Occurrence and potential risks of organophosphate esters in agricultural soils: A case study of Fuzhou City, Southeast China.

Fifty agricultural soil samples collected from Fuzhou, southeast China, were first investigated for the occurrence, distribution, and potential risks of twelve organophosphate esters (OPEs). The total concentration of OPEs (ΣOPEs) in soil ranged from 1.33 to 96.5 ng/g dry weight (dw), with an average value of 17.1 ng/g dw. Especially, halogenated-OPEs were the predominant group with a mean level of 9.75 ng/g dw, and tris(1-chloro-2-propyl) phosphate (TCIPP) was the most abundant OPEs, accounting for 51.1% of ΣOPEs. The concentrations of TCIPP and ∑OPEs were found to be significantly higher (P < 0.05) in soils of urban areas than those in suburban areas. In addition, the use of agricultural plastic films and total organic carbon had a positive effect on the occurrence of OPE in this study. The positive matrix factorization model suggested complex sources of OPEs in agricultural soils from Fuzhou. The ecological risk assessment demonstrated that tricresyl phosphate presented a medium risk to land-based organisms (0.1 ≤ risk quotient < 1.0). Nevertheless, the carcinogenic and non-carcinogenic risks for human exposure to OPEs through soil ingestion and dermal absorption were negligible. These findings would facilitate further investigations into the pollution management and risk control of OPEs.

Legacy and emerging flame retardants in sediments and wastewater treatment plant-derived biosolids.

A baseline assessment of legacy and emerging flame retardant chemicals was performed in inland and transitional sediments as well as biosolids emanating from a selection of wastewater treatment plants (WWTPs) in Ireland. A selection of 24 polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and chlorinated organophosphate esters (Cl-OPEs) were quantified in: 81 inland and transitional sediment samples collected during 2023; 39 transitional sediments collected between 2018 and 2022; and 21 biosolid samples collected from 7 WWTPs over 4-month intervals in January, May, and September 2023. Highest concentrations of BDE-209 and several Cl-OPEs were detected in both sediment and biosolid samples, while most PCBs and penta-/octa-BDEs were comparatively low. Moderate levels of PBDEs and Cl-OPEs were detected in Irish sediments compared to similar studies conducted internationally. In biosolid samples, levels of BDE-209 were on the higher end of figured reported worldwide while levels of Σ8Cl-OPEs were the highest relative to comparable international studies. PCBs meanwhile are on the lower end of international levels for both biosolids and sediments. Based on available predicted no-effect concentrations (PNECs), the majority of compounds assessed were found to be of low-risk based on their levels in sediments with the exception of TCIPP (Risk Quotient - RQ = 1.354 = high risk) as well as EHDPP, TEHP, PCB-118, and PCB-52 (RQ = 0.948, 0.576, 0.446, and 0.257 respectively = moderate risk). Similar risk assessment could not be performed on contaminants in biosolids, though levels of BDE-209 were on the higher end of figured reported worldwide (avg = 3155 ng/g) while levels of Σ8Cl-OPEs were the highest relative to comparable international studies (avg8 = 3290 ng/g). As the legacy PBDEs and PCBs have been listed as persistent organic pollutants (POPs) and replacement flame retardants such as Cl-OPEs have been flagged by programmes such as human biomonitoring for EU (HBM4EU) and the NORMAN Network as chemicals of emerging concern, continued monitoring of these moderate and high-risk contaminants in sediments, as well as an investigation of potential contamination of the food chain through land-spreading of biosolids on agricultural lands, would be warranted.

Fast determination of organophosphate esters and their metabolites in human matrices by a straightforward cold-induced strategy coupled with HPLC-MS/MS.

Organophosphate esters (OPEs) are commonly used chemicals and are also regarded as emerging environmental pollutants. Recently, it has been proved that metabolites of OPEs (mOPEs) could also cause health concerns. However, analytical methods for the concurrent measurement of OPEs and mOPEs in human matrices are still complicated. In this study, a convenient and efficient analytical method combining a cold-induced strategy and HPLC-MS/MS was developed to simultaneously determine 18 OPEs and 10 mOPEs in human serum, urine, and human milk. In brief, after the sample was extracted with acetonitrile, a "one-step" treatment combining purification and enrichment was accomplished by cold-induced liquid-liquid extraction (CI-LLE), and analytes were then quantified by HPLC-ESI-MS/MS. The ratio of acetonitrile/water, and the temperature and time set in the CI-LLE procedure were optimized for achieving the highest enrichment factors. Under the best conditions, linearity, limits of detection (LODs), recovery, precision, and matrix effects of OPEs/mOPEs were verified. LODs of OPEs/mOPEs in serum, urine, and human milk were 0.1-113 pg/mL, 0.1-22 pg/mL, and 0.2-22 pg/mL, respectively. Average recoveries ranged from 80 to 123%, with relative standard deviations lower than 15% for most analytes. The matrix effect test showed slight signal enhancement or inhibition, and the use of isotopically labeled internal standards (ISs) could compensate for the effects. In real sample analysis, both OPEs and mOPEs showed high detecting frequency, which indicated their ubiquity in humans.

Migration patterns of organophosphate esters from plastic food packaging simulants to foods: Donors, behaviours, and influencing factors.

In recent years, organophosphate esters (OPEs) have been widely produced and used as flame retardants and plasticizer additives, posing significant ecological and health risks. Dietary intake is considered to be the primary route of human exposure to OPEs. Plastic food packaging materials are considered a crucial source for contamination of OPEs in food. However, the migration behaviour of OPEs from plastic food packaging materials into foods has received limited attention. In this study, we employed a novel method to prepare migration donors containing 13 kinds of OPEs. The migration behaviours of OPEs from food packaging simulants (polypropylene) to foods (full-fat milk powder) were simulated, and factors influencing the migration of OPEs were examined, including the properties of the target compounds, migration temperature, fat content of the migration receptors, and mass transfer mode. The results indicated that OPEs exhibited a significant migration tendency. Low molecular weight OPEs (< 300 Da) had faster migration efficiency compared to high molecular weight OPEs. The mean migration efficiencies of various OPEs showed a significant negative correlation with their molecular weights (p < 0.01) and a significant positive correlation with temperature (p < 0.01). Except for resorcinol bis(diphenyl phosphate) (RDP), which showed almost no migration, the mean migration efficiencies of other OPEs at 25 °C, 40 °C, and 60 °C were 3.1-37.5 %, 9.0-60.0 %, and 23.9-80.4 %, respectively. Most of the OPEs demonstrated higher migration efficiency in high-fat content food than low-fat content food. The migration of OPEs from food packaging simulants to foods primarily occurred through contact rather than gas-phase mass transfer. Overall, this study uncovers the migration behaviours of OPEs from food packaging simulants to foods and scrutinized the relevant factors influencing the migration. It is expected that the research in terms of the contamination control of OPEs in food will benefit from this work.

Association between exposure to organophosphate esters metabolites and sarcopenia prevalence: A cross-sectional study using NHANES data.

Organophosphate esters (OPEs) are an emerging group of environmental pollutants linked to numerous health concerns, and their increasing prevalence in the environment is alarming. However, the impact of OPEs exposure on sarcopenia, a condition characterized by muscle loss and weakness, remains unknown. In this study, the connection between urinary metabolites of OPEs and the occurrence of sarcopenia was investigated using data from the National Health and Nutrition Examination Survey (NHANES) covering a period from 2011 to 2018. The analysis found that two specific urinary metabolites, Dibutyl phosphate (DBUP) and Bis (2-chloroethyl) phosphate (BCEP), were positively correlated with an increased risk of sarcopenia. Among these metabolites, DBUP had the highest contribution to sarcopenia development according to weighted quantile sum (WQS) model analysis. Additionally, it was observed that inflammation mediated the relationship between urinary exposure to DBUP/BCEP and the prevalence of sarcopenia. Overall, this research emphasizes the role of OPEs in the progression of sarcopenia, prompting concerns regarding their potential impact on health and advocating for further prospective investigations into their correlation with the risk of developing sarcopenia.

Biomagnification potential and health risks of organophosphate esters in prey to humpback dolphins based on dietary correction.

Information on the biomagnification of organophosphate esters (OPEs) is limited, and the results are inconclusive, mainly because precise predatorprey relationships have not been determined. Herein, we first evaluated the biomagnification potential and dietary exposure risk of 15 OPEs in 14 prey species (n = 234) to Indo-Pacific humpback dolphins from the northern South China Sea using quantitative fatty acid signature analysis (QFASA). QFASA identified Chinese gizzard shad as the primary prey of dolphins. Among the 15 OPEs, 86.7 % (13/15) had a diet-adjusted biomagnification factor (BMFQFASA) greater than 1, indicating the biomagnification potential between dolphins and their diet. Moreover, BMFQFASA exhibited a considerable positive correlation with the log octanolwater partitioning coefficient of OPEs, indicating that lipophilicity may affect the bioamplification of OPEs. Risk assessments showed that although current OPE levels may not pose substantial health risks to dolphins via diet intake, the nondiet-adjusted hazard quotient/hazard index underestimated the exposure risk of OPEs to this vulnerable dolphin species. This study provides novel evidence regarding the biomagnification and dietary exposure risks of OPEs in cetaceans, emphasizing the importance of estimating the dietary composition of predators in such analyses.

Plasticizers levels in four fish species from the Ligurian Sea and Central Adriatic Sea (Mediterranean Sea) and potential risk for human consumption.

Plastic materials contain additives such as plasticizers and flame retardants, which are not covalently bound to plastic polymers and can therefore be unintentionally released into the marine environment. This study investigated three families of compounds, phthalates (PAEs), organophosphate esters (OPEs), and non-phthalate plasticizers (NPPs) currently used as plastic additives, in 48 muscle samples of bogue (Boops boops), European hake (Merluccius merluccius), red mullet (Mullus barbatus), and European pilchard (Sardina pilchardus) sampled in the Central Adriatic and the Ligurian Seas. The additional goal of this study is to assess the potential risk to human health from fish consumption with the objective of determining whether the detected levels might potentially pose a concern. PAEs represent the majority of the plastic additives detected in the selected species, with ubiquitous distribution across the study areas, whereas for OPEs and NPPs, there is a more pronounced difference between the two study areas, suggesting that these compounds may represent different exposure levels in the two seas. Among PAEs, bis(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP), and diisobutyl phthalate (DIBP) were the most abundant compounds, reaching levels up to 455 ng/g ww. OPEs were detected at higher concentrations in samples from the Ligurian Sea, and triethyl phosphate (TEP) was the most abundant compound. Among the NPPs, acetyl tributyl citrate (ATBC) was most frequently detected. From the results obtained, fish consumption may not pose a risk to human health (Hazard Quotient<1) but needs to be considered in future studies. Given the limited number of studies on PAEs, OPEs and NPPs in the Mediterranean Sea, further research is necessary to understand their potential bioaccumulation in marine organisms.

Dermal exposure assessment of formal e-waste dismantlers to flame retardants and plasticizers using passive sampling methodologies.

The recycling of e-waste can lead to the release of organic chemicals when materials containing additives are subjected to dismantling and grinding. In this context, the exposure of workers from a Catalonian e-waste facility to flame retardants and plasticizers (including organophosphate esters (OPEs), polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs) and dechloranes) was assessed using T-shirts and wristbands as passive samplers. The study area includes an area exclusively dedicated to cathodic ray-tube (CRT) TVs dismantling, and a grinding area where the rest of e-waste is ground. All the families of compounds were detected in both T-shirts and wristbands, with the highest concentration levels corresponding to OPEs, followed by PBDEs, NBFRs, and dechloranes. The CRT area presented higher concentration levels than the grinding area. The compounds with higher concentrations in T-shirts were 2-ethylhexyl diphenyl phosphate (EHDPP), diphenyl cresyl phosphate (DCP) and triphenyl phosphate (TPHP), and the total concentration of all groups ranged between 293 and 8324 ng/dm2-h (hour). In the case of the wristbands, the most abundant compounds were DCP, TPHP, and BDE-209, with total concentrations between 188 and 2248 ng/dm2-h. The two sampling methods appear to be complementary, as T-shirts collect coarser particles, while wristbands also capture volatile compounds. Based on normalized surface and time concentrations, the estimated daily intake (EDI) through dermal contact was calculated and carcinogenic and non-carcinogenic risks (CR and non-CR) associated with this activity assessed. The results show median CR 29 and 16 times below the threshold in CRT and grinding areas respectively. The non-CR medians were 2 and 3 times below the threshold, although in the CRT area one exceptional value surpassed the threshold, suggesting that risk can exist for some workers in the facility.

Regulation of Ocean Surface Currents and Seasonal Sea Ice Variations on the Occurrence and Transport of Organophosphate Esters in the Central Arctic Ocean.

Organophosphate esters (OPEs) have been observed in the remote Arctic Ocean, yet the influence of hydrodynamics and seasonal sea ice variations on the occurrence and transport of waterborne OPEs remains unclear. This study comprehensively examines OPEs in surface seawater of the central Arctic Ocean during the summer of 2020, integrating surface ocean current and sea ice concentration data. The results confirm significant spatiotemporal variations of the OPEs, with the total concentration of seven major OPEs averaging 780 ± 970 pg/L. Chlorinated OPEs, particularly tris(1-chloro-2-propyl) phosphate (TCPP), were dominant. The significant impact of hydrodynamics on the OPE transport is demonstrated by higher OPE concentrations in regions with strong surface currents, especially at the edge of the Beaufort Gyre and the confluence of the Beaufort Gyre and the Transpolar Drift. Furthermore, OPE levels were generally higher in drifting-ice-covered regions compared to ice-free regions, attributed to the volatilization of dissolved OPEs formerly trapped below the sea ice or newly released from melting snow and sea ice. Notably, TCPP decreased by only 19% in the ice-free area, while the more volatile triphenyl phosphate decreased by 63% compared with the partial ice region.

Comprehensive dietary exposure assessment of the Chinese population to organophosphate esters (OPEs): Results of the sixth China total diet study.

Organophosphate esters (OPEs) are emerging pollutants, while data on their occurrence in foods and human dietary intake are limited. Based on the 6th China total diet study conducted in 2016-2019, this study implemented a comprehensive survey of OPEs in plant-derived foods of cereals, potatoes, legumes, fruits, vegetables, and further assessed dietary exposure from both plant- and animal-derived food. The sum concentrations of 15 OPEs in the plant-derived samples ranged from 0.567 to 106 ng/g ww. 2-Ethylhexyl diphenyl phosphate (EHDPP) (median: 1.14 ng/g ww) had the highest level in plant-derived foods, with a proportion of 35.6% in the total median OPEs. Regional distribution analysis showed a higher contamination of OPEs in plant-derived food from northern area of China. Estimated dietary intakes (EDIs) of ∑OPEs for Chinese population were from 109 ng/kg bw/day in Beijing to 1164 ng/kg bw/day in Gansu province, with mean and median of 296 and 222 ng/kg bw/day, respectively. Although animal-derived foods had higher levels of OPEs, plant-derived foods, specifically cereals, was the major source of dietary OPE intake. The EDIs were much lower than reference doses, which suggested the intakes of OPEs via food consumption could not cause significant health risks to the Chinese population at present.

Characterizing organophosphate esters and chlorinated paraffins in surface soils affected by diverse e-waste disassembling process in South China: Occurrence, distinct emission, and risk assessment.

E-waste recycling activities are a crucial emission source of organic pollutants, posing potential risks to the surrounding environment and human health. To understand the potential impact related to diverse e-waste dismantling activities, we investigated two categories of popular flame retardants (i.e., organophosphate esters (OPEs) and chlorinated paraffins (CPs) and their resultant possible ecological risk in 53 surface soil samples from Qingyuan, a well-known e-waste recycling region in South China. Varied concentrations of ΣOPEs (20.5-8720 ng/g) and ΣCPs (920-16800 ng/g) were observed at diverse dismantling sites, while relatively low levels of ΣOPEs (6.13-1240 ng/g) and ΣCPs (14.8-2870 ng/g) were found in surrounding soils. These results indicated that primitive e-waste dismantling processes were the primary emission source of OPEs and CPs in the studied area, with e-waste dumping and manual dismantling being the most important emission sources for OPEs and CPs. More importantly, CPs could be degraded/transformed into more toxic intermediates via dechlorination and decarbonization during the burning of e-waste. Furthermore, our results indicated the potential ecological risks posed by OPEs and CPs related to e-waste recycling.

Occurrence, Bioaccumulation, and Risk Assessment of Organophosphate Esters in Rivers Receiving Different Effluents.

Organophosphate esters (OPEs), as alternatives to brominated flame retardants, are extensively used in both production and daily life, with their environmental contamination and toxic effects being a concern. This study investigated the concentration levels, bioaccumulation, and ecological effects of OPEs in five different effluent-receiving rivers. The results demonstrate that the concentration range of Σ13OPEs across the five rivers was between 142.23 and 304.56 ng/L (mean: 193.50 ng/L). The highest pollution levels of OPEs were found in rivers receiving airport and industrial wastewater, followed by agricultural wastewater, mixed wastewater, and domestic wastewater. Tris(2-chloroisopropyl) phosphate (TCPP), triethyl phosphate (TEP), and tricresyl phosphate (TCrP) were identified as the main pollutants. The accumulation concentrations of OPEs in fish ranged from 54.0 to 1080.88 ng/g dw, with the highest bioaccumulation found in Pelteobagrus fulvidraco, followed by Carassius auratus and Misgurnus anguillicaudatus. The brain was the primary organ of accumulation, followed by the liver, gills, intestine, and muscle. Tri-n-propyl phosphate (TPeP) and TEP exhibited the highest bioconcentration, with log BAF values exceeding three. The bioaccumulation of OPEs was influenced by pollutant concentration levels, hydrophobic properties, and biological metabolism. Ecological risk assessment revealed that the cumulative risk values of Σ13OPEs ranged from 0.025 to 16.76, with TCrP being the major contributor. It posed a medium-low risk to algae but a high risk to crustaceans and fish.

Spatial variation, emissions, transport, and risk assessment of organophosphate esters in two large petrochemical complexes in southern China.

Organophosphate esters (OPEs) serve as significant flame retardants and plasticizers in various petrochemical downstream products. The petrochemical industry could be a potential source of atmospheric OPEs, but their emissions from this industry are poorly understood. The present study revealed the spatial variation, emission, and atmospheric transport of traditional and novel OPEs (TOPEs and NOPEs, respectively) in atmospheric particulate matter (PM) across Hainan and Guangdong petrochemical complexes (HNPC and GDPC, respectively) in southern China. The total concentrations of TOPEs ranged from 232 to 46,002 pg/m3 and from 200 to 20,347 pg/m3 in the HNPC and GDPC, respectively, which were substantially higher than those of NOPEs (HNPC: 23.5-147 pg/m3, GDPC: 13.9-465 pg/m3). Enterprises involved in the production of downstream petrochemical products presented relatively high concentrations of OPEs, indicating evident emissions of these pollutants in the petrochemical industry. The correlations of PM-bound OPEs in the atmosphere are determined mainly by their coaddition to industrial products or their coexistence in technical mixtures. The annual emissions of TOPEs and NOPEs in the HNPC were 42.6 kg and 0.34 kg, respectively, and those in the GDPC were 116 kg and 1.85 kg, respectively. OPEs from the HNPC can reach Vietnam, Cambodia, and Guangxi Province, China, and those from the GDPC can reach Guangxi Province and Hunan Province via atmospheric transmission after 24 h of emission. The OPE concentrations reaching the receptor regions were generally less than 3.20 pg/m3. Risk assessment revealed that OPE inhalation exposure on two petrochemical complexes likely poses minor risks for people living in the study areas, but the risk resulting from two chlorinated OPEs should be noted since they are close to the threshold values. This study has implications for enhancing control measures for OPE emissions to reduce health risks related to the petrochemical industry.

Characteristics and partitions of traditional and emerging organophosphate esters in soil and groundwater based on machine learning.

Organophosphate esters (OPEs) pose hazards to both humans and the environment. This study applied target screening to analyze the concentrations and detection frequencies of OPEs in the soil and groundwater of representative contaminated sites in the Pearl River Delta. The clusters and correlation characteristics of OPEs in soil and groundwater were calculated by self-organizing map (SOM). The risk assessment and partitions of OPEs in industrial park soil and groundwater were conducted. The results revealed that 14 out of 23 types of OPEs were detected. The total concentrations (Σ23OPEs) ranged from 1.931 to 743.571 ng/L in the groundwater, and 0.218 to 79.578 ng/g in the soil, the former showed highly soluble OPEs with high detection frequencies and concentrations, whereas the latter exhibited the opposite trend. SOM analysis revealed that the distribution of OPEs in the soil differed significantly from that in the groundwater. In the industrial park, OPEs posed acceptable risks in both the soil and groundwater. The soil could be categorized into Zone I and II, and the groundwater into Zone I, II, and III, with corresponding management recommendations. Applying SOM to analyze the characteristics and partitions of OPEs may provide references for other new pollutants and contaminated sites.

Comprehensive risk assessment of the inhalation of plasticizers from the use of face masks.

Disposable masks, formed mainly from polymers, often incorporate various chemical additives to enhance their performance. These additives, which include plasticizers, may be released during mask usage, presenting a novel source of human exposure to these compounds. In this study, the presence of 16 organophosphate esters (OPEs), 11 phthalates, and four alternative plasticizers, in four various types of face masks, were studied, as well as their release during simulated mask use (artificial laboratory conditions). Total plasticizer concentrations exhibited minimal variation across different mask types, with mean values of 7.27 µg/face mask for surgical, 8.61 µg/face mask for reusable, 11.0 µg/face mask for KN-95, and 13.9 µg/face mask for FFP2 masks. To explore plasticizer release behavior, inhalation experiments were conducted under different conditions. The findings revealed a significant temperature-dependent enhancement in plasticizer release from masks, subsequently increasing human inhalation exposure. The inhalation experiments showed variation in the release percentages, ranging from 0.1 to 95 %, depending on the specific compound and mask type. Notably, OPEs exhibited a mean release percentage of 1.0 %, similar to phthalates, which showed a 1.2 % release. Although alternative plasticizers were less frequently released, they still presented a notable percentage of release of 4.1 %. Daily intake estimations via inhalation ranged from 0.01 to 9.04 ng/kg body weight (bw)/day for these additives. Using these estimations, carcinogenic and non-carcinogenic risks associated with this exposure to these compounds were evaluated. All calculated values for the specific compounds studied in this paper remained below the established threshold limits. However, they do represent an additional exposure pathway that, when considered alongside other more predominant routes such as indoor/outdoor inhalation, dermal absorption, and dietary intake, makes the total exposure worthy of consideration.

Exposure to organophosphate esters and early menopause: A population-based cross-sectional study.

Organophosphate esters (OPEs), increasingly used as new flame retardants and plasticizers in various products, have been found to have reproductive toxicity with overt endocrine disruption potential, yet the relationship between OPEs and early menopause remains unexplored. In the present study, we included 2429 women who participated in the U.S. National Health and Nutrition Examination Survey data (2011-2020) and had data of five urinary OPE metabolite levels and information of menopause characteristics, to investigate the associations of OPEs exposure with premature ovarian insufficiency (POI) and age of menopause. Multivariable adjusted linear and logistic regression were used to assess the associations of urinary OPE metabolites with age of menopause and POI, respectively. Quantile g computation (QGC) models were used to assess the relative contribution of individual metabolites to associations of OPE metabolites mixture. After adjusting for covariates, urinary bis(2-chloroethyl) phosphate (BCEP) concentration was inversely associated with menopause age (ß = - 0.21; 95% confidence interval (CI): 0.41, - 0.002). Higher urinary BCEP level (>median) was associated with earlier age at menopause (ß = -1.14, 95% CI: 1.83, - 0.46), and elevated odds of having POI (OR = 1.93; 95% CI: 1.02, 3.66). These associations were robust to the further adjustment of cardiometabolic diseases and related traits (e.g., body mass index). Further QGC analyses confirmed that BCEP was the dominant metabolite contributing most to the associations of OPEs mixture with age of menopause (weight = 49.5%) and POI (weight = 75.1%). No significant associations were found for the other four OPE metabolites. In this cross-sectional study, urinary BCEP level was associated with earlier menopause and increased odds of POI, highlighting the potential negative impacts of this chemical and its parent compound tris(2-chloroethyl) phosphate on ovarian function. Further studies are required to validate our findings and reveal potential underlying mechanisms.

Kinetics of uptake, translocation, and metabolism of organophosphate esters in japonica rice (Oryza sativa L.): Hydroponic experiment combined with model.

Hydroponics combined with fugacity model was employed to investigate the kinetics of uptake, accumulation, and metabolism of organophosphate esters (OPEs) by japonica rice. The time-dependent process for uptake and accumulation of 5 OPEs and their diester-metabolites in both rice root and shoot fitted well with the pseudo-first-order kinetic model. The peak OPE accumulations in rice root and shoot were significantly positively or negatively correlated with their octanol-water partition coefficient (logKow) respectively, but not for their apparent accumulation rates. Root concentration factors (RCFs) and root-to-shoot translocation factors (TFs) of OPEs were found to be positively and negatively correlated with their logKow, respectively. Triphenyl phosphate with benzene ring substituents showed the highest RCF, but the lowest TF, because of its high potential for root adsorption due to the π electron-rich structures. Sterilized root exudates can hinder the root adsorption and absorption of OPEs from solution probably through competitive adsorption of OPEs with root surface. The first-hand transport and metabolism rates were also obtained by generating these rates to fit the dynamic fugacity model with the measurement values. The simulation indicated that the kinetics of OPE accumulation in rice plants may be controlled by multiple processes and physicochemical properties besides Kow.

Associations of prenatal exposure to individual and mixed organophosphate esters with ADHD symptom trajectories in preschool children: The modifying effects of maternal Vitamin D.

BACKGROUND: Organophosphate esters (OPEs) are a class of environmental chemicals with endocrine-disrupting properties. Epidemiologic studies have demonstrated that prenatal OPEs exposure is associated with neurodevelopmental disorders in offspring. However, studies assessing the effects of prenatal OPEs exposure on the dynamic changes in attention deficit hyperactivity disorder (ADHD) symptoms in preschoolers are scarce. Since vitamin D has been demonstrated to have a "neuroprotective" effect, the modifying effects of maternal vitamin D were estimated. METHODS: The present study included 2410 pregnant women from the Ma'anshan Birth Cohort. The levels of OPEs in the mothers' urine were examined in the three trimesters. The Chinese version of the Conners Abbreviated Symptom Questionnaire was used to examine preschoolers' ADHD symptoms at 3, 5, and 6 years of age. ADHD symptom trajectories were fitted via group-based trajectory modeling. We used multinomial logistic regression, Bayesian kernel machine regression, quantile-based g-computation, and generalized linear models to assess individual and mixed relationships between OPEs during pregnancy and preschoolers' ADHD symptoms and trajectories. RESULTS: Preschoolers' ADHD symptom scores were fitted to 3 trajectories, including the low-score, moderate-score, and high-score groups. First-trimester dibutyl phosphate (DBP), second-trimester bis(2-butoxyethyl) phosphate (BBOEP), and third-trimester diphenyl phosphate (DPHP) were associated with an increased risk in the high-score group (p < 0.05). BBOEP in the third trimester was associated with decreased risk in the moderate-score group (OR = 0.89, 95% CI: 0.79, 1.00). For mothers with 25(OH)D deficiency, a positive relationship was observed between OPEs during pregnancy and symptom trajectories. Our results did not reveal any mixed effects of OPEs on ADHD symptom trajectories. CONCLUSION: Prenatal exposure to OPEs had heterogeneous associations with ADHD symptom trajectories in preschoolers. Additionally, the effect of individual OPEs on symptom trajectories was intensified by vitamin D deficiency.

Organophosphate Esters in Raw Cow Milk and Cow's Drinking Water and Feed from China: Occurrence, Regional Distribution, and Dietary Exposure Assessment.

Organophosphate esters (OPEs) have been widely produced and used, while little is known about their occurrence in the food chain and potential sources. In this study, raw cow milk, cow drinking water, and feed were collected from pastures across China, and OPEs were tested to explore the occurrence and transmission of OPEs in the food chain and to further assess daily OPE intakes for cows and humans via certain food consumption. The median level of ∑OPEs (sum of 15 OPEs) in raw milk was 2140 pg/mL, and tris(1-chloro-2-propyl) phosphate (TCIPP) was the most abundant OPE. Levels of OPEs in water were lower than those in raw milk except for triethyl phosphate (TEP), while levels of most OPEs in feed were significantly higher than those in raw milk (adjusted by dry weight). The estimated dietary intake of OPEs via feed for cows was 2530 ng/kg bw/day, which was much higher than that via water (742 ng/kg bw/day), indicating that feed was a more critical exposure source. For liquid milk consumers, the high-exposure (95th) estimated daily intakes (EDIs) of ∑15OPE were 20 and 7.11 ng/kg bw/day for 3-17 years and adults, respectively, and it is obvious that cows had much heavier OPE intake. Finally, the calculated hazard indexes (HIs) suggested that the intake of OPEs via cow milk consumption would not pose significant health risks to the Chinese population.

Organophosphorus flame retardants in the Qiantang River of China: occurrence, source and ecological risk assessment.

In recent years, the prevalence and danger of organophosphorus flame retardants (OPFRs) have drawn attention from all around the world. This study examined twenty-five OPFRs observed in water and sediment samples from the Qiantang River in eastern China, as well as their occurrence, spatial distribution, possible origins, and ecological hazards. All the 25 OPFRs were detected in water and sediment samples. The levels of Σ25OPFRs in water and sediment were 35.5-192 ng/L and 8.84-48.5 ng/g dw, respectively. Chlorinated OPFRs were the main contributions in water, whereas alkyl-OPFRs were the most common congeners found in sediment. Spatial analysis revealed that sample locations in neighboring cities had somewhat higher water concentrations of OPFRs. Slowing down the river current and making the reservoir the main sink of OPFRs, the dam can prevent OPFRs from moving via the Qiantang River. Positive matrix factorization indicated that plasticizer in polyvinyl chloride, polyester resins, and polyurethane foam made the greatest contributions in water, whereas polyurethane foam and textile were the predominant source in sediment. Analysis of sediment-water exchange of OPFRs showed that twelve OPFRs in sediments can re-enter into the water body. The risk quotients showed the ecological risk was low to medium, but trixylyl phosphate exposures posed high ecological risk to aquatic organisms.