Ultrasensitive detection of trace Hg(â ¡) in acidic conditions using DMABR loaded on sepiolite: Function, application and mechanism studies.

Fast and real-time detection of trace Hg(Ⅱ) by fluorescent probes under acidic conditions is urgently required due to the high toxicity and accessibility to creatures and human being. However, fluorescent probes for Hg(Ⅱ) detection in environmental samples are rarely reported due to the protonation potential of acidic mercury sources. In this study, the SD probe was developed by 5-(p-dimethylaminobenzylidene) rhodanine (DMABR) loaded on sepiolite by hydrothermal treatment, and showed excellent Hg(Ⅱ) detection performances for mercury sources at pH 4-10 due to buffering ability of the hyperconjugated lactam rings. Sepiolite functioned as the support skeleton to decrease intermolecular transition, and thus increased the sensitivity. At pH 4, the SD probe showed high selectivity and sensitivity for Hg(Ⅱ) among various species, with low LOD and binding constant of 4.78 × 10-9 M and 1.34 × 106 M-1, respectively. Through DFT calculations, MAS 1H NMR and 2D-COS analysis, the detection mechanism was demonstrated as SN1 substitution of the spontaneous leaving H on amino groups in the transient state during tautomeric equilibrium, rather than the expected high-affinity sulphydryl. Additionally, the SD probe exhibited promising potential in quantifying water-soluble and bioavailable Hg(Ⅱ) in acidic polluted soil and water samples. Moreover, real-time detection was realized by paper-based strips.

Predicting the bioavailability of polycyclic aromatic hydrocarbons in rhizosphere soil using a new novel in situ solid-phase microextraction technique.

In situ measurement of the bioavailability of organic pollutants in soil is crucial for understanding their environmental behavior and assessing health risks. Due to the high heterogeneity of soil, microscale determination is crucial for achieving high accuracy, but few methods are available. In this study, microsized probes coated with polydimethylsiloxane (PDMS) were used to measure the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in soil in situ. The concentrations of PAHs enriched by the PDMS-coated probes correlated well with the results of bioassays using earthworms (R2 = 0.92-0.99) and ryegrass roots (R2 = 0.92-0.99). Compared with other chemical extraction methods, such as n-butanol extraction, the proposed method has advantages such as in situ operation, microvolume analysis, and negligible interference to the soil environment. In the soil rhizosphere zone, PAHs bioavailability decreased in the following order: rhizosphere > near-rhizosphere > far-rhizosphere. The bioavailability of PAHs in soil amended with biochar was also successfully characterized by the proposed method. Thus, this study developed an in situ and microscale method to predict the bioavailability of organic pollutants in contaminated soils and provides new insight into migration and transformation processes in rhizosphere soil.

Aging of biodegradable-mulch-derived microplastics reduces their sorption capacity of atrazine.

Degradable plastics are gradually regarded as alternatives of conventional, synthetic organic polymers to reduce the plastics or microplastics (MPs) pollution; however, the reports upon environmental risk of degradable plastics are still limited. In order to evaluate the potential vector effect of biodegradable MPs on coexisting contaminants, sorption of atrazine onto pristine and ultraviolet-aged (UV) polybutylene adipate co-terephthalate (PBAT) MPs and polybutylene succinate co-terephthalate (PBST) MPs were investigated. The results showed that, UV aging led to more wrinkles and cracks on the surface, increased homogeneous chains proportion, enhanced hydrophobicity, and enlarged crystallinity of both MPs. The sorption kinetics of atrazine to MPs fitted well into pseudo-first-order (R2 = 0.809-0.996) and pseudo-second-order (R2 = 0.889-0.994) models. In the concentration range of 0.5-25 mg L-1, the sorption isotherm fitted into linear (R2 = 0.967-0.996) and Freundlich model (R2 = 0.972-0.997), indicating that the absorption partitioning was the dominant sorption mechanism. The partition coefficient (Kd) of atrazine to PBAT- MPs (40.11-66.01 L kg-1) was higher than that of PBST- MPs (34.34-57.96 L kg-1), and the Kd values of both MPs declined for aged MPs. The specific surface area, hydrophobicity, polarity and crystallinity of MPs jointly interpreted the changing sorption capacity of the MPs. In the present study, both aged PBAT- and aged PBST- MPs exhibited lower vector potential to atrazine than pristine MPs, suggesting reduced risk of being a pollutant carrier, which is of great significance for the development of biodegradable plastics.

Interactions between white and black carbon in water: A case study of concurrent aging of microplastics and biochar.

Microplastics and biochar, as particulate matter that is prevalent in the water environment, will inevitably encounter and interact with each other during environmental aging. The potential interaction of microplastics and biochar, and the associated impact on their environmental behavior remains largely unknown. In this study, we exposed microplastics and biochar concurrently to ultraviolet light to mimic the aging process, investigated the release and fluorescence characteristics of dissolved organic matter (DOM) in water, and analyzed the effects of co-existing microplastics and biochar on their sorption of organic contaminants. We demonstrate that early-stage interactions of microplastics and biochar could entangle to promote the release of DOM from biochar, while their long-term interactions after light irradiation resulted in the sorption of hydrophobic and small molecules of microbial byproduct-like DOM. Simultaneously, early-stage interactions of microplastics and biochar showed a promotion for sorption of organic contaminants with an increase of 5.3-17.7%. After aging, however, long-term interactions between microplastics and biochar made it no longer promote the sorption of organic contaminants due to the influence of heterogeneous aggregation. Our results provide new insights into the time-dependent interactions between microplastics and biochar and highlight the need to incorporate their interactions into future environmental risk assessments for microplastics in the water environment.

Novel insights into the predominant factors affecting the bioavailability of polycyclic aromatic hydrocarbons in industrial contaminated areas using PLS-developed model.

Bioavailability is recognized as a useful technical standard for risk assessment and pollution rehabilitation. However, knowledge on the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in contaminated site soils is still limited, especially concerning the influential mechanism. With an abundance of soil collections from nine industrial areas in China, the bioavailabilities, as conceptually defined as bioconcentration factors (BCFs) of PAHs were analyzed using biomimetic extraction of hydroxypropyl-ß-cyclodextrin (HPCD). Apart from the total content of PAHs varying with the different pyrogenic sources, the BCFs were greatly dependent on the soil physicochemical properties from the spatial scale and inversely proportional to the number of rings. Pearson correlation analysis indicated a weak relationship between bioavailability and the soil dissolved organic matter (DOM), pH and particle size. To incorporate the soil physicochemical properties and structural characteristics of PAHs determined by density functional theory (DFT), the optimum model for bioavailability was developed for BCFs by partial least square (PLS) analysis. The PLS-derived model was shown to be predictive within the applicability domain (AD). The structural characteristics, e.g., molecular polarizability and frontier orbital energy level that favor the soil adsorption of PAH isomers via dispersion interactions, and electron exchanges were indicated to be more impactful on bioavailability than soil environmental factors. However, soil factors should not be neglected, because the pH, DOM, etc. were significantly influential. It makes sense that the higher DOM causes greater bioavailability via increasing the free-dissolved fractions of PAHs. Interestingly, the effect of pH on bioavailability was spectrally validated by excitation-emission matrix (EEM) fluorescence, showing that the interaction between DOM and pyrene strengthened the fluorescence quenching of chromophores with the decline in pH.

Transcriptomic and metabolomic changes in lettuce triggered by microplastics-stress.

Microplastics (MPs) are a global threat to the environment, and plant uptake of MP particles (≤0.2 µm) is a particular cause for concern. However, physiological and molecular mechanisms underlying MP-induced growth inhibition need to be clarified. Towards this goal, we conducted a hydroponic experiment to investigate the accumulation of MPs, changes in physiology, gene expression, and metabolites in lettuce from a series of concentrations of fluorescence-labelled polystyrene MPs (0, 10, 20, 30, 40, 50 mg L-1, ∼0.2 µm). Our results showed that MPs accumulated in the lettuce root tips and leaf veins, resulting in the hypertonic injury of lettuce, and the down-regulation of genes related to ion homeostasis. Stress-related genes were up-regulated, and sphingolipid metabolism increased in response to MP additions, causing increased biosynthesis of ascorbic acid, terpenoid, and flavonoids in root exudates. Our findings provide a molecular-scale perspective on the response of leafy vegetables to MP-stress at a range of concentrations. This enables more comprehensive evaluation of the risks of MPs to human health and the ecological environment.

Major biotransformation of phthalic acid esters in Eisenia fetida: Mechanistic insights and association with catalytic enzymes and intestinal symbionts.

Phthalic acid esters (PAEs) are an important group of organic pollutants that are widely used as plasticizers in the environment. The PAEs in soil organisms are likely to be biotransformed into a variety of metabolites, and the combined toxicity of PAEs and their metabolites might be more serious than PAEs alone. However, there are only a few studies on PAE biotransformation by terrestrial animals, e.g. earthworms. Herein, the key biotransformation pathways of PAEs and their association with catalytic enzymes and intestinal symbionts in earthworms were studied using in vivo and in vitro incubation approaches. The widely distributed PAE in soil, dibutyl phthalate (DBP), was proven to be biotransformed rapidly together with apparent bioaccumulation in earthworms. The biotransformation of PAE congeners with medium or long side chains appeared to be faster compared with those with short side chains. DBP was biotransformed into butyl methyl phthalate (BMP), monobutyl phthalate (MBP), and phthalic acid (PA) through esterolysis and transesterification. Besides, the generation of small quantities of low-molecular weight metabolites via ß-oxidation, decarboxylation or ring-cleavage, was also observed, especially when the appropriate proportion of NADPH coenzyme was applied to transfer electrons for oxidases. Interestingly, the esterolysis of PAEs was mainly regulated by the cytoplasmic carboxylesterase (CarE) in earthworms, with a Michaelis constant (Km) of 0.416 mM in the catalysis of DBP. The stronger esterolysis in non-intestinal tissues indicated that the CarE was primarily secreted by non-intestinal tissues of earthworms. Additionally, the intestinal symbiotic bacteria of earthworms could respond to PAE stress, leading to the changes in their diversity and composition. The enrichment of some genera e.g. Bacillus and Paracoccus, and the enhancement of metabolism function, e.g. amino acids, energy, lipids biosynthesis and oxidase secretion, indicated their important role in the degradation of PAEs.

Manure- and straw-derived biochars reduce the ecological risk of PBDE and promote nitrogen cycling by shaping microbiomes in PBDE-contaminated soil.

Pyrolysis of agricultural waste into biochar for soil remediation is a useful solid waste management strategy. However, it is still unclear how different agricultural feedstocks affect the properties of biochars and their effectiveness in remediation of PBDE-contaminated soil. In this study, we systematically investigated dynamic alterations of soil properties, microbial communities, and PBDE dissipation and bioavailability induced by the application of biochars from manure (MBC) and straw (SBC) to PBDE-contaminated soil. The results showed that soil properties, microbial community structure, and diversity changed differently with the incorporation of the two biochars. MBC had a larger surface area (17.4 m2/g) and a higher nutrient content (45.1% ash content), making it more suitable for use as a soil additive to improve soil quality and nutrient conditions, as well as to stimulate microbial growth. SBC showed higher adsorption capacity for 2,2',4,4'-Tetrabromodiphenyl Ether (BDE-47) (26.73 ± 0.65 mg/g), thus lowering the bioavailability and ecological risk of BDE-47 in soil. BDE-47 was stepwise debrominated into lower brominated PBDE by PBDE-degrading bacteria. MBC accelerated the debromination of BDE-47 (10.1%) by promoting PBDE-degrading microorganisms, while this was inhibited by SBC (3.5%) due to strong adsorption of BDE-47. In addition, we found that both types of biochar favored Nitrospirae bacteria and promoted N cycling. Overall, biochars from manure and straw can positively shape soil microbial communities differently by altering soil properties, soil fertility and nutrient availability, and the fate and the effects of contaminants, which ultimately led to a difference in the potential of biochars for their use in soil remediation.

Visualizing the Distribution of Phthalate Esters and Plant Metabolites in Carrot by Matrix-Assisted Laser Desorption/Ionization Imaging Mass Spectrometry.

The accumulation of organic pollutants in vegetables is a major global food safety issue. The concentrations of pollutants in vegetables usually differ across different tissues because of different transport and accumulation pathways. However, owing to the limitations of conventional methods, in situ localization of typical organic pollutants such as phthalate esters (PAEs) in plant tissues has not yet been studied. Here, we developed a quick and efficient method for in situ detection and imaging of the spatial distribution of PAEs in a typical root vegetable, carrot, using matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS). The use of a 2,5-dihydroxybenzoic acid matrix with a spray-sublimation coating method led to the successful identification of PAEs ion signals. The IMS results showed that a typical PAE-di-(2-ethylhexyl)phthalate (DEHP) was broadly distributed in the cortex, phloem, and metaxylem, but was barely detectable in the cambium and protoxylem. Interestingly, MALDI-IMS data also revealed for the first time the spatial distribution of sugars and ß-carotene in carrots. In summary, the developed method offers a new and practical methodology for the in situ analysis of PAEs and plant metabolites in plant tissues. As a result, it could provide a more intuitive understanding of the movement and transformation of organic pollutants in soil-plant systems.

Positively Charged Microplastics Induce Strong Lettuce Stress Responses from Physiological, Transcriptomic, and Metabolomic Perspectives.

Microplastics (MPs) can enter plants through the foliar pathway and are potential hazards to ecosystems and human health. However, studies related to the molecular mechanisms underlying the impact of foliar exposure to differently charged MPs to leafy vegetables are limited. Because the surfaces of MPs in the environment are often charged, we explored the uptake pathways, accumulation concentration of MPs, physiological responses, and molecular mechanisms of lettuce foliarly exposed to MPs carrying positive (MP+) and negative charges (MP-). MPs largely accumulated in the lettuce leaves, and stomatal uptake and cuticle entry could be the main pathways for MPs to get inside lettuce leaves. More MP+ entered lettuce leaves and induced physiological, transcriptomic, and metabolomic changes, including a decrease in biomass and photosynthetic pigments, an increase in reactive oxygen species and antioxidant activities, a differential expression of genes, and a change of metabolite profiles. In particular, MP+ caused the upregulation of circadian rhythm-related genes, and this may play a major role in the greater physiological toxicity of MP+ to lettuce, compared to MP-. These findings provide direct evidence that MPs can enter plant leaves following foliar exposure and a molecular-scale perspective on the response of leafy vegetables to differently charged MPs.

Assisting the carbonization of biowaste with potassium formate to fabricate oxygen-doped porous biochar sorbents for removing organic pollutant from aqueous solution.

In contrast to the efforts dedicated to applying porous biochars in environmental remediation, the search for green synthesis methods, which are crucial for industrialized production, is often neglected. Herein, oxygen-doped porous biochars were prepared for the first time by the assisted carbonization of hydrochar with a novel noncorrosive activator, potassium formate, and these biochars displayed a porous structure with large amounts of micropores (surface area: 1242 âˆ¼ 1386 m2 g-1). Interestingly, the biochars contained an abundance of oxygen element (20 âˆ¼ 26%), which formed many functional groups. Through sorption experiments, it was demonstrated that the oxygen-doped porous biochars were excellent sorbents for diethyl phthalate, and maximum sorption quantity reached 453 mg g-1. Monolayer sorption by pore filling, hydrogen bonding, electrostatic interaction and π-π stacking was the potential mechanism. This finding indicated that potassium formate was promising as an activator to greenly convert biowaste into advanced biochars for removing organic pollutants from aqueous solutions.

Comparison of the performance of hydrochar, raw biomass, and pyrochar as precursors to prepare porous biochar for the efficient sorption of phthalate esters.

In this study, three high-performance porous biochars were synthesized by the cocarbonization of Pistia stratiotes-derived precursors (raw biomass, hydrochar and pyrochar) with potassium hydroxide and utilized for the sorption of diethyl phthalate from aqueous solution. The developed pore structure, surface functional groups, high hydrophobicity characteristic and graphene structure of porous biochars contributed to the excellent sorption quantity of up to 813 mg g-1 (Ce, 25 mg L-1). Among the three precursors, hydrochar-derived porous biochar showed better properties in terms of its specific surface area and hydrophobicity, and it displayed the highest sorption capacity. The sorption kinetics and isotherm experiments confirmed that pore filling and partitioning dominated the sorption capacity while the mass transfer, hydrogen bonding and π-π stacking in the hydrochar limited the sorption rate. This finding helped to propose a feasible method for the efficient utilization of invasive aquatic plants and provided novel insight into the selection of precursors for preparing porous biochars.

Bioaccessibility and Toxicity Assessment of Polycyclic Aromatic Hydrocarbons in Two Contaminated Sites.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous soil contaminants, and their bioaccessibility determines their environmental risks in contaminated land. In the present study, the residual concentrations of PAHs in the soils of two industrial sites were determined, and their bioaccessibility was estimated by the hydroxypropyl-ß-cyclodextrin extraction (HPCD) extraction method. The results showed heavy PAH contamination at both site S1 (0.38-3342.5 mg kg-1) and site S2 (0.2-138.18 mg kg-1), of which high molecular weight (HMW) PAHs (4-, 5-, and 6-ring compounds) accounted for approximately 80%. The average bioaccessibility of PAHs at sites S1 and S2 was 52.02% and 29.28%, respectively. The bioaccessibility of certain PAH compounds decreased with increasing ring number of the molecule. Lower PAH bioaccessibility was detected in loamy and silty soil textures than in sandy soil. Moreover, among the soil properties, the dissolved organic matter, total organic carbon, total potassium, and total manganese concentrations had significant effects on the bioaccessibility of PAHs. The toxicity analysis showed that the composition and bioaccessibility of PAHs could affect their potential toxicity in soil. We suggest that bioaccessibility should be taken into consideration when assessing the toxicity of PAHs in soil, and more attention should be given to low-ring PAHs with high bioaccessibility.

Attachment of positively and negatively charged submicron polystyrene plastics on nine typical soils.

Microplastics (MPs) have attracted increasing concern as emerging contaminants of global importance in recent years. Soil is considered an important sink for MPs. Due to environmental weathering, MP surfaces are often charged, but there are limited studies on the interaction of differentially charged MP with soils. This study constructed Derjaguin-Landau-Verwey-Overbeek (DLVO) potential energy profiles, investigated the interaction mechanism of polystyrene MPs (0.2 µm) with positive (MP+) and negative (MP-) charges on nine typical soils through quantitative analysis of fluorescence intensity. The attachment of MPs to different soils fitted the pseudo-second-order kinetic model well. The attachment isotherm data of MP+ fitted the linear model better, while the MP- data fitted the Langmuir model. The attachment capacity of MPs was significantly correlated with the zeta potential of soils. These results, as well as the fourier transform infrared spectroscopy (FTIR) spectra and scanning electronic microscopy (SEM) images of soils, indicated that electrostatic interactions and physical trapping were the dominant mechanisms for MP attachment to soils. These results showed a strong affinity for MPs attachment on soil and gave insights to predict the transport, fate and ecological effect of different charged MPs in soil.

Degradation of mineral-immobilized pyrene by ferrate oxidation: Role of mineral type and intermediate oxidative iron species.

Ferrate (Fe(VI)) salts like K2FeO4 are efficient green oxidants to remediate organic contaminants in water treatment. Minerals are efficient sorbents of contaminants and also excellent solid heterogeneous catalysts which might affect Fe(VI) remediation processes. By targeting the typical polycyclic aromatic hydrocarbon compound - pyrene, the application of Fe(VI) for oxidation of pyrene immobilized on three minerals, i.e., montmorillonite, kaolinite and goethite was studied for the first time. Pyrene immobilized on the three minerals was efficiently oxidized by Fe(VI), with 87%-99% of pyrene (10 µM) being degraded at pH 9.0 in the presence of a 50-fold molar excess Fe(VI). Different minerals favored different pH optima for pyrene degradation, with pH optima from neutral to alkaline following the order of montmorillonite (pH 7.0), kaolinite (pH 8.0), and goethite (pH 9.0). Although goethite revealed the highest catalytic activity on pyrene degradation by Fe(VI), the greater noneffective loss of the oxidative species by ready self-decay in the goethite system resulted in lower degradation efficiency compared to montmorillonite. Protonation and Lewis acid on montmorillonite and goethite assisted Fe(VI) oxidation of pyrene. The intermediate ferrate species (Fe(V)/Fe(IV)) were the dominant oxidative species accountable for pyrene oxidation, while the contribution of Fe(VI) species was negligible. Hydroxyl radical was involved in mineral-immobilized pyrene degradation and contributed to 11.5%-27.4% of the pyrene degradation in montmorillonite system, followed by kaolinite (10.8%-21.4%) and goethite (5.1%-12.2%) according to the hydroxyl radical quenching experiments. Cations abundant in the matrix and dissolved humic acid hampered pyrene degradation. Finally, two different degradation pathways both producing phthalic acid were identified. This study demonstrates efficient Fe(VI) oxidation of pyrene immobilized on minerals and contributes to the development of efficient environmentally friendly Fe(VI) based remediation techniques.

Different performance of pyrene biodegradation on metal-modified montmorillonite: Role of surface metal ions from a bioelectrochemical perspective.

Microbial extracellular electron transfer (EET) at microbe-mineral interface has been reported to play a significant role in pollutant biotransformation. Different metals often co-exist with organic pollutants and are immobilized on mineral surfaces. However, little is known about the influence of mineral surface metal ions on organic pollutant biodegradation and the involved electron transfer mechanism. To address this knowledge gap, pyrene was used as a model compound to investigate the biodegradation of polycyclic aromatic hydrocarbon on montmorillonite mineral saturated with metal ions (Na(I), Ni(II), Co(II), Cu(II) and Fe(III)) by Mycobacteria strain NJS-1. Further, the possible underlying electron transfer mechanism by electrochemical approaches was investigated. The results show that pyrene biodegradation on montmorillonite was markedly influenced by surface metal ions, with degradation efficiency following the order Fe(III) > Na(I) ≈ Co(II) > Ni(II) ≈ Cu(II). Bioelectrochemical analysis showed that electron transfer activities (i.e., electron donating capacity and electron transport system activity) varied in different metal-modified montmorillonites and were closely related to pyrene biodegradation. Fe(III) modification greatly stimulated degrading enzyme activities (i.e., peroxidase and dioxygenase) and electron transfer activities resulting in enhanced pyrene biodegradation, which highlights its potential as a technique for pollutant bioremediation. The bacterial extracellular protein and humic substances played important roles in EET processes. Membrane-bound cytochrome C protein and extracellular riboflavin were identified as the electron shuttles responsible for transmembrane and cross extracellular matrix electron transfer, respectively. Additions of exogenetic electron mediators of riboflavin, humic acid and potassium ferricyanide accelerated pyrene biodegradation which further verified the critical role of EET in PAH transformation at bacteria-mineral interfaces. These results support the development of clay mineral based advanced bioremediation techniques through regulating the electron transfer processes at the microbe-mineral interfaces by mineral surface modification.

Hierarchical porous biochars with controlled pore structures derived from co-pyrolysis of potassium/calcium carbonate with cotton straw for efficient sorption of diethyl phthalate from aqueous solution.

A one-pot co-pyrolysis of potassium/calcium carbonate with biowaste-derived hydrochar strategy was proposed to prepare hierarchical porous biochars (HPBs) for the first time. The pore structure, especially the pore size distribution, could be designed by adjusting the mass ratios of different carbonates. HPBs were hydrophobic, nitrogen doped, graphitized, and contained surface functional groups. HPBs showed unexpected sorption quantity for diethyl phthalate (DEP) that reached 657 mg g-1, which much higher than that of the reported sorbents. The sorption was multilayered and had multiple action modes, and was limited by the chemical sorption and the sorption quantity was dominated by the physical sorption. Lewis acid-base interaction, π-π stacking interaction, hydrogen bonding interaction, partitioning and pore filling were the potential sorption mechanisms. This work proposed a simple, environmentally friendly and low-cost method to convert biowaste into advanced HPBs and confirmed that produced HPBs represent ideal sorbents for the removal of organic pollutants.

Mechanistic insights into primary biotransformation of diethyl phthalate in earthworm and significant SOD inhibitory effect of esterolytic products.

Phthalic acid esters (PAEs) are used as plasticizer or modifier in artificially-manufactured products. Though the rapid biotransformation of phthalates in microbes and plants have been well documented, it is less studied yet in terrestrial animals, e.g. earthworm. In this study, the major biotransformation of diethyl phthalate (DEP) in Eisenia fetida was illustrated using in vitro incubation of earthworm crude enzymes. DEP could be substantially biotransformed into phthalate monoester (MEP) and a small amount of phthalic acid (PA) through esterolysis, which was verified to be driven by endogenous carboxylesterase. Despite the inferior contribution, the oxidation of DEP might also occur under the initiated electron transfer by NADPH coenzyme. The dominant metabolite MEP showed a higher inhibition of superoxide dismutase (SOD) activity than DEP with EC50 of 0.0082 ± 0.0016 mmol/L, so the higher ecological risks of MEP would be marked. The inhibition effect of PA was validated to be even stronger than MEP though it was slightly generated. The direct binding interaction with SOD was proved to be an important molecular event for regulation of SOD activity. Besides the static quenching mechanism, the caused conformational changes including despiralization of α-helix and spatial reorientation of tryptophan were spectrally believed to affect binding and underlie inhibition efficiency of SOD activity.

Strategy for Mitigating Antibiotic Resistance by Biochar and Hyperaccumulators in Cadmium and Oxytetracycline Co-contaminated Soil.

The global prevalence of antibiotic resistance genes (ARGs) is of increasing concern as a serious threat to ecological security and human health. Irrigation with sewage and farmland application of manure or biosolids in agricultural practices introduce substantial selective agents such as antibiotics and toxic metals, aggravating the transfer of ARGs from the soil environment to humans via the food chain. To address this issue, a hyperaccumulator (Sedum plumbizincicola) combined with biochar amendment was first used to investigate the mitigation of the prevalence of ARGs in cadmium and oxytetracycline co-contaminated soil by conducting a pot experiment. The addition of biochar affected the distribution of ARGs in soil and plants differently by enhancing their prevalence in the soil but restraining transmission from the soil to S. plumbizincicola. The planting of S. plumbizincicola resulted in an increase in ARGs in the soil environment. A structural equation model illustrated that mobile genetic elements played a dominant role in shaping the profile of ARGs. Taken together, these findings provide a practical understanding for mitigating the prevalence of ARGs in this soil system with complex contamination and can have profound significance for agricultural management in regard to ARG dissemination control.

Mechanistic insight into hydroxylation of 2,2',4,4'-tetrabromodiphenyl ether during biodegradation by typical aerobic bacteria: Experimental and computational studies.

Polybrominated diphenyl ethers (PBDEs) are a group of persistent pollutants in the environment. Though aerobic biodegradation of PBDEs have been extensively studied, the involved hydroxylation mechanism decisive for whole biotransformation is not clear yet. During the effective biodegradation of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) by B. xenovorans LB400, the depletion of endogenous ∙OH by scavenger could bring about the significant decrease of biodegradation efficiency whereas ·O2- was nearly not influential. Given the importance of ∙OH in hydroxylation, the reaction mechanisms along major pathways of electrophilic addition and hydrogen abstraction were theoretically examined by density functional theory (DFT). For the less demand of activation energy, the relative preference of electrophilic addition was shown at aromatic C3-site. When the secondary reaction was considered after addition at C4-site, the barrierless association of ∙OH at C3-site and deprotonation by H2O was validated as the energetically-favorable pathway that may cause dihydroxylation of BDE-47 into 3,4-dihydroxyl-BDE-17. The electrophilic addition followed by seconary barrierless trans-association of ∙OH and then dehydration seemed favorable for monohydroxylation as regards energetic barrier merely up to 194.01 kJ mol-1, while the hydrogen abstraction by ∙OH from C5-site was more privileged actually. The theoretical insights would help well understand the hydroxylation mechanism of PBDEs by aerobes.