In soil environments, sorption/desorption reactions as well as chemical complexation with inorganic and organic ligands and redox reactions, both biotic and abiotic, are of great importance in controlling their bioavailability, leaching and toxicity. These reactions are affected by many factors such as pH, nature of the sorbents, presence and concentration of organic and inorganic ligands, including humic and fulvic acid, root exudates, microbial metabolites and nutrients. In this review, we highlight the impact of physical, chemical, and biological interfacial interactions on bioavailability and mobility of metals and metalloids in soil. Special attention is devoted to: i) the sorption/desorption processes of metals and metalloids on/from soil components and soils; ii) their precipitation and reduction-oxidation reactions in solution and onto surfaces of soil components; iii) their chemical speciation, fractionation and bioavailability.

Sorption and desorption of AsO4 on or from different soil components may have a dominant role in regulating As mobility in soils. The objectives of this work were to provide information on the factors that influence the competitive sorption of AsO4 and PO4 in soil. We studied the competitive sorption of PO4 and AsO4 on selected phyllosilicates, metal oxides, synthetic organo‐mineral complexes, and soil samples as affected by pH (4.0–8.0), ligands concentration, surface coverage of the oxyanions on the samples and the residence time. We found that Mn, Fe, and Ti oxides and phyllosilicates particularly rich in Fe (nontronite, ferruginous smectites) were more effective in sorbing AsO4 than PO4 In fact, by adding AsO4 and PO4 as a mixture (AsO4/PO4 molar ratio of 1) more AsO4 than PO4 was usually sorbed on birnessite, pyrolusite, goethite, nontronite, and ferruginous smectite, but more PO4 than AsO4 was sorbed on noncrystalline Al precipitation products, gibbsite, boehmite, allophane, and kaolinite. For example, at pH 5.0 the sorbed AsO4/sorbed PO4 molar ratio (rf) was 1.81 for birnessite, 1.05 for nontronite, but was only 0.45 for kaolinite and 0.14 for allophane. For montmorillonite, illite, and vermiculite the rf values were slightly <1. For soil samples, particularly rich in kaolinite, halloysite, allophane, and containing relatively large amounts of organic C, the rf values were usually much <1. For all the samples, the rf values increased by decreasing the pH and with the residence time of the oxyanions. The sorption of AsO4 (or PO4) on goethite and gibbsite decreased by increasing the initial PO4/AsO4 (or AsO4/PO4 molar ratio) up to 2.0. However, PO4 inhibited AsO4 sorption more on gibbsite than on goethite, whereas AsO4 prevented PO4 sorption more on goethite than on gibbsite. The data reported in this paper suggest that the mobility, the bioavailability, and the toxicity of As in soil environments may be greatly affected by the nature of soil components, pH, presence of anions (PO4), and residence time.

Coprecipitation of arsenic with iron or aluminum occurs in natural environments and is a remediation technology used to remove this toxic metalloid from drinking water and hydrometallurgical solutions. In this work, we studied the nature, mineralogy, and reactivity toward phosphate of iron-arsenate coprecipitates formed at As(V)/Fe(III) molar ratios (R) of 0, 0.01, or 0.1 and at pH 4.0, 7.0, and 10.0 aged for 30 or 210 days at 50 degrees C and studied the desorption of arsenate. At R = 0, goethite and hematite (with ferrihydrite at pH 4.0 and 7.0) crystallized, whereas at R = 0.01, the formation of ferrihydrite increased and hematite crystallization was favored over goethite. In some samples, the morphology of hematite changed from rounded platy crystals to ellipsoids. At R = 0.1, ferrihydrite formed in all the coprecipitates and remained unchanged even after 210 days of aging. The surface area and chemical composition of the precipitates were affected by pH, R, and aging. Chemical dissolution of the samples showed that arsenate was present mainly in ferrihydrite, but at R = 0.01, it was partially incorporated into the structures of crystalline Fe oxides. The sorption of phosphate on to the coprecipitates was affected not only by the mineralogy and surface area of the samples but also by the amounts of arsenate present in the oxides. The samples formed at pH 4.0 and 7.0 and at R = 0.1 sorbed lower amounts of phosphate than the precipitates obtained at R = 0 or 0.01, despite the former having a larger surface area and showing only a presence of short-range ordered materials. This is mainly due to the fact that in the coprecipitates at R = 0.1 arsenate occupied many sorption sites, thus preventing phosphate sorption. Less than 20% of the arsenate present in the coprecipitates formed at R = 0.1 was removed by phosphate and more from the samples synthesized at pH 7.0 or 10.0 than at pH 4.0. Moreover, we found that more arsenate was desorbed by phosphate from a ferrihydrite on which arsenate was added than from an iron-arsenate coprecipitate, attributed to the partial occlusion of some arsenate anions into the framework of the coprecipitate. XPS analyses confirmed these findings.

Arsenic mobilization in soils is mainly controlled by sorption/desorption processes, but arsenic also may be coprecipitated with aluminum and/or iron in natural environments. Although coprecipitation of arsenic with aluminum and iron oxides is an effective treatment process for arsenic removal from drinking water, the nature and reactivity of aluminum- or iron-arsenic coprecipitates has received little attention. We studied the mineralogy, chemical composition, and surface properties of aluminum-arsenate coprecipitates, as well as the sorption of phosphate on and the loss of arsenate from these precipitates. Aluminum-arsenate coprecipitates were synthesized at pH 4.0, 7.0, or 10.0 and As/Al molar ratio (R) of 0, 0.01, or 0.1 and were aged 30 or 210 d at 50 degrees C. In the absence of arsenate, gibbsite (pH 4.0 or 7.0) and bayerite (pH 10.0) formed, whereas in the presence of arsenate, very poorly crystalline precipitates formed. Short-range ordered materials (mainly poorly crystalline boehmite) formed at pH 4.0 (R = 0.01 and 0.1), 7.0, and 10.0 (R= 0.1) and did not transform into Al(OH)3 polymorphs even after prolonged aging. The surface properties and chemical composition of the aluminum precipitates were affected by the initial pH, R, and aging. Chemical dissolution of the samples by 6 mol L(-1) HCl and 0.2 mol L(-1) oxalic acid/ oxalate solution indicated that arsenate was present mainly in the short-range ordered precipitates. The sorption of phosphate onto the precipitates was influenced by the nature of the samples and the amounts of arsenate present in the precipitates. Large amounts of phosphate partially replaced arsenate only from the samples formed at R = 0.1. The quantities of arsenate desorbed from these coprecipitates by phosphate increased with increasing phosphate concentration, reaction time, and precipitate age butwere always lessthan 30% of the amounts of arsenate present in the materials and were particularly low (<4%) from the sample prepared at pH 4.0. Arsenate appeared to be occluded within the network of short-range ordered materials and/or sorbed onto the external surfaces of the precipitates, but sorption on the external surfaces seemed to increase by increasing pH of sample preparation and aging. Furthermore, at pH 4.0 more than in neutral or alkaline systems the formation of aluminum arsenate precipitates seemed to be favored. Finally, we have observed that greater amounts of phosphate were sorbed on an aluminum-arsenate coprecipitate than on a preformed aluminum oxide equilibrated with arsenate under the same conditions (R = 0.1, pH 7.0). In contrast, the opposite occurred for arsenate desorption, which was attributed to the larger amounts of arsenate occluded in the coprecipitate.

In this study we have investigated the uptake and distribution of arsenic (As) and phosphate (P i ) in roots, shoots, and grain of wheat grown in an uncontaminated soil irrigated with solutions containing As at three different concentrations (0.5, 1 and 2 mg l −1 ) and in the presence or in the absence of P fertilization. Arsenic in irrigation water reduced plants growth and decreased grain yield. When P i was not added (P−), plants were more greatly impacted compared to the plus P i (P+) treatments. The differences in mean biomass between P− and P+ treatments at the higher As concentrations demonstrated the role of P i in preventing As toxicity and growth inhibition. Arsenic concentrations in root, shoot and grain increased with increasing As concentration in irrigation water. It appears that P fertilization minimizes the translocation of As to the shoots and grain whilst enhancing P status of plant. The observation that P fertilization minimises the translocation of arsenic to the shoots and grain is interesting and may be useful for certain regions of the world that has high levels of As in groundwater or soils.

Sorption and desorption processes control the mobility, toxicity, and availability of As in natural environments. Surface coverage and residence time may affect the kinetics of As sorption–desorption from soil components and the transformation of As from desorbable into resistant or undesorbable forms. We performed kinetic studies on the sorption of As(V) onto crystalline or poorly crystalline metal oxides (noncrystalline Al(OH)x, gibbsite, ferrihydrite, and goethite) and its desorption by PO4 at pH 6.0 as affected by the residence time and the surface coverage (50 or 100%) of As(V). Significant amounts of As(V) were sorbed during the initial period of 0.167 h, ranging from 37.9 to 71.8% when the surface coverage was about 100%. The kinetic data, explained best by the Elovich kinetic model, indicated the following order in As(V) sorption: gibbsite < Al(OH)x < goethite < ferrihydrite. By adding PO4 immediately after complete sorption of As(V) onto the oxides (50% surface coverage; PO4 added/As(V) sorbed molar ratio of 4), a much higher proportion of As(V) was desorbed after 24 h of reaction from Al oxides (48–56%) than from Fe oxides (18–23%). The amount of As(V) desorbed decreased with increasing residence time. The kinetics of As(V) desorption by PO4 as a function of residence time was explained best by the Elovich kinetic model. The kinetics described the rate of rearrangement of As(V) from desorbable into resistant or undesorbable forms, which occurred more rapidly in Al than Fe oxides. After a residence time of 360 h, the percentage of As(V) desorbed from the oxides was reduced significantly (<13%).

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