Distribution, traceability, and risk assessment of organophosphate flame retardants in agricultural soils along the Yangtze River Delta in China.

Severe pollution threatens the ecosystem and human health in the Yangtze River Delta (YRD) in China because of the rapid development of industry in this area. This study examines the types, distribution, concentration, and origin of fourteen typical organophosphate flame retardants (OPFRs) in agricultural soils within the YRD region to offer insights for pollutant control and policy-making. The total concentration of OPFRs (ΣOPFRs) varied between 79.19 and 699.58 µg/kg dry weight (dw), averaging at 209.61 µg/kg dw. Among the OPFRs detected, tributoxyethyl phosphate (TBEP) was identified as the main congener, followed by tri-n-butyl phosphate (TnBP), tris(2-chloroisopropyl) phosphate (TCPP), and trimethyl phosphate (TMP). Source analysis, conducted through correlation coefficients and PCA, indicated that OPFRs in agricultural soils within the YRD region mainly originate from emissions related to plastic products and transportation. The health risk exposure to ΣOPFRs in agricultural soil was considered negligible for farmers, with values below 1.24 × 10-2 and 1.76 × 10-9 for noncarcinogenic and carcinogenic risks, respectively. However, the ecological risk of ΣOPFRs in all the samples ranged from 0.08-1.08, indicating a medium to high risk level. The results offer a comprehensive understanding of OPFR pollution in agricultural soils in the YRD region and can be useful for pollution control that mitigates ecological and health risks in this region.

Metagenomic and proteomic insights into the self-adaptive cell surface hydrophobicity of Sphingomonas sp. strain PAH02 reducing the migration of cadmium-phenanthrene co-pollutant in rice.

Cell surface hydrophobicity (CSH) dominates the interactions between rhizobacteria and pollutants at the soil-water interface, which is critical for understanding the dissipation of pollutants in the rhizosphere microzone of rice. Herein, we explored the effects of self-adaptive CSH of Sphingomonas sp. strain PAH02 on the translocation and biotransformation behaviour of cadmium-phenanthrene (Cd-Phe) co-pollutant in rice and rhizosphere microbiome. We evidenced that strain PAH02 reduced the adsorption of Cd-Phe co-pollutant on the rice root surface while enhancing the degradation of Phe and adsorption of Cd via its self-adaptive CSH in the hydroponic experiment. The significant upregulation of key protein expression levels such as MerR, ARHDs and enoyl-CoA hydratase/isomerase, ensures self-adaptive CSH to cope with the stress of Cd-Phe co-pollutant. Consistently, the bioaugmentation of strain PAH02 promoted the formation of core microbiota in the rhizosphere soil of rice (Oryza sativa L.), such as Bradyrhizobium and Streptomyces and induced gene enrichment of CusA and PobA that are strongly associated with pollutant transformation. Consequently, the contents of Cd and Phe in rice grains at maturity decreased by 17.2% ± 0.2% and 65.7% ± 0.3%, respectively, after the bioaugmentation of strain PAH02. These findings present new opportunities for the implementation of rhizosphere bioremediation strategies of co-contaminants in paddy fields.

Photosynthetic mechanisms of carbon fixation reduction in rice by cadmium and polycyclic aromatic hydrocarbons.

Environmental pollutants interfere with plant photosynthesis, thus reduce the crop yield and carbon storage capacity of farmland. This study comparatively explored the effects and mechanisms of polycyclic aromatic hydrocarbons (PAHs, e.g., phenanthrene, pyrene, and benzo[a]pyrene) and cadmium (Cd) on the carbon fixation capacity of rice throughout the growth period. Cd posed severer inhibition on the net carbon fixation of rice than PAHs, with the inhibition rates of 1.40-14.8-fold over PAHs at the concentrations of 0.5 or 5 mg/kg soil. Ribulose diphosphate carboxylase/oxygenase (Rubisco) involved in the Calvin cycle was identified as the common target of these pollutants to inhibit the photosynthetic carbon fixation. Further investigation demonstrated that the different inhibitory effects of Cd and PAHs was resulted from their different interference on the dual catalysis function (carboxylation and oxygenation) of Rubisco. Cd disturbed the balance of the intercellular CO2/O2, thus promoting the oxygenation and inhibiting the carboxylation of the substrate of Rubisco. Under the stress of Cd, the downstream metabolites (e.g. glycolate, glyoxylate, and serine) of Rubisco oxygenation were upregulated by over 2.01-3.24-fold, whereas the carboxylation efficiency (Vcmax) was decreased by 5.58-29.3%. Comparatively, PAHs inhibited both the carboxylation and oxygenation by down-regulating the expression of Rubisco coding gene (OsRBCS2, Log2FC < -2). This study broadens the understanding of the mechanisms of different environmental pollutants on the carbon fixation, providing valuable information for the quantitative estimation of their impacts on the farmland carbon sink. The results would be constructive to develop strategies for eliminating the adverse effects of contaminants and assist the carbon-neutral programs.

Predicting soil concentrations and remediation target values of BTEX by an off-gas based mass transfer model.

Soil vapor extraction (SVE) is a widely used technology for the remediation of volatile organic compounds (VOCs) contaminated soils. Residual concentrations of VOCs are crucial for assessing the SVE process and planning when to stop this process, however, the measurement of their residual concentrations in the soil is complicated. Herein, a pseudo-first-order sequential reaction model was established to predict the mass transfer of the BTEX (benzene, toluene, ethylbenzene, xylene) between the soil and off-gas during the SVE process. Based on this mass transfer model, the residual concentrations of BTEX in the soil during the trailing stage could be accurately estimated (R2 > 0.89) by their off-gas concentrations that were directly monitored in real time. Considering the removal efficiency and operating costs, a concept of the remediation target values (RTV) was proposed for the SVE technology, and its relevant model (R2 > 0.92, NRMSE = 6.4-16.8 %) was established based on the experimental data. The remediation endpoint can be further estimated based on the RTV with an overall accuracy of 84-100 %. These findings provide a simple and fast way to predict VOC concentrations in soil with easy-to-know factors and online monitoring of off-gas concentrations and will guide and optimize the SVE process toward more economical and efficient techniques for soil remediation.

Interaction between Phthalate Ester and Rice Plants: Novel Transformation Pathways and Metabolic-Network Perturbations.

Our understanding is limited concerning the interaction mechanism between widespread phthalate esters and staple crops, which have strong implications for human exposure. Therefore, this study was aimed at illuminating the transformation pathways of di-n-butyl phthalate (DnBP) in rice using an untargeted screening method. UPLC-QTOF-MS identified 16 intermediate transformation products formed through hydroxylation, hydrolysis, and oxidation in phase I metabolism and further by conjugation with amino acids, glutathione, and carbohydrates in phase II metabolism. Mono-2-hydroxy-n-butyl phthalate-l-aspartic acid (MHBP-asp) and mono-2-hydroxy-n-butyl phthalate-d-alanyl-ß-d-glucoside (MHBP-ala-glu) products were observed for the first time. The proteomic analysis demonstrated that DnBP upregulated the expression of rice proteins associated with transporter activity, antioxidant synthesis, and oxidative stress response and downregulated that of proteins involved in photosynthesis, photorespiration, chlorophyll binding, and mono-oxygenase activity. Molecular docking revealed that DnBP can affect protein molecular activity via pi-sigma, pi-alkyl, and pi-pi interactions or by forming carbon-hydrogen bonds. The metabolomic analysis showed that key metabolic pathways including citrate cycle, biosynthesis of aminoacyl-tRNA, and metabolism of amino acids, sphingolipids, carbohydrates, nucleotides, and glutathione were activated in rice plants exposed to DnBP and its primary metabolite mono-n-butyl phthalate (MnBP). Furthermore, exposure to 80 ng/mL MnBP significantly perturbed the metabolic profile and molecular function in plants, with downregulation of the levels of beta-alanine (0.56-fold), cytosine (0.48-fold), thymine (0.62-fold), uracil (0.48-fold), glucose (0.59-fold), and glucose-1-phosphate (0.33-fold), as well as upregulation of the levels of l-glutamic acid (2.97-fold), l-cystine (2.69-fold), and phytosphingosine (38.38-fold). Therefore, the degradation intermediates of DnBP pose a potentially risk to plant metabolism and raise concerns for crop safety related to plasticizer pollution.

Removal of organic pollutants in shale gas fracturing flowback and produced water: A review.

Shale gas has been developed as an alternative to conventional energy worldwide, resulting in a large amount of shale gas fracturing flowback and produced water (FPW). Previous studies focus on total dissolved solids reduction using membrane desalination. However, there is a lack of efficient and stable techniques to remove organic pollutants, resulting in severe membrane fouling in downstream processes. This review focuses on the concentration and chemical composition of organic matter in shale gas FPW in China, as well as the hazards of organic pollutants. Organic removal techniques, including advanced oxidation processes, coagulation, sorption, microbial degradation, and membrane treatment are systematically reviewed. In particular, the influences of high salt on each technique are highlighted. Finally, different treatment techniques are evaluated in terms of energy consumption, cost, and organic removal efficiency. It is concluded that integrated coagulation-sorption-Fenton-membrane filtration represents a promising treatment process for FPW. This review provides valuable information for the feasible design, practical operation, and optimization of FPW treatment.

Chlorinated nucleotides and analogs as potential disinfection byproducts in drinking water.

Identification of emerging disinfection byproducts (DBPs) of health relevance is important to uncover the health risk of drinking water observed in epidemiology studies. In this study, mutagenic chlorinated nucleotides were proposed as potential DBPs in drinking water, and the formation and transformation pathways of these DBPs in chlorination of nucleotides were carefully investigated. A total of eleven chlorinated nucleotides and analogs were provisionally identified as potential DBPs, such as monochloro uridine/cytidine/adenosine acid and dichloro cytidine acid, and the formation mechanisms involved chlorination, decarbonization, hydrolysis, oxidation and decarboxylation. The active sites of nucleotides that reacted with chlorine were on the aromatic heterocyclic rings of nucleobases, and the carbon among the two nitrogen atoms in the nucleobases tended to be transformed into carboxyl group or be eliminated, further forming ring-opening or reorganization products. Approximately 0.2-4.0 % (mol/mol) of these chlorinated nucleotides and analogs finally decomposed to small-molecule aliphatic DBPs, primarily including haloacetic acids, trichloromethane, and trichloroacetaldehyde. Eight intermediates, particularly chlorinated imino-D-ribose and imino-D-ribose, were tentatively identified in chlorination of uridine. This study provides the first set of preliminary evidence for indicating the promising occurrence of chlorinated nucleotides and analogs as potential toxicological-relevant DBPs after disinfection of drinking water.

Predicting laterite redox potential with iron activity and electron transfer term.

Predicting the redox behavior of organic contaminants and heavy metals in soils is challenging because there are few soil redox potential (Eh) models. In particular, current aqueous and suspension models usually show a significant deviation for complex laterites with few Fe(II). Here, we measured the Eh of simulated laterites over a range of soil conditions (2450 tests). The impacts of soil pH, organic carbon, and Fe speciation on the Fe activity were quantified as Fe activity coefficients, respectively, using a two-step Universal Global Optimization method. Integrating these Fe activity coefficients and electron transfer terms into the formula significantly improved the correlation of measured and modeled Eh values (R2 = 0.92), and the estimated Eh values closely matched the relevant measured Eh values (accuracy R2 = 0.93). The developed model was further verified with natural laterites, presenting a linear fit and accuracy R2 of 0.89 and 0.86, respectively. These findings provide compelling evidence that integrating Fe activity into the Nernst formula could accurately calculate the Eh if the Fe(III)/Fe(II) couple does not work. The developed model could help to predict the soil Eh toward controllable and selective oxidation-reduction of contaminants for soil remediation.

Methoxylated Modification of Glutathione-Mediated Metabolism of Halobenzoquinones In Vivo and In Vitro.

Xenobiotics were generally detoxified in organisms through interaction with endogenous molecules, which may also generate metabolites of increased toxicity. Halobenzoquinones (HBQs), a group of highly toxic emerging disinfection byproducts (DBPs), can be metabolized by reacting with glutathione (GSH) to form various glutathionylated conjugates (SG-HBQs). In this study, the cytotoxicity of HBQs in CHO-K1 cells showed a wavy curve as a function of increased GSH dosage, which was inconsistent with the commonly recognized progressive detoxification curve. We hypothesized that the formation and cytotoxicity of GSH-mediated HBQ metabolites contribute to the unusual wave-shaped cytotoxicity curve. Results showed that glutathionyl-methoxyl HBQs (SG-MeO-HBQs) were identified to be the primary metabolites significantly correlated with the unusual cytotoxicity variation of HBQs. The formation pathway was initiated by stepwise metabolism via hydroxylation and glutathionylation to produce detoxified hydroxyl HBQs (OH-HBQs) and SG-HBQs, followed by methylation to generate SG-MeO-HBQs of potentiated toxicity. To further verify the occurrence of the aforementioned metabolism in vivo, SG-HBQs and SG-MeO-HBQs were detected in the liver, kidney, spleen, testis, bladder, and feces of HBQ-exposed mice, with the highest concentration quantified in the liver. The present study supported that the co-occurrence of metabolism can be antagonistic, which enhanced our understanding of the toxicity and metabolic mechanism of HBQs.

Attenuation of tetracyclines and related resistance genes in soil when exposed to nanoscale zero-valent iron.

Antibiotics pollution in soil poses increasing threats to human health due to stimulated proliferation and transmission of antibiotic resistance genes (ARGs). Nanoscale zero-valent iron (NZVI) is a promising material for the remediation of antibiotics, but how NZVI affects the diversity, abundance, and horizontal gene transfer potentials of ARGs remains unclear. Herein, the biotic and abiotic effects of NZVI at different concentrations on tetracyclines (TCs) and the associated ARGs were investigated. Results showed NZVI could effectively accelerate the degradation of TCs, which increased from 51.38% (without NZVI) to 57.96%- 71.66% (1-10 g NZVI/kg) in 20 days. Biotic degradation contributed to 66.10%- 76.30% of the total TCs removal. NZVI induced TCs biodegradation was probably due to alleviated toxicity of TCs on cells and increased microbial biomass and enzyme activities. Additionally, TCs-related ARGs were attenuated with decreased horizontal gene transfer potentials of intI1 and ISCR1, but opposite effects were observed for non TC-related ARGs, especially during excess exposure to NZVI. This study illustrated the possibility of remediating of antibiotic contaminated soil by NZVI and meanwhile reducing the potential risks of ARGs.

Effects of iron mineral adhesion on bacterial conjugation: Interfering the transmission of antibiotic resistance genes through an interfacial process.

Bacterial conjugation is one of the most prominent ways for antibiotic resistance genes (ARGs) transmission in the environment. Interfacial interactions between natural colloidal minerals and bacteria can alter the effective contact of bacteria, thereby affecting ARGs conjugation. Understanding the impact of iron minerals, a core component of colloidal minerals, on ARGs conjugation can help assess and intervene in the risk of ARGs transmission. With three selected iron minerals perturbation experiments, it was found that the conjugative transfer of plasmid that carried kanamycin resistance gene was 1.35 - 3.91-fold promoted by low concentrations of iron minerals (i.e., 5 - 100 mg L-1), but inhibited at high concentrations (i.e., 1000 - 2000 mg L-1) as 0.10 - 0.22-fold. Conjugation occurrence was highly relevant to the number of bacteria adhering per unit mass of mineral, thus switch in the adhesion modes of mineral-bacterial determined whether the conjugate transfer of ARGs was facilitated or inhibited. In addition, a unified model was formularized upon the physicochemical and physiological effects of adhesion on conjugation, and it can be used in estimating the critical inhibitory concentration of different iron minerals on conjugation. Our findings indicate natural colloidal minerals have great potential for applications in preventing the environmental propagation of ARGs through interfacial interactions.

Molecular Structure and Sulfur Content Affect Reductive Dechlorination of Chlorinated Ethenes by Sulfidized Nanoscale Zerovalent Iron.

Sulfidized nanoscale zerovalent iron (SNZVI) with desirable properties and reactivity has recently emerged as a promising groundwater remediation agent. However, little information is available on how the molecular structure of chlorinated ethenes (CEs) affects their dechlorination by SNZVI or whether the sulfur content of SNZVI can alter their dechlorination pathway and reactivity. Here, we show that the reactivity (up to 30-fold) and selectivity (up to 70-fold) improvements of SNZVI (compared to NZVI) toward CEs depended on the chlorine number, chlorine position, and sulfur content. Low CEs (i.e., vinyl chloride and cis-1,2-dichloroethene) and high CEs (perchloroethene) tended to be dechlorinated by SNZVI primarily via atomic H and direct electron transfer, respectively, while SNZVI could efficiently and selectively dechlorinate trichloroethene and trans-1,2-dichloroethene via both pathways. Increasing the sulfidation degree of SNZVI suppressed its ability to produce atomic H but promoted electron transfer and thus altered the relative contributions of atomic H and electron transfer to the CE dechlorination, resulting in different reactivities and selectivities. These were indicated by the correlations of CE dechlorination rates and improvements with CE molecular descriptors, H2 evolution rates, and electron transfer indicators of SNZVI. These mechanistic insights indicate the importance of determining the structure-specific properties and reactivity of both SNZVI materials and their target contaminants and can lead to a more rational design of SNZVI for in situ groundwater remediation of various CEs.

Quantitative identification of halo-methyl-benzoquinones as disinfection byproducts in drinking water using a pseudo-targeted LC-MS/MS method.

Halobenzoquinones (HBQs) as disinfection byproducts (DBPs) in drinking water is prioritized for research due to their prevalent occurrence and high toxicity. However, only fifteen HBQs can be identified among a high diversity using targeted LC-MS/MS analysis in previous studies due to the lack of chemical standards. In this study, we developed a pseudo-targeted LC-MS/MS method for detecting and quantifying diverse HBQs. Distinct fragment characteristics of HBQs was observed according to the halogen substituent effects, and extended to the development of a multiple-reaction-monitoring (MRM) method for the quantification of the 46 HBQs that were observed in simulated drinking water using non-targeted analysis. The fragmentation mechanism was supported by the changes of Gibbs free energy (ΔG), and a linear relationship between the ΔG and the ionization efficiency of analytes was developed accordingly for quantification of these 46 HBQs, 30 of which were lack of chemical standards. It is noted that 29 of the 30 newly-identified HBQs were halo-methyl-benzoquinones (HMBQs), which were predicted to be carcinogens related with drinking-water bladder cancer risk and be more toxic than non-methyl HBQs. Using the new method, twelve HMBQs were detected in actual drinking water samples with concentrations up to 100.4 ng/L, 3 times higher than that reported previously. The cytotoxicity in CHO cells of HMBQs was over 1-fold higher than that of non-methyl-HBQs. Therefore, HMBQs are an essential, highly toxic group of HBQs in drinking water, which deserve particular monitoring and control.

Effect of Shixiao San on inflammatory factors and pain in rats with endometriosis.

ETHNOPHARMACOLOGICAL RELEVANCE: In the practice of traditional Chinese medicine, endometriosis is believed to be caused by blood stasis and is characterised by dysmenorrhea, which is difficult to control. Shixiao San (SXS) has a long history of use in the treatment of gynaecological diseases. The prescriptions composed of SXS include Typhae Pollen and Faeces Trogopterori, both of which have anti-inflammatory activity. In addition, Typhae Pollen can be used to treat many kinds of blood stasis diseases. AIM OF THE STUDY: The purpose of the present study was to investigate the effect of SXS on pain relief in rats with endometriosis and to preliminarily explore its mechanism of action in alleviating pain. MATERIAL AND METHODS: Ten rats received sham operation as the Sham group, and 30 endometriosis model rats were randomly divided into three groups: the Model, Shixiao San-Low (SXS-L), and Shixiao San-High (SXS-H) groups. The rats were administered the appropriate treatment via intragastric gavage for 4 weeks. The thermal radiation pain and mechanical pain thresholds of the rats were measured every 7 days after treatment. Finally, the distribution density of nerve fibres in endometrial tissue, the inflammatory infiltration of the dorsal root ganglion (DRG), the expression of TRPV1 in the DRG, and the expression of IL-1ß, TNF-α, and IL-6 in ectopic tissue were measured. RESULTS: After SXS treatment, the growth of ectopic tissue in rats with endometriosis was significantly suppressed, their thermal radiation pain and mechanical pain thresholds increased, the density of nerve fibres and the expression of inflammatory factors in ectopic tissues reduced, and inflammatory cells infiltration in the DRG of the animals alleviated. Meanwhile, the expression of TRPV1 in the DRG was downregulated in rats with endometriosis. CONCLUSIONS: SXS could possibly inhibit the development of endometriosis and relieve pain in patients with endometriosis by reducing inflammatory responses in ectopic tissue and the DRG.

Transformation of sulfamethoxazole by sulfidated nanoscale zerovalent iron activated persulfate: Mechanism and risk assessment using environmental metabolomics.

The threat caused by the misuse of antibiotics to ecology and human health has been aroused an extensive attention. Developing cost-effective techniques for removing antibiotics needs to put on the agenda. In current research, the degradation mechanism of sulfamethoxazole (SMX) by sulfidated nanoscale zerovalent iron (S-nZVI) driven persulfate, together with the potential risk of intermediates were studied. The degradation of SMX followed a pseudo-first order kinetics reaction with kobs at 0.1176 min-1. Both SO4•- and •OH were responsible for the degradation of SMX, and SO4•- was the predominant free radical. XPS analysis demonstrated that reduced sulfide species promoted the conversion of Fe (III) to Fe (II), resulting in the higher transformation rate of SMX. Six intermediates products were generated through hydroxylation, dehydration condensation, nucleophilic reaction, and hydrolysis. The risk of intermediates products is subsequently assessed using E. coli as a model microorganism. After E.coli exposure to intermediates for 24 h, the upmetabolism of carbohydrate, nucleotide, citrate acid cycle and downmetabolism of glutathione, sphingolipid, galactose by metabolomics analysis identified that SMX was effectively detoxified by oxidation treatment. These findings not only clarified the superiority of S-nZVI/persulfate, but also generated a novel insight into the security of advanced oxidation processes.

Analytical characterization of nucleotides and their concentration variation in drinking water treatment process.

Nucleotides, as the basic building blocks of nucleic acids, widely exist in aqueous environment. In this study, we developed a solid phase extraction-high performance liquid chromatography-tandem mass spectrometry (SPE-UPLC-MS/MS) method for the analysis of 5'-adenosine monophosphate (AMP), 5'-uridine monophosphate (UMP), 5'-cytidine monophosphate (CMP) and 5'-guanosine monophosphate (GMP). The method achieved limits of detection (LODs) of 0.1-1.0 ng/L, and recoveries of 85-95% for the four tested nucleotides. The occurrence and concentrations of the four nucleotides in water from eight representative drinking water treatment and distribution systems in China were determined using this method. All four nucleotides were detectable in water treatment plant (WTP) influent and effluent, at concentrations of up to 30 ng/L and with occurrence frequency of around 90%. The concentrations of identified nucleotides increased 3-10 times after 10 km of water age in the water distribution system. Biological filters and coagulation increased the concentrations of nucleotides, conversely, active carbon, ozonation, and ultrafiltration membrane removed nucleotides in water. The effects of active carbon and coagulation were further confirmed using laboratory-controlled experiment. In addition, monochlorinated nucleotides were identified as the chlorination products of nucleotides.

Triton X-100 improves the reactivity and selectivity of sulfidized nanoscale zerovalent iron toward tetrabromobisphenol A: Implications for groundwater and soil remediation.

Sulfidized nanoscale zerovalent iron (SNZVI) with improved reactivity and selectivity has shown great potential for environmental remediation. However, it is unclear if SNZVI could be applied for the remediation of soil washing solution, and how a soil-washing surfactant affects the reactivity and selectivity of SNZVI. Here, we assess the impact of Triton X-100 (TX-100) on the reactivity and selectivity of a sulfidized commercial NZVI toward tetrabromobisphenol A (TBBPA). While sulfidation of NZVI improved its reactivity and electron efficiency toward TBBPA, TX-100 could further improve these promoting effects, which was 8-21 and 4-7 times higher than those without TX-100, respectively, depending on TX-100 concentration. Because TX-100 could induce the solubilization of TBBPA, sorb onto the SNZVI surface, and favor the subsequent sorption and degradation of TBBPA. SNZVI performance for successive treatments of TBBPA contaminated water was also greatly improved by TX-100. Moreover, washing the TBBPA-contaminated soil with TX-100 could efficiently extract the TBBPA, and almost all of the TBBPA in the soil washing solution could be efficiently degraded by SNZVI. These results suggest that TX-100 is a good additive to SNZVI for improving its performance, and SNZVI coupled with TX-100 can be a promising technology for the remediation of TBBPA-contaminated soil.

Nano-Zoo Interfacial Interaction as a Design Principle for Hybrid Soil Remediation Technology.

Using nanotechnology to remediate contaminated agricultural soil is promising but faces notable technical and economic challenges. Importantly, widely distributed soil invertebrates can potentially act as natural mobile facilitators for in situ nanoscale remediation of contaminated soil. Herein, we have drawn inspiration from nano-bio interaction and established a hybrid remediation framework using nanoscale zerovalent iron (nZVI) and nematodes for organochlorine-contaminated soil. Approximately 80% pentachlorophenol (PCP, initially 50 mg/kg) was synergistically degraded by nZVI and nematodes within 3 days. Mechanistically, exposure to nZVI stimulated the synthesis of reductive biomolecules (including collagen, glutathione, and l-cysteine) which acted as a bioreductive barrier and significantly mitigated the toxicity of PCP. At the microinterface, collagen distributed in the epidermis chelated nZVI; subsequently, l-cysteine and glutathione strongly accelerated nZVI-induced PCP dechlorination by facilitating the reductive dissolution of nZVI oxide shell and electron transfer from Fe0 core to PCP. On the basis of the interfacial interaction, an optimized soil remediation approach composed of nZVI, nematodes, and l-cysteine was established, demonstrating a 2.1-fold increase in removal efficiency with only 48.5% nZVI consumption compared with the nZVI treatment alone. This work provides a heuristic model for developing cost-efficient remediation technologies with the synergistic force of functional materials and indigenous biota, which may be widely applicable to a range of environmental contamination scenarios.

Iron Sulfide Enhanced the Dechlorination of Trichloroethene by Dehalococcoides mccartyi Strain 195.

Iron sulfide (FeS) nanoparticles have great potential in environmental remediation. Using the representative species Dehalococcoides mccartyi strain 195 (Dhc 195), the effect of FeS on trichloroethene (TCE) dechlorination was studied with hydrogen and acetate as the electron donor and carbon source, respectively. With the addition of 0.2 mM Fe2+ and S2-, the dechlorination rate of TCE was enhanced from 25.46 ± 1.15 to 37.84 ± 1.89 µmol⋅L-1⋅day-1 by the in situ formed FeS nanoparticles, as revealed through X-ray diffraction. Comparing the tceA gene copy numbers between with FeS and without FeS, real-time polymerase chain reaction (PCR) indicated that the abundance of the tceA gene increased from (2.83 ± 0.13) × 107 to (4.27 ± 0.21) × 108 copies/ml on day 12. The transcriptional activity of key genes involved in the electron transport chain was upregulated after the addition of FeS, including those responsible for the iron-sulfur cluster assembly protein gene (DET1632) and transmembrane transport of iron (DET1503, DET0685), cobalamin (DET0685, DET1139), and molybdenum (DET1161) genes. Meanwhile, the reverse transcription of tceA was increased approximately five times on the 12th day. These upregulations together suggested that the electron transport of D. mccartyi strain 195 was enhanced by FeS for apparent TCE dechlorination. Overall, the present study provided an eco-friendly and effective method to achieve high remediation efficiency for organohalide-polluted groundwater and soil.

Remediation of soil contaminated with organic compounds by nanoscale zero-valent iron: A review.

In recent years, nanoscale zero-valent iron (nZVI) has been gradually applied in soil remediation due to its strong reducing ability and large specific surface area. Compared to conventional remediation solutions, in situ remediation using nZVI offers some unique advantages. In this review, respective merits and demerits of each approach to nZVI synthesis are summarized in detail, particularly the most commonly used aqueous-phase reduction method featuring surface modification. In order to overcome undesired oxidation and agglomeration of fresh nZVI due to its high reactivity, modifications of nZVI have been developed such as doping with transition metals, stabilization using macromolecules or surfactants, and sulfidation. Mechanisms underlying efficient removal of organic pollutants enabled by the modified nZVI lie in alleviative oxidation and agglomeration of nZVI and enhanced electron utilization efficiency. In addition to chemical modification, other assisting methods for further improving nZVI mobility and reactivity, such as electrokinetics and microbial technologies, are evaluated. The effects of different remediation technologies and soil physicochemical properties on remediation performance of nZVI are also summarized. Overall, this review offers an up-to-date comprehensive understanding of nZVI-driven soil remediation from scientific and practical perspectives.