Tris(2-chloroisopropyl) Phosphate Research Articles

Serum organophosphate flame retardants and plasticizers in Chinese females of childbearing age: Association with serum reproductive and thyroid hormones

Organophosphate flame retardants (OPFRs) are extensively used as flame retardants and plasticizers, but their endocrine disrupting potentials have raised concerns. However, the impacts of OPFR exposures on reproductive and thyroid hormones in females remains unclear. In this study, serum concentrations of OPFRs were investigated, and levels of reproductive and thyroid hormones, including follicle-stimulating hormone (FSH), luteinizing hormone (LH), estradiol, anti-Müllerian hormone, prolactin (PRL), testosterone (T), and thyroid stimulating hormone, were analyzed in childbearing-age females undergoing in-vitro fertilization treatment from Tianjin, a coastal city in China (n = 319). Tris (2-chloroethyl) phosphate (TCEP) was the predominant OPFR, with a median concentration of 0.33 ng/mL and a detection frequency of 96.6%. In the whole population, tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and tris(2-chloroisopropyl) phosphate (TCIPP) were positively associated with T (p < 0.05), while triethyl phosphate (TEP) was negatively associated with LH (p < 0.05) and LH/FSH (p < 0.01). Particularly, TCIPP was negatively associated with PRL in the younger subgroup (age≤30, p < 0.05). Moreover, TCIPP was negatively associated with diagnostic antral follicle counting (AFC) in the mediation analysis by a dominating direct effect (p < 0.01). In conclusion, serum levels of OPFRs were significantly associated with reproductive and thyroid hormone levels and a risk of decreased ovarian reserve in childbearing-age females, with age and body mass index being significant influencing factors.

Concentrations, spatial and seasonal variations of Organophosphate esters in UK freshwater Sediment

This study provides the first report of organophosphate esters (OPEs) in UK freshwater sediments with a focus on the possible impact of factors such as spatial/seasonal variation and wastewater treatment plants (WWTPs) on the measured OPE concentrations in surficial sediment from 3 UK rivers and 1 canal. Detection frequencies of: (tris (chloroethyl) phosphate (TCEP), tris (2-chloroisopropyl) phosphate (TClPP), tris (1,3-dichloro-2 propyl) phosphate (TDClPP), tri-n-butyl phosphate (TNBP), tris (2-butoxyethyl) phosphate (TBOEP), 2-ethylhexyl diphenyl phosphate (EHDPP), tris (phenyl) phosphate (TPHP), and tri-m-tolyl phosphate (TmTP)) ranged from 58% to 100%. The concentration of Σ8OPEs ranged from 107 ng g−1 (dry weight - dw) (in the Worcester-Birmingham canal) to 52 ng g−1 (dw) in both Rivers Severn and Sowe). The highest ∑8OPE concentration for all study locations was recorded during the autumn months (September, October, and November), and concentrations of ∑8OPEs in sediment samples from the River Severn, River Tame, and River Sowe all varied inversely with the river level and flow rate. The average concentrations of each target OPE in each study location were lower than those reported elsewhere but fell broadly within the range of concentrations reported from other countries. The potential risk posed by target OPEs in all study locations was found to be low, except for a moderate risk identified for EHDPP in the Worcester - Birmingham canal.

Effects of TCPP and TCEP exposure on human corneal epithelial cells: Oxidative damage, cell cycle arrest, and pyroptosis

Tris(2-chloroisopropyl) phosphate (TCPP) and Tris(2-chloroethyl) phosphate (TCEP) are the widely used organophosphorus flame retardants indoors and easily accessible to the eyes as the common adhesive components of dust and particle matter, however, hardly any evidence has demonstrated their corneal toxicity. In this study, the adverse effects of TCPP, TCEP, and TCPP + TCEP exposure on human corneal epithelial cells (HCECs) were investigated. The cell viability and morphology, intracellular reactive oxygen species (ROS), cell cycle, and the expressions of cell cycle and pyroptosis-related genes were assessed to explain the underlying mechanisms. Compared to individual exposure, co-exposure to TCPP20+TCEP20 showed higher cytotoxicity with a sharp decrease of >30% in viability and more serious oxidative damage by increasing ROS production to 110.92% compared to the control group. Furthermore, the cell cycle arrested at the S phase (36.20%) was observed after combined treatment, evidenced by the upregulation of cyclin D1, CDK2, CDK4, CDK6, p21, and p27. Interestingly, pyroptosis-related genes GSDMD, Caspase-1, NLRP3, IL-1β, IL-18, NLRP1, and NLRC4 expressions were promoted with cell swelling and glowing morphology. Oxidative stress and cell cycle arrest probably acted as a key role in TCPP20+TCEP20-induced cytotoxicity and pyroptosis in HCECs. Our results suggested that TCPP20+TCEP20 co-exposure induced severer corneal damage, further illustrating its significance in estimating indoor health hazards to humans.

Human exposure to organophosphate esters in water and packed beverages

Drinks are an essential part of human diet, which makes them a source of human exposure to plasticizers such as organophosphate esters (OPEs). The current study provides new information about sixteen OPE levels in 75 different samples (tap water, packed water, cola drinks, juice, wine and hot drinks). Tap water mean levels (40.9 ng/L) were statistically higher than packed water mean levels (4.82 ng/L), mainly due to the contribution of tris(2-chloroisopropyl) phosphate (TCIPP) and tris(2-butoxyethyl) phosphate (TBOEP) that may come from PVC water pipes. Over 90% of samples presented at least one OPE, where regular cola drinks had the highest mean concentrations (2876 ng/L). There was a significantly higher presence of OPEs in added sugar beverages than sugar free drinks, especially for 2-ethylhexyl diphenyl phosphate (EHDPP), which might be related not only to packaging materials but to the added sugar content. Estimated daily intakes (EDIs) in normal and high-exposure scenarios were 2.52 ng/kg bw/day and 7.43 ng/kg bw/day, respectively. Human risk associated with beverages ingestion showed regular cola drinks, juice and tap water as the groups with the highest hazard quotients (HQs). Although OPE exposure was below to safety limits, it should be noted that EHDPP values for regular cola group must be cause of concern, and other routes of exposure such as food ingestion or air inhalation should be also considered.

Organophosphate flame retardants and plastics in soil from an abandoned e-waste recycling site: significant ecological risks derived from plastic debris

The distribution of 9 organophosphate flame retardants (OPFRs) was determined in plastic debris and soil samples separated from twenty soil samples collected from an abandoned e-waste recycling area. Tris-(chloroisopropyl) phosphate (TCPP) and triphenyl phosphate (TPhP) were the main chemicals, with median concentrations of 124-1930ng/g and 143-1170ng/g in soil, and 712-803ng/g and 600-953ng/g in plastics, respectively. Plastics contributed less than 10% of the total OPFR mass in bulk soil samples. No apparent OPFR distribution trend was observed in different sizes of plastics and soil. The ecological risks of plastics and OPFRs were estimated by the species sensitivity distributions (SSDs) method, which resulted in lower predicted no-effect concentrations (PNECs) of TPhP and decabromodiphenyl ether 209 (BDE 209) than the standard values derived from limited toxicity tests. In addition, the PNEC of polyethene (PE) was lower than the plastic concentration in the soil of a previous study. TPhP and BDE 209 had high ecological risks with risk quotients (RQs) > 0.1, and RQ of TPhP was among the highest values in literature.

Exposure to Organophosphate Ester Flame Retardants in the Occupational Environment

Rationale: Flame retardants (FR) are commonly used in consumer products, electronics, and safety equipment. Organophosphate esters (OPEs) are a sub-class of FRs and are widely used in various industries. Occupational risk of exposure is expected for many workers in various industries. However, the evidence of occupational exposure to OPE FRs is limited.&#x0D; Objectives: This study aimed to summarize evidence of occupational exposure to OPE FRs.&#x0D; Methods: A scoping review was conducted using Scopus (April-2022) and Google Scholar (January-2022). Search terms included ""occupational"", ""exposure"", ""flame retardants"", ""organophosphate"" and similar. Studies with quantitative measures of OPE exposure in workplaces were retained. Information on sample types, exposure levels, routes of exposure, and contextual information was extracted and summarized.&#x0D; Results: To-date, 15 studies have met the inclusion criteria. Groups most frequently assessed for OPE exposure include workers in e-waste recycling facilities and constructions. Published studies have described inhalation exposure, incidental ingestion, and dermal absorption routes. Sampling methods included active air sampling, passive air sampling, biological sampling, and dermal sampling. Triphenyl phosphate (TPhP), Tris(2-chloroisopropyl) phosphate (TCIPP), and Tris(2-chloroethyl) phosphate (TCEP) were the three most common sampled OPEs.&#x0D; Conclusions: There is evidence of OPE exposure in a limited number of industries and occupations at levels higher than the general population. The adverse health effects associated with OPE exposure included reproductive complications, endocrine disruption, and potential carcinogenicity. More research is needed to understand the prevalence and level of occupational exposure to OPE FRs and the potential work-related health impacts.

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.

Efficient biodegradation of tris-(2-chloroisopropyl) phosphate by a novel strain Amycolatopsis sp. FT-1: Process optimization, mechanism studies and toxicity changes.

In this study, a newly isolated strain Amycolatopsis sp. FT-1 was confirmed to be an efficient tris-(2-chloroisopropyl) phosphate (TCPP) degrader. The maximum degradation efficiency of 100 % was achieved when glucose concentration was 6.0g/L, TCPP concentration was 1.1mg/L, pH was 6.3 and temperature was 35°C. Proteome analysis indicated that TCPP was transformed into diester, monoester and ketone product through hydrolysis by phosphoesterase and oxidation mediated by proteins involved in bio-Fenton reaction. The increased expression of proteins serving as organic hydroperoxides scavenger and two subunits of xanthine dehydrogenase enabled Amycolatopsis sp. FT-1 to defend against TCPP-induced oxidative damage. Meanwhile, proteins involved in the resistance to proteotoxic stress were found to be up-regulated, including Hsp70 protein, ATP-dependent Clp protease proteolytic subunit, elongation factor G and trehalose synthesis-related enzymes. The overexpression of TetR/AcrR family transcriptional regulator and multidrug efflux transporter also benefited the survival of Amycolatopsis sp. FT-1 under TCPP stress. Luminescent bacteria test showed that biotoxicity of TCPP was remarkably decreased after biodegradation by Amycolatopsis sp. FT-1. To the best of our knowledge, this is the first study to report the biotransformation of TCPP by pure strain and to offer important insights into the proteomic mechanisms of TCPP microbial degradation.

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.

Typical organic contaminants in hair of adult residents between inland and coastal capital cities in China: Differences in levels and composition profiles, and potential impact factors

The growing of urbanization, industrialization, and agricultural production have resulted in the increasing contamination of typical organic contaminants (OCs) in China. However, data on differences in exposure characteristics of typical OCs between the coastal and inland cities among residents in China are limited. In this study, hair samples were collected from adult residents in 10 and 17 provincial capital cities in coastal and inland China, respectively, to investigate the differences in the levels and composition profiles of typical OCs. The potential factors impacting the human exposure to OCs were also examined based on the relationship among the hair OC levels and the population characteristics and statistical indicators. The median concentrations of dichlorodiphenyltrichloroethane's (DDTs), polybrominated diphenyl ethers (PBDEs), and organophosphorus flame retardants (PFRs) in hair of coastal urban residents were 3.64, 5.58, and 268 ng/g, respectively, while their concentrations in samples from inland urban residents were 1.84, 3.85, and 202 ng/g, respectively. Coastal residents showed significantly higher hair OC concentrations than inland residents (p < 0.05). BDE209 and p,p′-DDE were the predominant chemicals for PBDEs and DDTs, respectively, in both coastal and inland cities. Tris(2-chloroisopropyl) phosphate (TCIPP) was the dominant PFR in coastal residents' hair, while triphenyl phosphate (TPHP) was the major PFR in inland residents' hair, possibly owing to the different usages of the PFRs. Significant gender differences were observed in the levels and composition profiles of OCs (p < 0.05). The levels of p,p′-DDE and TCIPP were significantly related to the gross domestic product (GDP), gross secondary industry product, and the per capita consumption of aquatic products (p < 0.05). This study provides scientific data for evaluating human exposure to OCs in urban residents at a large scale and its associations with statistical indicators including urbanization, industrialization, agricultural production, and diet in China.

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.

Organophosphate esters in indoor and outdoor air in Birmingham, UK: implications for human exposure

We report concentrations of organophosphate esters (OPEs) in air from living rooms, bedrooms, and offices in Birmingham, UK. To place concentrations in these commonly frequented indoor microenvironments in context, we also measured the same OPEs in air samples collected from an outdoor location on the University of Birmingham campus. Concentrations of tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), and tri-n-butyl phosphate (TnBP) in indoor air significantly exceeded (P &gt; 0.05) those in outdoor air. In contrast, concentrations of tris(1,3-dichloroisopropyl) phosphate (TDCIPP), triphenyl phosphate (TPhP), and 2-ethylhexyl diphenyl phosphate (EHDPP) in indoor and outdoor air were statistically indistinguishable (P &lt; 0.05). Comparison of estimates of human exposure via inhalation derived from our data with previous estimates of exposure via dust ingestion, diet, drinking water, and dermal contact with furniture reveals that inhalation is the most important contributor to aggregate UK adult exposure to TCIPP (85% exposure) and TCEP (67% exposure). While average aggregate exposures of UK adults were well below health-based reference dose values, continued evaluation of human exposure is recommended as high-end exposures of some individuals (e.g., those inhabiting microenvironments containing concentrations of TCIPP at the high end of the range reported here) likely exceed substantially average exposures.

Organophosphate esters (OPEs) in a coral reef food web of the Xisha Islands, South China Sea: Occurrence, trophodynamic, and exposure risk

Despite organophosphate esters (OPEs) are widely prevalent in the environment, however, limited information is available regarding their occurrence, trophodynamics, and exposure risks in coral reef ecosystems. In this study, 11 OPEs were investigated in a tropical marine food web (7 fish species and 9 benthos species) from the Xisha (XS) Islands, South China Sea (SCS). The ∑11OPEs were 1.52 ± 0.33 ng/L, 2227 ± 2062 ng/g lipid weight (lw), 1024 ± 606 ng/g lw, and 1800 ± 1344 ng/g lw in seawater, fish, molluscs, and corals, respectively. Tris (2-chloroisopropyl) phosphate (TCIPPs) were the dominant OPEs in seawater, fish, and molluscs, while tris (2-butoxyethyl) phosphate (TBOEP) predominated in coral tissues. Abiotic and biotic factors jointly affect the OPEs enrichment in marine organisms. Trophic magnification factors (TMFs) (range: 1.31–39.2) indicated the biomagnification potency of OPEs. A dietary exposure risk assessment indicated that OPEs at current levels in coral reef fish posed a low risk to human health but were not negligible. Overall, this study contributes to a further understanding of the environmental behaviors of OPEs in coral reef ecosystems.

Reregulated mitochondrial dysfunction reverses cisplatin resistance microenvironment in colorectal cancer.

Chemotherapy is one of the most basic and important treatments for malignant tumors. However, most chemotherapeutic drugs suffer from the resistance of tumor cells and lead to chemotherapy failure. Multidrug resistance (MDR) of tumor cells is the main obstacle to chemotherapy failure. The generation of MDR is not only the result of the performance of tumor cells, but the tumor microenvironment (TEM) also plays an important role in this process. The simultaneous dual intervention of cancer cells and the TEM has the potential to provide surprising results in overcoming MDR tumor therapy. Therefore, in this study, we designed a folate acid ligand-modified nanoparticle (FA-NPs) with a size of about 145nm targeting multidrug-resistant colorectal cancer and successfully co-loaded cisplatin and Tris(2-chloroisopropyl) phosphate (TCPP). FA-NPs can enrich tumor sites through receptor-mediated endocytosis. In vitro mechanism studies have shown that nanoparticles can reverse cisplatin resistance mainly by further increasing the level of reactive oxygen species in tumor cells, breaking the homeostasis of the internal environment, then trigging mitochondrial stress, regulating drug resistance-related pathways, and improving the tumor drug resistance microenvironment; finally, the cisplatin recovers the antitumor effect with assistance from TCPP.

Occurrence of emerging brominated flame retardants and organophosphate esters in marine wildlife from the Norwegian Arctic

To understand the exposure and potential sources of emerging brominated flame retardants (EBFR) and organophosphate esters (OPEs) in marine wildlife from the Norwegian Arctic, we investigated concentrations of EBFRs in 157 tissue samples from nine species of marine vertebrates and OPEs in 34 samples from three whale species. The samples, collected from a wide range of species with contrasting areal use and diets, included blubber of blue whales, fin whales, humpback whales, white whales, killer whales, walruses and ringed seals and adipose tissue and plasma from polar bears, as well as adipose tissue from glaucous gulls. Tris(2-ethylhexyl) phosphate (TEHP) and tris(2-chloroisopropyl) phosphate (TCIPP) ranged from <0.61 to 164 and < 0.8–41 ng/g lipid weight, respectively, in blue whales and fin whales. All other EBRFs and OPEs were below the detection limit or detected only at low concentration. In addition to the baseline information on the occurrence of EBFRs and OPEs in marine wildlife from the Arctic, we provide an in-depth discussion regarding potential sources of the detected compounds. This information is important for future monitoring and management of EBFRs and OPEs.

Infants' diminished response to DTaP vaccine is associated with exposure to organophosphate esters.

Organophosphate esters (OPEs) are commonly applied as flame retardants and plasticizers. Toxicological studies suggest exposure effects on immune endpoints, raising concerns as infants' OPE exposures are elevated compared to older children and adults due to hand-to-mouth behavior and breastfeeding. Here, we sought to evaluate the immune responsiveness of infants to a neoantigen (e.g., a newly encountered antigen) in the presence of OPE exposures. As a proxy for immune responsiveness, children were given three doses of the Diphtheria, Tetanus, and Pertussis (DTaP) vaccine as recommended, and diphtheria and tetanus antibodies were evaluated in serum samples collected when children were 12 months old (n = 84). Titers were compared, based on maximum sample overlap, to measurements of OPE metabolites in spot urine samples collected before vaccination (age 2 months, n = 73) and at the time of antibody assessment (12 months of age, n = 46). Metabolites of two chlorinated OPEs were significantly associated with diminished antibodies for diphtheria and tetanus. A metabolite of tris (1,3-dichloroisopropyl)phosphate (TDCIPP) measured at 2 months was associated with decreased diphtheria antibodies (-0.07 IU/mL per log10 increase in metabolite). One metabolite of tris(2-chloroisopropyl)phosphate (TCIPP) measured at 12 months was associated with decreased tetanus antibodies (-0.57 IU/mL per log10 increase in metabolite). These results provide some preliminary insights for OPE exposure impacts on vaccine responses in early life and may have important implications for immune health through childhood and adulthood.

Occurrence, correlation, and partitioning of organophosphate esters in soil and tree bark from a megacity, Western China.

Concern over the influences of constant addition of emerging anthropogenic chemicals to the environment has become a public issue during the rapid urbanization. Here, we investigated the occurrence of organophosphate esters (OPEs) in soil and corresponding tree bark in a megacity, Western China. Our results showed levels of OPEs in tree bark (1250 ± 573ng/g dry weight (dw)) were 1-2 orders of magnitude higher than those in soil (40.4 ± 30.8ng/g dw). Rooster Mountain is a background mountain area, exhibiting significantly lower concentrations of OPEs in soil and tree bark than those in other sites with relatively high population density. This result highlights the effect of human activities on the distribution of OPEs in environmental matrices. Alkyl-OPEs were predominant compounds in soil, whereas halogenated- (Cl-) OPEs were characterized in tree bark. Furthermore, tris(2-chloroethyl) phosphate (TCEP) positively correlated with tris(2-chloroisopropyl) phosphate (TCIPP) in soil (r2 = 0.43, P < 0.05) while negatively correlated with TCIPP in tree bark (r2 = 0.31, P < 0.05). The ratios of logarithm concentrations of OPEs in tree bark to those in soil correlated well with logKOA values of OPEs from 6 to 10, indicating the equilibrium status was achieved between OPE partitioning in soil and in tree bark. Nevertheless, tris (2-butoxyethyl) phosphate (TBEP) and tris(2-ethylhexyl) phosphate (TEHP) with high values of logKOA deviated from this linear tendency, which was possibly due to the fact that they were subjected to the particle-bound deposition process, leading to partition into the soil.

Exposure of men living in the greater Montreal area to organophosphate esters: Association with hormonal balance and semen quality

Exposure to organophosphate esters (OPEs) is extensive, yet few studies have investigated their association with hormone levels or semen quality. Here, we studied the association between urinary concentrations of OPEs and their metabolites with hormone levels and semen parameters in men (n=117) predominantly in the 20-29years age range who were recruited from the greater Montreal area between 2009 and 2012. Urine, serum, and semen samples were analyzed for OPEs, hormones, and semen quality, respectively. Bis(2-ethylhexyl) phosphate (BEHP), bis(2,4-di-tert-butylphenyl) hydrogen phosphate (B2,4DtBPP), tris(2-chloroisopropyl) phosphate (TCIPP), diphenyl phosphate (DPHP), bis (2-butoxyethyl) phosphate (BBOEP) and di-cresyl phosphate (DCPs) were detected in urine at a frequency≥95%. The highest geometric mean concentration was observed for DPHP (18.54ng/mL) and the second highest was B2,4DtBPP (6.23ng/mL). Associations between a doubling in analyte concentrations in urine and hormone levels and semen quality parameters were estimated using multivariable linear regression. B2,4DtBPP levels were positively associated with total T3 (β=0.09; 95% CI: 0.01, 0.17). DPHP was inversely associated with estradiol (β=-2.56; 95% CI: -5.00, -0.17), and TCIPP was inversely associated with testosterone (β=-0.78; 95% CI: -1.40, -0.17). Concentrations of BCIPP were inversely associated with sperm concentrations (β=-7.76; 95% CI: -14.40, -0.61), progressive motility (β = - 4.98; 95% CI: -8.71, -1.09), and the sperm motility index (β=-9.72; 95% CI: -17.71, -0.96). In contrast, urinary DPHP concentrations were positively associated with the sperm motility (β=4.37; 95% CI: 0.76, 8.12) and fertility indices (β=6.64; 95% CI: 1.96, 11.53). Thus, OPE detection rates were high and exposure to several OPEs was associated with altered hormone levels and semen parameters. The possibility that OPEs affect male reproduction warrants further investigation.

Distribution, partitioning, and health risk assessment of organophosphate esters in a major tributary of middle Yangtze River using Monte Carlo simulation

Globally, organophosphate esters (OPEs) have attracted substantial attention because of their ubiquity in the environment, toxicity, and potential ecological and health risks. This study comprehensively investigated the occurrence, partitioning, and spatial distribution of nine ordinary monomeric OPEs (m-OPEs) and three emerging oligomeric OPEs (o-OPEs) in a major tributary of the middle Yangtze River, which is the Zijiang River (ZR), and their associated potential health risks. Total OPE concentrations ranged from 18.8 to 439 ng L−1, 1.40 to 19.1 ng L−1, and 3.71 to 77.3 ng g−1 dw in the surface water, suspended particulate matter (SPM), and sediment, respectively. Tris (2-chloroisopropyl) phosphate (TCPP) dominated the water (61.3%) and sediment (60.1%) samples, whereas tris (2-butoxyethyl) phosphate (TBOEP) was present in the SPM (59.0%) samples. The proportion of o-OPEs was low in all three media, ranging from 0.60% to 1.90%. Field-based log Koc values of the frequently detected OPEs were higher than those predicted by EPI Suite and were negatively correlated with temperature. The spatial distribution of OPEs in the water and hierarchical cluster analysis suggested that sewage treatment plant effluents and the mining industry were the main sources of OPEs in the ZR. The total noncarcinogenic and carcinogenic risks of OPEs in the water were low at the detected concentrations, even in the high-exposure scenario.

Aggregation of Fe2O3 nanoparticle in the presence of organophosphate esters (OPEs).

Aggregation is a key process for determining the environmental behavior and impact of a nanoparticle (NP). Since organophosphate esters (OPEs), which are recognized as emerging contaminants, are distributed widely in the natural aquatic environment, they may contribute to interacting with NPs and ultimately influence their transport and fate. Here, we investigated two typical organophosphate esters OPEs on aggregation the Fe2O3 NP in aquatic environments. The results showed that both tri-ethylhexyl phosphate (TEHP) and tris (chloroisopropyl) phosphate (TCPP) improved the colloidal stability of Fe2O3 NP in artificial water and environmental matrices. TEHP exhibited an obvious effect than TCPP on the Zeta potential and aggregation rates of Fe2O3 NP in artificial water. In the presence of electrolyte, 10 mg/L TCPP and TEHP increased the critical coagulation concentration (CCC) by 3.6 times and 17.4 times, respectively. Compared with pore-water, the aggregation rates of Fe2O3 NP in river water were slightly higher than those in pore-water, which can be attributed to the higher DOC in pore-water. We suggested that the high hydrophobicity and molecular weight of OPEs were considered important factors against the aggregation of Fe2O3 NP in water. Greater surface charge and steric hindrance originating from TCPP and TEHP dominated the colloidal stability of Fe2O3 NP.