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.

Different sulfide to arsenic ratios driving arsenic speciation and microbial community interactions in two alkaline hot springs.

Arsenic (As) is ubiquitous in geothermal fluids, which threatens both water supply safety and local ecology. The co-occurrence of sulfur (S) and As increases the complexity of As migration and transformation in hot springs. Microorganisms play important roles in As-S transformation processes. In the present study, two Tibetan alkaline hot springs (designated Gulu [GL] and Daba [DB]) with different total As concentrations (0.88 mg/L and 12.42 mg/L, respectively) and different sulfide/As ratios (3.97 and 0.008, respectively) were selected for investigating interactions between As-S geochemistry and microbial communities along the outflow channels. The results showed that As-S transformation processes were similar, although concentrations and percentages of As and S species differed between the two hot springs. Thioarsenates were detected at the vents of the hot springs (18% and 0.32%, respectively), and were desulfurized to arsenite along the drainage channel. Arsenite was finally oxidized to arsenate (532 µg/L and 12,700 µg/L, respectively). Monothioarsenate, total As, and sulfate were the key factors shaping the changes in microbial communities with geochemical gradients. The relative abundances of sulfur reduction genes (dsrAB) and arsenate reduction genes (arsC) were higher in upstream portions of GL explaining high thiolation. Arsenite oxidation genes (aoxAB) were relatively abundant in downstream parts of GL and at the vent of DB explaining low thiolation. Sulfur oxidation genes (soxABXYZ) were abundant in GL and DB. Putative sulfate-reducing bacteria (SRB), such as Desulfuromusa and Clostridium, might be involved in forming thioarsenates by producing reduced S for chemical reactions with arsenite. Sulfur-oxidizing bacteria (SOB), such as Elioraea, Pseudoxanthomonas and Pseudomonas, and arsenite-oxidizing bacteria (AsOB) such as Thermus, Sulfurihydrogenibium and Hydrogenophaga, may be responsible for the oxidation of As-bound S, thereby desulfurizing thioarsenates, forming arsenite and, by further abiotic or microbial oxidation, arsenate. This study improves our understanding of As and S biogeochemistry in hot springs.

Effect of coexisting ions on adsorptive removal of arsenate by Mg-Fe-(CO3) LDH: multi-component adsorption and ANN-based multivariate modeling.

The adsorptive removal of a pollutant from water is significantly affected by the presence of coexisting ions with various concentrations. Here, we have studied adsorption of arsenate [As(V)] by calcined Mg-Fe-(CO3)-LDH in the presence of different cations (Mg2+, Na+, K+, Ca2+, and Fe3+) and anions (CO32‒, Cl‒, PO43‒, SO42‒, and NO3‒) with their different concentrations to simulate the field condition. The experimental results indicated that Ca2+, Mg2+, and Fe3+ have a synergistic effect on removal efficiency of As(V), whereas PO43‒ and CO32‒ ions have a significant antagonistic impact. Overall, the order of inhibiting effect of coexisting anions on adsorption of As(V) was arrived as NO3-˂Cl-

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.

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.

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 exposure in northern Mexican women.

OBJECTIVE: To describe interindividual metabolism variations and sociodemographic characteristics associated to urinary arsenic, and to estimate the arsenic contamination in water from urinary total arsenic (TAs). MATERIALS AND METHODS: Women (n=1 028) from northern Mexico were interviewed about their sociodemographic characteristics and their urinary concentrations of arsenic species were measured by liquid chromatography. Inorganic arsenic (iAs) in water was estimated from urinary TAs. RESULTS: Women were 20-88 years old. TAs in urine ranged from p10=3.41 to p90=56.93 µg/L; 74% of women had levels >6.4 µg/L. iAs in water varied from p10=3.04 to p90=202.12 µg/L; 65% of women had concentrations >10 µg/L, and 41%, concentrations >25 µg/L. Large variations in iAs metabolism were observed. TAs was significantly negatively associated with age and schooling, and positively with the state of residence. CONCLUSIONS: Exposure to iAs is an environmental problem in Mexico. Individual variations in metabolism are a challenge to design prevention and control programs.

OBJETIVO: Describir las variaciones interindividuales del metabolismo y las características sociodemográficas asociadas con el arsénico urinario, así como estimar su contaminación en el agua. MATERIAL Y MÉTODOS: Se entrevistó a 1 028 mujeres del norte de México; por cromatografía de líquidos se midieron los metabolitos urinarios de arsénico y, a partir de ellos, se estimó la concentración en agua. RESULTADOS: Las mujeres tuvieron 20-88 años. El arsénico urinario varió de p10=3.41 a p90=56.93 µg/L; 74% de las mujeres tuvieron niveles >6.4 µg/L. El arsénico en agua varió de p10=3.04 a p90=202.12 µg/L; 65% de las mujeres tenían concentraciones >10 µg/L, y 41%, >25 µg/L. Se observaron amplias variaciones en el metabolismo del arsénico. El arsénico urinario se asoció negativamente con la edad y escolaridad, y positivamente con el estado de residencia. CONCLUSIONES: La exposición a arsénico es un problema ambiental en México. Las variaciones individuales en su metabolismo son un desafío para diseñar programas de prevención y control.

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.

Immobilization of ssDNA on a metal-organic framework derived magnetic porous carbon (MPC) composite as a fluorescent sensing platform for the detection of arsenate ions.

In this work, we fabricated a metal-organic framework derived magnetic porous carbon (MPC) composite using a one-pot solid state template method. The formation of the synthesized composite was confirmed with various spectroscopic techniques, and it was proved that the composite can effectively quench the fluorescence of ssDNA. This property was utilized in the specific and efficient recognition of harmful arsenate ions. FAM-labelled single strand DNA (FAM-ssDNA) was adsorbed on the surface of the MPC composite and immobilized viaπ-π stacking interactions, which resulted in the fluorescence emission being quenched. A fluorescence quenching efficiency of 96% was achieved, due to the huge surface area of the MPC composite. Upon the addition of As(v) ions into our sensing system, the fluorescence emission dramatically increased, due to the strong affinity for As(v) of the surface of the MPC composite. Consequently, the adsorbed FAM-ssDNA was spontaneously displaced from the surface of the MPC composite, and so the fluorescence intensity was regained. Based on this mechanism, the fabricated biosensor exhibited a highly sensitive fluorescence response to As(v) in the range from 0 to 15 nM, with a detection limit as low as 630 pM. Furthermore, the sensing system is suitable for diverse biological and environmental samples.

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.

Mixed plantation of wheat and accumulators in arsenic contaminated plots: A novel way to reduce the uptake of arsenic in wheat and load on antioxidative defence of plant.

Wheat (W) and accumulators (A) were planted in plots (arsenic amended soil and without arsenic) designed with ecotoxicological concern for arsenic safe-grains. For the study sixteen plots of 2 × 2 × 0.5 m (l × b × h) size were prepared. Arsenic (As) in the form of sodium arsenate was applied at 50 mg/kg in plots. Out of these sixteen plots eight plots had arsenic amended soil and rest 8 without any arsenic (C). Accumulator's viz. Pteris vittata (PV), Phragmites australis (PA) and Vetiveria zizanioides (VZ) were planted along with wheat in combination (W + PV, W + PA and W + VZ) in twelve plots (6 AWAs plots and 6 AWC plots). In the rest 4 plots (2 WAs plots and 2 WC plots), only wheat was planted. The study was conducted for two cropping seasons, where accumulators were left in the plots between the cropping seasons except that before 2nd cropping accumulators were properly pruned and extra tillers were removed. The germination % of wheat in WAs in 1st and the 2nd cropping season was found to be 55 and 57%, while in AWAs and AWC plots it was between 86 and 92% (W + VZ, 56 and 73%). The physiological activity was found to be reduced in WAs plots compared to AWAs (except for vetiver combination) and AWC plots in both cropping seasons. The antioxidant activity was enhanced in WAs compared with AWAs. The arsenic concentration in grains of wheat was within the permissible limit set by WHO and GOI in AWAs plots while it exceeded the limit in W + VZ (in 1st cropping) and WAs in both cropings.

CdSe/ZnS quantum dots coated with carboxy-PEG and modified with the terbium(III) complex of guanosine 5'-monophosphate as a fluorescent nanoprobe for ratiometric determination of arsenate via its inhibition of acid phosphatase activity.

A ratiometric fluorometric method is described for the determination of arsenate via its inhibitory effect on the activity of the enzyme acid phosphatase. A nanoprobe was designed that consists of CdSe/ZnS quantum dots (QDs) coated with the terbium(III) complex of guanosine monophosphate (Tb-GMP). The nanoprobe was synthesized from carboxylated QDs, Tb(III) and GMP via binding of Tb(III) by both the carboxy and the phosphate groups. The nanoprobe, under single-wavelength excitation (at 280 nm), displays dual (red and green) emission, with peaks at around 652 nm from the QDs, and at 547 nm from the Tb-GMP coordination polymers. It is shown to be a viable nanoprobe for fluorometric determination of As(V) detection through it inhibitory action on the activity of acid phosphatase (ACP). The enzyme destroys the Tb-GMP structure via hydrolysis of GMP, and hence the fluorescence of the Tb-GMP complex is quenched. In contrast, the fluorescence of the CdSe/ZnS QDs remains inert to ACP. It therefore can serve as an internal reference signal. In the presence of arsenate (an analog of phosphate), the activity of ACP is inhibited due to competitive binding. Thus, hydrolysis of GMP is prevented. These findings were used to design a ratiometric fluorometric method for the quantification of As(V). The ratio of fluorescences at 547 and 652 nm increases linearly in the 0.5 to 200 ppb As(V) concentation range, and the limit of detection is 0.39 ppb. Under a UV lamp, the probe shows distinguishable color from green to red on increasing the concentration of As(V). Graphical abstract Schematic illustration of CdSe/ZnS quantum dot coated with carboxy-PEG and modified with the terbium(III)-GMP complex as a fluorescent nanoprobe for ratiometric determination of arsenate via its inhibition of ACP activity.

Colorimetric and electrochemical arsenate assays by exploiting the peroxidase-like activity of FeOOH nanorods.

The authors describe an electrochemical and an optical method for the determination of As(V) by using iron oxyhydroxide (FeOOH) nanorods that display peroxidase-mimicking activity. The nanorods catalyze the oxidation of substrate ABTS by H2O2 to form a green product with an absorption maximum at 418 nm. If, however, As(V) is electrostatically adsorbed on the nanorods, the oxidation is gradually inhibited. A colorimetric assay was worked out based on these findings. Response is linear in the 0 to 8 ppb and 8 to 200 ppb As(V) concentration range, and the detection limit is 0.1 ppb. Even higher sensitivity is achieved in an electrochemical method which is based on the excellent electrical conductivity of FeOOH nanorods. Electrochemical analysis of As(V) was achieved by first adsorbing As(V) on the nanorods. This inhibits the ABTS reduction current signal, best measured at a potential of 150 mV (vs. Ag/AgCl). The linear range extends from 0.04 to 200 ppb, and the detection limit is as low as 12 ppt. Graphical abstract Schematic representation of FeOOH nanorod-based colorimetric and electrochemical assays for arsenate (As(V)). As(V) adsorbed on FeOOH nanorods inhibits the peroxidase-mimicking activity of nanorods, and a colorimetric and electrochemical dual-signal assay was constructed to achieve sensitive determination of As(V).

Pharmacokinetic Properties of Arsenic Species after Intravenous and Intragastrical Administration of Arsenic Trioxide Solution in Cynomolgus Macaques Using HPLC-ICP-MS.

A rapid and sensitive method was established for arsenic (As) speciation based on high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). This method was validated for the quantification of four arsenic species, including arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMAV) and dimethylarsinic acid (DMAV) in cynomolgus macaque plasma. Separation was achieved in just 3.7 min with an alkyl reverse phase column and highly aqueous mobile phase containing 20 mM citric acid and 5 mM sodium hexanesulfonate (pH = 4.3). The calibration curves were linear over the range of 5⁻500 ng·mL-1 (measured as As), with r > 0.99. The above method was validated for selectivity, precision, accuracy, matrix effect, recovery, carryover effect and stability, and applied in a comparative pharmacokinetic study of arsenic species in cynomolgus macaque samples following intravenous and intragastrical administration of arsenic trioxide solution (0.80 mg·kg-1; 0.61 mg·kg-1 of arsenic); in addition, the absolute oral bioavailability of the active ingredient AsIII of arsenic trioxide in cynomolgus macaque samples was derived as 60.9 ± 16.1%.

Enrichment of indigenous arsenate reducing anaerobic bacteria from arsenic rich aquifer sediment of Brahmaputra river basin and their potential role in as mobilization.

Anaerobic enrichment of As5+ reducing bacteria in the presence and/or absence of organic carbon (OC) and As5+ from As contaminated soil of Brahmaputra river basin (BRB) (Jorhat, Assam) was performed. Denaturing gradient gel electrophoresis of the 16SrRNA gene sequences amplified from the enriched microbial community indicated occurrence of maximum diversity under conditions receiving no OC (MSM) followed by moderate OC (LB). However, higher OC or As showed antagonistic effect on bacterial enrichment whereas together (BB + As) they showed a synergistic effect. Phylogenetic analysis of the prominent bands revealed an overall abundance of Lachnoanaerobaculum (39%), Clostridium (39%), Bacillus, Peptostreptococcaceae, Anaerostipes (13%), and Desulfotomaculum (8.7%). Moderate OC (LB) led to maximum As mobilization i.e. 27.42 µg/L, whereas presence of added As together with high OC (BB + As) enhanced the mobilization process. Mineralogical analyses of the sediments after incubation showed prominent weathering and loss of crystallinity in MSM and LB. Appearance of a new peak corresponding to arsenolamprite (As) in LB and LB + As indicated opening up of secondary phases of the minerals harboring As due to microbial leaching under moderate OC. This is the first study reporting Lachnoanaerobaculumas a potent As5+ dissimilating bacterium isolated from As contaminated subsurface sediment of BRB.

CeO2 Nanowire-BODIPY-Adenosine Triphosphate Fluorescent Sensing Platform for Highly Specific and Sensitive Detection of Arsenate.

Effective and sensitive monitoring of arsenate in drinking water is significant for risk management of public health. Here, we demonstrated that a CeO2 nanowire acted as an efficient quencher for small fluorescent molecules with a phosphate group, BODIPY-adenosine triphosphate (BODIPY-ATP) and riboflavin-5'-phosphate (Rf-P), and developed a CeO2 nanowire-BODIPY-ATP platform for highly selective and sensitive detection of arsenate. The response strategy was based on the competitive coordination chemistry of CeO2 nanowire between arsenate and phosphate group of BODIPY-ATP. Arsenate displaced adsorbed BODIPY-ATP to enhance fluorescence, allowing detection of arsenate down to 7.8 nM, which is lower than the WHO-defined limit of 130 nM. An excellent linear range of 20-150 and 150-1000 nM was obtained. Importantly, this system was simple in design and convenient in operation. Also, the platform exhibited excellent selectivity for arsenate without the interference of phosphate ions. Finally, the proposed method had been successfully employed for determination of arsenate in real water samples.

Effects of elevated sulfate concentration on the mobility of arsenic in the sediment-water interface.

The adsorption/desorption of arsenic (As) at the sediment-water interface in lakes is the key to understanding whether As can enter the ecosystem and participate in material circulation. In this study, the concentrations of As(III), total arsenic [As(T)], sulfide, iron (Fe), and dissolved organic carbon (DOC) in overlying water were observed after the initial sulfate (SO42-) concentrations were increased by four gradients in the presence and absence of microbial systems. The results indicate that increased SO42- concentrations in overlying water triggered As desorption from sediments. Approximately 10% of the desorbed As was desorbed directly as arsenite or arsenate by competitive adsorption sites on the iron salt surface; 21% was due to the reduction of iron (hydr)oxides; and 69% was due to microbial activity, as compared with a system with no microbial activity. The intensity of microbial activity was controlled by the SO42- and DOC concentrations in the overlying water. In anaerobic systems, which had SO42- and DOC concentrations higher than 47 and 7 mg/L, respectively, microbial activity was promoted by SO42- and DOC; As(III) was desorbed under these indoor simulation conditions. When either the SO42- or DOC concentration was lower than its respective threshold of 47 or 7 mg/L, or when either of these indices was below its concentration limit, it was difficult for microorganisms to use SO42- and DOC to enhance their own activities. Therefore, conditions were insufficient for As desorption. The migration of As in lake sediments was dominated by microbial activity, which was co-limited by SO42- and DOC. The concentrations of SO42- and DOC in the overlying water are thus important for the prevention and control of As pollution in lakes. We recommend controlling SO42- and DOC concentrations as a method for controlling As inner-source pollution in lake water.

Chemical and toxicological assessment of arsenic sorption onto Fe-sericite composite powder and beads.

Batch sorption and leaching of arsenic (1-30mgL-1) on Fe-sericite composite powder and beads were investigated in this study. Fe-sericite composite powder was made from natural sericite modified with iron, and alginate was used to transform the powder into beads. The maximum sorption capacities of the Fe-sericite composite powder (15.04 and 13.21mgg-1 for As(III) and As(V), respectively) were higher than those of the corresponding beads (9.02 and 7.11mgg-1 for As(III) and As(V), respectively) owing to the higher specific surface area of the powder. In addition, the leaching amounts of As(III) from Fe-sericite composite beads (≤ 15.03%) were higher than those of the corresponding powder (≤ 5.71%). However, acute toxicity of As(III)-sorbed Fe-sericite composite beads toward Daphnia magna was not significantly different from that of the corresponding powder (p > 0.05). Considering higher uptake of the powder particles by the daphnids, Fe-sericite composite beads seem to be a more appropriate and safer sorbent for arsenic removal in practical application. Based on Fe content, Fe-sericite composite beads had similar or higher maximum sorption capacities (71.19 and 56.11mgg-1 Fe for As(III) and As(V), respectively) than those of previously reported sorbents.

Effectiveness of Ferric, Ferrous, and Aluminum (Hydr)Oxide Coprecipitation to Treat Water Contaminated with Arsenate.

Coprecipitation of Fe and Al (hydr)oxides has been considered a low-cost process to remove As from wastewater. Arsenate is the most stable form of As in aerobic environments such as surface water, soils, and sediments and can be removed from water through methods based on this process. Iron/aluminum molar ratios of 100:0, 80:20, and 60:40 were used to treat water contaminated with As at concentrations of 50 and 500 mg L. Aluminum, ferrous, and ferric sulfates were used to coprecipitate Al and Fe (hydr)oxides at high pH. Maghemite, magnetite, lepidocrocite, and goethite were detected in precipitates from Fe(II), whereas hematite and ferrihydrite were identified in Fe(III) treatments. Segregation of Al (hydr)oxides as gibbsite and bayerite as well as the Al isomorphic substitution in Fe (hydr)oxides were detected in the presence of Al. The precipitates were classified as nonhazardous according to the leaching test based on Brazilian Technical Standard NBR 10005. The presence of Al increased the stability of the sludge from Fe(II) treatments but did not affect the stability of precipitates from Fe(III) treatments. High efficiencies for As removal from water were obtained for all treatments, but concentrations of soluble As were, in general, lower for Fe(III) treatments especially, in the absence of Al. Treatments were efficient in reaching the threshold to effluent discharge (0.5 mg L), but only treatments with initially 50 mg L of As reached the threshold for drinking water (10 µg L).

Statistical optimization of arsenic biosorption by microbial enzyme via Ca-alginate beads.

Bioremediation of arsenic using green technology via microbial enzymes has attracted scientists due to its simplicity and cost effectiveness. Statistical optimization of arsenate bioremediation was conducted by the enzyme arsenate reductase extracted from arsenic tolerant bacterium Pseudomonas alcaligenes. Response surface methodology based on Box-Behnken design matrix was performed to determine the optimal operational conditions of a multivariable system and their interactive effects on the bioremediation process. The highest biosorptive activity of 96.2 µg gm-1 of beads was achieved under optimized conditions (pH = 7.0; As (V) concentration = 1000 ppb; time = 2 h). SEM analysis showed the morphological changes on the surface of enzyme immobilized gluteraldehyde crosslinked Ca-alginate beads. The immobilized enzyme retained its activity for 8 cycles. ANOVA with a high correlation coefficient (R2 > 0.99) and lower "Prob > F"value (<0.0001) corroborated the second-order polynomial model for the biosorption process. This study on the adsorptive removal of As (V) by enzyme-loaded biosorbent revealed a possible way of its application in large scale treatment of As (V)-contaminated water bodies.