Peroxydisulfate-Driven Reductive Dechlorination as Affected by Soil Constituents: Free Radical Formation and Conversion.

We report a previously unrecognized but efficient reductive degradation pathway in peroxydisulfate (PDS)-driven soil remediation. With supplements of naturally occurring low-molecular-weight organic acids (LMWOAs) in anaerobic biochar-activated PDS systems, degradation rates of 12 γ-hexachlorocyclohexanes (HCH)-spiked soils boosted from 40% without LMWOAs to a maximum of 99% with 1 mM malic acid. Structural analysis revealed that an increase in α-hydroxyl groups and a diminution in pKa1 values of LMWOAs facilitated the formation of reductive carboxyl anion radicals (COO•-) via electrophilic attack by SO4•-/•OH. Furthermore, degradation kinetics were strongly correlated with soil organic matter (SOM) contents than iron minerals. Combining a newly developed in situ fluorescence detector of reductive radicals with quenching experiments, we showed that for soils with high, medium, and low SOM contents, dominant reactive species switched from singlet oxygen/semiquinone radicals to SO4•-/•OH and then to COO•- (contribution increased from 30.8 to 66.7%), yielding superior HCH degradation. Validation experiments using SOM model compounds highlighted critical roles of redox-active moieties, such as phenolic - OH and quinones, in radical formation and conversion. Our study provides insights into environmental behaviors related to radical activation of persulfate in a broader soil horizon and inspiration for more advanced reduction technologies.

Exploring additives beyond phthalates: Release from plastic mulching films, biodegradation and occurrence in agricultural soils.

It is widely recognized that applications of plastic films result in plastic pollution in agroecosystems. However, there is limited knowledge on the release and occurrence of additives beyond phthalates in agricultural soil. In this study, the rates of release and biodegradation of various additives, including phthalates, bisphenols, organophosphate esters, phenolic antioxidants, and ultraviolet absorbents from mulching films in soil were quantified by laboratory incubation. The rates of release and biodegradation ranged from 0.069 d-1 to 5.893 d-1 and from 1.43 × 10-3 d-1 to 0.600 d-1, respectively. Both of these rates were affected by temperature, flooding, and the properties of additives, films, and soils. An estimated 4000 metric tons of these additives were released into soil annually in China exclusively. The total concentrations of these additives in 80 agricultural soils varied between 228 and 3455 µg kg-1, with phenolic antioxidants, phthalates, and bisphenols accounting for 54.1%, 25.2%, and 17.9% of the total concentrations, respectively. A preliminary risk assessment suggested that the current levels of these additives could potentially present moderate hazards to the soil ecosystem.

A tripartite evolutionary game behavior analysis of the implementation strategy of the internal carbon pricing of enterprises under governments supervision.

Internal Carbon Pricing (ICP) represents an innovative approach to carbon emission reduction. The implementation of the ICP involves enterprises and internal organizations, with its outcomes closely tied to government actions. In this study, a tripartite evolutionary game model comprising these subjects was constructed, and subsequent simulation analyses were conducted. The results revealed the following key findings: (1) When the combined total of carbon fees and governments' emission reduction subsidies surpasses the aggregate of carbon fees returned to internal organizations and ICP implementation costs, and when enterprises' revenues exceed governments' subsidies, all three parties will evolve towards ESS (1,1,1). This signifies that enterprises opt for the ICP, internal organizations actively reduce emissions, and governments engage in proactive regulation. (2) Reducing the cost of implementing ICP, increasing the carbon fee rebate ratio, raising governments' subsidies, and elevating the internal carbon price all contribute to promoting the attainment of the evolutionary game results ESS (1,1,1). However, it's important to note that higher governments' subsidies and carbon fee rebate ratios do not necessarily lead to a greater incentive for the three parties to reach the ESS(1,1,1). These findings provide a solid theoretical foundation for enterprises considering the implementation of the ICP in the future.

Simultaneous regulation of biocathodic γ-HCH dechlorination and CH4 production by tailoring the structure and function of biofilms based on quorum sensing.

Dechlorination of chlorinated organic pollutants and methanogenesis are attractive biocathode reductions in microbial electrolysis cells (MECs). Quorum sensing (QS) is applied to regulate microbial communications. However, how acyl-homoserine lactones (AHLs)-dependent QS organize the assembly of the biocathode microbial community, and then regulate multiple biocathode reductions remains unclear. By applying N-butanoyl homoserine lactone (C4-HSL), N-hexanoyl homoserine lactone (C6-HSL) and 3-oxo-hexanoyl homoserine lactone (3OC6-HSL) in γ-hexachlorocyclohexane (γ-HCH) contaminated MECs, this study investigated the changes of biofilm microbial structure and function and the mechanisms of AHLs-QS on γ-HCH dechlorination and CH4 production. Exogenous C4-HSL and 3OC6-HSL increased cytochrome c production and enriched dechlorinators, electroactive bacteria but not methanogens to accelerate γ-HCH dechlorination and inhibit CH4 production. C6-HSL facilitated dechlorination and CH4 production by enhancing biofilm electroactivity and increasing membrane transportation. Besides, exogenous C6-HSL restored the electron transfer capacity that was damaged by the concurrent addition of acylase, an endogenous AHL quencher. From the perspective of microbial assembly, this study sheds insights into and provides an efficient strategy to selectively accelerate dechlorination and CH4 production by harnessing microbial structure based on QS systems to meet various environmental demands.

Release of Additives from Agricultural Plastic Films in Water: Experiment and Modeling.

Globally, more than 6 million metric tons of agricultural plastic films are used to increase crop yields and reduce the use of water and herbicides, resulting in the contamination of soil and water by plastic debris and additives. However, knowledge of the occurrence and release of additives from agricultural films is limited. In this study, suspect screening with high-resolution mass spectrometry, one-dimensional Fickian diffusion models, and linear free energy relationships (LFERs) were used to determine the occurrence and mass transfer of various additives from agricultural plastic films. A total of 89 additives were tentatively identified in 40 films, and 62 of them were further validated and quantified. The aqueous concentrations of 26 released additives reached mg L-1 after a 28 day incubation at 25 °C. Diffusion models and LFERs demonstrated that the film-water partition coefficient and the diffusivity in the polymer, the two critical parameters controlling the mass transfer, could be predicted using Abraham descriptors. The findings of this study highlighted the need for future research on the environmental fate and risk assessment of previously neglected additives in agricultural plastic films and other similar products.

Neglected but Efficient Electron Utilization Driven by Biochar-Coactivated Phenols and Peroxydisulfate: Polyphenol Accumulation Rather than Mineralization.

We report an unrecognized but efficient nonradical mechanism in biochar-activated peroxydisulfate (PDS) systems. Combining a newly developed fluorescence trapper of reactive oxygen species with steady-state concentration calculations, we showed that raising pyrolysis temperatures of biochar (BC) from 400 to 800 °C remarkably enhanced trichlorophenol degradation but inhibited the catalytic production of radicals (SO4•- and •OH) in water and soil, thereby switching a radical-based activation into an electron-transfer-dominated nonradical pathway (contribution increased from 12.9 to 76.9%). Distinct from previously reported PDS* complex-determined oxidation, in situ Raman and electrochemical results of this study demonstrated that the simultaneous activation of phenols and PDS on the biochar surface triggers the potential difference-driven electron transfer. The formed phenoxy radicals subsequently undergo coupling and polymerization reactions to generate dimeric and oligomeric intermediates, which are eventually accumulated on the biochar surface and removed. Such a unique nonmineralizing oxidation achieved an ultrahigh electron utilization efficiency (ephenols/ePDS) of 182%. Through biochar molecular modeling and theoretical calculations, we highlighted the critical role of graphitic domains rather than redox-active moieties in lowering band-gap energy to facilitate electron transfer. Our work provides insights into outstanding contradictions and controversies related to nonradical oxidation and inspiration for more oxidant-saving remediation technologies.

Conductive Materials on Biocathodes Altered the Electron-Transfer Paths and Modulated γ-HCH Dechlorination and CH4 Production in Microbial Electrochemical Systems.

Adding conductive materials to the cathode of a microbial electrochemical system (MES) can alter the route of interspecies electron transfer and the kinetics of reduction reactions. We tested reductive dechlorination of γ-hexachlorocyclohexane (γ-HCH), along with CH4 production, in MES systems whose cathodes were coated with conductive magnetite nanoparticles (NaFe), biochar (BC), magnetic biochar (FeBC), or anti-conductive silica biochar (SiBC). Coating with NaFe enriched electroactive microorganisms, boosted electro-bioreduction, and accelerated γ-HCH dechlorination and CH4 production. In contrast, BC only accelerated dechlorination, while FeBC only accelerated methanogenesis, because of their assemblies of functional taxa that selectively transferred electrons to those electron sinks. SiBC, which decreased electro-bioreduction, yielded the highest CH4 production and increased methanogens and the mcrA gene. This study provides a strategy to selectively control the distribution of electrons between reductive dechlorination and methanogenesis by adding conductive or anti-conductive materials to the MES's cathode. If the goal is to maximize dechlorination and minimize methane generation, then BC is the optimal conductive material. If the goal is to accelerate electro-bioreduction, then the best addition is NaFe. If the goal is to increase the rate of methanogenesis, adding anti-conductive SiBC is the best.

Potential risk of co-occurrence of microplastics and chlorinated persistent organic pollutants to coastal wetlands: Evidence from a case study.

Microplastic (MP) pollution in coastal wetlands is of a global concern. Little attention has been paid to the co-occurrence and corresponding risk of MPs with pollutants, especially refractory chlorinated persistent organic pollutants (CPOPs). A case study of Zhejiang, China was conducted to investigate the occurrence of MPs and targeted CPOPs in coastal wetlands. MPs were 100% detected, but with the lowest abundance in coastal wetlands (average: 666.1 ± 159.1 items kg-1), as compared to other 6 terrestrial ecosystems (average: 1293.9 ± 163.7 items kg-1) including paddy field, upland, facility vegetable field, forestland, urban soil, and grassland. A total of 35 kinds CPOPs were also detected in all studied coastal wetlands, with their concentration almost under 10 µg kg-1 (90.1%). Both enrichment of MPs and CPOPs was affected by sediment TOC, wetland vegetation and land use simultaneously. Interestingly, the occurrence of MPs was significantly correlated with polychlorinated biphenyls (PCBs) but not organochlorine pesticides (OCPs). Results of co-occurrence pollution assessment of MPs and CPOPs further indicated only Hangzhou Bay showed the ecological risk among all tested wetlands. This would suggest a potential risk of co-occurrence of MPs and modern CPOPs in coastal wetland in economic development area. Possible reason may lie on strong MP vector effect to CPOPs. More attention should thus be paid to other wetlands polluted by MPs and MP-carrying CPOPs in area with relatively great environmental pressure induced by human activity. This study may provide reference for a better understanding with respect to the risk level posed by co-occurrence of MPs and CPOPs to global coastal wetlands.

Accelerating Fe2+/Fe3+ cycle via biochar to improve catalytic degradation efficiency of the Fe3+/persulfate oxidation.

The sluggish Fe3+/Fe2+ cycle was the rate-limiting step in the Fenton-like reaction, and metal-free carbonaceous materials are considered as emerging alternatives to solve this problem. However, the effect of carbon material properties on the distribution of reactive species remains poorly understood. This study investigated the possibility and mechanism of using biochar to accelerate the Fe3+/Fe2+ cycle to overcome the low efficiency of Fe3+/persulfate (PS) catalytic oxidation of phenanthrene. More importantly, the contribution of reactive species in the reaction systems with the variation of biochar pyrolysis temperatures was quantitatively studied. The results showed that medium-temperature derived biochar (BC500) had the greatest ability to enhance the Fenton-like system compared to the low- and high-temperature (BC350/700), and the first-order rate constant achieved 5.2 and 35.7-fold increase against the biochar/PS and Fe3+/PS systems, respectively. Using electrochemical evidence, sulfoxide probe tests, and steady-state concentration calculations, radicals yields were found to rise and then reduce with decreasing pyrolysis temperature, while the nonradical contribution of Fe(IV) increased to 56.3%. Electron paramagnetic resonance, Boehm titration, and Raman spectroscopy unraveled that the enhanced effect of biochar resulted from itself persistent free radicals, phenolic-OH, and edge defects, which enabled electron transfer between Fe3+ and biochar. Fe2+ was thus continuously generated and effectively activated the PS. This work enables a better understanding of the Fe3+-mediated Fenton-like reaction in the presence of biochar and provides a sustainable green strategy for Fenton chemistry with potential applications.

Co-occurrence of light microplastics and phthalate esters in soils of China.

The terrestrial environment is both a critical source and sink for microplastics (MPs). However, further efforts into the risk assessment, management, and mitigation activities of MPs in the terrestrial environment were limited by the scant data on their occurrence. In this study, we investigated the co-occurrence and correlations of light MPs and phthalate esters (PAEs) in the soils of China's hotspots and non-hotspot regions. Light MPs and PAEs were detected in all agricultural and urban soils (n = 125). In soils from hotspots (Shihezi, Xinjiang) where intense plastic mulching was used, the concentrations of MPs and phthalate diesters (di-PAEs) were 650-36,450 pcs kg-1 and 55.60-1236.64 µg kg-1, respectively. In hotspots but not in non-hotspot regions of China, a positive correlation between MPs and PAEs was established, suggesting PAEs may serve as an indicator of MP contamination in hotspots. High quantities of MPs (1143-5911 pcs kg-1) and PAEs (67.3-1236.64 µg kg-1) were also detected in urban park soils, demonstrating a need for future research on MP in urban soils. In addition, the ubiquitous co-occurrence of MPs and PAEs in all 125 investigated soils revealed that potential joint toxicity, co-transformation, and co-transportation of MPs and PAEs should not be disregarded.

An enlarging ecological risk: Review on co-occurrence and migration of microplastics and microplastic-carrying organic pollutants in natural and constructed wetlands.

Wetlands are a key hub for the accumulation of microplastics (MPs) and have great load capacity to organic pollutants (OPs), thus, have been a hot research topic. It has shown that OPs adsorbed on MPs could be transported to anywhere and MP-associated biofilms also affects the co-occurrence of MPs and OPs. This would induce the desorption of MP-carrying OPs into environment again, increasing latent migration and convergence of MPs and OPs in wetlands. Considering MPs vector effect and MP-associated biofilms, it is necessary to integrate MPs information on its occurrence characteristics and migration behavior for an improved assessment of ecological risk brought by MPs and MP-carrying OPs to whole wetland ecosystems. In this review, we studied papers published from 2010 to 2020, focused on the interaction of MPs with OPs and the role of their co-occurrence and migration on ecological risk to wetlands. Results suggested the interaction between MPs and OPs dominated by adsorption altered their toxicity and environmental behavior, and the corresponding ecological risk induced by their co-occurrence to wetlands is various and complicated. Especially, constructed wetlands as the special hub for the migration of MPs and MP-carrying OPs might facilitate their convergence between natural and constructed wetlands, posing a potential enlarging ecological risk to whole wetlands. Since the study of MPs in wetlands has still been in a primary stage, we hope to provide a new sight to set forth the potential harm of MPs and MP-carrying OPs to wetlands and useful information for follow-up study.

Suspecting screening "known unknown" pesticides and transformation products in soil at pesticide manufacturing sites.

The occurrence and risks of pesticides and their transformation products in soil at the manufacturing sites are "known unknowns." In this study, pesticides and their transformation products were screened in soil at 6 pesticide manufacturing sites across China using liquid and gas chromatography coupled with quadrupole time-of-flight mass spectrometry. The screening strategy can correctly identify 75% of 209 pesticides spiked at 50 ng g-1. A total of 212 pesticides were identified; 23.1% of pesticides detected were above 200 ng g-1, and the maximum concentration was 1.5 × 105 ng g-1. The risk quotients of 20% pesticides were greater than 1, and the maximum risk quotient of imidacloprid reached 6.3 × 104. The most recent site showed a larger number of pesticides with higher diversity, whereas older sites were dominated by organochlorine insecticides. The extended screen identified 163 transformation products with concentrations up to 6.6 × 104 ng g-1. Half of the transformation products had higher concentrations than their parent compounds, and metabolic ratios up to 371 were observed. The results of this study validate the prevalence of pesticides and their transformation products in soil at pesticide manufacturing sites. The results also highlight the importance of comprehensive screening at industrial sites and call for improved management and regulation of pesticide manufacturing, particularly for in-service facilities.

Rhizobium Symbiotic Capacity Shapes Root-Associated Microbiomes in Soybean.

Root-microbiome interactions are of central importance for plant performance and yield. A distinctive feature of legumes is that they engage in symbiosis with N2-fixing rhizobia. If and how the rhizobial symbiotic capacity modulates root-associated microbiomes are still not yet well understood. We determined root-associated microbiomes of soybean inoculated with wild type (WT) or a noeI mutant of Bradyrhizobium diazoefficiens USDA 110 by amplicon sequencing. UPLC-MS/MS was used to analyze root exudates. The noeI gene is responsible for fucose-methylation of Nod factor secreted by USDA 110 WT strain. Soybean roots inoculated with the noeI mutant showed a significant decrease in nodulation and root-flavonoid exudation compared to roots inoculated with WT strain. The noeI mutant-inoculated roots exhibited strong changes in microbiome assembly in the rhizosphere and rhizoplane, including reduced diversity, changed co-occurrence interactions and a substantial depletion of root microbes. Root exudates and soil physiochemical properties were significantly correlated with microbial community shift in the rhizosphere between different rhizobial treatments. These results illustrate that rhizobial symbiotic capacity dramatically alters root-associated microbiomes, in which root exudation and edaphic patterns play a vital role. This study has important implications for understanding the evolution of plant-microbiome interactions.

Combination of high specific activity carbon-14 labeling and high resolution mass spectrometry to study pesticide metabolism in crops: Metabolism of cycloxaprid in rice.

The study of pesticide metabolism in crops is critical for assessing the mode of action and environmental risks of pesticides. However, the study of pesticide metabolism in crops is usually complicated and it is often a daunting challenge to accurately screen the metabolites of novel pesticides in complex matrices. This study demonstrated a combined use of high-specific activity carbon-14 labeling and high-resolution mass spectrometry (HSA-14C-HRMS) for metabolism profiling of a novel neonicotinoid cycloxaprid in rice. By generating the characteristic radioactive peaks on the liquid chromatogram, the use of 14C can eliminate the severe interference of complex matrices and quickly probe target compounds; by producing ion pairs with unique abundance ratios on HRMS, high-specific activity labeling can effectively exclude false matrix positives and promote the elucidation of metabolite structure. The structures of 15 metabolites were identified, three of which were further confirmed by authentic standards. Based on these metabolites, a metabolic profile of cycloxaprid was established, which includes denitrification, demethylation, imidazolidine hydroxylation and ring cleavage olefin formation, oxidation and carboxylation reactions. The strategy of combining high-specific activity 14C labeling and HRMS offers unique advantages and provides a powerful solution for profiling unknown metabolites of novel pesticides in complex matrices, especially when traditional non-labeling methods are not feasible.

Regulating the dechlorination and methanogenesis synchronously to achieve a win-win remediation solution for γ-hexachlorocyclohexane polluted anaerobic environment.

The wish for rapid degradation of chlorinated organic pollutants along with the increase concern with respect to greenhouse effect and bioenergy methane production have created urgent needs to explore synchronous regulation approach. Microbial electrolysis cell was established under four degressive cathode potential settings (from -0.15V to -0.60V) to regulate γ-hexachlorocyclohexane (γ-HCH) reduction while CH4 cumulation in this study. The synchronous facilitation of γ-HCH reduction and CH4 cumulation was occurred in -0.15V treatment while the facilitation of γ-HCH reductive removal together with the inhibition of CH4 cumulation was showed in -0.30V treatment. Electrochemical patterns via cyclic voltammetry and morphological performances via scanning electron microscopy illustrated bioelectrostimulation promoted redox reactions and helped to construct mature biofilms located on bioelectrodes. Also, bioelectrostimulated regulation pronouncedly affected the bacteria and archaeal communities and subsequently assembled distinctly core sensitive responders across bioanode, biocathode and plankton. Clostridum, Longilinea and Methanothrix relatively accumulated in the plankton, and Cupriavidus and Methanospirillum, and Perimonas and Nonoarcheaum in biocathode and bioanode, respectively; while Pseudomonas, Stenotrophomonas, Methanoculleus and Methanosarcina were diffusely enriched. Microbial interactions in the ecological network were more complicated in -0.15V and -0.30V cathodic potential treatments, coincident with the increasement of γ-HCH reduction. The co-existence between putative dechlorinators and methanogens was less significant in -0.30V treatment when compared to that in -0.15V treatment, relevant with the variations of CH4 cumulation. In all, this study firstly corroborated the availability to synchronously regulate γ-HCH reductive removal and methanogenesis. Besides, it paves an advanced approach controlling γ-HCH reduction in cooperation with CH4 cumulation, of which to achieve γ-HCH degradation facilitation along with biogas (CH4) production promotion with -0.15V cathode potential during anaerobic γ-HCH contaminated wastewater digestion, or to realize γ-HCH degradation facilitation with the inhibition of CH4 emission with -0.30V cathode potential for an all-win remediation in γ-HCH polluted anaerobic environment such as paddy soil.

Microbial and abiotic factors of flooded soil that affect redox biodegradation of lindane.

Pollution induces pressure to soil microorganism; and conversely, the degradation of pollutants is reported largely regulated by the soil microbiome assembly in situ. However, the specific-dependent core taxa of degraders were barely confirmed, which is not conducive to improving the soil remediation strategy. Taking pollution of a typical organochlorine pesticide (OCP), lindane, as an example, we explored the microbial community assembly in flooded soils and simultaneously quantified the corresponding dynamics of typical soil redox processes. Contrasting initial status of microbial diversity was set up by gamma irradiation or not, with additives (acetate, NaNO3, acetate + NaNO3) capable of modifying microbial growth employed simultaneously. Microorganism under lindane stress was reflected by microbial adaptability within complex co-occurrence networks, wherein some environment-dependent core taxa (e.g., Clostridia, Bacteroidia, Bacilli) were highly resilient to pollution and sterilization disturbances. Lindane had higher degradation rate in irradiated soil (0.96 mg kg-1 d-1) than non-irradiated soil (0.83 mg kg-1 d-1). In non-irradiated soil, addition of acetate promoted lindane degradation and methanogenesis, whereas nitrate inhibited lindane degradation but promoted denitrification. No significant differences in lindane degradation were observed in irradiated soils, which exhibited low-diversity microbiomes in parallel to stronger Fe reduction and methanogenesis. The varied corresponding trigger effects on soil redox processes are likely due to differences of soil microbiome, specifically, deterministic or stochastic assembly, in response to pollution stress under high or low initial microbial diversity conditions. Our results improve the knowledge of the adaptability of disturbed microbiomes and their feedback on microbial functional development in OCP-polluted soils, achieving for a more reliable understanding with respect to the ecological risk of soils resided with OCPs under the fact of global microbial diversity loss.

Quantification of the sorption of organic pollutants to minerals via an improved mathematical model accounting for associations between minerals and soil organic matter.

The retention of organic pollutant (OP) in soils is commonly attributed to interactions with soil organic matter (SOM), perhaps overlooking substantial involvement of soil minerals. In this study, 36 soil samples with far-ranging ratios of clay to organic carbon were used to examine contribution of minerals on soil sorption of pentachlorophenol (PCP) and phenanthrene (PHE). Sorption isotherms (n = 216) were fit individually using three typical sorption models, with the most fitted Kd values screened out for quantification of the net mineral contribution to total sorption via development of mathematical model accounting for associations between minerals and SOM. Two mineral-relevant parameters [adsorption distribution coefficient (Kmin) and mineral contribution index (MCI)] were simultaneously defined. Previously reported soil sorption data of PCP, PHE and butachlor (13, 12 and 46, respectively) were also extracted and included to improve the credibility of mathematic model. The average MCI values were calculated as 0.421, 0.405 and 0.512 in PCP, PHE and butachlor treated soils, respectively, very close to or even over than the minerals dominant critical value (0.5). This suggested the significant, or even predominant, contribution of minerals - as compared to SOM. Significant dependence of MCI with four conventional parameters of soil property further offered the possibility to roughly evaluate mineral contributions based on estimated threshold values of soil property parameters (especially TOC). This study provides an accessible approach for predicting the contribution of minerals in soil OP retention, especially highlighting their predominant roles vs. SOM in regulating OP removal in most of subsurface soil or contaminated brownfields where organic carbon content of soil was very low, that was not like what previously believed.

Determination and occurrence of bisphenol A and thirteen structural analogs in soil.

Bisphenol A is a phenolic plasticizer used in the production of various plastic products. Its endocrine-disrupting effects on ecological and human health lead to replacement with its structural analogs. The occurrence of these analogs in the soil environment, which is an important sink for bisphenols, has been rarely reported. In this study, a robust method was developed to determine bisphenol A and 13 analogs in soil using accelerated solvent extraction combined with in-line purification for fast and efficient extraction and ultra-performance liquid chromatography-tandem mass spectrometry for simultaneous and accurate quantification. The method detection limits of 14 bisphenols were between 0.01 and 0.39 ng g-1, and the recoveries were in the range of 80%-120%. The developed method was applied to 29 agricultural and urban soil samples from 21 provinces in China, and 12 bisphenols were detected. Among them, the contents of bisphenol A, F, and P were up to 166.0, 212.9, and 78.2 ng g-1 dry weight, respectively. The maximum concentration of bisphenol P was at least ten times higher than literature values in food and other environmental matrices. The results of this study showed that "hot spots" existed for bisphenol pollution in soil and that further investigations were necessary to avoid regrettable substitutions.

Methane-associated micro-ecological processes crucially improve the self-purification of lindane-polluted paddy soil.

Reductive dechlorination, an efficient pathway for complete removal of organic chlorinated pollutants (OCPs), is commonly reported to be coupled to oxidation of methane (CH4) or methanogenesis in anaerobic environments. However, the relationship between dechlorination and CH4-associated bioprocesses is unclear. Based on the hypothesis that CH4 supplementation could facilitate OCP dechlorination, we investigated the role of CH4-associated bioprocesses in the self-purification of flooded lindane-spiked paddy soils. Four treatments were conducted for up to 28 days: sterilized soil (S), sterilized soil + CH4 (SC), non-sterilized soil (NS), and non-sterilized soil + CH4 (NSC). Results indicated that both sterilization and addition of CH4 promoted lindane degradation and CH4 emissions in the flooded paddy soils. In the NS treatment, lindane had the lowest degradation rate when CH4 emissions were barely detected; while in the SC treatment, lindane had the highest degradation rate when CH4 achieved its highest emissions from anaerobic soil. Also, sterilization led to microbial diversity loss and functional recession, but increased ferrous ion [Fe(II)] concentrations compared to non-sterilized soils. Methanogenic communities and mcrA gene recovered faster than the majority of microorganisms (e.g., Fe bacteria, Bdellovibrionaceae, Rhizobiaceae, Dehalogenimonas) or functional genes (e.g., Dhc, Geo, narG, nirS). Collectively, we assume the enhanced removal of lindane may partly be due to both abiotic dechlorination promoted by chemical Fe redox processes and methanogenesis-derived biotic dechlorination. Revealing the coupling between dechlorination and CH4-associated bioprocesses is helpful to resolve both pollution remediation and mitigation of CH4 emissions in anaerobic contaminated sites.

Contrasting effects of microplastics on sorption of diazepam and phenanthrene in soil.

Microplastics have attracted extensive attention regarding their role in the cycling of organic pollutants in aquatic environments. However, the influence of microplastics on the sorption of organic pollutants in soil is unclear. Herein, we investigated the sorption of polar diazepam and nonpolar phenanthrene to two soils (Inceptisol and Oxisol). Batch sorption experiments were used to evaluate the effect of polyethylene (PE), polypropylene (PP), and polystyrene (PS) microplastics at addition rates of 0.1%, 1%, and 10% (w/w). The addition of microplastics significantly decreased the overall sorption of diazepam at 10%, and increased the sorption of phenanthrene at 1%, while the effects were negligible at other addition rates. Decreased sorption of diazepam was attributed to its lower sorption affinity to microplastics than to soil. Microplastics, even at 0.1%, substantially decreased the relative distribution of phenanthrene in soil, particularly for PE in the Oxisol with lower foc. The sorption affinity of phenanthrene followed the order PE > soil organic carbon (SOC) > PP > PS, suggesting that PE can be a significant sink of phenanthrene in contaminated soils. Overall, microplastics can change the sorption of diazepam and phenanthrene to soil and therefore affect their mobility and environmental risk in soil ecosystems.