Effect of biochar-derived DOM on contrasting redistribution of chromate during Schwertmannite dissolution and recrystallization.

Biochar-derived dissolved organic matter (BDOM), is extensively involved in the recrystallization of minerals and the speciation alteration of associated toxic metals. This study investigates how BDOM extracted from tobacco petiole (TP) or tobacco stalk (TS) biochar influences the speciation repartitioning of Cr(VI) in environments impacted by acid mine drainage (AMD), focusing on interactions with secondary minerals during Schwertmannite (Sch) dissolution and recrystallization. TP-BDOM, rich in lignin-like substances, slowed down the Cr-Sch dissolution and Cr release under acidic conditions compared to TS-BDOM. TP-BDOM's higher O/C component exerts a delayed impact on Cr-Sch stability and Cr(VI) reduction. In-situ ATR-FTIR and 2D-COS analysis showed that carboxylic and aromatic N-OH groups in BDOM could interact with Cr-Sch surfaces, affecting sulfate and Cr(VI) release. It was also observed that slight recrystallization occurred from Cr-Sch to goethite, along with increased Cr incorporation into secondary minerals within TS-BDOM. This enhances our understanding of BDOM's role in Cr(VI) speciation changes in AMD-contaminated sites.

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.

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.

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.

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.

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.

Degradation efficiency and mechanism of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) by thermally activated persulfate system.

Polybrominated diphenyl ethers (PBDEs) as a typical brominated flame retardant (BFR) have attracted worldwide attention due to the high environmental risk and resistance to conventional remediation processes. In this study, thermally activated persulfate (TAP) process was applied to degrade 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), which is the most toxic and representative PBDEs in e-waste dismantling sites. Impact factors such as PDS dosage, heating temperature, and initial pH were evaluated. Results showed that BDE-47 can be 100% degraded within 180 min under the condition of PDS:BDE-47 = 1000:1, 60 °C, and pH = 7. Quenching experiments combined with EPR analysis further proved the important role of SO4·- in oxidating BDE-47. According to high-resolution mass spectrometry (HRMS) analysis, only one oxidation product of low toxicity was detected during the oxidation process. Theoretical calculations further revealed that the oxidation process mainly involved radical attack at C-Br bond, cleavage of C-Br bond, and fission of ether bond, and HSO4· may also play an important role in BDE-47 degradation in TAP system. In addition, TAP system exhibited universality as all selected PBDE congeners can be degraded, and the degradation rate of PBDEs was greatly affected by the number of substituted Br atoms in a negative trend. Overall, these findings indicate that TAP can be applied as an effective method for removal of PBDEs, and we provide a new insight for the practical application of TAP technology in BDE-47 degradation from experimental and theoretical aspects.

Microbial reduction of schwertmannite by co-cultured iron- and sulfate-reducing bacteria.

Schwertmannite (Sch) is an iron-hydroxysulfate mineral commonly found in acid mine drainage contaminated environment. The transformation mechanism of Sch mediated by pure cultured iron-reducing bacteria (FeRB) or sulfate-reducing bacteria (SRB) has been studied. However, FeRB and SRB widely coexist in the environment, the mechanism of Sch transformation by the consortia of FeRB and SRB is still unclear. This study investigated the Sch reduction by co-cultured Shewanella oneidensis (FeRB) and Desulfosporosinus meridiei (SRB). The results showed that co-culture of FeRB and SRB could accelerate the reductive dissolution of Sch, but not synergistically, and there were two distinct phases in the reduction of Sch mediated by FeRB and SRB: an initial phase in which FeRB predominated and Fe3+ in Sch was reduced, accompanied with the release of SO42-, and the detected secondary minerals were mainly vivianite; the second phase in which SRB predominated and mediated the reduction of SO42-, producing minerals including mackinawite and siderite in addition to vivianite. Compared to pure culture, the abundance of FeRB and SRB in the consortia decreased, and more minerals aggregated inside and outside the cell; correspondingly, the transcription levels of genes (cymA, omcA, and mtrCBA) related to Fe3+ reduction in co-culture was down-regulated, while the transcription levels of SO42--reducing genes (sat, aprAB, dsr(C)) was generally up-regulated. These phenomena suggested that secondary minerals produced in co-culture limited but did not inhibit bacterial growth, and the presence of SRB was detrimental to dissimilatory Fe3+ reduction, while existed FeRB was in favor of dissimilatory SO42- reduction. SRB mediated SO42- reduction by up-regulating the expression of SO42- reduction-related genes when its abundance was limited, which may be a strategy to cope with external coercion. These findings allow for a better understanding of the process and mechanism of microbial mediated reduction of Sch in the environment.

Polycyclic Aromatic Hydrocarbons Pollution Characteristics in Agricultural Soils of the Pearl River Delta Region, China.

In order to investigate the pollution status of polycyclic aromatic hydrocarbons (PAHs) in the agricultural soil, 240 agricultural soil topsoil samples were collected from nine Pearl River Delta cities from June to September 2019. In addition, 72 samples were collected for vertical soil profiles, which soil profiles were excavated to a depth of 80 cm. After sample preparation, GC-MS was used for the separation of compounds on a HP-5MS quartz capillary column. ArcGIS software was used to map the spatial distribution. Health risk assessment was conducted using USEPA standard. The results showed that the total concentration of 16 PAHs ranged from 43.4 to 5630 ng/g, with an average of 219 ng/g. The spatial distribution showed that most of the seriously polluted areas were in the coastal area, near the port, and there was point source pollution in the Gaoming of Foshan. Vertically distributed display Zhuhai, Jiangmen, Zhaoqing, Shenzhen and Dongguan increased and then decreased from bottom to bottom, showing a low-high-low pattern, the concentration of PAHs in Zhongshan and Foshan decreased with the soil depth, while the concentration of PAHs in Guangzhou and Huizhou was enriched with human activities. The PAHs components in soil samples were mainly medium and high rings (4−6 rings). The analysis of the origin of PAH in soil samples showed that the mixture of incomplete combustion sources of fossil fuels such as coal and biomass and traffic emission sources were the main sources of soil PAHs. A small amount can be attributed to oil sources such as oil spills. The human health risk assessment showed no cancer risk for children, while for adults, may cause a potential risk of cancer, which needs to be noticed. Spearman correlation analysis showed that PAH content was significantly correlated with SOC (p < 0.01) and pH (p < 0.05). Port transport, road emissions and industrial production make the area a pollution hot topic, and supervision should be strengthened to protect the environment and food safety.

Characteristics and Health Risks of Phthalate Ester Contamination in Soil and Plants in Coastal Areas of South China.

Phthalate esters (PAEs) are widely used as plasticizers in industrial and commercial products, and are classified as endocrine-disrupting compounds. In this study, we investigated the contamination characteristics and health risks of PAEs in the soil-plant system in coastal areas of South China. PAEs were detected in soil and plant samples at all 37 sampling sites. The total concentration of the 15 PAEs in soil samples ranged from 0.445 to 4.437 mg/kg, and the mean concentration was 1.582 ± 0.937 mg/kg. The total concentration of the 15 PAEs in plant samples ranged from 2.176 to 30.276 mg/kg, and the mean concentration was 8.712 ± 5.840 mg/kg. Di(2-Ethylhexyl) phthalate (DEHP) and di-n-butyl phthalate (DnBP) were the major PAEs compounds in all samples. The selected contaminants exhibited completely different spatial distributions within the study area. Notably, higher concentrations of PAEs were found in the coastal Guangdong Province of South China. The average noncarcinogenic risks of Σ6 PAEs were at acceptable levels via dietary and nondietary routes. However, the noncarcinogenic risks posed by DEHP and DBP at some sampling sites were relatively high. Furthermore, dietary and nondietary carcinogenic risks were very low for BBP, but carcinogenic risks posed by DEHP via diet. The results suggest that PAEs in the coastal soil-plant system in South China, through human risk assessment, will induce some adverse effects on human health, especially in children. This study provides an important basis for risk management of PAEs in agriculture, and safety in coastal areas of South China.

Hierarchical health risk assessment and influence factors of an ecological post-restoration oil shale mining area based on metal bioavailability.

The environmental problems caused by mining are continuous and multifaceted, in order to help manage and plan restored mining areas, the bioavailability of metals is an effective tool for measuring the potential risks to human health. This study analyzes the geochemical fractions of eight metals (As, Cd, Cr, Cu, Mn, Ni, Pb, and Zn) to compare their bioavailability and establishes a Hierarchical health risk (HHR) model to assess the human health risks of the mine area after restoration. The results indicated that children have the highest non-carcinogenic risks exposed through ingestion (HI-ingestion) due to their special behaviors; HI-dermal may be enriched in the body; and HI-inhalation is lowest, as it is related to soil particle size. Affected by local economic development, environmental climate, soil type, and mining, the carcinogenic risk of exposure through the skin (CR-dermal) for adults significantly exceeds the acceptable safety level (ASL). The spatial distribution shows that the harm of mining to human health is a continuous process. There was still a significant CR for adults after remediation, and the HI of tailings exposure was more serious. The Classification and Regression Tree (CART) model of metal bioavailability was developed by integrating the extrinsic and intrinsic factors of metals to explore the effects of different factors on metal bioavailability and predict. The results showed that the bioavailability of metals was a dynamic process that combined land use, the distance to traffic roads, physicochemical properties of soil, and geochemical fractions of metal, and that it affects human health both directly and indirectly. Due to the fragility and sensitivity of the ecosystem after the mining area is restored, it may face greater environmental health risks.

A collaborative strategy for elevated reduction and immobilization of Cr(VI) using nano zero valent iron assisted by schwertmannite: Removal performance and mechanism.

A novel collaborative strategy for enhanced removal of Cr(VI) using nano zero valent iron (nZVI) assisted by schwertmannite (Sch) with two synthesis methods was designed. Batch experiments demonstrated that nZVI/Sch-AP (synthesized by abiotic precipitation of Fe3+ species) exhibited excellent removal performance for Cr(VI) than nZVI/Sch-CO (synthesized by chemical oxidation of Fe2+ species). The results indicated that the removal efficiencies of Cr(VI) by nZVI/Sch-AP and nZVI/Sch-CO were highly pH-dependent and achieved to be 99.99% and 98.01% under the optimal conditions of 10 mg L-1 Cr(VI) concentration, a pH of 6.3 and a Fe(0)/Cr(VI) molar ratio of 12. But nZVI/Sch-AP emerged greater k of 0.1097 min-1 than that of nZVI/Sch-CO (0.0485 min-1). Humic acid exhibited promotion effect on the Cr(VI) removal in low concentration of 1 mg L-1. Results of XRD and XPS demonstrated that α-FeOOH was the dominant products in both incubations of nZVI/Sch-AP and nZVI/Sch-CO, accompanied with FeCr2O4 and CrFe mixed (oxy)hydroxides, and γ-FeOOH was found alone in the incubations of nZVI/Sch-CO. We proposed a consecutive and simultaneous process involving surface absorption-reduction and co-precipitation/immobilization for the removal. This study provides new insights into the elimination of Cr(VI) from wastewater by nZVI/Sch, especially in acid mine drainage.

Integrated ecological risk assessment of heavy metals in an oil shale mining area after restoration.

Although the mining area has been restored, the environmental problems caused by years of large-scale oil shale mining are still continuing, coupled with the intensive distribution of the surrounding petrochemical industry, posing a serious threat to the local ecological environment. In this study, we investigated eight heavy metals (Cu, Ni, Pb, Cd, As, Cr, Mn and Zn) contamination and distribution around mining area, evaluated the potential risks of environment, identified the main sources of metal pollution and performed source apportionment. The results showed that the original north and south dumps were seriously polluted, and the CF values were significantly higher than other sampling sites. Ni, Zn and Mn have high coefficients of variation, which may be greatly affected by human factors and especially the waste slag piled up. The concentration of heavy metals in the water was lower than in the soil; soil particles, pH, Eh and acid mine drainage influence the variation of heavy metal concentrations. As and Cd have very high RAC values, and accordingly they were mainly present in the exchangeable and reduced fractions. Mn was exposed to higher ecological risks, followed by Pb, although there were high loads on carbonate bound and oxidizable fractions. APCS-MLL receptor model was used to identify and apportionment three main sources of contamination. The mean contribution rates of industrial activity, atmospheric deposition and mixed sources accounted for 39.77%, 22.24% and 37.99%, respectively. Cluster analysis further classified the metal pollution sources according to the spatial distance of sampling points.

Improved extraction of acid-insoluble monosulfide minerals by stannous chloride reduction and its application to the separation of mono- and disulfide minerals in the presence of ferric iron.

Metal sulfides, which are important indicators of sulfur cycling, are usually divided into two categories according to sulfur chemical valence: (1) monosulfides (S2-) and (2) disulfides (S22-). The two sulfur species are separated and quantified by a sequential-extraction method. Specifically, monosulfides are extracted as acid-volatile sulfide (AVS) using 6 M HCl prior to the extraction of disulfides using acidic CrCl2, which is defined as chromium-reducible sulfur (CRS). However, the conventional AVS procedure does not result in the quantitative extraction of S2- from the acid-insoluble metal monosulfide, copper sulfide (CuS). Consequently, residual sulfur in CuS (CuS-S) may be extracted as CRS resulting in the inaccurate separation of these two sulfur species. In this study, we used stannous chloride (SnCl2) to improve CuS-S recovery in the AVS procedure and permit the separate extraction of sulfur from CuS and pyrite (FeS2), the most abundant disulfide in nature. Our results show that the addition of SnCl2 increased the recovery of CuS-S as AVS from less than 36% to as high as 92% in the absence of pyrite and Fe3+ and 89% in the presence of pyrite and Fe3+. In addition, based on the observed correlation between the concentration of SnCl2 and the dissolution of FeS2, we identified the appropriate concentration of SnCl2 needed to avoid the dissolution of FeS2 in the AVS procedure. SnCl2 also minimized the oxidation of CuS-S by Fe3+ released from ferric minerals during the extraction of AVS. Based on the results of a series of sequential-extraction experiments, we show that an amendment of SnCl2 in the AVS procedure followed by CRS permits the quantitative separation of CuS-S and FeS2-S while also preventing interference by Fe3+. Our method will find application in research concerned with the fate of metals and the biogeochemistry of sulfur in the environment.

Effects of ferric ion on the photo-treatment of nonionic surfactant Brij35 washing waste containing 2,2',4,4'-terabromodiphenyl ether.

The effects of ferric iron on the photo-treatment of simulated BDE-47 (2,2',4,4'- terabromodiphenyl ether)-Brij35 (Polyoxyethylene lauryl ether) washing waste were studied to evaluate the influences of ferric iron on BDE-47 removal and Brij35 recovery. The results show that Fe3+ accelerated BDE-47 degradation at lower concentrations (<0.5 mM) but attenuated it at higher concentrations (0.5-5 mM) and that Brij35 loss was increased with increasing Fe3+. These results likely are caused by changes in the rate of •OH production due to the ferric ion, association of Fe3+ and electron transfer from Brij35, and light attenuation at high concentration. The BDE-47 and Brij35 had different degradation rates at different pH values and at different dissolved oxygen concentrations. The BDE-47 products were identified by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). The results indicated that BDE-47 transformed into mainly lower-brominated products, a few bromodibenzofurans, some rearrangement products, and some hydroxylated polybrominated diphenyl ethers. A series of Brij35 oxidization products were detected by ultra-performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS), including hydroxylation products, carboxylation products, and some hydrophilic chain-breaking products. Brij35 was mainly oxidized by Fe3+ and/or reactive oxygen species (ROS) with the final products of CO2 and H2O. The iron ions apparently cycled from ferric to ferrous ions in the micelles such that the Fe3+-Brij35 complex dominated the main redox reaction, leading to both BDE-47 and Brij35 degradation. It appears that in any applied soil washing system, the ferric ions in the washing waste need to be removed because of the adverse effects on BDE-47 removal and eluate reuse.

Removal of heavy metal ions and polybrominated biphenyl ethers by sulfurized nanoscale zerovalent iron: Compound effects and removal mechanism.

Sulfurized nanoscale zerovalent iron (S-nZVI) has been widely reported to be able to quickly remove heavy metals/persistent organic pollutants, but the limited understanding of the complicated removal process of heavy metals-organic combined pollutants restricts the application of S-nZVI. Here, we demonstrate that there is significant difference in the effectiveness of S-nZVI for removing single pollutant and complex pollutants. The removal kinetic constant (kobs) of heavy metals by S-nZVI followed a sequence of Cr(VI)>Pb(II)>Ni(II)>Cd(II) with or without polybrominated diphenyl ethers (PBDEs). While the capacity of co-existing cations increasing the kobs of PBDEs followed the order: Ni(II)>Pb(II)>Cd(II), and the co-existence of Cr(VI) anion inhibited the reduction of PBDE by S-nZVI because the generated Cr-Fe precipitate hindered the electron transfer. The de-passivation process on S-nZVI surface by Cd(II) ions slightly accelerated the transformation rate of electron. Nevertheless, the co-existing Pb(II) significantly accelerated the transformation of BDE-209 via the galvanic effect from the generated Pb0/Fe0 bimetal. Interestingly, the kobs of BDE-47 in Ni(II)/S-nZVI system was 5.51 times higher than that of Pb(II)/S-nZVI system, implying that an atomic hydrogen mechanism dominated the reduction of BDE-47 by Ni(II)/S-nZVI. In conclusion, the results provided a deep comprehending of removal mechanism of heavy metal-organic complex pollutants by S-nZVI.

Transcriptome profiling of Pseudomonas aeruginosa YH reveals mechanisms of 2, 2', 4, 4'-tetrabrominated diphenyl ether tolerance and biotransformation.

Aerobic degradation of 2, 2', 4, 4'-tetrabrominated diphenyl ether (BDE-47) by Pseudomonas aeruginosa YH (P. aeruginosa YH) were investigated in this study. BDE-47 degradation was mainly through the biological action of intracellular enzymes, and the metabolites included debrominated metabolites (BDE-28 and BDE-7), hydroxylated metabolites (6-OH-BDE-47, 5-OH-BDE-47, 2'-OH-BDE-28 and 4'-OH-BDE-17), and brominated phenols (2,4-DBP and 4-BP). P. aeruginosa YH also exhibited exceptional ability to degrade intermediates, and the degradation rates of 50 µg/L BDE-28, BDE-7, and 2,4-DBP were 68.4%, 82.3% and 92.7% on the 5th day, separately. Transcriptome sequencing revealed that 991 genes were up-regulated, and 923 genes were down-regulated in P. aeruginosa YH after exposure to 0.5 mg/L BDE-47 (FDR ≤ 0.001, |log2Ratio| ≥ 1). The differentially expressed genes were related to transport, metabolism and stress response. Harf inhibitory concentration (IC50) of BDE-47 decreased from 167.5 mg/L to 68.4 mg/L when multidrug efflux pump was inactivated by 20 mg/L andrographolide, indicating that it helped the bacterial tolerance against BDE-47. Moreover, efflux pump inhibition would accelerate the adsorption of BDE-47. The adsorption rate obtained equilibrium at approximately 70% in 2 days, while 5 days in the control group. Degradation efficiency of 2 mg/L BDE-47 decreased from 26.8% to 13.9% when multidrug efflux was suppressed.

Photoassisted degradation of 2,2',4,4'-tetrabrominated diphenyl ether in simulated soil washing system containing Triton X series surfactants.

This study aims to use ultraviolet (UV) irradiation to decompose polybrominated diphenyl ethers (PBDEs) in the elutes and then reuse the surfactants. The results indicate that UV can remove 2,2',4,4'-tetrabrominated diphenyl ether (BDE-47) from surfactant eluents and Triton X series surfactants also can remove BDE-47 from the soil. Triton X-100 (TX-100) is the most promising surfactant during the washing and photodegradation processes. Quench experiments suggest that both 1O2 and OH• were involved in the TX-100 decomposition but only 1O2 is responsible for the degradation of BDE-47. In analysis of the photoproducts of BDE-47 by Gas Chromatography Mass Spectrum (GC-MS) and Liquid Chromatography High Resolution Mass Spectrometry (LC-HRMS), BDE-47 was mainly debrominated to the lower-brominated BDEs and then oxidized to ring-opening products. The little loss of TX-100 can mainly be attributed to the breakage of polyethylene oxide (PEO) chain. Nevertheless, the washing wastes treated by UV light can exhibit higher solubility for BDE-47 than before, indicating they can be reused for BDE-47 removal from soil. The toxicity assessment experiments were performed using Escherichia coli (E.coli) as an indicator. The results indicate that the removal of BDE-47 by UV irradiation can reduce the toxicity of eluent.