Arsenate Anions Research Articles

Colorimetric sensors for discriminatory detection of arsenite ions: Application in milk, honey and water samples and molecular logic gates

Millions of people are exposed to dangerous arsenic levels in drinking water, highlighting the urgent need for affordable, continuous on-site arsenic monitoring methods. It is crucial to specifically detect arsenite among inorganic arsenic anions because it is more poisonous than arsenate. Addressing these concerns, the present study developed 5-(4-nitrophenyl)-2-furaldehyde based two colorimetric chemosensors, N5R3 and N5R4, with different signaling groups for the selective detection of arsenite anions over arsenate in DMSO/H2O (6:4, v/v). The red-shift in the UV–Vis absorption spectra supported the distinct color changes of sensors N5R3 and N5R4 displayed upon binding with arsenite. Sensors demonstrated stability over a pH range of 6 to 12 and exhibited stability over a considerable time period. Among the chemosensors, N5R3 exhibited the lowest detection limit of 7.41 ppb with a high binding constant of 2.9976 × 106 M−1 for arsenite. The 1:1 binding interactions between the chemosensors and arsenite were confirmed using B-H plot and Job’s plot analysis. The intramolecular charge transfer (ICT) mechanism for detecting arsenite was proposed through UV and 1H NMR titrations, electrochemical studies, mass spectral analysis and DFT calculations. The interactions between the sensor and arsenite anions were further analyzed using global reactivity parameters (GRPs). Practical applications were demonstrated through the utilization of test strips and molecular logic gates. Both chemosensors efficiently recognized arsenite in real water, honey, and milk samples.

Adsorption of Bichromate and Arsenate Anions by a Sorbent Based on Bentonite Clay Modified with Polyhydroxocations of Iron and Aluminum by the "Co-Precipitation" Method.

The physicochemical properties of natural bentonite and its sorbents were studied. It has been established the modification of natural bentonites using polyhydroxoxides of iron (III) (mod.1_Fe_5-c) and aluminum (III) (mod.1_Al_5-c) by the "co-precipitation" method led to changes in their chemical composition, structure, and sorption properties. It was shown that modified sorbents based on natural bentonite are finely porous (nanostructured) objects with a predominance of pores of 1.5-8.0 nm in size. The modification of bentonite with iron (III) and aluminum compounds by the "co-precipitation" method also leads to an increase in the sorption capacity of the obtained sorbents with respect to bichromate and arsenate anions. A kinetic analysis showed that, at the initial stage, the sorption process was controlled by an external diffusion factor, that is, the diffusion of the sorbent from the solution to the liquid film on the surface of the sorbent. The sorption process then began to proceed in a mixed diffusion mode when it limited both the external diffusion factor and the intra-diffusion factor (diffusion of the sorbent to the active centers through the system of pores and capillaries). To clarify the contribution of the chemical stage to the rate of adsorption of bichromate and arsenate anions by the sorbents under study, kinetic curves were processed using equations of chemical kinetics (pseudo-first-order, pseudo-second-order, and Elovich models). It was found that the adsorption of the studied anions by the modified sorbents based on natural bentonite was best described by a pseudo-second-order kinetic model. The high value of the correlation coefficient for the Elovich model (R2 > 0.9) allows us to conclude that there are structural disorders in the porous system of the studied sorbents, and their surfaces can be considered heterogeneous. Considering that heterogeneous processes occur on the surface of the sorbent, it is natural that all surface properties (structure, chemical composition of the surface layer, etc.) play an important role in anion adsorption.

Arsenate Anion-π Interactions on Amine-Modified Polydivinylbenzene in Aqueous Systems: Experimental and Theoretical Investigation.

Anion-π interactions aiding in the adsorption of anions in the solution phase, though challenging to quantify, have attracted a lot of attention in supramolecular chemistry. We present the design of a polymer adsorbent that quantifies the adsorption of arsenate ions experimentally by optimizing anion-π interactions in a purely aqueous system and use density functional theory to compare these results with theoretical data. Arsenate anions are removed from water by amine-functionalized polydivinylbenzene using the comonomer 1-vinyl-1,2,4-triazole, which was cross-linked with divinylbenzene via radical polymerization in a hydrothermal procedure. The amine-functionalized polydivinylbenzene successfully removed arsenate anions from water with a capacity of 46 mg g-1, a 70% increase compared to the nonfunctionalized polydivinylbenzene (27 mg g-1) capacity under the same conditions. Adsorption is best described by the Sips isotherm model with a correlation coefficient R2 factor of 0.99, indicating that adsorption sites are homogeneous, and adsorption occurred by forming a monolayer. Kinetic studies indicated that adsorption is second order in the amine-functionalized polydivinylbenzene. Computational studies using density functional theory showed that the 1-vinyl-1,2,4-triazole comonomer improved the thermodynamic stability of the anionic-π interactions of polydivinylbenzene with arsenate anions. Electrostatic interactions dominate the mechanism of adsorption in polydivinylbenzene compared to the anion-induced interactions that dominate adsorption in amine-functionalized polydivinylbenzene.

Colorimetric differentiation of arsenite and arsenate anions using a bithiophene sensor with two binding sites: DFT studies and application in food and water samples.

Chemosensor N7R1 with two acidic binding sites was synthesized, and the ability of the sensor to differentiate arsenite and arsenate in the organo-aqueous medium was evaluated using colorimetric sensing methods. N7R1 distinguished arsenite with a peacock blue color and arsenate with a pale green color in a DMSO/H2O (9 : 1, v/v) solvent mixture. The specific selectivity for arsenite was achieved in DMSO/H2O (7 : 3, v/v). The sensor demonstrated stability over a pH range of 5 to 12. The computed high binding constant of 9.3176 × 1011 M-2 and a lower detection limit of 11.48 ppb for arsenite exposed the chemosensor's higher potential for arsenite detection. The binding mechanism with a 1 : 2 binding process is confirmed using UV-Vis and 1H NMR titrations, electrochemical studies, mass spectral analysis and DFT calculations. Practical applications were demonstrated by utilizing test strips and molecular logic gates. Chemosensor N7R1 successfully detected arsenite in real water samples, as well as honey and milk samples.

Aloe vera mucilage as a sustainable biopolymer flocculant for efficient arsenate anion removal from water

In recent years, utilization of biopolymers as natural coagulant–flocculant systems has become an area of interest, due to their sustainable nature and potential utility as alternative systems for synthetic flocculants.

Effect of electrokinetic process on in situ stabilization and detoxification of arsenic-contaminated soil with high content of calcium

Owing to the high risk of human exposure to arsenic-contaminated soil, reducing its toxicity is essential. This study used the electrokinetic (EK) process with iron-rich electrodes to synchronously achieve the accumulate, stabilize and detoxify soil arsenic. Changes in arsenic valence, leaching toxicity, and microbial communities related to toxicity were comprehensively considered. The results demonstrated that arsenic was mainly transported toward the anode and accumulated by electromigration owing to the negatively charged arsenic anions under EK conditions. The cathode approaching effectively promote arsenic movement to the anode; the largest As(T) transportation rate of 30.61% was achieved near the cathode (S4). The transportation ratio of As(III) was 1.84 times more than that of As(V). The As(III) content and leaching toxicity of soil arsenic in all treatments decreased after applying the EK process. In particular, the anode approaching effectively elevated the average ratios of soil As(III) oxidation and stabilization to 37.88% and 61.73%, respectively. Correspondingly, the total phospholipid fatty acid content increased substantially after EK treatment and showed a pollution stress elimination effect. The electrokinetic effect can essentially cause highly active and easily migrated arsenic to accumulate near the anode and middle sections. The electric field mediated iron mineralization and stabilized arsenic by oxidizing As(III) and reacting with newly formed iron-rich phases (S). Meanwhile, the electric field regulated the form of soil calcium from CaCO3 to CaSO4 and caused calcium-bound arsenic to change to a more stable form. According to these results, in situ stabilization and detoxification of arsenic-contaminated soil can be realized by the EK process, avoiding stabilizer addition and excavation.

Cleft Receptor for the Recognition and Extraction of Tetrahedral Oxyanions

We report the design and synthesis of a new cleft-shaped bis-urea receptor for the recognition of tetrahedral oxyanions from a foldameric N,N′-dimethyl-N,N′-diphenylurea scaffold. The receptor forms 3:1 host–guest complexes with sulfate, phosphate, and arsenate anions in the solid state by readily binding them through hydrogen bonding. 1H NMR analysis of binding events in a competitive medium (DMSO-d6/H2O, 90:10) revealed that the receptor has a strong and selective affinity for arsenate (Ka(3:1) = 2.41 (±0.79) × 108 M–3) in comparison with phosphate and no affinity for sulfate. The receptor extracts the three oxyanions from water into chlorinated organic solvents when the tetra-n-butyl ammonium ion is used as a cationic support. The receptor also crystallizes out the arsenate anion from water with faster kinetics in acetonitrile solution with a similar cationic support.

Colorimetric chemosensors for the selective detection of arsenite over arsenate anions in aqueous medium: Application in environmental water samples and DFT studies

Novel organic receptors N3R1- N3R3 were developed for the selective colorimetric recognition of arsenite ions in the organo-aqueous media. In the 50% aq. acetonitrile media and 70% aq. DMSO media, receptors N3R2 and N3R3 showed specific sensitivity and selectivity towards arsenite anions over arsenate anions. Receptor N3R1 showed discriminating recognition of arsenite in the 40% aq. DMSO medium. All three receptors formed a 1:1 complex with arsenite and stable for a pH range of 6–12. The receptors N3R2 and N3R3 achieved a detection limit of 0.008 ppm (8 ppb) and 0.0246 ppm, respectively, for arsenite. Initial hydrogen bonding on binding with the arsenite followed by the deprotonation mechanism was well supported by the UV–Vis titration, 1H- NMR titration, electrochemical studies, and the DFT studies. Colorimetric test strips were fabricated using N3R1- N3R3 for the on-site detection of arsenite anion. The receptors are also employed for sensing arsenite ions in various environmental water samples with high accuracy.

Colorimetric recognition of water-polluting inorganic arsenic anions using near-infrared chemosensors in organic and semi-aqueous medium

Colorimetric recognition of water-polluting inorganic arsenic anions using near-infrared chemosensors in organic and semi-aqueous medium

Immobilizing arsenic in soil via amine metal complex: a case study using iron-ethylenediamine.

Fe-based nanomaterials have been extensively investigated for their application in mitigating arsenic (As) pollution in groundwater, sediment, and soils. Here, an iron-ethylenediamine (Fe-EDA) complex was synthesized and characterized using Fourier transform-infrared spectroscopy and X-ray photoelectron spectroscopy before its use as an amendment to ameliorate As-polluted soils. Column leaching tests at three Fe-EDA application rates (1%, 3%, and 5%) were conducted, and their results were compared with those acquired after using nano zerovalent iron (nZVI) and Fe3O4, to assess their efficiency to amend As-contaminated paddy soils. After leaching, stabilization efficiency and soil chemical characteristics were determined. Additionally, As fractions were measured using inductively coupled plasma-mass spectroscopy by employing a sequential extraction procedure to evaluate the performance of the treatments and understand the underlying their mechanisms. Compared with the control treatment, the Fe-EDA treatment reduced As release by more than 35.33% in the 2nd leaching cycle, whereas nZVI and Fe3O4 decreased the As release by 11.84% and 24.60%, respectively. Moreover, the optimal addition of the Fe-EDA chelate was 5%, which stabilized more than 50% As in the soil from the 7th to 11th leaching cycles. After sequential extraction, the Fe-Mn oxide binding fraction, which was originally 12.65%, increased to 21.5%, 18.23%, and 21.71% after the application of nZVI, Fe3O4, and Fe-EDA amendments, respectively. Furthermore, our treatments promoted the binding of the As fraction with crystalline Fe (III) (oxyhydr)oxide (F3); however, other fractions did not increase considerably, suggesting that the Fe-EDA complex could effectively stabilize As through electrostatic attraction between the arsenate anion and EDA, as well as As-O-Fe bond formation via a coordinating reaction. Overall, Fe-EDA was found to be a potent amendment for mitigating As-polluted soil.

Synthesis, crystal structure and dielectric properties of a hybrid dihydrogen arsenate salt: (C9H11N4)H2AsO4

The use of the organic aromatic amine molecule 5-amino-3-methyl-1-phenyl-1H-1,2,4-triazole to synthesize a dihydrogen arsenate hybrid salt leads to a supramolecular structure type. Single crystals of (C9H11N4)H2AsO4 were grown through slow evaporation in solution. The synthesized compound crystallizes in the monoclinic system with the non-centrosymmetric P21 space group according to the following parameters; a = 9.655 (3) Å, b = 4.7090 (15) Å, c = 14.022 (4) Å, β = 108.147 (5)° and Z = 4. The mineral part building from dihydrogen arsenate anions [H2AsO4]− is linked together and to the organic cations [C9H11N4]+ by hydrogen bonds only. The results of Hirshfeld’s analysis show that in all possible molecular contacts, the hydrogen–hydrogen and the oxygen–hydrogen are the most important interaction in the crystal (37.5 and 31.9%, respectively). The Fourier transform infrared (FT-IR) confirms the existence of vibrational modes corresponding to the organic amine molecule and mineral arsenate tetrahedron. The optimized molecular structure and the vibrational spectra were calculated by the density functional theory DFT methods and the semi-empirical PM3 calculations. Dielectric study of this compound has been measured in order to determine the electrical conductivity type giving rise to an activation energy of ΔEσ = 0.17 eV.

High efficiency of magnetite nanoparticles for the arsenic removal from an aqueous solution and natural water taken from Tambo River in Peru.

Water is an essential compound on earth and necessary for life. The presence of highly toxic contaminants such as arsenic and others, in many cases, represents one of the biggest problems facing the earth´s population. Treatment of contaminated water with magnetite (Fe3O4) nanoparticles (NPs) can play a crucial role in arsenic removal. In this report, we demonstrate arsenic removal from an aqueous solution and natural water taken from the Peruvian river (Tambo River in Arequipa, Peru) using magnetite NPs synthesized by the coprecipitation method. XRD data analysis of Fe3O4 NPs revealed the formation of the cubic-spinel phase of magnetite with an average crystallite size of ~ 13nm, which is found in good agreement with the physical size assessed from TEM image analysis. Magnetic results evidence that our NPs show a superparamagnetic-like behavior with a thermal relaxation of magnetic moments mediated by strong particle-particle interactions. FTIR absorption band shows the interactions between arsenate anions and Fe-O and Fe-OH groups through a complex mechanism. The experimental results showed that arsenic adsorption is fast during the first 10min; while the equilibrium is reached within 60min, providing an arsenic removal efficiency of ~ 97%. Adsorption kinetics is well modeled using the pseudo-second-order kinetic equation, suggesting that the adsorption process is related to the chemisorption model. According to Langmuir's model, the maximum arsenic adsorption capacity of 81.04mg·g- 1 at pH = 2.5 was estimated, which describes the adsorption process as being monolayer, However, our results suggest that multilayer adsorption can be produced after monolayer saturation in agreement with the Freundlich model. This finding was corroborated by the Sips model, which showed a good correlation to the experimental data. Tests using natural water taken from Tambo River indicate a significant reduction of arsenic concentration from 356µg L- 1 to 7.38µg L- 1, the latter is below the limit imposed by World Health Organization (10µg L- 1), suggesting that magnetite NPs show great potential for the arsenic removal.

Preparation of Two Calix[4]arene-Functionalized Biopolymers and Evaluations of Their Extraction Abilities Against Cr(VI)/As(V) Anions

Two calixarene-functionalized biopolymers (calixarene-functionalized chitosan and calixarene-functionalized cellulose) have been synthesized and duly characterized using FTIR, TGA and elemental analysis techniques. Furthermore, their anion extraction behaviors at various pH values have been evaluated toward dichromate and arsenate anions. Results indicated that calixarene-functionalized chitosan against dichromate ion exhibited higher extraction capability than calixarene-functionalized cellulose. Intriguingly, although a less extraction efficiency against dichromate anion was obtained by calixarene-functionalized cellulose, the arsenate anion extraction results showed that calixarene-functionalized cellulose is more effective ionophore than calixarene-functionalized chitosan.

Mechanochemical synthesis of bismuth-based anion exchange materials to immobilize arsenic pollution - Prospects for advanced treatment of anion-containing wastewater

Many types of anionic pollutants exit in the aqueous environment including the group containing halogen (F-, I-, IO3-, BrO3-, ClO3−), the group containing heavy metals (VO43−, AsO33−, CrO42−, AsO43−), and eutrophic elements resulting from agricultural, aquacultural, urban and industrial activities (NO3−, PO43−). Except for layered double hydroxide, anionic exchangeable resin, few choices are available to work for the treatment of the anionic pollutants. In this study, a new type of anion exchangeable compound was reported as an alternative. Sulfate-based layered bismuth oxide with the formula of Bi2O(OH)2SO4 as a clear crystalline phase was prepared simply by ball milling Bi oxide and sulfate together. Several analytical methods such as XRD, XPS, FTIR were used to characterize the products after the As (V) adsorption to understand the ions exchange mechanism. The excellent performance to fix arsenate anion reaching over 99.9% of As(V) removal percentage with Bi2O(OH)AsO4 as adsorption product was understood probably due to the synergistic effect of several exchangeable anions inside the prepared sample. This research may open a promising way to effectively remove toxic and harmful anions by the newly prepared anion exchangeable materials.

One-step construction of hierarchical porous channels on electrospun MOF/polymer/graphene oxide composite nanofibers for effective arsenate removal from water

Excessive toxic arsenic in surface water and groundwater is a prevalent worldwide problem. A novel hierarchical porous fibrous membrane (PG/MOF), incorporating Zr-based metal organic framework (MOF-808) and graphene oxide (GO), was fabricated for arsenate removal. The well-developed nanoporous fibrous skeleton allows the exposure of adsorption sites of MOF-808 for effective arsenate removal and avoids leakage. Systematic studies on adsorption isotherms, kinetics, and filtration processes determined the practical applicability of the PG/MOF. The maximum adsorption capacity obtained from the Langmuir model was over 180 mg/g. Mechanistic analysis via SEM, FTIR, and XPS revealed that coordination and π − π interaction is responsible for the superior adsorption performance. Adsorption energy and Bader charge analysis based on DFT calculations indicated that arsenate anions are spontaneously adsorbed near the benzene ring of MOF-808 on PG/MOF. This study identified a promising method for fabricating hierarchical porous MOF-based nanofibers and provides insight into the mechanisms of arsenate adsorption.

Simultaneous reduction and adsorption of arsenite anions by green synthesis of iron nanoparticles using pomegranate peel extract.

Arsenic is a toxic metalloid that is present in the environment as arsenate and arsenite anions. Exposure to arsenic anions caused skin problems, degenerative diseases, kidney, liver, and lung cancer. The synthesized iron nanoparticles (NPs) were examined as a green low-cost adsorbent for the removal of arsenite anions from aqueous solution via batch adsorption procedure. Iron NPs were prepared in a single step by the reaction of Fe+3 0.01M solution with a fresh aqueous solution of 2% w/v pomegranate peel extract (PPE) as both reducing and capping agents. The physicochemical properties of peel were investigated by some experiments and functional groups were determined by the FT-IR spectrum. The electrochemical behavior of PPE was studied using cyclic voltammetry on a glassy carbon electrode as produced a cathodic peak at range 120-400mV. The progress of nZVI production was monitored by a decrease of 372nm wavelength UV-Vis spectra of PPE. The 27 adsorption experiments were carried out as a function of solution pH, initial arsenite concentration, mass adsorbent, and contact time according to DOE. The rapid rate of adsorption was observed at 20-60min, indicating that the principal mechanism dominating the sorption process was reduction and chemical adsorption. The arsenite removal efficiency was found to be dependent on the solution pH, adsorbent dose, and initial concentration, respectively. The experimental data show the ability of the synthesized iron NPs to remove arsenate from solution in both synthetic and polluted natural water. The thermodynamic study suggested the spontaneous and endothermic nature of adsorption of arsenite by green synthesized iron NPs. The iron NPs synthesized with PPE increased the removal of arsenite with an increase in the active surface, indicating some chemical interactions between the adsorbent and oxoanions.

M2As2Q5 (M = Ba, Pb; Q = S, Se): a source of infrared nonlinear optical materials with excellent overall performance activated by multiple discrete arsenate anions

M2As2Q5 (M = Ba, Pb; Q = S, Se) have been screened out by combined experiments and theoretical calculations as a new source of IR NLO materials. Interestingly, they exhibit excellent overall performance activated by multiple discrete arsenate anions.

Species and Distribution of Arsenic in Soil After Remediation by Electrokinetics Coupled with Permeable Reactive Barrier

Arsenic-polluted soil from a mining area in China was treated by electrokinetics coupled with permeable reaction barrier (EK/PRB). Batch tests with PRB media of zero valent iron (ZVI) under electric potential of 2 V cm−1 for 120 h were conducted. Species and distribution of arsenic in soil after remediation were investigated to evaluate the removal mechanisms of arsenic. Results showed that ZVI-PRB was the dominant role in the removal of arsenic in the EK/PRB systems. Arsenic transferring toward the anode was greater than cathode, due to the negatively charged arsenic anions which moved to the anode chamber by electromigration. Pentavalent arsenic (As(V)) in soil could not be reduced to more poisonous trivalent arsenic (As(III)), no matter if it were treated by EK alone or EK/ZVI-PRB. The surface characterization of ZVI, which was carried out using X-ray photoelectron spectrometry (XPS), showed that the ratio of As(V)/As(III) on the surface of PRB media was lower than that in the initial soil; no As(0) was detected on the surface of used ZVI, which indicates that arsenic was removed by surface adsorption/precipitation on ZVI-PRB, accompanied by As(V) partially reduced to As(III). The results reported in this study will be beneficial to optimizing the design of batch EK/PRB system and to enlarging the field-scale system.

Dichromate and arsenate anion removal by PEI microgel, cryogel, and bulkgel

Among the various metal ions, chromate (Cr(VI)) and arsenate (As(V)) are the two most hazardous toxic ion species and are found in nature in the form of dichromate and arsenate anions. In this investigation, polyethyleneimine (PEI)-based hydrogels were prepared with microgel, cryogel, and bulkgel morphologies employing glycerol diglycidyl ether as a crosslinker. The prepared PEI-based hydrogels were used to remove dichromate and arsenate anions from aqueous media. PEI microgel, cryogel, and bulkgels weighing 50 mg of each adsorbed 84.7 ± 0.8, 76.5 ± 5.2, and 108.9 ± 2.4 mg.g−1 of dichromate anions and 15.9 ± 0.7, 45.4 ± 1.9, and 79.2 ± 11.6 mg.g−1 of arsenate anions in 30, 120, and 240 min, respectively. The dichromate and arsenate anions adsorption of PEI-based hydrogels were found to fit to the pseudo-second-order kinetic, and nonlinear Langmuir isotherm models, respectively with higher R2 values. The highest distribution coefficient (Kd) value of PEI-based hydrogels for dichromate adsorption was obtained on the cryogel forms of PEI as 1.89 ± 0.05. Likewise, the highest Kd value for the arsenate adsorption was calculated on PEI-based bulkgels as 0.46 ± 0.01. The thermodynamic parameters of PEI based hydrogels in the adsorption of dichromate and arsenate anions e.g., ΔG (all negative (except for the arsenate adsorption by PEI microgels), and ΔH that is around 2−10 kJ.mol−1, and ΔS what is around 0.01−0.02 kJ.mol−1. K−1 were calculated. The reusability studies showed that PEI-based hydrogels can be used for at least 5 consecutive adsorption-desorption cycles with almost 70 % anion removal efficiency after the fifth cycle.

Structural Variations in Complex Sodium Thorium Arsenates

Three new sodium thorium arsenates, Na5Th4(AsO4)7 (1), Na5Th(AsO4)3 (2), and Na4Th(As2O7)2 (3) were synthesized via a high temperature route and their structures and optical properties were studied. Compound 1 adopts a three‐dimensional structure that consists of tetrameric fundamental building blocks (FBBs) [Th4(AsO4)7]5–, which are constructed by ThO8 and ThO9 polyhedra. The structures of 2 and 3 are based on open frameworks with channels running along the a or c axes, respectively, which are occupied by Na cations. Structural relations between the structures of 2 and 3 have been discussed regarding their composition. In contrast to the other two compounds, the arsenate anions in the structure of 2 play role of bridging ligands and do not connect more than two Th atoms. Owing to this, the underlying net of this compound contains only Th nodes has a lon topology. The Raman spectra of 1 and 2 contain similar peaks due to As–O vibrations of AsO4 groups, while the Raman spectrum of 3 differs significantly owing to the presence of As–O–As bridging group in As2O74– anions.