Biochemical insights into the biodegradation mechanism of typical sulfonylureas herbicides and association with active enzymes and physiological response of fungal microbes: A multi-omics approach.

The extensive use of sulfonylurea herbicides has raised major concerns regarding their long-term soil residues and agroecological risks despite their role in agricultural protection. Microbial degradation is an important approach to remove sulfonylureas, whereas understanding the associated biodegradation mechanisms, enzymes, and physiological responses remains incomplete. Based on the rapid biodegradation of nicosulfuron by typical fungal isolate Talaromyces flavus LZM1, the dependency on cellular accumulation and environmental conditions, e.g. pH and nutrient supplies, was shown in the study. The biodegradation of nicosulfuron occurred intracellularly and followed the cascade of reactions including hydrolysis, Smile contraction rearrangement, hydroxylation, and opening of the pyrimidine ring. Besides 2-amino-4,6-dimethoxypyrimidine (ADMP) and 2-aminosulfonyl-N,N-dimethylnicotinamide (ASDM), numerous products and intermediates were newly identified and the structural forms of methoxypyrimidine and sulfonylurea bridge contraction rearrangement are predicted to be more toxic than nicosulfuron. The biodegradation should be enzymatically regulated by glycosylphosphatidylinositol transaminase (GPI-T) and P450s, which were manifested with the significant upregulation in proteomics. It is the first time that the hydrolysis of nicosulfuron into ADMP and ASDM have been associated with GPI-T. The integrated pathways of biodegradation were further elucidated through the involvement of various active enzymes. Except for the enzymatic catalysis, the physiological responses verified by metabolo-proteomics were critical not only to regulate material synthesis, uptake, utilization, and energy transfer but also to maintain antioxidant homeostasis, biodegradability, and tolerance of nicosulfuron by the differentially expressed metabolites, such as acetolactate synthase and 3-isopropylmalate dehydratase. The obtained results would help understand the biodegradation mechanism of sulfonylurea from chemicobiology and enzymology and promote the use of fungal biodegradation in pollution rehabilitation.

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.

Emerging contaminants: A One Health perspective.

Environmental pollution is escalating due to rapid global development that often prioritizes human needs over planetary health. Despite global efforts to mitigate legacy pollutants, the continuous introduction of new substances remains a major threat to both people and the planet. In response, global initiatives are focusing on risk assessment and regulation of emerging contaminants, as demonstrated by the ongoing efforts to establish the UN's Intergovernmental Science-Policy Panel on Chemicals, Waste, and Pollution Prevention. This review identifies the sources and impacts of emerging contaminants on planetary health, emphasizing the importance of adopting a One Health approach. Strategies for monitoring and addressing these pollutants are discussed, underscoring the need for robust and socially equitable environmental policies at both regional and international levels. Urgent actions are needed to transition toward sustainable pollution management practices to safeguard our planet for future generations.

Degradation of the emerging brominated flame retardant tetrabromobisphenol S using organo-montmorillonite supported nanoscale zero-valent iron.

The widespread occurrence of emerging brominated flame retardant tetrabromobisphenol S (TBBPS) has become a major environmental concern. In this study, a nanoscale zero-valent iron (nZVI) impregnated organic montmorillonite composite (nZVI-OMT) was successfully prepared and utilized to degrade TBBPS in aqueous solution. The results show that the nZVI-OMT composite was very stable and reusable as the nZVI was well dispersed on the organic montmorillonite. Organic montmorillonite clay layers provide a strong support, facilitate well dispersion of the nZVI chains, and accelerate the overall TBBPS transformation with a degradation rate constant 5.5 times higher than that of the original nZVI. Four major intermediates, including tribromobisphenol S (tri-BBPS), dibromobisphenol S (di-BBPS), bromobisphenol S (BBPS), and bisphenol S (BPS), were detected by high-resolution mass spectrometry (HRMS), indicating sequential reductive debromination of TBBPS mediated by nZVI-OMT. The effective elimination of acute ecotoxicity predicted by toxicity analysis also suggests that the debromination process is a safe and viable option for the treatment of TBBPS. Our results have shown for the first time that TBBPS can be rapidly degraded by an nZVI-OMT composite, expanding the potential use of clay-supported nZVI composites as an environmentally friendly material for wastewater treatment and groundwater remediation.

[Adsorption Performance and Mechanism of Oxytetracycline in Water by KOH Modified Biochar Derived from Corn Straw].

The pollution control of tetracycline antibiotics in the environment has become a hot topic, and biochar adsorption has become an important technology to remove organic pollutants. Pyrolytic biochars (BC400, BC500, and BC600) were prepared from corn straw and then were modified by KOH to obtain KBC400, KBC500, and KBC600. Among them, KBC400 was selected for secondary pyrolysis activation at 400-600℃ to obtain AKBC400, AKBC500, and AKBC600. The structure characteristics and surface properties of AKBC were also characterized. The adsorption kinetics and thermodynamic characteristics of oxytetracycline hydrochloride (OTC) in the solution by AKBC were investigated using batch experiments. Compared to that of BC400, the specific surface area and pore structure of AKBC were significantly improved, and the aromaticity was also enhanced, resulting in the notable enhancement of the adsorption capacities for OTC. The pseudo-second-order kinetics model could better fit the adsorption process, and AKBC500 had the largest adsorption rate constant and capacity. Both the intraparticle diffusion and film diffusion were the rate-limiting steps. The Langmuir, Freundlich, and Temkin models could fit the adsorption isotherms perfectly. The adsorption of OTC on AKBC was a spontaneous, endothermic, and entropy-increasing process by both physisorption and chemisorption. The pH values in the range of 3.0-7.0 were favorable for the adsorption of OTC by AKBC. The adsorption capacity decreased with the humic acid concentration over 10 mg·L-1. The adsorption mechanism of OTC by AKBC involved pore filling, hydrogen bonding, π-π conjugation, cation-π bond, and strong electrostatic effect. AKBC still had good reusability for OTC removal after five times of regeneration. The obtained AKBC is a potential adsorbent for OTC removal from water due to the good pore structure, high adsorption capacity, and stable adsorption effect.

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.

Comparative evaluation and prioritization of key influences on biodegradation of 2,2',4,4'-tetrabrominated diphenyl ether by bacterial isolate B. xenovorans LB400.

Polybrominated diphenyl ethers (PBDEs) are a class of persistent organic pollutants being widely distributed and harmful to human health and wildlife, and the development of sustainable rehabilitation strategies including microbial degradation is of great concern. Although the increasing number of bacteria, especially the broad-spectrum and potent aerobes have been isolated for the efficient removal of PBDEs, the external influences and the corresponding influential mechanism on biodegradation are not fully understood yet. Given the wide-spectrum biodegradability of aerobic bacterial isolate, B. xenovorans LB400 for PBDEs, the dual impacts of many pivotal factors including pH, temperature, presence of dissolved organic matter (DOM) and cadmium ion etc. were comprehensively revealed on biodegradation of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47). Due to the structural resemblance and stimulation of specific enzyme activity in bacteria, the biphenyl as substrates showed the greater capacity than non-aromatic compounds in improving biodegradation. The individual adaptation to neutrality and cultivation at about 30 °C was beneficial for biodegradation since the bacterial cellular viability and enzyme activity was mostly preserved. Although it was possibly good for the induction of hormesis and favorable to enhance the permeability or bioavailability of pollutant, the exceeding increase of Cd2+ or DOM may not give the profitable increase of biodegradation yet for the detrimental effect. For biodegradation, the mechanistic relationship that took account of the integrative correlation with the influential factors was artfully developed using partial least square (PLS) regression technique. Relative to the most significant influence of culture time and initial concentration of BDE-47, the larger relevance of other factors primarily marked as pH and DOM was consecutively shown after the quantitative prioritization. This may not only help understand the influential mechanism but provide a prioritizing regulation strategy for biodegradation of BDE-47. The PLS-derived relationship was validated with the certain predictability in biodegradation, and could be used as an alternative to accelerate a priori evaluation of suitability or improve the feasibility of such bacteria in remediation of PBDEs in the 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.

Congener-specificity, dioxygenation dependency and association with enzyme binding for biodegradation of polybrominated diphenyl ethers by typical aerobic bacteria: Experimental and theoretical studies.

Polybrominated diphenyl ethers (PBDEs) are a group of organic pollutants that have attracted much concerns of scientific community over the ubiquitous distribution, chemical persistence and toxicological risks in the environment. Though a great number of aerobic bacteria have been isolated for the rapid removal of PBDEs, the knowledge about biodegradation characteristics and mechanism is less provided yet. Herein, the congener-specificity of aerobic biodegradation of PBDEs by typical bacteria, i.e. B. xenovorans LB400 was identified with the different biodegradation kinetics, of which the changes were largely hinged on the bromination pattern. The more bromination isomerically at ortho-sites other than meta-sites or the single bromination at one of aromatic rings might always exert the positive effect. The biodegradation of PBDEs should be thermodynamically constrained to some extent because the calculated Gibbs free energy changes of initial dioxygenation by quantum chemical method increased with the increase of bromination. Within the transition state theory, the high correlativity between the apparent biodegradation rates and Gibbs free energy changes implied the predominance and rate-limiting character of initial dioxygenation, while the regioselectivity of dioxygenation at the ortho/meta-sites was also manifested for the more negative charge population. The molecular binding with the active domain of dioxygenase BphA1 in aerobe was firstly investigated using docking approach. As significantly illustrated with the positive relationship, the higher binding affinity with BphA1 should probably signify the more rapid biodegradation. Besides the edge-on π-π stacking of PBDEs with F227 or Y277 and π-cation formulation with histidines (H233, H239) in BphA1, the reticular hydrophobic contacts appeared as the major force to underpin the high binding affinity and rapid biodegradation of PBDEs. Overall, the experimental and theoretical results would not only help understand the aerobic biodegradation mechanism, but facilitate enhancing applicability or strategy development of engineering bacteria for bioremediation of PBDEs in the environment.

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.

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.

Enhanced reductive debromination of decabromodiphenyl ether by organic-attapulgite supported Fe/Pd nanoparticles: Synergetic effect and mechanism.

Effective removal of polybrominated diphenyl ethers (PBDEs) from the environment is essential for the ecosystem and human health. Reductive debromination of PBDEs by nanoscale zerovalent iron (nZVI) has become an important technology. However, the agglomeration and low persistence catalytic activity of nZVI particles have become urgent problems to be improved. Herein, we report the first application of a new organo-attapulgite (OA) supported Fe/Pd nanoparticles (OA-Fe/Pd) composite for decabromodiphenyl ether (BDE209) removal. BDE209 was efficiently removed using OA-Fe/Pd with a reaction rate that was 9.97 times greater than that of the nZVI due to the synergetic effect of support material OA and Pd loading. OA could prevent nZVI particles from agglomeration and adsorb BDE209 molecules to its surface. Pd could supply atomic hydrogen and also prevent the oxidation of nZVI particles. The degradation of BDE209 by OA-Fe/Pd was affected by many factors and followed pseudo first-order kinetics. The degradation of BDE209 by OA-Fe/Pd underwent a stepwise debromination manner with the H-transfer dominant mechanism. BDE209 (25 mg∙L-1) could be degraded to penta-BDEs to diphenyl ether (DE) by 3.0 g∙L-1 OA-Fe/Pd within 240 min under neutral condition. This study provides some inspiration for improving the removal efficiency of PBDEs with nZVI-based materials.

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.

Highly efficient debromination of 4,4'-dibrominated diphenyl ether by organic palygorskite-supported Pd/Fe nanoparticles.

Organic palygorskite (OP)-supported Pd/Fe nanoparticles composite (OP-Pd/Fe) was prepared by stepwise reduction method. The removal capacity of 4,4'-dibrominated diphenyl ether (BDE15) by OP-Pd/Fe was compared with other various materials. For better understanding the possible mechanism, the synthesized and reacted OP-Pd/Fe materials were characterized by TEM, SEM, XRD, and XPS, respectively. The effects of major influencing parameters on the degradation of BDE15 were also studied. Benefit from the synergistic effect of the carrier and bimetallic nanoparticles, BDE15 could be completely debrominated into diphenyl ether (DE) under suitable conditions. A two-stage adsorption/debromination removal mechanism was proposed. The degradation of BDE15 with OP-Pd/Fe was mainly stepwise debromination reaction, and hydrogen transfer mode was assumed as the dominated debromination mechanism. The removal process fitted well to the pseudo first-order kinetic equation. The observed rate constants increased with increasing Pd loading and OP-Pd/Fe dosage while decreased with increasing initial BDE15 concentration, the tetrahydrofuran/water ratio, and the initial pH of the solution. The work provides a new approach for the treatment of PBDEs pollution.

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.

Study on active response of superoxide dismutase and relevant binding interaction with bioaccumulated phthalates and key metabolites in Eisenia fetida.

Phthalic acid esters (PAEs) are a group of widespread persistent organic pollutants in the environment. Though the harmful effect of PAEs including activity inhibition of superoxide dismutase (SOD) to arouse oxidative stress were well documented, the deep insights into mechanisms that are relevant with SOD activity are still lacking. By 7d-cultivation of Eisenia fetida in artificially-polluted soil, the different active responses of SOD in earthworm were shown to PAE congeners. Despite the less bioaccumulation and bioavailability, the di-butyl phthalate (DBP) etc. structurally coupled with longer ester-chains appeared more effective to trigger the up-regulation and then the slight decline of SOD activity. Given the remarkable biotransformation especially for short-chain PAEs, the SOD activity response in earthworm should be regarded as joint effect with their metabolites, e.g. monophthalates (MAEs) and phthalic acid (PA). The in vitro SOD activity was shown with the obvious inhibition of 21.31% by DBP, 88.93% by MBP, and 58.57% by PA respectively when the concentrations were elevated up to 0.03 mM. The SOD activity inhibition confirmed the molecular binding with pollutants as an essential event besides the biological regulation for activity. The binding interaction was thermodynamically exothermic, spontaneous and strengthened primarily by Van der Waals force and hydrogen bonds, and was spectrally diagnosed with the conformational changes including diminution of α-helix content and spatial reorientation of fluorophore tryptophan. As coherently illustrated with the larger fluorescence quenching constants (3.65*104-4.47*104/mol) than DBP, the metabolites should be the priority concern due to stronger activity inhibition and toxicological risks.

Risk Assessment of Agricultural Plastic Films Based on Release Kinetics of Phthalate Acid Esters.

Plastic films have become an integral part of fruit and vegetable production systems, but their release of phthalate acid esters (PAEs) is a threat to human health. The release kinetics of PAEs and measures of risk are still not well understood. We investigated 50 agricultural films, with concentrations ranging from 2.59 to 282,000 mg kg-1. The seven commercially available film types included were polyvinylchloride (PVC), metallocene polyethylene (mPE), ethylene vinyl acetate (EVA), polyolefin (PO), and three mulch films. Bis(2-ethylhexyl) phthalate (DEHP) was detected in most of films, and its release fitted well into the first-order kinetic model. The release rate of DEHP was negatively related to the film thickness. The potential carcinogenic risks of DEHP in the air of six kinds of plastic greenhouses to human health were estimated. We found that the carcinogenic risks associated with PVC and mPE greenhouse films warrant greater attention. Though EVA, PO greenhouse, and mulch films were lower risk, we advise keeping plastic greenhouses well ventilated during the first month of use to reduce direct human exposure to volatile PAEs.

Insights into the mechanisms underlying efficient Rhizodegradation of PAHs in biochar-amended soil: From microbial communities to soil metabolomics.

The combined effects of biochar amendment and the rhizosphere on the soil metabolic microbiome during the remediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soil remain unknown. In this study, we attempted to characterize a PAH degradation network by coupling the direct PAH degradation with soil carbon cycling. From microbial community structure and functions to metabolic pathways, we revealed the modulation strategies by which biochar and the rhizosphere benefited PAH degradation in soil. Firstly, some PAH degraders were enriched by biochar and the rhizosphere, and their combination promoted the cooperation among these PAH degraders. Simultaneously, under the combined effects of biochar and the rhizosphere, the functional genes participating in upstream PAH degradation were greatly upregulated. Secondly, there were strong co-occurrences between soil microbial community members and metabolites, in particular, some PAH degraders and the metabolites, such as PAH degradation products or common carbon resources, were highlighted in the networks. It shows that the overall downstream carbon metabolism of PAH degradation was also greatly upregulated by the combined effects of biochar and plant roots, showing good survival of the soil microbiome and contributing to PAH biodegradation. Taken together, both soil carbon metabolism and direct contaminant biodegradation are likely to be modulated by the combined effects of biochar and plant roots, jointly benefitting to PAH degradation by soil microbiome. Our study is the first to link PAH degradation with native carbon metabolism by coupling sequencing and soil metabolomics technology, providing new insights into a systematic understanding of PAH degradation by indigenous soil microbiome and their networks.