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.

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.

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.

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.

Mechanistic studies of congener-specific adsorption and bioaccumulation of polycyclic aromatic hydrocarbons and phthalates in soil by novel QSARs.

Polycyclic aromatic hydrocarbons (PAHs) and phthalic acid esters (PAEs) which are structurally featured with one or more aromatic skeletons are often regarded as two important groups of organic pollutants due to the widespread distribution and notorious toxic effects in soils. Relative to the great number of structural analogues or congeners detected in soil, however, the soil adsorption and bioaccumulation of PAHs/PAEs by plant is far less studied for the insufficiency of experimental determinations or lack of insights into the inherent structural requirements. To mechanistically evaluate the congener-specific soil adsorption and bioaccumulation for PAHs/PAEs, the quantitative structure-activity relationships (QSARs) were successfully developed by density functional theory (DFT) computation and partial least squares (PLS) analysis. As verified with the higher cumulative variance coefficients and cross-validated correlation coefficients for strong stability, interpretability and predictability, the QSARs could be used for prediction of unknown adsorption potency or bioavailability within the specified applicability domain, respectively. It was indicated by QSAR that the structural requirements of PAHs/PAEs necessary for strengthening the soil adsorption were mainly attributed to the molecular polarizability and the associated dispersion interaction with soil. As regards the bioaccumulation by carrot, the aggravation of spherical polarity change of molecules and the involved electrostatic interaction with soil entity or electron transfer from the highest occupied molecular orbital (HOMO) of PAHs/PAEs was implied to be inherently decisive for the variance of bioavailability among congeners. Based on the holistic view of negative correlation relationship, the soil adsorption seemed to act as the forceful constraint in decreasing the bioaccumulation of PAHs/PAEs and could also be alternatively gauged as the preliminary evaluation of bioavailability and risks on soil ecosystem. It would thus help better understand the soil adsorption and bioaccumulation with the informative mechanistic insights and provide data support for ecological risk assessment of PAHs/PAEs in soils.

Does Biochar Induce Similar Successions of Microbial Community Structures Among Different Soils?

In this study, the responses of soil bacterial communities to biochar amendment in different soils were investigated. Biochar amendment had not significantly changed the bacterial richness and diversity in black soil, fluvo-aquic soil and red soil, but shifted all the soil bacterial community structures. Biochar amendment mainly increased the growth of low-abundance bacteria in fluvo-aquic soil and that of high-abundance bacteria in red soil. The most abundant bacterial phylum in black soil and fluvo-aquic soil, Proteobacteria, increased after biochar addition, while Chloroflexi, the most abundant phylum in red soil, decreased after biochar addition. Some bacterial phyla responded consistently to biochar amendment. However, many more bacterial phyla responded differently to biochar amendment in different soils, especially those phyla present at low abundances. Therefore, our study confirmed that the responses of soil bacterial communities to the same biochar were specific to both soil type and bacterial phylum.

Effect of cetyltrimethyl ammonium bromide on uptake of polycyclic aromatic hydrocarbons by carrots.

This is the first study investigating the effect of cationic surfactants on the mobility of polycyclic aromatic hydrocarbons (PAHs) in aged contaminated soils and on PAH bioaccumulation in tuberous vegetables. In an aerobic soil incubation experiment, 150 mg/kg cetyltrimethyl ammonium bromide (CTMAB) decreased the bioavailability of PAHs primarily via immobilization (by 13%). In a carrot pot experiment, the effectiveness of CTMAB to reduce PAH uptake by carrots decreased with time. Accordingly, the bioavailability of PAHs in the soil decreased in the first 90 days and then increased and remained stable until harvest. In the leaching test, the leaching loss of CTMAB (15%) was lower in soils treated with small amounts of CTMAB in several applications than it was in soils (24%) treated once with CTMAB. Therefore, CTMAB, when applied in appropriate doses via addition methods, can effectively reduce the environmental risk of PAH entering humans and livestock through the food chain.

A nanoporous carbon material coated onto steel wires for solid-phase microextraction of chlorobenzenes prior to their quantitation by gas chromatography.

A nanoporous carbon material was synthesized by heating potassium citrate without using a template or an activating agent. It is shown to represent a viable coating for use in solid-phase microextraction. The material is thermally stable and mainly consists of amorphous sheets of sp2-bonded carbon. It has an extensive pore structure and a surface area as large as 1236 m2·g-1. The nanoporous carbon was deposited on the surface of steel wires, and the resulting fibers were applied to the extraction of trace levels of chlorobenzenes in water samples. Following extraction by absorbing, the chlorobenzenes were quantified by gas chromatograph in combination with electron capture detection. Extraction temperature and time, and desorption temperature were optimized (80 °C, 10 min and 310 °C). Under optimized conditions, the calibration plots are linear in the following concentration ranges: 2.5 to 100 ng·L-1 (pentachlorobenzene), 5 to 200 ng·L-1 (1,2,3,4-tetrachlorobenzene), 10 to 100 ng·L-1 (hexachlorobenzene) and 10 to 500 ng·L-1 (1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene). Other figures of merit include (a) high enrichment factors (8324 to 9920), (b) low limits of detection (0.10-1.03 ng·L-1), and (c) good reproducibility (relative standard deviations including intra-day and inter-day with a single fiber and fiber-to-fiber were below 6.4% at a mixed concentration level of 2.5, 5, and 10 ng·L-1 respectively in ultra-water). This method was successfully applied to the determination of chlorobenzenes in (spiked) lake waters where it gave recoveries between 82.3% and 104.5%. Graphical abstract A nanoporous carbon material was synthesized by heating potassium citrate without using a template or an activating agent and used as a viable coating of solid-phase microextraction for chlorobenzenes.

Aquamicrobium terrae sp. nov., isolated from the polluted soil near a chemical factory.

A Gram-negative, aerobic, non-motile bacterial strain hun6(T) isolated from the polluted soil near a chemical factory in northern Nanjing, China was investigated to clarify its taxonomic position. Growth of strain hun6(T) occurred between 10 and 45 °C (optimum, 30 °C) and between pH 6.0 and 8.0 (optimum, pH 7.0). No growth occurred at NaCl concentrations greater than 5 % (w/v). The 16S rRNA gene sequence analysis indicated that strain hun6(T) belongs to the genus Aquamicrobium. The sequence similarities of strain hun6(T) to other type strains of Aquamicrobium genus were all below 98.5 %. The presence of ubiquinone-10, the predominant fatty acid summed feature 8 (C18:1 ω7c and/or C18:1 ω6c) and C19:0 cyclo ω8c, a polar lipid pattern with phosphatidylglycerol, phosphatidylcholine, diphosphatidylglycerol, phosphatidylethanolamine and phophatidylmonomethylethanoamine were in accord with the characteristics of the genus Aquamicrobium. The G+C content of the genomic DNA was determined to be 63.5 mol%. The results of DNA-DNA hybridization, physiological and biochemical tests and chemotaxonomic properties allowed genotypic and phenotypic differentiation of strain hun6(T) from all known Aquamicrobium species. Therefore, strain hun6(T) can be assigned to a new species of this genus for which the name Aquamicrobium terrae sp. nov. is proposed. The type strain is hun6(T) (= CICC 10733(T) = DSM 27865(T)).

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.

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.

[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.

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.

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.

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.

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.

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.

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.

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.