The pH-dependent role of different manganese oxides in the fate of arsenic during microbial reduction of arsenate-bearing goethite.

Manganese oxides reduce arsenic (As) toxicity by promoting aqueous-phase As(III) oxidation and immobilization in natural aquatic ecosystems. In anaerobic water-sediment systems, arsenic exists both in a free state in the liquid phase and in an adsorbed state on iron (Fe) minerals. However, the influence of different manganese oxides on the fate of As in this system remains unclear. Therefore, in this study, we constructed an anaerobic microbial As(V) reduction environment and investigated the effects of three different manganese oxides on the fate of both aqueous-phase and goethite-adsorbed As under different pH conditions. The results showed that δ-MnO2 had a superior As(III) oxidation ability in both aqueous and solid phase due not only to the higher SSA, but also to its wrinkled crystalline morphology, less favorable structure for bacterial reduction, structure conducive to ion exchange, and less interference caused by the formation of secondary Fe-minerals compared to α-MnO2 and γ-MnO2. Regarding aqueous-phase As, δ-MnO2, α-MnO2, and γ-MnO2 required an alkaline condition (pH 9) to exhibit their strongest As(III) oxidation and immobilization capability. For goethite-adsorbed As, under microbial-reducing conditions, all manganese oxides had the highest As immobilization effect in neutral pH environments and the strongest As oxidation effect in alkaline environments. This was because at pH 7, Fe(II) and Mn(II) formed hydrated complexes, which was more favorable for As adsorption. At pH 9, the negatively charged state of goethite hindered As adsorption but promoted the adsorption and oxidation of As by the manganese oxides. Our research offers new insights for optimizing As removal from water using various manganese oxides and for controlling the mobilization of As in water-sediment system under different pH conditions.

Low-molecular-weight organic acids inhibit the methane-dependent arsenate reduction process in paddy soils.

Anaerobic methane oxidation (AOM) can drive soil arsenate reduction, a process known as methane-dependent arsenate reduction (M-AsR), which is a critical driver of arsenic (As) release in soil. Low molecular weight organic acids (LMWOAs), an important component of rice root exudates, have an unclear influence and mechanism on the M-AsR process. To narrow this knowledge gap, three typical LMWOAs-citric acid, oxalic acid, and acetic acid-were selected and added to As-contaminated paddy soils, followed by the injection of 13CH4 and incubation under anaerobic conditions. The results showed that LMWOAs inhibited the M-AsR process and reduced the As(III) concentration in soil porewater by 35.1-65.7 % after 14 days of incubation. Among the LMWOAs, acetic acid exhibited the strongest inhibition, followed by oxalic and citric acid. Moreover, LMWOAs significantly altered the concentrations of ferrous iron and dissolved organic carbon in the soil porewater, consequently impacting the release of As in the soil. The results of qPCR and sequencing analysis indicated that LMWOAs inhibited the M-AsR process by simultaneously suppressing microbes associated with ANME-2d and arrA. Our findings provide a theoretical basis for modulating the M-AsR process and enhance our understanding of the biogeochemical cycling of As in paddy soils under rhizosphere conditions.

Arsenosugar extracted from algae: Assessment of countercurrent chromatography for isolation.

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.(NH4)2SO4/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 PO4-Sug, 90.4 % in SO3-Sug and 96.1 % in SO4-Sug.

Effect and mechanism of coexistence of microplastics on arsenate adsorption capacity in water.

Arsenic pollution control technology in water was important to ensure environmental health and quality safety of agricultural products. Therefore, the adsorption performance of three adsorbents for chitosan, sepiolite, and Zeolitic Imidazolate Framework-8 (ZIF-8) were investigated in arsenate contaminated water. The results revealed that the adsorption capacity of ZIF-8 was higher than that of chitosan and sepiolite. The analysis of adsorption isotherm models showed that the behavior of ZIF-8 was more consistent with the Langmuir model. Furthermore, the adsorption mechanisms of three adsorbents for arsenate were investigated by Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The analysis of FTIR showed that ZIF-8 maintained the stability of the interaction with arsenate by forming As-O chemical bonds. However, the effect of chitosan and sepiolite with arsenate was mainly physical adsorption. The analysis of XPS showed that the absorption of ZIF-8 with arsenate involved metal sites and nitrogen through the characteristic peak and the change of the binding energy. Furthermore, the impact of microplastics as a widespread coexistence pollutant in the water on adsorbent performance was investigated. The results indicated that the adsorption capacity of ZIF-8 was almost not affected by microplastics. The maximum adsorption amount of arsenate was changed from 73.45 mg/g to 81.89 mg/g. However, the maximum adsorption amount of chitosan and sepiolite decreased by 31.4 % and 11.6 %, respectively. The analysis of FTIR and XPS revealed that ZIF-8 enhances arsenate adsorption by forming N-O-As bonds in the presence of microplastics. This study provides scientific evidence for the management of arsenate pollution in water bodies, especially in complex water bodies containing microplastics.

Enhanced Arsenate Immobilization by Kaolinite via Heterogeneous Pathways during Ferrous Iron Oxidation.

Clay minerals are ubiquitous in subsurface environments and have long been recognized as having a limited or negligible impact on the fate of arsenic (As) due to their negatively charged surfaces. Here, we demonstrate the significant role of kaolinite (Kln), a pervasive clay mineral, in enhancing As(V) immobilization during ferrous iron (Fe(II)) oxidation at near-neutral pH. Our results showed that Fe(II) oxidation alone was not capable of immobilizing As(V) at relatively low Fe/As molar ratios (≤2) due to the generation of Fe(III)-As(V) nanocolloids that could still migrate easily as truly dissolved As did. In the presence of kaolinite, dissolved As(V) was significantly immobilized on the kaolinite surfaces via forming Kln-Fe(III)-As(V) ternary precipitates, which had large sizes (at micrometer levels) to reduce the As mobility. The kaolinite-induced heterogeneous pathways for As(V) immobilization involved Fe(II) adsorption, heterogeneous oxidation of adsorbed Fe(II), and finally heterogeneous nucleation/precipitation of Fe(III)-As(V) phases on the edge surfaces of kaolinite. The surface precipitates were mixtures of amorphous basic Fe(III)-arsenate and As-rich hydrous ferric oxide. Our findings provide new insights into the role of clay minerals in As transformation, which is significant for the fate of As in natural and engineered systems.

Comparison of two carbonaceous supported Fe-rich adsorbents for arsenate removal: A functionalisation and mechanistic study with applicability to groundwater treatment.

The presence of arsenic in groundwater, and through this in drinking water, has been shown to present a serious risk to public health in many regions of the world. In this study, two iron-rich carbonous adsorbents were compared for the removal of arsenate (As(V)) from groundwater. Biochars (FeO-biochar and FeO-pyrochar) derived from biomass waste were functionalised in two different ways with iron chloride for comparation. Batch and dynamic parameters were optimised to achieve >99% As(V) removal efficiency. Experimental data were best described by the pseudo-second order kinetic model, while multi-stage diffusion appeared to limit mass transfer of As(V). Among the isotherm models evaluated, the Freundlich model best described the experimental results with high correlation coefficients (R2 ≥ 0.94) for both adsorbents. Monolayer adsorption capacities were found to be 4.34 mg/g and 8.66 mg/g for FeO-biochar and FeO-pyrochar, respectively. Batch studies followed by instrumental characterisation of the materials indicated the removal mechanisms involved to be electrostatic interactions (outer-sphere), OH- ligand exchange (inner-sphere complexation) and hydrogen bonding with functional groups. Higher pHpzc (9.1), SBET (167.2 m2/g), and iron/elemental content for the FeO-pyrochar (compared with the FeO-biochar) suggested that both surface chemistry and porosity/surface area were important in adsorption. Dynamic studies showed FeO-pyrochar can be used to remove As(V) from groundwater even at low 'environmental' concentrations relevant to legislative limits (<10 µg/L), whereby 7 g of FeO-pyrochar was able to treat 5.4 L groundwater.

Arsenate removal using chitosan-coated bentonite via fixed-bed system: a process integration by fuzzy optimization.

Groundwater contamination is a global concern that has detrimental effect on public health and the environment. Sustainable groundwater treatment technologies such as adsorption require attaining a high removal efficiency at a minimal cost. This study investigated the adsorption of arsenate from groundwater utilizing chitosan-coated bentonite (CCB) under a fixed-bed column setup. Fuzzy multi-objective optimization was applied to identify the most favorable conditions for process variables, including volumetric flow rate, initial arsenate concentration, and CCB dosage. Empirical models were employed to examine how initial concentration, flow rate, and adsorbent dosage affect adsorption capacity at breakthrough, energy consumption, and total operational cost during optimization. The ε-constraint process was used in identifying the Pareto frontier, effectively illustrating the trade-off between adsorption capacity at breakthrough and the cost of the fixed-bed system. The integration of fuzzy optimization for adsorption capacity and its total operating cost utilized the global solver function in LINGO 20 software. A crucial equation derived from the Box-Behnken design and a cost equation based on energy and material usage in the fixed-bed system was employed. The results from identifying the Pareto front determined boundary limits for adsorption capacity at breakthrough (ranging from 12.96 ± 0.19 to 12.34 ± 0.42 µg/g) and total operating cost (ranging from 955.83 to 1106.32 USD/kg). An overall satisfaction level of 35.46% was achieved in the fuzzy optimization process. This results in a compromise solution of 12.90 µg/g for adsorption capacity at breakthrough and 1052.96 USD/kg for total operating cost. Henceforth, this can allow a suitable strategic decision-making approach for key stakeholders in future applications of the adsorption fixed-bed system.

Prediction of Cr(VI) and As(V) adsorption on goethite using hybrid surface complexation-machine learning model.

This study aimed to develop surface complexation modeling-machine learning (SCM-ML) hybrid model for chromate and arsenate adsorption on goethite. The feasibility of two SCM-ML hybrid modeling approaches was investigated. Firstly, we attempted to utilize ML algorithms and establish the parameter model, to link factors influencing the adsorption amount of oxyanions with optimized surface complexation constants. However, the results revealed the optimized chromate or arsenate surface complexation constants might fall into local extrema, making it unable to establish a reasonable mapping relationship between adsorption conditions and surface complexation constants by ML algorithms. In contrast, species-informed models were successfully obtained, by incorporating the surface species information calculated from the unoptimized SCM with the adsorption condition as input features. Compared with the optimized SCM, the species-informed model could make more accurate predictions on pH edges, isotherms, and kinetic data for various input conditions (for chromate: root mean square error (RMSE) on test set = 5.90 %; for arsenate: RMSE on test set = 4.84 %). Furthermore, the utilization of the interpretable formula based on Local Interpretable Model-Agnostic Explanations (LIME) enabled the species-informed model to provide surface species information like SCM. The species-informed SCM-ML hybrid modeling method proposed in this study has great practicality and application potential, and is expected to become a new paradigm in surface adsorption model.

Speciation of arsenic in milk from cows fed seaweed.

BACKGROUND: Including seaweed in cattle feed has gained increased interest, but it is important to take into account that the concentration of toxic metals, especially arsenic, is high in seaweed. This study investigated the arsenic species in milk from seaweed-fed cows. RESULTS: Total arsenic in milk of control diets (9.3 ± 1.0 µg As kg-1, n = 4, dry mass) was significantly higher than seaweed-based diet (high-seaweed diet: 7.8 ± 0.4 µg As kg-1, P < 0.05, n = 4, dry mass; low-seaweed diet: 6.2 ± 1.0 µg As kg-1, P < 0.01, n = 4, dry mass). Arsenic speciation showed that the main species present were arsenobetaine (AB) and arsenate (As(V)) (37% and 24% of the total arsenic, respectively). Trace amounts of dimethylarsinic acid (DMA) and arsenocholine (AC) have also been detected in milk. Apart from arsenate being significantly lower (P < 0.001) in milk from seaweed-fed cows than in milk from the control group, other arsenic species showed no significant differences between groups. CONCLUSION: The lower total arsenic and arsenate in seaweed diet groups indicates a possible competition of uptake between arsenate and phosphate, and the presence of AC indicates that a reduction of AB occurred in the digestive tract. Feeding a seaweed blend (91% Ascophyllum nodosum and 9% Laminaria digitata) does not raise As-related safety concerns for milk. © 2024 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Simultaneous adsorption of chromate and arsenate onto ferrihydrite/alginate composite beads: Competition and mechanism.

Ferrihydrite is an effective adsorbent of chromate and arsenate. In order to gain insight into the application of ferrihydrite in water treatment, macroporous alginate/ferrihydrite beads, synthesized using two different methods (internal and encapsulation processes), were used in this work. The properties of the ferrihydrite were assessed using various techniques, including X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Brunauer-Emmett-Teller (BET) theory, and zetametry. The results showed that the specific surface area of the ferrihydrite was 242 m2/g, and the PZC was pH8. The kinetic and isotherm adsorption properties of the ferrihydrite were evaluated in this study. The results indicate that the pseudo second-order and Freundlich models accurately describe the kinetic and isotherm adsorption properties of chromates and arsenates. For chromate removal, ferrihydrite exhibited a relatively high adsorption capacity (40.7 mgCr/g) compared to other adsorbents. However, the arsenate adsorption capacity of MFHB-SI (140.8 mgAs/g) was shown to be the most optimal. The internal synthesis process was suitable for arsenate retention due to the resulting arsenate precipitation. The competitive adsorption analyses indicated that the presence of chromate does not limit the adsorption of arsenate. However, the presence of arsenate almost completely inhibits the adsorption of chromate when the arsenate concentration is above 50 mg/L, due to the precipitation reaction of arsenate.

Static and dynamic adsorption of arsenate from water by Fe3+ complexed with 3-aminopropyltriethoxysilane-modified carboxymethyl chitosan.

Fe3+ complexed with 3-aminopropyltriethoxysilane (APTES)-modified carboxymethyl chitosan (CMC) named Fe-ACMC was synthesized by a one-step method at room temperature and pressure. The surface morphology and chemical structure of Fe-ACMC were characterized by SEM-EDS, XRD, BET, FT-IR, XPS, and ζ-potential. In batch adsorption, the optimum pH for arsenate [As(V)] adsorption onto Fe-ACMC was 3-9 with removal efficiency > 99%. The adsorption of As(V) could reach equilibrium within 25 min and the maximum adsorption capacity was 84.18 mg g-1. The pseudo-second-order model fitted well the kinetic data (R2 = 0.995), while the Freundlich model well described the adsorption isotherm of As(V) on Fe-ACMC (R2 = 0.979). The co-existing anions (NO3-, CO32-, and SO42-) exhibited a slight impact on the As(V) adsorption efficiency, whereas PO43- inhibited As(V) adsorption on Fe-ACMC. The real applicability of Fe-ACMC was achieved to remove ca. 10.0 mg L-1 of As(V) from natural waters to below 0.05 mg L-1. The regeneration and reuse of Fe-ACMC for As(V) adsorption were achieved by adding 0.2 mol L-1 HCl. The main adsorption mechanism of As(V) on Fe-ACMC was attributed to electrostatic attraction and inner-sphere complexation between -NH2···Fe3+ and As(V). In fixed-bed column adsorption, the Thomas model was the most suitable model to elucidate the dynamic adsorption behavior of As(V). The loading capacity of the Fe-ACMC packed column for As(V) was 47.04 mg g-1 at pH 7 with an initial concentration of 60 mg L-1, flow rate of 3 mL min-1, and bed height of 0.6 cm.

Comparative study of Fe(II)/sulfite, Fe(II)/PDS and Fe(II)/PMS for p-arsanilic acid treatment: Efficient organic arsenic degradation and contrasting total arsenic removal.

As a widely used feed additives, p-arsanilic acid (p-AsA) frequently detected in the environment poses serious threats to aquatic ecology and water security due to its potential in releasing more toxic inorganic arsenic. In this work, the efficiency of Fe(II)/sulfite, Fe(II)/PDS and Fe(II)/PMS systems in p-AsA degradation and simultaneous arsenic removal was comparatively investigated for the first time. Efficient p-AsA abatement was achieved in theses Fe-based systems, while notable discrepancy in total arsenic removal was observed under identical acidic condition. By using chemical probing method, quenching experiments, isotopically labeled water experiments, p-AsA degradation was ascribed to the combined contribution of high-valent Fe(IV) and SO4•-in these Fe(II)-based system. In particular, the relative contribution of Fe(IV) and SO4•- in the Fe(II)/sulfite system was highly dependent on the molar ratio of [Fe(II)] and [sulfite]. Negligible arsenic removal was observed in the Fe(II)/sulfite and Fe(II)/PDS systems, while ∼80% arsenic was removed in the Fe(II)/PMS system under identical acidic condition. This interesting phenomenon was due to that ferric precipitation only occurred in the Fe(II)/PMS system. As(V) was further removed via adsorption onto the iron precipitate or the formation of ferric arsenate-sulfate compounds, which was confirmed by particle diameter measurements, fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Through tuning solution pH, complete removal of total arsenic could achieve in all three systems. Among these three Fe-based technologies, the hybrid oxidation-coagulation Fe(II)/PMS system demonstrated potential superiority for arsenic immobilization by not requiring pH adjustment for coagulation and facilitating the in-situ generation of ferric arsenate-sulfate compounds with comparably low solubility levels like scorodite. These findings would deepen the understanding of these three Fe-based Fenton-like technologies for decontamination in water treatment.

Insights into the selectivity of metallic oxides for arsenic and phosphate from EXAFS and DFT calculations.

Phosphate is the biggest competitor for arsenic removal. Nanoscale metal oxides (NMOs) are commonly used to treat arsenic-contaminated water, yet their selective adsorption mechanisms for arsenic and phosphate are poorly understood. We quantified the selectivity of iron oxide (Fe2O3), zinc oxide (ZnO), and titanium dioxide (TiO2) nanosheets for arsenic in systems containing arsenic and phosphate, and determined the interaction of phosphate and arsenate/arsenite on metal oxide surfaces through batch experiments, spectroscopic techniques, and DFT calculations. We found that Fe2O3, TiO2, and ZnO nanosheets exhibit selectivity for arsenate/arsenite in the presence of phosphate, with Fe2O3 the most selective, followed by TiO2 and ZnO. The bonding mechanism on these metallic oxide surfaces dominates the selectivity. The more stable inner-sphere complexes of arsenate on the surfaces of Fe2O3 (bidentate binuclear), TiO2 (bidentate binuclear), and ZnO nanosheets (tridentate trinuclear) contribute to their preference for arsenate over phosphate. This difference in arsenate selectivity can be reflected in the difference in adsorption energy, net electron transfer number, and M - O bond length of the most stable inner sphere complexes. Overall, our study elucidated the selective adsorption mechanisms of arsenate/arsenite on Fe2O3, TiO2, and ZnO surfaces and highlighted the need to consider the competition between arsenate and phosphate during their removal from contaminated water.

Arsenic triggered nano-sized uranyl arsenate precipitation on the surface of Kocuria rosea.

Arsenic (As) and uranium (U) frequently occur together naturally and, in consequence, transform into cocontaminants at sites of uranium mining and processing, yet the simultaneous interaction process of arsenic and uranium has not been well documented. In the present contribution, the influence of arsenate on the removal and reduction of uranyl by the indigenous microorganism Kocuria rosea was characterized using batch experiments combined with species distribution calculation, SEM-EDS, FTIR, XRD and XPS. The results showed that the coexistence of arsenic plays an active role in Kocuria rosea growth and the removal of uranium under neutral and slightly acidic conditions. U-As complex species of UO2HAsO4 (aq) had a positive effect on uranium removal, while Kocuria rosea cells appeared to have a large specific surface area serving as attachment sites. Furthermore, a large number of nano-sized flaky precipitates, constituted by uranium and arsenic, attached to the surface of Kocuria rosea cells at pH 5 through P=O, COO-, and C=O groups in phospholipids, polysaccharides, and proteins. The biological reduction of U(VI) and As(V) took place in a successive way, and the formation of a chadwickite-like uranyl arsenate precipitate further inhibited U(VI) reduction. The results will help to design more effective bioremediation strategies for arsenic-uranium cocontamination.

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

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

Highly effective remediation of high arsenic-bearing wastewater using aluminum-containing waste residue.

Wastewater from non-ferrous metal smelting is known as one of the most dangerous sources of arsenic (As) due to its high acidity and high arsenic content. Herein, we propose a new environmental protection process for the efficient purification and removal of arsenic from wastewater by the formation of an AlAsO4@silicate core-shell structure based on the characteristics of aluminum-containing waste residue (AWR). At room temperature, the investigation with AWR almost achieved 100% As removal efficiency from wastewater, reducing the arsenic concentration from 5500 mg/L to 52 µg/L. With Al/As molar ratio of 3.5, the structural properties of AWR provided good adsorption sites for arsenic adsorption, leading to the formation of arsenate and insoluble aluminum arsenate with As. As-containing AWR silicate shells were produced under alkaline conditions, resulting in an arsenic leaching concentration of 1.32 mg/L in the TCLP test. AWR, as an efficient As removal and fixation agent, shows great potential in the treatment of copper smelting wastewater, and is expected to achieve large-scale industrial As removal.

Selective recognition and extraction of arsenate by a urea-functionalized tripodal receptor from competitive aqueous media.

A second-generation hydrogen bond donor (HBD) anion receptor with an inner amide cavity and an outer urea cavity can selectively and efficiently extract arsenate (AsO43-) from water in the presence of competitive oxoanions and halides. The X-ray structure showed encapsulation of AsO43- in a π-stacked dimeric capsular assembly of the receptor, the first crystallography-based example of pentavalent AsO43- trianion recognition by a HBD receptor.

Mobilization of arsenic from As-containing iron minerals under irrigation: Effects of exogenous substances, redox condition, and intermittent flow.

Irrigation activities can cause strong geochemical and hydrological fluctuations in the unsaturated zone, and affect arsenic (As) migration and transformation. The As geochemical cycle in the unsaturated zone is coupled with that of iron minerals through sorption-desorption, coprecipitation and redox processes. Dynamic batch experiments and wetting-drying cycling column experiments were conducted to evaluate As mobilization behaviors under the effects of exogenous substances, redox condition and intermittent flow. Our results show that As release under exogenous substances carried by irrigation (e.g., phosphate, carbonate, fulvic acid, humic acid, etc.) followed three trends with the types of exogenous inputs. Inorganic anions and organic matter resulted in opposite trends of arsenate release in different redox conditions. In anoxic environments, As(V) release was favored by the addition of phosphate and carbonate, while in oxic environments, the mobilization of As(V) was promoted by the addition of fulvic acid (FA). Further, intermittent irrigation promoted the reductive dissolution of Fe oxides and the mobilization of As. The addition of humic acid (HA) resulted in the mobilization of arsenate as As-Fe-HA ternary complexes. The mechanism of arsenic mobilization under irrigation has importance for prevention of arsenic exposure through soil to food chain transfer in typical high arsenic farmland.

Key factors in the adsorption of natural organic matter to metal (hydr)oxides: Fractionation and conformational change.

Adsorption of natural organic matter (NOM) to mineral surfaces is an important process determining the environmental fate and biogeochemical cycling of many elements. Natural organic matter consists of a heterogeneous mixture of soft and flexible organic molecules. Upon adsorption, size fractionation may occur, as well as changes in molecular conformation. Although very important, these phenomena have been omitted in existing adsorption models. Filling this gap, a novel framework for NOM adsorption to metal (hydr)oxides is presented. Humic acid (HA) was used as an analog for studying experimentally the NOM adsorption to goethite and its size fractionation as a function of pH, ionic strength, and surface loading. Size fractionation was evaluated for adsorption isotherms collected at pH 4 and 6, showing HA molecules of low molar mass were preferentially adsorbed. This phenomenon was incorporated into the new model. Consistent description of the HA adsorption data over the entire range of pH (3-11), ionic strength (2-100 mM), and surface loading (0.1-3 mg m-2) indicated that the spatial distribution of HA molecules adsorbed in the interface is a trade-off between maximizing the interaction of the HA ligands with the oxide surface and minimizing the electrostatic repulsion between HA particles as a result of interfacial crowding. Our advanced consistent framework is able to quantify changes in molar mass and molecular conformation, thereby significantly contributing to an improved understanding of the competitive power of HA for interacting on oxides with other adsorbed small organic acids as well as environmentally important oxyanions, such as phosphate, arsenate, and others.

Effects of aluminum incorporation on the schwertmannite structure and surface properties.

Schwertmannite is a common nanomineral in acid sulfate environments such as Acid Mine Drainage (AMD) and Acid Sulfate Soils (ASS). Its high surface area and positively charged surface result in a strong affinity towards toxic oxyanions such as arsenate in solution. However, natural precipitation of schwertmannite also involves the accumulation of other impurities, in particular aluminum, an element that is often incorporated into the structure of Fe-oxide minerals, such as goethite and ferrihydrite, affecting their structural and surface properties. However, little is known about the effect of Al incorporation in schwertmannite on the removal capacity of toxic oxyanions found in AMD and ASS (e.g. arsenate). In this paper, schwertmannite samples with variable Al concentration were synthetized and employed in arsenate adsorption isotherm experiments at a constant pH of 3.5. Solid samples before and after arsenate adsorption were characterized using high energy X-ray diffraction and pair distribution function analyses in order to identify structural differences correlated with the Al content as well as variations in the coordination of arsenate adsorbed on the mineral surface. These analyses showed limited Al accumulation on schwertmannite (up to 5%) with a low effect on its structure. The maximum arsenate sorption capacity (258 mmolH2AsO4 molFe-1) was in the range of that with pure schwertmannite, but a higher proportion of inner-sphere coordination was observed. Finally, Al was found to desorb from schwertmannite, with adsorbed arsenate preventing this effect and increasing the stability of the mineral. These results are useful to interpret observations from the field, in particular from river water affected by AMD and ASS, where similar conditions are observed, and where aluminum incorporation is expected.