environment and that methylated thioarsenicals should be accurately monitored and controlled.

This study explored the potential of Acacia mangium to remediate arsenic present in mine wastes and to determine the remediation mechanism of this plant for removing arsenic. A preliminary test using soil spiked with various arsenic concentrations showed that Acacia mangium was able to survive on arsenic‐contaminated soil with concentrations up to 500 mg kg−1 arsenic. Ex situ phytoremediation studies using mine wastes containing approximately 790 mg kg−1 arsenic also showed no toxicity effect on Acacia mangium throughout 5 months of treatment. Bioconcentration and translocation factors indicate that Acacia mangium utilizes phytostabilization as its main mechanism to uptake arsenic into the plant tissues. The use of the chemical lixiviants monoammonium phosphate and citric acid was also found to increase the translocation of arsenic from roots to stems of Acacia mangium with a 12‐ and sixfold increase, respectively, compared with the un‐dosed plants. Further speciation analysis revealed that arsenic in the form of arsenate was the only arsenic species detected in the stems after being amended with monoammonium phosphate; thereby, suggesting a sensible strategy for more efficient targeted arsenic phytoremediation by Acacia mangium.

To understand the arsenic (As) toxicity to aquatic organisms in the phosphors-polluted aquatic ecosystem, the growth, the physiological response of Chlorella vulgaris exposed to As (V), and the underlying mechanism were investigated under different phosphorus (P) levels (0, 6, 13, 32 μM). Results showed that As toxicity to the marine microalga C. vulgaris was enhanced under P-limited condition. P supply distinctly altered the effect of As on the light-harvesting efficiency of photosystem. Insufficient P supply also resulted in an enhanced level of membrane integrity loss, which probably facilitated As entering cells and led to stronger toxicity to C. vulgaris under low P supply. At high concentrations of As, the relative superoxide dismutase (SOD) activity was significantly enhanced. When phosphorus was limited, the activation of peroxidase (POD) was significantly enhanced after adding As (V). When intracellular SOD activity was at its highest level, the level of membrane peroxidation (MDA) was also at the highest level, and membrane peroxidation level was positively related to the level of membrane integrity loss (Pearson R2=0.8977). These results suggested that alternation of light-harvesting efficiency of photosystem and As-induced oxidative damage, resulting in membrane peroxidation and integrity loss, were the possible mechanism of As toxicity to C. vulgaris. This study provided insight into the understanding of As toxicity to algae in the eutrophication aquatic system and the potential application of algae in As remediation.

Treatment of aqueous leachate from acid mine tailings with pristine biochar (BC) resulted in the removal of more than 90% of the dissolved arsenic with an attendant rapid and sustained pH buffering from 3 to 4. Pine forest waste BC was transformed to a highly effective adsorbent for arsenic remediation of acid mine drainage (AMD) because the dissolved iron induced “activation” of BC through accumulation of highly reactive ferric hydroxide surface sites. Physicochemical properties of the BC surface, and molecular mechanisms of Fe, S, and As phase transfer, were investigated using a multi-method, micro-scale approach (SEM, XRD, FTIR, XANES, EXAFS, and STXM). Co-located carbon and iron analysis with STXM indicated preferential iron neo-precipitates at carboxylic BC surface sites. Iron and arsenic X-ray spectroscopy showed an initial precipitation of ferrihydrite on BC, with concurrent adsorption/coprecipitation of arsenate. The molecular mechanism of arsenic removal involved bidentate, binuclear inner-sphere complexation of arsenate at the surfaces of pioneering ferric precipitates. Nucleation and crystal growth of ferrihydrite and goethite were observed after 1 h of reaction. The high sulfate activity in AMD promoted schwertmannite precipitation beginning at 6 h of reaction. At reaction times beyond 6 h, goethite and schwertmannite accumulated at the expense of ferrihydrite. Results indicate that the highly functionalized surface of BC acts as a scaffolding for the precipitation and activation of positively charged ferric hydroxy(sulf)oxide surface sites from iron-rich AMD, which then complex oxyanion arsenate, effectively removing it from porewaters. Graphical abstract Supplementary Information The online version contains supplementary material available at 10.1007/s11356-021-13869-8.

Schwertmannite effectively sorbs chromate (Cr(VI)), yet the sorption mechanisms remain elusive. We determined the Cr(VI) sorption mechanisms on schwertmannite at pH 3.2 and 5 using combined macroscopic sorption experiments with molecular-scale characterization and by comparing them to arsenate (As(V)) sorption. Cr(VI) adsorbs as bidentate-binuclear (BB) inner-sphere complexes through exchanging more sulfate and less >Fe-OH/OH2, with 0.59-0.71 sulfate released per Cr(VI) sorbed. While As(V) also forms BB complexes, it exchanges sulfate and >Fe-OH/OH2 equally with 0.49-0.52 sulfate released per As(V) sorbed. At high As(V) loadings, As(V) precipitates as amorphous FeAsO4, particularly at low pH. The abovementioned differences between Cr(VI) and As(V) can be related to their different ionic radii and binding strength. Moreover, Cr(VI) and As(V) preferentially exchange sulfate inner-sphere complexes, increasing the proportion of sulfate outer-sphere complexes in schwertmannite. In turn, the concentration of sulfate outer-sphere complexes increases and then decreases with increasing Cr(VI) loading. Results suggest that an oxyanion, which would form inner-sphere complexes on a mineral surface, preferentially exchanges inner-spherically bound oxyanions than outer-spherically bound ones on the surface, even though both are exchanged. This study improves our understanding of the sorption of oxyanions on schwertmannite and their capabilities to template schwertmannite formation and stabilize its structure.

Arsenic, in addition to being a confirmed carcinogen, is one of the most toxic elements found in nature, and should therefore be removed if the concentration is greater than 10 μg/L. Nanofiltration (NF) membranes have succeeded in arsenate As (V) ions removal from water almost completely. It is reported in this review that, like reverse osmosis (RO) membranes, NF membranes have not yet performed alone arsenite As (III) ion rejection without being associated with another technology. Commercial NF membranes exhibited a rejection between 86 and 99% towards arsenate As (V) while As (V) removal reached 99.8% for synthesized NF membranes. Since commercial NF membranes have shown their limit, scientists have prepared novel NF membranes that demonstrated long-term efficiency, fouling reduction, cost reduction, an increase in separation of multivalent ions, rejection performance, or a high flux achievement, depending on the area of use. For small treatment plants, NF is a more cost-effective method. The review succinctly reported arsenic as a serious global contamination issue and focused on novel nanofiltration processes for arsenic rejection to safeguard water security. This article also developed a comparative study of nanofiltration and reverse osmosis techniques concerning arsenic removal. Finally, future trends and perspectives have been highlighted with particular emphasis on emerging synthesis techniques of NF membranes without hiding the unpleasant fouling issue that limits its competitiveness. Highlights Commercial nanofiltration (NF) membranes for arsenic removal.; Novel synthesized nanofiltration membranes.; Potential and limitation of nanofiltration membranes in arsenic removal.; Influence of operating parameters on arsenic removal.; Performance comparison of reverse osmosis (RO) and nanofiltration (NF) membranes in the context of arsenic removal.

In the present work, the arsenate [As(V)] adsorption by loam and sandy loam soil was carried out as a function of initial As(V) concentration, pH, contact time, and adsorbent dose to ensure As adso...

Vicia villosa Roth is a legume species with a growing application in Argentina as a cover crop (CC), a practice that favors the sustainable development of agricultural systems. However, several areas where the use of this CC provides numerous advantages are affected by high concentrations of arsenic (As). Thus, in the present work we studied hairy vetch ability to cope with arsenate [As(V)], arsenite [As(III)], and the mixture of both along with oxidative stress indexes [chlorophyll content, malondialdehyde (MDA) equivalents] as well as anatomical and histological changes in the root structure. The results obtained suggested a different behavior of hairy vetch depending on its growth stage and on metal(oid) concentration. The roots treated with the contaminant showed less turgidity, thickening of the epidermal and subepidermal parenchymal outer layers, and the presence of dark deposits. The morpho-anatomic parameters (cortex length, vascular cylinder diameter, total diameter, and vascular cylinder area) were altered in plants treated with As(V) and As(V)/As(III) whereas the roots of plants treated with As(III) did not show significant differences respect to the control. Moreover V. villosa could tolerate and remove As from soil, thus the use of this legume species seems an attractive approach to remediate As while protecting contaminated soils.

Arsenic (As), a heavy metalloid, occupies the topmost position in the list of the top ten hazardous chemicals published by the World Health Organization. The contamination of arsenic in groundwater predominantly utilized for irrigation and drinking is responsible for serious public health issues across the globe. The two most common arsenic species, i.e., inorganic arsenate and arsenite, are toxic and environmental pollutants. The toxicity of arsenic and its speciation are impacted by bacterial biotransformations. Bacteria have evolved several systems to deal with arsenic toxicity in their vicinity through detoxification and metabolism. The knowledge about these processes provides insight into the strategies employed by bacteria for arsenic biotransformation. In this study, we comprehensively discuss the genetics and molecular mechanisms of arsenate reduction, arsenite oxidation, methylation/demethylation, and other arsenic biotransformations. Relatively recent scientific discoveries and the use of molecular approaches have notably enhanced our understanding of these microbial processes present in the environment. The present review intends to focus on the diverse categories of arsenic-transforming and -metabolizing bacterial species and their genetics, recent advances in the mechanisms of the microbe-mediated As-biotransformation pathways, and their implications on the biogeochemical cycling of arsenic in nature. This review will further help to develop a better understanding of bacterial response to arsenic, bioremediation strategies, and future research fields.

During the aging process, ferrihydrite was transformed into mineral mixtures composed of different proportions of ferrihydrite, goethite, lepidocrocite and hematite. Such a transformation may affect the fixed ability of arsenic. In this study, the stability of Fe-As composites formed with As(V) and the minerals aged for 0, 1, 4, 10 and 30 days of ferrihydrite were systematically examined, and the effects of molar of ratios Fe/As were also clarified using kinetic methods combined with multiple spectroscopic techniques. The results indicated that As(V) was rapidly adsorbed on minerals during the initial polymerization process, which delayed both the ferrihydrite conversion and the hematite formation. When the Fe/As molar ratio was 1.875 and 5.66, the As(V) adsorbed by ferrihydrite began to release after 6 hr and 12 hr, respectively. The corresponding release amounts of As(V) were 0.55 g/L and 0.07 g/L, and the adsorption rates were 92.43% and 97.50% at 60 days, respectively. However, the As(V) adsorbed by the transformation products aged for 30 days of ferrihydrite began to release after adsorbed 30 days. The corresponding release amounts of As(V) were 0.25 g/L and 0.03 g/L, and the adsorption rates were 84.23% and 92.18% after adsorbed 60 days, for the Fe/As=1.875 and 5.66, respectively. Overall, the combination of As(V) with ferrihydrite and aged products transformed from a thermodynamically metastable phase to a dynamically stable state within a certain duration. Moreover, the aging process of ferrihydrite reduced the sorption ability of arsenate by iron (hydr)oxide but enhanced the stability of the Fe-As composites.

Arsenic is a toxic and carcinogenic element present in groundwater as arsenite, As(III) and/or arsenate, As(V), due to natural lixiviation or because of anthropogenic activities. The World Health Organization threshold in drinking water is 10 μg/L, well below the concentration found in the water resources of numerous populations, as in the Duero basin (Spain). As(V) can be easily removed by adsorption onto iron-based adsorbents, whereas As(III) is harder to remove. Therefore, in this work we propose the use of ilmenite (FeTiO3), a low-cost catalyst, as both photocatalyst and adsorbent in the UV-A assisted Catalytic Wet Peroxide Oxidation process. The main aim of this technology is to oxidize arsenite into arsenate, for its subsequent adsorption onto the Fe sites of the catalyst. This technology has proven to be effective for the oxidation and removal of 10 mg/L As(III) working at 1000 mg/L ilmenite, 60 mg/L H2O2, 0, pH0: 7 and room temperature (25 °C), in both ultrapure water and groundwater collected from Lastras de Cuellar (Segovia, Spain). Furthermore, we propose a complete kinetic model which comprises the H2O2 decomposition, As(III) oxidation and As(V) adsorption, which is in agreement with the experimental data.

The application of zero-valent iron particles (ZVI) for the treatment of heavily polluted environment and its biological effects have been studied for at least two decades. Still, information on the impact on bacterial metabolic pathways is lacking. This study describes the effect of microscale and nanoscale ZVI (mZVI and nZVI) on the abundance of different metabolic pathways in freshwater bacterial communities. The metabolic pathways were inferred from metabolism modelling based on 16S rRNA gene sequence data using paprica pipeline. The nZVI changed the abundance of numerous metabolic pathways compared to a less influencing mZVI. We identified the 50 most affected pathways, where 31 were related to degradation, 17 to biosynthesis, and 2 to detoxification. The linkage between pathways was two times higher in nZVI samples compared to mZVI, and was specifically higher considering the arsenate detoxification II pathway. Limnohabitans and Roseiflexus were linked to the same pathways in both nZVI and mZVI. The prediction of metabolic pathways increases our knowledge of the impacts of nZVI and mZVI on freshwater bacterioplankton.

The molecular resistance mechanism of Aspergillus oryzae (A. oryzae) under arsenate (As(V)) stress was investigated by comparative transcriptome analysis. In total, 4911 differentially expressed ge...

Roxarsone (ROX) has been widely used as an organoarsenic additive in animal feeding operations and poses a risk to the environment. Here, we first report the efficient degradation of ROX by UV/chlorine, where the kinetics, removal of total arsenic (As), and cytotoxicity were investigated. The kinetics study presented that reactive chlorine species (RCS) and HO• were the dominant species to react with ROX. Furthermore, the degradation rate of ROX can reach the maximum value at pH 7.5 due to the formation of more RCS. The degradation of ROX was affected by the amount of chlorine, pH, and water matrix. Through product analysis and Gauss theoretical calculation, two possible ROX degradation pathways were proposed. The free radicals attacked the As-C bond of ROX and resulted in releasing arsenate (As(V)). It was the reason that for an enhancement of the removal of total As by ferrous appeared after UV/chlorine, and over 98% of the total As was removed. In addition, cytotoxicity studies indicated that the cytotoxicity significantly enhanced during the degradation of ROX by UV/chlorine. However, by combination of UV/chlorine and adsorption, cytotoxicity can be greatly eliminated, probably due to the removal of As(V) and chlorinated products. These results further demonstrated that UV/chlorine treatment could be an effective method for the control of the potential environmental risks posed by organoarsenic.

This review explains the transport, mobility, resistance and detoxification of toxic metalloid arsenic (As) in plants. Arsenic is ubiquitously present in Earth’s crust; however, numerous human interventions such as rapid industrialization use of As-based pesticides, insecticides and discharge of industrial wastes in water bodies leads to cumulative increase in As in the environment and has become a global challenge. Arsenic exists in different organic and inorganic forms, but inorganic forms such as pentavalent arsenate (AsV) and trivalent arsenite (AsIII) are more toxic and actively taken up by plants. Its toxicity is marked by generation of reactive oxygen species (ROS) that are capable of degrading various biomolecules of the cellular systems. To keep the ROS under the limit, plants have an array of enzymatic antioxidants such as superoxide dismutase (SOD), peroxidase (POD), catalase (CAT), ascorbate peroxidase (APX), glutathione reductase (GR) and glutathione-S-transferase (GST); and non-enzymatic antioxidant like ascorbate, proline, and cysteine. Contrary to this, As-hyper-accumulator plants survive under high concentration of As through the strenuous action of Asv reduction into AsIII followed by the vacuolar compartmentalization of complex or inorganic As. Hence, this review focuses on the potential sources of As in the environment, its speciation and toxicity, and tolerance strategies in plants.

The roots of aquatic plants, including rice, release oxygen into the subsurface, precipitating reduced metals, such as iron (Fe) and manganese (Mn), as plaques that form on the surface of the roots. These plaques are a unique habitat for microorganisms and a hotspot for biogeochemical cycling, including the toxic trace metalloid arsenic (As). However, studying plaque deposition and mineral composition in this spatially and temporally heterogeneous environment is challenging, particularly in situ. Here, we describe a new technique for nondestructive and repeated rhizosphere sampling. We placed vinyl films that adhere Fe deposits from roots growing adjacent to the films into soil. The films were removed and replaced throughout plant growth and were characterized using a variety of spectroscopic (XRF imaging and Fe EXAFS) and microscopic (SEM and confocal) techniques. Fe deposits were most concentrated at lateral junctions and heterogeneity was apparent in the location and speciation of Fe-associated As in both pot and field studies. XRF imaging at multiple incident beam energies revealed that this As was mostly arsenate, although arsenite was present on the edge of the Fe deposit. Iron deposits were typically micron sized and consisted mostly of ferrihydrite, consistent with the data reported using conventional techniques. Moreover, Fe deposits were occupied by a variety of microorganisms. These films are a suitable technique to study a range of spatial and temporal questions regarding the biogeochemistry of aquatic plant roots.

There is a strong impetus to establish a circular phosphorus economy by securing internally renewable phosphate (Pi ) resources for use as agricultural fertilizers. Reversible Pi adsorption technologies such as ion exchange can remove and recover Pi from water/wastewater for reuse. However, existing reversible adsorbents cannot effectively discriminate against arsenate (As(V)) due to the similarity between As(V) and Pi chemical structure. If As(V) is co-recovered with Pi , the value of the recovered products for agricultural reuse is low. The objective of this study was to construct an immobilized phosphate-binding protein (PBP)-based Pi removal and recovery system and analyze its selectivity for Pi adsorption in the presence of As(V). A range of conditions was tested, including independent, sequential, and simultaneous exposure of the two oxyanions to immobilized PBP (PBP resin). The purity of the recovered Pi product was assessed after inducing controlled desorption of the adsorbed oxyanions at high pH (pH 12.5). Pi constituted more than 97% of the adsorbed oxyanions in the recovered product, even when As(V) was initially present at twofold higher concentrations than Pi . Therefore, PBP resin has potential to selectively remove Pi , as well as release high-purity Pi free of As(V) contamination suitable for subsequent agricultural reuse. PRACTITIONER POINTS: Existing reversible phosphate (Pi ) adsorbents cannot effectively discriminate against arsenate (As(V)) due to the similarity in their chemical structure. Co-recovery of As(V) with Pi can reduce the recovered product's reuse as a fertilizer. An immobilized phosphate-binding protein (PBP)-based system can be highly selective for Pi even in the presence of As(V). Pi constituted more than 97% of the recovered product, even when As(V) was present at 2-fold higher concentrations than Pi . Immobilized PBP offers advantages over existing Pi adsorbents by providing high-purity Pi products free of As(V) contamination for reuse.

This study is focusing on the comparative study of arsenite and arsenate adsorption from the water via indigenous iron ores. The Sindh and Punjab provinces of Pakistan are badly affected by Arsenic (As) toxicity as the people are consuming arsenic contaminated groundwater. The aim of this study is to investigate the effect of anions on adsorption of arsenite As(III) and arsenate As(V). Impact of pH, contact time, adsorbent dose and shaking speed on adsorption of arsenite and arsenate is studied with the two selected iron ores from Hoshi and Shikarap from Balochistan. Hoshi and Shikarap ores exhibited higher As(III) and As (V) adsorption, respectively thus selected for further removal studies. Hoshi iron ore without sodium carbonate yields higher adsorption as compared to the samples with 100 mg/L and 1000 mg/L sodium carbonate in both As(III) and As(V). Hoshi ore exhibited the highest adsorption of 85% for As (V) without sodium phosphate dibasic and 83% for As(III). Shikarap ore for As(V) adsorbs 75% without sodium phosphate dibasic and 67% adsorption for As(III) without sodium phosphate dibasic. Shikarap ore with sodium silicate at 100 mg/L adsorbs 62% As(III) and at 1000 mg/L adsorb 52% As(III). Shikarap ore As(V) adsorption decreases from 75% without sodium silicate to 70% at 100 mg/L and even lower adsorption of 65% at a higher concentration of 1000 mg/L.

Anaerobic methane oxidation is coupled to the reduction of electron acceptors, such as sulfate, and contributes to their biogeochemical cycling in the environment. However, whether arsenate acts as an alternative electron acceptor of anaerobic methane oxidation and how this influences global arsenic transformations remains elusive. Here, we present incubations of arsenate-contaminated wetland soils from seven provinces in China. Using isotopically labelled methane, we find that anaerobic methane oxidation was linked to arsenate reduction at a rate approaching the theoretical arsenic/methane stoichiometric ratio of 4. In microcosm incubations with natural wetland soils, we find that the coupled pathway of anaerobic methane oxidation and arsenate reduction contributed 26 to 49% of total arsenic release from soils, with arsenic in the more soluble and toxic form arsenite. Comparative gene quantification and metagenomic sequencing suggest that the coupled pathway was facilitated by anaerobic methanotrophs, either independently or synergistically with arsenate-reducing bacteria through reverse methanogenesis and respiratory arsenate reduction. Further bioinformatic analyses show that genes coding for reverse methanogenesis and respiratory arsenate reduction are universally co-distributed in nature. This suggests that coupling of anaerobic methane oxidation and arsenate reduction is a potentially global but previously overlooked process, with implications for arsenic mobilization and environmental contamination. The coupling of anaerobic oxidation of methane and arsenate reduction is an important pathway of releasing arsenic from soils, according to incubation experiments of arsenate-contaminated wetland soils.

Arsenite (As(III)) is far more toxic than arsenate (As(V)) to human health. To investigate the potential effects of petroleum exploitation activities on the relative abundance of inorganic As(III) ...

Microbial antimonate [Sb(V)] respiratory reduction is an important process regulating Sb redox transformation in the environment. However, little is known about the microbial respiratory reductase for Sb(V). Herein, we report Sb(V)-respiring reduction by Shewanella sp. ANA-3 through an arsenate respiratory reductase encoded by arrAB. Incubation experiments showed that Shewanella sp. ANA-3 mediated Sb(V)-respiring reduction, which was dependent on the cell concentration. Both protein analysis and reverse transcriptase-polymerase chain reaction results revealed that arrAB was highly expressed in Sb(V)-respiring reduction. In vivo evidence with mutants indicated that neither ANA-3-ΔarrA nor ANA-3-ΔarrB was capable of reducing Sb(V) as efficiently as the wild type, whereas complementation by the wild-type sequences of arrA and arrB rescued the mutants' ability. Our in vitro results showed that ArrAB purified by His-Tag was able to mediate Sb(V) reduction, though with much suppressed catalytic kinetics compared with As(V) reduction. The cell-concentration-dependent reduction of Sb(V) was regulated by quorum sensing via the luxS gene. This study opens a new chapter in the mechanistic understanding of microbial Sb(V) respiratory reduction.

Effective and substantial remediation of contaminants especially heavy metals from water is still a big challenge in terms of both environmental and biological perspectives because of their adverse effects on the human health. Many techniques including adsorption, ion exchange, co-precipitation, chemical reduction, ultrafiltration, etc. are reported for eliminating heavy metal ions from the water. However, adsorption has preferred because of its simple and easy handlings. Several types of adsorbents are observed and documented well for the purpose. Recently, highly porous metal-organic frameworks (MOFs) were developed by incorporating metals and organic ligands together and claimed as potent adsorbents for the remediation of highly toxic heavy metals from the aqueous solutions due to their unique features like greater surface area, high chemical stability, green and reuse material, etc. In this review, the authors discussed systematically some recent developments about secure MOFs to eliminate the toxic metals such as arsenic (both arsenite and arsenate), chromium(VI), cadmium (Cd), mercury (Hg) and lead (Pb). MOFs are observed as the most efficient adsorbents with greater selectivity as well as high adsorption capacity for metallic contamination. Graphical abstract.

Environmental contamination has been a cause of concern worldwide, being aggravated by anthropogenic activities carried out without the correct disposal of toxic products in the various habitats on our planet. In Brazil, mining companies are responsible for the contamination of large river basins with toxic elements from mining activities. Among these elements, arsenic draws attention because it is highly carcinogenic and found in waters in concentrations above those recommended by regulatory agencies. Here, Fe2(MoO4)3 nanoparticles are synthesized and used as a filter medium in water purification systems contaminated with arsenic. The adsorption kinetics of arsenic by Fe2(MoO4)3 nanoparticles is fast, showing pseudo-second-order rate constants of 0.0044, 0.0080, and 0.0106 g mg−1 min−1 for As3+, As5+, and MMA, respectively. The adsorption isotherms are better adjusted with the Langmuir and Redlich-Peterson models, indicating that the arsenic adsorption occurs in monolayers on the Fe2(MoO4)3 surface. The Fe2(MoO4)3 adsorption capacities determined for the As3+, As5+, and MMA species are 16.1, 23.1, and 23.5 mg g−1, respectively. The Fe2(MoO4)3 filter is efficient in purifying arsenic-contaminated water, reducing its initial concentration from 1000 μg L−1 to levels close to zero. Biological tests indicate that Fe2(MoO4)3 nanoparticles and filtered water have no cytotoxic, genotoxic, and mutagenic risks to human life. Those results suggest that the Fe2(MoO4)3 filter can be used as an efficient and safe technology for the purification of water contaminated by arsenic.

The aim of this study was to assess the spatial variation in the concentrations of total arsenic (Astotal), arsenite (As(III)), arsenate (As(V)), monomethylarsonic acid (MMAs(V)), and dimethylarsinic acid (DMAs(V)) in fine particulate matter (PM2.5) and to explore the influence of local emission sources based on the monitoring data from 18 sampling sites in Nanjing, China. The results showed that the average concentration of Astotal in the PM2.5 was 6.81 ng/m3 in Nanjing, which exceeded the standard limit of 6 ng/m3 in China. As(V) was the dominant species and varied between 71 and 81% of water-extractible As in the PM2.5. The results of the spatial variation coefficients (CVs) showed that Astotal, As(III), and As(V) displayed moderate levels of spatial heterogeneity (CV = 0.23), while DMAs(V) a considerably high level (CV = 0.60). The concentrations of Astotal and As species can be arranged in the following order: urban background ~ urban street < suburban < rural < industrial sampling sites. This pattern was connected to the influence of three local emission sources (industrial source, road traffic, and biovolatilization), which were quantified by multiple linear regression. Results showed that local road traffic sources had the smallest value of standardized regression coefficient (0.26) among these three sources, indicating that local road traffic sources contributed less to the concentration of As in PM2.5 than industrial source emissions and biovolatilization. Our findings indicate that the spatial heterogeneity of As species should be considered in exposure assessments and As biovolatilization is linked to the high heterogeneity.

Since arsenic (As) exposure is largely due to geochemical contamination, this study focused on the remediated area of Santana do Morro, a district of Santa Barbara, Minas Gerais, Brazil, which was previously contaminated with As due to gold mining. Total As concentrations in sediment, soil and plants were determined, next to As species, anionic arsenic compounds As(III), As(V), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA), in plants samples. Total As concentrations in soil and sediments were slightly elevated (16-18 µg g -1 ) and most of the plants contained low levels of As (< 1 µg g -1 ). The exception was a native plant Eleocharis geniculata (L.) which contained elevated levels of As (4 µg g -1 ). The exposure of this plant to As under controlled conditions (hydroponics) indicated its possible tolerance to elevated As levels and suggesting its potential use in phytomonitoring of As-contaminated sites. This plant is able to metabolize arsenate to arsenite and contained MMA and DMA, both in its natural habitat and under controlled conditions.

Lanthanum-modified bentonite (LMB, Phoslock®) is a well-known capping agent for phosphorus immobilization in sediments. Herein, LMB was used to immobilize As in sediments. Batch capacity experiments for arsenate and arsenite adsorption were carried out to obtain adsorption isotherms and kinetics using the Langmuir and Freundlich model calculations. High-resolution (HR) diffusive gradients in thin films (DGT) were applied to monitor the changes of weakly bound As fraction near sediment-water interface (SWI). The interaction of As(III) and As(V) with LMB was influenced by pH and initial mineral composition. As(V) was more obviously adsorbed than As(III) at pH 4 to 9, with mean adsorption of 3.89 mg g-1 and 0.04 mg g-1, respectively, while at pH > 9 As(III) was preferentially adsorbed. After LMB amendment for 2 months, the maximum As removal efficiency in the pore and overlying water reached 84.5% and 99.3%, respectively. The capping agent remained stable in the top sediments, while the maximum DGT labile As content decreased to 0.89 and 0.51 μg L-1 in dosage-and time-treatments. The As concentration inflection point moved down to a deeper layer. As species changed from labile exchangeable-As to Fe-oxide-bound and residual As. The proportion of mobile As finally decreased to 10.5% of the total As in the upper 20-mm layer sediment. The increase of Kd (the distribution coefficient at SWI) and k1 (adsorption rate constant) and the decrease of Tc (response time of (de)sorption) in the DGT-induced fluxes model (DIFS) indicated the time-dependent impediment of As release from the sediment due to LMB immobilization.

A hydroponic experiment was conducted to establish the response of exogenous silicon [Si] in alleviating arsenate [As (V)] prompted alterations on antioxidant enzyme activities and thiol metabolism in wheat (Triticum aestivum L. cv PBW 343) seedlings. Objective of the work was to validate the hypothesis whether silicate may alleviate arsenate-provoked oxidative stress in wheat through diverse metabolic pathways with an endeavor to improve food safety and health. Arsenate treatment significantly enhanced oxidative stress and was associated with modifications in non-enzymatic and enzymatic antioxidants. The activities of arsenate reductase [AR] and the enzymes related to thiol metabolism revealed dose-dependent enhancements with increase in arsenate along with enhanced production of phytochelatins [PCs] in the cultivar. Simultaneous supplementations of silicate with arsenate in the nutrient formulation reduced arsenate uptake along with arsenate reductase activity and consequently lowered arsenite [As (III)] accumulation. The antioxidative defense was upregulated and phytochelatin production was lowered causing an appreciable revival from the arsenate-imposed consequences that eventually augmented growth.

Birnessite not only oxidizes arsenite into arsenate but also interacts with organic matter in various ways. However, effects of organic matter on interaction between As and birnessite remain unclear. This study investigated effects of citrate and EDTA (3.12 and 2.05 mM, respectively) on oxidation of As(III) (1.07 mM) and adsorption of As(V) (0.67 mM) on birnessite (5.19 mM as Mn) at near-neutral pH. We found that As(V) adsorption on birnessite was enhanced by citrate and EDTA, which resulted from the increase in active adsorption sites via dissolution of birnessite. In comparison with citrate batches, more As was adsorbed on birnessite in EDTA batches, where dissolved Mn was mainly presented as Mn(III)-EDTA complex. Citrate or EDTA-induced dissolution of birnessite did not decrease the As(III) oxidation rate in the initial stage where As(III) oxidation rate was rapid. Afterwards, As(III) oxidation was conspicuously suppressed in citrate-amended batches, which was mainly attributed to the decrease in adsorption sites by adsorption of citrate/Mn(II)-citrate complex. This suppression was enhanced by the increase in concentrations of dissolved Mn(II). Citrate inhibited As adsorption after As(III) oxidation due to the strong competitive adsorption of citrate/Mn(II)-citrate complex. However, the As(III) oxidation rate was increased in EDTA-amended batches in the late stage, which mainly derived from the increase in the active sites via birnessite dissolution. The strong complexation ability of EDTA led to formation of Mn(III)-EDTA complex. Arsenic adsorption was not affected due to the limited competitive adsorption of the complex on the solid. This work reveals the critical role of low molecular weight organic acids in geochemical behaviors of As and Mn in aqueous environment.

The ubiquitous arsenic in groundwater poses a great risk to human health due to its environmental toxicity and carcinogenicity. In the present work, a new adsorbent, δ-MnO2 modified activated carbon, was prepared, and its performance for the uptake of arsenate and arsenite species from aqueous solutions was investigated by batch experiments. Various techniques, including FESEM-EDX, p-XRD, XPS and BET surface area analysis, were employed to characterize the properties of the adsorbent and the arsenic adsorption mechanisms. The results showed that δ-MnO2 covered on the surface and padded in the pores of the activated carbon. Adsorption kinetic studies revealed that approximately 90.1% and 76.8% of As(III) and As(V), respectively, were removed by the adsorbent in the first 9 hr, and adsorption achieved equilibrium within 48 hr. The maximum adsorption capacities of As(V) and As(III) at pH 4.0 calculated from Langmuir adsorption isotherms were 13.30 and 12.56 mg/g, respectively. The effect of pH on As(V) and As(III) removal was similar, and the removal efficiency significantly reduced with the increase of solution pH. Arsenite oxidation and adsorption kinetics showed that the As(V) concentration in solution due to As(III) oxidation and reductive dissolution of MnO2 increased rapidly during the first 12 min, and then gradually decreased. Based on the XPS analysis, nearly 93.3% of As(III) had been oxidized to As(V) on the adsorbent surface and around 38.9% of Mn(IV) had been reduced to Mn(II) after As(III) adsorption. This approach provides a possible method for the purification of arsenic-contaminated groundwater.

Plants used in phytoremediation should accumulate and tolerate a specific pollutant. Here, we aimed at evaluating a possible arsenic (As) accumulation and mechanisms of tolerance against As-induced...

Manganese and arsenic both threaten groundwater quality globally, but their chemical behavior leads to both co-contamination and separation of these contaminants from individual well to regional scales. Here we tested manganese and arsenic retention under conditions commonly found within aquifer redox fluctuating and transition zones where both arsenic and iron phases are present in oxidized forms, but manganese persists as reduced and soluble Mn(II). Analysis of column aqueous breakthrough data and characterization of solid-phase products using X-ray photoelectron (XPS) and absorption spectroscopies (XAS) show that the addition of bicarbonate increased manganese retention but decreased arsenic retention, while the presence of manganese and arsenic together increased both arsenic and manganese retention. In the presence of O(2) arsenic remained oxidized as arsenate under all conditions measured; however, reduced Mn(II) was oxidized to an average Mn oxidation state of ~3 in the absence of arsenate. The presence of arsenate partially inhibited Mn(II) oxidation likely by blocking ferrihydrite surfaces needed to catalyze Mn(II) oxidation by O(2) and by stabilizing Mn(II) via ternary complex formation. These results highlight the interactions between reduced and oxidized contaminants that can contribute to the co-occurrence or physical separation of manganese and arsenic in groundwater systems under changing or stratified redox conditions.

Cerium oxide (CeO2) nanoparticles (NPs) are massively used as abrasives in the chemical and mechanical polishing (CMP), an essential process to manufacture semiconductor wafers. The CMP process for arsenide-based semiconductor materials produces wastewater with co-occurring arsenic (As) ions and CeO2 NPs. We found that CeO2 NPs adsorbed both arsenite (As(III)) and arsenate (As(V)) ions and the adsorption isotherms suggested different adsorption energies and capacities of the two species. Applying the ferric reducing ability for nanoparticle assay, we revealed that the adsorbed As(III) and As(V) each reduced CeO2 NP surface reactivity but followed different mechanisms. The adsorbed As(III) ions below a critical coverage (110 mmol/kg) increased occupation of Ce 4f orbitals and thus reduced electron mobility of the original CeO2 NPs. The adsorbed As(V) ions withdrew electrons from Ce 4f orbitals and likely became oxidizing agents that greatly inhibited the original surface reducing ability. Electron paramagnetic resonance analysis further revealed that adsorbed As(III) and As(V) ions decreased the propensity of CeO2 NPs to produce reactive oxygen species. This work highlights the importance of examining NPs in their post-use phases in which surface reactivity and hazard potential can be greatly altered by chemical exposure history and NP surface transformations.

Adsorption of arsenate, a common soil contaminant, on natural occurring iron oxides controls arsenate adsorption on soils, especially on iron rich soils. However, soils contain multiple iron minerals and their contributions for arsenate adsorption on the bulk soil are unclear. In this study, Wenzel's sequential extraction procedure (SEP) was used to characterize different fractions of iron oxides in the paddy soils from Guangxi, China. Soils treated with different extractants in the SEP (i.e. soils contained different iron fractions) were used to study arsenate adsorption on different iron fractions in the soil. Langmuir model was used to assess arsenate adsorption capacities of those iron fractions. The results showed that though amorphous iron made up only 16% of the total iron in the soil, it accounted for 82% of the soil adsorption capacity. Besides, arsenate adsorption capacity on the soils could be estimated by linear addition of arsenate adsorption capacity on the amorphous iron oxides fraction and that on the other iron oxides fraction. This study implied a possibility to use iron fractions characterized by Wenzel's SEP to evaluate arsenate adsorption on the bulk soils.

This study was conducted to optimize the preparation of fungal-algal pellets for use in the removal of arsenite (As(III)) and arsenate (As(V)) from water. Three parameters, i.e., glucose concentration, shaking speed, and pH, were investigated to show their effects on the immobilization efficiency of algal biomass attached to fungal mycelial pellets. The highest immobilization efficiency was achieved at 5 g glucose L−1, 140 rpm, and pH 7. Furthermore, the fungal-algal pellets with different initial algal biomass were tested regarding the stability and their capability of removing As(III) and As(V). The fungal-algal pellets could not keep good stability when the initial algal biomass was more than 4.8 × 107 cells mL−1. The highest removal rates of As(III) and As(V) were obtained by the fungal-algal pellets with initial algal biomass of 4.8 × 107 cells mL−1, and the removal rate of As(V) was much higher compared with that of As(III). Similar trends were observed for the concentrations of total arsenic as well as As(III) and As(V) in fungal-algal pellets. The fungal-algal pellets with initial algal biomass of 4.8 × 107 cells mL−1 showed a significant potential for removing As(V) from water, and microalgae might play a key role in the absorption and transformation of inorganic arsenic. Adsorption kinetics studies suggested that the adsorption of As(V) onto fungal-algal pellets followed the pseudo-second-order kinetic model, and the pseudo-first-order kinetic model was more appropriate for describing the adsorption of As(III).

Natural clinoptilolite (Clin) was modified with iron oxide using three different methods including precipitation, wet-impregnation and ion-exchange and then the modified adsorbent with highest As(V...

Development of novel adsorbents often neglects the competitive adsorption between co-occurring oxo-anions, overestimating realistic pollutant removal potentials, and overlooking the need to improve selectivity of materials. This critical review focuses on adsorptive competition between commonly co-occurring oxo-anions in water and mechanistic approaches for the design and development of selective adsorbents. Six "target" oxo-anion pollutants (arsenate, arsenite, selenate, selenite, chromate, and perchlorate) were selected for study. Five "competing" co-occurring oxo-anions (phosphate, sulfate, bicarbonate, silicate, and nitrate) were selected due to their potential to compete with target oxo-anions for sorption sites resulting in decreased removal of the target oxo-anions. First, a comprehensive review of competition between target and competitor oxo-anions to sorb on commonly used, nonselective, metal (hydr)oxide materials is presented, and the strength of competition between each target and competitive oxo-anion pair is classified. This is followed by a critical discussion of the different equations and models used to quantify selectivity. Next, four mechanisms that have been successfully utilized in the development of selective adsorbents are reviewed: variation in surface complexation, Lewis acid/base hardness, steric hindrance, and electrostatic interactions. For each mechanism, the oxo-anions, both target and competitors, are ranked in terms of adsorptive attraction and technologies that exploit this mechanism are reviewed. Third, given the significant effort to evaluate these systems empirically, the potential to use computational quantum techniques, such as density functional theory (DFT), for modeling and prediction is explored. Finally, areas within the field of selective adsorption requiring further research are detailed with guidance on priorities for screening and defining selective adsorbents.

Leptolyngbya boryana (L. boryana) is a typical filamentous cyanobacterium that is widely distributed in aquatic ecosystems and is considered to play an important role in the arsenic biogeochemical cycle. Our results showed that L. boryana resisted arsenite (As(III)) and arsenate (As(V)) concentrations up to 0.25 mM and 5 mM, respectively. When exposed to 100 μM As(III) or As(V) for 4 weeks, L. boryana accumulated as much arsenic as 570.0 mg kg−1 and 268.5 mg kg−1, respectively. After the 4-week exposure to As(III) and As(V), organoarsenicals including dimethylarsenate (DMAs(V)) and oxo-arsenosugar-phosphate (Oxo-PO4) were detected in the cells of L. boryana, while inorganic arsenic, especially As(V), was still the main species in both the cells and medium. Furthermore, arsenic oxidation was observed to be solely caused by L. boryana cells and was considered the dominant detoxification pathway. In conclusion, due to its powerful arsenic accumulation, biotransformation, and detoxification abilities, L. boryana might play an important role in arsenic remediation in aquatic environments.