Arsenic Mobilization Research Articles

Synergistic effect between biochar and nitrate fertilizer facilitated arsenic immobilization in an anaerobic contaminated paddy soil

Nitrate nitrogen fertilizer was usually used to mitigate arsenic (As) release and mobilization in the anaerobic contaminated paddy soil. However, the effect of the interplay between nitrate fertilizer and biochar on As availability as well as the involved mechanism were poorly understood. Herein, the effects and mechanisms of biochar, nitrate fertilizer, and biochar-based nitrate fertilizer on the availability of As in the contaminated paddy soil were investigated via a microcosm incubation experiment. Results indicated that the application of biochar-based nitrate fertilizer significantly lessened the available As concentration in the contaminated paddy soil from 3.01 ± 0.03 (control group) to 2.24 ± 0.08 mg kg−1, which presented an immobilization efficiency of 26.6 % better than those of individual biochar (13.5 %) and nitrate fertilizer (17.6 %), exhibiting a synergistic effect. Moreover, the biochar-based nitrate fertilizer also facilitated the transformation of more toxic arsenite in the contaminated soil to less toxic arsenate. Further, biochar-based nitrate fertilizer increased soil redox potential (Eh), dissolved organic carbon, organic matter, and nitrate yet decreased soil pH and ammonium, which changed the microbial community in the soil, enhancing the relative abundance of Bacillus, Arthrobacter, and Paenibacillus. These functional microorganisms drove the coupled transformation between nitrate denitrification and Fe(II) or As(III) oxidation, favoring As immobilization in the anaerobic paddy soil. Additionally, the co-application of biochar offset the negative effect of single nitrate fertilizer on microbial community diversity. Overall, biochar-based nitrate fertilizer could be a promising candidate for the effective immobilization of As in the anaerobic paddy soil. The current research can provide a valuable reference to the remediation of As-contaminated paddy soil and the production of safe rice.

The roles of nanoparticle-enriched biochars in improving soil enzyme activities and nutrient uptake by basil plants under arsenic toxicity

Enriched biochar with improved properties and functionality can play a significant role in providing sustainable solutions for mitigating heavy metal contamination in soil. In this experiment, the effects of solid and enriched biochars (potassium-enriched biochar (BC-K), magnesium-enriched biochar (BC-Mg), both individually and combined) were examined on soil microbial and enzyme activities, as well as nutrient uptake by basil plants cultivated in a soil with three levels of arsenic (nontoxic, 50 mg As kg−1 soil, and 100 mg As kg−1 soil). Biochar-related treatments, increased soil organic matter (65–76%), while decreased availability of arsenic (6–55%) in the soil. The microbial biomass carbon (by about 123%) and soil basal respiration (by about 256%), and soil enzymatic activities (β-glucosidase, urease, alkaline phosphatase, and dehydrogenase) were enhanced by enriched biochars under arsenic toxicity. The solid and particularly enriched biochars decreased arsenic content and improved nitrogen and phosphorus contents of roots and shoots, root length, root activity, and root and shoot biomass in basil plants. Therefore, it is conceivable to suggest that enriched biochars are superior treatments for improving nutrient absorption rates and basil growth under arsenic toxicity through decreasing arsenic mobility and increasing soil microbial activities.

Mobilization mechanisms and spatial distribution of arsenic in groundwater of western Bangladesh: Evaluating water quality and health risk using EWQI and Monte Carlo simulation

Arsenic (As) contamination in groundwater is emerging as a significant global concern, posing serious risks to the safety of drinking water and public health. To understand the release mechanisms, mobilization processes, spatial distribution, and probabilistic health risks of As in western Bangladesh, forty-seven samples were collected and analyzed using an atomic absorption spectrometer (AAS). The As concentrations in groundwater ranged from 1.97 to 697.4 μg L⁻1 (mean: 229.9), significantly exceeding recommended levels. The dominant hydrochemistry of As-enriched groundwater was Ca–Mg–HCO₃, with the primary sources of arsenic in groundwater being the dissolution of arsenic-bearing minerals in sediment and the recharge of aquifers from the Ganges River Basin. The assessment using the Entropy Water Quality Index revealed that the groundwater is unsuitable for drinking, with 89.36% (n = 42) of the samples surpassing the WHO's limit for arsenic. Rock-water interactions, including calcite dissolution and silicate weathering within the confined aquifer, predominantly influenced hydrochemical properties. The significant relationships among Fe, Mn, and As indicate that the reductive dissolution of FeOOH and/or MnOOH considerably contributes to the release of As from sediment into groundwater. Geochemical modeling analysis revealed that siderite and rhodochrosite precipitate into aquifer solids, suggesting a weak to moderate relationship among As, Fe, and Mn. The long residence time of groundwater, combined with the presence of a clayey aquitard, likely controls the mobilization of arsenic in the aquifer. For the first time, Monte Carlo simulations have been used in arsenic-prone areas to assess the severity of arsenic contamination in western Bangladesh. The analysis indicates that out of 100,000 people, 10 may develop cancer as a result of drinking arsenic-contaminated water, with children being more susceptible than adults.

Infiltration of secondary treated wastewater into an oxic aquifer: Hydrochemical insights from a large-scale sand tank experiment

To mitigate groundwater level decline, managed aquifer recharge (MAR) with secondary treated wastewater (STWW) is increasingly considered and implemented. However, the effectiveness and potential risks of such systems need evaluation prior to implementation. In this study, we present a large-scale sand tank experiment to analyse processes related to the infiltration of real STWW through the vadose zone and subsequent mixing with oxic native groundwater. The varying composition of STWW from 15 infiltration cycles over six months of operation and the retention times were the main drivers of the observed processes, which were characterized by a wide range of analytical techniques such as in situ high-resolution oxidation–reduction potential (ORP) measurements, closed mass balances of solutes, characterization of dissolved organic carbon (DOC), stable nitrate isotopes analysis, as well as numerical flow and transport modelling. Depending on the composition and infiltration rates of the STWW, both nitrification and denitrification could be observed, even simultaneously at different locations in the tank. Furthermore, due to the variability of the real STWW we observed enhanced arsenic mobilisation during times of elevated phosphate concentrations of the infiltrating STWW. Additionally, uranium was mobilised in our experimental system via carbonate mineral dissolution caused by the infiltrating STWW which was undersaturated of calcite for all infiltration cycles. Overall, our results showed the importance of conducting studies with waters of complex matrix, such as real STWW, and considering mixing with groundwater to assess the full range of possible processes encountered at MAR field sites.

Sulfate-mediated Fe(III) mineral reduction accelerates arsenic mobilization by a Desulfovibrio strain isolated from paddy soil

The biogeochemical cycling of arsenic (As) is often intertwined with iron (Fe) and sulfur (S) cycles, wherein Fe(III)- and sulfate-reducing bacteria (SRB) play a crucial role. Here, we isolated strain DS-1, a strictly anaerobic Fe(III)- and sulfate-reducing bacterium, from As-contaminated paddy soil. Using 16S rRNA gene sequence analysis, strain DS-1 was identified as a member of the genus Desulfovibrio. Strain DS-1 utilized energy derived from ferrihydrite reduction to support its cellular growth. Under anoxic sulfate-reducing conditions, the presence of strain DS-1 significantly increased As mobilization compared to sulfate-free conditions. Mechanistically, SRB-produced sulfide reacts with Fe(III) to form FeS, which disrupts Fe(III) minerals, thereby enhancing As release. These findings highlight the critical role of redox disequilibrium in As mobilization and suggest that SRB-produced sulfide may permeate to the rice rhizosphere, increasing As mobilization through Fe(III) reduction.

Interactions between arsenic and nitrogen regulate nitrogen availability and arsenic mobility in flooded paddy soils

In paddy soils, arsenic (As) stress influences nitrogen (N) transformation while application of N fertilizers during rice cropping affects As transformation. However, specific interactive effects between As and N in flooded paddy soils on As mobility and N availability were unclear. Here, we examined N and As dynamics in flooded paddy soils treated with four As levels (0, 30, 80 and 150 mg kg−1) and three urea additions (0, 4 and 8 mmol N kg−1). Arsenic contamination inhibited diazotrophs (nifH) and fungi but promoted AOA and denitrification genes (narG, nirK, nirS), decreasing dissolved organic N, NH4+-N and NO3–-N. Besides, urea application stimulated As- and Fe-reducing bacteria (arrA and Geo) coupled with anammox. On Day 28, the addition of 8 mmol N kg–1 increased total As concentrations in solutions of soils treated with 30 and 80 mg As kg−1 by 2.4 and 1.8 times compared with the nil-N control. In contrast, at 150 mg As kg−1, it decreased the total As concentration in soil solution by 63 % through facilitating As(III) oxidation coupled with NO3–-N reduction. These results indicate that As contamination decreases N availability, but urea application affects As mobility, depending on As contamination level.

Simultaneously reducing methane emissions and arsenic mobility by birnessite in flooded paddy soil: Overlooked key role of organic polymerisation

Flooding of paddy fields enhances methane (CH4) emissions and arsenic (As) mobilisation, which are crucial issues for agricultural greenhouse gas emissions and food safety. Birnessite (δ-MnO2) is a common natural oxidant and scavenger for heavy metals. In this study, birnessite was applied to As-contaminated paddy soil. The capacity for simultaneously alleviating CH4 emissions and As mobility was explored. Soil microcosm incubation results indicated that birnessite addition simultaneously reduced CH4 emissions by 47 %–54 % and As release by 38 %–85 %. The addition of birnessite decreased the dissolved organic carbon (DOC) contents and altered its chemical properties. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) results showed that birnessite reduced the labile fractions of proteins, carbohydrates, lignins, tannins, and unsaturated hydrocarbons, however, increased the abundance of condensed aromatic structures, suggesting the polymerisation of dissolved organic matter (DOM) by birnessite. The degradation of labile fractions and the polymerisation of DOM resulted in an inventory of recalcitrant DOM, which is difficult for microbes to metabolise, thus inhibiting methanogenesis. In contrast, birnessite addition increased CH4 oxidation, as the particulate methane monooxygenase (pmoA) gene abundance increased by 30 %. The enhanced polymerisation of DOM by birnessite also increased As complexation with organics, leading to the transfer of As to the organic bound phase. In addition, the decrease in ferrous ion [Fe(II)] concentrations with birnessite indicated that the reductive dissolution of Fe oxides was suppressed, which limited the release of arsenite [As(III)] under reducing conditions. Furthermore, birnessite decreased As methylation and shaped the soil microbial community structure by enriching the metal-reducing bacterium Bacillus. Overall, our results provide a promising method to suppress greenhouse gas emissions and the risk of As contamination in paddy soils, although further studies are needed to verify its efficacy and effectiveness under field conditions.

Identification of key factors and mechanism determining arsenic mobilization in paddy soil-porewater-rice system

Arsenic (As) mobilization in paddy fields poses significant health risks, necessitating a thorough understanding of the controlling factors and mechanisms to safeguard human health. We conducted a comprehensive investigation of the soil-porewater-rice system throughout the rice life cycle, focusing on monitoring arsenic distribution and porewater characteristics in typical paddy field plots. Soil pH ranged from 4.79 to 7.98, while porewater pH was weakly alkaline, varying from 7.2 to 7.47. Total arsenic content in paddy soils ranged from 6.8 to 17.2 mg/kg, with arsenic concentrations in porewater during rice growth ranging from 2.97 to 14.85 μg/L. Specifically, arsenite concentrations in porewater ranged from 0.48 to 7.91 μg/L, and arsenate concentrations ranged from 0.73 to 5.83 μg/L. Through principal component analysis (PCA) and analysis of redox factors, we identified that arsenic concentration in porewater is predominantly influenced by the interplay of reduction and desorption processes, contributing 43.5 % collectively. Specifically, the reductive dissolution of iron oxides associated with organic carbon accounted for 23.3 % of arsenic concentration dynamics in porewater. Additionally, arsenic release from the soil followed a sequence starting with nitrate reduction, followed by ferric ion reduction, and subsequently sulfate reduction. Our findings provide valuable insights into the mechanisms governing arsenic mobilization within the paddy soil-porewater-rice system. These insights could inform strategies for irrigation management aimed at mitigating arsenic toxicity and associated health risks.

Comparative assessment of fluoride and arsenic mobilization mechanisms among the groundwater of the major affected river basins of India

ABSTRACT The high exposure of fluoride and arsenic in the groundwater of India is a serious challenge that is currently threatening human health, agriculture, livestock, and livelihood. The increased dependency on groundwater due to monsoonal uncertainties amplifies the risk by several folds. Due to the high population density in the affected regions, policies on prevention, monitoring, and mitigation have become extremely challenging to implement. The pursuit of improved human health in the affected regions cannot be completed until and unless there is sufficient urbanization and industrialization to support the livelihood, which again aggravates the situation due to improper disposal of anthropogenic contaminants owing to the lack of knowledge about the natural cycle of contaminants. The present review article is an attempt to understand the problem of fluoride and arsenic in the scenario of Indian floodplains by first explaining the globally identified mobilization mechanisms of these contaminants and then developing a compendium of knowledge through which the risk on the Indian floodplains can be analysed. Then the study compares the similarity/dissimilarity in the enrichment mechanism followed by a detailed investigation of the available mitigation techniques. In totality, the present study adds a new dimension to our understanding of the risk due to contaminants.

Unexpected enhancement effects of phosphate on co-immobilization of uranyl arsenate under acidic conditions

Understanding the formation of uranyl-arsenate compounds (M(UO2)2(AsO4)2·nH2O, M represents divalent metallic cations) is of great importance in controlling the mobility and fate of uranium (U) and arsenic (As) in the natural environment. Phosphate is a ubiquitous coexisting ion with properties similar to arsenate and can complex with uranyl to form uranyl phosphate compounds, thus potentially affecting the formation of uranyl-arsenate compounds. Herein, the effect of phosphate, on the immobilization of uranyl, arsenate and divalent metallic cations (e.g., Fe2+, Mg2+, Ni2+, Cu2+) was explored. Surprisingly, the presence of phosphate promoted the immobilization of uranyl arsenate with the divalent metallic cations under acidic conditions. For example, at pH 3.0, the immobilization efficiency of uranyl and arsenate in the uranyl-arsenate-Fe2+ system increased from 20.6 % and 18.6 % to 82.6 % and 52.2 %, respectively. Moreover, the chemical stability of the formed uranyl arsenate-bearing compounds in the presence of phosphate is significantly improved, and the TCLP leachability of As and U decreased by 81 % and 97 %, respectively. The experimental results illustrated that with PO43- served as a proton acceptor, uranyl and arsenate species were changed and more metallic cations participate in immobilization. Gibbs free energy and Gibbs free energies change also illustrated that the formation of Fe(UO2)2(AsO4)2·5H2O was relatively thermodynamically favorable in the presence of phosphate. The results of thermodynamic calculations could account for the enhancement effects of phosphate on immobilization of uranyl arsenate. The findings have important implications for the mobility and fate of U and As and the solution of their co-contamination, especially in acidic environments.

Arsenic immobilization and greenhouse gas emission depend on quantity and frequency of nitrogen fertilization in paddy soil

Nitrogen (N) fertilization in paddy soils decreases arsenic mobility and methane emissions. However, it is unknown how quantity and frequency of N fertilization affects the interlinked redox reactions of iron(II)-driven denitrification, iron mineral (trans-)formation with subsequent arsenic (im-)mobilization, methane and nitrous oxide emissions, and how this links to microbiome composition. Thus, we incubated paddy soil from Vercelli, Italy, over 129 days and applied nitrate fertilizer at different concentrations (control: 0, low: ∼35, medium: ∼100, high: ∼200 mg N kg−1 soil−1) once at the beginning and after 49 days. In the high N treatment, nitrate reduction was coupled to oxidation of dissolved and solid-phase iron(II), while naturally occurring arsenic was retained on iron minerals due to suppression of reductive iron(III) mineral dissolution. In the low N treatment, 40 μg L−1 of arsenic was mobilized into solution after nitrate depletion, with 69 % being immobilized after a second nitrate application. In the non-fertilized control, concentrations of dissolved arsenic were as high as 76 μg L−1, driven by mobilization of 36 % of the initial mineral-bound arsenic. Generally, N fertilization led to 1.5-fold higher total GHG emissions (sum of CO2, CH4 and N2O as CO2 equivalents), 158-fold higher N2O, and 7.5-fold lower CH4 emissions compared to non-fertilization. On day 37, Gallionellaceae, Comamonadaceae and Rhodospirillales were more abundant in the high N treatment compared to the non-fertilized control, indicating their potential role as key players in nitrate reduction coupled to iron(II) oxidation. The findings underscore the dual effect of N fertilization, immobilizing arsenic in the short-term (low/medium N) or long-term (high N), while simultaneously increasing N2O and lowering CH4 emissions. This highlights the significance of both the quantity and frequency of N fertilizer application in paddy soils.

Characteristics of three organic fertilizers and their influence on the mobility of cadmium and arsenic in a soil-rice (Oryza sativa L.) system.

The properties of different organic fertilizers and their potential for stabilizing toxic metals(loids) in soil have not been fully investigated. This study characterized and evaluated three organic fertilizers from different raw materials. The mushroom residue organic fertilizer (MO) had higher C, H, and O contents and more functional groups (-OH, C-H, and C = O). Its application significantly increased pH (1.00 ~ 1.32 units), organic matter (OM) content (26.58 ~ 69.11%), and cation exchange capacity (CEC) (31.52 ~ 39.91%) of soil. MO treatments can simultaneously reduce the bioavailable TCLP-Cd and TCLP-As in soil, solving the difficulties of remediating the combined Cd and As pollution. MO treatments inhibited the migration of Cd and As from soil to plant, promoting plant growth. Redundancy analysis (RDA) revealed that metal(loid) variations in plants were related to soil properties (40.09%) and TCLP-Cd/As (44.74%). Furthermore, the toxic metals(loids) risk assessment for all organic fertilizers was at safe levels. This study provided a valuable reference for choosing organic fertilizers and presented a novel option for the "producing while remediating" of farmlands with low pollution.

Prediction of As and Cd dissolution in various soils under flooding condition

Although the mobility of arsenic (As) and cadmium (Cd) in soils during the flooding-drainage process has been intensively studied, predicting their dissolution among various soils still remains a challenge. After comprehensively monitoring multiple parameters related to As and Cd dissolution in 8 soils for a 60-day anaerobic incubation, the redundancy analysis (RDA) and structural equation model (SEM) were employed to identify the key factors and influencing pathways controlling the dynamic release of As and Cd. Results showed that pH alone explained 90.5 % Cd dissolution, while the dissolved-Fe(II) and 5 M-HCl extractable Fe(II) jointly only explained 50.6 % As dissolution. After data normalization, the ratio of Fe(II) to 5 M-HCl extracted total Fe (i.e. FetotII/Fetot) significantly improved the correlation to R2 = 0.824 (p < 0.001) with a fixed slope of 0.393 among the 8 soils. Our results highlight the crucial role played by the reduction degree of total iron contents in determining both the reduction and dissolution of As during flooding. In contrast, dissolved-Fe(II) was too vulnerable to soil properties to be a stable indicator of As dissolution. Therefore, we propose to replace the dissolved-Fe(II) with this novel ratio as the key index to quantitatively assess the kinetic change of As solubility potential across various soils under flooding conditions.

A kinetics-coupled multi-surface complexation model deciphering arsenic adsorption and mobility across soil types

The diversity of soil adsorbents for arsenic (As) and the often-overlooked influence of manganese (Mn) on As(III) oxidation impose challenges in predicting As adsorption in soils. This study uses Mössbauer spectroscopy, X-ray diffraction of oriented clay, and batch experiments to develop a kinetic coupled multi-surface complexation model that characterizes As adsorbents in natural soils and quantifies their contributions to As adsorption. The model integrates dynamic adsorption behaviors and Mn-oxide interactions with unified thermodynamic and kinetic parameters. The results indicate that As adsorption is governed by five primary adsorbents: poorly crystalline Fe oxides, well crystalline Fe oxides, Fe-rich clay, Fe-depletion clay, and organic carbon (OC). Fe oxides dominate As adsorption at low As concentrations. However, at higher As concentrations, soils from carbonate strata, with higher content of Fe-rich clay, exhibit stronger As adsorption capabilities than soils from Quaternary sediment strata. The enrichment in Fe-rich clay can enhance the resistance of adsorbed As to reduction processes affecting Fe oxides. Additionally, extensive redox cycles in paddy fields increase OC levels, enhancing their As adsorption compared to upland fields. This model framework provides novel insights into the intricate dynamics of As within soils and a versatile tool for predicting As adsorption across diverse soils.

Prediction of arsenic concentration in groundwater of Chapainawabganj, Bangladesh: machine learning-based approach to spatial modeling.

Groundwater in northwestern parts of Bangladesh, mainly in the Chapainawabganj District, has been contaminated by arsenic. This research documents the geographical distribution of arsenic concentrations utilizing machine learning techniques. The study aims to enhance the accuracy of model predictions by precisely identifying occurrences of groundwater arsenic, enabling effective mitigation actions and yielding more beneficial results. The reductive dissolution of arsenic-rich iron oxides/hydroxides is identified as the primary mechanism responsible for the release of arsenic from sediment into groundwater. The study reveals that in the research region, alongside elevated arsenic concentrations, significant levels of sodium (Na), iron (Fe), manganese (Mn), and calcium (Ca) were present. Statistical analysis was employed for feature selection, identifying pH, electrical conductivity (EC), sulfate (SO4), nitrate (NO3), Fe, Mn, Na, K, Ca, Mg, bicarbonate (HCO3), phosphate (PO4), and As as features closely associated with arsenic mobilization. Subsequently, various machine learning models, including Naïve Bayes, Random Forest, Support Vector Machine, Decision Tree, and logistic regression, were employed. The models utilized normalized arsenic concentrations categorized as high concentration (HC) or low concentration (LC), along with physiochemical properties as features, to predict arsenic occurrences. Among all machine learning models, the logistic regression and support vector machine models demonstrated high performance based on accuracy and confusion matrix analysis. In this study, a spatial distribution prediction map was generated to identify arsenic-prone areas. The prediction map also displays that Baroghoria Union and Rajarampur region under Chapainawabganj municipality are high-risk areas and Maharajpur Union and Baliadanga Union are comparatively low-risk areas of the research area. This map will facilitate researchers and legislators in implementing mitigation strategies. Logistic regression (LR) and support vector machine (SVM) models will be utilized to monitor arsenic concentration values continuously.

Promoting the transformation of green rust for As immobilization with Acidovorax sp. strain BoFeN1

Microbially mediated Fe(II) oxidation has a great potential for attenuating arsenic (As) mobility in an anoxic groundwaters. Green rust (GR), a common Fe(II)-bearing phase in such environments, could be easily oxidized into Fe (oxyhydr)oxides through microbial activity. This study focused on Acidovorax sp. strain BoFeN1, an anaerobic nitrate-reducing Fe(II)-oxidizing (NRFO) bacterium, to promote the transformation of GR. In biotic GR transformation experiments, magnetite formation occurred at [As]ini = 5 mg/L while lepidocrocite and goethite were formed at [As]ini = 10 mg/L. In the absence of bacterium, the GR persisted throughout the 120-h experiment. Meanwhile, with the addition of strain BoFeN1, the final aqueous As concentration significantly decreased from 0.237 to 0.004 mg/L (C0 = 5 mg/L) and from 1.457 to 0.096 mg/L (C0 = 10 mg/L) at 120 h. It was indicated that strain BoFeN1 played a crucial role in promoting the GR transformation and enhancing As immobilization. Further investigations revealed that the role of strain BoFeN1 extended beyond Fe-oxidation. With nitrite (the intermediate of nitrate bioreduction) as oxidizer, lepidocrocite/goethite were formed in the chemical-oxidation system, excluding magnetite. In the Bio - [As]ini = 5 mg/L, the occurrence of lepidocrocite via the bio-oxidation of Fe(II) in GR at 24 h, along with the metabolism of strain BoFeN1 reducing nitrate accompanied with H+ consumption, it should be reasonably deduced that the alkaline micro-environment of periplasm induced by strain BoFeN1 were vital for the transformation of lepidocrocite to magnetite triggered by trace Fe(II). However, in the Bio - [As]ini = 10 mg/L, more As adsorbed on GR inhibiting the adsorption of bacterium, so the alkaline micro-environment had no obvious effect on such transformation. This study helps to understand the interdependence between GR and anaerobic NRFO bacterium, and provides a new perspective for more effective As remediation strategies in anoxic groundwaters.

Competitive adsorption behavior of As(V) and Sb(V) on Hematite: Facet and pH dependent coordination affinity and role of outer-sphere complexes

The environmental mobility and fate of arsenic (As) and antimony (Sb) are influenced by ubiquitous iron minerals, but little is known about whether their co-adsorption behavior is affected by the exposed facets. Herein, we used cubic and rod-shaped hematite nanocrystals (HNC and HNR) to investigate the effect of exposed facets on competitive adsorption behaviors. TEM analysis indicated that the primary exposed facets of HNC and HNR were {110} and {012}, separately. Calculations supported the predictions of our model, revealing that the competition in acidic and alkaline environments was mainly influenced by the affinity and bond stability of facet-related adsorption configurations. However, the competition in neutral conditions was jointly influenced by facet-related coordination and adsorption behavior, due to the dependence of Sb(V) on protonation sites. On HNR (pH = 3), the adsorption of Sb(V) (50.6 %) was approximately twice that of As(V) (27.8 %) for its significant advantage in bidentate coordination on the {110} facet, whereas on HNC, As(V) (65.9 %) and Sb(V) (69.3 %) exhibited similar competitiveness. Notably, As(V) and Sb(V) tend to be adsorbed through outer-sphere coordination under alkaline conditions. On the {012} facet, As(V) and Sb(V) exhibited similar competitiveness for outer-sphere sites, whereas on the {110} facet, As(V) outer-sphere coordination showed stronger affinity, giving it an edge in competing on HNR. Overall, this study elucidated the critical role of varying exposed facets in the competitive adsorption process and proposed novel strategies for the selective removal of coexisting As(V) and Sb(V) through tailored fixed-facet iron oxides.

Temperature and Dissolved Oxygen Drive Arsenic Mobility at the Sediment-Water Interface in the Lake Taihu.

In this study examining the effects of temperature and dissolved oxygen (DO) on arsenic (As) release at the sediment-water interface (SWI), it was found that an increase in temperature promoted the formation of an anaerobic environment and the reduction and desorption of As fractions within the sediments. A temperature of 32 °C was the most favorable condition for As release at the SWI, and low DO conditions aggravated this process. Even under high DO conditions, the release of sediment As was significantly accelerated under high-temperature conditions, allowing dissolved As to rapidly migrate to the overlying water. In this process, the release of As from sediments was a consequence of the transformation of As fractions in the sediments.

Effects of Nitrogen Fertilizer Application on Soil Properties and Arsenic Mobilization in Paddy Soil

Anthropogenic nitrogen (N) fertilization may substantially alter arsenic (As) behavior in the soil. However, a comprehensive understanding of how the soil As cycle responds to external N addition remains elusive. This study investigates the effects of various N fertilizers on soil properties and As mobility in paddy soil. Regardless of N sources, the concentrations of soluble As and SPLP-extractable As decreased with all N applications. Similarly, soil acidification occurred and dissolved iron (Fe) increased in most treatments, except for KNO3 addition. However, only the KNO3 application could reduce As desorption from soil minerals based on phosphate extraction. Also, KNO3 enhanced both soil catalase (S-CAT) and dehydrogenase (S-DEH) activities. Other N treatments decreased S-CAT activities, but increased S-DEH activities. Principal components analysis indicated that phosphate extractable As was associated with NH4+-N concentration and S-DEH activity, while the concentrations of soluble As and SPLP-extractable As were associated with pH, S-CAT activity, and dissolved Fe. These results demonstrated that the soil properties induced by the N application are the main drivers of As desorption in paddy soil and that KNO3 application is more eco-friendly than other N sources in As-contaminated paddy soil. This study shed light on the reasonable application of N-bearing fertilizers and the importance of soil properties to assess As mobility in As-contaminated paddy soil.

Enhancement of Soil Arsenic Mobilization through Hydrochar from Arsenic-Contaminated Boehmeria Nivea: Roles of Alkali-Modification and Soil Microbial Modulation

Enhancement of Soil Arsenic Mobilization through Hydrochar from Arsenic-Contaminated Boehmeria Nivea: Roles of Alkali-Modification and Soil Microbial Modulation