The significant role of aquatic phytoplankton in global primary productivity, accounting for approximately 50 % on an annual basis, has been recognized as a crucial factor in the reduction of Hg(II). In this study, we compared the efficiency of Hg(II) photoreduction mediated by three types of algae leaching dissolved organic matter (DOM) and humic acid (DOM-HA). Especially, we investigated the potential effects of algae-leached DOM on the photoreduction of Hg(II) and its subsequent uptake by lettuce, which serves as an indicator of Hg bioavailability for aquatic plants. The results revealed that under light conditions, the conversion of Hg(II) to Hg(0) mediated by algae-leached DOM and DOM-HA was 6.4- 39.9 % higher compared to dark condition. Furthermore, the free radical quenching experiment demonstrated that the reduction of Hg(II) mediated by DOM-HA was higher than algae-leached DOM, mainly due to its ability to generate superoxide anion (O-2(center dot-)). Moreover, the photoreduction efficiences of Hg(II) mediated by algae-leached DOM were 29-18 % lower compared to DOM-HA. The FT-IR analysis revealed that the production of-SH from algae-leached DOM led to the formation of strong metalcomplexes, which restricts the reduction process from Hg(II) to Hg(0). Finally, the hydroponics experiment demonstrated that algae-leached DOM inhibited the bioavailability of Hg(II) to plants more effectively than DOM-HA. Our research emphasizes the significant functional roles and potential mechanisms of algae in reducing Hg levels, thereby influencing the availability of Hg in aquatic ecosystems.

Straw amendment is a prevalent agricultural practice worldwide, which can reduce air pollution and improve soil fertility. However, the impact of aging straw amendment on the bioavailability of mercury (Hg) and methylmercury (MeHg) in paddy soil remains unclear. To investigate this, incubation experiments were conducted using the diffusive gradient in thin-film technique. Results showed that amendments of dry-wet aging (DRS), photochemical aging (LRS), and freeze-thaw aging rice straw (FRS) reduced the bioavailable MeHg in paddy soil by 2.2-27.6%, 13.5-69.8%, and 23.5-86.1%, respectively, compared to fresh rice straw (RS) amendment. This result could be due to changes in soil properties such as soil pH and overlying water Fe and Mn as well as microbial abundance (including Clostridiaceae, Firmicutes, and Actinobacteriota). Simultaneously, The LRS and FRS amendments reduced bioavailable Hg in paddy soil by 20.0-40.8% and 17.1-48.6%, respectively, while DRS increased the bioavailable Hg by 15.8-120.0%. This could be attributed to changes in soil oxidation-reduction potential and overlying water SO42- content. Additionally, the results of sand culture experiments showed that the concentrations of Hg uptake by rice seedlings were 97.1-118.2%, 28.1-35.6%, and 198.0-217.1% higher in dissolved organic matter (DOM) derived from DRS, LRS, and FRS than RS, indicating that aging straw leached DOM may promote the Hg bioavailable when straw amendment. This result could be due to lower molecular weight and higher CO functional group content. These results provide new insight into how aging straw amendment affects the bioavailability of Hg and MeHg in paddy soil under different climates.

Methylmercury is a neurotoxic compound that can enter rice fields through rainfall or irrigation with contaminated wastewater, and then contaminate the human food chain through the consumption of rice. Flooded paddy soil has a porous structure that facilitates air exchange with the atmosphere, but the presence of trace amounts of oxygen in flooded rice field soil and its impact on microbial-mediated formation of methylmercury is still unclear. We compared the microbial communities and their functions in oxygen-depleted and oxygen-limited paddy soil. We discovered that oxygen-limited paddy soil had higher methylmercury concentration, which was strongly correlated with soil properties and methylation potential. Compared with oxygen-depleted soil, oxygen-limited soil altered the microbial composition based on 16 S rRNA sequences, but not based on hgcA sequences. Moreover, oxygen-limited soil enhanced microbial activity significantly, increasing the abundance of more than half of the KEGG pathways, especially the metabolic pathways that might be involved in methylation. Our study unveils how microbial communities influence methylmercury formation in oxygen-limited paddy soil. Environmental implications: This study examined how low oxygen input affects microbial-induced MeHg formation in anaerobic paddy soil. We found that oxygen-limited soil produced more MeHg than oxygen-depleted soil. Oxygen input altered the microbial community structure of 16 S rRNA sequencing in anaerobic paddy soil, but had little impact on the hgcA sequencing community structure. Microbial activity and metabolic functions related to MeHg formation were also higher in oxygen-limited paddy soil. We suggest that oxygen may not be a limiting factor for Hg methylators, and that insufficient oxygen input in flooded paddy soil increases the risk of human exposure to MeHg from rice consumption.

Biochar can effectively reduce the phytoavailability of mercury (Hg) in soil, but the mechanisms are not fully understood. In this study, the dynamic changes in Hg content adsorbed by the biochar (BC-Hg), Hg phytoavailability in the soil (P-Hg), and soil dissolved organic matter (DOM) characteristics were determined over a 60-day treatment period. Biochar obtained at 300 °C, 500 °C and 700 °C reduced the P-Hg concentration assessed by MgCl2 extraction by 9.4%, 23.5% and 32.7%, respectively. However, biochar showed a very limited adsorption on Hg, with the maximum BC-Hg content only accounting for 1.1% of the total amount. High-resolution scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS) results showed that the proportion of Hg atoms in biochar after 60 d was barely detectable. Biochar treatment can shift soil DOM toward higher aromatic content and molecular weight. Additionally, the addition of high-temperature biochar increased more humus-like components, but low-temperature biochar increased more protein-like components. Correlation analysis and partial least squares path modeling (PLS-PM) showed that biochar promoted humus-like fractions formation to reduce the Hg phytoavailability. This research has deepened the understanding of the mechanisms by which biochar stabilizes Hg in agricultural soils.

The photochemical behavior of dissolved organic matter (DOM) in surface water and its effect on Hg(II) photoreduction has been extensively studied, but the contribution of DOM in paddy water to Hg(II) photore-duction is largely unknown. Herein, the effect of DOM from biochar (BCDOM), rice straw (RSDOM), and chicken manure (CMDOM) on Hg(II) photoreduction were examined. The comparable reduction efficiency of Hg(II) suggested that DOM-like fraction (62.3-63.7%) contributes more than suspended particulate matter-like fraction (17.7-23.4%) and bacteria-like fraction (13.0-20.0%) in paddy water. Under irradiation, the typical DOM significantly promoted Hg(II) photoreduction, and the reduction efficiency of BCDOM (65.5 +/- 2.1%) was higher than that of CMDOM (48.3 +/- 2.6%) and RSDOM (32.8 +/- 2.4%) in 6 h. The quenching and kinetics experiments showed that superoxide anion (O-2(center dot-)) was the main reactive species for Hg(II) photoreduction. Fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry revealed that DOM with a higher degree of lignin/carboxy-rich acyclic molecules, condensed aromatics structures, and phenolic compounds could promote the formation of O-2(center dot-). These findings highlight the importance of DOM in Hg(II) photoreduction and provide new ideas for regulating Hg cycling and bioavailability in paddy environments.

Traditional NOx treatment methods require external reducing reagents and harsh reaction conditions, which is not conducive to effectively eliminate NOx at low concentration, especially at ppb levels. Fortunately, low concentration NOx can be removed by photocatalytic oxidation under mild reaction conditions. Bismuth (Bi)-based photocatalysts with the layered structure have obtained considerable concerns of photocatalytic NOx oxidation. This review focused on typical layered Bi-based photocatalysts (Bi2WO6, Bi2O2CO3, BiOY (YCl, Br, and I), BiOIO3, and BiOCOOH) with the structure of [Bi2O2]2+ layer for photocatalytic NOx oxidation. The strategies (morphological control, defect engineering, heterostructure construction, etc.) to improve photocatalytic oxidation activity were summarized. Furthermore, the mechanism involving various free radicals (hydroxyl radical, superoxide radical, etc.) of photocatalytic oxidation of NOx was proposed. In addition, the non-NO2 selectivity was also illuminated. Lastly, the current drawbacks and further research directions for photocatalytic NOx oxidation were elaborated. The development of photocatalysts with high photocatalytic activity, wide light absorption range, and non-NO2 selectivity is the focus of future research. This review aims to provide a pandect and theoretical guidance for the practical application of photocatalytic oxidation of NOx.

The transformation of Hg(II) and Hg(0) in aqueous systems governs the speciation and biogeochemical cycling of Hg. However, with the increasing amount of microplastics in the aqueous environment, little is known about the different effects of microplastic particles and their leached DOM on the photoreduction of Hg(II) to Hg(0) after long-term photoaging. In this study, we found that aged microplastic particles significantly inhibited the photoreduction efficiency (6.40-15.64 %) of Hg(II) compared to the control without any microplastic (31.02 %) and pristine microplastic particles (9.95-34.10 %). This inhibition was due to the adsorption of Hg by the microplastic particles, which decreased the amount of available Hg(II) (Hg(II)RED) that could participate in the photoreduction reaction. The characteristics of aged microplastic particles also indicated rougher surfaces and more oxygen-containing functional groups after photoaging, which may enhance their adsorption capacity compared to pristine microplastic. Interestingly, the photoreduction efficiency of Hg(II) was 11.58-53.28 % higher in the presence of microplastic leach DOM compared to the control. With increasing age, the microplastic leach DOM obviously promotes the photoreduction of Hg(II). Free radical inhibition and electron paramagnetic resonance spectra demonstrated that O2- in microplastic leach DOM contributed to the photoreduction of Hg(II) under light irradiation. Moreover, X-ray absorption near edge structure analyses demonstrated that microplastic leach DOM produced Hg(I) as the primary photoproduct, accounting for 43.17 % of the total Hg in the photoreaction solution and likely reducing it to Hg(0). This study provides novel insights into forecasting the synthesized risks of microplastic aging in the biogeochemical cycle of Hg within aqueous environments.

Mercury (Hg) poses a significant risk in paddy fields, particularly when it is converted to methylmercury (MeHg) and accumulates in rice. However, the bioavailability and resupply kinetics of Hg in the paddy soil-water environment are not well understood. In this study, the diffusive gradients in thin films (DGT) and the 'DGT-induced fluxes in sediments' model (DIFS) were first adopted to investigate the Hg resupply kinetics, diffusion fluxes and bioavailability in a paddy environment subjected to flood-drain-reflood treatment and straw amendment. Our results show that although the straw amendment limited the bioavailability of Hg (38.2%- 47.9% lower than control) in porewater by decreasing its resupply capacity, especially with smaller straw par-ticles, the net production of MeHg in paddy fields was significantly increased after straw amendment (73.5%- 77.9% higher than control). The results of microbial sequencing indicate that enhanced methylators (e.g., family Geobacter) and non-Hg methylators (e.g., Methanosarcinaceae) played a crucial role in MeHg production following straw amendment. Moreover, Hg-containing paddy soils generally tend to release Hg into the overlying water, while drain-reflood treatment changes the direction of Hg diffusion fluxes in the paddy soil-water interface. The drainage-reflooded treatment decreases the Hg reactive and resupply capacity of the paddy soil, thereby hindering the release of Hg from soil into overlying water during the early stages of reflooding. Overall, this study provides novel insights into the behavior of Hg in paddy soil-water surface microlayers.

Traditional Fenton reaction takes place at a low pH and generates waste. Additionally, the storage and transportation of liquid H2O2 may pose safety risks. To overcome these disadvantages, an eco-friendly, efficient advanced oxidation process was established with ultrathin-C3N5 photocatalyst coupling sodium percarbonate (SPC). Under visible light irradiation, up to 93.97% of SMZ was removed within 120 min. Such efficient removal was attributed to the high carriers separation efficiency of U-C3N5, which was certified by DFT calculations and characterization methods. All the factors (various anions, pH values, fulvic acid, light sources, and water matrices) had a slight influence on SMZ degradation. Moreover, the toxicities of SMZ and its intermediates were reduced after degradation. Finally, a gelatin aerogel/U-C3N5 composite was obtained to facilitate the recycling of U-C3N5. This work highlights the combination of metal-free photocatalysis with SPC to degrade sulfonamide antibiotics and furthers the development of advanced oxidation process for micropollutant removal.

A 3D hierarchical RP/BP/BiOCOOH double heterostructures with abundant oxygen vacancies (OVs) was obtained by hydrothermal process and its photocatalytic activity was investigated by degradation of TC-HCl with different light sources and various natural water. The physicochemical characteristics of RP/BP/BiOCOOH heterojunctions were systematically characterized via TEM, XPS, EPR, EIS et al. Compared with BiOCOOH, the photocatalytic activity of RP/BP/BiOCOOH was obviously enhanced. Under simulated solar light irradiation, 60.5% of TC-HCl was removed by 3%RP/BP/BiOCOOH. And the rate constant of 3%RP/BP/BiOCOOH was 2.95 times than that of BiOCOOH. Traces of small molecular organics were beneficial to improve photocatalytic efficiency. The process of photocatalytic degradation and the cytotoxicity of intermedia products of TC-HCl were discussed via HPLC-MS, 3D-EEM, and antibacterial properties test. Based on the results of trapping experiments and ESR tests, •OH and •O2- were the most significant reactive oxygen species. The enhanced photocatalytic activity was ascribed to two reasons: 1 double heterojunctions structure enhanced the separation efficiency of carriers, 2 the introduction of OVs and BP/RP expanded the response range of light. This work provides a feasible strategy that non-metallic element semiconductor is used to modify the wide band gap semiconductor to enhance the photocatalytic efficiency.

Microplastics are widespread in estuarine, coastal, and deep sea sediments. The influence of microplastics on mercury (Hg) methylation in paddy soils with different characteristics, however, has not been well reported. In this research, we conducted a microcosmic experiment using red soil and alkaline soil with 2%, 7% and 10% polyvinyl chloride microplastics (PVC-MPs). Diffusive gradients in thin film (DGT) were used to test bioavailable Hg2+ and bioavailable methylmercury (MeHg) in soils. Results showed that PVC-MPs could decrease bioavailable MeHg concentrations both in red soil and alkaline soil. We demonstrated that these decreases could be due to three possible mechanisms: (1) PVC-MPs affected DOM composition, which resulted in a difference in combining capacity for bioavailable Hg2+; (2) PVC-MPs decreased MeHg via changing soil properties (including sulfate and dissolved Fe); (3) PVC-MPs affected the abundance of Proteobacteria, Firmicutes, and hgcA gene in soils. Our results emphasized the significance of investigating effects of microplastics on specific contaminants to implement effective environmental remediation strategies in polluted paddy soils.

Increased chloride concentration can cause salinization, which has become a serious and widespread environmental problem nowadays. This review aims at providing comprehensive and state-of-the-art knowledge and insights of technologies for chloride removal. Mechanisms for chloride removal mainly include chemical precipitation, adsorption, oxidation and membrane separation. In chemical precipitation, chloride removal by forming CuCl, AgCl, BiOCl and Friedel's salt. Adsorbents used in chloride removal mainly include ion exchangers, bimetal oxides and carbon-based electrodes. Oxidation for chloride removal contains ozone-based, electrochemical and sulfate radical-based oxidation. Membrane separation for chloride removal consists of diffusion dialysis, nanofiltration, reverse osmosis and electrodialysis. In this review, we specifically proposed the factors that affect chloride removal process and the corresponding strategies for improving removal efficiency. In the last section, the remaining challenges of method explorations and material developments were stated to provide guidelines for future development of chloride removal technologies.

Hg methylation traditionally occurs in an oxygen-depleted environment but was recently reported in oxygen-limited habitats such as settling particles or sediments surface. Flooding paddy soil is a standard oxygen-limited environment and is a hotspot of MeHg production. However, little is known about how oxygen dissolution shapes MeHg formation. Here, we conducted a microcosm experiment that compared the limited oxygen exposure of flooding paddy soil with strict anaerobic under natural conditions in three bacterial modification amendments covering low redox potentials from -230 to -130 mV. One striking aspect of our finding is the variability in the MeHg duration between oxygen exposure or not, emphasizing that, at different oxygen conditions, oxygen-specific characteristics have a greater effect on MeHg production, than solely considering the MeHg concentration in the soil. Community abundance analysis and principal coordinate analysis suggested a marked shift in bacterial community composition between the oxygen-limited and anaerobic treatments. However, the addition of MoO 4 2- had little effect on the community composition. Moreover, LEfSe analysis indicated that oxygen input modulated Hg methylation in flooding paddy soils, resulting from a Fe-reducing Hg methylated bacterium ( Geobacteraceae ) and multiple non-Hg methylated bacteria of Proteobacteria . Our study provides insights into the hitherto overlooked role of oxygen content in Hg methylation in flooding paddy soil.

Semiconductor-based CO2 photoreduction for generating chemical energy has recently attracted special attention owing to its tremendous potential for solving increasingly grim energy crises and environmental concerns. Among them, Cadmium sulfide (CdS)-based nanomaterials have attracted enormous attention on account of the relatively narrow band gap for harvesting visible-light and well-suited band position for CO2 photoreduction. Herein, the comprehensive review focus on the application and progress in CO2 photoreduction over CdS-based photocatalysts. In this review, we begin with a detailed discussion of CdS materials in CO2 photoreduction, including fundamental of CO2 photoreduction as well as products selectivity. In particular, we will highlight the modification of CdS materials for efficient CO2 photoreduction. And the utilization of density functional theory (DFT) in the study of CO2 photoreduction over CdS-based photocatalysts is emphasized. Moreover, the remaining challenges to investigate and optimize the catalyzing ability of CdS-based catalysts are stated to indicate possible future development of CdS.

The low separation efficiency of carriers and weak light response of photocatalysts severely limit the application of photocatalysis technology. Herein, we prepared a visible light responsive self-assembled micro-flowers of ultrathin bismuth oxide formate nanosheets supported by gold nanoparticles (Au/BiOCOOH) composite photocatalyst via hydrothermal method. The physicochemical and photoelectric properties of obtainedphotocatalysts were completely analyzed via a range of characterization means. Compared with bare BiOCOOH, the photocatalytic activity of Au/BiOCOOH was significantly improved. 2.0%Au/BiOCOOH possessed the highest rate constant of 0.0054 min-1 for degradation of tetracycline hydrochloride (TC-HCl), which was nearly 13.5 times higher than that of BiOCOOH. The intermediate products were analyzed by 3D EEM and HPLC/MS, and the antibacterial ability of intermediate products with 2.0%Au/BiOCOOH significantly descended. In order to explore the potential of practical applications, photocatalytic experiments were also implemented through different water sources and solar light irradiation. Furthermore, the photocatalytic activity was also investigated by photocatalytic reduction of carbon dioxide (CO2). The excellent photocatalytic activity owed to the enhanced separation of charge carriers and light absorption ability by the surface plasmon resonance (SPR) effect of Au nanoparticles. The work may provide a feasible strategy to obtain efficient BiOCOOH-based photocatalyst.

A paradigm shift is underway in wastewater treatment from pollution removal to resource or energy recovery. However, conventional activated sludge (CAS) as the core technology of wastewater treatment is confronted with severe challenges on high energy consumption, sludge disposal and inevitable greenhouse gas emission, which are posing a serious impact on the current wastewater industry. It is urgent to find new alternative methods to remedy these defects. Photosynthetic bacteria (PSB) have flexible metabolic modes and high tolerance, which enhance the removal of nutrients, heavy metals and organic contaminants efficiency in different wastewater. The unique phototrophic growth of PSB breaks the restriction of nutrient metabolism in the CAS system. Recent studies have shown that PSB-based technologies can not only achieve the recovery of nutrient and energy, but also improve the degradation efficiency of refractory substances. If the application parameters can be determined, there will be great prospects and economic effects. This review summarizes the research breakthroughs and application promotion of PSB-based wastewater treatment technology in recent years. Comparing discussed the superiority and inferiority from the perspective of application range, performance differences and recovery possibility. Pathways involved in the nutrient substance and the corresponding influencing parameters are also described in detail. The mode of PSB biodegradation processes presented a promising alternative for new wastewater treatment scheme. In the future, more mechanical and model studies, deterministic operating parameters, revolutionary process design is need for large-scale industrial promotion of PSB-based wastewater treatment.

The microbiome in artificial lake water and its impact on mercury (Hg) methylation remain largely unknown. We selected the largest artificial lake in southeastern china, Changshou Lake (CSL), which has high background levels of Hg, for our investigation of Hg transformation microorganisms. Five different sections of the water column of CSL were sampled during four seasons. The water samples were subjected to analysis of geochemical parameters, various Hg species and microbiome information. High concentrations of total mercury (THg) were detected in CSL in comparison with those found in natural lakes. Significant differences in microbial community structure and Hg species abundance existed among seasons. High dissolved methyl mercury (DMeHg) formation and high bacterial richness and diversity occurred in the fall. The microbiome was dominated by Proteobacteria, Actinobacteria, Bacteroidetes, Deinococcus-Thermus and many unclassified bacteria. Significant correlations were found between seasonal bacterial communities and Hg levels. Hg methylation was strongly linked to the abundance of Cyanobacteria. Methylators, including Syntrophus, Desulfovibrio and Desulfomonile species, were detected only in samples collected in the fall. The results of enzyme functional analyses revealed that many unknown types of bacteria could also be responsible for Hg transformation. This study was the first to investigate the impact of various Hg species on the microbiome of artificial lake water. The findings of this study illuminate the role of seasonal bacteria in Hg transformation.

Chlorinated aliphatic hydrocarbons (CAHs) with characteristics of high toxicity, biological accumulation and recalcitrance to degradation as well as carcinogenicity, teratogenesis and mutagenicity, are seriously harmful to human health and ecological environment. CAHs degradation depends on biotic and abiotic responses that exist diversified interactive effects, so it is important to clarify the mechanism of CAHs degradation via biotic and abiotic mutual promoting to significantly enhance the CAHs-contaminated site restoration. In this work, a series of pathways for CAHs degradation was first introduced and summarized as three means on reductive dechlorination, aerobic cometabolism and direct oxidation, and biotic and abiotic typical factors affecting CAHs degradation were concluded from these. Then, mechanisms of induced degradation and synergistic degradation were indicated from the perspective of mutual promoting degradation both with biotic and abiotic responses, and furthermore, the application and technical limitations of CAHs degradation enhanced via biotic and abiotic mutual promoting were reviewed and analyzed. Finally, the development of CAHs degradation technology in future was prospected.

Copper plays a key role in regulating the expression of enzymes that promote biodegradation of contaminants in methanotrophic consortia (MC). Here, we utilized MC isolated from landfill cover to investigate cometabolic degradation of trichloroethylene (TCE) at nine different copper (Cu2+) concentrations. The results demonstrated that an increase in Cu2+ concentration from 0 to 15 mu M altered the specific first-order rate constant k(1,TCE), the expression levels of methane monooxygenase (pmoA and mmoX) genes, and the specific activity of soluble methane monooxygenase (sMMO). High efficiency TCE degradation (95%) and the expression levels of methane monooxygenase (MMO) were detected at a Cu2+ concentration of 0.03 mu M. Notably, sMMO-specific activity ranged from 74.41 nmol/(mg(cell) h) in 15 mu M Cu2+ to 654.99 nmol/(mg(cell) h) in 0.03 mu M Cu2+, which contrasts with cultures of pure methanotrophs in which sMMO activity is depressed at high Cu2+ concentrations, indicating a special regulatory role for Cu2+ in MC. The results of MiSeq pyrosequencing indicated that higher Cu2+ concentrations stimulated the growth of methanotrophic microorganisms in MC. These findings have important implications for the elucidation of copper-mediated regulatory mechanisms in MC.