Zinc N,N-bis(2-picolyl)amine Chelates Show Substitution-Dependent Cleavage of Phosphodiesters in Models as Well as of PNAzyme-RNA Bulges.

PNAzymes are a group of artificial enzymes which show promising results in selective and efficient cleavage of RNA targets. In the present study, we introduce a series of metal chelating groups based on N,N-bis(2-picolyl) groups (parent, 6-methyl and 6-amino substituted) as the active sites of novel PNAzymes. An improved synthetic route for the 6-amino analogues is described. The catalytic activity of the chelating groups for cleaving phosphodiesters were assessed with the model substrate 2-hydroxypropyl p-nitrophenyl phosphate (HPNPP), confirming that the zinc complexes have the reactivity order of parent < 2-methyl < 2-amino. The three ligands were conjugated to a PNA oligomer to form three PNAzymes which showed the same order of reactivity and some sensitivity to the size of the RNA bulge designed into the catalyst-substrate complex. This work demonstrates that the kinetic activity observed for the model substrate HPNPP could be translated onto the PNAzymes, but that more reactive Zn complexes are required for such PNAzymes to be viable therapeutic agents.

Biomarkers of Organophosphate and Polybrominated Diphenyl Ether (PBDE) Flame Retardants of American Workers and Associations with Inhalation and Dermal Exposures.

This study evaluated workers' exposures to flame retardants, including polybrominated diphenyl ethers (PBDEs), organophosphate esters (OPEs), and other brominated flame retardants (BFRs), in various industries. The study aimed to characterize OPE metabolite urinary concentrations and PBDE serum concentrations among workers from different industries, compare these concentrations between industries and the general population, and evaluate the likely route of exposure (dermal or inhalation). The results showed that workers from chemical manufacturing had significantly higher (p <0.05) urinary concentrations of OPE metabolites compared to other industries. Spray polyurethane foam workers had significantly higher (p <0.05) urinary concentrations of bis(1-chloro-2-propyl) phosphate (BCPP) compared to other industries. Electronic scrap workers had higher serum concentrations of certain PBDE congeners compared to the general population. Correlations were observed between hand wipe samples and air samples containing specific flame-retardant parent chemicals and urinary metabolite concentrations for some industries, suggesting both dermal absorption and inhalation as primary routes of exposure for OPEs. Overall, this study provides insights into occupational exposure to flame retardants in different industries and highlights the need for further research on emerging flame retardants and exposure reduction interventions.

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.

Associations between organophosphate esters and bone mineral density in adults in the United States: 2011-2018 NHANES.

BACKGROUND: Organophosphate esters (OPEs) are used extensively as flame retardants and plasticizers. Laboratory studies have shown that OPEs exhibit osteotoxicity by inhibiting osteoblast differentiation; however, little is known about how OPEs exposure is associated with bone health in humans. OBJECTIVES: We conducted a cross-sectional study to investigate the association between OPEs exposure and bone mineral density (BMD) in adults in the United States using data from the 2011-2018 National Health and Nutrition Examination Survey (NHANES). METHODS: Multivariate linear regression models were used to assess the association between concentrations of individual OPE metabolites and BMDs. We also used the Bayesian kernel machine regression (BKMR) and quantile g-computation (qgcomp) models to estimate joint associations between OPE mixture exposure and BMDs. All the analyses were stratified according to gender. RESULTS: A total of 3546 participants (median age, 40 years [IQR, 30-50 years]; 50.11% male) were included in this study. Five urinary OPE metabolites with a detection rate of > 50% were analyzed. After adjusting for the potential confounders, OPE metabolite concentrations were associated with decreased total-body BMD and lumbar spine BMD in males, although some associations only reached significance for bis(1-chloro-2-propyl) phosphate (BCPP), dibutyl phosphate (DBUP), and bis(2-chloroethyl) phosphate (BCEP) (ß = -0.013, 95% CI: -0.026, -0.001 for BCPP and total-body BMD; ß = -0.022, 95% CI: -0.043, -0.0001 for DBUP and lumbar spine BMD; ß=-0.018, 95% CI: -0.034, -0.002 for BCEP and lumbar spine BMD). OPE mixture exposure was also inversely associated with BMD in males, as demonstrated in the BMKR and qgcomp models. CONCLUSIONS: This study provides preliminary evidence that urinary OPE metabolite concentrations are inversely associated with BMD. The results also suggested that males were more vulnerable than females. However, further studies are required to confirm these findings.

Pollution characteristics and risk assessment of organophosphate esters (OPEs) in typical industrial parks in Southwest China.

As alternative substances of PBDEs, organophosphate esters (OPEs), an emerging organic pollutant, were increasingly produced and used in many kinds of industries and consumer products. However, OPEs also have various adverse toxic effects. Information on the pollution levels and exposure to OPEs in related industries is still limited. This study presented data on OPE contamination in the soil, leaf, and river water samples from seven typical industrial parks in Southwest China. Total concentration of seven OPEs (Σ7OPE) including tri-n-butyl phosphate (TnBP), tris-(2-ethylhexyl) phosphate (TEHP), tris-(2-butoxyethyl) phosphate (TBEP), tris-(2-carboxyethyl) phosphine (TCEP), triphenyl phosphate (TPhP), tris-(1,3-dichloro-2-propyl) ester (TDCPP), and tris-(chlorisopropyl) phosphate (TCPP) in the soil samples (36.2 ~ 219.7 ng/g) and the surrounding river water samples (118.9 ~ 287.7 ng/L) were mostly lower than those in other studies, while the Σ7OPE level in the leaves (2053.3 ~ 8152.7 ng/g) was relatively high. There were significant differences in the concentration and distribution of OPEs in the surrounding environment of different industrial parks. TDCPP, TnBP, and TCPP could be used as the characteristic compound in soil samples from auto industrial park, river samples from shoe making industrial park, and leaf samples from logistics park, respectively. The parameter m (the content ratio of chlorinated OPEs to alkyl OPEs) was suggested to distinguish the types of industrial park preliminary. When m ≥ 1, it mainly refers to heavy industries sources such as automobiles, electronics, and machinery, etc. When m<1, it mainly for the light industrial sources such as textile industry, transportation services, and resources processing, etc. For logistics park, furniture park and Wuhou comprehensive industrial park, the volatilization of materials was the main sources of OPEs in the surrounding environment, while more effort was required to strengthen the pollution control and management of the waste water and soil in the pharmacy industrial park, shoe making industrial park and auto industrial park. Risk assessment showed that there was a negligible non-cancer and carcinogenic risk in the soil, while high attention should be paid to the non-cancer risk for children.

Distribution patterns and origins of organophosphate esters in soils from different climate systems on the Tibetan Plateau.

Organophosphate esters (OPEs) are extensively applied in various materials as flame retardants and plasticizers, and have high biological toxicity. OPEs are detected worldwide, even in distant polar regions and the Tibetan Plateau (TP). However, few studies have been performed to evaluate the distribution patterns and origins of OPEs in different climate systems on the TP. This study investigated the distribution characteristics, possible sources, and ecological risks of OPEs in soils from the different climate systems on the TP and its surroundings. The total concentrations of OPEs in soil varied from 468 to 17,451 pg g-1 dry weight, with greater concentrations in southeast Tibet (monsoon zone), followed by Qinghai (transition zone) and, finally, southern Xingjiang (westerly zone). OPE composition profiles also differed among the three areas with tri-n-butyl phosphate dominant in the westerly zone and tris(2-butoxyethyl) phosphate dominant in the Indian monsoon zone. Correlations between different compounds and altitude, soil organic carbon, or longitude varied in different climate zones, indicating that OPE distribution originates from both long-range atmospheric transport and local emissions. Ecological risk assessment showed that tris(2-chloroethyl) phosphate and tri-phenyl phosphate exhibited medium risks in soil at several sites in southeast Tibet. Considering the sensitivity and vulnerability of TP ecosystems to anthropogenic pollutants, the ecological risks potentially caused by OPEs in this region should be further assessed.

Occurrence of organophosphorus flame retardants in Xiangjiang River: Spatiotemporal variations, potential affecting factors, and source apportionment.

The environmental occurrence of organophosphorus flame retardants (OPFRs) is receiving increasing attention. However, their distribution in the Xiangjiang River, an important tributary in the middle reaches of the Yangtze River, is still uncharacterized, and the potential factors influencing their distribution have not been adequately surveyed. In this study, the occurrence of OPFRs in the Xiangjiang River was comprehensively investigated from upstream to downstream seasonally. Fourteen OPFRs were detected in the sampling area, with a total concentration (∑OPFRs) ranging from 3.16 to 462 ng/L, among which tris(1-chloro-2-propyl) phosphate was identified as the primary pollutant (ND - 379 ng/L). Specifically, ∑OPFRs were significantly lower in the wet season than in the dry season, which may be due to the dilution effect of river flow and enhanced volatilization caused by higher water temperatures. Additionally, Changsha (during the dry season) and Zhuzhou (during the wet season) exhibited higher pollution levels than other cities. According to the Redundancy analysis, water quality parameters accounted for 35.7% of the variation in the occurrence of OPFRs, in which temperature, ammonia nitrogen content, dissolved oxygen, and chemical oxygen demand were identified as the potential influencing factors, accounting for 28.1%, 27.2%, 24.1%, and 11.5% of the total variation, respectively. The results of the Positive Matrix Factorization analysis revealed that transport and industrial emissions were the major sources of OPFRs in Xiangjiang River. In addition, there were no high-ecological risk cases for any individual OPFRs, although tris(2-ethylhexyl) phosphate and tributoxyethyl phosphate presented a low-to-medium risk level. And the results of mixture risk quotients indicated that medium-risk sites were concentrated in the Chang-Zhu-Tan region. This study enriches the global data of OPFRs pollution and contributes to the scientific management and control of pollution.

Transcriptomic analysis of Anopheles gambiae from Benin reveals overexpression of salivary and cuticular proteins associated with cross-resistance to pyrethroids and organophosphates.

BACKGROUND: Insecticide resistance (IR) is one of the major threats to malaria vector control programs in endemic countries. However, the mechanisms underlying IR are poorly understood. Thus, investigating gene expression patterns related to IR can offer important insights into the molecular basis of IR in mosquitoes. In this study, RNA-Seq was used to characterize gene expression in Anopheles gambiae surviving exposure to pyrethroids (deltamethrin, alphacypermethrin) and an organophosphate (pirimiphos-methyl). RESULTS: Larvae of An. gambiae s.s. collected from Bassila and Djougou in Benin were reared to adulthood and phenotyped for IR using a modified CDC intensity bottle bioassay. The results showed that mosquitoes from Djougou were more resistant to pyrethroids (5X deltamethrin: 51.7% mortality; 2X alphacypermethrin: 47.4%) than Bassila (1X deltamethrin: 70.7%; 1X alphacypermethrin: 77.7%), while the latter were more resistant to pirimiphos-methyl (1.5X: 48.3% in Bassila and 1X: 21.5% in Djougou). RNA-seq was then conducted on resistant mosquitoes, non-exposed mosquitoes from the same locations and the laboratory-susceptible An. gambiae s.s. Kisumu strain. The results showed overexpression of detoxification genes, including cytochrome P450s (CYP12F2, CYP12F3, CYP4H15, CYP4H17, CYP6Z3, CYP9K1, CYP4G16, and CYP4D17), carboxylesterase genes (COEJHE5E, COE22933) and glutathione S-transferases (GSTE2 and GSTMS3) in all three resistant mosquito groups analyzed. Genes encoding cuticular proteins (CPR130, CPR10, CPR15, CPR16, CPR127, CPAP3-C, CPAP3-B, and CPR76) were also overexpressed in all the resistant groups, indicating their potential role in cross resistance in An. gambiae. Salivary gland protein genes related to 'salivary cysteine-rich peptide' and 'salivary secreted mucin 3' were also over-expressed and shared across all resistant groups. CONCLUSION: Our results suggest that in addition to metabolic enzymes, cuticular and salivary gland proteins could play an important role in cross-resistance to multiple classes of insecticides in Benin. These genes warrant further investigation to validate their functional role in An. gambiae resistance to insecticides.

Prenatal organophosphate esters exposure and neurodevelopment trajectory in infancy: Evidence from the Shanghai Maternal-Child Pairs Cohort.

BACKGROUND: Concerns remain about the neurotoxic properties of the ubiquitous organophosphate esters (OPEs), the replacement of the toxicant polybrominated diphenyl ethers. OBJECTIVES: We examined the associations of prenatal exposure to OPEs and their mixtures with early-life neurodevelopment trajectories. METHODS: Totally 1276 mother-child pairs were recruited from the Shanghai Maternal-Child Pairs Cohort. A high-performance liquid chromatography-triple quadrupole mass spectrometer was used to measure the levels of 7 OPEs in cord serum. Ages and Stages Questionnaires was used to examine children's neuropsychological development at 2, 6, 12, and 24 months of age. Group-based trajectory models were applied to derive the neurodevelopmental trajectories. Multiple linear regression and logistic regression model were performed to assess the relationships between OPEs exposure and neurodevelopment and trajectories. Mixtures for widely detected OPEs (n = 4) were investigated using quantile-based g-computation. RESULTS: Tributyl phosphate (TBP), tris (2-butoxy ethyl) phosphate (TBEP), tris(1,3-dichloro-2-propyl) phosphate (TDCPP), and 2-ethylhexyl diphenyl phosphate (EHDPP), had detection rates >50 %. TDCPP had the highest median concentration (1.02 µg/L) in cord serum. EHDPP concentrations were negatively associated with scores in most domains at 12 months of age, with effect values (ß) ranging from -1.89 to -0.57. EHDPP could negatively affect the total ASQ (OR = 1.07, 95 % CI: 1, 1.15) and gross-motor (OR = 1.09, 95 % CI: 1.02, 1.17) trajectory in infancy. Joint exposure to OPEs was associated with decreased scores in the total ASQ, gross-motor, fine-motor and problem-solving domain of 12-month-old infants, with ß ranging from -5.93 to -1.25. In addition, the qgcomp models indicated significant positive associations between the concentrations of OPEs mixtures and risks of the persistently low group of the total ASQ, gross-motor and fine-motor development in early childhood. The impact of OPEs was more pronounced in boys. DISCUSSION: Our findings suggested OPEs, especially EHDPP, had a persistently negative effect on neurodevelopment during the first 2 years.

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.

Personal environmental exposure to plasticizers and organophosphate flame retardants using silicone wristbands and urine: Patterns, comparisons, and correlations.

Plasticizers (PLs) and organophosphate flame retardants (OPFRs) are ubiquitous in the environment due to their widespread use and potential for leaching from consumer products. Environmental exposure is a critical aspect of the human exposome, revealing complex interactions between environmental contaminants and potential health effects. Silicone wristbands (SWBs) have emerged as a novel and non-invasive sampling device for assessing personal external exposure. In this study, SWBs were used as a proxy to estimate personal dermal adsorption (EDdermal) to PLs and OPFRs in Belgian participants for one week; four morning urine samples were also collected and analyzed for estimated daily intake (EDI). The results of the SWBs samples showed that all the participants were exposed to these chemicals, and the exposure was found to be highest for the legacy and alternative plasticizers (LP and AP), followed by the legacy and emerging OPFRs (LOPFR and EOPFR). In urine samples, the highest levels were observed for metabolites of diethyl phthalate (DEP), di-isobutyl phthalate (DiBP) and di-n-butyl phthalate (DnBP) among LPs and di(2-ethylhexyl) terephthalate (DEHT) for APs. Outliers among the participants indicated that there were other sources of exposure that were not identified. Results showed a significant correlation between EDdermal and EDI for DiBP, tris (2-butoxyethyl) phosphate (TBOEP) and triphenyl phosphate (TPhP). These correlations indicated their suitability for predicting exposure via SWB monitoring for total chemical exposure. The results of this pilot study advance our understanding of SWB sampling and its relevance for predicting aggregate environmental chemical exposures, while highlighting the potential of SWBs as low-cost, non-invasive personal samplers for future research. This innovative approach has the potential to advance the assessment of environmental exposures and their impact on public health.

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.

Organophosphorus Flame Retardant TPP-Induced Human Corneal Epithelial Cell Apoptosis through Caspase-Dependent Mitochondrial Pathway.

A widely used organophosphate flame retardant (OPFR), triphenyl phosphate (TPP), is frequently detected in various environmental media and humans. However, there is little known on the human corneal epithelium of health risk when exposed to TPP. In this study, human normal corneal epithelial cells (HCECs) were used to investigate the cell viability, morphology, apoptosis, and mitochondrial membrane potential after they were exposed to TPP, as well as their underlying molecular mechanisms. We found that TPP decreased cell viability in a concentration-dependent manner, with a half maximal inhibitory concentration (IC50) of 220 µM. Furthermore, TPP significantly induced HCEC apoptosis, decreased mitochondrial membrane potential in a dose-dependent manner, and changed the mRNA levels of the apoptosis biomarker genes (Cyt c, Caspase-9, Caspase-3, Bcl-2, and Bax). The results showed that TPP induced cytotoxicity in HCECs, eventually leading to apoptosis and changes in mitochondrial membrane potential. In addition, the caspase-dependent mitochondrial pathways may be involved in TPP-induced HCEC apoptosis. This study provides a reference for the human corneal toxicity of TPP, indicating that the risks of OPFR to human health cannot be ignored.

Potential adverse outcome pathway of neurodevelopmental toxicity, inflammatory response, and oxidative stress induction mediated by three alkyl organophosphate flame retardants in zebrafish larvae.

Following restrictions on polybrominated flame retardants, trimethyl phosphate (TMP), triethyl phosphate (TEP), and tris(2-butoxyethyl) phosphate (TBEP) have been frequently used as plasticizers for fire-resistant plastics. This study investigated the neurodevelopmental effects, inflammatory response, and oxidative stress induction of three alkyl organophosphate flame retardants using a zebrafish embryo/larvae model. After exposure of zebrafish embryos to TMP, TEP, and TBEP (0, 0.02, 0.2, 2, 20, and 200 µg L-1) for 96 h, survival, development, swimming behavior, changes in acetylcholinesterase (AChE) activity, dopamine, tumor necrosis factor-alpha (TNF-α), interleukin (IL), reactive oxygen species (ROS), and antioxidant enzyme activities were observed. Concentrations of TMP, TEP, and TBEP were also measured in the whole body of exposed larvae. Our results showed that exposure to 200 µg L-1 TEP and ≥20 µg L-1 TBEP significantly reduced larval body length; however, TMP had no significant effects on developmental parameters up to 200 µg L-1. After 96 h of exposure to TBEP, total distance moved, mean velocity, AChE, and dopamine concentrations were significantly decreased. Exposure to TEP and TBEP decreased the expression of genes that regulate central nervous system development (e.g. gap43 and mbpa), whereas ROS, antioxidant enzymes, TNF-α, and IL-1ß concentrations were significantly increased. Notably, pretreatment with an antioxidant N-acetylcysteine reduced neurotoxicity and oxidative stress caused by TEP and TBEP. The results of this study demonstrated that exposure to TEP and TBEP causes oxidative stress and has adverse effects on the neurobehavioral and immune system of zebrafish, leading to hypoactivity and ultimately impairing development.

Occurrence, distribution, and sources of organophosphate esters (OPEs) in the air of the Indo-China Peninsula Based on a Passive Air Monitoring Network.

Organophosphate esters (OPEs) are a class of emerging and ubiquitous contaminants that are attracting increasing attention, and their large-scale use as flame retardants and plasticizers has led to their pervasive presence in the environment, although their broader impacts remain unknown. In this study, 11 OPEs were measured in the atmosphere of Southeast Asia and Southwest China during 2016. The ∑11OPEs were higher in this region (78.0-1670 pg/m3, mean 458 pg/m3) than in many remote areas, lower than in developed regions, and comparable to levels in many developing country cities. Generally, the ∑11OPEs were higher in urban (105-1670 pg/m3, mean 538 pg/m3) than in suburban (78.0-1350 pg/m3, mean 388 pg/m3). Seasonal variations of OPEs in the air were more pronounced in Cambodia and Laos, especially for Triphenyl Phosphate (TPHP). Seasonal variations of ∑11OPEs in most regions correspond to changes in temperature and rainfall. Biomass burning may be also a factor in facilitating OPE emissions from biomass materials or soil into the atmosphere of Southeast Asia. The random forest analysis showed that among these, rainfall had the greatest effect on the seasonal variation of atmospheric OPE concentrations, followed by biomass burning and temperature. The inter-regional variation of ∑11OPEs in Southeast Asia was related to population and economic development in each region. Airflow trajectories indicated that the OPEs in this region were mainly from local sources. The health risk assessment revealed that the inhalation exposure risks of OPEs to the residents in the study areas were very low during the sampling period, but may be increasing.

Development of Nontargeted Workflow of Occupational Exposure by Infrared Ion Spectroscopy and Silicone Wristbands' Passive Sampling.

A new approach using orthogonal analytical techniques is developed for chemical identification. High resolution mass spectrometry and infrared ion spectroscopy are applied through a 5-level confidence paradigm to demonstrate the effectiveness of nontargeted workflow for the identification of hazardous organophosphates. Triphenyl phosphate is used as a surrogate organophosphate for occupational exposure, and silicone wristbands are used to represent personal samplers. Spectral data of a target compound is combined with spectral data of the sodium adduct and quantum chemical calculations to achieve a confirmed identification. Here, we demonstrate a nontargeted workflow that identifies organophosphate exposure and provides a mechanism for selecting validated methods for quantitative analyses.

Organophosphate Pesticide Exposure: Effect on Farmers' Sperm Quality in the Mekong Delta, Vietnam.

OBJECTIVES: Using pesticides in the An Giang province is widespread. However, studies on the health effect of organophosphate pesticide have not been updated within the past 12 years. This study aimed to assess exposure to organophosphate pesticides and their effects on sperm quality among farmers in the An Giang Province, Mekong Delta, Vietnam. METHODS: During the winter - spring crop season of December 2021 to February 2022, a cross-sectional study was conducted on farmers aged 18 to 60 years-old based on seven communes' health checkup programs. The pesticide spray group included farmers who had sprayed pesticides in the previous week and had a history of working in agriculture for more than 2 years. The control group was defined as those who lived in the same community, had not worked in agriculture, and had never sprayed pesticides. Demographic characteristics and blood, urine, and semen samples were collected and analyzed. RESULTS: Data for 184 eligible participants were analyzed, including 116 farmers in the pesticide spray group and 68 non-farmers in the control group. Pesticide spray contributed to a decrease in the sperm quality index of 6.253 units (95% CI, 4.472-8.749). Increasing each pseudocholinesterase (PChE) unit (kIU/L) was associated with an increase of 1.181 units in the sperm quality index (95% CI, 0.757-0.947). CONCLUSIONS: Preventive methods for organophosphate pesticide exposure, such as administrative controls, engineering controls, substitution, and personal protective equipment should be applied to control health risks. In the An Giang setting, personal protective equipment is feasible, but most types of equipment are not used. The immediate priority is to determine the cause of personal protective equipment not being used and to find solutions to encourage people to use them.

Organophosphate pesticide residue impact on water quality and changes in macroinvertebrate community in an Afrotropical stream flowing through farmlands.

River Chanchaga has experienced significant agricultural practices around its catchment, which involved the indiscriminate use of pesticides. However, residents of the study area are not well aware of the negative impact of pesticides on water quality and macroinvertebrates. In this study, the first report on the influence of organophosphate pesticide contamination on the abundance of the macroinvertebrate community was provided. Sampling for the determination of organophosphate pesticide residues was carried out during the peak of the two seasons, while macroinvertebrates and physicochemical variables were observed for 6 months. We examined 11 organophosphate pesticide residues using gas chromatography coupled with mass spectrometry, 12 water quality variables, and 625 macroinvertebrate individuals. The concentration of recorded organophosphate pesticide residues ranged from 0.01 to 0.52 µg/L. From the Canonical Correspondence Analysis plot, malathion, chlorine, and paraffin show a positive correlation with Unima sp., Hydrocanthus sp., Chironomus sp., and Potadoma sp. At station 3, depth shows a positive correlation with Biomphalaria sp. and Zyxomma sp., indicating poor water quality as most of these macroinvertebrates are indicators of water pollution. Diuron and carbofuran show a negative correlation with Lestes sp. and Pseudocloeon sp., and these are pollution-sensitive macroinvertebrates. The total mean concentration of organophosphate pesticide residues was above international drinking water standards set by the World Health Organization except for paraffin, chlorpyrifos, and diuron. In conclusion, the observations recorded from this research are useful in managing pesticide applications around the river catchment.

Factors impacting human exposure to legacy and emerging contaminants in residential dust in Beijing, China: Characteristics of indoor microenvironment.

Exposure to indoor dust is of concern since dust may be contaminated by various toxic chemicals and people spend considerable time indoors. Factors impacting human exposure risks to contaminants in indoor dust may differ from those affecting the loadings of contaminants, but the dominant factors have not yet been well clarified. In this study, the occurrence, human exposure, and related influencing factors of several classes of legacy and emerging contaminants in residential dust across Beijing were investigated, including per- and polyfluoroalkyl substances (PFASs) and three types of flame retardants (FRs), i.e., organophosphate esters (OPEs), polybrominated diphenyl ethers (PBDEs), and novel halogenated FRs (NHFRs). OPEs (median: 3847 ng/g) were the most abundant group, followed by PBDEs (1046 ng/g) and NHFRs (520 ng/g). PFASs (14.3 ng/g) were one to two orders of magnitude lower than FRs. The estimated daily intakes of these contaminants were relatively higher for toddlers than other age groups, with oral ingestion being the main exposure pathway compared with dermal contact. Higher human exposure risks were found in new buildings or newly finished homes due to the elevated intake of emerging contaminants (such as OPEs). Furthermore, higher risks were also found in homes with wooden floors, which were mainly associated with higher levels of PFASs, chloroalkyl and alkyl OPEs, compared with tile floors. Citizens in the urban area also showed higher exposure risks than those in the suburban area. The quantity of household appliances and finishing styles (simple or luxurious) showed an insignificant impact on overall human exposure risks despite their significant effect on the levels of some of the dust contaminants. Results in this study are of importance in understanding human exposure to the co-existence of multiple contaminants in indoor dust.

Global responses to tris(1-chloro-2-propyl) phosphate and tris(2-butoxyethyl) phosphate in Escherichia coli: Evidences from biomarkers, and metabolic disturbance using GC-MS and LC-MS metabolomics analyses.

Tris(1-chloro-2-propyl) phosphate (TCPP) and tris(2-butoxyethyl) phosphate (TBEP) as pollutants of emerging concern have aroused the rising attention due to their potential risks on aquatic ecosystem and public health. Nevertheless, there is a lack of toxicological mechanisms exploration of TCPP and TBEP at molecular levels. Herein, the toxicity effects and molecular mechanism of them were fully researched and summarized on Escherichia coli (E.coli). Acute exposure to them significantly activated antioxidant defense system and caused lipid peroxidation, as proved by the changes of antioxidant enzymes and MDA. The ROS overload resulted in the drop of membrane potential as well as the downregulated synthesis of ATPase, endorsing that E. coli cytotoxicity was ascribed to oxidative stress damage induced by TCPP and TBEP. The combination of GC-MS and LC-MS based metabolomics validated that TCPP and TBEP induced metabolic reprogramming in E.coli. More specifically, the responsive metabolites in carbohydrate metabolism, lipids metabolism, nucleotide metabolism, amino acid metabolism, and organic acids metabolism were significantly disturbed by TCPP and TBEP, confirming the negative effects on metabolic functions and key bioprocesses. Additionally, several biomarkers including PE(16:1(5Z)/15:0), PA(17:1(9Z)/18:2(9Z,12Z)), PE(19:1(9Z)/0:0), and LysoPE(0:0/18:1(11Z)) were remarkably upregulated, verifying that the protection of cellular membrane was conducted by regulating the expression of lipids-associated metabolites. Collectively, this work sheds new light on the potential molecular toxicity mechanism of TCPP and TBEP on aquatic organisms, and these findings using GC-MS and LC-MS metabolomics generate a fresh insight into assessing the effects of OPFRs on target and non-target aquatic organisms.