A Comprehensive Review on Pesticide Residues in Human Urine.

Numerous studies worldwide have evaluated pesticide residues detected in urine. This review serves as a contribution to this field by presenting an overview of scientific research studies published from 2001 to 2023, including details of study characteristics and research scope. Encompassing 72 papers, the review further delves into addressing key challenges in study design and method used such as sampling and analytical approaches, results adjustments, risk assessment, estimations, and results evaluation. The review explores urinary concentrations and detection frequency of metabolites of organophosphates and pyrethroids, as well as herbicides such as 2,4-D and glyphosate and their metabolites, across various studies. The association of the results with demographic and lifestyle variables were explored. While farmers generally have higher pesticide exposure, adopting organic farming practices can reduce the levels of pesticides detected in their urine. Residence close to agricultural areas has shown high exposure in some cases. Dietary exposure is especially high among people adopting a conventionally grown plant-rich dietary pattern. A higher detection level and frequency of detection are generally found in females and children compared to males. The implications of transitioning to organic and sustainable plant-rich diets for reducing pesticide exposure and potential health benefits for both adults and children require further investigation.

Co-exposure with Copper Alters the Uptake, Accumulation, Subcellular Distribution, and Biotransformation of Organophosphate Triesters in Rice (Oryza sativa L.).

This study investigated the uptake pathways, acropetal translocation, subcellular distribution, and biotransformation of OPEs by rice (Oryza sativa L.) after Cu exposure. The symplastic pathway was noted as the major pathway for the uptake of organophosphate triesters (tri-OPEs) and diesters (di-OPEs) by rice roots. Cu exposure enhanced the accumulation of tri-OPEs in rice roots, and such enhancement was positively correlated with Cu concentrations, attributing to the Cu-induced root damage. The hydrophilic Cl-OPEs in the cell-soluble fraction of rice tissues were enhanced after Cu exposure, while the subcellular distributions of alkyl- and aryl-OPEs were not affected by Cu exposure. Significantly higher biotransformation rates of tri-OPEs to di-OPEs occurred in leaves, followed by those in stems and roots. Our study reveals the mechanisms associated with the uptake, translocation, and biotransformation of various OPEs in rice after Cu exposure, which provides new insights regarding the phytoremediation of soils cocontaminated with heavy metal and OPEs.

Decontamination promotes the release of incorporated organic contaminants in hair: Novel insights into non-invasive biomonitoring.

Human hair is increasingly employed as a non-invasive biomonitoring matrix for exposure to organic contaminants (OCs). Decontamination procedures are generally needed to remove external contamination from hair prior to analysis of OCs. Despite various existing decontamination protocols, their impacts on internally incorporated (endogenous) OCs in hair remain poorly understood. This study aims to quantitatively assess the impact of decontamination procedures on endogenous OCs in hair, and investigate optimal decontamination processes and factors influencing the removal of endogenous OCs. In this study, guinea pig was exposed to 6 OCs (triphenyl phosphate (TPHP), tris(1,3-dichloro-2-propyl) phosphate (TDCPP), and tri-n-butyl phosphate (TNBP), bisphenol A (BPA), perfluorooctanoic acid (PFOA), and phenanthrene (PHE)), and 6 decontamination procedures with different solvents (methanol, n-hexane, acetone, ultrapure water, Triton X-100, and sodium dodecyl sulfate) were used to rinse exposed guinea pig hair. All OCs and three metabolites (diphenyl phosphate (DPHP), dibutyl phosphate (DBP), and bis(1,3-dichloro-2-propyl) phosphate (BDCPP)) were detected in the majority of washing solutions. The decontamination procedures apparently resulted in the release of endogenous OCs from hair. The percentages of residual OCs in hair exhibited a linear or exponential decrease with more washing cycles. Furthermore, the residuals of OCs in hair washed with organic and aqueous solvents showed negative correlations with molecular weight, polarizability, and their initial concentrations. Although these findings need to be validated with a broader range of OCs, the results obtained in this study provide compelling evidence that current hair decontamination procedures have significant impacts on the analysis of endogenous OCs in hair. Therefore, it is important to interpret quantitative data on hair OC concentrations with caution and to thoroughly consider each decontamination procedure during analysis.

A network of acetyl phosphate-dependent modification modulates c-di-AMP homeostasis in Actinobacteria.

Cyclic purine nucleotides are important signal transduction molecules across all domains of life. 3',5'-cyclic di-adenosine monophosphate (c-di-AMP) has roles in both prokaryotes and eukaryotes, while the signals that adjust intracellular c-di-AMP and the molecular machinery enabling a network-wide homeostatic response remain largely unknown. Here, we present evidence for an acetyl phosphate (AcP)-governed network responsible for c-di-AMP homeostasis through two distinct substrates, the diadenylate cyclase DNA integrity scanning protein (DisA) and its newly identified transcriptional repressor, DasR. Correspondingly, we found that AcP-induced acetylation exerts these regulatory actions by disrupting protein multimerization, thus impairing c-di-AMP synthesis via K66 acetylation of DisA. Conversely, the transcriptional inhibition of disA was relieved during DasR acetylation at K78. These findings establish a pivotal physiological role for AcP as a mediator to balance c-di-AMP homeostasis. Further studies revealed that acetylated DisA and DasR undergo conformational changes that play crucial roles in differentiation. Considering the broad distribution of AcP-induced acetylation in response to environmental stress, as well as the high conservation of the identified key sites, we propose that this unique regulation of c-di-AMP homeostasis may constitute a fundamental property of central circuits in Actinobacteria and thus the global control of cellular physiology.IMPORTANCESince the identification of c-di-AMP is required for bacterial growth and cellular physiology, a major challenge is the cell signals and stimuli that feed into the decision-making process of c-di-AMP concentration and how that information is integrated into the regulatory pathways. Using the bacterium Saccharopolyspora erythraea as a model, we established that AcP-dependent acetylation of the diadenylate cyclase DisA and its newly identified transcriptional repressor DasR is involved in coordinating environmental and intracellular signals, which are crucial for c-di-AMP homeostasis. Specifically, DisA acetylated at K66 directly inactivates its diadenylate cyclase activity, hence the production of c-di-AMP, whereas DasR acetylation at K78 leads to increased disA expression and c-di-AMP levels. Thus, AcP represents an essential molecular switch in c-di-AMP maintenance, responding to environmental changes and possibly hampering efficient development. Therefore, AcP-mediated posttranslational processes constitute a network beyond the usual and well-characterized synthetase/hydrolase governing c-di-AMP homeostasis.

Fugacity- and biotransformation-based mechanistic insights into the trophic transfer of organophosphate flame retardants in a subtropical coastal food web from the Northern Beibu Gulf of China.

The bioaccumulation and trophic transfer of organophosphate flame retardants (OPFRs) in marine ecosystems have attracted great attention in recent research, but our understanding of the trophic transfer mechanisms involved is limited. In this study, we investigated the trophodynamics of OPFRs and their metabolites in a subtropical coastal food web collected from the northern Beibu Gulf, China, and characterized their trophodynamics using fugacity- and biotransformation-based approaches. Eleven OPFRs and all seven metabolites were simultaneously quantified in the shellfish, crustacean, pelagic fish, and benthic fish samples, with total concentrations ranging from 164 to 4.11 × 104 and 4.56-4.28 × 103 ng/g lipid weight, respectively. Significant biomagnification was observed only for tris (phenyl) phosphate (TPHP) and tris (2-ethylhexyl) phosphate (TEHP), while other compounds except for tris(2-chloroethyl) phosphate (TCEP) displayed biomagnification trends based on Monte Carlo simulations. Using a fugacity-based approach to normalize the accumulation of OPFRs in biota to their relative biological phase composition, storage lipid is the predominant biological phase for the mass distribution of 2-ethylhexyl diphenyl phosphate (EHDPHP) and TPHP. The water content and structure protein are equally important for TCEP, whereas lipid and structure protein are the two most important phases for other OPFRs. The mass distribution of these OPFRs along with TLs can explain their trophodynamics in the food web. The organophosphate diesters (as OPFR metabolites) also displayed biomagnification trends based on bootstrapped estimation. The correlation analysis and Korganism-water results jointly suggested the metabolites accumulation in high-TL organisms was related to biotransformation processes. The metabolite-backtracked trophic magnification factors for tri-n­butyl phosphate (TNBP) and TPHP were both greater than the values that accounted for only the parent compounds. This study highlights the incorporation of fugacity and biotransformation analysis to characterize the trophodynamic processes of OPFRs and other emerging pollutants in food webs.

Organophosphate esters (OPEs) pollution characteristics, bioaccumulation and human consumption implication in wild marine organisms from the Yellow River Estuary, China.

As the substitutes of polybrominated diphenyl ethers, organophosphate esters (OPEs) with high concentrations have accumulated in the estuaries, bays, and harbors. However, limited information is available about the OPEs in the estuary organism categories, especially under the multiple industrial pressure. This study investigated the occurrence, bioaccumulation and human consumption implication in wild marine organisms from the Yellow River Estuary, where located many petroleum and chemical manufacturing industries. This study found that concentrations of Σ13OPEs ranged from 547 ng/L to 1164 ng/L in seawater (median: 802 ng/L), from 384 to 1366 ng/g dw in the sediment (median: 601 ng/g dw), and from 419 to 959 ng/g dw (median: 560 ng/g dw) in the marine organisms. The congener compositions in the organisms were dominated by alkyl-OPEs (80.7 %), followed by halogenated-OPEs (18.8 %) and aryl-OPEs (0.5 %). Based on the principal component analysis, petrochemical pollution, and industrial wastewater discharge were distinguished as the main plausible sources of OPEs to the YRE ecosystem. Most OPEs had potential or strong bioaccumulation capacity on the organisms, with a positive correlation between log BAF (Bioaccumulation Factor) and log Kow of OPEs. The highest estimated daily intake value of OPEs was tri-n-propyl phosphate, exceeding 300 ng/kg·bw/day via consuming fish. The highest hazard quotients from OPEs ranged from 0.001 to 0.1, indicating a low risk to human health by consuming marine organisms in the YRE. As the consumption of OPEs increases year by year, the risks of OPEs still cannot be ignored.

Elucidating the detoxification efficacy of Periplaneta americana delta glutathione S-transferase 1 (PaGSTd1) against organophosphates.

As an important class of detoxifying enzymes, glutathione S-transferases (GSTs) are pivotal in decreasing insecticide toxicity to insects. Periplaneta americana GSTd1 (PaGSTd1) has been verified as a key enzyme in detoxifying pyrethroid insecticides, but its detoxification capability against a broader spectrum of insecticides has never been investigated. It is revealed that PaGSTd1 expression showed a rapid and significant increase upon exposure to various insecticides (organophosphates, neonicotinoids, and fipronil). Subsequent in vitro metabolic assays indicated that organophosphates, particularly chlorpyrifos-methyl, can be effectively metabolized by PaGSTd1. Further knockdown of PaGSTd1 via RNA interference significantly heightened the susceptibility of P. americana to chlorpyrifos-methyl, underscoring the enzyme's key role in detoxifying chlorpyrifos-methyl. Additionally, this study confirmed that PaGSTd1 cannot mitigate insecticide toxicity through countering oxidative stress. Collectively, these findings elucidate the involvement of PaGSTd1 in the detoxification processes for organophosphates, offering a comprehensive insight into the metabolic mechanisms mediated by GSTs in P. americana. This research provides a foundational understanding for managing GSTs-mediated metabolic resistance in this species, which is crucial for effective pest control strategies.

Organophosphate esters and their metabolites in silver pomfret (Pampus argenteus) of the Vietnamese coastal areas: Spatial-temporal distribution and exposure risk.

A large number of studies on organophosphate esters (tri-OPEs) in marine organisms have not assessed the simultaneous occurrence of tri-OPEs and their metabolites (di-OPEs) in these species. This research investigated the concentration and geographical distribution of 15 tri-OPEs and 7 di-OPEs in 172 samples of Pampus argenteus that were collected annually from 2021 to 2023 at three distinct locations along the Vietnamese coast. As a result, tri-OPEs and di-OPEs were detected in numerous fish samples, indicating their widespread spatial and temporal occurrence in marine fish and pointing out the importance of monitoring their levels. The tri-OPEs and di-OPEs ranged within 2.1-38.9 ng g-1 dry weight (dw) and 3.2-263.4 ng g-1 dw, respectively. The mean concentrations of tri-OPEs ranged from 0.4 (TIPrP) to 5.4 ng g-1 dw (TBOEP), with TBOEP and TEHP having the highest mean values. In addition, the profiles of tri-OPEs in fish exhibited a descending order: Σalkyl OPEs > ΣCl-alkyl OPEs > Σaryl OPEs. The di-OPEs, namely BEHP and DMP, had the highest mean levels, measuring 33.4 ng g-1 dw and 23.8 ng g-1 dw, respectively. Furthermore, there have been significant findings of strong positive correlations between di-OPEs and tri-OPE pairs (p < 0.05). It is worth noting that there is a noticeable difference in the composition of tri-OPEs between the North and other regions. Despite these findings, the presence of OPE-contaminated fish did not pose any health risks to Vietnam's coastal population.

Mechanistic insights into tris(2-chloroisopropyl) phosphate biomineralization coupled with lead (II) biostabilization driven by denitrifying bacteria.

The ubiquity and persistence of organophosphate esters (OPEs) and heavy metal (HMs) pose global environmental risks. This study explored tris(2-chloroisopropyl)phosphate (TCPP) biomineralization coupled to lead (Pb2+) biostabilization driven by denitrifying bacteria (DNB). The domesticated DNB achieved synergistic bioremoval of TCPP and Pb2+ in the batch bioreactor (efficiency: 98 %).TCPP mineralized into PO43- and Cl-, and Pb2+ precipitated with PO43-. The TCPP-degrading/Pb2+-resistant DNB: Achromobacter, Pseudomonas, Citrobacter, and Stenotrophomonas, dominated the bacterial community, and synergized TCPP biomineralization and Pb2+ biostabilization. Metagenomics and metaproteomics revealed TCPP underwent dechlorination, hydrolysis, the TCA cycle-based dissimilation, and assimilation; Pb2+ was detoxified via bioprecipitation, bacterial membrane biosorption, EPS biocomplexation, and efflux out of cells. TCPP, as an initial donor, along with NO3-, as the terminal acceptor, formed a respiratory redox as the primary energy metabolism. Both TCPP and Pb2+ can stimulate phosphatase expression, which established the mutual enhancements between their bioconversions by catalyzing TCPP dephosphorylation and facilitating Pb2+ bioprecipitation. TCPP may alleviate the Pb2+-induced oxidative stress by aiding protein phosphorylation. 80 % of Pb2+ converted into crystalized pyromorphite. These results provide the mechanistic foundations and help develop greener strategies for synergistic bioremediation of OPEs and HMs.

Organophosphate esters uptake, translocation and accumulation in rice (Oryza sativa L.): impacts of lipid transporters and chemical properties.

To explore key factors involved in the uptake, translocation and accumulation of organophosphate esters (OPEs), computer simulation analysis and hydroponic experiments were executed. Lipid transporters with stocky-like active (SAC) cavities usually showed stronger binding affinities with the OPEs, especially when the SAC cavities belong to the Fish Trap model according to molecular docking. In our hydroponic trial, the binding affinity and gene expression of the lipid transporters and log Kow of the OPEs could be charged to the uptake, translocation and accumulation of the OPEs; however, these three factors played various important roles in roots and shoots. In detail, the effect of gene expression and binding affinity were stronger than log Kow in roots uptake and accumulation, but the result was the opposite in the shoots translocation. Transporters OsTIL and OsLTPL1 among all investigated transporters could play key roles in transporter-mediated OPE uptake, translocation and accumulation in the roots and shoots. OsMLP could be involved in the bidirected vertical translocation of the OPEs. OsLTP2 and OsLTP4 mainly acted as transporters of the OPEs in roots.

Alterations of gut microbiota and its metabolomics in children with 6PPDQ, PBDE, PCB, and metal(loid) exposure.

The composition and metabolites of the gut microbiota can be altered by environmental pollutants. However, the effect of co-exposure to multiple pollutants on the human gut microbiota has not been sufficiently studied. In this study, gut microorganisms and their metabolites were compared between 33 children from Guiyu, an e-waste dismantling and recycling area, and 34 children from Haojiang, a healthy environment. The exposure level was assessed by estimating the daily intake (EDI) of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), 6PPD-quinone (6PPDQ), and metal(loid)s in kindergarten dust. Significant correlations were found between the EDIs of 6PPDQ, BDE28, PCB52, Ni, Cu, and the composition of gut microbiota and specific metabolites. The Bayesian kernel machine regression model showed negative correlations between the EDIs of five pollutants (6PPDQ, BDE28, PCB52, Ni, and Cu) and the composition of gut microbiota. The EDIs of these five pollutants were positively correlated with the levels of the metabolite 2,4-diaminobutyric acid, while negatively correlated with the levels of d-erythro-sphingosine and d-threitol. Our study suggests that exposure to 6PPDQ, BDE28, PCB52, Ni, and Cu in kindergarten dust is associated with alterations in the composition and metabolites of the gut microbiota. These alterations may be associated with children's health.

Method optimization for a simultaneous determination of neonicotinoid, carbamate/thiocarbamate, triazole, organophosphate and pyrethroid pesticides and their metabolites in urine using UPLC-MS/MS.

An accurate and sensitive method for the determination of a total of 23 pesticides and their metabolites in human urine has been optimised. The methodology is based on a previously published method based on solid-phase extraction with methanol and acetone followed by ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) in the selected reaction mode (SRM) with both positive and negative electrospray ionization (ESI+/-). The detection settings of the previous method, which allowed to determine the metabolites from 6 organophosphate and 2 pyrethroid pesticides, were optimised in order to include further pesticide groups, such as 11 neonicotinoids, 3 carbamates/thiocarbamates and 2 triazoles. The 5-windows method enduring 22 min was optimized with acceptable results in relation to accuracy (recoveries >75 %), precision (coefficients of variation <26 %) and linearity (R2> 0.9915). The limits of detection ranged between 0.012 ng/mL and 0.058 ng/mL. Samples from the German External Quality Assessment Scheme (G-EQUAS) encompassing 2 pyrethroids, 2 organophosphate and one neonicotinoid (6-chloronicotinic acid, a common metabolite of imidacloprid and acetamiprid) were analysed, and the latter, included in this newest optimization, provided good reference results. The method is optimal as a human biomonitoring tool for health risk assessment in large population surveys.

Metabolomics Simultaneously Derives Benchmark Dose Estimates and Discovers Metabolic Biotransformations in a Rat Bioassay.

Benchmark dose (BMD) modeling estimates the dose of a chemical that causes a perturbation from baseline. Transcriptional BMDs have been shown to be relatively consistent with apical end point BMDs, opening the door to using molecular BMDs to derive human health-based guidance values for chemical exposure. Metabolomics measures the responses of small-molecule endogenous metabolites to chemical exposure, complementing transcriptomics by characterizing downstream molecular phenotypes that are more closely associated with apical end points. The aim of this study was to apply BMD modeling to in vivo metabolomics data, to compare metabolic BMDs to both transcriptional and apical end point BMDs. This builds upon our previous application of transcriptomics and BMD modeling to a 5-day rat study of triphenyl phosphate (TPhP), applying metabolomics to the same archived tissues. Specifically, liver from rats exposed to five doses of TPhP was investigated using liquid chromatography-mass spectrometry and 1H nuclear magnetic resonance spectroscopy-based metabolomics. Following the application of BMDExpress2 software, 2903 endogenous metabolic features yielded viable dose-response models, confirming a perturbation to the liver metabolome. Metabolic BMD estimates were similarly sensitive to transcriptional BMDs, and more sensitive than both clinical chemistry and apical end point BMDs. Pathway analysis of the multiomics data sets revealed a major effect of TPhP exposure on cholesterol (and downstream) pathways, consistent with clinical chemistry measurements. Additionally, the transcriptomics data indicated that TPhP activated xenobiotic metabolism pathways, which was confirmed by using the underexploited capability of metabolomics to detect xenobiotic-related compounds. Eleven biotransformation products of TPhP were discovered, and their levels were highly correlated with multiple xenobiotic metabolism genes. This work provides a case study showing how metabolomics and transcriptomics can estimate mechanistically anchored points-of-departure. Furthermore, the study demonstrates how metabolomics can also discover biotransformation products, which could be of value within a regulatory setting, for example, as an enhancement of OECD Test Guideline 417 (toxicokinetics).

Field study on the uptake pathways and their contributions to the accumulation of organophosphate esters, phthalates, and polycyclic aromatic hydrocarbons in upland rice.

Plant uptake of organic contaminants generally occurs through either root, gas-phase foliar, or particle-phase foliar uptake. Understanding these pathways is essential for food-system practitioners to reduce human exposures, and to clean contaminated-sites with phytoremediation. Herein, we conducted a field-based experiment using an improved specific exposure chamber to elucidate the uptake pathways of organophosphate esters, phthalates, and polycyclic aromatic compounds, and quantitatively assessed their contributions to organic contaminant accumulations in field-grown rice. For most target compounds, all three uptake pathways (root, foliar gas, and foliar particle uptakes) contributed substantially to the overall contaminant burden in rice. Compounds with lower octanol-water partition coefficients (Kow) were more readily translocated from roots to leaves, and compounds with higher octanol-air partition coefficients (Koa) tended to enter rice leaves mostly through particle deposition. Most compounds were mostly stored in the inner leaves (55.3-98.2 %), whereas the relatively volatile compounds were more readily absorbed by the waxy layer and then transferred to the inner leaves. Air particle desorption was a key process regulating foliar uptake of low-volatility compounds. The results can help us to better understand and predict the environmental fate of those contaminants, and develop more effective management strategies for reducing their human exposure through food ingestion.

Tris (2-chloroethyl) phosphate presence inhibits methane production from anaerobic digestion: Alterations in organic matter transformation, cell physiological status, and microbial community.

Organophosphate flame retardants (OPFRs) are widely used in consumer products, leading to their unavoidable release into the environment, especially accumulation in anaerobic environments and posing potential risks. This study focused on Tris(2-chloroethyl) phosphate (TCEP), a representative OPFR, to investigate its effects on carbon transformation and methane production in anaerobic digestion. Increasing TCEP concentrations from control to 16 mg/L resulted in decreased cumulative methane yield (from 235.4 to 196.3 mL/g COD) and maximum daily methane yield (from 40.8 to 16.17 mL/(g COD·d)), along with an extended optimal anaerobic digestion time (from 15 to 20 days). Mechanistic analysis revealed TCEP binding to tyrosine-like proteins in extracellular polymeric substances, causing cell membrane integrity impairment. The TCEP-caused alteration of the physiological status of cells was demonstrated to be a significant contribution to the inhibited bioprocesses including acidogenesis, acetogenesis, and methanogenesis. Illumina Miseq sequencing showed TCEP decreasing the relative abundance of acidogens (58.8 % to 46.0 %) and acetogens (7.1 % to 5.0 %), partly shifting the methanogenesis pathway from acetoclastic to hydrogenotrophic methanogenesis. These findings enhance understanding of TCEP's impact on anaerobic digestion, emphasizing the environmental risk associated with its continued accumulation.

Molecular insight on the binding of halogenated organic phosphate esters to human serum albumin and its effect on cytotoxicity of halogenated organic phosphate esters.

Halogenated Organic Phosphate Esters (OPEs) are commonly found in plasticizers and flame retardants. However, they are one kind of persistent contaminants that can pose a significant threat to human health and ecosystem as new environmental estrogen. In this study, two representative halogenated OPEs, tris(1,3-dichloro-2-propyl) phosphate (TDCP) and tris(2,3-dibromopropyl) phosphate (TDBP), were selected as experimental subjects to investigate their interaction with human serum albumin (HSA). Despite having similar structures, the two ligands exhibited contrasting effects on enzyme activity of HSA, TDCP inhibiting enzyme activity and TDBP activating it. Furthermore, both TDCP and TDBP could bind to HSA at site I, interacted with Arg222 and other residues, and made the conformation of HSA unfolded. Thermodynamic parameters indicated the main driving forces between TDBP and HSA were hydrogen bonding and van der Waals forces, while TDCP was mainly hydrophobic force. Molecular simulations found that more hydrogen bonds of HSA-TDBP formed during the binding process, and the larger charge area of TDBP than TDCP could partially account for the differences observed in their binding abilities to HSA. Notably, the cytotoxicity of TDBP/TDCP was inversely proportional to their binding ability to HSA, implying a new method for determining the cytotoxicity of halogenated OPEs in vitro.

Identification and characterization of a promiscuous metallohydrolase in metallo-ß-lactamase superfamily from a locally isolated organophosphate-degrading Bacillus sp. strain S3wahi.

In this present study, characteristics and structure-function relationship of an organophosphate-degrading enzyme from Bacillus sp. S3wahi were described. S3wahi metallohydrolase, designated as S3wahi-MH (probable metallohydrolase YqjP), featured the conserved αß/ßα metallo-ß-lactamase-fold (MBL-fold) domain and a zinc bimetal at its catalytic site. The metal binding site of S3wahi-MH also preserves the H-X-H-X-D-H motif, consisting of specific amino acids at Zn1 (Asp69, His70, Asp182, and His230) and Zn2 (His65, His67, and His137). The multifunctionality of S3wahi-MH was demonstrated through a steady-state kinetic study, revealing its highest binding affinity (KM) and catalytic efficiency (kcat/KM) for OP compound, paraoxon, with values of 8.09 × 10-6 M and 4.94 × 105 M-1 s-1, respectively. Using OP compound, paraoxon, as S3wahi-MH native substrate, S3wahi-MH exhibited remarkable stability over a broad temperature range, 20 °C - 60 °C and a broad pH tolerance, pH 6-10. Corresponded to S3wahi-MH thermal stability characterization, the estimated melting temperature (Tm) was found to be 72.12 °C. S3wahi-MH was also characterized with optimum catalytic activity at 30 °C and pH 8. Additionally, the activity of purified S3wahi-MH was greatly enhanced in the presence of 1 mM and 5 mM of manganese (Mn2+), showing relative activities of 1323.68 % and 2073.68 %, respectively. The activity of S3wahi-MH was also enhanced in the presence of DMSO and DMF, showing relative activities of 270.37 % and 307.41 %, respectively. The purified S3wahi-MH retained >60 % residual activity after exposure to non-ionic Tween series surfactants. Nevertheless, the catalytic activity of S3wahi-MH was severely impacted by the treatment of SDS, even at low concentrations. Considering its enzymatic properties and promiscuity, S3wahi-MH emerges as a promising candidate as a bioremediation tool in wide industrial applications, including agriculture industry.

The dissipation of organophosphate esters mediated by ryegrass root exudate oxalic acid in soil: Analysis of enzymes activities, microorganism.

Complex rhizoremediation is the main mechanism of phytoremediation in organic-contaminated soil. Low molecular weight organic acids (LMWOAs) in root exudates have been shown to increase the bioavailability of contaminants and are essential for promoting the dissipation of contaminants. The effects of root exudates on the dissipation of organophosphate esters (OPEs) in soil are unclear. Consequently, we studied the combined effects of root exudates, soil enzymes and microorganisms on OPEs (tri (1-chloro-2-propyl) phosphate (TCPP) and triphenyl phosphate (TPP)) dissipation through pot experiments. Oxalic acid (OA) was confirmed to be the main component of LMWOAs in root exudates of ryegrass. The existence of OA increased the dissipation rate of OPEs by 6.04%-25.50%. Catalase and dehydrogenase activities were firstly activated and then inhibited in soil. While, urease activity was activated and alkaline phosphatase activity was inhibited during the exposure period. More bacteria enrichment (e.g., Sphingomonas, Pseudomonas, Flavisolibacter, Pontibacter, Methylophilus and Massilia) improved the biodegradation of OPEs. In addition, the transformation paths of OPEs hydrolysis and methylation under the action of root exudates were observed. This study provided theoretical insights into reducing the pollution risk of OPEs in the soil.

Gender-specific abdominal fat distribution and insulin resistance associated with organophosphate esters and phthalate metabolites exposure.

The worldwide prevalence of obesity highlights the potential contribution of endocrine-disrupting chemicals (EDCs). However, common epidemiological measures such as body mass index and waist circumference may misrepresent the intricate obesity risks these chemicals pose across genders. This study delves deeper into abdominal fat by differentiating between subcutaneous and visceral regions by analyzing data from National Health and Nutrition Examination Surveys (NHANES). We particularly investigated the gender-specific associations between organophosphorus flame-retardant metabolites (mOPFRs), phthalates (mPAEs) and accumulated fat indexes from 2536 people. Aiding by Bayesian Kernel Machine Regression (BKMR), we found while co-exposure to mOPFRs and mPAEs was linked to general and abdominal obesity across the entire and gender-specific populations, a gender-specific fat distribution emerged. For women, urinary BDCPP and MBzP were linked to an increased subcutaneous fat index (SFI) [BDCPP OR: 1.12 (95% CI: 1.03-1.21), MBzP OR: 1.09 (95% CI: 1.01-1.18)], but not to visceral fat index (VFI). These metabolites had a combined linkage with SFI, with BDCPP (weighting 22.0%) and DPHP (weighting 31.0%) being the most influential in Quantile g-computation model (qgcomp) model. In men, BCEP exposure exclusively associated with the elevated VFI [OR: 1.14 (95% CI: 1.03-1.26)], a trend further highlighted in mixture models with BCEP as the predominant association. Intriguingly, only males displayed a marked correlation between these metabolites and insulin resistance in subpopulation. An attempted mediation analysis revealed that elevated C-reactive protein mediated 12.1% of the association between urinary BCEP and insulin resistance, suggesting a potential role of inflammation. In conclusion, the gender-specific fat distribution and insulin resistance that associated with mOPFRs represented the potential risk of these chemicals to man.

Organophosphate esters (OPEs) in corals of the South China Sea: Occurrence, distribution, and bioaccumulation.

Organophosphate esters (OPEs) have garnered significant attention in recent years. In view of the enormous ecosystem services value and severe degradation of coral reefs in the South China Sea, this study investigated the occurrence, distribution, and bioaccumulation of 11 OPEs in five coral regions: Daya Bay (DY), Weizhou Island (WZ), Sanya Luhuitou (LHT), Xisha (XS) Islands, and Nansha (NS) Islands. Although OPEs were detected at a high rate, their concentration in South China Sea seawater (1.56 ± 0.89 ng L-1) remained relatively low compared to global levels. All OPEs were identified in coral tissues, with Luhuitou (575 ± 242 ng g-1 dw) showing the highest pollution levels, attributed to intense human activities. Coral mucus, acting as a defense against environmental stresses, accumulated higher ∑11OPEs (414 ± 461 ng g-1 dw) than coral tissues (412 ± 197 ng g-1 dw) (nonparametric test, p < 0.05), and their compositional characteristics varied greatly. In the case of harsh aquatic environments, corals increase mucus secretion and then accumulate organic pollutants. Tissue-mucus partitioning varied among coral species. Most OPEs were found to be bioaccumulative (BAFs >5000 L kg-1) in a few coral tissue samples besides Triphenyl phosphate (TPHP). Mucus' role in the bioaccumulation of OPEs in coral shouldn't be ignored.