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.

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.

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.

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.

Adsorption behavior of hierarchical porous biochar from shrimp shell for tris(2-chloroethyl) phosphate (TCEP): Sorption experiments and DFT calculations.

Tris(2-chloroethyl) phosphate (TCEP) as a new type of flame retardant exists in various water environments, causing great risks to humans and the environment. In this study, shrimp shell was used to prepare an economical and environmental-friendly adsorbent for the efficient removal of TCEP. The systematic studies including characterization, removal performance, and adsorption mechanism of shrimp shell biochar toward TCEP were carried out. Adsorption kinetics and thermodynamics showed that fast equilibrium reached within 30 min, the maximum adsorption capacity qm was 108 µmol g-1 at 298 K, and the adsorption process is spontaneous and exothermic. The environmental factor, such as temperature, pH, inorganic anions and organic matter hardly affected the adsorption performance. Structural characterization indicated that the hierarchical porous structure of shrimp shell biochar is the key to excellent adsorption performance. The adsorption mechanisms were further revealed using density functional theory (DFT) calculations, and the hydrogen bond, van der Waals interactions, Cl-H interactions, and pi-H interactions were identified as potential interaction mechanisms between TCEP and specific biochar structures. The calculated binding energy between TCEP and simplified biochar structure suggested that oxygen-containing groups especially carboxyl, hydroxyl and aldehyde facilitate the adsorption. Our work not only provides a novel strategy for the quick remediation of organophosphate-contaminated water environments but also offers new opportunities for crustacean waste biomass valorization.

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·.

Kinetics, mechanism, and application of sodium persulfate activated by sodium hydroxide for removing 1,2-dichloroethane from groundwater.

1,2-Dichloroethane (1,2-DCA) is a common compound found in groundwater contaminated with organics. This compound is difficult to remove from groundwater and has the potential to inflict significant harm on human health and the environment. This study used sodium persulfate (Na2S2O8) activated by sodium hydroxide (NaOH) to remove 1,2-DCA from aqueous solutions. Density functional theory was employed to calculate the potential energy surface of the reactants, intermediates, transient states, and products to thoroughly analyze the degradation pathways. The computations were performed in combination with in situ remediation of a 1,2-DCA plume from a point source to verify the industrial applicability of the technology. The results showed the 1,2-DCA removal efficiency was impacted considerably by the Na2S2O8 dosage and the dosing sequence of Na2S2O8 and NaOH, with the mean removal ratio reaching 96.24%. A free radical reaction was the main pathway of 1,2-DCA degradation; superoxide radical (O2•-) existed stably and played a key role in the reaction, and the main transformation proceeded via a vinyl chloride intermediate. The maximum removal of 1,2-DCA reached 91.79% in the in situ remediation. The developed technology exhibits important advantages in enabling flexible control over chemical dosages, long durations of effective activity, and rapid full-cycle remediation.

Transport and fate of Cu and Cd in contaminated paddy soil under acid mine drainage.

Long-term heavy metals accumulation caused by acid mine drainage (AMD) irrigation in paddy soils poses a severe threat to environmental health. However, the soil adsorption mechanisms under AMD flooding remain unclear. This study provides key insights into the fate of heavy metals in soil, particularly the retention and mobility mechanisms of Cu (copper) and Cd (cadmium) after AMD flooding. The migration and fate of Cu and Cd in uncontaminated paddy soils treated by AMD in Dabaoshan Mining area was investigated via column leaching experiments in the laboratory. The maximum adsorption capacities of Cu (658.04 mg kg-1) and Cd (335.20 mg kg-1) cations were predicted and the breakthrough curves were fitted using the Thomas and Yoon-Nelson models. Our findings demonstrated that Cd was more mobile than Cu. Furthermore, the soil had a greater adsorption capacity for Cu than Cd. Tessier's five-step extraction method was used to determine Cu and Cd fractions in leached soils at different depths and times. After AMD leaching, the relative and absolute concentrations of the easily mobile forms were all increased at different soil depths, thus increasing the potential risk to the groundwater system. Mineralogical characterization of the soil indicated that AMD flooding leads to the formation of mackinawite. This study provides insights into the distribution and transportation processes of soil Cu and Cd and their ecological effects under AMD flooding, as well as a theoretical basis for the establishment of corresponding geochemical evolution models and environmental governance in mining areas.

Fe(II)-mediated transformation of schwertmannite associated with calcium from acid mine drainage treatment.

Schwertmannite is an important Fe(III)-oxyhydroxysulfate in acid mine drainage (AMD) polluted areas and its stability depends on surrounding environmental factors and previously bound elements. The treatment and neutralization of AMD normally involve the use of lime, which leads to the discharge of abundant Ca in the mining area. Such an environmental disturbance brings up an important and less considered problem of how the reductive transformation of schwertmannite associated with coexisting Ca occurred. Here, the Fe(II)-mediated transformation of Ca-adsorbed schwertmannite and subsequent Ca repartitioning behaviors were investigated. Results showed that adsorbed Ca had a weak inhibitory effect on Fe(II)-mediated schwertmannite transformation. Release of SO42- and SEM images both indicated that transformation rates of schwertmannite decreased under the influence of adsorbed Ca. XRD patterns indicated that adsorbed Ca altered schwertmannite transformation pathways and product compositions upon treatment with 0.4 mmol/L Fe(II). The end products of Sch notably contained both goethite and lepidocrocite; however, transformation products of SchCa only contained goethite all along. Approximately 33.5% of the surface adsorbed-Ca was released into solution within 6 hr after Fe(II) injection. Aqueous Ca behaved in a "first release and then im-mobilization" manner, which indicated dissolution and secondary mineralization drove Ca migration during the Fe(II)-mediated transformation of SchCa. Adsorbed Ca blocked the surface sites for subsequent Fe(II) adsorption, limited the Fe(II)-Fe(III) ETAE, and decreased the transformation rates. This work sheds light on the complex geochemical behavior of schwertmannite under the influences of environmental perturbations in AMD environments.

Efficient removal of polybrominated diphenyl ethers from soil washing effluent by dummy molecular imprinted adsorbents: Selectivity and mechanisms.

Surfactant enhanced elution is an effective method for removing hydrophobic organic pollutants from soils. The key to the development of leaching technology is selective removal of targeted pollutants in soil washing effluent and recycling of surfactant solutions. In this study, a molecular imprinting technique was applied to selectively sorb polybrominated diphenyl ethers (PBDEs) in soil washing effluent. The novel molecular imprinted polymers (MIPs) using different template molecules were synthesized by precipitation polymerization. Adsorption behaviors and mechanisms of MIPs were studied through experiments and theoretical calculations. The results show that 4-bromo-4'-hydroxybiphenyl and toluene can be effective imprinting molecule for MIPs synthesis. The maximal adsorption capacity of selected dummy molecular imprinted polymer (D1-MIP) was 1032.36 µmol/g, and that of part molecular imprinted polymer (P-MIP) was 981.13 µmol/g. Their imprinting factors in 5 PBDEs adsorption ranged from 2.13 to 5.88, the recovery percentage of Triton X-100 can reach 99.09%, confirming the feasibility of reusing surfactant. Various PBDEs could be removed by MIPs, and Quantitative Structure Property Relationship analysis revealed that PBDEs' molecular volume, planarity, polarity, and hydrophobicity have major influences on their adsorption performance. DFT calculation revealed that Van der Waals force and hydrogen bonding played important roles during selective adsorption. These results can provide effective theoretical guidance for surfactant enhanced soil elution in practical engineering applications.

Spatial and temporal variations of metal fractions in paddy soil flooding with acid mine drainage.

Environmental release of acid mine drainage (AMD) poses a potential threat to the environment and human health due to its high content of heavy metals. The impact of AMD flooding on unpolluted soil leads to serious pollution over time via a complex process, related to the geochemical behavior of toxic metals that so far has only been partially investigated. Here, a soil column study was conducted to investigate the migration of Cu and Cd fractions in unpolluted paddy soil following treatment with AMD collected from the Dabaoshan Mining area. Tessier's sequential extraction was performed to fractionate the metals at various depths over time. After 160 days of experimental flooding, the soil pH stabilized at 2.52 at a column depth of 5 cm. The fractions of Cu and Cd that were highly mobile increased significantly during AMD flooding. For Cd, the latter already occurred on day 67. At a depth of 20 cm, the total content of Cu maximally increased from initially 26.89 mg kg-1 to 696.96 mg kg-1 on day 160, while the content of Cd maximally increased from 0.22 mg kg-1 to 391.30 mg kg-1 on day 67. Reduced partition index analysis conformed that the mobility of both Cu and Cd significantly increased in contaminated soil during continuous AMD flooding. Scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS) identified a changed distribution of the elements in the soil, with Fe appearing to have aggregated. The correlation analysis between Cu and Cd in pore water and in different fractions in the soil's solid phase identified a dynamic distribution of these metals in certain geochemical components during their migration. The results of this study contribute to a scientific foundation to describe the geochemical behavior of heavy metals in soil subject to AMD flooding.

Remediation of Cd-, Pb-, Cu-, and Zn-contaminated soil using cow bone meal and oyster shell meal.

To understand the environmental friendliness and high efficiency of organic materials during remediating soil polluted by heavy metals by assessing the feedback of soil ecosystems after organic materials were put into polluted soil. Incubation research was undertaken to examine the impact of amendments ranging from 0.1% to 3.0% (w/w), including single cow bone meal (BM), single oyster shell meal (OS), and a composite of 50% BM mixed with 50% OS (BO) on soil biochemical properties. The findings revealed that the implementation of BM and OS increased soil pH, the content of certain nutrients, and the activities of catalase (S-CAT), and urease (S-UE) while decreasing the availability of Cd, Pb, Cu, and Zn. Overall, the immobilization effect on Cd and Zn after a 108-day incubation was ranked as follows: BM group > OS group ≥ BO group, and the order of the immobilization effect of Pb and Cu was OS group > BO group > BM group. In addition, the dominant bacterial community flora shifted toward alleviating the re-dissolution of metal ions from the soil and promoting nutrient recycling in soil within 108 days of cultivation. RNA analyses showed that the strongest determinants for microbial communities between BM application and OS application at the genus level were soil pH, CEC, and heavy metal (Cd, Pb). These results increase our understanding of the leaching performance of Cd, Pb, Cu and Zn and the evolution trend of microorganisms when organic amendments remediate heavy metal contaminated soil.

Adsorption of Organic Compounds by Biomass Chars: Direct Role of Aromatic Condensation (Ring Cluster Size) Revealed by Experimental and Theoretical Studies.

Biomass chars are a major component of the soil environmental black carbon pool and prepared forms are a potentially useful tool in remediation. A function critical to the roles of both environmental and prepared chars is sorption of organic compounds. Char properties known to control sorption include surface area, porosity, functional group composition, and percent aromatic carbon. Here, we show that sorption affinity (but not maximum capacity) of organic compounds is directly related to the degree of condensation of the aromatic fraction. The Dubinin-Ashtakov characteristic sorption energy (EDA, kJ mol-1) of 22 compounds on a thermoseries of bamboo chars correlates strongly with the DP/MAS-13C NMR-determined bridgehead aromatic carbon fraction (χb), which relates to the mean ring cluster size. Density functional theory-computed binding energy (Ebd) for five of the compounds on a representative series of polybenzenoid hydrocarbon open-face sheets also correlates positively with χb, leveling off for rings larger than ∼C55. The Ebd, in turn, correlates strongly with EDA. An increase in Ebd with cluster size is also found for sorption, both monolayer and bilayer, between parallel sheets representing slit micropores. The increasing sorption energy with cluster size is shown to be due to increasing cluster polarizability, which strengthens dispersion forces with the sorbate. The findings underscore a previously overlooked explicit role of aromatic condensation in sorption energy, and illustrate the utility of EDA-Ebd comparison for predicting sorption.

Sulfate migration and transformation characteristics in paddy soil profile affected by acid mine drainage.

SO42-, a major component of acid mine drainage (AMD), plays an important role in study environment of AMD. We investigated the distribution and adsorption-desorption mechanisms of SO42- and the variation of stable isotope of sulfur (δ34S) values in the soil profile polluted by AMD. Results showed that the species and 34S values of SO42- differed significantly among different soil depths. In the surface soil (0-20 cm), native water-soluble SO42- (WSS) in the range ~85 % total SO42- was the dominant species. There was a peak of adsorption, which correlated significantly with amorphous oxide Fe, indicating that iron oxides and pH was fundamentally proportional to SO42- forms. The high concentrations of Cu2+ and Pb2+ also played important roles in form of SO42- in soil profile. Desorption kinetics of explained three SO42--bound forms. The trend mean δ34S values of WSS and AS in soil vertical profile was very similar with increasing from surface to subsurface, and have lower δ34S values than those of total sulfur, indicating that mineralization of organic sulfur should produce SO42- that was more depleted in δ34S. SO42- desorbed and trend δ34S values could provide reasonable explanation for the migration of SO42-. In the AMD irrigation scope, the higher SO42- concentration was reserved by immobilized as organic sulfur, and then main approach of SO42- migration was desorption and organic sulfur mineralize in now stage.

Bacterial communities and functional genes stimulated during phenanthrene degradation in soil by bio-microcapsules.

In this study, a taxonomic and functional metagenomic method was used to investigate the difference produced between degrading bacteria immobilized in layer-by-layer assembly (LBL) microcapsules or not during the bioremediation of a soil polluted with phenanthrene (PHE). Bioaugmentation with LBL microcapsule immobilized degrading bacteria could result in different changes of native microbial communities, shifting the functional gene constructions of polluted soils. The LBL treatment enhanced PHE degradation (initial concentration of 100 mg kg-1 dry soil) by 60% after 25 d compared to the free bacteria (FB). The enhancing effect of PHE degradation produced by the LBL treatment was found to be significantly associated with some crucial phyla (e.g., Bacteroides, Gemmatimonadetes and Acidobacteria) and genera including Streptomyces, Ramlibacter, Mycobacterium, Phycicoccus, Gemmatirosa, Flavisolibacter, Micromonospora, Acid_Candidatus_Koribacter and Gemmatimonas. The main differences of functional metagenomics between LBL and FB treatments were observed in higher levels in metabolism of aromatic hydrocarbons and its related functions or enzymes in the former, e.g., membrane transport systems, binding, substrate transporter, cleavage enzymes, dehydrogenation, oxidase, esterase and glycosidase, greatly favoring PHE mineralization. Therefore, our results provide useful findings on understanding of how immobilization strategies can influence the taxonomic and functional gene composition in soils, as well as polycyclic aromatic hydrocarbons (PAH) degradation.

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.

Co-metabolic and biochar-promoted biodegradation of mixed PAHs by highly efficient microbial consortium QY1.

Polycyclic aromatic hydrocarbons (PAHs), typical representatives of the persistent organic pollutants (POPs), have become ubiquitous in the environment. In this study, a novel microbial consortium QY1 that performed outstanding PAHs-degrading capacity has been enriched. The degradation characteristics of single and mixed PAHs treated with QY1 were studied, and the effect of biochar on biodegradation of mixed PAHs and the potential of biochar in PAHs-heavy metal combined pollution bioremediation were also investigated. Results showed that, in single substrate system, QY1 degraded 94.5% of 500 mg/L phenanthrene (PHE) and 17.8% of 10 mg/L pyrene (PYR) after 7 days, while in PHE-PYR mixture system, the biodegradation efficiencies of PHE (500 mg/L) and PYR (10 mg/L) reached 94.0% and 96.2%, respectively, since PHE served as co-metabolic substrate to have significantly improved PYR biodegradation. Notably, with the cooperation of biochar, the biodegradations of PHE and PYR were greatly accelerated. Further, biochar could reduce the adverse impact of heavy metals (Cd2+, Cu2+, Cr2O72-) on PYR biodegradation remarkably. The sequencing analysis revealed that Methylobacterium, Burkholderia and Stenotrophomonas were the dominant genera of QY1 in almost all treatments, indicating that these genera might play key roles in PAHs biodegradation. Overall, this study provided new insights into the efficient bioremediation of PAHs-contaminated site.

Acidity and metallic elements release from AMD-affected river sediments: Effect of AMD standstill and dilution.

In acid mine drainage (AMD) polluted rivers, considerable fraction of potential toxic elements are temporarily sequestered by sediments. There are two main potential environmental hazards associated with the sediments, acidity liberation and re-mobilization of metallic elements, during environmental conditions change. The effects of AMD standstill and water dilution on metallic elements migration were assessed in an AMD standstill test and a dialysis experiment. Maintaining AMD standstill, often occurring in AMD damming process, could induce the occurrence of iron secondary minerals precipitation along with attenuation of dissolved elements and a decrease in water pH value. Both field sediments and lab precipitates were confirmed as being dominant with schwertmannite which was the most important source and sink for acidity and metallic elements. The mechanism of cation heavy metals scavenging implied by FTIR results mostly depended on the exchanging of H+ from surface hydroxyl groups (-OH) in schwertmannite-rich sediments. For arsenic oxyanion, its adsorption included surface complexation with iron hydroxyl groups at the mineral surface, as well as anion exchange of SO42- present in the structure. The quantities of acidity release differed significantly from 20 to 3714 mol H+/t depending on the iron hydroxyl minerals type and their contents in the corresponding sediments in 35 d dialysis, with the release rate well fitted by the second order model. Slight degree of phase transformation in schwertmannite dominant sediment had resulted in a high risk of metallic element release during the 35 d dilution duration. The significant risk of metallic elements release was ranked in the order of Cd > Mn > Zn > Pb, and with more than 89% of Cd released from FS6 and 82% from LPS1. Relatively, Cu and As in sediments were much more stable. Overall, damming was an effective and low cost pretreatment strategy for AMD pollution control. Knowledge of the characteristics of iron secondary minerals in river sediments is essential premise for both comprehensive assessment of site contamination status and effective remediation strategy decision.

Co-metabolic degradation of tetrabromobisphenol A by Pseudomonas aeruginosa and its auto-poisoning effect caused during degradation process.

In this study, Pseudomonas aeruginosa was applied to degrade tetrabromobisphenol A (TBBPA) with glucose as a co-metabolic substrate. Influencing factors of co-metabolic degradation such as pH, TBBPA and glucose concentration were examined and the degradation efficiency under optimal condition reached about 50% on the 7th day. The study also proved that the extracellular action, rather than intracellular one, played a leading role in TBBPA degradation. Five metabolites including debromination and beta-scission products were identified in this study. The extracellular active substance pyocyanin was considered as the origin of H2O2 and OH·. The variation of concentrations of H2O2 and OH· shared the same trend, they increased in the early days and then declined gradually. On the 1st day, the OD600 of P.aeruginosa in the co-metabolic group was 6.0 times higher than the initial value while total organic carbon (TOC) decreased about 78%, which might lead to the occurrence of pyocyanin auto-poisoning. Flow cytometry was applied to detect the cellular state of P.aeruginosa during degradation. The increasing intracellular ROS showed that cells were suffering from oxidative stress and the change of membrane potential revealed that cellular dysfunction had occurred since the 1st day. This research indicated that the toxic effect on P.aeruginosa was probably not directly correlated with TBBPA, but was caused by pyocyanin auto-poisoning.

Bacterial communities on soil microplastic at Guiyu, an E-Waste dismantling zone of China.

Recent studies of microplastic have focused on aquatic environment, but its impacts on soil ecosystems were poorly understood, particularly on bacterial communities. In this study, the bacterial taxon and functional composition of soil microplastic-attached communities at Guiyu, a notorious e-waste dismantling area in Guangdong Province, China, were investigated by means of high-throughput sequencing. The results revealed that fundamental difference in bacterial communities existed among microplastics selected from three plots with different dismantling methods and their surroundings, suggesting that microplastic surface created a new ecological niche in soil environment, and the bacteria adapted well to the surface-related lifestyle. The formation of microplastic-attached bacteria depended not only on various dismantled plastic materials, but also on disassembly methods that caused different soil physicochemical characters which might also influence the bacterial communities. As the hydrocarbon degraders, the family Hyphomonadaceae were also found on soil microplastic, further confirming that microorganisms played a role in biodegrading microplastic in e-waste zone. The analysis of functional profiles speculated that microplastic-attached bacteria had the potential to degrade pollutants. This study provides a new perspective for exploring microplastic-associated bacteria and increasing our understanding of microplastic pollution in terrestrial ecosystems.