Investigation of the protective effect of chitosan against arsenic-induced nephrotoxicity and oxidative damage in rat kidney tissue.

Arsenic is an important metalloid that can cause poisoning in humans and domestic animals. Exposure to arsenic causes cell damage, increasing the production of reactive oxygen species. Chitosan is a biopolymer obtained by deacetylation of chitin with antioxidant and metal ion chelating properties. In this study, the protective effect of chitosan on arsenic-induced nephrotoxicity and oxidative damage was investigated. 32 male Wistar-albino rats were divided into 4 groups of 8 rats each as control group (C), chitosan group (CS group), arsenic group (AS group), and arsenic+chitosan group (AS+CS group). The C group was given distilled water by oral gavage, the AS group was given 100 ppm/day Na-arsenite ad libitum with drinking water, the CS group was given 200 mg/kg/day chitosan dissolved in saline by oral gavage, the AS+CS group was given 100 ppm/day Na-arsenite ad libitum with drinking water and 200 mg/kg/day chitosan dissolved in saline by oral gavage for 30 days. At the end of the 30-day experimental period, 90 mg/kg ketamine was administered intraperitoneally to all rats, and blood samples and kidney tissues were collected. Urea, uric acid, creatinine, P, Mg, K, Ca, Na, Cystatin C (CYS-C), Neutrophil Gelatinase Associated Lipocalin (NGAL) and Kidney Injury Molecule 1 (KIM-1) levels were measured in serum samples. Malondialdehyde (MDA), Glutathione (GSH), Catalase (CAT) and Superoxide dismutase (SOD) levels in the supernatant obtained from kidney tissue were analyzed by ELISA method. Compared with AS group, uric acid and creatinine levels of the AS+CS group were significantly decreased (p<0.001), urea, KIM-1, CYS-C, NGAL, and MDA levels were numerically decreased and CAT, GSH, and SOD levels were numerically increased (p>0.05). In conclusion, based on both biochemical and histopathological-immunohistochemical- immunofluorescence findings, it can be concluded that chitosan attenuates kidney injury and protects the kidney.

Ecotoxicity characterization assisted performance assessment of electro-bioremediation reactors for nitrate and arsenite elimination.

The performance of combined reduction of nitrate (NO3 - ) to dinitrogen gas (N2 ) and oxidation of arsenite (As[III]) to arsenate (As[V]) by a bioelectrochemical system was assessed, supported by ecotoxicity characterization. For the comprehensive toxicity characterization of the untreated model groundwater and the treated reactor effluents, a problem-specific ecotoxicity test battery was established. The performance of the applied technology in terms of toxicity and target pollutant elimination was compared and analyzed. The highest toxicity attenuation was achieved under continuous flow mode with hydraulic retention time (HRT) = 7.5 h, with 95%, nitrate removal rate and complete oxidation of arsenite to arsenate. Daphnia magna proved to be the most sensitive test organism. The results of the D. magna lethality test supported the choice of the ideal operational conditions based on chemical data analysis. The outcomes of the study demonstrated that the applied technology was able to improve the groundwater quality in terms of both chemical and ecotoxicological characteristics. The importance of ecotoxicity evaluation was also highlighted, given that significant target contaminant elimination did not necessarily lower the environmental impact of the initial, untreated medium, in addition, anomalies might occur during the technology operational process which in some instances, could result in elevated toxicity levels.

Effects of nitrate and Fe/As molar ratio on direct iron(III)-arsenite precipitation in high-sulfate-chloride wastewaters.

The addition of an arsenite-chloride solution into an arsenite-sulfate solution is extremely beneficial for the removal of As(III) via Fe(III) salt precipitation at pH 2.3. However, the applicability of this method to complicated high-As(III) metallurgical wastewaters still requires further verification. This work investigated the effects of nitrate and Fe/As molar ratio on As(III) immobilization using Fe(III) in three acid radical media including sulfate, chloride, and nitrate at pH 2.3. Our results indicated that 72.1‒93.5% of As(III) was precipitated, which was 5‒10% less than those obtained in the nitrate-free systems. The Fe/As molar ratio of 4 was the optimal condition with an average of 93% As(III) removal based on a broad sulfate/chloride molar ratio range (1:1‒16). However, a maximum of 96% As(III) removal was observed under the Fe/As molar ratio of 1.5 and the sulfate/chloride condition of 1:16. The negative correlation between complexation and precipitation was attributed to the enhanced initial complexation by the synergistic effect of the mononitratoiron complex and FeH2AsO32+. The variation of Fe/As molar ratios resulted in the diverse solid species, thus further affecting the As(III) removal efficiency. Despite producing tooeleite as a major As(III) host phase, ferrihydrite and poorly crystalline ferric arsenite hydroxysulfate formed simultaneously at the Fe/As molar ratio of 4 participated in As(III) immobilization compared with the solid products at Fe/As molar ratios ≤ 2.

Active microbial arsenic methylation in saline-alkaline paddy soil.

Seawater rice has been cultivated to ensure food security. The salt-tolerant rice strains are resistant to saline and alkali but may be vulnerable to elevated arsenic (As) near coastal regions. Herein, the saline-alkaline paddy soil was incubated with natural irrigation river for three months to explore the mobility and transformation of As. The incubation results showed that 65 ± 1.2 % solid-bound As(V) was reduced to As(III) within two weeks with the release of As(III) to porewater. The dissolved As(III) was methylated after two weeks, resulting in dimethyl arsenate (DMA) as the dominant As species (87 %-100 %). The elevated As methylation was attributed to the most abundant arsenite methyltransferase gene (arsM) (4.1-10.4 × 107/g dry soil), over three orders of magnitude higher than As redox-related genes. The analysis of arsM operational taxonomic units (OTUs) suggested the highest sequence similarity to Proteobacteria (25.7-39.5 %), Actinobacteria (24.9-30.5 %), Gemmatimonadetes (7.5-11.9 %), Basidiomycota (5.1-12.5 %), and Chloroflexi (4.1-8.7 %). Specifically, Chloroflexi and Actinobacteria are salt-tolerant bacteria, probably responsible for As methylation. The As in grain was within a safe regulatory level, and the dominance of methylated As in porewater did not enhance its accumulation in rice grains.

A novel antimony-selective ArsR transcriptional repressor and its specific detection of antimony trioxide in environmental samples via bacterial biosensor.

Extensively industrial applications and ever-accelerated anthropogenic activities have resulted in the dramatic accumulation of Sb2O3 contaminant in the environment, leading to adverse health effects on humans and ecosystems. Although arsenite has been subjected to numerous studies and ArsR-based whole-cell biosensors have been successfully applied in field testing of arsenite, there is limited information on the biological recognition element of Sb2O3 and its actual application in biosensor construction and environmental monitoring. In this study, we identified a specific recognition element of Sb2O3, SxArsR, in Sphingobium xenophagum C1 by the induced bioluminescent signal analysis of gene expression in response to Sb2O3 exposure. Compared to the other four groups of characterized ArsRs, the novel SxArsR lacks the third cysteine residue for binding of arsenite and has a conserved histidine-cysteine "HCXC" binding site that directly and specifically binds for Sb2O3. Sb2O3 can remove SxArsR from the core operator/promoter binding sequence in the -79 region upstream of the start codon of sxarsR. Based on the specificity of SxArsR protein and the sensitivity of SxArsR-binding DNA sequence, SxArsR-based whole-cell biosensor was constructed and showed a linear relationship (R2 = 0.99) from 0.01 to 6.0 µM of Sb2O3 with a detection limit of 0.01 µM. The novel bacterial biosensor also exhibited a good performance in the detection of Sb2O3 in environmental water and sediment samples. Overall, SxArsR-based biosensor represents a promising strategy for Sb2O3 detection and may have a profound impact on further practical application of ArsR biosensor in the dual-signal simultaneous detection of arsenite and Sb2O3.

Simultaneous removal of arsenate and arsenite in water using a novel functional halloysite nanotube composite.

This work aims at exploring a novel environment-friendly nanomaterial based on natural clay minerals for arsenic removal in aqueous samples. Halloysite nanotubes (HNTs) were selected as the substrate with Mn oxides loaded on the surface to enhance its arsenic adsorption ability and then grafted onto the SiO2-coated Fe3O4 microsphere to get a just enough magnetic performance facilitating the material's post-treatment. The prepared composite (Fe3O4@SiO2@Mn-HNTs) was extensively characterized by various instruments including Fourier transform infrared spectroscope (FTIR), scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TG), vibrating sample magnetometer (VSM), X-ray photoelectron spectroscope (XPS), and X-ray diffraction (XRD). Batch experiments were carried out to get the optimum test conditions for arsenic adsorption by the composite, including pH, loading amount of Mn oxides, adsorbent dosage, and the co-existing ions. The adsorption of AsIII and AsV on Fe3O4@SiO2@Mn-HNTs were both well fitted with the pseudo-second-order kinetic model as well as the Langmuir adsorption isotherm model revealing the chemisorption between arsenic and Fe3O4@SiO2@Mn-HNTs. The adsorption process of AsIII and AsV were both endothermic and spontaneous displayed by the thermodynamic study. The capacities of the prepared composite are 3.28 mg g-1 for AsIII and 3.52 mg g-1 for AsV, respectively, which are comparable or better than those of many reported materials in the references. Toxicity characteristic leaching procedure (TCLP) and synthetic precipitation leaching procedure (SPLP) tests were carried out to access the secondary environmental risk of the composite and showed that it was quite environmentally stable and can be safely disposed. The composite was successfully applied in environmental water samples indicating its great potential applicability in future.

Arsenic speciation analysis in porewater by a novel colorimetric assay.

Arsenic is common toxic contaminant, but tracking its mobility through submerged soils is difficult because microscale processes dictate its speciation and affinity to minerals. Analyses on environmental dissolved arsenic (As) species such as arsenate and arsenite currently require highly specialized equipment and large sample volumes. In an effort to unravel arsenic dynamics in sedimentary porewater, a novel, highly sensitive, and field-usable colorimetric assay requiring 100 µL of sample was developed. Two complementary protocols are presented, suitable for sub-micromolar and micromolar ranges. Phosphate is a main interfering substance, but can be separated by measuring phosphate and arsenate under two different acidities. Arsenite is assessed by oxidation of arsenite to arsenate in the low-acidity reagent. Optimization of the protocol and spectral analyses resulted in elimination of various interferences (silicate, iron, sulfide, sulfate), and the assay is applicable across a wide range of salinities and porewater compositions. The new assay was used to study As mobilization processes through the soil of a contaminated brook. Water column sources of arsenic were limited to a modest input by a groundwater source along the flow path. In one of the sites, the arsenite and arsenate porewater profiles showed active iron-driven As redox cycling in the soil, which may play a role in arsenic mobilization and releases arsenite and arsenate into the brook water column. Low arsenic concentrations downstream from the source sites indicated arsenic retention by soil and dilution with additional sources of water. Arsenic is thus retained by the Bossegraben before it merges with larger rivers.

OFF-switching property of quorum sensor LuxR via As(III)-induced insoluble form.

Whole-cell sensors for arsenite detection have been developed exclusively based on the natural arsenite (As(III)) sensory protein ArsR for arsenic metabolism. This study reports that the quorum-sensing LuxR/Plux system from Vibrio fischeri, which is completely unrelated to arsenic metabolism, responds to As(III) in a dose-dependent manner. Due to as many as 9 cysteine residues, which has a high binding affinity with As(III), LuxR underwent As(III)-induced insoluble form, thereby reducing its effective cellular concentration. Accordingly, the expression level of green fluorescent protein under the control of Plux gradually decreased with increasing As(III) concentration in the medium. This is a novel As(III)-detection system that has never been proposed before, with a unique ON-to-OFF transfer function.

Arsenic speciation in rice samples for trace level determination by high performance liquid chromatography-inductively coupled plasma-mass spectrometry.

Six arsenic species, namely arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB) and arsenocholine (AsC) were speciated using a combination of high-performance liquid chromatography and inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Under optimum chromatographic conditions, six arsenic species were well separated, and the performance of the combined system (HPLC-ICP-MS) for the species was determined. The limits of detection were calculated in the range of 0.14-0.29 ng/mL, and the corresponding quantification limits ranged between 0.45 and 0.97 ng mL-1 for the species. Spike recovery experiments performed on rice samples were used to validate the method's applicability to complex matrices. The recovery results calculated ranged between 93 and 109%, validating the method's applicability. Triplicate measurements for all spiked samples recorded percent relative standard deviation values below 10%.

Improved grain yield and lowered arsenic accumulation in rice plants by inoculation with arsenite-oxidizing Achromobacter xylosoxidans GD03.

Arsenite is the predominant arsenic species in flooded paddy soil, and arsenite bioaccumulation in rice grains has been identified as a major problem in many Asian countries. Lowering arsenite level in rice plants and grain via accelerating arsenite oxidation is a potential strategy to help populations, who depended on rice consumption, to reduce the internal exposure level of arsenic. We herein isolated a strain, Achromobacter xylosoxidans GD03, with the high arsenite-oxidizing ability and plant growth-promoting traits. We observed that arsenite exposure could promote A. xylosoxidans GD03 to excrete indole-3-acetic acid and thus promoted rice growth. The pot culture experiments of Indica rice cultivar Guang You Ming 118 (GYM118) demonstrated that A. xylosoxidans GD03 inoculation of paddy soil (4.5-180 × 108 CFU GD03/kg soil) significantly accelerated arsenite oxidation in flooded soil. The daily arsenic oxidation rate with GD03 inoculation was 1.5-3.3 times as that without strain GD03 inoculation within the whole growth period of Indica GYM118 in the presence of the native microflora. It thus led to a 34-69%, 43-74%, 24-76% and 35-57% decrease in arsenite concentration of the stems, leaves, bran and grain of Indica GYM118 respectively and a 59-96% increase in rice grain yield. The paddy soil inoculated with 40.0 mL/kg of A. xylosoxidans GD03 resulted in a lowest As(III) concentrations in all rice organs of Indica GYM118, which equivalent to only 24-50% of the As(III) concentrations in the group without GD03 inoculation. The results highlight that a highly arsenite-oxidizing bacterium could accelerate arsenite oxidation of paddy soil when facing competition with the native microflora, thus decrease arsenic toxicity and bioavailable soil arsenic.

SPE based soil processing and aptasensor integrated detection system for rapid on site screening of arsenic contamination in soil.

Rapid industrialization and urbanization have resulted in serious environmental deterioration, especially in terms of heavy metal contamination in soil. Arsenic is one of the primary heavy metal contaminants in the soil and possesses a severe threat to all the plants and animals including humans. The conventional methods for analyzing arsenic contamination in soil have tedious, time-consuming sample preparation steps and require laboratory equipped instruments and skilled personnel. The present work demonstrates a novel method for arsenic As(III) detection in the contaminated soil based on field applicable sample preparation and smartphone-based optical sensing. Soil sample preparation has been simplified and optimized using acid extraction and serial application of different solid phase extraction (SPE) cartridges for the removal of interfering ions with high arsenic yield in one step. The acidic extraction and SPE efficiencies were found to be 35.4% and 54.0%, respectively, for arsenic contaminated field soil samples. The quantification of As(III) was performed by aptamer-AuNPs based colorimetric assay with a smartphone coupled optical unit. This aptasensor integrated detection system (ADS) has shown a detection limit of 14.44 ppb for aqueous samples and 1.97 ppm for field soil samples. In the accuracy comparison with ICP-MS, arsenic contaminated field soils from various sources have been tested and the results depicted a highly significant correlation coefficient of 0.997 with an average difference of 1.67 ppm. By integrating all the required analytical steps into a portable format, the presented setup enables on-site tests of arsenic contamination in soil.

Bioaccessibility of arsenic from gastropod along the Xiangjiang River: Assessing human health risks using an in vitro digestion model.

The bioaccessibility of total arsenic (tAs) and arsenic species in Bellamya aeruginosa collected from Xiangjiang River was evaluated using an in vitro digestion model, to assess the potential health risks to local residents. The tAs concentrations in gastropod samples ranged from 1.98 to 6.33 mg kg-1 (mean 3.79 ± 1.60 mg kg-1). Five arsenic species including arsenite [As(III)], arsenate [As(V)], dimethylarsinic acid (DMA), arsenobetaine (AsB), and arsenocholine (AsC) were detected. Inorganic arsenic (iAs) concentrations, which were about a half of organic arsenic (oAs), were higher than the maximum permissible limit (≤0.50 mg kg-1 in aquatic products). Bioaccessible concentrations of tAs in digestive juices were found to be decreased in the order: intestinal phase > gastric phase > salivary phase. As(III) and AsC were the predominant species, but AsB was not detectable in all digestive juices. Bioaccessible iAs concentrations, which were close to the level of bioaccessible oAs, were not significantly different among three digestive juices, but also above 0.50 mg kg-1. Accordingly, bioaccessibility of tAs was highest in intestinal phase (48%), then in gastric phase (40%), and lowest in salivary phase (33%). Bioaccessibility of As(III) was close to 100%, and bioaccessibility of iAs was much higher than that of oAs. The mean values of target hazard quotient (THQ) and bioaccessible THQ were 0.80 and 0.70, respectively. The probability of experiencing non-carcinogenic effects was reduced to 18% down from 22% as considering iAs bioaccessibility. The mean values of carcinogenic risk (CR) and bioaccessible CR were higher than the acceptable value (1 × 10-4). Gastropod consumption from sampling sites may cause a potential carcinogenic risk.

Arsenic(III) biotransformation to tooeleite associated with the oxidation of Fe(II) via Acidithiobacillus ferrooxidans.

Tooeleite (Fe6(AsO3)4(SO4)(OH)4·4H2O), the only known ferric arsenite sulfate bearing mineral, has great potential for arsenic remediation due to its structure favoring incorporation of As(III). Based on the natural attenuation of removing As(III) directly by the formation of tooeleite via microorganisms, an iron-oxidizing bacterial strain Acidithiobacillus ferrooxidans ATCC 23270 (At.ferrooxidans) was selected to facilitate the formation of tooeleite. The optimized condition for the biogenic tooeleite was obtained at pH of 2.0, 30 °C and an initial arsenic of 500 mg/L. The process of biological mineralization is accompanied by the removal of 95.4% arsenic. What's more, biosynthetic tooeleite crystallization via a three-stage process was revealed using a combination of liquid and solid analyses (ICP-OES, XRD, XPS, FT-IR, SEM, STEM, particle distribution). The three stages included Fe2+ oxidation by At.ferrooxidans, Fe3+ hydrolysis and an initial Fe-As amorphous precursors formation, and finally transforming to tooeleite crystal. Moreover, RT-qPCR was used to reveal the relationship between functional gene expression of At.ferrooxidans and the mineral formation. The results showed the biogenic tooeleite exerts significant control on the geochemistry of arsenic contaminated systems.

Antimony sensing whole-cell bioreporters derived from ArsR genetic engineering.

Despite the known hazardous effects of antimony (Sb) on human health, Sb monitoring biosensors have not been as actively investigated as arsenic (As) biosensors. Whole-cell bioreporters (WCBs) employing an arsenic-responsive operon and a regulatory protein (ArsR) are reportedly capable of monitoring arsenite, arsenate, and antimonite. However, the potential of WCBs as Sb biosensors has been largely ignored. Here, the metal-binding site of ArsR (sequenced as ELCVCDLCTA from amino acid number 30 to 39) was modified via genetic engineering to enhance Sb specificity. By relocating cysteine residues and introducing point mutations, nine ArsR mutants were generated and tested for metal(loid) ion specificity. The Sb specificity of WCBs was enhanced by the C37S/A39C and L36C/C37S mutations on the As binding site of ArsR. Additionally, WCBs with other ArsR mutants exhibited new target sensing capabilities toward Cd and Pb. Although further research is required to enhance the specificity and sensitivity of WCBs and to broaden their practical applications, our proposed strategy based on genetic engineering of regulatory proteins provides a valuable basis to generate WCBs to monitor novel targets.

Investigating photo-driven arsenics' behavior and their glucose metabolite toxicity by the typical metallic oxides in ambient PM2.5.

It is essential and challenged to understand the atmospheric arsenic pollution because it is much more complicated than in water and top-soil. Herein the different behavior of arsenic species firstly were discovered within the ambient PM2.5 collected during daytime and nighttime, winter and summer. The diurnal variation of arsenic species in PMs is significantly correlated with the presence of metallic oxides, specifically, ferrous, titanium and zinc oxides, which might play a key role in the process of the photo-oxidation of As(III) to As(V) with the meteorological parameters and regional factors excluded. Subsequently, the photo conversion of arsenite was detected on metal-loaded glass-fiber filters under visible light. The photo-generated superoxide radical was found to be predominantly responsible for the oxidation of As(III). In order to reveal toxicity differences induced by oxidation As(III), HepG2 cells were exposed to various arsenic mixture solution. We found that the antioxidant enzyme activities suppressed with increasing the As(III)/As(V) ratio in total, followed by the accumulation of intracellular ROS level. The glucose consumption and glycogen content also displayed an obvious reduction in insulin-stimulated cells. Compared to the expression levels of IRS-1, AKT and GLUT4, GLUT2 might be more vulnerable to arsenic exposure and lead to the abnormalities of glucose metabolism in HepG2 cells. Taken together, these findings clarify that the health risk posed by inhalation exposure to As-pollution air might be alleviated owing to the photo-driven conversion in presence of metal oxides.

Arsenic speciation in the bracket fungus Fomitopsis betulina from contaminated and pristine sites.

Uptake, distribution and speciation of arsenic (As) were determined in the bracket fungus Fomitopsis betulina (previously Piptoporus betulinus), commonly known as the birch polypore, collected from a woodland adjacent to a highly contaminated former mine in the Southwest UK and at an uncontaminated site in Quebec, Canada, with no past or present mining activity. The fruiting body was divided into cap, centre and pores representing the top, middle and underside to identify trends in the distribution and transformation of As. Total As, determined by inductively coupled plasma-mass spectrometry (ICP-MS), was approximately tenfold higher in the mushroom from the contaminated compared to the uncontaminated site. Overall, accumulation of As was low relative to values reported for some soil-dwelling species, with maximum levels of 1.6 mg/kg at the contaminated site. Arsenic speciation was performed on aqueous extracts via both anion and cation high-performance liquid chromatography-ICP-MS (HPLC-ICP-MS) and on whole dried samples using X-ray absorption near edge structure (XANES) analysis. Seven As species were detected in F. betulina from the contaminated site by HPLC-ICP-MS: arsenite (AsIII), arsenate (AsV), dimethylarsinate (DMAV), methylarsonate (MAV), trimethylarsine oxide (TMAO), tetramethylarsonium ion (Tetra) and trace levels of arsenobetaine (AB). The same As species were observed at the uncontaminated site with the exception of TMAO and Tetra. Arsenic species were localized throughout the fruiting body at the contaminated site, with the cap and pores containing a majority of AsV, only the cap containing TMAO, and the pores containing higher concentrations of DMAV and MAV as well as tetra and a trace of AB. XANES analysis demonstrated that the predominant form of As at the contaminated site was inorganic AsIII coordinated with sulphur or oxygen and AsV coordinated with oxygen. This is the first account of arsenic speciation in F. betulina or any fungi of the family Fomitopsidaceae.

Design and synthesis new colorimetric receptors for naked-eye detection of biologically important fluoride and acetate anions in organic and arsenite in aqueous medium based on ICT mechanism: DFT study and test strip application.

Novel three colorimetric anion receptors R1, R2 and R3 have been designed and synthesized via condensation reaction and characterized using IR, MS, and NMR spectroscopic techniques. Anion sensing properties were studied using colorimetric, UV-vis titration, 1H NMR titration, and Cyclic Voltammetric Studies. Comparing the UV-visible titration data of the receptors R1 and R2, R2 showed high redshift (∆λmax) in the mixed competitive solution (DMSO: H2O, 9: 1; v/v) of about 155 nm, 157 nm, 169 nm for Na+F-, Na+AcO-, and Na+AsO2- ions with LOD of 0.23 ppm, 0.18 ppm, and 0.30 ppm, respectively. The observed spectral change of receptor R2 is due to the anion-induced deprotonation of the OH proton, which is confirmed by UV-vis titration, 1HNMR titration, and cyclic voltammetric studies. Theoretical studies via DFT calculation were carried for R1 and R2 to optimize the structure and to explain the anion-binding mechanism. The application of designed receptor R2 was successfully demonstrated for the detection of F- and AsO2- ions using a test strip. The receptors R1 and R2 proved itself to be potentially useful for real-life application by sensing F- and AcO- ions in real samples like toothpaste, mouthwash, vinegar and seawater in a complete aqueous medium.

Humic acid promotes arsenopyrite bio-oxidation and arsenic immobilization.

The bio-oxidative dissolution of arsenopyrite, the most severe arsenic contamination source, can be mediated by organic substances, but pertinent studies on this subject are scarce. In this study, the bio-oxidative dissolution of arsenopyrite by Sulfobacillus thermosulfidooxidans and arsenic immobilization were evaluated in the presence of humic acid (HA). The mineral dissolution was monitored through analyses of the parameters in solution, phase and element speciation transformations on the mineral surface, and arsenic immobilization on the surfaces of cells and jarosites-HA. The results show that the presence of HA enhances the dissolution of arsenopyrite, e.g., 7.1% of arsenopyrite was in the residue after 12 d of bio-oxidation compared to 19.3% in the absence of HA. Meanwhile, the presence of HA led to changes of the fates of As and Fe and no accumulation of elemental sulfur (S0) or ferric arsenate on the mineral surface. Moreover, a flocculent porous structure was formed on the surfaces of both microbial cells and jarosites, on which a large amount of arsenic was adsorbed. These results clearly indicate that HA can simultaneously promote the dissolution of arsenopyrite and arsenic immobilization, which may be significant for bioleaching of arsenopyrite-bearing contaminated sites.

Speciation analysis of arsenic in samples containing high concentrations of chloride by LC-HG-AFS.

Chloride widely exists in the environment and will cause serious interference for arsenic speciation analysis. The determination of four arsenic species including arsenite (As(III)), arsenate (As(V)), monomethylarsenate (MMA), and dimethylarsonate (DMA) in samples containing high concentrations of Cl- was carried out in this work by coupling of liquid chromatography (LC) with hydride generation atomic fluorescence spectrometry (HG-AFS). The interference of Cl- was successfully eliminated by coupling two anion-exchange chromatographic columns in series and eluting with 35.0 mmol L-1 (NH4)2HPO4 (pH = 6.00). A novel pre-treatment system was subsequently developed to realize on-line column switch and pre-reduction of As(V). The analysis time was shortened by an isocratic elution but programmed flow rate method, and the sensitivity of As(V) was also enhanced by the introduction of pre-reduction using the developed system. The proposed method can resist at least 10 g L-1 Cl- without any pre-treatment operations. Since LC-HG-AFS is low-cost and can be afforded or self-assembled by most labs, the developed method can be adopted as a routine analysis method for arsenic species in chloride-bearing samples, such as urine and seawater. Graphical abstract.