Divergent redistribution behavior of divalent metal cations associated with Fe(II)-mediated jarosite phase transformation.

The Fe(II)/Fe(III) cycle is an important driving force for dissolution and transformation of jarosite. Divalent heavy metals usually coexist with jarosite; however, their effects on Fe(II)-induced jarosite transformation and different repartitioning behavior during mineral dissolution-recrystallization are still unclear. Here, we investigated Fe(II)-induced (1 mM Fe(II)) jarosite conversion in the presence of Cd(II), Mn(II), Co(II), Ni(II) and Pb(II) (denoted as Me(II), 1 mM), respectively, under anaerobic condition at neutral pH. The results showed that all co-existing Me(II) retarded Fe(II)-induced jarosite dissolution. In the Fe(II)-only system, jarosite first rapidly transformed to lepidocrocite (an intermediate product) and then slowly to goethite; lepidocrocite was the main product. In Fe(II)-Cd(II), -Mn(II), and -Pb(II) systems, coexisting Cd(II), Mn(II) and Pb(II) retarded the above process and lepidocrocite was still the dominant conversion product. In Fe(II)-Co(II) system, coexisting Co(II) promoted lepidocrocite transformation into goethite. In Fe(II)-Ni(II) system, jarosite appeared to be directly converted into goethite, although small amounts of lepidocrocite were detected in the final product. In all treatments, the appearance or accumulation of lepidocrocite may be also related to the re-adsorption of released sulfate. By the end of reaction, 6.0 %, 4.0 %, 76.0 % 11.3 % and 19.2 % of total Cd(II), Mn(II), Pb(II) Co(II) and Ni(II) were adsorbed on the surface of solid products. Up to 49.6 %, 44.3 %, and 21.6 % of Co(II), Ni(II), and Pb(II) incorporated into solid product, with the reaction indicating that the dynamic process of Fe(II) interaction with goethite may promote the continuous incorporation of Co(II), Ni(II), and Pb(II).

Prediction of Cr(VI) and As(V) adsorption on goethite using hybrid surface complexation-machine learning model.

This study aimed to develop surface complexation modeling-machine learning (SCM-ML) hybrid model for chromate and arsenate adsorption on goethite. The feasibility of two SCM-ML hybrid modeling approaches was investigated. Firstly, we attempted to utilize ML algorithms and establish the parameter model, to link factors influencing the adsorption amount of oxyanions with optimized surface complexation constants. However, the results revealed the optimized chromate or arsenate surface complexation constants might fall into local extrema, making it unable to establish a reasonable mapping relationship between adsorption conditions and surface complexation constants by ML algorithms. In contrast, species-informed models were successfully obtained, by incorporating the surface species information calculated from the unoptimized SCM with the adsorption condition as input features. Compared with the optimized SCM, the species-informed model could make more accurate predictions on pH edges, isotherms, and kinetic data for various input conditions (for chromate: root mean square error (RMSE) on test set = 5.90 %; for arsenate: RMSE on test set = 4.84 %). Furthermore, the utilization of the interpretable formula based on Local Interpretable Model-Agnostic Explanations (LIME) enabled the species-informed model to provide surface species information like SCM. The species-informed SCM-ML hybrid modeling method proposed in this study has great practicality and application potential, and is expected to become a new paradigm in surface adsorption model.

Iron-enhanced microscale laboratory aerated filters in the treatment of artificial mariculture wastewater: A study on nitrogen removal performance and the impact on microbial community structure.

This study investigates the nitrogen removal efficacy and microbial community dynamics in seawater aquaculture effluent treatment using three different substrate combinations of microscale laboratory aerated filters (MFs) - MF1 (LECA), MF2 (LECA/Fe-C), and MF3 (LECA/Pyrite). The findings indicated that the COD removal exceeded 95% across all MFs, with higher removal efficiencies in MF2 and MF3. In terms of nitrogen removal performance, MF2 exhibited the highest average nitrogen removal of 93.17%, achieving a 12.35% and 3.56% increase compared to MF1 (80.82%) and MF3 (89.61%), respectively. High-throughput sequencing analysis revealed that the Fe-C substrate significantly enhanced the diversity of the microbial community. Notably, in MF2, the salinophilic denitrifying bacterium Halomonas was significantly enriched, accounting for 42.6% of the total microbial community, which was beneficial for nitrogen removal. Moreover, an in-depth analysis of nitrogen metabolic pathways and microbial enzymes indicated that MF2 and MF3 possessed a high abundance of nitrification and denitrification enzymes, related to the high removal rates of NH4+-N and NO3--N. Therefore, the combination of LECA with iron-based materials significantly enhances the nitrogen removal efficiency from mariculture wastewater.

Non-targeted screening and photolysis transformation of tire-related compounds in roadway runoff.

Roadway runoff serves as a crucial pathway for transporting contaminants of emerging concern (CECs) from urban environments to receiving water bodies. Tire-related compounds originating from tire wear particles (TWPs) have been frequently detected, posing a potential ecological threat. Yet, the photolysis of tire-related compounds within roadway runoff remains inadequately acknowledged. Addressing this deficit, our study utilized high-resolution mass spectrometry (HRMS) to characterize the chemical profile of roadway runoff across eight strategically selected sites in Guangzhou, China. 219 chemicals were identified or detected within different confidence levels. Among them, 29 tire-related contaminants were validated with reference standards, including hexa(methoxymethyl)melamine (HMMM), 1,3-diphenylguanidine (DPG), dicyclohexylurea (DCU), and N-cyclohexyl-2-benzothiazol-amine (DCMA). HMMM exhibited with the abundance ranging from 2.30 × 104-3.10 × 106, followed by DPG, 1.69 × 104-8.34 × 106. Runoff sample were exposed to irradiation of 500 W mercury lamp for photodegradation experiment. Photolysis results indicated that tire-related compounds with a low photolysis rate, notably DCU, DCMA, and DPG, are more likely to persist within the runoff. The photolytic rates were significantly correlated with the spatial distribution patterns of these contaminants. Our findings underscore TWPs as a significant source of pollution in water bodies, emphasizing the need for enhanced environmental monitoring and assessment strategies.

Enhancing compound confidence in suspect and non-target screening through machine learning-based retention time prediction.

The retention time (RT) of contaminants of emerging concern (CECs) in liquid chromatography-high-resolution mass spectrometry (LC-HRMS) is crucial for database matching in non-targeted screening (NTS) analysis. In this study, we developed a machine learning (ML) model to predict RTs of CECs in NTS analysis. Using 1051 CEC standards, we evaluated Random Forest (RF), XGBoost, Support Vector Regression (SVR), and Artificial Neural Network (ANN) with molecular fingerprints and chemical descriptors to establish an optimal model. The SVR model utilizing chemical descriptors resulted in good predictive capacity with R2ext = 0.850 and r2 = 0.925. The model was further validated through laboratory NTS compound characterization. When applied to examine CEC occurrence in a large wastewater treatment plant, we identified 40 level S1 CECs (confirmed structure by reference standard) and 234 level S2 compounds (probable structure by library spectrum match). The model predicted RTs for level S2 compounds, leading to the classification of 153 level S2 compounds with high confidence (ΔRT <2 min). The model served as a robust filtering mechanism within the analytical framework. This study emphasizes the importance of predicted RTs in NTS analysis and highlights the potential of prediction models. Our research introduces a workflow that enhances NTS analysis by utilizing RT prediction models to determine compound confidence levels.

Efficient removal of heavy metals in water utilizing facile cross-link conjugated linoleic acid micelles.

Micellar-enhanced ultrafiltration (MEUF) technology is an effective method to treat low-concentration heavy metal wastewater. However, the leakage of surfactants in the ultrafiltration (UF) process will inevitably cause secondary pollution. In this study, a biosurfactant of conjugated linoleic acid (CLA) with conjugated double bonds was selected to bind its micelles by simple thermal crosslinking to obtain morphologically stable stearic acid (SA) nanoparticles. The pure SA nanoparticles were obtained by repeated dialysis. The stability of the SA nanoparticles was verified by comparing the particle size distribution and solubility of the materials before and after crosslinking at different pH levels. The effectiveness of SA nanoparticle-enhanced UF in removing heavy metals was verified by exploring the adsorption performance of SA nanoparticles. The dialysis device was used to simplify the UF device, wherein SA nanoparticles were assessed as adsorbents for the elimination of Cu2+, Pb2+, and Cd2+ ions from aqueous solutions under diverse process parameters, including pH, contact time, metal ion concentration, and coexisting ions. The findings indicate that the SA nanoparticles have no evidence of secondary contamination in UF and exhibit compatibility with a broad pH range and coexisting ions. The maximum adsorption capacities for Cu2+, Pb2+, and Cd2+ were determined to be 152.77, 403.56, and 271.46 mg/g, respectively.

Optimization and verification of selective removal of organophosphate esters from wastewater by molecularly imprinted adsorbent.

Tributyl phosphate (TNBP), a new type of flame retardant, is an emerging pollutant and has been frequently detected in various matrices such as wastewater. Efficient removal of TNBP is critical for wastewater treatment. In this study, molecularly imprinted polymer (MIP) was prepared using precipitation polymerization for selective adsorption of TNBP. The results showed that MIP had a porous structure and formed effective imprinting cavities, which was primarily responsible for its superior adsorption ability. The adsorption of TNBP by MIP was carried out following both the pseudo-secondary kinetic model and the Langmuir isothermal adsorption model. MIP adsorbed TNBP rapidly and reached adsorption equilibrium within 30 min with 923 µmol g-1 at 298 K. The adsorption capacity and adsorption rate of MIP were respectively 2 and 5.49 times those of non-molecularly imprinted polymers. In addition, MIP could effectively counter disturbances from external parameters like temperature and pH, exhibiting strong environmental flexibility. MIP can specifically adsorb organophosphate esters, and can selectively adsorb TNBP under the interference of coexisting contaminants such as1,3-diphenylguanidine and isazofos. In actual bodies of water, MIP's highly selective adsorption of TNBP retains its advantage. The selective adsorption of MIP was mainly due to the common phosphate skeleton, and the specific substituent of organophosphate esters played an important role in the imprinting process. Hydrogen bonding might be involved in the polymerization process of TNBP with acrylamide and the adsorption process of TNBP by MIP.MIP exhibited good reuse efficiency, the total adsorption capacity decreased by no more than 25% after 7 reuse cycles. This study provides a simple and efficient method for selective removal of organophosphate from wastewater.

Insight into the interaction of tetrabromobisphenol A with sediment-derived dissolved organic carbon in a multiphase system by direct immersion solid phase microextraction.

Tetrabromobisphenol A (TBBPA), a ubiquitously used commercial brominated flame retardant (BFR), has been widely detected in aquatic environments, and has aroused much attention due to its potential adverse effects on aquatic organisms. However, current research on the environmental fate and transport of TBBPA in the sediment-dissolved organic carbon (DOC)-water polyphase system is lacking. In this study, the sorption behavior of TBBPA in a water-DOC-sediment system was investigated using the direct-immersion solid-phase microextraction (DI-SPME) method, and the free dissolved concentration (Cw-SPME) and DOC adsorption concentration (CDOC) of TBBPA in water were measured by applying this DI-SPME approach. In addition, the effects of pH, ionic strength, and soluble organic concentration on the adsorption of TBBPA in the multiphase system were evaluated. The adsorption kinetics experimental results show that the adsorption behavior of TBBPA on sediments conforms to a linear model, suggesting that it could be mainly absorbed by sediments. The solid-water partition coefficient (Kd) of TBBPA was artificially reduced 1.54 times using the traditional liquid-liquid extraction method because the sorption behavior of the DOC was ignored, which could be accurately corrected using the DI-SPME method. The logKd and logKOC of TBBPA in the multiphase system were 4.12 ± 0.25 and 6.48 ± 0.25, respectively. Finally, the interference experiment revealed that the sorption behavior of TBBPA was affected by the pH, ionic strength (calcium ion), and humic acid concentration, apart from the lead ion concentration itself.

Application of Nontarget High-Resolution Mass Spectrometry Fingerprints for Qualitative and Quantitative Source Apportionment: A Real Case Study.

High-resolution mass spectrometry (HRMS) provides extensive chemical data, facilitating the differentiation and quantification of contaminants of emerging concerns (CECs) in aquatic environments. This study utilizes liquid chromatography-HRMS for source apportionment in Chebei Stream, an urban water stream in Guangzhou, South China. Initially, 254 features were identified as potential CECs by the nontarget screening (NTS) method. We then established 1689, 1317, and 15,759 source-specific HRMS fingerprints for three distinct sources, the mainstream (C3), the tributary (T2), and the rain runoff (R1), qualitatively assessing the contribution from each source downstream. Subsequently, 32, 55, and 3142 quantitative fingerprints were isolated for sites C3, T2, and R1, respectively, employing dilution curve screening for source attribution. The final contribution estimates downstream from sites C3, T2, and R1 span 32-96, 12-23, and 8-23%, respectively. Cumulative contributions from these sources accurately mirrored actual conditions, fluctuating between 103 and 114% across C6 to C8 sites. Yet, with further tributary integration, the overall source contribution dipped to 52%. The findings from this research present a pioneering instance of applying HRMS fingerprints for qualitative and quantitative source tracking in real-world scenarios, which empowers the development of more effective strategies for environmental protection.

Using machine learning to explore oxyanion adsorption ability of goethite with different specific surface area.

In this study, we developed prediction models for the adsorption of divalent and trivalent oxyanions on goethite based on machine learning algorithms. After verifying the reliability of the models, the importance of goethite specific surface area (SSA) and the average oxyanion adsorption capacities of goethite with different SSAs were calculated by shapley additive explanations (SHAP) importance analysis and partial dependence (PD) analysis. Despite there were differences in the feature importance of divalent and trivalent oxyanions, the contribution of goethite's SSA to the adsorption amount ranked the fourth based on SHAP importance, indicating SSA played the important role in oxyanion adsorption. Meanwhile, the PD values of SSA and the optimized complexation constants from surface complexation modeling (SCM) both indicated a non-monotonic relationship between the goethite with different SSA and its oxyanions binding capacity. When the total site concentration and crystal face composition were used as the machine learning model input features, the SHAP importance values of crystal faces and the PD decomposition results indicated that the (001) face showed the crucial influence on oxyanions adsorption amount. These findings demonstrated the important role of crystal face composition in goethite's adsorption ability, and provided a theoretical explanation for the variations of oxyanions adsorption amount on different SSA goethite.

Facet-Dependent Competitive Adsorption Mechanisms of Chromate and Oxalic Acid on γ-FeO(OH) Nanocrystals.

Facet-dependent toxic metal adsorption of iron oxides widely occurred in natural environments. It is known that organic acids can alter the adsorption behaviors of trace elements by cooperative or competitive effects. However, the coadsorption mechanisms of the specific facets are still not fully understood. In the current investigation, Cr(VI) adsorption onto the lepidocrocite (γ-FeO(OH))-exposed facets in the presence of oxalic acid (OA) was studied using macroexperiments, in situ attenuated total reflectance Fourier transform infrared spectroscopy, X-ray adsorption fine structure, and density functional theory calculations. Rod-like lepidocrocite (R-LEP) with a high ratio of {001}/{010} facet showed excellent Cr(VI) adsorption capacity than that of plate-like lepidocrocite (P-LEP, the dominant facet is {010}) in the absence/presence of OA. Interestingly, OA reacted with R-LEP would be easier to diminish Cr(VI) adsorption than with P-LEP. The competitive adsorption occurred on the {001} facet due to the formation of inner-sphere OA configurations (monodentate mononuclear and bidentate mononuclear structures) and a bidentate binuclear Cr(VI) complex. However, OA coordinated with {010} facets via the outer-sphere complexes, while Cr(VI) could form a protonated monodentate binuclear configuration. These observations suggest that the competitive adsorption processes between OA and Cr(VI) exhibit facet dependence. Furthermore, lepidocrocite-exposed facets determine the interfacial interactions and geochemical behaviors of Cr(VI) in polluted environments.

Application of apatite particles for remediation of contaminated soil and groundwater: A review and perspectives.

With rapid industrial development and population growth, the pollution of soil and groundwater has become a critical concern all over the world. Yet, remediation of contaminated soil and water remains a major challenge. In recent years, apatite has gained a surging interest in environmental remediation because of its high treatment efficiency, low cost, and environmental benignity. This review summarizes recent advances in: (1) natural apatite of phosphate ores and biological source; (2) synthesis of engineered apatite particles (including stabilized or surface-modified apatite nanoparticles); (3) treatment effectiveness of apatite towards various environmental pollutants in soil and groundwater, including heavy metals (e.g., Pb, Zn, Cu, Cd, and Ni), inorganic anions (e.g., As oxyanions and F-), radionuclides (e.g., thorium (Th), strontium (Sr), and uranium (U)), and organic pollutants (e.g., antibiotics, dyes, and pesticides); and (4) the removal and/or interaction mechanisms of apatite towards the different contaminants. Lastly, the knowledge or technology gaps are identified and future research needs are proposed.

Validation of quenching effectiveness and pollutant degradation ability of singlet oxygen through model reaction system.

Quenching method is widely used to assess the contribution of specified reactive species through the probe inhibition efficiency (IE) caused by adding excessive quencher. However, for reactive species with weak ability such as singlet oxygen (1O2), the quenching results are prone to ambiguity. In this study, an 1O2 system using furfuryl alcohol (FFA) as a probe was successfully constructed by methylene-blue-N vis-photosensitization, to discuss the quenching, interference elimination and pollutant degradation ability of 1O2. Inhibition of FFA transformation caused by both quenching and interrupting of 1O2 production was found. The quenching is affected by quencher dosage and ability, which depends on the second-order-rate constant (k). A high k means a strong ability, and less dosage is required to achieve the same IE. Comparison between the calculated ratio of reactive species consumed by quencher and experimental IE helps to judge the interruption of 1O2 production. None of the organic-solvents (methanol, ethanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, tetrahydrofuran, acetonitrile, acetone and chloroform) scavenged 1O2, which would be used as screening-agent for other reactive species (e.g., hydroxyl radicals) that would interrupt 1O2 contribution assessment. Besides, 1O2 was powerless to degrade most selected pollutants. These results encourage proper use of quenchers and better experimental design.

Enhanced arsenic(III) sequestration via sulfidated zero-valent iron in aerobic conditions: Adsorption and oxidation coupling processes.

Sulfidated zero-valent iron (S-ZVI) has shown significant potential for the removal of arsenic(III). However, little attention has been paid to the mechanism of As(III) sequestration enhancement and how the phase transformation for S-ZVI strengthens this process in aerobic conditions. In this work, sulfidated ZVI was created by ball-milling (S-ZVIbm) and liquid-mixing (S-ZVIlm) of ZVI with elemental sulfur(S0) to investigate the performance and mechanisms of As(III) sequestration in air-saturated water. Sulfidation was found to significantly enhance the As(III) removal rate constant, which was 2.8 âˆ¼ 6.7 times (S-ZVIbm) and 3.1 âˆ¼ 17.1 times (S-ZVIlm) higher than that without sulfidation. FeS was identified as the predominant sulfur species in the S-ZVI samples using S K-edge XANES spectra. The enhanced electron transfer and ZVI corrosion after sulfidation were verified via electrochemical tests. XANES and Mössbauer spectra suggested that lepidocrocite(γ-FeOOH) was the predominant corrosion product generated on the ZVI surface with the presence of oxygen, and DFT calculations further confirmed the improved performance of γ-FeOOH for As(III) sequestration. Besides, As(III) oxidation occurred dominantly on the heterogeneous surface rather than in solution, and the As(III) sequestration pathway of adsorption followed by oxidation was proposed. This study provides new insight into the enhanced As(III) sequestration by S-ZVI in aerobic conditions.

Divergent repartitioning of antimony and arsenic during jarosite transformation: A comparative study under aerobic and anaerobic conditions.

Jarosite is the host mineral of Sb(V) and As(V) in mining environments. However, the repartitioning of Sb and As during its transformation is poorly understood. Additionally, the mutual effect between the redistribution behavior of As and Sb during jarosite conversion remains unclear. Here, we investigated the transformation of Sb(V)-, As(V)- and Sb(V)-As(V)-jarosite at pH 5.5 under aerobic and anaerobic conditions without a reductant. The results indicated that co-precipitated Sb(V) promotes jarosite dissolution, and the final products were mainly goethite and hematite. In contrast, the co-precipitated As(V) retarded jarosite dissolution and altered the transformation pathway, mainly forming lepidocrocite, which might be attributed to the formation of As-Fe complexes on the jarosite surface. The inhibiting or promoting effect increased with the increase in co-precipitated As or Sb concentration. In the treatment with Sb(V)-As(V)-jarosite, the inhibition effect of co-precipitated As(V) on mineral dissolution was predominant, but the end-products were mainly goethite and hematite. Compared with the aerobic system, the dissolution and transformation of jarosite in treatments in the anaerobic system occurred faster, although without a reductant, which was possibly associated with the reduced CO2 content in the reaction solutions after degassing. In all treatments, the release of Sb(aq) and As(aq) into the solution was negligible during jarosite transformation. The transformation processes drove As into the surface-bound exchangeable and poorly crystalline phases, while Sb was typically redistributed in the poorly crystalline phase. During the transformation of Sb(V)-As(V)-jarosite, the co-existence of As significantly increased the proportion of Sb distributed on the solid surface and in the poorly crystalline phase. These findings are valuable for predicting the long-term fate of Sb and As in mining environments.

Oxidation of 1,3-diphenylguanidine (DPG) by goethite activated persulfate: Mechanisms, products identification and reaction sites prediction.

As emerging pollutants continue to be discovered, studies on the degradation behavior of emerging pollutants have proliferated, but few studies have focused on the reactivity of the new pollutants themselves. The work investigated the oxidation of a representative roadway runoff-derived organic contaminant, 1,3-diphenylguanidine (DPG) by goethite activated persulfate (PS). DPG exhibited the highest degradation rate (kd = 0.42 h-1) with present of PS and goethite at pH 5.0, then started to decrease with increasing pH. Chloride ion inhibited DPG degradation by scavenging HO·. Both HO· and SO4-· were generated in goethite activated PS system. Competitive kinetic experiments and flash photolysis experiments were conducted to investigate free radical reaction rate. The second-order reaction rate constants for DPG reacting with HO· and SO4-· were quantified (kDPG + HO·,kDPG + SO4-·), which both reached above 109 M-1 s-1. Chemical structures of five products were identified, four of them were previously detected in DPG photodegradation, bromination and chlorination processes. By density functional theory (DFT) calculations, ortho- and para- C were more easily attacked by both HO· and SO4-·. Abstraction of H on N by HO· and SO4-· were the favorable pathways, and the product TP-210 might be generated by cyclization of DPG radical from abstraction of H on N (3). The results of this study help us to better understand the reactivity of DPG with SO4-· and HO·.

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.

Insight into the application of magnetic molecularly imprinted polymers in soil-washing effluent: Selective removal of 4,4'-dibromodiphenyl ether, high adaptivity of material and efficient recovery of eluent.

Soil washing techniques can effectively remove soil polybrominated diphenyl ethers (PBDEs), but further removal of PBDEs from washing effluent is disrupted by environmental factors and coexisting organic matter. Hence, this work prepared novel magnetic molecularly imprinted polymers (MMIPs) to selectively remove PBDEs in soil washing effluent and recycling surfactants, with Fe3O4 nanoparticles as the magnetic core, methacrylic acid (MAA) as the functional monomer, and ethylene glycol dimethacrylate (EGDMA) as the cross-linker. Later, the prepared MMIPs were applied to adsorb 4,4'-dibromodiphenyl ether (BDE-15) in Triton X-100 soil-washing effluent and characterized by scanning electron microscopy (SEM), infrared spectrometry (FT-IR), nitrogen adsorption and desorption experiments. According to our observations, BDE-15 equilibrium adsorptions on dummy-template magnetic molecularly imprinted adsorbent (D-MMIP, 4-bromo-4'-hydroxyl biphenyl as template) and part-template magnetic molecularly imprinted adsorbent (P-MMIP, toluene as template) were reached within 40 min, and their equilibrium adsorption capacities were 164.54 µmol/g and 145.55 µmol/g, respectively, with imprinted factor α > 2.03, selectivity factor ß > 2.14, and selectivity S > 18.05. MMIPs exhibited good adaptability to pH, temperature, and cosolvent. Our Triton X-100 recovery rate reached as high as 99.9%, and MMIPs maintained a more than 95% adsorption capacity after being recycled five times. Our results offer a novel approach to selectively remove PBDEs in soil-washing effluent, with efficient recovery of surfactants and adsorbents in soil-washing effluent.

New insight into phytometabolism and phytotoxicity mechanism of widespread plasticizer di (2-ethylhexyl) phthalate in rice plants.

Di-(2-ethylhexyl) phthalate (DEHP) as widely utilized plasticizer has aroused increasing concerns since its endocrine disrupting effects and continuous accumulation in biota. To date, the interaction mechanism between DEHP and rice plants has not been clearly illustrated at molecular level. Here, we investigated biological transformation and response of rice plants (Oryza sativa L.) to DEHP at realistic exposure concentrations. Nontargeted screening by UPLC-QTOF-MS was used to verify 21 transformation products derived from phase I metabolism (hydroxylation and hydrolysis) and phase II metabolism (conjugation with amino acids, glutathione, and carbohydrates) in rice. MEHHP-asp, MEHHP-tyr, MEHHP-ala, MECPP-tyr and MEOHP-tyr as the conjugation products with amino acids are observed for the first time. Transcriptomics analyses unraveled that DEHP exposure had strong negative effects on genes associated with antioxidative components synthesis, DNA binding, nucleotide excision repair, intracellular homeostasis, and anabolism. Untargeted metabolomics revealed that metabolic network reprogramming in rice roots was induced by DEHP, including nucleotide metabolism, carbohydrate metabolism, amino acid synthesis, lipid metabolism, synthesis of antioxidant component, organic acid metabolism and phenylpropanoid biosynthesis. The integrated analyses of interaction between differentially expressed genes (DEGs) and differentially expressed metabolites (DEMs) endorsed that metabolic network regulated by DEGs was significantly interfered by DEHP, resulting in cell dysfunction of roots and visible growth inhibition. Overall, these finding generated fresh perspective for crops security caused by plasticizer pollution and enhanced the public focus on dietary risk.

Hydrogen-Donor-Controlled Polybrominated Dibenzofuran (PBDF) Formation from Polybrominated Diphenyl Ether (PBDE) Photolysis in Solutions: Competition Mechanisms of Radical-Based Cyclization and Hydrogen Abstraction Reactions.

Polybrominated dibenzofurans (PBDFs) are characteristic dioxin-like products of polybrominated diphenyl ether (PBDE) photolysis. In this study, competition mechanisms of radical-based cyclization and hydrogen abstraction reactions are proposed in PBDF formation. Commonly, the ortho C-Br bond dissociation during photolysis generates aryl radicals, which undergo intramolecular cyclization to form PBDFs or hydrogen abstraction with hydrogen donors (such as organic solvents and water) to form lower brominated PBDEs. By using 2,4,4'-tribromodiphenyl ether (BDE-28) as the model reactant, the experimental PBDF formation ratios in various solutions are explained quantitatively by the calculated rate constants of cyclization and hydrogen abstraction reactions using the density functional theory (DFT) method. The solvent effect of pure and mixed solvents on PBDF formation is illustrated successfully. The structure-related hydrogen donation ability for hydrogen abstraction controls the bias of competition reactions and influences PBDF formation. Water resulted to be the most significant generation of PBDFs. Fulvic and humic acid display higher hydrogen donation ability than small-molecule organics due to the partitioning effect in aqueous solution. Quantitative structure-activity relationship (QSAR) models of the calculated rate constants for 512 cyclization and 319 hydrogen abstraction reactions using 189 PBDEs as the initial reactants in water are established, revealing the high risk of PBDF formation in aqueous solution.