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.

Abandoned nonferrous metal(loid) tailings sites are anthropogenic, and represent unique and extreme ecological niches for microbial communities. Tailings contain elevated and toxic content of metal(loid)s that had negative effects on local human health and regional ecosystems. Microbial communities in these typical tailings undergoing natural attenuation are often very poorly examined. The diversity and inferred functions of bacterial communities were examined at seven nonferrous metal(loid) tailings sites in Guangxi (China), which were abandoned between 3 and 31 years ago. The acidity of the tailings sites rose over 31 years of site inactivity. Desulfurivibrio, which were always coupled with sulfur/sulfide oxidation to dissimilate the reduction of nitrate/nitrite, were specific in tailings with 3 years abandonment. However, genus beneficial to plant growth (Rhizobium), and iron/sulfur-oxidizing bacteria and metal(loid)-related genera (Acidiferrobacter and Acidithiobacillus) were specific within tailings abandoned for 23 years or more. The increased abundance of acid-generating iron/sulfur-oxidizing and metal(loid)-related bacteria and specific bacterial communities during the natural attenuation could provide new insights for understanding microbial ecosystem functioning in mine tailings. OTUs related to Sulfuriferula, Bacillus, Sulfurifustis, Gaiella, and Thiobacillus genera were the main contributors differentiating the bacterial communities between the different tailing sites. Multiple correlation analyses between bacterial communities and geochemical parameters indicated that pH, TOC, TN, As, Pb, and Cu were the main drivers influencing the bacterial community structures. PICRUSt functional exploration revealed that the main functions were related to DNA repair and recombination, important functions for bacterial adaptation to cope with the multi-contamination of tailings. Such information provides new insights to guide future metagenomic studies for the identification of key functions beyond metal-transformation/resistance. As well, our results offers novel outlooks for the management of bacterial communities during natural attenuation of multi-contaminated nonferrous metal(loid) tailings sites.

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 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.

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 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.

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.

Inductively coupled plasma – mass spectrometry (ICP-MS) analysis of airborne particulate bound mercury was carried out utilizing a high sulfur containing organic compound as a preservation agent to limit the negative bias that affects the determination of low levels of mercury. Between 600% and 1000% more Hg was detected with the use of the additive, lithium tetrathiafulvalene carboxylate (LiCTTF), during the microwave assisted acid digestion sample processing step without influencing the determination of other trace elements. The average Hg concentration was 0.05 ng m⁻³ and 0.4 ng m⁻³ in the absence and presence of LiCTTF, respectively. Stabilization of the mercury ions with the preservation agent resulted in higher precision for ICP-MS measurements with relative standard deviation (RSD) values ranging from 1.07% to 4.36%. The results obtained in this study emphasize the necessity of using a preservation agent in the atomic spectroscopic determination of mercury to prevent losses and is especially critical in low-level analyses such as those routinely performed in environmental mercury pollution trend assessments.

Pyrite weathering often occurs in nature and causes heavy metal ion pollution and acid mine drainage during the process. Humic acid (HA) is a critical natural organic material that can bind metal ions, thus affecting metal transfer and transformation. In this work, in situ electrochemical techniques combined with spectroscopic analysis were adopted to investigate the interfacial processes involved in pyrite weathering with/without HA. The results showed that the pyrite weathering mechanism with/without HA is FeS₂ → Fe²⁺ + 2S⁰ + 2e⁻. The presence of HA did not change the pyrite weathering mechanism, but HA adsorbs on the pyrite surface and inhibits the further transformation of sulfur. Furthermore, HA and Fe(II) ions can form complex at 45.0 °C. Increased concentration of HA, decreased HA solution acidity or decreased environmental temperature would all weaken the pyrite weathering, for the above conditions cause pyrite weathering to have a larger resistance of the double layer and a larger passive film resistance. Pyrite will release 73.7 g m⁻²·y⁻¹ Fe²⁺ to solution at pH 4.5, and the amount decreases to 36.8 g m⁻²·y⁻¹ in the presence of 100 mg/L HA. This study provides an in situ electrochemical method for the assessment of pyrite weathering.