Arsenic Immobilization Research Articles

Slag-based stabilization/solidification of hazardous arsenic-bearing tailings as cemented paste backfill: Strength and arsenic immobilization assessment

The widespread occurrence of toxic arsenic in sulfidic and non-ferrous waste tailings hinders its disposal as cement paste backfill (CPB). Alkali activated slag (AAS) has recently begun to be practiced as an alternative to normal Portland cement (OPC). Nevertheless, technical information on arsenic immobilization and mechanical characteristics of arsenic-rich AAS-CPB is rather few. The impacts of activator nature, cure temperature and arsenic content on strength and arsenic immobilization of AAS-CPB explored. Despite AAS-CPB having greater strength, OPC-CPB consistently has a stronger (1.7–21.1% higher) ability to immobilize arsenic. The optimum silica modulus for maximal strength and arsenic immobilization capability depends on curing time. Strength at3 days is enhanced by higher activator doses, whereas strength at later ages (≥ 28 days) is decreased. At all curing ages, the lowest arsenic immobilization capacity is produced by medium activator concentration (0.35). Irrespective of cement type, strength increases as curing temperature rose, however OPC-CPB's strength is more responsive to temperature changes than AAS-CPB's. At room temperature (20°C), OPC-CPB has a higher (6.0–21.1% greater) arsenic immobilization efficiency (AIE) than AAS-CPB, but the opposite is true at lower (5°C) and higher (35°C) temperatures (i.e., 5.4–12.0% and 4.4–12.0% lower at 5 and 35°C respectively). Early on, the influence of arsenic content on strength is not immediately apparent, but it tends to become more obvious with longer curing times. As a role of cement type and elapsed time, high arsenic contents cause a rise or a decrease in AIE. Notably, there is no apparent connection between UCS and AIE. Electrical conductivity and moisture content can be steadily employed to portray the hydration progression of both arsenic-free and arsenic-containing CPB.

Rapid immobilization of arsenic in contaminated soils by microwave irradiation combined with magnetic biochar: Microwave-induced electron transfer for oxidation and immobilization of arsenic (III)

Biochar with adjustable redox activity is an effective strategy for immobilization of excess arsenic (As(III)) contaminated soil. However, biochar exhibits limitations in terms of electron transfer efficiency and immobilization efficiency due to insufficient activation energy. In this study, As(III) in the soil was rapidly immobilized by adding magnetic biochar (Fe-BC) and introducing microwave irradiation energy to enhance electron transport efficiency. The results showed that the pore structure and iron species (ZVI, Fe3O4) loaded onto the biochar could be modulated by controlling the temperature and time of microwave pyrolysis, which enhanced the microwave absorption capacity and the immobilization performance of As. After adding Fe-BC (10 wt%) and treating with microwave irradiation for 3 h, the content of As(III) in the soil was reduced to 54.56 %. Compared with the conventional heating treatment, the percentage of stabilized As (residual form) increased by 11.21 %. The localized hot spots formed through the absorption of microwave energy by biochar promote the formation of arsenic-containing mineral crystals (FeAsO4 and Fe3AsO7), thus enhancing the immobilization efficiency. In addition, microwave-induced electron transfer facilitated the oxidation of As(III) to As(V) by surface quinone and carbonyl groups on the Fe-BC. Density functional theory calculation further proved that the surface groups of the Fe-BC had a stronger electron-withdrawing ability under microwave irradiation, thereby promoting the adsorption and immobilization of As(III). This work provided a new perspective on the technology of rapid remediation of heavy metals contaminated soil using biochar.

Unravelling the impacts of soluble Mn(III)-NOM on arsenic immobilization by ferrihydrite or goethite under aquifer conditions

The environmental fate of arsenic (As) relies substantially on its speciation, which occurs frequently coupled to the redox transformation of manganese. While trivalent manganese (Mn(III)), which is known for its high reactivity, is believed to play a role in As mobilization by iron (oxyhydr)oxides in dynamic aquifers, the exact roles and underlying mechanisms are still poorly understood. Using increasingly complex batch experiments that mimick As-affected aquifer conditions in combination with time-resolved characterization, we demonstrate that Mn(III)-NOM complexes play a crucial role in the manganese-mediated immobilization of As(III) by ferrihydrite and goethite. Under anaerobic condition, Mn(III)-fulvic acid (FA) rapidly oxidized 31.8% of aqueous As(III) and bound both As(III) and As(V). Furthermore, Mn(III)-FA exerted significantly different effects on the adsorption of As by ferrihydrite and goethite. Mn(III)-FA increased the adsorption of As by 6–16% due to the higher affinity of oxidation-produced As(V) for ferrihydrite under circumneutral conditions. In contrast, As adsorption by crystalline goethite was eventually inhibited due to the competitive effect of Mn(III)-FA. To summarize, our results reveal that Mn(III)-NOM complexes play dual roles in As retention by iron oxides, depending on the their crystallization. This highlights the importance of Mn(III) for the fate of As particularly in redox fluctuating groundwater environments.

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.

Simultaneous immobilization of sediment internal phosphorus, arsenic and tungsten by lanthanum carbonate capping

In this study, lanthanum carbonate (LC) was selected as a capping agent to examine its effectiveness in immobilizing sediment internal phosphorus (P), arsenic (As) and tungsten (W). With a 180-day incubation experiment, it was determined that LC capping efficiently reduced the concentrations of soluble reactive P (SRP), soluble As and soluble W in pore water, with the highest reduction rate of 83.39%, 56.21% and 68.52%, respectively. The primary mechanisms involved in the adsorption of P, As and W by LC were precipitation reactions and ligand exchange. Additionally, P, As and W were immobilized by LC capping through the transformation of fractions from mobile and less stable forms to more stable forms. Furthermore, LC capping led to an increase in the Eh value, which promoted the oxidation of soluble Fe (Ⅱ) and soluble Mn. The significantly positive correlation and synchronized variations observed between SRP, soluble As, soluble W, and soluble Fe (II) indicated that the effects of LC on Fe redox played a crucial role in immobilizing sediment internal P, As and W. However, the oxidation of Mn, promoted by LC, played a more significant role in immobilizing sediment internal As than P and W. These effects resulted in LC capping achieving the highest reduction of SRP, soluble As and soluble W flux at 145.22, 22.19, and 0.58 μg m−2d−1. It is of note that LC capping did not lead to an elevated release hazard of Co, Ni, Cu, and Pb, barring Cd. Besides, LC capping did not modify the entire microbial communities in the sediment, but altered the proportional representation of specific microorganisms. Generally, LC has potential as a capping agent capable of simultaneously immobilizing sediment internal P, As and W.

Degradation of roxarsone and simultaneous immobilization of inorganic arsenic by L-cys modified FeMnNi-LDH activated persulfate system

A series of novel L-cysteine (L-cys) modified iron-manganic-nickel hydrotalcite (L-cys-LDH) were synthesized and used for heterogeneous catalytic activation of monopersulfate (PMS) to degrade roxarsone (ROX) and adsorption of released inorganic arsenic. The catalyst was characterized by TEM, XRD, FTIR, XPS, and other characterization techniques to analyze its structure and functional properties. The degradation experiment results showed that the activity of the catalyst was effectively improved after L-cys loading on LDH. In the pH range of 3–9, 0.2 g/L L-cys-LDH and 0.2 mM PMS could degrade more than 90 % of ROX in 20 min, three times higher than that of ordinary FeMnNi-LDH. Besides, the residual amount of inorganic arsenic in the solution was less than 0.01 mg/L. The electron paramagnetic resonance (EPR) test and quenching investigation identified surface-bound SO4-· and surface-bound ·OH as the main contributors to organic degradation. Mechanism studies have shown that cysteine embedded in LDH accelerated the conversion rate of Fe(III)/Mn(III) to Fe(II)/Mn(II) by self-oxidation to cystine, thereby improving the efficiency of catalyst activation of PMS. In addition, the main degradation products were obtained by LC-MS analysis, and the possible pathway of ROX degradation was given in L-cys-LDH/PMS system combined with DFT theoretical calculation. The work showed that L-cys-LDH exhibited excellent catalytic performance and inorganic arsenic adsorption capacity. It provides an idea for the improvement of hydrotalcite-based catalysts. It also sheds some light on the degrade of novel hydrotalcite-based catalysts for the one step degradation and adsorption of ROX.

Predicting the efficiency of arsenic immobilization in soils by biochar using machine learning

Arsenic (As) pollution in soils is a pervasive environmental issue. Biochar immobilization offers a promising solution for addressing soil As contamination. The efficiency of biochar in immobilizing As in soils primarily hinges on the characteristics of both the soil and the biochar. However, the influence of a specific property on As immobilization varies among different studies, and the development and application of arsenic passivation materials based on biochar often rely on empirical knowledge. To enhance immobilization efficiency and reduce labor and time costs, a machine learning (ML) model was employed to predict As immobilization efficiency before biochar application. In this study, we collected a dataset comprising 182 data points on As immobilization efficiency from 17 publications to construct three ML models. The results demonstrated that the random forest (RF) model outperformed gradient boost regression tree and support vector regression models in predictive performance. Relative importance analysis and partial dependence plots based on the RF model were conducted to identify the most crucial factors influencing As immobilization. These findings highlighted the significant roles of biochar application time and biochar pH in As immobilization efficiency in soils. Furthermore, the study revealed that Fe-modified biochar exhibited a substantial improvement in As immobilization. These insights can facilitate targeted biochar property design and optimization of biochar application conditions to enhance As immobilization efficiency.

Arsenic Immobilization for Paddy Field and Improvement of Rice (Oryza sativa L.) Growth through Cerium–Manganese Modified Wheat Straw Biochar Application

Arsenic (As) frequently emerges in paddy soils, necessitating measures to combat soil pollution and protect rice crops from As contamination. In this study, a novel functional biochar (MBC) by loading cerium manganese oxide was prepared, and its effects on soil As immobilization and As uptake by rice in two different As-contaminated paddy soils of 68.99 and 158.52 mgAs·kg−1 (marked as soil-L and soil-H, respectively) were detected. The pot experiment manifested that MBC performed better in stabilizing soil As than original biochar. The incorporation of MBC facilitated the conversion of soil active As to the stable state, promoted the growth of rice plants, and reduced As uptake by rice. Specifically, the total plant biomasses for MBC treatment were increased by 16.13–70.07% and 12.36–92.58% in soil-L and soil-H compared with CK (without material input), respectively. MBC treatments resulted in a reduction of As contents by 34.67–60.13% in roots, 43.68–66.90% in stems, and 54.72–64.65% in leaves for soil-L. Furthermore, in soil-H, the As content in rice roots, stems, and leaves showed a decrease by 49.26–79.03%, 87.10–94.63%, and 75.79–85.71% respectively. This study provides important insights for the remediation of As-contaminated paddy soil using MBC.

Simultaneous immobilization of lead, cadmium and arsenic in soil by iron-manganese modified biochar

Cationic lead/cadmium and anionic arsenic exhibit opposite geochemical behaviors in soils, which makes the synchronous remediation of As, Cd, and Pb challenging. In this study, we developed an iron-manganese modified biochar (BC-Fe-Mn) that prepared from straw with iron (Fe) and manganese (Mn) loading at a pyrolysis temperature of 550 °C. After BC-Fe-Mn immobilization for 90 days, the simultaneous immobilization efficiency of Pb, Cd, and As reached 57%, 51%, and 35%, respectively. Speciation distributions shows that As transformed from specific bound state into weakly low crystallinity iron bound state. Cd transformed from carbonate fraction into Fe-Mn oxide bound fraction, and Pb transformed from carbonate fraction into residual state. During the procedure, simultaneous immobilization mechanisms might involve heavy metal morphological transformation, precipitation/co-precipitation, and surface complexation. Cd and Pb absorbed onto BC-Fe-Mn. Then the increased free iron oxides (Fed) reacted with the dissolved As to form iron-arsenic precipitation. The results show that BC-Fe-Mn is a promising material for the simultaneous immobilization of Pb, Cd, and As in multi-metal contaminated soil.

Immobilizing arsenic in contaminated anoxic aquifer sediment using sulfidated and uncoated zero-valent iron (ZVI)

Arsenic (As) is carcinogenic and of major concern in groundwater. We collected sediment material from a contaminated anoxic aquifer in Sweden and investigated the immobilization of As by four commercial zero-valent iron (ZVI) particles. Solid-phase As and Fe speciation was assessed using X-ray absorption spectroscopy (XAS) and solution-phase As speciation using chromatographic separation. Without ZVI addition, arsenite dominated in solution and As(V) species in the solid phase. Adding ZVI caused a sharp increase in solution pH (9.3–9.8), favoring As oxidation despite a lowered redox potential. ZVI greatly improved As retention by complex binding of arsenate to the Fe(III) (hydr)oxides formed by ZVI corrosion. Uncoated ZVI, both in nano- and microscale, performed better than their sulfidated counterparts, partly due to occlusion of As by the Fe(III) (hydr)oxides formed. The effect of particle size (micro vs. nano ZVI) on As immobilization was small, likely because immobilization was related to the corrosion products formed, rather than the initial size of the particles. Our results provide a strong geochemical background for the application of ZVI particles to remove As in contaminated aquifers under anoxic conditions and illustrate that immobilization mechanisms can differ between ZVI in As spiked solutions and sediment suspensions. Environmental implicationArsenic ranks first on the list by the US ATSDR of substances posing a threat to human health and the WHO considers groundwater the riskiest source for human intake of As. However, dealing with As contamination remains a scientific challenge. We studied the immobilization of groundwater As by commercially available ZVI particles at field-realistic conditions. Arsenic immobilization was highly efficient in most cases, and the results suggest this is a promising in situ strategy with long-term performance. Our results provide a strong geochemical background for using ZVI to remove As in contaminated anoxic aquifers.

Immobilization of arsenic in soil using modified bentonite and red mud to reduce its bio-availability in Brassica juncea

The influence of modified clay mineral and red mud on biological yield and arsenic bioavailability to mustard were investigated. The total biomass of the mustard was increased by application of clay mineral and red mud products. At higher doses (5.00 g/kg), Fe-bentonite treated soil recorded the highest total plant biomass (11.2 g/pot). DMSO-bentonite (1.23 mg/kg) and Fe-bentonite (1.28 mg/kg) were proved to be most effective in reducing the extractable arsenic concentration in soil at the rate of 5.00 g/kg doses. These products also help in lowering the hazard quotient (0.20–0.08) values for human consumption of arsenic through mustard leaf. This means that modified types of bentonites and red mud boost mustard productivity by reducing arsenic concentration.

Unraveling the aging dynamics in the simultaneous immobilization of soil metal(loid)s using oxides

Immobilization represents the most extensively utilized technique for the remediation of soils contaminated by heavy metals and metalloids. However, it is crucial to acknowledge that contaminants are not removed during this process, thereby leaving room for potential mobilization over time. Currently, our comprehension of the temporal variations in immobilization efficacy, specifically in relation to amendments suitable for industrial sites, remains very limited. To address this knowledge gap, our research delved into the aging characteristics of diverse oxides, hydroxides, and hydroxy-oxides (collectively referred to as oxides) for the simultaneous immobilization of arsenic (As), cadmium (Cd), and antimony (Sb) in soils procured from 16 contaminated industrial sites. Our findings unveiled that Ca-oxides initially showed excellent immobilization performance for As and Sb within 7 days but experienced substantial mobilization by up to 71 and 13 times within 1 year, respectively. In contrast, the efficacy of Cd immobilization by Ca-oxides was enhanced with the passage of time. Fe- and Mg-oxides, which primarily operate through encapsulation or surface complexation, exhibited steady immobilization performances over time. This reliable and commendable immobilization effect was observed across distinct soils characterized by varying physicochemical properties, including pH, texture, CEC, TOC, and EC, underscoring the suitability of such amendments for immobilizing metal(loid)s in diverse soil types. MgO, in particular, displayed even superior immobilization performance over time, owing primarily to gradual hydration and physical entrapment effects. Remarkably, Mg-Al LDHs emerged as the most effective candidate for the simultaneous immobilization of As, Cd, and Sb. The results obtained from this study furnish valuable data for future investigations on the immobilization of metals and metalloids in industrial soils. They enable the projection of immobilization performance and offer practical guidance in selecting suitable amendments for the immobilization of metal(loid)s.

In-situ immobilization of arsenic and antimony containing acid mine drainage through chemically forming layered double hydroxides

Acid mine drainage (AMD) rich in arsenic (As) and antimony (Sb) is considered as a significant environmental challenge internationally. However, simultaneous removal of As and Sb from AMD is still inadequately studied. In this study, a highly effective and simple approach was proposed for mitigating As and Sb-rich AMD, which involves in-situ formation of layered double hydroxides (LDHs). Following the treatment, the residual concentrations of iron (Fe), magnesium (Mg), sulfate, As and Sb in field AMD were decreased from their initial concentrations of 1690, 1524, 2055, 7.8 and 10.6 mg L−1, respectively, to 1.3, 12.4, 623, 0.006 and 0.004 mg L−1, respectively. Chemical formula of the resulting As and Sb-loaded LDHs can be identified as Mg4.226Fe2.024OH2SO4AsSb0.006∙mH2O. The dissolution rates of metal(loid)s in As and Sb-loaded LDH were lower than 1% under strongly acidic and alkaline environments. In presence of the mixed adsorbates, the As immobilization capacity by LDHs was significantly decreased, with an apparent intervention from Sb. However, As did not have a significant effect on the immobilization of Sb by LDH. As was immobilized by LDHs through anion exchange and complexation with —OH groups, while Sb was captured by anion exchange and complexation with MgH2O62+. Density functional theory (DFT) calculations further proved the above conclusions. This novel approach is effective and can be applied for in-situ AMD treatment from abandoned mines.

Modified Biochar for Arsenic Immobilization in Soil: A Critical Review

Modified Biochar for Arsenic Immobilization in Soil: A Critical Review

Effects of four amendments on cadmium and arsenic immobilization and their exposure risks from pakchoi consumption

Exposure to heavy metal(loid)s (HM) through contaminated food chains poses significant health risks to humans. While soil amendments are known to reduce HM bioavailability, their effects on bioaccessibility and health risks in soil-pakchoi-human systems remain unclear. To address this knowledge gap, we conducted a greenhouse pot experiment coupling soil immobilization with bioaccessibility-based health risk assessment for Cd and As exposure from pakchoi consumption. Four amendments (attapulgite, shell powder, nanoscale zero-valent iron, and biochar) were applied to soil, resulting in changes to soil characteristics (pH and organic matter), plant dry weight, and exchangeable fractions of As and Cd. Among the tested amendments, biochar exhibited the highest effectiveness in reducing the risk of Cd and As exposure from pakchoi consumption. The bioaccessibility-based health risk assessment revealed that the application of 5% biochar resulted in the lowest hazard index, significantly decreasing it from 1.36 to 0.33 in contaminated soil. Furthermore, the structural equation model demonstrated that pH played a critical role in influencing remediation efficiency, impacting the exposure of the human body to Cd and As. In conclusion, our study offers a new perspective on mitigating exposure risks of soil HM and promoting safe crop production. The results underscore the importance of considering bioaccessibility in health risk assessment and highlight the potential of biochar as a promising amendment for reducing Cd and As exposure from pakchoi consumption.

Immobilizing arsenic-enriched wastewater from utilization of crude antimony oxides as scorodite using a novel multivalent iron source

Arsenic–enriched wastewater (A–EW) is a hypertoxic sewage from the utilization of crude antimony oxides in lead anode slime metallurgy. In traditional methods, the H+ accumulation inhibits the arsenic immobilization during scorodite synthesis. In this study, a novel multivalent iron source comprised of Fe(OH)3 and FeSO4·7H2O was proposed to resolve the adverse effects of pH fluctuation during immobilizing A–EW as scorodite. Various approaches, such as scanning electron microscopy and X–ray photoelectron spectroscopy, were applied to characterize the synthesized scorodite. This work was divided into two parts. In thermodynamics, HnAsO4(3−n)- (n = 1, 2, 3) and Fe(OH)n(3−n)+ (n = 0, 1, 2, 3) can feasibly coprecipitate as scorodite according to their △rGm,Tθ ranged from −111.10 kJ mol−1 to −33.53 kJ mol−1. In experimental research, A–EW was immobilized as scorodite by optimizing conditions as initial pH = 2.0, molar ratio of Fe to As = 1.2, molar ratio of Fe(II) to Fe(III) = 4:6, arsenic concentration = 40 g/L, and temperature = 95 °C. The arsenic precipitation ratio is 99.60%, and the micromorphology of synthesized scorodite presents a regular octahedron having size of 5–10 μm. The low leachability of As (0.41 mg/L) in toxicity characteristic leaching procedure (TCLP) confirmed that the prepared scorodite is nonhazardous. The solution pH is stable at 2.0 as the H+ depletion (0.5660 mol) by Fe(OH)3 dissolution and Fe2+ oxidization balanced with that (0.5657 mol) generated from As(V)–Fe(III) coprecipitation. In general, the A–EW was effectively immobilized by proposed multivalent iron source, and can be potentially applied to safely dispose other industrial effluents, such as high arsenic leachates and arsenic–bearing waste acid from nonferrous metallurgy.

Exploring the effect of isomorphically Al-substituted on the thermodynamical and structural properties of hematite and goethite – A DFT investigation

Hematite (Hem) and Goethite (Goe) are the two most abundant iron oxides in the natural environment. The formation of isomorphically Al-substituted iron oxyhydroxides is observed in many geochemical processes and synthetic samples. The Al-substituted minerals have been pointed out as a key point in the arsenic immobilization in tailing dams rich in latosols. The structural and thermodynamic properties of the formation of Al-substituted Hem and Goe have been investigated based on Density Functional calculations. Exploratory analysis based on Cluster Expansion (CE) of Al-substitution in Goe and Hem demonstrate that the Al substitution is mostly a local phenomenon and independent of the degree of substitution reached. This is corroborated with the cohesive energy of Al-bearing systems which lies in a linear correlation with the Al content. The structural changes upon Al-substitution were detailed discussed. The formation free energies of the Al-bearing systems were estimated based on the DFT calculations combined with the reported experimental data. The effect of pH, Al/Fe ratio, concentration and humidity on the formation free energies have been analyzed and discussed. The pristine Goe and Hem are favored in comparison with the Al-bearing systems for all conditions analyzed. This reinforces that the separation in two phases – one Al rich and other Fe rich – is the thermodynamic favored process and the presence of natural samples of Al-substituted Hem and Goe is controlled by kinetic factors at geochemical timescales.

Enhanced immobilization of Arsenic(III) and Auto-oxidation to Arsenic(V) by titanium oxide (TiO2), due to Single-Atom vacancies and oxyanion formation

Pollution control of As(III), a naturally occurring carcinogen, has recently gained a global attention, while due to the dominance of neutral H3AsO3 over a wide pH range, As(III) immobilization by most minerals is not efficient as As(V) immobilization. TiO2 shows promise for controlling As(III) pollution, and herein, a comprehensive study about As(III) adsorption by TiO2 and oxyanion formation is conducted by means of DFT + D3 methods. Both anatase and rutile are effective for As(III) adsorption, while As(III) adsorption affinities differ significantly and are −1.48 and −3.79 eV for pristine surfaces, ascend to −3.85 and −5.08 eV for O vacancies, and further to −5.37 and −5.26 eV for Ti vacancies, respectively. The bidentate binuclear complexes dominate for pristine surfaces, and O vacancies prefer OAs insertion into TiO2 lattice, while for Ti vacancies, all As(III) centers are auto-oxidized to As(V). Ti-3d, O-2p or/and As-4p rather than other orbitals contribute significantly to As adsorption, and O and Ti vacancies promote adsorption through stronger orbital hybridization. The superior adsorption for Ti vacancies originates from As(V) formation instead of bonding interactions. The formation of As oxyanions, which may occur spontaneously at pristine surfaces and is greatly promoted by O and Ti vacancies, enhances As(III) adsorption pronouncedly and becomes a viable strategy for As(III) immobilization. H2AsO3- and HAsO32- dominate for pristine surfaces and O vacancies, and for Ti vacancies, H2AsO4- and HAsO42- dominate over anatase whereas AsO43- also makes an important contribution over rutile. Results rationalize experimental observations available, and provide significantly new insights about the migration, bioavailability and fate of As(III) over TiO2 surfaces that facilitate the exploration of scavengers for As and other pollutants.

Simultaneous immobilization of lead and arsenic and improved phosphorus availability in contaminated soil using biochar composite modified with hydroxyapatite and oxidation: Findings from a pot experiment

Multi-metals/metalloids contaminated soil has received extensive attention because of their adverse health effects on the safety of the food chain and environmental health. In order to provide additional insight and aid in mitigating environmental risks, a pot experiment was directed to assess the impacts of biochars derived from rice straw (BC), and modified biochars i-e., hydroxyapatite modified (HAP-BC) and oxidized biochars (Ox-BC) on the redistribution, phytoavailability and bioavailability of phosphorus (P), lead (Pb), and Arsenic (As), as well as their effects on the growth of maize (Zea mays L.) in a Lead (Pb)/Arsenic (As) contaminated soil. The results showed that HAP-BC increased the soil total and available P, compared with raw biochar and control treatment. HAP-BC improved soil properties by elevating soil pH and electric conductivity (EC). The Hedley fractionation scheme revealed that HAP-BC enhanced the labile and moderately labile P species in soil. Both HAP-BC and Ox-BC assisted in the P build-up in plant roots and shoots. The BCR (European Community Bureau of Reference) sequential extraction data for Pb and As in soil showed the pronounced effects of HAP-BC towards the transformation of labile Pb and As forms into more stable species. Compared with control, HAP-BC significantly (P ≤ 0.05) decreased the DTPA-extractable Pb and As by 55% and 28%, respectively, subsequently, resulting in reduced Pb and As plant uptakes. HAP-BC application increased the plant fresh and dry root/shoot biomass by 239%, 72%, 222% and 190%, respectively. The Pb/As immobilization by HAP-BC was mainly driven by precipitation, ion exchange and surface complexation mechanisms in soil. In general, HAP-BC application indicated a great capability to be employed as an effective alternative soil amendment for improving P acquisition in soil, simultaneously immobilizing Pb and As in the soil-plant systems.

Immobilization capacity assessment of a binder from arsenic-containing biohydrometallurgy waste: Effects of halloysite nanotubes and biochar addition

The aim of this study was to improve the immobilization capacity of a binder prepared from As-containing biohydrometallurgy waste (BAW) on arsenic (As) by modifying it with halloysite nanotubes (HNTs) and biochar (BC). The study investigated the influence of HNTs and BC on the chemical fractions and leaching characteristics of As, as well as the influence on the compressive strength of BAW. The results indicated that the addition of HNTs and BC effectively decreased As leaching. The presence of 1.0 wt% HNTs decreased the As leaching concentration from 1.08 mg/L to 0.15 mg/L, with the corresponding immobilization rate reaching about 90.9 %. A high amount of BC seemed to show better performance in improving the As immobilization capacity of BAW. However, a strongly reduced early compressive strength of BAW was observed, making it unsuitable to be used as an additive in this situation. The effects of HNTs on the increase of As immobilization capacity of BAW were attributed to two aspects. Firstly, As species were adsorbed onto the surface of HNTs via H-bonds, which was verified via density functional theory calculation. Secondly, the addition of HNTs decreased the pore volume of BAW, leading to a more compact structure, and hence increasing the physical encapsulation capacity for As. Environmental implicationThe rational disposal of arsenic-containing biohydrometallurgy waste has always been a top priority for the green and low-carbon development of the metallurgical industry. In this article, we have taken the perspective of large-scale resource utilization of solid waste and pollution control, and developed arsenic-containing biohydrometallurgy waste into a cementitious material, and enhancing arsenic immobilization capacity with the addition of HNTs and BC. This study provides an effective method for the rational disposal of arsenic-containing biohydrometallurgy waste.