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.

Time-varying contributions of FeII and FeIII to AsV immobilization under anoxic/oxic conditions: The impacts of biochar and dissolved organic carbon.

Engineering black carbon (e.g. biochar) has been widely found in natural environments due to natural processes and extensive applications in engineering systems, and could influence the geochemical processes of coexisting arsenic (AsV) and FeII, especially when they are exposed to oxic conditions. Here, we studied time-varying kinetics and efficiencies of AsV immobilization by solid-phase FeII (FeIIsolid) and FeIII (FeIIIsolid) in FeII-AsV-biochar systems under both anoxic and oxic conditions at pH 7.0, with focuses on the effects of biochar surface and biochar-derived dissolved organic carbon (DOC). Under anoxic conditions, FeII could rapidly immobilize AsV via co-adsorption onto biochar surfaces, which also serves as the dominant pathway of AsV immobilization at the initial stage of reaction (0-5 min) under oxic conditions at high biochar concentrations. Subsequently, with increasing biochar concentrations, FeIIIsolid precipitation from aqueous FeII (FeIIaq) oxidation (5-60 min) starts to play an important role in AsV immobilization but in decreased efficiencies of AsV immobilization per unit iron. In the following stage (60-300 min), FeIIsolid oxidation is suppressed and leads to AsV release into solutions at >1.0 g·L-1 biochar. The decreasing efficiency of AsV immobilization over time is attributed to the gradual release of DOC into solution from biochar particles, which significantly inhibit AsV immobilization when FeIIIsolid is generated from FeIIsolid oxidation in the vicinity of biochar surfaces. Specifically, 4.06 mg·L of biochar-derived DOC can completely inhibit the immobilization of AsV in the 100 µM FeII system under oxic conditions. The findings are crucial to comprehensively understand and predict the behavior of FeII and AsV with coexisting engineering black carbon in natural environments.

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.

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.

Magnetite enhances As immobilization during nitrate reduction and Fe(II) oxidation by Acidovorax sp. strain BoFeN1.

Arsenic (As) cycling in groundwater is commonly coupled to the biogeochemical cycling of iron (Fe) and the associated transformation of Fe minerals present. Numerous laboratory studies suggested that Fe minerals can act as nucleation sites for further crystal growth and as catalysts for abiotic Fe(II) oxidation. In view of the widespread existence of magnetite in anoxic environments where As is often dissolved, we firstly exploited magnetite to enhance As immobilization during nitrate-reducing Fe(II) oxidation (NRFO) induced by Acidovorax sp. strain BoFeN1, a mixotrophic nitrate-reducing Fe(II)-oxidizing bacterium that can oxidize Fe(II) through both enzymatic and abiotic pathways. Subsequently, we investigated how magnetite affects NRFO and As immobilization. Results demonstrated a significant increase in As(III) removal efficiency from 75.4 % to 97.2 % with magnetite, attributed to the higher amount of NRFO and As(III) oxidation promoted by magnetite. It was found that magnetite stimulated the production of extracellular polymeric substances (EPS), which could decrease the diffusion of nitrate in the periplasm of bacteria and shield them against encrustation, resulting in a more rapid reduction of nitrate in the system with magnetite than that without magnetite. Meanwhile, Fe(II) was almost completely oxidized in the presence of magnetite during the whole 72 h experiment, while in the absence of magnetite, 47.7 % of Fe(II) remained, indicating that magnetite could obviously accelerate the chemical oxidation of Fe(II) with nitrite (the intermediates of nitrate bioreduction). Furthermore, the formation of labile Fe(III), an intermediate product of electron transfer between Fe(II) and magnetite, was reasonably deduced to be vital for anoxic As(III) oxidation. Additionally, the XPS analysis of the solid phase confirmed the oxidation of 43.8 % of As(III) to As(V). This study helps to understand the biogeochemical cycling of Fe and As in the environment, and provides a cost-effective and environmentally friendly option for in situ remediation of As-contaminated groundwater.

Sustaining Irrigation Supplies through Immobilization of Groundwater Arsenic In Situ.

Geogenic arsenic (As) in groundwater is widespread, affecting drinking water and irrigation supplies globally, with food security and safety concerns on the rise. Here, we present push-pull tests that demonstrate field-scale As immobilization through the injection of small amounts of ferrous iron (Fe) and nitrate, two readily available agricultural fertilizers. Such injections into an aquifer with As-rich (200 ± 52 µg/L) reducing groundwater led to the formation of a regenerable As reactive filter in situ, producing 15 m3 of groundwater meeting the irrigation water quality standard of 50 µg/L. Concurrently, sediment magnetic properties were markedly enhanced around the well screen, pointing to neo-formed magnetite-like minerals. A reactive transport modeling approach was used to quantitatively evaluate the experimental observations and assess potential strategies for larger-scale implementation. The modeling results demonstrate that As removal was primarily achieved by adsorption onto neo-formed minerals and that an increased adsorption site density coincides with the finer-grained textures of the target aquifer. Up-scaled model simulations with 80-fold more Fe-nitrate reactants suggest that enough As-safe water can be produced to irrigate 1000 m2 of arid land for one season of water-intense rice cultivation at a low cost without causing undue contamination in surface soils that threatens agricultural sustainability.

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.

Selenium-oxidizing Agrobacterium sp. T3F4 decreases arsenic uptake by Brassica rapa L. under a native polluted soil.

Toxic arsenic (As) and trace element selenium (Se) are transformed by microorganisms but their complex interactions in soil-plant systems have not been fully understood. An As- and Se- oxidizing bacterium, Agrobacterium sp. T3F4, was applied to a native seleniferous As-polluted soil to investigate As/Se uptake by the vegetable Brassica rapa L. and As-Se interaction as mediated by strain T3F4. The Se content in the aboveground plants was significantly enhanced by 34.1%, but the As content was significantly decreased by 20.5% in the T3F4-inoculated pot culture compared to the control (P < 0.05). Similar result was shown in treatment with additional 5 mg/kg of Se(IV) in soil. In addition, the As contents in roots were significantly decreased by more than 35% under T3F4 or Se(IV) treatments (P<0.05). Analysis of As-Se-bacterium interaction in a soil simulation experiment showed that the bioavailability of Se significantly increased and As was immobilized with the addition of the T3F4 strain (P < 0.05). Furthermore, an As/Se co-exposure hydroponic experiment demonstrated that As uptake and accumulation in plants was reduced by increasing Se(IV) concentrations. The 50% growth inhibition concentration (IC50) values for As in plants were increased about one-fold and two-fold under co-exposure with 5 and 10 µmol/L Se(IV), respectively. In conclusion, strain T3F4 improves Se uptake but decreases As uptake by plants via oxidation of As and Se, resulting in decrease of soil As bioavailability and As/Se competitive absorption by plants. This provides a potential bioremediation strategy for Se biofortification and As immobilization in As-polluted soil.

[Mechanism and Environmental Effect on Nitrogen Addition to Microbial Process of Arsenic Immobilization in Flooding Paddy Soils].

China is one of the largest rice producers in the world, and rice production plays an important role in food security. Currently, arsenic pollution in paddy soils is one of most serious soil pollutions in China. Since paddy soils are maintained in a flooding anoxic condition for long periods, the rate and extent of arsenic transformation processes governed by microbial activities are stronger than that of chemical processes. Thus, understanding the key processes and relating mechanisms of microbial arsenic fixation in paddy soils will provide a theoretical basis for controlling arsenic pollution in paddy soils. In this study, based on a comprehensive analysis of arsenic migration in paddy soils and relating influencing factors, two important pathways relating to As(Ⅲ) fixation through microbial activities were illustrated:microbial CFe(Ⅱ) oxidation coupled with As(Ⅲ) fixation (indirect process) and direct fixation through microbial As(Ⅲ) oxidation (direct process). Additionally, the influences of speciation and the distribution of nitrogen in paddy soils to the processes of microbial arsenic fixations were discussed and by extension, the expressions of key genes and metabolic mechanisms relating to microbial arsenic fixation and nitrogen transformation. Finally, the recent advances in microbial remediation used to control arsenic pollution in paddy soils were summarized, and relating future perspectives targeting microbial remediation were proposed.

Release and fate of As mobilized via bio-oxidation of arsenopyrite in acid mine drainage: Importance of As/Fe/S speciation and As(III) immobilization.

Mining activities expose sulfidic minerals including arsenopyrite (FeAsS) to acid mine drainage (AMD). The subsequent release of toxic arsenic (As) can have great negative implications for the environment and human health. This study investigated the evolution of secondary products and As speciation transformations during arsenopyrite bio-oxidation in AMD collected from a polymetallic mine. Immobilization of the As solubilized via arsenopyrite bio-oxidation using red mud (RM) was also studied. The results show that the high ionic strength (concentrations of dissolved Fe3+, SO42-, and Ca2+ reached values up to 0.75, 3.38, and 0.35 g/L, respectively) and redox potential (up to +621 mV) of AMD (caused primarily by Fe3+) enhanced the dissolution of arsenopyrite. A high [Fe]aq/[As]aq ratio in the AMD favored the precipitation of tooeleite during arsenopyrite bio-oxidation, and the formation of other poorly crystalline products such as schwertmannite and amorphous ferric arsenate also contributed to As immobilization. Bacterial cells served as important nucleation sites for the precipitation of mineral phases. Arsenopyrite completely dissolved after 12 days of bio-oxidation in AMD and the [As]aq (mainly present as As(III)) reached 1.92 g/L, while a greater [As]aq was observed in a basal salts medium (BSM) assay (reaching 3.02 g/L). An RM addition significantly promoted As(III) immobilization, with final [As(III)]aq decreasing to 0.16 and 1.43 g/L in AMD and BSM assays respectively. No oxidation of As(III) was detected during the immobilization process. These findings can help predict As release from arsenopyrite on contact with AMD and, on a broader scale, assist in designing remediation and treatment strategies to mitigate As contamination in mining.

Arsenic removal characteristics of natural Mn-Fe binary coating on waste filter sand from a water treatment facility.

In this study, the arsenic (As) removal characteristics of a Mn-Fe binary coating formed on waste sand filter of an acid mine drainage treatment facility are investigated. Owing to the Mn-Fe binary coating forming on the surfaces of the sand grains, its potential for arsenic removal, particularly As(III), was evaluated and characterized through batch experiments and x-ray absorption spectroscopy. Sorption isotherms reveal that the Mn-Fe binary coating exhibits comparable removal efficiencies for As(III) and As(V) under low initial As concentrations. However, at higher initial As(III) and As(V) concentrations, the As(III) removal efficiency increases because of newly formed active adsorption sites from reductive dissolution of Mn. The oxidation of the As(III) and reduction of the Mn oxide phases are verified through As K-edge and Mn K-edge X-ray absorption near edge fine structure analysis. The outstanding As(III) removal efficiency of the Mn-Fe binary coating suggests synergy of Fe- and Mn-oxides, highlighting a potential application for this coating system. The natural formation of binary coating through acid mine drainage treatment reported in this study indicates that similar coating can form naturally in other environments, thus, providing plausible natural attenuation processes for arsenic immobilization.

A novel arsenic immobilization strategy via a two-step process: Arsenic concentration from dilute solution using schwertmannite and immobilization in Ca-Fe-AsO4 compounds.

Acid mine drainage (AMD) with toxic arsenic (As) is commonly generated from the tailings storage facilities (TSFs) of sulfide mines due to the presence of As-bearing sulfide minerals (e.g., arsenopyrite, realgar, orpiment, etc.). To suppress As contamination to the nearby environments, As immobilization by Ca-Fe-AsO4 compounds is considered one of the most promising techniques; however, this technique is only applicable when As concentration is high enough (>1 g/L). To immobilize As from wastewater with low As concentration (~10 mg/L), this study investigated a two-step process consisting of concentration of dilute As solution by sorption/desorption using schwertmannite (Fe8O8(OH)8-2x(SO4)x; where (1 ≤ x ≤ 1.75)) and formation of Ca-Fe-AsO4 compounds. Arsenic sorption tests indicated that As(V) was well adsorbed onto schwertmannite at pH 3 (Qmax = 116.3 mg/g), but its sorption was limited at pH 13 (Qmax = 16.1 mg/g). A dilute As solution (~11.2 mg/L As) could be concentrated by sorption with large volume of dilute As solution at pH 3 followed by desorption with small volume of eluent of which pH was 13. The formation of Ca-Fe-AsO4 compounds from As concentrate solution (2 g/L As(V)) was strongly affected by temperature and pH. At low temperature (25-50 °C), amorphous ferric arsenate was formed, while at high temperature (95 °C), yukonite (Ca2Fe3-5(AsO4)3(OH)4-10·xH2O; where x = 2-11) and johnbaumite (Ca5(AsO4)3OH) were formed at pH 8 and 12, respectively. Among the synthesized products, johnbaumite showed strongest As retention ability even under acidic (pH < 2) and alkaline (pH > 9) conditions.

Sustainable stabilization/solidification of arsenic-containing soil by blast slag and cement blends.

Arsenic (As) is a naturally occurring trace element that may pose a threat to human health and the ecosystem, while effective remediation and sustainable reuse of As-containing soil is a challenge. This study investigated the geoenvironmental characteristics of a geogenic As-rich soil, and green binders (ground granulated blast slag (GGBS) and cement blends) were employed for the stabilization/solidification (S/S) of the soil under field-relevant conditions. Results indicate that the use of 10% binder could effectively immobilize As and chemical stabilization/physical encapsulation jointly determined the leaching characteristics of the S/S soils. The geogenic As could be effectively immobilized at the pH range of 5.5-6.5. The increasing use of GGBS enhanced the strength of the 28-d cured S/S soils because of long-term pozzolanic reaction, but also slightly improved the As leachability. Besides, the moisture content of the contaminated soils should be suitably adjusted to allow for desirable compaction of S/S soils, which resulted in high compressive strength and low of As leachability. Results show that soil moisture content of 20% was the most appropriate, which resulted in the highest strength and relatively lower As leaching. In summary, this study presents a sustainable S/S binder for recycling As-contaminated soil by using a combination of cement and GGBS.

Simulated solar light driven Fe(III)/Fe(II) redox cycle for roxarsone degradation and simultaneous arsenate immobilization.

Organoarsenicals remediation requires degrading organoarsenicals and simultaneously immobilizing the resulted inorganic arsenic, and is thus a great challenge. In this study, a simulated solar light driven Fe(III)/Fe(II) cycle strategy was developed to degrade roxarsone and immobilize the generated inorganic arsenic via tuning the degree of Fe(III) hydrolysis. At pH values of 2.0 and 3.0, the hydrolysis of Fe(III) in the solution was suppressed to produce photoreactive Fe(III)-hydroxyl complexes, which could be excited by simulated solar light to generate OH for 85.3 % of roxarsone degradation into arsenate within 60 min. Density functional theory calculations suggested that Fe(OH)(H2O)52+ with lower energy separation gap was the most photoactive Fe(III)-hydroxyl complex for OH generation. With further increasing pH value to 6.0, the hydrolysis of Fe(III) was promoted to precipitate the arsenate for its immobilization, accompanying with the decrease of final iron ions and arsenate concentrations to 0.012 mmol L-1 and 58 µg L-1, respectively. Meanwhile, the undegraded roxarsone was also adsorbed by the precipitate, increasing the overall roxarsone removal efficiency to 99.0 %. This study offers a promising strategy for the efficient organoarsenicals treatment, and also sheds light on the dual effects of iron based materials in organic pollutants degradation and heavy metal ions immobilization.

Humic acid promotes arsenopyrite bio-oxidation and arsenic immobilization.

The bio-oxidative dissolution of arsenopyrite, the most severe arsenic contamination source, can be mediated by organic substances, but pertinent studies on this subject are scarce. In this study, the bio-oxidative dissolution of arsenopyrite by Sulfobacillus thermosulfidooxidans and arsenic immobilization were evaluated in the presence of humic acid (HA). The mineral dissolution was monitored through analyses of the parameters in solution, phase and element speciation transformations on the mineral surface, and arsenic immobilization on the surfaces of cells and jarosites-HA. The results show that the presence of HA enhances the dissolution of arsenopyrite, e.g., 7.1% of arsenopyrite was in the residue after 12 d of bio-oxidation compared to 19.3% in the absence of HA. Meanwhile, the presence of HA led to changes of the fates of As and Fe and no accumulation of elemental sulfur (S0) or ferric arsenate on the mineral surface. Moreover, a flocculent porous structure was formed on the surfaces of both microbial cells and jarosites, on which a large amount of arsenic was adsorbed. These results clearly indicate that HA can simultaneously promote the dissolution of arsenopyrite and arsenic immobilization, which may be significant for bioleaching of arsenopyrite-bearing contaminated sites.

Arsenic immobilization through regulated ferrolysis in paddy field amendment with bismuth impregnated biochar.

Iron minerals are important for arsenic immobilization in paddy fields; however, intensive ferrolysis causes arsenic (As) release. Bismuth-impregnated biochar derived from wheat straw (BiBC) was synthesized to immobilize arsenic by regulating the ferrolysis process in a paddy field. Further X-ray based analysis (XRD and XPS) results demonstrated that crystal particles of bismuth oxide and bismuth oxychloride were loaded on the biochar surface, helped create additional micropores and improved its specific surface area. The bioavailability of As, as determined via (non)specifically adsorbed As, decreased as the amended dosage of BiBC increased, while wheat straw biochar (WBC) resulted in arsenic release. The presence of biochar caused a faster reduction rate of iron oxides; however, BiBC promoted the sequential co-precipitation of iron and arsenic ions. Adsorption kinetic experiments indicated that ferrous ions facilitated precipitation of As on the surface of BiBC. The XRD analysis of soil samples showed BiBC facilitated the formation/stability of FeOOH. Thus, amendment with BiBC regulated ferrolysis to buffer iron leaching, which contributed to arsenic immobilization under flooding conditions. This study demonstrated the feasibility of As immobilization by metal-impregnated biochar in paddy soils.

The influence of irrigation-induced water table fluctuation on iron redistribution and arsenic immobilization within the unsaturation zone.

Given the long-term potential risk of arsenic (As)-contaminated agricultural soil to public health, the redistribution of iron (Fe) and immobilization of As within the unsaturation zone during irrigation and consequent water table fluctuations were studied via a column experiment and corresponding geochemical modeling. Experimental results show that As and Fe accumulated significantly at the top of the column during irrigation. A tremendous increase in As and Fe accumulation rates exists after water table recovery. It was deduced that Fe(II) and As(III) were oxidized directly by O2 at the period of low water table. But the production of hydroxyl radical (OH) was promoted at the period of high water table due to the oxidation of adsorbed Fe(II). The generated OH further accelerate the oxidation of Fe(II) and As(III). Moreover, the combination of As and Fe is more stronger at the top of the column due to the transformation of combined states of As from surface complexation into surface precipitation with the growth of Fe(III) minerals. This study details the processes and mechanisms of As and Fe immobilization within the unsaturation zone during different irrigation periods and accordingly provides some insights to mitigate As accumulation in topsoil.

Arsenic uptake by arugula (Eruca vesicaria, L.) cultivars as affected by phosphate availability.

To assess the importance of variation among arugula (Eruca vesicaria subsp. sativa) cultivars in the ability to accumulate arsenic (As) in above-ground tissues, uptake of As by 16 cultivars was measured in the field and in hydroponic culture. In the field trial on soil contaminated by past pesticide use, As soil-plant uptake coefficients varied by a factor of 2.7 among different cultivars, approaching a value of one for the strongest accumulators. Compared to the field assay, hydroponically grown arugula accumulated much lower concentrations of As when nutrient solutions contained standard (high) concentrations of phosphate along with 1.0 mg L-1 As in the form of soluble arsenate. However, As accumulation was much greater in hydroponic culture using low-P nutrient solutions, an indication that phosphate strongly competed with arsenate for root uptake. Analysis of arugula roots after exposure to arsenate at 1.0 mg As L-1 and low phosphate revealed from 24 to 400 times greater As concentration in roots than tops, with S concentrations significantly greater in As-exposed than control roots. This indicated greater sulfate uptake by roots exposed to arsenate, and suggested that thiol-mediated As immobilization occurred in the roots which strongly restricted translocation to the tops.

Arsenic entrapment by nanocrystals of Al-magnetite: The role of Al in crystal growth and As retention.

The nature of As-Al-Fe co-precipitates aged for 120 days are investigated in detail by High Resolution Transmission Electron Microscopy (HRTEM), Scanning TEM (STEM), electron diffraction, Energy Dispersive X-Ray Spectroscopy (EDS), Electron Energy-Loss Spectroscopy (EELS), and Energy Filtered Transmission Electron Microscopy (EFTEM). The Al present in magnetite is shown to favour As incorporation (up to 1.10 wt%) relative to Al-free magnetite and Al-goethite, but As uptake by Al-magnetite decreases with increasing Al substitution (3.53-11.37 mol% Al). Arsenic-bearing magnetite and goethite mesocrystals (MCs) are formed by oriented aggregation (OA) of primary nanoparticles (NPs). Well-crystalline magnetite likely formed by Otswald ripening was predominant in the Al-free system. The As content in Al-goethite MCs (having approximately 13% substituted Al) was close to the EDS detection limit (0.1 wt% As), but was below detection in Al-goethites with 23.00-32.19 mol% Al. Our results show for the first time the capacity of Al-magnetite to incorporate more As than Al-free magnetite, and the role of Al in favouring OA-based crystal growth under the experimental conditions, and therefore As retention in the formed MCs. The proposed mechanism of As incorporation involves adsorption of As onto the newly formed NPs. Arsenic is then trapped in the MCs as they grow by self-assembly OA upon attachment of the NPs. We conclude that Al may diffuse to the crystal faces with high surface energy to reduce the total energy of the system during the attachment events, thus favouring the oriented aggregation.