The main intent of the current research was to appraise if combined application of hydrogen sulfide (H₂S, 0.2 mM) and silicon (Si 2.0 mM) could improve tolerance of tomato plants to arsenic (As as sodium hydrogen arsenate heptahydrate, 0.2 mM) stress. Plant growth, chlorophylls (Chl), PSII maximum efficiency (Fv/Fm), H₂S concentration and L-cysteine desulfhydrase activity were found to be suppressed, but leaf and root As, leaf proline content, phytochelatins, malondialdehyde (MDA) and H₂O₂ as well as the activity of lipoxygenase (LOX) increased under As stress. H₂S and Si supplied together or alone enhanced the concentrations of key antioxidant biomolecules such as ascorbic acid, and reduced glutathione and the activities of key antioxidant system enzymes including catalase (CAT), superoxide dismutase (SOD), dehydroascorbate reductase (DHAR), glutathione reductase (GR), and glutathione S-transferase (GST). In comparison with individual application of H₂S or Si, the joint supplementation of both had better effect in improving growth and key biochemical processes, and reducing tissue As content, suggesting a putative collaborative role of both molecules in improving tolerance to As-toxicity in tomato plants.

Bacteria play crucial roles in the biogeochemical cycle of arsenic (As) and selenium (Se) as these elements are metabolized via detoxification, energy generation (anaerobic respiration) and biosynthesis (e.g. selenocysteine) strategies. To date, arsenic and selenium biomineralization in bacteria were studied separately. In this study, the anaerobic metabolism of As and Se in Shewanella sp. O23S was investigated separately and mixed, with an emphasis put on the biomineralization products of this process. Multiple analytical techniques including ICP-MS, TEM-EDS, XRD, Micro-Raman, spectrophotometry and surface charge (zeta potential) were employed. Shewanella sp. O23S is capable of reducing selenate (SeO₄²⁻) and selenite (SeO₃²⁻) to red Se(-S)⁰, and arsenate (AsO₄³⁻) to arsenite (AsO₃³⁻). The release of H₂S from cysteine led to the precipitation of AsS minerals: nanorod AsS and granular As₂S₃. When As and Se oxyanions were mixed, both As–S and Se(-S)⁰ biominerals were synthesized. All biominerals were extracellular, amorphous and presented a negative surface charge (−24 to −38 mV). Kinetic analysis indicated the following reduction yields: SeO₃²⁻ (90%), AsO₄³⁻ (60%), and SeO₄²⁻ (<10%). The mix of SeO₃²⁻ with AsO₄³⁻ led to a decrease in As removal to 30%, while Se reduction yield was unaffected (88%). Interestingly, SeO₄²⁻ incubated with AsO₄³⁻ boosted the Se removal (71%). The exclusive extracellular formation of As and Se biominerals might indicate an extracellular respiratory process characteristic of various Shewanella species and strains. This is the first study documenting a complex interplay between As and Se oxyanions: selenite decreased arsenate reduction, whereas arsenate stimulated selenate reduction. Further investigation needs to clarify whether Shewanella sp. O23S employs multi-substrate respiratory enzymes or separate, high affinity enzymes for As and Se oxyanion respiration.

Arsenic (As) toxicity is a problem that needs to be solved in terms of both human health and agricultural production in the vast majority of the world. The presence of As causes biomass loss by disrupting the balance of biochemical processes in plants and preventing growth/water absorption in the roots and accumulating in the edible parts of the plant and entering the food chain. A critical method of combating As toxicity is the use of biosafe, natural, bioactive compounds such as hesperidin (HP) or chlorogenic acid (CA). To this end, in this study, the physiological and biochemical effects of HP (100 μM) and CA (50 μM) were investigated in Zea mays under arsenate stress (100 μM). Relative water content, osmotic potential, photosynthesis-related parameters were suppressed under stress. It was determined that stress decreased the activities of the antioxidant system and increased the level of saturated fatty acids and, gene expression of PHT transporters involved in the uptake and translocation of arsenate. After being exposed to stress, HP and CA improved the capacity of superoxide dismutase (SOD), catalase (CAT), peroxidase (POX), glutathione S-transferase (GST) and glutathione peroxidase (GPX) and then ROS accumulation (H₂O₂) and lipid peroxidation (TBARS) were effectively removed. These phenolic compounds contributed to maintaining the cellular redox status by regulating enzyme/non-enzyme activity/contents involved in the AsA-GSH cycle. HP and CA reversed the adverse effects of excessive metal ion accumulation by re-regulated expression of the PHT1.1 and PHT1.3 genes in response to stress. Exogenously applied HP and CA effectively maintained membrane integrity by regulating saturated/unsaturated fatty acid content. However, the combined application of HP and CA did not show a synergistic protective activity against As stress and had a negative effect on the antioxidant capacity of maize leaves. As a result, HP and CA have great potentials to provide tolerance to maize under As stress by reducing oxidative injury and preserving the biochemical reactions of photosynthesis.

Dissolved organic matter (DOM) and dissolved ions are two integral parameters to affect the environmental fate of As in different ways. Numerous studies chose surrogate of DOM, humic substances (HSs), to investigate the As complexation behavior. However, microbial secretion (protein and polysaccharide) was also considered for a great proportion in surface aquatic system, and its effect was still not fully understood. The present research distinguished the As complexation behavior with different DOM components (HSs, protein, polysaccharide and synthetic organic matter) in natural and simulated water samples. The results indicated that different DOM components exhibited various binding capacities for As. HSs showed the strongest affinity for As, followed by long-chain compounds (polysaccharide and synthetic organic matter) and proteins. In water source, HSs were probably the primary parameter for As complexation. In eutrophic water system, however, polysaccharide maybe the main DOM component to bind As. Cationic bridge function was prone to occur in the presence of HSs, but not observed in the presence of protein. PO₄³⁻ competed for binding sites with As, consequently decreasing the As complexation with all the DOM components. The research implied that a comprehensive and meticulous analyses of DOM fractions and coexist ions are the prerequisite to understanding the behavior of As (or other pollutants) in different natural aquatic systems.

Iron nanoparticles (Fe NPs) have often been used for in situ remediation of both groundwater and soil. However, the impact of Fe NPs on the distribution and transformation of As species in contaminated soil is still largely unknown. In this study, green iron oxide nanoparticles synthesized using a euphorbia cochinchinensis leaf extract (GION) were used to stabilize As in a contaminated soil. GION exhibited excellent As stabilization effects, where As in non-specifically-bound and specifically-bound fractions decreased by 27.1% and 67.3% after 120 days incubation. While both arsenate (As (V)) and arsenite (As (III)) decreased after GION application, As (V) remained the dominant species in soil. X-ray photoelectron spectroscopy (XPS) confirmed that As (V) was the dominant species in specifically-bound fractions, while As (III) was the dominant species in amorphous and poorly-crystalline hydrous oxides of Fe and Al. Correlation analysis showed that while highly available As fractions were negatively correlated to oxalate and DCB extractable Fe, they were positively correlated to Fe²⁺ content, which indicated that Fe cycling was the main process influencing changes in As availability. X-ray fluorescence (XRF) spectroscopy also showed that the Fe₂O₃ content increased by 47.9% following GION soil treatments. Overall, this work indicated that As would be transformed to more stable fractions during the cycling of Fe following GION application and that the application of GION, even in small doses, provides a low-cost and ecofriendly method for the stabilization of As in soil.

Previous studies have indicated that natural organic matter in the aquatic environment could affect arsenic bioaccumulation and biotransformation to aquatic organisms. However, the differences between the effects of arsenite and arsenate exposure have not been studied and compared in fish exposure models. In this study, adult zebrafish (Danio rerio) were exposed to 5 mg/L inorganic As solutions, in the presence of a range of humic acid (HA) concentrations (1, 2.5, 5, 10, 20 mg/L) in 96 h waterborne exposure. Results showed that in the presence of HA, total As bioaccumulation was significantly reduced in zebrafish following arsenite exposure, while this reduction was not observed during arsenate exposure. The reduction in total arsenic bioaccumulation for arsenite exposure can be explained by the fact that HA forming a surface coating on the cell surface, hindering transport and internalization. However, this reduction in total As was not observed due to differences in uptake pathways for arsenate exposure. Results also showed that Arsenobetaine (AsB) was the main biotransformation product in zebrafish following inorganic As exposure, accounting for 44.8%–64.7% of extracted arsenic species in all exposure groups. The addition of HA caused levels of MMA and As(III) to decrease, while the distribution of AsB significantly increased in arsenite exposure groups. The increase in AsB could be because the As(III)-HA complex was formed, affecting the methylation of As(III). In contrast, the addition of HA to arsenate exposure groups, did not affect the reduction of As(V) to As(III) and therefore, an increase in the distribution of AsB was not observed in arsenate exposure groups. This study provides useful information on the mechanisms of toxicity, for improved risk assessment of As in natural aquatic environments.

Nano-silica as an important part of soil is an ideal carrier of passivator material. In this paper, nano-silica was modified by silane coupling agent containing mercapto group and iron (II) salt to afford an organic-inorganic hybrid containing –S-Fe-S functional group (coded as RNS-SFe) on the surface of nano-silica. Results demonstrate that the RNS-SFe nanoparticle has network-like spheroidal shape and a primary particle size is about 18.0 nm. The RNS-SFe hybrid as a potential immobilization agent for heavy metal in soil shows excellent performance for the remediation of the contaminated soil. Specifically, with a dosage of 3.0% (mass ratio) in the soil, it can immobilize bioavailable Pb, Cd, and As by 97.1%, 85.0%, and 80.1%, respectively. Namely, the RNS-SFe hybrid can transform the bioavailable Pb, Cd, and As into insoluble mercapto metal compounds (–S-Pb-S- and –S-Cd-S-) and less soluble iron arsenate (Fe₃(AsO₄)₂, FeAsO₄) precipitate on the surface of nano-silica particle, thereby reducing the toxicity and mobility of the toxic contaminant fractions. In the meantime, the immobilized products of the Pb, Cd and As fractions have good resistance against acid leaching. These results are contributive to the application of RNS-SFe for the remediation of multi-heavy metal-contaminated soils in field.

Dietary arsenic (As) intake from food is of great concern, and developing a reliable model capable of predicting As concentrations in plant edible parts is desirable. In this study, pot experiments were performed with 16 Chinese upland soils spiked with arsenate [As(V)] to develop a predictive model for As concentrations in pepper fruits (Capsicum annum L.). Our results showed that after three months’ aging, concentrations of bioavailable As (extracted by 0.05 M NH₄H₂PO₄) in various soils varied widely, depending on soil total As concentrations and soil properties such as soil pH and amorphous iron (Fe) contents. Furthermore, both the bioconcentration factor (BCF, denoted as the ratio of fruit As to soil As) and total As concentrations in pepper fruits were largely determined by concentrations of bioavailable As, which explained 27% and 69% variations in the BCF and fruit As concentrations, respectively. Apart from bioavailable As, soil pH and Fe contents were another two important factors influencing As accumulation in pepper fruits. Taking the three factors into account, concentrations of fruit As can be well predicted using a stepwise multiple linear regression (SMLR) analysis (R² = 0.80, RMSE = 0.17). Arsenic species in soils and edible parts were also analyzed. Although As(V) predominated in soils (>96%), As in pepper fruits presented as As(V) (46%) and arsenite [As(III)] (39%) with small amount of methylated As (<15%). Aggregated boosted tree (ABT) analysis revealed that inorganic As concentrations in pepper fruits were determined by concentrations of bioavailable As, phosphorus (P) and Fe in soils. In contrast to inorganic As, methylated As concentrations were not correlated with those factors in soils. Taken together, this study established an empirical model for predicting As concentrations in pepper fruits. The predictive model can be used for establishing the As threshold in fruit vegetable farming soils.

Roxarsone (3-nitro-4-hydroxyphenylarsonic acid, ROX) is an arsenic-containing compound widely used as a feed additive in poultry industries. ROX excreted in chicken manure can be transformed by microbes to different arsenic species in the environment. To date, most of the studies on microbial transformation of ROX have focused on anaerobic microorganisms. Here, we isolated a pure cultured aerobic ROX-transforming bacterial strain, CZ-1, from an arsenic-contaminated paddy soil. On the basis of 16S rRNA gene sequence, strain CZ-1 was classified as a member of the genus Enterobacter. During ROX biotransformation by strain CZ-1, five metabolites including arsenate (As[V]), arsenite (As[III]), N-acetyl-4-hydroxy-m-arsanilic acid (N-AHPAA), 3-amino-4-hydroxyphenylarsonic acid (3-AHPAA) and a novel sulfur-containing arsenic species (AsC₉H₁₃N₂O₆S) were detected and identified based on high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS), HPLC-ICP-MS/electrospray ionization mass spectrometry (ESI-MS) and HPLC-electrospray ionization hybrid quadrupole time-of-flight mass spectrometry (ESI-qTOF-MS) analyses. N-AHPAA and 3-AHPAA were the main products, and 3-AHPAA could also be transformed to N-AHPAA. Based on the results, we propose a novel ROX biotransformation pathway by Enterobacter. sp CZ-1, in which the nitro group of ROX is first reduced to amino group (3-AHPAA) and then acetylated to N-AHPAA.

Only limited information is available on the effects of dissolved organic phosphorus (DOP) on arsenate (As(V)) bioaccumulation and biotransformation in organisms. In this study, we examined the influence of three different DOP forms (β-sodium glycerophosphate (βP), adenosine 5′-triphosphate (ATP), and D-Glucose-6-phosphate disodium (GP) salts) and inorganic phosphate (IP) on As(V) toxicity, accumulation, and biotransformation in Microcystis aeruginosa. Results showed that M. aeruginosa utilized the three DOP forms to sustain its growth. At a subcellular level, the higher phosphorus (P) distribution in metal-sensitive fractions (MSF) observed in the IP treatments could explain the comparatively lower toxic stress of algae compared to the DOP treatments. Meanwhile, the higher MSF distribution of arsenic (As) in M. aeruginosa in the presence of DOP could explain the higher toxicity with lower 96-h half maximal effective concentration (EC50) values. Although we observed As(V) and P discrimination in M. aeruginosa under IP treatments with high intracellular P/As, we did not find this discrimination under the DOP treatments. As accumulation in algal cells was therefore greatly enhanced by DOP, especially βP, given its lower transformation rate to phosphate compared to ATP and GP in media. Additionally, As(V) reduction and, subsequently, As(III) methylation were greatly facilitated in M. aeruginosa by the presence of DOP, particularly GP, which was confirmed by the higher relative expression of its two functional genes (arsC and arsM). Our findings indicate that As(V) accumulation and its subsequent biotransformation were enhanced by organic P forms, which provides new insight into how DOP modulates As metabolism in algae.