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Arsenosugars are the predominant species of arsenic in most seaweed. The analysis of these compounds is hampered by the lack of calibration standards needed in their unambiguous identification and quantification. This affects the availability of reliable information on their potential toxicity, which is scarce and controversial. Knowing the potential of centrifugal partition chromatography (CPC) as a preparative separation technique applied to a number of natural compounds, the aim of this work is to investigate the feasibility of CPC in the case of isolation and purification of arsenosugars from algae extracts. Several biphasic solvents systems have been studied to evaluate the distribution of the As species. Given the physical characteristics of these compounds, the presence of strong acids, the formation of ionic pairs or the presence of salts at high ionic strength have been considered. System 1-BuOH/EtOH/sat.(NH 4 ) 2 SO 4 /water at a volume ratio 0.2:1:1:1 originates adequate distribution constants of analytes that allows the required separation. The total arsenic content and the arsenic speciation of the eluted solutions from CPC were analyzed by ICP-MS and IC-ICP-MS, respectively. The developed CPC procedure allows us to obtain of the three arsenosugars with a purity of 98.7 % in PO 4 -Sug, 90.4 % in SO 3 -Sug and 96.1 % in SO 4 -Sug., Competing Interests: Declaration of competing interest The autors declare that they have no known competint finantial interest or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

In this study, graphene oxide and composites of graphene oxide-iron modified clinoptilolite were synthesized and used for arsenate removal from aqueous solution. All adsorbents were characterized using X-ray diffraction and specific surface area analysis. The specific surface areas of composites were found to be less than the iron modified clinoptilolite. The time required to reach equilibrium was determined as 3 hours for all adsorbents. The Box-Behnken statistical experiment design method was used to determine the effects of initial arsenate concentration, pH and the amount of adsorbent on the percent arsenate removal. Graphene oxide was not as effective as composites for arsenate adsorption from water. Arsenate adsorption on composites was showed good compatibility with the Freundlich isotherm. The maximum arsenate uptake was realized at pH 4 for graphene oxide and at pH 7 for composites. The maximum adsorption capacities obtained at the optimum points determined by using the Box-Behnken design method were calculated as 39.49, 117.98 and 124.64 µg.g -1 for graphene oxide and composites, respectively.

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-(CO 3 )-LDH in the presence of different cations (Mg 2+ , Na + , K + , Ca 2+ , and Fe 3+ ) and anions (CO 3 2‒ , Cl ‒ , PO 4 3‒ , SO 4 2‒ , and NO 3 ‒ ) with their different concentrations to simulate the field condition. The experimental results indicated that Ca 2+ , Mg 2+ , and Fe 3+ have a synergistic effect on removal efficiency of As(V), whereas PO 4 3‒ and CO 3 2‒ ions have a significant antagonistic impact. Overall, the order of inhibiting effect of coexisting anions on adsorption of As(V) was arrived as NO 3 - ˂Cl - 4 2- 3 2 - 4 3 - . Among them, competitive adsorption of phosphate with arsenic at different initial phosphate concentrations was found to be responsive to formulate a binary adsorption system. We have also developed a modified non-competitive Langmuir and Langmuir-Freundlich models; however, the modified competitive Langmuir model was arrived to be the most adequate model for this binary system. An Artificial Neural Network based multivariate prediction model was developed, delineating the impact of coexisting ions on the adsorption system. The proposed method may appropriately demonstrate the overall system and exhibited a significantly adequate prediction model with high R 2 , high F-value, and low error values.

Sulfate (SO 4 -sug) and sulfonate (SO 3 -sug) arsenosugar standard solutions were obtained using preparative liquid chromatography. Several commercial algae samples were characterized (total contents and speciation) to select the most appropriate in relation to their arsenosugar contents. Water extracts from the selected sample (Fucus vesiculosus) were fractionated using a Hamilton PRP-X100 preparative column, and the presence of arsenic species in the isolated fractions was ascertained by IC-ICP-MS. Two of the fractions successfully presented only one arsenic species corresponding to sulfate and sulfonate arsenosugars at suitable concentrations. To unequivocally confirm the presence of both compounds, high-resolution mass spectrometry (ESI-TOF/MS) was used and the exact mass determined with errors lower than 0.5 ppm. The standard solutions obtained were successfully used to identify and quantify SO 4 -sug and SO 3 -sug in several edible algae samples purchased in local market. Total arsenic content for analyzed samples ranged from 34 to 57 mg kg -1 , concentration values found for SO 3 -sug ranged from 5 to 36 mg As kg -1 and SO 4 -sug was only found in fucus with a concentration of 9.3 mg As kg -1 ., (Copyright © 2019. Published by Elsevier B.V.)

In the present research, treatment of contaminated groundwater via adsorption of As(V) with an initial concentration of 50.99 µg/L using chitosan-coated bentonite (CCB) was investigated. The effect of adsorbent mass (0.001 to 2.0 g), temperature (298 to 328 K), and contact time (1 to 180 min) on the removal efficiency was examined. Adsorption data was evaluated using isotherm models such as Langmuir, Freundlich, and Dubinin-Radushkevich. Isotherm study showed that the Langmuir ( R 2 > 0.9899; χ 2 ≤ 0.91; RMSE ≤ 4.87) model best correlates with the experimental data. Kinetics studies revealed that pseudo-second order equation adequately describes the experimental data ( R 2 ≥ 0.9951; χ 2 ≤ 0.8.33; RMSE ≤ 4.31) where equilibrium was attained after 60 min. Thermodynamics study shows that the As(V) adsorption is non-spontaneous (Δ G 0 ≥ 0) and endothermic (Δ H 0 = 8.31 J/mol) that would result in an increase in randomness (Δ S 0 = 29.10 kJ/mol•K) within the CCB-solution interface. FT-IR analysis reveals that hydroxyl and amino groups are involved in the adsorption of As(V) from groundwater. Results of the present research serve as a tool to determine whether CCB is an environmentally safe and cost effective material that could be utilized in a permeable reactive barrier system for the remediation of As(V) from contaminated groundwater.

This paper reports a simple, facile and rapid preparation of 3‑mercapto‑propanoic acid (MPA) modified cellulose filter paper (MPA-Cell paper) for arsenate removal from drinking water. The MPA was covalently grafted to the cellulose filter paper (Cell) by esterification process through the formation of O‑acylisourea intermediate and characterized by the FTIR, SEM, EDS and XPS analyses. The arsenate adsorption efficiency was studied for batch and semi-continuous systems while exploring the adsorption kinetics, isotherm and the effect of pH for the former. The experimental data fitted well with Langmuir, Dubinin-Radushkevich (DR) and pseudo second order kinetic models. The mechanism of adsorption was studied by FTIR spectroscopy utilizing the adsorption isotherm, kinetic model and XPS results. The modified filter paper performed well at nearly neutral pH in arsenate removal through adsorption and demonstrated a significant arsenate uptake capacity of 92.59 mg/g. The DR and FTIR results indicated that the adsorption of arsenate ion occurred through ion exchange process. The MPA-Cell paper could have a potential use as low-cost but efficient commercial adsorbent for arsenate abatement from contaminated drinking water by both batch as well as semi-continuous operating systems. The MPA-Cell paper could purify ground water containing high level of arsenate., (Copyright © 2018. Published by Elsevier B.V.)

Elevated arsenic and selenium concentrations in water cause health problems to both humans and wildlife. Natural and anthropogenic activities have caused contamination of these elements in waters worldwide, making the development of efficient cost-effective methods in their removal essential. In this work, removal of arsenate and selenite from water by adsorption onto a natural goethite (α-FeOOH) sample was studied at varying conditions. The data was then compared with other arsenate, selenite/goethite adsorption systems as much of literature shows discrepancies due to varying adsorption conditions. Characterization of the goethite was completed using inductively coupled plasma mass spectrometry, X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, and Brunauer-Emmett-Teller surface area analysis. Pseudo-first order (PFO) and pseudo-second order (PSO) kinetic models were applied; including comparisons of different regression methods. Various adsorption isotherm models were applied to determine the best fitting model and to compare adsorption capacitates with other works. Desorption/leaching of arsenate and selenite was studied though the addition of phosphate and hydroxyl ions. Langmuir isotherm modeling resulted in maximum adsorption capacities of 6.204 and 7.740 mg/g for arsenate and selenite adsorption, respectively. The PSO model applied with a non-linear regression resulted in the best kinetic fits for both adsorption and desorption of arsenate and selenite. Adsorption decreased with increasing pH. Phosphate induced desorption resulted in the highest percentage of arsenate and selenite desorbed, while hydroxide induced resulted in the fastest desorption kinetics., (Copyright © 2018. Published by Elsevier B.V.)

When low-cost adsorbents are being used to remove contaminant ions (e.g. arsenate, vanadate, and molybdate) from wastewater, competitive adsorption/desorption are central processes determining their removal efficiency. Competitive adsorption of As, V, and Mo was investigated using equimolar oxyanion concentrations in single, binary, and tertiary combinations in adsorption isotherm and pH envelope studies while desorption of previously adsorbed oxyanions was examined in solutions containing single and binary oxyanion combinations. The low-cost adsorbent materials used were alum water treatment sludge (amorphous hydroxy-Al) and bauxite ore (crystalline Al oxides). Adsorption isotherm and pH envelope studies showed that Mo had only a small effect in decreasing adsorption of As and V but V and As had substantial and similar effects in reducing adsorption of the other. As had a greater effect than V in reducing adsorption of Mo and it was concluded that the affinity of oxyanions for the surfaces of water treatment sludge and bauxite followed the order As > V >> Mo. In 0.3 M NaCl electrolyte, desorption of previously adsorbed oxyanions amounted to 0.3-3.4% for V and As, and 11-20% for Mo. As had approximately four times greater effect than Mo in increasing desorption of V while V had about three times the effect of Mo in increasing desorption of As. Thus, the order of oxyanions in inducing desorption of the other oxyanions (i.e. As on V and As) was the same as that for adsorption selectivity: As > V >> Mo. Water treatment sludge was a more effective adsorbent than bauxite because it had a greater adsorption capacity for all three anions and, in addition, they were held more strongly so desorption in the background electrolyte was proportionately less. It was concluded that at similar molar concentrations, arsenate would tend to reduce adsorption of vanadate as well as displace vanadate already held on adsorbent surfaces while both anions will compete effectively with molybdate. The limiting factor for simultaneous removal of As, V, and Mo from multielement solutions by adsorption will therefore be the removal of Mo.

The modification of the fly ash (FA) by magnetite (M) was performed to obtain FAM adsorbent with improved adsorption efficiency for arsenate removal from water. The novel low cost adsorbents are characterized by liquid nitrogen porosimetry (BET), scanning electron microscopy (SEM), X-ray diffraction (XRD), Mössbauer spectroscopy (MB) and Fourier transform infrared (FTIR) spectroscopy. The optimal conditions and key factors influencing the adsorbent synthesis are assessed using the response surface method (RSM). The adsorption experiment was carried out in a batch system by varying the contact time, temperature, pH, and mass of the adsorbent. The adsorption capacity of the FAM adsorbent for As(V), calculated by Langmuir model, was 19.14 mg g -1 . The thermodynamic parameters showed spontaneity of adsorption with low endothermic character. The kinetic data followed the pseudo-second-order kinetic model (PSO), and Weber-Morris model indicated intra-particle diffusion as rate limiting step. Alternative to low desorption capability of the FAM was found by five consecutive adsorption/magnetite precipitation processes which gave exhausted layered adsorbent with 65.78 mg g -1 capacity. This research also has shed light on the mechanism of As(V)-ion adsorption, presenting a promising solution for the valorization of a widely abundant industrial waste., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Arsenate and phosphate have similar properties due to their electrochemical structures, but their environmental impacts are unique. The abundance and competition of arsenate and phosphate determine their bioavailability and leachability; thus, it is essential to understand their fate in the soil environment. In this study, the effects of pH and surface loading on the competitive adsorption of arsenate and phosphate on four iron (hydr)oxides were evaluated by employing the Langmuir isotherm, competitive sorption ratio (CSR), and competition effect (CE). The stability and transformation of the iron (hydr)oxides were also assessed. Various adsorption patterns were observed in the single and mixed treatments by controlling the addition of oxyanions, pH, surface loading, and type of iron (hydr)oxides. Arsenate was preferentially adsorbed at a low pH, whereas phosphate showed the opposite trend. The CE As(V),P(V) was close to zero at low surface density (no competition) and sequentially changed to negative or positive values with increasing surface density, indirectly indicating the sequential development of promotive and competitive effects. Transformation in goethite was identified at a high pH with the presence of oxyanions, except that no transformation was observed upon the addition of oxyanions and with pH change. However, the stability of the iron (hydr)oxides decreased at a low pH and with the presence of phosphate, arsenate, or both. The hematite showed a significant promotive effect regardless of the pH. Our study revealed that the pH, surface loading, and type of iron (hydr)oxides are intercorrelated and simultaneously affect the adsorption characteristics of oxyanions and the stability of iron (hydr)oxides.

The magnetite particles were chemically synthesized from the waste of hot rolling steel industry. The characterization of the synthesized magnetite was done by using Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), Energy Dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The synthesized magnetite particles were used for the adsorptive removal of arsenate from the contaminated water. The maximum adsorption capacity of 7.69 mg was found on the surface of 1 g of the magnetite. The point of zero charge for magnetite is determined at the pH 6. The adsorption capacity of magnetite particles was successfully restored with alkali cleaning. Newly synthesized particles were found to be effective for arsenate removal up to 5 times with regeneration. The synthesis of magnetite from raw mill scale and its application for arsenate adsorption is a cost effective and ecofriendly process., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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 (R 2 > 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.

The mechanism of As(V) removal from the drinking water and industrial effluents by iron materials remains unclear at the molecular level. In this work, the association of Fe-based materials with As(V) species was explored using density functional theory and ab initio calculations. Solvent separated ion pair structures of [FeH 2 AsO 4 ] 2+ aq species may be dominant in an acidic solution of FeAs complex. The association trend of H 2 AsO 4 - species by Fe 3+ aq is found to be quite weak in the aqueous solution, which may be attributed to the strong hydration of Fe 3+ aq and [FeH 2 AsO 4 ] 2+ species. However, the association of H 2 AsO 4 - species by colloidal clusters is quite strong, due to the weakened hydration of Fe(III) in colloidal structures. The hydrophobicity of Fe-based materials may be one of the key factors for their As(V) removal efficiency in an aqueous phase. When the number of OH - coordinated with Fe(III) increases, the association trend of As(V) by colloidal ferric hydroxides weakens accordingly. This study provides insights into understanding the coprecipitation and adsorption mechanisms of arsenate removal and revealing the high efficiency of arsenate removal by colloidal ferric hydroxides or iron salts under moderate pH conditions., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Because of the devastating impact of arsenic on terrestrial and aquatic organisms, the recovery, removal, disposal, and management of arsenic-contaminated water is a considerable challenge and has become an urgent necessity in the field of water treatment. This study reports the controlled fabrication of a low-cost adsorbent based on microscopic C-,N-doped NiO hollow spheres with geode shells composed of poly-CN nanospherical nodules (100 nm) that were intrinsically stacked and wrapped around the hollow spheres to form a shell with a thickness of 500-700 nm. This C-,N-doped NiO hollow-sphere adsorbent (termed CNN) with multiple diffusion routes through open pores and caves with connected open macro/meso windows over the entire surface and well-dispersed hollow-sphere particles that create vesicle traps for the capture, extraction, and separation of arsenate (AsO 4 3- ) species from aqueous solution. The CNN structures are considered to be a potentially attractive adsorbent for AsO 4 3- species due to 1) superior removal and trapping capacity from water samples and 2) selective trapping of AsO 4 3- from real water samples that mainly contained chloride and nitrate anions and Fe 2+ , and Mn 2+ , Ca 2+ , and Mg 2+ cations. The structural stability of the hierarchal geodes was evident after 20 cycles without any significant decrease in the recovery efficiency of AsO 4 3- species. To achieve low-cost adsorbents and toxic-waste management, this superior CNN AsO 4 3- dead-end trapping and recovery system evidently enabled the continuous control of AsO 4 3- disposal in water-scarce environments, presents a low-cost and eco-friendly adsorbent for AsO 4 3- species, and selectively produced water-free arsenate species. These CNN geode traps show potential as excellent adsorbent candidates in environment remediation tools and human healthcare., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In present study, a novel method was developed to synthesize siderite under high temperature and high pressure (SID-HTP). SID-HTP was characterized by N 2 adsorption-desorption isotherms (BET), XRD, SEM, and FTIR and utilized to remove arsenic(V) (As(V)) from aqueous solution. Results showed that, under oxic condition, pH had ignorable effect on As(V) adsorption. However, adsorption capacity increased with increasing pH from 2 to 7 and remained relatively constant at higher pH until 10 under anoxic condition. Higher adsorption was obtained in the presence of oxygen, showing oxygen-enhanced As(V) adsorption on SID-HTP. In both cases, adsorption equilibrium was achieved within 12 h and adsorption process was better described by pseudo-second-order kinetic model. The equilibrium data fitted well with Langmuir isotherm model for As(V) adsorption. The maximum adsorption capacity increased with increasing temperature, which was up to 42 mg g -1 at 55 °C in the presence of oxygen. Thermodynamic study revealed that the adsorption was a spontaneous and endothermic process. The mechanism of oxygen-enhanced adsorption was mainly ascribed to the -OH on the surface of FeOOH (goethite and lepidocrocite) in the SID-HTP. It suggested that SID-HTP would be a potentially attractive adsorbent for As(V) removal.

Layered double hydroxides have been proposed as effective sorbents for As(V), but studies investigating adsorption mechanisms usually lack a comprehensive mechanistic/modeling approach. In this work, we propose coupling surface complexation modeling with various spectroscopic techniques. To this end, a series of batch experiments at different pH values were performed. Kinetic data were well fitted by a pseudo-second order kinetic model, and the equilibrium data were fitted by the Freundlich model. Moreover, the pH-dependent As(V) sorption data were satisfactorily fitted by a diffuse layer model, which described the formation of >SOAsO 3 H - monodentate and >(SO) 2 AsO 2 - bidentate inner-sphere complexes (">S" represents a crystallographically-bound group on the surface). Additionally, XPS analyses confirmed the adsorption mechanisms. The sorption mechanisms were affected by anion exchange, which was responsible for the formation of outer sphere complexes, as identified by XRD and FTIR analyses. Furthermore, a homogenous distribution of As(V) was determined by HR-TEM with elemental mapping. Using low-temperature Mössbauer spectroscopy on isotope 57 Fe, a slight shift of the hyperfine parameters towards higher values following As(V) sorption was measured, indicating a higher degree of structural disorder. In general, mechanistic adsorption modeling coupled with solid state analyses presents a powerful approach for investigating the adsorption mechanism of As(V) on Mg-Fe LDH or other sorbents., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

A new rapid monitoring method by means of high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) following the heat-assisted extraction was developed for measurement of total inorganic arsenic species in rice flour. As(III) and As(V) eluted at the same retention time and completely separated from organoarsenic species by an isocratic elution program on a reversed phase column. Therefore, neither ambiguous oxidation of arsenite to arsenate nor the integration of two peaks were necessary to determine directly the target analyte inorganic arsenic. Rapid injection allowed measuring 3 replicates within 6min and this combined with a quantitative extraction of all arsenic species from rice flour by a 15min HNO 3 -H 2 O 2 extraction makes this the fastest laboratory based method for inorganic arsenic in rice flour., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The aim of this research was to investigate sulphate removal from mine water by precipitation as ettringite (Ca6Al2(SO4)3(OH)12·26H2O) and the utilisation of the precipitate as a sorbent for arsenate removal. The mine water sulphate concentration was reduced by 85-90% from the initial 1400 mg/L during ettringite precipitation depending on the treatment method. The precipitation conditions were also simulated with MINEQL + software, and the computational results were compared with the experimental results. The precipitated solids were characterised with X-ray diffraction and a scanning electron microscope. The precipitated solids were tested as sorbents for arsenate removal from the model solution. The arsenic(V) model solution concentration reduced 86-96% from the initial 1.5 mg/L with a 1 g/L sorbent dosage. The effect of initial arsenate concentration on the sorption of arsenate on the precipitate was studied and Langmuir, Freundlich, and Langmuir-Freundlich sorption isotherm models were fitted to the experimental data. The maximum arsenate sorption capacity (qm = 11.2 ± 4.7 mg/g) of the precipitate was obtained from the Langmuir-Freundlich isotherm. The results indicate that the precipitate produced during sulphate removal from mine water by precipitation as ettringite could be further used as a sorbent for arsenate removal., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Magnetic biochars (MW) prepared by chemical co-precipitation of Fe(2+)/Fe(3+) on water hyacinth biomass followed by pyrolysis exhibited important potential in aqueous As(V) elimination. In comparison, MW2501 outperformed other MWs and exhibited the highest As(V) sorption capacity which was estimated to be 7.4 mg g(-1) based on Langmuir-Freundlic model. With solution pH ranging from 3 to 10, As(V) removal efficiency by MW2501 kept stable and consistently higher than 90%. Besides, ∼100% removal of 0.5 mM As(V) can be obtained in the presence of P ≤ 0.1 mM or Cr/Sb ≤ 0.5 mM, indicating a wide applicability of MW2501 for treatment of As-containing water. The predominance of Fe3O4 on MW2501 surface was evidenced by XRD. Ligand exchange between As(V) anion and the hydroxylated surface of Fe3O4 as well as H bond was largely responsible for As(V) sorption as suggested by FTIR. XPS analysis further revealed the dominance of As(V) in the sorbed As on MW2501 surface with co-occurrence of a minor proportion of As(III) (11.45%). In parallel, oxidative transformation of Fe3O4 to Fe2O3 was also suggested by XPS. By a lab-scale column test, the potential and suitability of MW2501 in As-containing water treatment was further confirmed, which could also provide an alternative way to manage and utilize this highly problematic invasive species., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

A novel bioflocculant (MBF-79) prepared using formaldehyde wastewater as carbon resource was investigated in the study. The optimal conditions for bioflocculant production were determined to be an inoculum size of 7.0%, initial pH of 6.0, and formaldehyde concentration of 350 mg/L. An MBF-79 of 8.97 g/L was achieved as the maximum yield. Three main elements, namely C, H, and O, were present in MBF-79 with relative weigh percentages of 39.17%, 6.74%, and 34.55%, respectively. The Gel permeation chromatography analysis indicated that the approximate molecular weight (MW) of MBF-79 was 230 kDa. MBF-79 primarily comprised polysaccharide (71.2%) and protein (27.9%). Additionally, conditions for the removal of arsenic by MBF-79 were found to be MBF-79 at 120 mg/L, an initial pH 7.0, and a contact time 60 min. Under the optimal conditions, the removal efficiencies of arsenate (0.5 mg/L) and arsenite (0.5 mg/L) were 98.9% and 84.6%, respectively. Overall, these findings indicate bioflocculation offers an effective alternative method of decreasing arsenic during water treatment., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The aim of this study was to evaluate the stabilization/solidification (S/S) of trace element-contaminated soil using air pollution control residues (APCRs) prior to disposal in landfill sites. Two soil samples (with low and moderate concentrations of organic matter) were stabilized using three APCRs that originated from the incineration of municipal solid waste, bio-fuels and a mixture of coal and crushed olive kernels. Two APCR/soil mixtures were tested: 30% APCR/70% soil and 50% APCR/50% soil. A batch leaching test was used to study immobilization of As and co-occurring metals Cr, Cu, Pb and Zn. Solidification was evaluated by measuring the unconfined compression strength (UCS). Leaching of As was reduced by 39-93% in APCR/soil mixtures and decreased with increased amounts of added APCR. Immobilization of As positively correlated with the amount of Ca in the APCR and negatively with the amount of soil organic matter. According to geochemical modelling, the precipitation of calcium arsenate (Ca3(AsO4)2/4H2O) and incorporation of As in ettringite (Ca6Al2(SO4)3(OH)12 · 26H2O) in soil/APCR mixtures might explain the reduced leaching of As. A negative effect of the treatment was an increased leaching of Cu, Cr and dissolved organic carbon. Solidification of APCR/soil was considerably weakened by soil organic matter.

3D graphene macroscopic gel synthesized via self-assembly of GO nanosheets under basic conditions at low temperature is modified with polydopamine and Fe3O4 nanoparticles. The modification of polydopamine can not only strengthen the 3D graphene-based macroscopic architecture but also enhance the loadage and binding ability of Fe3O4 nanoparticles. The synthesized 3D Fe3O4-graphene macroscopic composites are characterized by SEM, XRD, XPS, BET, Raman and magnetic property and used as a versatile adsorbent for sub-ppm concentration of As(III) and As(V) removal from aqueous solutions. The experimental results suggest that the synthesized 3D Fe3O4-graphene macroscopic composites are promising for treating low concentration of arsenic contaminated water., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Blue green algae Anabaena sp. was cultivated in synthetic arsenite solution to investigate its bio-oxidation potential for arsenic species. Response surface methodology (RSM) was employed based on a 3-level full factorial design considering four factors, viz. initial arsenic (III) concentration, algal dose, temperature and time. Bio-oxidation (%) of arsenic (III) was considered as response for the design. The study revealed that about 100% conversion of As (III) to As (V) was obtained for initial As (III) concentration of 2.5-7.5 mg/L at 30 °C for 72 h of exposure using 3 g/L of algal dose signifying a unique bio-oxidation potential of Anabaena sp. The dissolved CO2 (DCO2) and oxygen (DO) concentration in solution was monitored during the process and based on the data, a probable mechanism was proposed wherein algal cell acts like a catalytic membrane surface and expedites the bio-oxidation process. Bioaccumulation of arsenic, as well as, surface adsorption on algal cell was found considerably low. Lipid content of algal biomass grown in arsenite solution was found slightly lower than that of algae grown in synthetic media. Toxicity effects on algal cells due to arsenic exposure were evaluated in terms of comet assay and chlorophyll a content which indicated DNA damage to some extent along with very little decrease in chlorophyll a content. In summary, the present study explored the potential application of Anabaena sp. as an ecofriendly and sustainable option for detoxification of arsenic contaminated natural water with value-added product generation., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Cationic poly(Acrylonitril-co-Acrylamidopropyl-trimethyl Ammonium Chloride) (p(AN-co-APTMACl)) hydrogels in bulk were synthesized by using acrylonitrile (AN) and 3-acrylamidopropyl-trimethyl ammonium chloride (APTMACl) as monomers. The prepared hydrogels were exposed to amidoximation reaction to replace hydrophobic nitrile groups with hydrophilic amidoxime groups that have metal ion binding ability. Those replacements were increased the hydrogels absorption capacity for As(V) and Cr(VI). Langmuir and Freundlich isotherms equations were utilized to obtain the best-fitted isotherm model for the absorption of the ions at different metal ion concentrations. The absorption data of As(V) ion were fitted well to Freundlich isotherm while those of Cr(VI) and Cr(III) ions were fitted well to Langmuir isotherm. The maximum absorption of poly(3-acrylamidopropyl-trimethyl ammonium chloride (p(APTMACl)) and amid-p(AN-co-APTMACl) macro gels were 22.39 mg and 21.83 mg for As(V), and 30.65 mg and 18.16 mg for Cr(VI) ion per unit gram dried gel, respectively. Kinetically, the absorption behaviors of Cr(III) and Cr(VI) ions were fitted well to a pseudo 2nd-order kinetic model and those of As(V) ions were fitted well to a pseudo 1st order kinetic model., (Copyright © 2015. Published by Elsevier Ltd.)

Pyridine based fluorescence probe, DFPPIC and its functionalized Merrifield polymer has been synthesized, characterized and used as an arsenate selective fluorescence sensor. Arsenate induced fluorescence enhancement is attributed to inter-molecular H-bonding assisted CHEF process. The detection limit for arsenate is 0.001 μM, much below the WHO recommended tolerance level in drinking water. DFPPIC can detect intracellular arsenate in drinking water of Purbasthali, West Bengal, India efficiently. Graphical Abstract DFPPIC and its Merrifield conjugate polymer are used for selective determination and removal of arsenate from real drinking water samples of Purbasthali, a highly arsenic contaminated region of West Bengal, India. DFPPIC is very promising to imaging arsenate in living cells.

Oxo-anion binding properties of the thermostable enzyme ferritin from Pyrococcus furiosus were characterized with radiography. Radioisotopes (32)P and (76)As present as oxoanions were used to measure the extent and the rate of their absorption by the ferritin. Thermostable ferritin proved to be an excellent system for rapid phosphate and arsenate removal from aqueous solutions down to residual concentrations at the picomolar level. These very low concentrations make thermostable ferritin a potential tool to considerably mitigate industrial biofouling by phosphate limitation or to remove arsenate from drinking water., (Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Desalination of impaired water can be hindered by the limited options for concentrate disposal. Selective removal of specific contaminants using inexpensive adsorbents is an attractive option to address the challenges of concentrate management. In this study, two types of ferric-based drinking water treatment solids (DWTS) were examined for arsenate removal from reverse osmosis concentrate during continuous-flow once-through column experiments. Arsenate sorption was investigated under different operating conditions including pH, arsenate concentration, hydraulic retention time, loading rate, temperature, and moisture content of the DWTS. Arsenate removal by the DWTS was affected primarily by surface complexation, electrostatic interactions, and arsenate speciation. Results indicated that arsenate sorption was highly dependent on initial pH and initial arsenate concentration. Acidic conditions enhanced arsenate sorption as a result of weaker electrostatic repulsion between predominantly monovalent H2AsO4(-) and negatively charged particles in the DWTS. High initial arsenate concentration increased the driving force for arsenate sorption to the DWTS surface. Tests revealed that the potential risks associated with the use of DWTS include the leaching of organic contaminants and ammonia, which can be alleviated by using wet DWTS or discarding the initially treated effluent that contains high organic concentration., (Copyright © 2015 Elsevier Inc. All rights reserved.)

This work explored two modification methods to improve biochar's ability to sorb arsenic (As) and lead (Pb). In one, pine wood feedstock was pyrolyzed in the presence of MnCl2·4H2O (MPB) and in the other it was impregnated with birnessite via precipitation following pyrolysis (BPB). The resulting biochars were characterized using thermogravimetry, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and energy-dispersive X-ray analyses. The dominant crystalline forms of Mn oxides in the MPB and BPB were manganosite and birnessite, respectively. Batch sorption studies were carried out to determine the kinetics and magnitude of As(V) and Pb(II) onto the biochars. As(V) and Pb(II) sorption capacities of MPB (0.59 and 4.91 g/kg) and BPB (0.91 and 47.05 g/kg) were significantly higher than that of the unmodified biochar (0.20 and 2.35 g/kg). BPB showed the highest sorption enhancement because of the strong As(V) and Pb(II) affinity of its birnessite particles., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Magnetic iron oxide/graphene oxide (MGO) with high iron loading (51 wt%) has been successfully synthesized using the co-precipitation method, and then used as adsorbents for the removal of arsenate and arsenite from aqueous solutions. The resulting MGO possesses desirable magnetic properties (12.8 emu g(-1)) and excellent adsorption properties for the removal of As(III) and As(IV) with significantly enhanced adsorption capacities of 54.18 mg g(-1) and 26.76 mg g(-1), respectively. These values are much higher than those of other GO-based composites reported previously. The kinetic, equilibrium and environmental effects (pH, ionic strength, coexist anion) of MGO were obtained experimentally. A synchrotron-based X-ray fluorescent microprobe was used to generate elemental distribution maps of adsorbents; the results suggest that As(v) became preferentially associated with iron oxides during the adsorption process, and that the distribution of Fe is directly correlated with the distribution of As.

The As removal process and mechanism from groundwater using ferric flocculation-direct filtration system was investigated using batch, field pilot tests, extended X-ray absorption fine structure ( EXAFS) spectroscopy, and charge-distribution multisite complexation (CD-MUSIC) model. The results showed that arsenate [As(V)] was the dominant As species in the groundwater with a concentration of 40 μg x L(-1). The treatment system could supply 64 984 L As-safe drinking water (< 10 μg L(-1)) using Fe 1.5 mg x L(-1). Toxicity characteristic leaching procedure (TCLP) demonstrated that the leachate As was 3.4 μg x L(-1), much lower than the EPA regulatory concentration (5 mg x L(-1)). EXAFS and CD-MUSIC model indicated that As(V) was adsorbed onto ferric hydroxide via bidentate binuclear complexes in the pH range of 3 to 9.5, while formation of precipitate with Ca or Mg dominated the As removal at pH > 9.5.

A series of copper(II), nickel(II) and zinc(II) dimetallic complexes were prepared and their affinities towards arsenate investigated. Indicator displacement assays (IDAs) were carried out to establish the complexes with best affinities towards arsenate. A di-zinc complex (3) was selected and its arsenate-binding abilities investigated by isothermal titration calorimetry (ITC). The X-ray crystal structure of this metallo-receptor bound to arsenate is also reported, which allowed us to establish the binding mode between 3 and this oxyanion. Immobilising 3 onto HypoGel resin yielded a novel adsorbent (Zn-HypoGel) with high affinity for arsenate. Adsorption of arsenate from competitive solutions and natural groundwater was greater than that of the commercially used iron oxide Bayoxide E33. Zn-HypoGel could be efficiently and simply regenerated by washing with sodium acetate solution., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This work presents results of FT-IR spectroscopic studies of anions-chromate, phosphate and arsenate - sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA(+)) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of organo-zeolites were measured. Their values are 17mmol/100g for chabazite, 4mmol/100g for mordenite and ferrierite and 10mmol/100g for clinoptilolite. The used initial inputs of HDTMA correspond to 100% and 200% ECEC of the minerals. Organo-modificated sorbents were subsequently used for immobilization of mentioned anions. It was proven that aforementioned anions' sorption causes changes in IR spectra of the HDTMA-zeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations are due to bands corresponding to the characteristic Si-O(Si,Al) vibrations (occurring in alumino- and silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations have also been observed. Systematic changes in the spectra connected with the anion concentration in the initial solution have been revealed. The amounts of sorbed CrO4(2-), AsO4(3-) and PO4(3-) ions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption experiments. Concentrations of anions were determined by spectrophotometric method., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The exposure of millions of people to unsafe levels of arsenite (AsIII) and arsenate (AsV) in drinking waters calls for the development of low-cost methods for on-site monitoring these two arsenic species in waters. Herein, for the first time, tetradecyl (trihexyl) phosphonium chloride ionic liquid was found to selectively bind with AsIII via extended X-ray absorption fine structure (EXAFS) analysis. Based on the finding, an AsIII-specific probe was developed by modifying gold nanoparticles with the ionic liquid. Futhermore, Hofmeister effect was primarily observed to significantly affect the sensitivity of gold nanoparticle probe. With the colorimetric probe, we developed a protocol for naked eye speciation test of AsIII and AsV at levels below the World Health Organization (WHO) guideline of 10 μg L(-1). This method featured with high tolerance to common coexisting ions such as 10 mM PO4(3-), and was validated by assaying certified reference and environmental water samples.

The achievement of reliable results in speciation analysis requires not only sensitive techniques but also sureness of species stability. Therefore, it is necessary to carry out stability studies because it is important to know with absolute certainty that there is not any species transformation during sample treatment and/or storage. Although several procedures have been recommended for the preservation of species integrity, there is no general agreement, as arsenic species stability depends on the sample matrix, the concentration level and the sample treatment procedure, so it is necessary to assess the arsenic species stability for each case. Thus, the present paper reports the stability tests of arsenic species carried out on the commercially available edible alga Hijiki (Hizikia fusiformis), from Japan, in both the dry sample and its water extracts, which were stored in amber glass and polystyrene containers at -18 and +4°C in the dark. Extractions were carried out with deionized water by microwave-assisted extraction, at a temperature of 90°C and three extraction steps of 5 min each, whereas arsenic speciation analysis was performed by anion exchange high performance liquid chromatography-photo-oxidation-hydride generation-atomic fluorescence spectrometry. The results obtained for the dry alga showed that the arsenic species present in it (arsenate (As(V)), dimethylarsinic acid (DMA) and the arsenosugars glycerol (Gly-sug), phosphate (PO4-sug), sulfonate (SO3-sug) and sulfate (SO4-sug)) were stable for at least 12 months when the sample was stored in polystyrene containers at +20°C in the dark. Regarding water extracts, the best storage conditions consisted of the use of polystyrene containers and a temperature of +4°C, for a maximum storage time of seven days. Therefore, the immediate analysis of Hijiki water extracts would not be necessary, and they could be stored for one week before analysis, ensuring arsenic species stability. This information about species integrity in extracts is especially useful when the sample treatment for arsenic species extraction is time-consuming., (Copyright © 2014 Elsevier B.V. All rights reserved.)

High levels of oxyanions are found in the soil environment, often as a result of human activity. At high concentrations, oxyanions can be harmful to both humans and wildlife. Information about the interactions between oxyanions and natural samples is essential for understanding the bioavailability, toxicity, and transport of these compounds in the environment. In the present study, the authors investigated the reactivity of different oxyanions (AsO4 , MoO4 , SeO4 , and CrO4 ) at different pH values in 2 horizons of a ferralic soil. By combining available microscopic data on iron oxides with the macroscopic data obtained, the authors were able to use the charge distribution model to accurately describe the adsorption of these 4 oxyanions and thus to determine the surface speciation. The charge distribution model was previously calibrated and evaluated using phosphate adsorption/desorption data. The adsorption behavior on ferralic soil is controlled mainly by the natural iron oxides present, and it is qualitatively analogous to that exhibited by synthetic iron oxides. The highest adsorption was found for arsenate ions, whereas the lowest was found for selenate, with chromate and molybdate ions showing an intermediate behavior., (© 2014 SETAC.)

In this study, a method is proposed for the selective retention of As(V) using diffusive gradient in thin film (DGT) samplers containing a strongly basic anion exchange resin (Amberlite IRA 910) supported on a polyacrylamide gel. In addition, the total arsenic content is determined by ferrihydrite gel discs. Subsequently, the concentration of As(III) was obtained by determining the difference between the total As and As(V). DGT experiments showed linear accumulation of As(V) (up to 280 ng) until a deployment time of 8 h deployment (R(2) > 0.99). The retention of As(V) was appropriate (97.9-112.3%) between pH 5 and 9. For a solution with an ionic strength ranging from 0.001 to 0.05 mol L(-1), the As(V) uptake ranged from 90-120%. The proposed method was applied for the speciation of arsenic in river water. For the analysis of spiked samples collected at the Furnas stream, the recoveries of total arsenic content ranged between 103.9% and 118.8%. However, the recoveries of As(III) and As(V) were 43.3-75.2% and 147.3-153.4%, respectively. These differences were probably because of the oxidation of As(III) to As(V) during deployments. For spiked samples collected at the Ribeirão Claro, the recoveries of dissolved As(III), As(V) and As(T) were 103.1%, 108.0% and 106.3%, respectively. Thus, the DGT technique with Amberlite IRA 910 resin as the binding phase can be employed for the in situ redox speciation of inorganic arsenic.

We consider the use of metallic iron nanoparticles for cleaning contaminated water, focusing our study in the sorption of arsenic compounds. In particular, we discuss the results of their sorption process on the surface of zerovalent iron nanoparticles (nZVI) by performing a complete characterization of the surface modifications. Using scanning electron microscopy, X-ray diffraction analysis and high-resolution transmission electron microscopy, spectroscopy diffraction measurements and elemental mapping, we typify the surface reconstruction during the sorption process of As(V) from aqueous solutions using nZVI when it goes into a crystalline parasymplesite structure. The experimental results were correlated to the Freundlich isotherm sorption where the sorption capacity is depleted by the increase in the pH from 4 to 7 and associated with the surface passivation of nZVI. These techniques confirm the dependence of the sorption of arsenic as a function of pH and describe the specific details on the modification of the surface area of the nanoparticles.

In this study, a weak magnetic field (WMF), superimposed with a permanent magnet, was utilized to improve ZVI corrosion and thereby enhance As(V)/As(III) removal by ZVI at pHini 3.0-9.0. The experiment with real arsenic-bearing groundwater revealed that WMF could greatly improve arsenic removal by ZVI even in the presence of various cations and anions. The WMF-induced improvement in As(V)/As(III) removal by ZVI should be primarily associated with accelerated ZVI corrosion, as evidenced by the pH variation, Fe(2+) release, and the formation of corrosion products as characterized with X-ray absorption fine structure spectroscopy. The arsenic species analysis in solution/solid phases at pHini 3.0 revealed that As(III) oxidation to As(V) in aqueous phase preceded its subsequent sequestration by the newly formed iron (hydr)oxides. However, both As(V) adsorption following As(III) oxidation to As(V) in solution and As(III) adsorption preceding its conversion to As(V) in solid phase were observed at pHini 5.0-9.0. The application of WMF accelerated the transformation of As(III) to As(V) in both aqueous and solid phases at pHini 5.0-9.0 and enhanced the oxidation of As(III) to As(V) in solution at pHini 3.0.

Nanoscale zero valent iron (NZVI) has high adsorption capacity of As(III) and As(V), but it is limited in practical use due to its small particle size and aggregation effect. Reduce graphite oxide (RGO) has been used as a support because of its high surface area. In order to utilize the advantage of NZVI and RGO as well as to avoid the disadvantage of NZVI, we loaded NZVI onto RGO via chemical reactions in this study. The adsorption capacity of As(III) and As(V), as determined from the Langmuir adsorption isotherms in batch experiments, was 35.83mgg(-1) and 29.04mgg(-1), respectively. And the adsorption kinetics fitted well with pseudo-second-order model. The residual concentration was found to meet the standard of WHO after the samples were treated with 0.4gL(-1) NZVI-RGO when the initial concentration of As(III) and As(V) were below 8ppm and 3ppm. Especially, when the initial concentration of As(III) was below 3ppm, the residual concentration was within 1ppb; whereas, the residual concentration was undetected when the initial concentration of As(III) was 1ppm., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Chitosan, a natural polysaccharide copolymer of glucosamine and N-acetyl-glucosamine, possesses one free primary amine and two free hydroxyl groups on each glucosamine unit. It has a polycationic nature and an abundance of amine functional groups. The sorption equilibrium and kinetics of arsenate onto chitosan flakes have been studied. The effect of pH on the adsorption capacity and the uptake kinetics is an important parameter to investigate the adsorption mechanism of anionic species such as arsenate ions on the protonated amine groups of chitosan. The equilibrium sorption and batch kinetic studies of arsenate ions on chitosan were performed at initial As concentration of 250-11,000 μg L(-1) and initial pH ranging from pH=3.50-5.50. The experimental results showed that initially for approximately the first 30 min there is a rapid and high adsorption of arsenate ions onto the chitosan leading to a maximum uptake capacity after this short time. However, this stage is followed by a slow desorption of arsenate from the chitosan with a steady increase in solution pH. A novel reversible pseudo-first order kinetic model was developed and applied to correlate this newly reported adsorption-desorption phenomenon. The physical and chemical properties of chitosan were studied and presented in terms of its surface and structural properties such as the degree of deacetylation, crystallinity, surface charge and its swelling properties., (Copyright © 2013 Elsevier Inc. All rights reserved.)

In order to optimize the adsorption of arsenate, we prepared silica based adsorbents by grafting Fe(3+)-coordinated N-(2-aminoethyl)-3-aminopropyltriethoxysilanes (aeaptes) in various Fe:aeaptes ratios (mixing ratios). Two kinds of mesoporous silica (MCM-41 and SBA-15) and fumed silica (Cab-O-sil M7D) were used as substrates. The adsorption of arsenate saturated at As/Fe=1, 2 and 3 on mesoporous silica based adsorbents from with Fe:aeaptes ratios of 1:1, 1:2 and 1:3, respectively. On the other hand, saturation occurred at As/Fe=1 on Cab-O-sil M7D-based adsorbents for all three Fe:aeaptes ratios. In addition to this dependence of the adsorption on the coordination conditions, two different modes were clearly distinguished in the adsorption isotherm for the MCM-41 based adsorbent prepared with a Fe:aeaptes ratio of 1:1. These two distinct adsorptions are likely to be due to the induction of well-defined coordination structures by this method. This result is significantly different from that found in a previous study where adsorbents were prepared by the grafting of aeaptes followed by the coordination of Fe(3+), where a single mode of adsorption was observed. The adsorptions were further analyzed using the Langmuir equation and by X-ray adsorption spectroscopy., (Copyright © 2013 Elsevier Inc. All rights reserved.)

Insights from the adverse effect of humic acid (HA) on arsenate removal with hydrous ferric oxide (HFO) coprecipitation can further our understanding of the fate of As(V) in water treatment process. The motivation of our study is to explore the competitive adsorption mechanisms of humic acid and As(V) on HFO on the molecular scale. Multiple complementary techniques were used including macroscopic adsorption experiments, surface enhanced Raman scattering (SERS), extended X-ray absorption fine structure (EXAFS) spectroscopy, flow-cell attenuated total reflectance Fourier transform infrared (ATR-FTIR) measurement, and charge distribution multisite complexation (CD-MUSIC) modeling. The As(V) removal efficiency was reduced from over 95% to about 10% with the increasing HA concentration to 25 times of As(V) mass concentration. The SERS analysis excluded the HA-As(V) complex formation. The EXAFS results indicate that As(V) formed bidentate binuclear surface complexes in the presence of HA as evidenced by an As-Fe distance of 3.26-3.31 angstroms. The in situ ATR-FTIR measurements show that As(V) replaces surface hydroxyl groups and forms innersphere complex. High concentrations of HA may physically block the surface sites and inhibit the As(V) access. The adsorption of As(V) and HA decreased the point of zero charge of HFO from 7.8 to 5.8 and 6.3, respectively. The CD-MUSIC model described the zeta potential curves and adsorption edges of As(V) and HA reasonably well.

We report the strategy of using the cationic surfactant cetyltrimethylammonium bromide (CTAB) and amino acid L-histidine (His) as co-templates to produce hierarchical ZIF-8 in an aqueous system at room temperature. The hierarchical ZIF-8 had both meso- and microporous structure, resulting in a high mesopore volume as well as specific surface area which can be controlled by the synthesis conditions. We put forward the hypothesis for the formation of a mesoporous structure and the enhancement of the porosity of ZIF-8 that the histidine plays a key role on the stabilization of CTAB micelles and avoiding the production of unexpected by-products therefore promotes the fabrication of pure phase ZIF-8 containing the mesopores interconnected with micropores. The prepared hierarchical ZIF-8 exhibited an excellent performance as a new kind of porous absorbent for efficient removal of the toxic arsenate.

Here we report a survey addressed to determine, at different pH values (pH 4.0, 7.0 and 9.0), the ability of two different water treatment residues, a Fe-based (Fe-WTR) and an Al-based (Al-WTR), to accumulate arsenate and phosphate anions from an aqueous solution and to define the mechanism which regulate the sorption of these anions. Fe-WTR showed a greater As(V) and P(V) sorption capacity respect to Al-WTR at all the pH values investigated, in particular at pH 4.0. The greater capacity of the Fe-WTR to accumulate phosphate at pH 4.0 seems to be linked to the higher content of manganese ions compared to Al-WTR, which can give rise, with phosphate ions, to the formation of MnHPO4 precipitates. Sequential extraction of As(V)- or P(V)-WTRs suggested that the main mechanism governing the sorption of both two anions likely involve the formation of inner-sphere surface complexes [Fe/Al-O-As(P)]. Such a coordination mode was supported by the FT-IR spectra that exhibit well resolved band at 865cm(-1) and 1040cm(-1) attributable to ν(As-O) or ν(P-O) stretching vibration, respectively., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A proof of concept of a novel pervaporation sequential injection (PSI) analysis method for automatic non-chromatographic speciation analysis of inorganic arsenic in complex aqueous samples is presented. The method is based on hydride generation of arsine followed by its on-line pervaporation-based membrane separation and CCD spectrophotometric detection. The concentrations of arsenite (As(III)) and arsenate (As(V)) are determined sequentially in a single sample zone. The leading section of the sample zone merges with a citric acid/citrate buffer solution (pH 4.5) for the selective reduction of As(III) to arsine while the trailing section of the sample zone merges with hydrochloric acid solution to allow the reduction of both As(III) and As(V) to arsine at pH lower than 1. Virtually identical analytical sensitivity is obtained for both As(III) and As(V) at this high acidity. The flow analyzer also accommodates in-line pH detector for monitoring of the acidity throughout the sample zone prior to hydride generation. Under optimal conditions the proposed PSI method is characterized by a limit of detection, linear calibration range and repeatability for As(III) of 22 μg L(-1) (3sblank level criterion), 50-1000 μg L(-1) and 3.0% at the 500 μg L(-1) level and for As(V) of 51 μg L(-1), 100-2000 μg L(-1) and 2.6% at the 500 μg L(-1) level, respectively. The method was validated with mixed As(III)/As(V) standard aqueous solutions and successfully applied to the determination of As(III) and As(V) in river water samples with elevated content of dissolved organic carbon and suspended particulate matter with no prior sample pretreatment. Excellent relative recoveries ranging from 98% to 104% were obtained for both As(III) and As(V)., (© 2013 Elsevier B.V. All rights reserved.)

Egg-shell membrane (ESM) is a promising adsorbent for heavy metal uptake. However, carboxylic groups on ESM surface barrier arsenic adsorption. Herein, ESM is modified by esterification and the methyl esterified egg-shell membrane (MESM) possesses positive charge within pH 1-9. As a novel green sorbent material, MESM exhibits 200-fold improvement on sorption capacity of arsenate with respect to bare ESM. It presents an ultra-high selectivity of 256:1 toward arsenate against arsenite. At pH 6, 100% sorption efficiency is achieved for 2 μg L(-1) As(V) by 10 mg MESM, while virtually no adsorption of As(III) is observed. This provides great potential for selective sorption of arsenate in the presence of arsenite. By loading 4.0 mL sample within 0.05-5.00 μg L(-1) As(V) followed by elution with 300 μL HCl (1.5 mol L(-1)), a detection limit of 15 ng L(-1) is obtained along with a RSD of 3.5% at 0.5 μg L(-1). Total inorganic arsenic is achieved by converting As(III) to As(V) and following the same sorption process. This procedure is applied for arsenate determination and inorganic arsenic speciation in Hijiki and water samples. The results are confirmed by graphite furnace atomic absorption spectrometry and spiking recovery., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In this study we investigated the role of arsenic-resistant bacteria Arthrobacter sp. biomass for removal of arsenite as well as arsenate from aqueous solution. The biomass sorption characteristics were studied as a function of biomass dose, contact time and pH. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the biosorption isotherm. The Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The biosorption capacity of the biomass for As(+3) and As(+5) was found to be 74.91 mg/g (pH 7.0) and 81.63 mg/g (pH 3.0), respectively using 1 g/L biomass with a contact time of 30 min at 28 degrees C. The mean sorption energy values calculated from the D-R model indicated that the biosorption of As(+3) and As(+5) onto Arthrobacter sp. biomass took place by chemical ion-exchange. The thermodynamic parameters showed that the biosorption of As(+3) and As(+5) ions onto Arthrobacter sp. biomass was feasible, spontaneous and exothermic in nature. Kinetic evaluation of experimental data showed that biosorption of As(+3) and As(+5) followed pseudo-second-order kinetics. Fourier transform infrared spectroscopy (FT-IR) analysis indicated the involvement of possible functional groups (-OH, -C=O and -NH) in the As(+3) and As(+5) biosorption process. Bacterial cell biomass can be used as a biosorbent for removal of arsenic from arsenic-contaminated water.

In this study, nanocrystallined Mg/Al layered double hydroxides (LDH-CO3) and chloridion intercalated nanocrystallined Mg/Al LDHs (LDH-Cl) were synthesized and used for simultaneous removal of arsenic and natural organic matter (NOM) from contaminated groundwater. Humic acid (HA) was selected as a model compound of NOM. The maximum adsorption capacities of arsenate (As(V)) on LDH-CO3 and LDH-Cl are 44.66 and 88.30 mg/g, respectively, and those of HA on LDH-CO3 and LDH-Cl are 53.16 and 269.24 mg/g, respectively. It was found that more than 98% of arsenic and 94% of NOM were eliminated by LDH-Cl from both arsenic and NOM-rich groundwater, which is used as drinking water in Togtoh County, Inner Mongolia, China. The arsenic concentration declined from 231 to 4 μg/L, which meets the drinking water standard. The adsorption mechanisms were determined by using X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and extended X-ray absorption fine structure spectroscopy techniques (EXAFS). The results showed that the removal of HA was mainly via surface complexation as well as coagulation at the surface of LDHs, while the adsorption of As(V) was mainly via ion-exchange process. The presence of HA exhibited little inhibiting effect on As(V) adsorption by occupying partial binding sites on LDH surfaces. Nevertheless, it could not affect the ion-exchange process of As(V) with the interlayer anions of LDHs. The removal of As(V) and HA can be carried out independently due to the different adsorption mechanisms. By integrating the experimental results, it is clear that LDH-Cl can be potentially used as a cost-effective material for the purification of both arsenic and NOM contaminated groundwater., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Effectiveness of arsenite adsorption by ferric and alum water treatment residuals (FARs) with different grain sizes was studied. The results indicated that the content of active Fe and Al, the specific surface area and pore volume in FARs with different grain sizes were in the range of 523.72-1 861.72 mmol x kg(-1), 28.15-265.59 m2 x g(-1) and 0.03-0.09 cm3 x g(-1), respectively. The contents of organic matter, fulvic acid, humic acid and humin were in the range of 46.97-91.58 mg x kg(-1), 0.02-32.27 mg x kg(-1), 22.27-34.09 mg x kg(-1) and 10.76-34.22 mg x kg(-1), respectively. Results of SEM and XRD analysis further demonstrated that FARs with different grain sizes were amorphousness. Batch experiments suggested that both the pseudo-first-order and pseudo-second-order equations could well describe the kinetics adsorption processes of arsenite by FARs. Moreover, the contents of arsenite absorbed by FARs increased with the increase of arsenite concentrations. The theoretical saturated adsorption capacities calculated from Langmuir isotherm model were in the range of 6.72-21.79 mg x g(-1). Interestingly, pH showed little effect on the arsenite adsorption capability of FARs. The capability of FARs had a close relationship with their physicochemical properties. Correlation analysis showed that the active Fe and Al contents and pore volume had major effects on the arsenite adsorption capability of FARs.

Schwertmannite was synthesized on a 2 m(3)-scale and fabricated to irregular, cylindrical and spherical shape granules using drum granulation, extrusion and spray coating, respectively. The granules were systematically evaluated for As(V) removal from drinking water in terms of both performance and safety. The irregular and cylindrical shape granules (IS and CS) had larger schwertmannite loadings, higher porosity, more abundant pore structure and larger micropore volumes than those with a spherical shape (SS). As(V) adsorption kinetics on IS, CS and SS schwertmannite granules followed a pseudo-second order rate equation and two-stages of intraparticle diffusion. The rate parameters were in an order of IS > CS > SS granules. The faster uptake kinetics of the IS granules was due to their largest pore volume and interparticle porosity. Furthermore, adsorption capacities of 34, 21 and 5 mg/g, for IS, CS and SS granular schwertmannite samples were achieved at an initial As(V) concentration of 20 mg/L and adsorbent dose of 0.5 g/L. IS and CS samples performed much better over a wide pH range versus SS samples. Except for humic acid, PO4(3-) and SiO4(4-) did not inhibit As(V) adsorption on IS and CS granular specimens. SS samples worked poorly even in the absence or presence of co-existing anions. Regeneration was achieved using 0.1 M NaOH. The recycled IS and CS granular specimens can be used for 4 different cycles with no or nominal loss of adsorption capacity. Column experiments were also conducted. The IS, CS and SS granular specimens treated 8100, 4200 and 120 bed volumes (BVs) of contaminated water. No heavy metals leached from the packed granular adsorbent and appeared in the column effluent. Furthermore, the toxicity characteristic leaching procedure (TCLP) showed that the spent IS and CS granules were inert and could safely be disposed of in landfills. In short, irregular-shaped granules (IS) fabricated by drum granulation is a good candidate for arsenic removal from drinking water with a high future application potential., (Copyright © 2013 Elsevier Ltd. All rights reserved.)