The bioavailability of the metalloid arsenic (As) in paddy soil is controlled by microbial cycling of As and other elements such as iron (Fe) and sulfur (S), which are strongly influenced by water management in paddy fields. In this study, we evaluated how water management affects As bioavailability by growing rice plants in a geogenic As-contaminated soil. We determined As speciation in soil porewater and the diversity of the associated microbial community. Continuous flooding enhanced the release of Fe and As and increased arsenite (As(III)) and methylated As species concentrations in the rice grain compared with aerobic treatment. Total inorganic and organic As in the grain was 84% and 81% lower, respectively, in the aerobic treatment compared with the continuous flooding treatment. The amounts of Fe(III)-reducing bacteria (FeRB) increased in the flooded rhizosphere soil. The abundance of FeRB in the soil correlated with the dissolution of Fe and As. Among the As-transformation genes quantified, the aioA gene for As(III) oxidation and arsM gene for As(III) methylation were most abundant. The arsM copy number correlated positively with the levels of dsrB (dissimilatory (bi) sulfite reductase β-subunit), suggesting that dissimilatory sulfate-reducing bacteria (SRB) may play an important role in dimethylarsenate (DMAs(V)) production in soil. Our results show that decreased populations of rhizosphere FeRB and SRB contributed to a lower bioavailability of As, and decreased production of methylated arsenicals under oxic conditions.

The effect of long-term nitrogen (N) and sulfur (S) deposition on litter mass loss and changes in carbon (C), N, and S composition and enzyme activities during litter decomposition was investigated in a boreal forest. This study included four N × S treatments: control (CK), N application (30 kg N ha−1 yr−1), S application (30 kg S ha−1 yr−1), and N plus S application (both at 30 kg ha−1 yr−1). Two experiments were conducted for 22 months: 1) a common litter decomposition experiment with litter bags containing a common litter (same litter chemistry) and 2) an in-situ litter decomposition experiment with litter from each treatment plot (and thus having different litter chemistry). Litterbags were placed onto the four treatment plots to investigate the direct effect of N and S addition and the combined effect of N and/or S addition and litter chemistry on litter decomposition, respectively. Regardless of the source of litter, N and/or S addition affected C, N and S composition at a certain period of the experiment but did not affect litter mass loss and enzyme activity throughout the experiment, indicating that the N and S addition rates were below the critical level required to affect C and N cycling in the studied ecosystem. However, the greater change in N composition per unit of litter mass loss in the N addition treatment than in the other treatments in the common litter but not in the in-situ litter experiment, suggests that the effect of N addition on N loss and retention depends on the initial litter chemistry. We conclude that the studied N and S addition rates did not affect litter decomposition and elemental cycling in the studied forest ecosystem even though the N and S addition rates were much greater than their ambient deposition rates.

Enhancing metals phytoextraction using gentile mobilizing agents might be an appropriate approach to increase the phytoextraction efficiency and to shorten the phytoremediation duration. The effect of sulfur-impregnated organoclay (SIOC) on the redistribution of potentially toxic elements (PTEs) among their geochemical fractions in soils and their plant uptake has not yet been studied. Therefore, our aim is to investigate the role of different SIOC application doses (1%, 3% and 5%) on operationally defined geochemical fractions (soluble + exchangeable; bound to carbonate; manganese oxide; organic matter; sulfide; poorly- and well-crystalline Fe oxide; and residual fraction) of Cd, Cr, Cu, Ni, Pb, and Zn, and their accumulation by pea (Pisum sativum) and corn (Zea mays) in a greenhouse pot experiment using a polluted floodplain soil. The SIOC caused a significant decrease in soil pH, and an increase in organic carbon and total sulfur content in the soil. The addition of SIOC increased significantly the soluble + exchangeable fraction and bioavailability of the metals. The SIOC leads to a transformation of the residual, organic, and Fe-Mn oxide fractions of Cd, Cu, Ni, and Zn to the soluble + exchangeable fraction. The SIOC addition increased the potential mobile (non-residual) fraction of Cr and Pb. The SIOC increased the sulfide fraction of Cr, Ni, and Zn, while it decreased the same fraction for Cd, Cu, and Pb. The effect of SIOC on the redistribution of metal fractions increased with enhancing application dosages. Pea accumulated more metals than corn with greater accumulation in the roots than shoots. Application of the higher dose of SIOC promoted the metals accumulation by roots and their translocation to shoots of pea and corn. Our results suggest the potential suitability of SIOC for enhancing the phytomanagement of PTEs polluted soils and reducing the environmental risk of these pollutants.

The toxic potentially toxic metals elements (PTEs) discharged from industrial activities and agricultural practices persistently pose multiple hazards to environment and living organisms. Microbe-assisted phytoremediation provide an effective approach to remediate PTEs-contaminated soils. A phytoextraction process involved the application of Streptomyces pactum (Act12, 1.0, 2.0 and 3.0 g kg⁻¹ dry soil, respectively) alone/jointly with sulfur was executed. The main texture of the tested soil was sandy loam and with a pH 8.27. The obtained results showed that the leaf pigments and plant biomass were improved after the application of the Act12, while the shoot fresh weight, chlorophyll a and chlorophyll b decreased by 57.8, 38.2 and 40.7%, respectively, after treatment with sulfur. Similarly, sulfur application facilitated the malondialdehyde (MDA) production by 18.4–33.6% compared to the control (no amendments). Both peroxidase (POD) and superoxide dismutase (SOD) activities were boosted, while the catalase (CAT) activity was suppressed with Act12 alone/jointly with sulfur treatment. The sulfur combined with elevated Act12 levels notably increased the cadmium (Cd) and zinc (Zn) concentrations both in shoots and roots, while the elemental extraction amount showed the removal efficiency following the order: Act12 alone ＞ control ＞ Act12 jointly with sulfur. Taken together, the results suggested that Streptomyces pactum and sulfur assisted the phytoremediation process, while further studies should be conducted in the field to test practical application.

Arsenic (As) tends to mobilize in flooded paddy soil due to the reductive dissolution of the iron (oxyhydr)oxides to which As sorbs, resulting in elevated As accumulation in rice that poses a potential risk to the food safety and human health. Microbial sulfate reduction is an important biogeochemical process in paddy soils, but its impact on As mobilization remains poorly understood. In this study, we incubated eight As-contaminated paddy soils under flooded conditions to investigate the effect of sulfate addition on As mobility. Porewater Fe and As concentrations and As species were determined. Among the eight soils, an addition of 50 mg S kg⁻¹ as sodium sulfate decreased porewater arsenite only in two soils, which also showed a high mobilization of Fe²⁺. Further experiments showed that the addition of sulfate to these two soils stimulated microbial sulfate reduction but decreased porewater concentrations of both arsenite and Fe²⁺. Additionally, the supply of sulfate increased the fractions of As associated with acid volatile sulfides in the solid phase and decreased As uptake by rice in pot experiments under similar conditions. The effect of sulfate addition on porewater As was diminished by the addition of molybdate, an inhibitor of sulfate reducing bacteria. These results suggest the formation of secondary FeS minerals which co-precipitate or sorb arsenite as a likely mechanism of As immobilization, which was also supported by thermodynamic modeling of the pore water. Thus, sulfate additions can immobilize As and reduce its availability to rice plants in paddy soils containing a high potential for microbial Fe reduction, providing an efficient way to mitigate the As transfer to the food chain.

Herein, we demonstrate a nanocomposite material Eu/ZnO/pPy for enhanced performance in photoelectrocatalytic degradation of chemical warfare agent sulphur mustard (SM) at ambient conditions which is growing concern of the Scientific Community amidst the current climate of terrorism. Eu/ZnO/pPy was electrochemically prepared on Au electrode at ambient conditions and was used for electrocatalytic reductive elimination of chloride from SM and results indicated one electron involvement process for the cleavage of the carbon-chloride bond. Surface morphology of Eu/pPy, ZnO/pPy and Eu/ZnO/pPy composites were characterized by SEM and confirmed the formation of the nanoparticles and nanorods on the modified electrode which leads to provide more surface area for the reductive elimination reaction. The elemental composition, functional groups and phase of materials on the modified electrode were deduced using EDX, Raman spectroscopy and XRD, respectively. Eu/ZnO/pPy/Au electrode was utilized for the photoelectrocatalytic degradation of SM as it exhibit excellent electrocatalytic activity and degradation products were analyzed by GC-MS. In the reductive elimination of SM, the following parameters were deduced (i) heterogeneous rate constant (0.127 s⁻¹), (ii) transfer coefficient (0.32) and (iii) number of electron involved (1.0). The enhanced photoelectrocatalytic capability of this nanocomposite could serve as a novel and promising catalyst in defence and environmental applications.

The aim of this study was to chemically characterize the fine particulate matter (PM₂.₅) at a subtropical forest in East Asia under the influences of anthropogenic and biogenic sources and a complex topographic setting. Four seasonal campaigns were conducted at the Xitou Experimental Forest in central Taiwan from the winter of 2013 to the autumn of 2014. The results indicated that the ambient levels and chemical features of PM₂.₅ exhibited pronounced seasonal variations. Non-sea-salt sulfate (nss-SO₄²⁻) constituted the major component of PM₂.₅, followed by ammonium (NH₄⁺) and nitrate (NO₃⁻) during winter, summer and autumn. However, it was revealed that the mass fraction of NO₃⁻ increased to be comparable with that of nss-SO₄²⁻ in springtime. The mass contribution of secondary organic carbon (SOC) to PM₂.₅ peaked in summer (13.2%), inferring the importance of enhanced photo-oxidation reactions in SOC formation. Diurnal variations of O₃ and SO₂ coincided with each other, suggesting the transport of aged pollutants from distant sources, whereas CO and NOₓ were shown to be under the influences of both local and regional sources. Notably high sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR) were observed, which were 0.93 ± 0.05 and 0.39 ± 0.20, respectively. Precursor gases (i.e. SO₂ and NOₓ) could be converted to sulfate and nitrate during the transport by the uphill winds. Furthermore, due to the high relative humidity at Xitou, enhanced aqueous-phase and/or heterogeneous reactions could further contribute to the formation of sulfate and nitrate at the site. This study demonstrated the significant transport of urban pollutants to a subtropical forest by the mountain-valley circulations as well as the long-range transport from regional sources, whereas the implications of which for regional climate change necessitated further investigation.

The Bohai Sea, one of the largest marginal seas in China, is extensively influenced by human and industrial activities. The pollutant loads from anthropogenic activities have induced severe ecological problems. The study investigates the physicochemical characteristics of seawater and sediments in Bohai Bay and Laizhou Bay of the Bohai Sea. The diversity and composition of microbial community in sediments are analyzed by 16S rRNA gene amplicon sequencing. The sequencing results present 16 phyla and 31 classes from the samples. Proteobacteria constituted a dominant phylum, of which the classes of Gamma-, Delta-, and Epsilon-are predominant sub-divisions. Nitrogen, phosphorus, and sulfur cycling related microbes present high abundance in both bays. The metabolism of organic matters is the main factor that influences the distribution of microbial communities in Bohai Bay, while the inflow of Yellow River is the dominant factor that influences the distribution of microbial communities in Laizhou Bay. Sulfur oxidizing process is expected to be positively influenced by heavy metals, while ammonia (NH4+) oxidizing process is prone to be negatively affected by heavy metals in both bays. Microbial communities in the offshore sediments of Laizhou Bay and the majority microbial communities in Bohai Bay sediments are subject to similar predominant controlling factors. This phenomenon is likely ascribed to ocean circulation. The results of this study can provide constructive guidelines on ecosystem management of marginal seas in Bohai and elsewhere.

Biochar has been used to remove heavy metals from aqueous solutions. In this study, a sulfurized wood biochar (SWB) by direct impregnation with elemental sulfur was produced and evaluated along with pristine wood biochar (WB) for adsorption characteristics and mechanism of mercury. Mercury adsorption by WB and SWB was well described by Langmuir model and pseudo second order model and the maximum adsorption capacities of WB and SWB were 57.8 and 107.5 mg g⁻¹, respectively. Intraparticle diffusion model showed that mercury adsorption was fast due to boundary layer and slow adsorption due to diffusion into biochar pores. Although, mercury adsorption by both WB and SWB was predominantly influenced by the pH, temperature, salt concentration, and biochar dosage, the SWB showed a relatively stable mercury adsorption compared to WB under different conditions, suggesting the strong affinity of SWB for mercury. The XPS analysis showed different adsorption mechanisms of mercury between WB and SWB. In particular, mercury adsorption in WB was due to Hg-Cπ bond formation and interaction with carboxyl and hydroxyl groups, whereas in SWB it is primarily due to mercury interaction with C-SOₓ-C and thiophenic groups in addition to Hg-Cπ bond formation and interaction with carboxyl groups. The SEM-EDS mapping also demonstrated that mercury in SWB was related to carbon, oxygen and sulfur. Overall, the sulfurized biochar was effective for removing mercury from aqueous solution, and its direct production through pyrolysis with elemental sulfur impregnation of wood chips could make it an economic option as absorbent for treating mercury-rich wastewater.

Nonferrous mine tailings have caused serious problems of co-contamination with metal(loid)s. It is still a global challenge to cost-effectively manage and mitigate the effect of the mining wastes. We conducted an in-situ bio-treatment of non-ferrous metal(loid) tailings using a microbial consortium of sulfate reducing bacteria (SRB). During the bio-treatment, the transformation of metal(loid)s (such as Cu, Fe, Mn, Pb, Sb, and Zn) into oxidizable and residual fractions in the subsurface tended to be higher than that observed in the surface. As well the mineral compositions changed becoming more complex, indicating that the sulfur reducing process of bio-treatment shaped the bio-transformation of metal(loid)s. The added SRB genera, especially Desulfotomaculum genus, colonized the tailings suggesting the coalescence of SRB consortia with indigenous communities of tailings. Such observation provides new insights for understanding the functional microbial community coalescence applied to bio-treatment. PICRUSt analysis revealed presence of genes involved in sulfate reduction, both assimilatory and dissimilatory. The potential for the utilization of both inorganic and organic sulfur compounds as S source, as well as the presence of sulfite oxidation genes indicated that SRB play an important role in the transformation of metal(loid)s. We advocate that the management of microorganisms involved in S-cycle is of paramount importance for the in situ bio-treatment of tailings, which provide new insights for the implementation of bio-treatments for mitigating the effect of tailings.