We investigated the effects of arsenic species on As accumulation, plant growth and rhizospheric changes in As−hyperaccumulator Pteris vittata (PV). PV was grown for 60−d in a soil spiked with 200 mg kg−1 arsenate (AsV−soil) or arsenite (AsIII−soil). Diffusive gradients in thin−films technique (DGT) were used to monitor As uptake by PV. Interestingly AsIII−soil produced the highest PV biomass at 8.6 g plant−1, 27% and 46% greater than AsV−soil and the control. Biomass increase was associated with As−induced P uptake by PV. Although AsIII was oxidized to AsV during the experiment, As species impacted As accumulation by PV, with 17.5% more As in AsIII−soil than AsV−soil (36 vs. 31 mg plant−1). As concentration in PV roots was 30% higher in AsV−soil whereas As concentration in PV fronds was 7.9% greater in AsIII−soil, suggesting more rapid translocation of AsIII than AsV. These findings were important to understand the mechanisms of As uptake, accumulation and translocation by PV.

Corn cob silica (CCS), produced via a modification of the sol-gel method, can reduce heavy metal availability and stabilize contaminated soil on abandoned mining sites. Adding 5 % (w/w) CCS to mining site soil increased pH from 4.0 to 7.7, and cation exchange capacity increased from 94.5 to 100.3 cmol+/kg. Sequential extraction showed that adding CCS decreased heavy metal availability in the soil. Mobility factor (MF) values indicated that CCS reduced Pb mobility more than that of Zn or Cu in all fractions. Pb concentrations in leachate from all fractions using the toxicity characteristic leaching procedure (TCLP) were greatly decreased by adding 3 % (w/w) CCS. CCS similarly reduced Zn concentrations in TCLP leachate. CCS addition did not impact Cu concentrations in leachate, likely because concentrations were much lower than those of the other metals. As was generally less mobile than the heavy metals; however, As mobility and leachability tended to increase with CCS addition because its oxyanions arsenite and arsenate have low affinity for negatively charged surfaces on the CCS. Shoot and root growth of Spinacia oleracea L. (spinach) was much greater in CCS-treated soil than in unamended soil. Results demonstrate the utility of CCS to stabilize heavy metals in contaminated mining site soil, but this treatment may not be ideal for As-contaminated soils.

The Janghang smelter in Chungnam, South Korea started in 1936 was subsequently shutdown in 1989 due to heavy metal (loid) pollution concerns in the vicinity. Thus, there is a need for the soil in the area to be remediated to make it usable again especially for agricultural purposes. The present study was conducted to exploit the potential of arsenic (As)-tolerant bacteria thriving in the vicinity of the smelter-polluted soils to enhance phytoremediation of hazardous As. We studied the genetic and taxonomic diversity of 21 As-tolerant bacteria isolated from soils nearer to and away from the smelter. These isolates belonging to the genera Brevibacterium, Pseudomonas, Microbacterium, Rhodococcus, Rahnella, and Paenibacillus, could tolerate high concentrations of arsenite (As(III)) and arsenate (As(V)) with the minimum inhibitory concentration ranging from 3 to >20 mM for NaAsO₂and 140 to 310 mM NaH₂AsO₄ · 7H₂O, respectively. All isolates exhibited As(V) reduction except Pseudomonas koreensis JS123, which exhibited both oxidation and reduction of As. Moreover, all the 21 isolates produced indole acetic acid (IAA), 13 isolates exhibited 1-aminocyclopropane-1-carboxylic acid (ACC) deaminase activity, 12 produced siderophore, 17 solubilized phosphate, and 13 were putative nitrogen fixers under in vitro conditions. Particularly, Rhodococcus aetherivorans JS2210, P. koreensis JS2214, and Pseudomonas sp. JS238 consistently increased root length of maize in the presence of 100 and 200 μM As(V). Possible utilization of these As-tolerant plant-growth-promoting bacteria can be a potential strategy in increasing the efficiency of phytoremediation in As-polluted soils.

Arsenic, a common poison, is known to react with sulfide in vivo, forming thioarsenates. The acute toxicity of the inorganic thioarsenates is currently unknown. Our experiments showed that a fourfold sulfide excess reduced acute arsenite cytotoxicity in human hepatocytes (HepG2) and urothelial cells (UROtsa) significantly, but had little effect on arsenate toxicity. Speciation analysis showed immediate formation of thioarsenates (up to 73 % of total arsenic) in case of arsenite, but no speciation changes for arsenate. Testing acute toxicity of mono- and trithioarsenate individually, both thioarsenates were found to be more toxic than their structural analogue arsenate, but less toxic than arsenite. Toxicity increased with the number of thio groups. The amount of cellular arsenic uptake after 24 h corresponded to the order of toxicity of the four compounds tested. The dominant to almost exclusive intracellular arsenic species was arsenite. The results imply that thiolation is a detoxification process for arsenite in sulfidic milieus. The mechanism could either be that thioarsenates regulate the amount of free arsenite available for cellular uptake without entering the cells themselves, or, based on their chemical similarity to arsenate, they could be taken up by similar transporters and reduced rapidly intracellularly to arsenite.

The adsorption of Cr(VI) and As(III) by amino-functionalized SBA-15 (NH₂-SBA-15) from single and binary systems were investigated in this work. The effects of pH and temperature on the adsorption of NH₂-SBA-15 were studied. Adsorption kinetics, isotherm model, and thermodynamics were studied to analyze the experimental data. pH 2 was the optimum condition for the adsorption of Cr(VI) and pH 4 for As(III) adsorption. Increasing temperature had a positive effect on the removal of both Cr(VI) and As(III). The Freundlich isotherm model can depict the adsorption process best. The pseudo-second-order kinetic model fitted well with the kinetic data of Cr(VI) and As(III) in the single-component system. In the binary system, the adsorption of As(III) by NH₂-SBA-15 was slightly enhanced with the presence of Cr(VI); however, As(III) had no obvious effect on the removal of Cr(VI). Regeneration experiments indicated that 0.1 mol/L NaHCO₃was an efficient desorbent for the recovery of Cr(VI) and As(III) from NH₂-SBA-15; the desorption rates for Cr(VI) and As(III) were 91.6 and 33.59 %, respectively. After five recycling cycles, the removal rates were 88 and 7 % for Cr(VI) and As(III) adsorption by NH₂-SBA-15, respectively.

Enhanced removal application of both forms of inorganic arsenic from arsenic-contaminated aquifers at near-neutral pH was studied using a novel electrospun chitosan/PVA/zerovalent iron (CPZ) nanofibrous mat. CPZ was carefully examined using scanning electron microscopy (SEM) equipped with energy-dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), atomic fluorescence spectroscopy (AFM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and thermal gravimetric analysis (TGA). Application of the adsorbent towards the removal of total inorganic arsenic in batch mode has also been studied. A suitable mechanism for the adsorption has also been discussed. CPZ nanofibers mat was found capable to remove 200.0 ± 10.0 mg g⁻¹of As(V) and 142.9 ± 7.2 mg g⁻¹of As(III) from aqueous solution of pH 7.0 at ambient condition. Addition of ethylenediaminetetraacetic acid (EDTA) enabled the stability of iron in zerovalent state (ZVI). Enhanced capacity of the fibrous mat could be attributed to the high surface area of the fibers, presence of ZVI, and presence of functional groups such as amino, carboxyl, and hydroxyl groups of the chitosan and EDTA. Both Langmuir and Freundlich adsorption isotherms were applicable to describe the removal process. The possible mechanism of adsorption has been explained in terms of electrostatic attraction between the protonated amino groups of chitosan/arsenate ions and oxidation of arsenite to arsenate by Fentons generated from ZVI and subsequent complexation of the arsenate with the oxidized iron. These CPZ nanofibrous mats has been prepared with environmentally benign naturally occurring biodegradable biopolymer chitosan, which offers unique advantage in the removal of arsenic from contaminated groundwater.

The response of maize (Zea mays L.) to inorganic arsenic exposure was studied, at the seedling stage under hydroponic conditions, preliminarily in sixteen lines (fourteen hybrids and two inbred lines) and then, more deeply, in six of these lines, selected by showing contrasting differences in their sensitivity to the metalloid. The results indicated that (i) maize is rather tolerant to arsenic toxicity, (ii) arsenite is more phytotoxic than arsenate, (iii) roots are less sensitive than shoots to the metalloid, (iv) a great accumulation of non-protein thiols (probably phytochelatins), without substantial effect on the glutathione content, is produced in roots but not in shoots of arsenic-exposed plants and (v) maize is able to accumulate high levels of arsenic in roots with very low translocation to shoots. The study, thus, suggests that maize, for its very low rate of acropetal transport of arsenic from roots to shoots, may be a safe crop in relation to the risk of entry of metalloid in the food chain and, for being an important bioenergy crop capable of expressing high levels of arsenic tolerance and accumulation in roots, may represent an interesting opportunity for the exploitation of agricultural useless arsenic contaminated lands.

Dissolved organic matter (DOM) affects arsenite [As(III)] toxicity by altering its sorption equilibrium at the cell wall interface. A better understanding of such mechanism is of great importance to assess As(III) ecotoxicity in aquatic systems. Batch experiments were conducted to study the effects of DOM on the regulation of As(III) sorption and toxicity in the diatom Navicula sp. The influence of humic acid (HA) on As(III) toxicity was assessed by measuring algal growth, chlorophyll a, and reactive oxygen species (ROS), whereas As(III) mobility across the cell wall was estimated by determining the concentration of intracellular, cell-wall-bound, and free As(III) ions in cell media. Results showed that the effects of HA on arsenite toxicity varied depending on various combinations of As(III)-HA concentrations. EC₅₀had an approximate threefold increase from 8.32 (HA-free control) to 22.39 μM (at 20 mg L⁻¹HA) when Navicula sp. was exposed to 1.0–100.0 μM of As(III), compared to an overall low complexation ratio of HA-As(III) in a range of 0.91–6.00 %. The cell wall-bound and intracellular arsenic content decreased by 19.8 and 20.3 %, respectively, despite the lower arsenite complexation (2.10 ± 0.16 % of the total As). Meanwhile, intracellular ROS was decreased by 12.6 % in response to 10.0 μM As(III) and 10 mg L⁻¹HA vs. the HA-free control. The significant contrast indicated that complexation alone could not explain the HA-induced reduction in arsenite toxicity and other factors including HA–cell surface interactions may come into play. Isotherms describing adsorption of HA to the Navicula sp. cells combined with morphological data by scanning electron microscopy revealed a protective HA floccule coating on the cell walls. Additional Fourier transform infrared spectroscopic data suggested the involvement of carboxylic groups during the adsorption of both HA and As(III) on the Navicula sp. cell surface. Collective data from this study suggest that cell wall-bound HA can moderate As(III) toxicity through the formation of a protective floccule coating occupying As(III) sorption sites and decreased effective functional groups capable of binding As(III). Our findings imply that As(III) toxicity can be alleviated due to the increased hindrance to cellular internalization of As(III) in the presence of naturally abundant DOM in water.

Bagasse fly ash (BFA, a sugar industrial waste) was used as low-cost adsorbent for the uptake of arsenate and arsenite species from water. The optimum conditions for the removal of both species of arsenic were as follows: pH 7.0, concentration 50.0 μg/L, contact time 50.0 min, adsorbent dose 3.0 g/L, and temperature 20.0 °C, with 95.0 and 89.5 % removal of arsenate and arsenite, respectively. The Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich adsorption isotherms were used to analyze the results. The results of these models indicated single-layer uniform adsorption on heterogeneous surface. Thermodynamic parameters, i.e., ΔG°, ΔH°, and ΔS°, were also calculated. At 20.0 to 30.0 °C, the values of ΔG° lie in the range of −4,722.75 to −4,878.82 and −4,308.80 to −4,451.73 while the values of ΔH° and ΔS° were −149.90 and −121.07, and 15.61 and 14.29 for arsenate and arsenite, respectively, indicating that adsorption is spontaneous and exothermic. Pseudo-first-order kinetics was followed. In column experiments, the adsorption decreased as the flow rate increased with the maximum removal of 98.9 and 95.6 % for arsenate and arsenite, respectively. The bed depth service time and Yoon and Nelson models were used to analyze the experimental data. The adsorption capacity (Nₒ) of BFA on column was 3.65 and 2.98 mg/cm³for arsenate and arsenite, respectively. The developed system for the removal of arsenate and arsenite species is economic, rapid, and capable of working under natural conditions. It may be used for the removal of arsenic species from any contaminated water resources.