Organophosphate Esters Concentrations Research Articles

Fate of organophosphate esters from the Northwestern Pacific to the Southern Ocean: Occurrence, distribution, and fugacity model simulation

Eleven organophosphate esters (OPEs) in the air and seawater were investigated from the northwestern Pacific Ocean to the Southern Ocean during the 2018 Chinese 34th Antarctic Scientific Expedition. The concentration of total OPEs ranged from 164.82 to 3501.79 pg/m3 in air and from 4.54 to 70.09 ng/L in seawater. Two halogenated OPEs, tri(chloropropyl) phosphate (TCPP) and tri (2-chloroethyl) phosphate (TCEP), were generally more abundant than the non-halogenated OPEs. A level III fugacity model was developed to simulate the transfer and fate of seven OPEs in the air and seawater regions of the central Ross Sea. The model results indicate that OPEs are transferred from the air to the seawater in the central Ross Sea in summer, during which the Ross Sea acts as a final OPE sink. Dry and wet deposition dominated the processes involving OPE transfer to seawater. The OPE degradation process was also found to be more pervasive in the atmosphere than in the seawater region. These findings highlights the importance of long-range transport of OPEs and their air–seawater interface behavior in the Antarctic.

Determination of polyoxymethylene-water partition coefficients for diverse organophosphate esters (OPEs) and prediction of the free-dissolved OPEs in OPE-contaminated soil

Increasing attention on the estimation of bioavailability of organophosphate esters (OPEs) in soil or sediment has urged the development of techniques to measure soil−/sediment-associated porewater concentrations of OPEs. In this study, we investigated the sorption dynamics of 8 OPEs to polyoxymethylene (POM) spanning one order of magnitude of aqueous OPE concentrations and proposed POM-water partitioning coefficients (Kpom/w) for OPEs. The results showed that the Kpom/w values were mainly affected by the hydrophobicity of OPEs. OPEs with high solubility preferentially partitioned into the aqueous phase indicated by the low log Kpom/w values; while lipophilic OPEs were observed to be taken up by POM. The concentration of lipophilic OPEs in the aqueous phase had a strong impact on their sorption dynamics on POM, with higher aqueous concentrations accelerating the sorption dynamics and shortening the time for equilibration. We proposed that the required time to reach equilibration for targeted OPEs should be 42 d. The proposed equilibration time and Kpom/w values were further validated by applying POM to soil artificially contaminated with OPEs to measure OPEs soil-water partitioning coefficients (Ks). The variations of Ks among soil types implied the need to elucidate the effects of soil properties and chemical properties of OPEs on their distribution between soil and water in the future.

Organophosphate esters in source, finished, and tap water in Wuhan, China

As important plasticizers and flame retardants, organophosphate esters (OPEs) have resulted in the contamination of various water bodies worldwide. However, their removal efficiency by different tap water treatment processes and seasonal variations in drinking water in China are not fully understood. In this study, source (n = 20), finished (n = 20), and tap (n = 165) water samples sourced from the Hanshui and the Yangtze River were collected in Wuhan, central China from July 2018 to April 2019 to measure selected OPE concentrations. The OPE concentrations in the source water samples ranged 10.5–113 ng/L (median: 64.6 ng/L). Most OPEs were not removed effectively by conventional tap water treatment, except for tris(2-chloroisopropyl) phosphate (TCIPP). Interestingly, trimethyl phosphate content was found to increase significantly during chlorination for water sourced from the Yangtze River. The OPEs could be removed more effectively by advanced processes with ozone and activated carbon (maximum removal efficiency of specific OPE was 91.0%). Similar cumulative OPE concentrations (ΣOPEs) values were found for the finished water and tap water in February rather than in July. The ΣOPEs (ng/L) in the tap water ranged 21.2–365 (median: 45.1). TCIPP and tris(2-chloroethyl) phosphate were the predominant OPEs in the studied water samples. Significant seasonal variations in the OPE residues in tap water were observed in this study. OPE exposure via tap water ingestion posed low health risks to human beings. This is the first study reporting the removal efficiencies of OPEs and the seasonal variations in tap water from central China. This is also the first study documenting the occurrence of cresyl diphenyl phosphate and 2,2-bis(chloromethyl)propane-1,3-diyltetrakis (2-chloroethyl) bisphosphate in tap water. Based on currently available data, the contamination of tap water by OPEs is in the order of Korea > eastern China > central China > New York State, the United States. Additionally, this study provides a method involving a trap column, to eliminate OPE contamination from the liquid chromatography system.

A preliminary report on the association between maternal serum organophosphate ester concentrations and gestational diabetes mellitus

Organophosphate esters (OPEs) are extensively manufactured and used in China. Whether exposure to OPEs during pregnancy increases the risk of gestational diabetes mellitus (GDM) is unknown. Between 2011 and 2012, a case-control study including 130 and 67 women with and without GDM, respectively, was conducted in Hangzhou, China. The levels of 10 OPEs in maternal serum samples at delivery were quantified, and the relationships between the OPE concentrations and GDM risk were investigated. The results show that in all participants, tri-n-butyl phosphate (TNBP, median: 2.02 ng/mL) was the most common OPE present in the serum, followed by tri-phenyl phosphate (TPHP, median: 1.74 ng/mL) and tri-iso-butyl phosphate (median: 1.68 ng/mL). With one-unit elevation in the tris (2-chloroethyl) phosphate, TNBP, TPHP, and tris (2-butoxy ethyl) phosphate (TBOEP) concentrations in maternal serum, 1-h glucose levels increased by 0.19 (95% confidence interval (CI): −0.01, 0.29), 0.11 (95% CI: −0.18, 0.62), 0.29 (95% CI: 0.12, 0.58), and 0.20 units (95% CI: 0.01, 0.44), respectively. In addition, a unit increase in TBOEP levels in maternal serum was associated with an increase of 0.26 units (95% CI: 0.09, 0.61) in 2-h glucose levels. After adjusting for covariate factors, serum TNBP (odds ratio (OR) = 2.07; 95% CI: 1.27, 3.41), TBOEP (OR = 2.63; 95% CI: 1.68, 4.11), and TPHP (OR = 1.03; 95% CI: 1.05, 1.51) concentrations were associated with GDM incidence in pregnant women. Overall, TNBP, TBOEP, and TPHP exposure during pregnancy is associated with GDM risk and increased glucose levels.

Gestational exposure to organophosphate esters and adiposity measures of children up to 6 years: Effect modification by breastfeeding

Organophosphate esters (OPEs) are synthetic chemicals used in various commercial products. Accumulating evidence has shown that they may act as metabolic disruptors. However, no study has investigated the long-term effects of gestational OPEs exposure on childhood adiposity. Breast milk represents the optimal nutritional form of feeding for infants and may protect against the adverse effects of gestational OPEs exposure on offspring development. Using data from the Shanghai-Minhang birth cohort study, we investigated the associations of gestational OPEs exposure with adiposity measures in children up to 6 years of age, and whether breastfeeding could modify these associations. A total of 733 mother-child pairs with available data on OPE concentrations and child anthropometry were included. Eight OPE metabolites were assessed in maternal urine samples collected at 12-16 weeks of pregnancy. Information on children's weight, height, arm circumference, and waist circumference was collected at birth and 0.5, 1, 4, and 6 years of age. Weight-for-age and body mass index-for-age z scores were calculated. The duration of children's breastfeeding was categorized as ≤4 months or >4 months. The generalized estimate equation and Bayesian Kernel Machine Regression models were used to examine the associations of OPEs exposure with children's adiposity measures. Selected OPEs exposure was associated with higher children's adiposity measures. Particularly, we found stronger associations of bis(1-chloro-2-propyl) phosphate (BCIPP), bis(2-chloroethyl) phosphate (BCEP), bis(1,3-dichloro-2-propyl) phosphate (BDCPP), and di-o-cresyl phosphate and di-p-cresyl phosphate (DCP) with higher adiposity measures in children breastfed for ≤4 months, while little evidence of associations was found among those breastfed for >4 months. Our study suggested that gestational OPEs exposure could alter children's adiposity measures, but the potential effects were attenuated if children were breastfed for >4 months.

Spatiotemporal variations and the ecological risks of organophosphate esters in Laizhou Bay waters between 2019 and 2021: Implying the impacts of the COVID-19 pandemic

Organophosphate esters (OPEs) are a group of synthetic chemicals used in numerous consumer products such as plastics and furniture. The Coronavirus Disease 2019 (COVID-19) pandemic significantly slowed anthropogenic activities and reduced the emissions of pollutants. Meanwhile, the mismanagement of large quantities of disposable plastic facemasks intensified the problems of plastic pollution and leachable pollutants in coastal waters. In this study, the joint effects of the COVID-19 outbreak on the occurrence of 12 targeted OPEs in the waters of Laizhou Bay (LZB) were investigated. The results showed that the median total OPE concentrations were 725, 363, and 109 ng L−1 in the sewage treatment plant effluent, river water, and bay water in 2021, decreased significantly (p < 0.05) by 67%, 68%, and 70%, respectively, compared with those before the COVID-19 outbreak. The release potential of targeted OPEs from disposable surgical masks in the LZB area was ∼0.24 kg yr−1, which was insufficient to increase the OPE concentration in the LZB waters. The concentrations of most individual OPEs significantly decreased in LZB waters from 2019 to 2021, except for TBOEP and TNBP. Spatially, a lower concentration of OPEs was found in the Yellow River estuary area in 2021 compared with that before the COVID-19 pandemic due to the high content of suspended particulate matter in the YR. A higher total OPE concentration was observed along the northeastern coast of LZB, mainly owing to the construction of an artificial island since 2020. The ecological risks of the OPE mixture in LZB waters were lower than those before the COVID-19 outbreak. However, TCEP, TNBP, and BDP should receive continuous attention because of their potential ecological risks to aquatic organisms.

Pollution profiles, influencing factors, and source apportionment of target and suspect organophosphate esters in ambient air: A case study in a typical city of Northern China.

Organophosphate esters (OPEs) are attracting attention because they pose risks to biota, including humans. Little research has been performed into the environmental fates of OPEs in the atmosphere. Here, target/suspect OPEs were determined in 122 atmosphere samples (gas phase (n=31), PM2.5 (n=30), PM10 (n=30), and total suspended particles (n=31)) from a city in Northern China. Pollution profiles were established, influencing factors identified, and sources apportioned. We found 12 target OPEs and 29 suspect OPEs. The target and suspect OPE concentrations in the ambient air samples were 2.2-172.5 and 0.7-53.9ng/m3, respectively. Tris(chloroethyl) phosphate, tris(1-chloro-2-propyl) phosphate, and tris(2,4-di-t-butylphenyl) phosphate were the dominant OPEs in all samples. The OPEs were not in equilibrium, indicated by a multi-parameter linear free energy relationship model. The air quality index and OPE concentrations significantly correlated, indicating that OPE pollution is often more serious during weather with worse air quality. The target and suspect screening strategy and a positive matrix factorization model allowed OPE sources to be apportioned, improving our understanding of OPE sources. The four dominant sources were (1) construction, (2) indoor emissions, (3) the plastic industry and industrial activities, and (4) traffic emissions, textiles, and foam products.

Occurrence, spatiotemporal variation, and ecological risks of organophosphate esters in the water and sediment of the middle and lower streams of the Yellow River and its important tributaries

Research on the environmental occurrence and behavior of organophosphate esters (OPEs) is very imperative. In this study, 12 targeted OPEs in the water and sediment samples collected from the middle and lower streams of the Yellow River (YR) and its tributaries during the dry, normal, and wet season were analyzed, to reveal their concentration, spatiotemporal variations, and ecological risks. The results indicated that the total concentration of OPEs (ΣOPE) ranged from 97.66 to 2433.30ng/L in water, and from 47.33 to 234.08ng/g in sediment. Tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl)phosphate (TCIPP), and triethyl phosphate (TEP) were the most abundant OPEs in the surface water and sediment. The OPEs levels in river water were ranked as the order of dry &gt;normal &gt;wet season. The ΣOPE concentrations in water and sediment were relatively high in the central and lower sections of the YR. The resorcinol-bis(diphenyl)phosphate (RDP) effectively transferred from the overlying water to the sediment. TCEP and RDP posed relatively higher ecological risk than other OPEs. Municipal and chemical industrial discharge might be sources of OPEs in the middle and lower streams of the YR.

Presence, source attribution, and human exposure to organophosphate esters in indoor dust from various microenvironments in Nigeria

Very few studies have reported the presence of the organophosphate esters (OPEs) in African indoor microenvironments. We therefore document here, the concentrations, profiles, and human exposure to eight organophosphate esters (OPEs) for the first time in indoor dust from various microenvironments in Nigeria, specifically: cars/buses (n = 10), homes (n = 20), offices (n = 20), and medical centres (n = 14). The concentrations of OPEs in these indoor dust samples were among the lowest reported internationally. Concentrations of ∑8OPEs varied substantially between individual samples and the predominant OPEs were: tris(2-butoxyethyl) phosphate (TBOEP) (detection frequency (DF) = 90–100%), tris(1-chloro-2-propyl) phosphate (TCIPP) (DF = 100%), and 2-ethylhexyl-diphenyl phosphate (EHDPP) (DF = 100%). There were no significant differences (P˃0.05) between ∑8OPEs concentrations in dust samples from cars/buses (average = 295 ng/g), offices (231 ng/g), homes (277 ng/g), and medical centres (127 ng/g). Concentrations of chlorinated OPEs: tris(2-chloroethyl) phosphate (TCEP), TCIPP, and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) were significantly correlated with those of triphenyl phosphate (TPhP), EHDPP, and TBOEP. Estimated daily intakes (EDI) of target OPEs via indoor dust ingestion and dermal absorption were lower than the corresponding reference dose (RfD) values, indicating that exposure to the studied OPEs in the indoor environment does not pose a significant health risk for the general population in Nigeria, even under a high-end exposure scenario.

Concentrations of organophosphate esters in drinking water from the United Kingdom: Implications for human exposure

Data on the presence of organophosphate esters (OPEs) in drinking water and its significance as a pathway of exposure are limited. In this study, we measure for the first time, concentrations of eight OPEs in 50 UK drinking water samples. Arithmetic mean concentrations of ∑8OPEs were: 6.4 and 11 ng/L in bottled (n = 25) and tap water samples (n = 25), respectively. Concentrations of ∑8OPEs in tap water (mean: 11 ng/L) exceed significantly those in bottled water (mean: 6.4 ng/L) (p ˂ 0.01). Moreover, UK tap water is more contaminated with chlorinated, aryl-, and alkyl-OPEs than bottled water. The predominant OPEs detected were: tris (butoxyethyl) phosphate (TBOEP), tris (2-chloroethyl) phosphate (TCEP), and tris(2-chloroisopropyl) phosphate (TCIPP) with arithmetic mean concentrations in the two water sample types ranging between (3.5–3.8 ng/L), (0.60–3.0 ng/L), and (1.02–2.9 ng/L), respectively. Estimated daily intakes (EDIs) (mean and high-end exposure) via drinking water for different sectors of the UK population were: infants (0.93 and 6.4 ng/kg bw/day) ˃ toddlers (0.46 and 3.1 ng/kg bw/day) ˃ children (0.35 and 2.3 ng/kg bw/day) ˃ adults (0.28 and 2.1 ng/kg bw/day). Based on these data, exposure to Σ8OPEs via drinking water is much lower than via: food, indoor dust ingestion, inhalation, and dermal uptake for adults and toddlers. Reassuringly, our EDIs were lower than relevant reference dose (RfD) values. However, combining our drinking water ingestion data with exposure via other pathways revealed overall exposure to 2-ethylhexyl diphenyl phosphate (EHDPP) and TCIPP to approach health-based limit values for UK toddlers under a high-end exposure scenario.

Effects of biochar on the degradation of organophosphate esters in sewage sludge aerobic composting.

In this study, the impact of biochar on the degradation of organophosphate esters (OPEs) during the aerobic composting of sewage sludge was investigated. Three treatments were conducted with different percentages of biochar in the compost, including 5 %, 10 %, and 20 %. The treatment with 10 % of biochar showed the longest thermophilic phase compared to that of 5 % and 20 % of biochar, which greatly promoted the decomposition of organic matter. In addition, the degradation rate of the hard-to-degrade chlorinated-OPEs was significantly increased by 10 % biochar, reaching to 57.2 %. Correspondingly, approximately 43.6 % of the total concentration of OPEs (Σ6OPEs) was eliminated in the presence of 10 % of biochar, which was higher than the treatments with 5 % and 20 % of biochar. Biochar significantly influenced the microbial community structure of compost, but the previously reported organophosphorus-degrading bacteria did not play a major role in the degradation of OPEs. The redox ability of the increased oxygen-containing functional groups such as quinone on the surface of biochar and the biochar-mediated electron transfer ability may play an essential role in the degradation of OPEs during the composting process.

Distribution and pollution characteristics of organophosphate esters: reflected by tree rings of arbor species.

Organophosphate esters (OPEs) are emerging pollutants. Currently, research on OPEs in tree rings is still limited. In this study, tree rings of five arbor species from Sichuan Province, China, were sampled to study the occurrence and distribution of six OPEs, which were quantitatively analyzed by gas chromatography-mass spectrometry (GC-MS). The total concentrations of OPEs in all samples ranged from 189.79 (Fir species) to 341.23ng/g (Toona sinensis), with average concentration of 284.77 ± 46.66ng/g. So, arbor could be used as good passive samplers for OPEs. The levels of OPEs among five arbor species showed no significant difference (p = 0.668 > 0.05), suggesting that the pollution status of OPEs in a region or country could be roughly assessed by any arbor tree species. In this study area, tris(2-butoxyethyl) phosphate (TBEP) was the dominant OPEs followed by tri(2-chloroethyl) phosphate (TCEP). Tris(2-ethylhexyl) phosphate (TEHP) and tri-n-butyl phosphate (TnBP) showed relatively stable concentrations in each arbor species, while the other four OPEs including TBEP, triphenyl phosphate (TPhP), tri(chloropropyl) phosphate (TCPP) and TCEP had significantly different concentrations. Interestingly, the absorption and accumulation of OPEs by tree rings of arbor species were quite different from that of inorganic elements reported by other studies.

Uptake, translocation, bioaccumulation, and bioavailability of organophosphate esters in rice paddy and maize fields

Rice and maize are two main crops with different growth habits in Northeast China. To investigate the uptake, translocation, and accumulation of organophosphate esters (OPEs) in those two crops, we measured the OPE concentrations in their agricultural soil-crop systems during different growing seasons. OPE concentrations were higher in paddy (221 ± 62.0 ng/g) than in maize (149 ± 31.6 ng/g) soil, with higher OPE levels in the rhizosphere than in bulk soil for rice, and the opposite in maize. Two-step extractions were used to obtain the labile and stable adsorption components of OPEs. The stable-adsorbed OPEs were activated to be more bioavailable by root exudates as rice grew. OPEs in rice increased linearly with the growing period. The uptake and translocation processes of OPEs by crops were not well-explained by logKow alone, indicating other processes such as growth dilution are significant for understanding OPE levels in plant. The translocation factors of OPEs from nutritive to reproductive organs indicated that OPEs in rice seeds may follow the translocation from root to leaf and then transfer to grains. Two genera, Sphingomonas and Geobacter, associated with degradation of organophosphorus compounds were enriched in rhizosphere soils, indicating enhanced OPE degradation.

Organophosphate esters in Chinese rice: Occurrence, distribution, and human exposure risks

Dietary intake is a crucial pathway of organophosphate esters (OPEs) exposure for human. However, information about the exposure risk of OPEs via rice consumption is still largely unknown. In the present study, a total of 234 rice samples from 25 provinces or city of China were collected and the concentrations of 24 OPEs were determined. Sixteen OPEs were detected in these rice samples and each rice sample was contaminated with at least 5 OPEs, indicating a ubiquitous occurrence of OPEs in Chinese rice. Moreover, the concentrations of Σ16 OPEs ranged from 1.46 to 552.65 μg/kg dry weight (dw), with a mean value of 64.74 μg/kg dw. For the composition profile of OPEs, three Cl-OPEs, including tris(2-chloroethyl) phosphate (TCEP), tri(2-chloroisopropyl) phosphate (TCIPP) and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), accounted for the highest proportion of Σ16 OPEs. For the spatial distribution of OPEs, although obvious spatial variations were observed among the 25 provinces or city, no obvious variations were found among the six rice-cultivating regions of China. Additionally, estimated dietary intakes (EDI) values of the 16 OPEs for adults and children were 1105.24 and 1399.13 ng/kg bw/day, respectively, under the high intake scenario. The hazard indexes of the 10 OPEs were 0.108 and 0.137 for adults and children, respectively. The risk assessment results indicated that Chinese adults and children did not suffer significant adverse effects from OPEs via rice intake.

Bioaccumulation and emission of organophosphate esters in plants affecting the atmosphere's phosphorus cycle

The imbalance of atmospheric, terrestrial and aquatic phosphorus budgets remains a research conundrum and global concern. In this work, the uptake, distribution, bioaccumulation and emission of organophosphate esters (OPEs) by clove trees (Syzygium aromaticum), lemon trees (Citrus limon) and cape jasmine trees (Gardenia jasminoides var. fortuniana) was investigated as conduits for phosphorus transfer or sinks and sources. The objective was to assess the role OPEs in soils play as atmospheric phosphorus sources through plant bioaccumulation and emission. Results demonstrated OPEs in experimental soil plots ranging from 0.01 to 81.0 ng g−1 dry weight, were absorbed and transported through plants to the atmosphere. The total emission of OPEs varied greatly from 0.2 to 588.9 pg g−1 L−1 h−1, with a mean of 47.6 pg g−1 L−1 h−1. There was a negative linear relationship between the concentrations of total phosphorus and four OPEs, tri-iso-butyl phosphate, tri-n-butyl phosphate, tris (2-chloroisopropyl) phosphate and tripentyl phosphate. Trimethyl phosphate levels were positively correlated with total nitrogen, and the concentrations of tri-iso-butyl phosphate, tri-n-butyl phosphate, tris (2-chloroisopropyl) phosphate and tripentyl phosphate decreased along with available potassium in leaves after 72 h. There was a significantly positive linear relationship between higher emission concentrations of OPEs and the emission factor of OPEs concentration (F = 4.2, P = 0.002), with lower emissions of OPEs and the bioaccumulation of OPEs in leaves (F = 4.8, P = 0.004). OPEs releases to the atmosphere were enriched in aerosols, and participate in atmospheric chemical reactions like photolysis, thereby affecting the phosphorus balance and cycling in the atmosphere.

Occurrence, bioaccumulation and trophic transfer of organophosphate esters in marine food webs: Evidence from three bays in Bohai Sea, China

Due to the widespread use of organophosphate esters (OPEs), the occurrence and trophic transfer of OPEs have attracted attentions in ecosystems. However, as the final sink for these chemicals, the bioaccumulations and trophodynamics of OPEs in marine ecosystems are still not clear. In this study, seawater, sediment and marine organisms collected from Bohai Bay (BHB), Laizhou Bay (LZB), and Liaodong Bay (LDB) in Bohai Sea (BS), China were analyzed to investigate the occurrence, bioaccumulation and trophic transfer of typical OPEs. Total concentration of OPEs (∑9 OPEs) in surface water in LZB (255.8 ± 36.44 ng/L) and BHB (209.6 ± 35.61 ng/L) was higher than that in LDB (170.0 ± 63.73 ng/L). Marine organisms in LZB accumulated the highest concentrations of OPEs among the 3 bays (∑10OPEs, 70.56 ± 61.36 ng/g ww). Average bioaccumulation factor (BAF) of OPEs in marine organism in BHB, LZB, and LDB was ranged from −2.48 to 0.16, from −2.96 to 1.78, and from −2.59 to 0.59. We also found that trophic magnification factors (TMF) are generally <1, which suggested trophic dilutions of OPEs in BS, China. Nevertheless, the relatively high OPEs levels in BS still may bring potential risks to ecosystem and human health.

Uptake, translocation and subcellular distribution of organophosphate esters in rice by co-exposure to organophosphate esters and copper oxide nanoparticle

This study investigated the influence of copper oxide nanoparticles (CuONPs) and Cu2+ on the uptake, translocation and subcellular distribution of organophosphate esters (OPEs) in rice seedlings using hydroponic experiments. The OPE concentrations in roots and shoots under the OPEs+CuONPs treatment were significantly lower than those with the OPEs+Cu2+ (low level) or OPEs-only treatments, indicating that CuONPs can hinder the uptake of OPEs by root via competitive adsorption under short-term exposure. The plasma membrane permeability and antioxidant enzyme activity implied that CuONPs had a negligible impact on rice seedlings and could even reduce the toxicity of OPEs to rice root. A significant negative correlation between translocation factor and octanol-water partition coefficient was observed for the three treatments, implying an important role of hydrophobicity on the acropetal translocation of OPEs. Relatively hydrophobic OPEs were mainly adsorbed on cell wall, while hydrophilic OPEs were concentrated in cell sap. The subcellular distributions of OPEs in the OPEs+Cu2+ (high level) or OPEs+CuONPs treatments slightly differed from the OPEs-only treatment, indicating that the coexistence of Cu2+ or CuONPs with OPEs can influence the subcellular distribution of OPEs by affecting their adsorption or partitioning processes. Inhibition experiment suggested that root uptake of OPEs is a non-energy-consuming facilitated diffusion mediated by aquaporin channel, which can be slightly changed by the co-exposure of CuONPs. This study improved the understanding of uptake and translocation of OPEs by rice under the co-exposure to CuONPs.

A scalable field study using leaves as a novel passive air sampler to evaluate the potential source of organophosphate esters in street dust

Organophosphate esters (OPEs) are widely used as flame retardants and plasticizers in industrial and commercial products. It is generally believed that OPEs in street dust mainly originate from road traffic and anthropogenic activities. The influence of atmospheric deposition is still unknown. In this study, leaves were employed as a novel passive air sampler to collect particle matters (PM) in 12 cities in the central province of Henan, China. Similar compositional profiles of OPEs were found in street dust and PM samples. The concentrations of individual OPEs in PM were 1–4 times higher than in street dust. Chlorinated OPEs concentration in PM shows a moderate correlation (r2 = 0.538, p < 0.01) with that in street dust. The concentration of alkyl OPEs in PM has a high correlation (r2 = 0.843, p < 0.01) with that in street dust. No significant correlation (r2 = 0.133, p = 0.132) was found on the aryl OPEs concentrations between street dust and PM. Spearman correlation reveals that the emission sources of tricresyl phosphate (TCrP) and triethyl phosphate (TEP) may be different from other OPEs in dust and PM samples. Principle component analysis (PCA) provides an appropriate explanation that tris (2-chloroethyl) phosphate (TCEP), triphenyl phosphate (TPhP), tris (chloropropyl) phosphate (TCPP), tributyl phosphate (TnBP), and TEP in street dust and PM may be emitted from the same sources, suggesting that PM has a significant influence on the occurrence of OPEs in street dust. The estimated dry deposition fluxes of particle-bound OPEs show a significant correlation (R2 = 0.969, p < 0.01) with OPEs concentrations in street dust, revealing that the input of atmospheric deposition could be a major source of OPEs in street dust.

Non-target screening and risk assessment of organophosphate esters (OPEs) in drinking water resource water, surface water, groundwater, and seawater.

By use of an integrated target, suspect, and non-target screening strategy, we investigated occurrence and spatial distribution of organophosphate esters (OPEs) in four types of water (drinking water resource water, surface water, groundwater, and seawater) collected from Jiangsu Province (China) in 2021 (n=111). Eighteen out of 23 target OPEs were detectable at least once in these analyzed samples, and the total concentrations (Σ18OPEs) of OPEs in various water samples exhibited a descending order following as: groundwater (67026ng/L)>surface water (35803ng/L)>drinking water resource water (21055ng/L)>seawater (17820ng/L). The highest concentration detected in groundwater may be ascribed to pollution from surrounding factories. Among the target OPEs, triethyl phosphate (TEP), tris(chloroethyl) phosphate (TCEP), and tris (1-chloro-2-propyl) phosphate (TCIPP) were the most abundant congeners with the average concentrations of 407ng/L, 143ng/L, and 475ng/L, respectively. Besides of 18 target OPEs, we further identified 17 suspect OPEs (3 of them were fully identified by authentic standards) on the basis of in-house suspect screening OPE database, and 2 non-target organophosphates (OPs) on the basis of feature fragments. One of these 2 non-target OPs was fully identified as bis(2-chloroethyl) 2-chloroethylphosphonate (B2CE2CEPP) by matching the retention time and MS/MS data with authentic standard, and the other one was preliminarily identified as 2,4,8,10-tetra-tert-butyl-6-methoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-one (TTBMDBDOPPO). We also observed that B2CE2CEPP shared a similar structure with TCEP, suggesting that they may have similar toxicological characteristics and commercial sources. The ecological and human health risk assessments indicated that all OPEs posed a low or negligible ecological risk to aquatic organisms (algae, crustacean, and fish), and negligible risk to human health except for trimethyl phosphate (TMP) in drinking water resource water.

Associations between organophosphate esters concentrations and markers of liver function in US adolescents aged 12–19 years: A mixture analysis

Liver disease has become a growing health burden, and little is known about the impairment of liver function caused by exposure to organophosphate esters (OPEs) in adolescents aged 12–19 years in the United States. To investigate the relationship between urinary metabolites of OPEs including diphenyl phosphate (DPHP), bis(1,3-dichloro-2-propyl) phosphate (BDCPP), bis(1-chloroethyl) phosphate (BCPP), bis(2-chloroethyl) phosphate (BCEP), and dibutyl phosphate (DBUP) and liver function in US adolescents aged 12–19 years. Liver function tests (LFTs) include aspartate aminotransferase (AST), albumin (ALB), alanine aminotransferase (ALT), alkaline phosphatase (ALP), gamma-glutamyl transferase (GGT), total bilirubin (TBIL), total protein (TP), and AST/ALT. Meanwhile, potential confounding and interaction effects were assessed. The study sample included 592 adolescents aged 12–19 from two consecutive NHANES cycles (2011–2012, 2013–2014). A composite statistical strategy combining traditional linear regression with advanced multi-pollutant models quantile based g-computation (QGC) and eXtreme Gradient Boosting (XGBoost) regression was used to analyze the joint effects of multiple OPEs on liver function indicators, and to describe the interaction between different OPEs in detail. 592 adolescent participants were 15 (14–17) years old, with similar numbers of males and females (304 vs. 288). The analysis results showed that (1) in the linear regression model, individual DPHP, BCEP exposure and ALP changes, BCEP and AST/ALT changes were positively associated. DPHP, BDCPP were negatively associated with TP changes. (2) The combined effects of various OPEs on ALB, ALT, ALP, GGT, TBIL, TP, and AST/ALT were statistically significant. (3) There is no potential interaction between different OPEs. Several OPEs and their combinations are closely related to the 8 LFT indicators. In addition, data suggest that exposure to OPEs in adolescents may be associated with liver damage. Due to limited evidence in the literature and potential limitations of the current study, our findings require more studies to confirm.