Tris(1,3-dichloroisopropyl) Phosphate Research Articles

Temperature dependent cholinergic synapse induced by triphenyl phosphate and tris(1.3-dichloroisopropyl) phosphate via thyroid hormone synthesis in Cyprinus carpio

Triphenyl phosphate (TPHP) and tris(1.3-dichloroisopropyl) phosphate (TDCIPP) are emerging contaminants that pervade diverse ecosystems and impair the thyroid and neural signaling pathways. The intricate interactions between thyroid and neurodevelopmental effects mediated by TPHP and TDCIPP remain elusive. This study integrates in vivo, in vitro, and in silico approaches to elucidate these mechanisms in Cyprinus carpio at varying temperatures. It showed that TPHP and TDCIPP hindered fish growth, particularly at low temperatures, by interfering with thyroid hormone synthesis and transport processes. Both compounds have been identified as environmental hormones that mimic thyroid hormone activity and potentially inhibit acetylcholinesterase, leading to neurodevelopmental disorders characterized by brain tissue damage and disrupted cholinergic synapses, such as axon guidance and regeneration. Notably, the bioaccumulation of TPHP was 881.54 % higher than that of TDCIPP, exhibiting temperature-dependent variations with higher levels of TDCIPP at low temperatures (20.50 % and 250.84 % above optimum and high temperatures, respectively), suggesting that temperature could exacerbate the toxicity effects of OPEs. This study sheds new light on the mechanisms underlying thyroid endocrine disruption and neurodevelopmental toxicity in C. carpio. More importantly, these findings indicate that temperature affects the environmental fate and effects of TPHP and TDCIPP, which could provide an important basis for ecological environmental zoning control of emerging contaminants in the future.

Organophosphate ester (OPE) exposure among waste recycling and administrative workers in Denmark using silicone wristbands

In a recent estimate, 96 million tons of hazardous waste were produced in the European Union, most of which were handled among the member states. Organophosphate esters (OPEs) are applied as flame retardants and plasticizers and are present in many products, e.g., electronics, which end up in the hazardous waste stream upon disposal. Given the growing body of information suggesting potential adverse health effects of OPEs, waste recycling workers who handle hazardous waste could potentially be at risk of elevated exposure to these chemicals. Using silicone wristbands, we evaluated OPE exposure among waste recycling workers who handled hazardous waste and compared their exposure to that of administrative workers from the same waste companies. Wristbands were extracted and analyzed for six OPEs, which were all detected in >75% of wristbands. Overall, the sum of tris(2-chloroisopropyl) phosphate (∑TCIPP) isomers was the most abundant OPE across all wristbands collected within the study. In general, the sum of tri(methyl phenyl) phosphate isomers (∑TMPP) was elevated for all waste workers (10β = 7.9), whereas tri-n-butyl phosphate (TnBP), tris(1,3-dichloroisopropyl) phosphate (TDCIPP), and ∑TMPP were 3–12 times higher among those specifically handling electronic and hazardous waste compared to the administrative workers (p < 0.05). Repeated wristband measurements from the same worker had fair to good consistency in OPE concentrations (intraclass correlation coefficients = 0.54–0.77), except for the two most volatile chlorinated OPEs. Taken together, our results suggest that waste recycling workers who handle electronic and hazardous waste have significantly elevated exposure to OPEs, and efforts to reduce these exposures should be considered.

Interactions of organophosphate flame retardants with human drug transporters

Organophosphate flame retardants (OPFRs) are environmental pollutants of increasing interest, widely distributed in the environment and exerting possible deleterious effects towards the human health. The present study investigates in vitro their possible interactions with human drug transporters, which are targets for environmental chemicals and actors of their toxicokinetics. Some OPFRs, i.e., tris(2-butoxyethyl) phosphate (TBOEP), tris(1,3-dichloroisopropyl) phosphate (TDCPP), tri-o-cresyl phosphate (TOCP) and triphenyl phosphate (TPHP), were found to inhibit activities of some transporters, such as organic anion transporter 3 (OAT3), organic anion transporting polypeptide (OATP) 1B1, OATP1B3, organic cation transporter 2 (OCT2) or breast cancer resistance protein (BCRP). These effects were concentration-dependent, with IC50 values ranging from 6.1 µM (for TDCPP-mediated inhibition of OCT2) to 51.4 µM (for TOCP-mediated inhibition of BCRP). OPFRs also blocked the transporter-dependent membrane passage of endogenous substrates, notably that of hormones. OAT3 however failed to transport TBOEP and TPHP. OPFRs additionally repressed mRNA expressions of some transporters in cultured human hepatic HepaRG cells, especially those of OAT2 and OCT1 in response to TOCP, with IC50 values of 2.3 µM and 2.5 µM, respectively. These data therefore add OPFRs to the expanding list of pollutants interacting with drug transporters, even if OPFR concentrations required to impact transporters, in the 2–50 µM range, are rather higher than those observed in humans environmentally or dietarily exposed to these chemicals.

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.

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.

Analysis of semi-volatile organic compounds in indoor dust and organic thin films by house type in South Korea

In this study, semi-volatile organic compounds (SVOCs) in samples of indoor dust and organic thin films obtained from 100 residential houses in South Korea, were examined, based on both target analysis using gas chromatography–mass spectrometry (GC-MS) and non-target analysis by gas chromatography–quadrupole time-of flight mass spectrometry (GC-QTOF-MS) screening. In the targeted approach, phthalates and polycyclic aromatic hydrocarbons (PAHs) were analyzed in dust and organic film samples, to find that both these classes of SVOCs were detected in dust and organic film samples, with the median concentrations of eight phthalates (Σ8 phthalate) and 16 PAHs (Σ16 PAH) being 1015.93 μg/g and 1824.97 ng/g in the dust samples, and 75.79 μg/m2 and 2252.78 ng/m2 in the organic film samples, respectively. Among the phthalates, in all house types. bis(2-ethylhexyl) phthalate (DEHP) was detected at the highest concentration, followed by dibutyl phthalate (DBP) and diisobuthyl phthalate (DiBP), with DEHP levels found to be highest in dwelling houses. DEHP levels were found to be significantly associated with building age and renovation status. Lower levels of DEHP were detected in houses less than 10 years old or that had undergone renovation in the previous 10 years. Among the assessed PAHs, a significant correlation was detected between benzo(a)pyrene in dust and building age (p < 0.05). These findings imply that the inhabitants of older houses are at a greater risk of exposure to SVOCs originating from indoor dust and organic films. Non-target screening of selected dust and organic film samples using GC-QTOF-MS data revealed the presence of numerous SVOC compounds, including triphenylphosphine oxide, (Z)-9-octadecenamide, and cyclosiloxanes, along with certain organophosphate flame retardants including tris(1-chloro-2-propyl) phosphate (TCPP) and tris(1,3-dichloroisopropyl) phosphate (TDCPP), and plasticizers. These compounds identified in the non-target screening are of emerging concern, and their presence in dust and organic films needs to be estimated.

Neurotoxicity of Tris (1,3-dichloroisopropyl) phosphate in Caenorhabditis elegans

As a new type of flame retardant, Organic Phosphate Flame Retardant has been widely used worldwide. The purpose of our research is to determine the neurotoxicity of Tris (1,3-dichloroisopropyl) phosphate (TDCPP) to Caenorhabditis elegans and its mechanism. L1 larvae wild-type C. elegans were exposed to different concentrations of TDCPP, and the effects on motor behavior (head thrashes, body bends, pumping times, chemotaxis index), ROS levels, and p38MAPK signaling pathway-related gene expression levels were measured. Three transgenic nematode strains, BZ555, DA1240, and EG1285, were also used to study the effects of TDCPP on nematode dopamine neurons, glutamate neurons, and GABA neurons. The results showed that TDCPP can inhibit the head thrashes and body bends of the nematode, reduce dopamine production, increase the level of ROS in the body, and affect the expression of genes related to the p38MAPK signaling pathway. We next employed ROS production and motor behavior as toxicity assessment endpoints to determine the involvement of p38 MAPK signaling in the regulation of response to TDCPP. The results showed that the nematodes with low expression of pmk-1 were less sensitive to the TDCPP. It was suggested that TDCPP had neurotoxicity and regulated neurotoxicity to C. elegans by activating the p38-MAPK signaling pathway. The research in this article provides important information for revealing the environmental health risks of organophosphorus flame retardants and their toxic mechanism of action.

Bone developmental toxicity of organophosphorus flame retardants TDCIPP and TPhP in marine medaka Oryzias melastigma

The global phase-out has decreased the use of polybrominated diphenyl ethers (PBDEs), thereby, rapidly increasing the production and use of their important surrogates, organophosphorus flame retardants (OPFRs). Currently, OPFRs are often found at higher levels in the environments compared to PBDEs. Although the two typical OPFRs, tris (1,3-dichloroisopropyl) phosphate (TDCIPP) and triphenyl phosphate (TPhP), have been frequently detected in marine environments with significant concentrations, their toxicity to marine organisms remains unknown. We used Oryzias melastigma to investigate and compare their developmental toxicity in marine organisms through two-generational chronic exposure. The results showed that TDCIPP and TPhP exposure shortened the body length and length of the pectoral fin of O. melastigma. Both TDCIPP and TPhP deformed the pectoral fins in the 1st fry and caused spinal curvature in adult fish. Therefore, these two chemicals may pose potential risks to marine fish and marine ecosystems. Further studies suggested that although these two chemicals caused similar developmental bone toxicity, they had different modes of modulating the expression of bone developmental genes such as, bmp4, bmp2 and runx2.

Exposure of children and mothers to organophosphate esters: Prediction by house dust and silicone wristbands

Ubiquitous human exposure to organophosphorus tri-esters (tri-OPEs) has been reported worldwide. Previous studies investigated the feasibility of using house dust and wristbands to assess human OPE exposure. We hypothesized that these two approaches could differ in relative effectiveness in the characterization of children and adult exposure. In the participants recruited from Guangzhou, South China, urinary levels of major OPE metabolites, including diphenyl phosphate (DPHP) and bis(butoxyethyl) phosphate (BBOEP), were significantly higher in children than their mothers (median 6.6 versus 3.7 ng/mL and 0.11 versus 0.06 ng/mL, respectively). The associations of dust or wristband-associated OPEs with urinary metabolites exhibited chemical-specific patterns, which also differed between children and mothers. Significant and marginally significant associations were determined between dust concentrations of triphenyl phosphate (TPHP), tris(2-butoxyethyl) phosphate (TBOEP), trimethylphenyl phosphate (TMPP), or tris(1-chloro-2-propyl) phosphate (TCIPP) and their metabolites in children urine and between dust tris(1,3-dichloroisopropyl) phosphate (TDCIPP), TPHP or TMPP and urinary metabolites in mothers. By contrast, wristbands exhibited better efficiency of predicting internal exposure to TDCIPP. While both house dust and wristbands exhibited the potential as a convenient approach for assessing long-term OPE exposure, their feasibility requires better investigations via larger-scale studies and standardized sampling protocols.

Do flame retardant concentrations change in dust after older upholstered furniture is replaced?

Upholstered furniture has been a major source of chemical flame retardant (FR) exposures in US homes since the 1970s. FRs are a large group of chemicals, many of which are associated with adverse health effects, including cancer, reproductive toxicity, and neurotoxicity. California homes have some of the highest dust concentrations of FRs, due to Technical Bulletin 117 (TB117), California’s outdated flammability standard for furniture foam that was generally followed across the US and Canada. In 2014, this standard was updated to a smolder standard for furniture fabric called TB117-2013, and it is no longer reliant on FRs. This update provided an opportunity to measure differences in FR dust levels in California homes before and after residents replaced older upholstered furniture, or its foam, with products that met the new standard and were expected to be FR-free. We collected dust from homes of participants who had plans to replace older upholstered furniture, or furniture foam, with FR-free options. We returned for follow-up dust collection six, 12, and 18 months following replacement. Concentrations of three polybrominated diphenyl ethers (PBDEs) (BDE-47, BDE-99, BDE-100), three chlorinated organophosphate ester FRs (tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), and tris(1,3-dichloroisopropyl) phosphate (TDCIPP)), and one aryl organophosphate ester FR triphenyl phosphate (TPHP), were widely detected in participant homes. All measured FRs decreased in nearly all homes after the older upholstered furniture was replaced. The decreases in FRs were significant in both homes that replaced entire pieces of furniture and those that replaced only the furniture foam. This study demonstrates that replacing older upholstered furniture or foam significantly reduces concentrations of a range of FRs in the home. Foam replacement offers a potentially more economic alternative that produces a lower volume of waste.

Occurrence and risk evaluation of organophosphorus flame retardants in two urban rivers in Yangtze River Delta

The occurrence and profiles of organophosphate flame retardants (OPFRs) were investigated in the Huangpu and Shiwuli Rivers, two urban rivers in the Yangtze River Delta, China. The total concentrations of OPEs were found at part-per-trillion ranges, with average concentrations that ranged from 424 to 1.84 × 103 ng L-1 for Huangpu River and 221 to 1.84 × 103 ng L-1 for Shiwuli River. Three chlorinated OPFRs including tris(chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), and tris(1,3-dichloroisopropyl) phosphate (TDCIPP) were the most abundant compounds among the investigated OPFRs, accounting for 90.6-99.8% of total concentrations. In Huangpu River, the OPFR concentrations were significantly higher in the dry season than in the wet season which indicates obvious seasonal variation. Chlorinated OPFR concentrations differed significantly between upstream and downstream reaches of the Shiwuli River, as the result of geographic features and wastewater discharge. Estimated risk was calculated to compare predicted no-effect concentrations (PNEC) to observed concentrations of OPFRs. The results indicated no significant acute adverse effects of OPFRs in the two urban rivers for fish, daphnia, or algae.

Aerobic and Anaerobic Biodegradability of Organophosphates in Activated Sludge Derived From Kitchen Garbage Biomass and Agricultural Residues

Organophosphates (also known as organophosphate esters, OPEs) have in recent years been found to be significant pollutants in both aerobic and anaerobic activated sludge. Food waste, such as kitchen garbage and agricultural residues, can be used as co-substrates to treat the active sludge in sewage treatment plants (STPs). We investigated the biodegradability of nine OPEs derived from kitchen garbage biomass and agricultural residues under different conditions. Under anaerobic conditions, the rate of removal of triphenyl ester OPEs was significantly higher than that of chloride and alkyl OPEs. The addition of FeCl3 and Fe powder increased the rate of degradation of triphenyl ester OPEs, with a DT50 for triphenyl ester OPEs of 1.7–3.8 d for FeCl3 and 1.3–4.7 d for Fe powder, compared to a DT50 of 4.3–6.9 d for the blank control. Addition of an electron donor and a rhamnolipid increased the rate of removal of chlorinated OPEs, with DT50 values for tris(2-carboxyethyl)phosphine) (TCEP) and tris(1,3-dichloroisopropyl)phosphate (TDCPP) of 18.4 and 10.0 d, respectively, following addition of the electron donor, and 13.7 and 3.0 d, respectively, following addition of the rhamnolipid. However, addition of an electron donor, electron acceptor, surfactant, and Fe powder did not always increase the degradation of different kinds of OPEs, which was closely related to the structure of the OPEs. No treatment increased the removal of alkyl OPEs due to their low anaerobic degradability. Tween 80, a non-ionic surfactant, inhibited anaerobic degradation to some degree for all OPEs. Under aerobic conditions, alkyl OPEs were more easily degraded, chlorinated OPEs needed a long adaptation period to degrade and finally attain a 90% removal rate, while the rates of degradation of triphenyl ester OPEs were significantly affected by the concentration of sludge. Higher sludge concentrations help microorganisms to adapt and remove OPEs. This study provides new insights into methods for eliminating emerging pollutants using activated sludge cultured with kitchen garbage biomass and agricultural residues.

Newly discovered bis-(2-ethylhexyl)-phenyl phosphate (BEHPP) was a ubiquitous contaminant in surface soils from a typical region, South China

The organophosphate ester (OPE), bis-(2-ethylhexyl)-phenyl phosphate (BEHPP), was recently identified as an abundant contaminant in indoor dust samples; however, its pollution status in other matrices remains unknown. Here, n = 95 surface soil samples were collected from a prefecture-level city (hereafter referred to as D city) in South China during 2019, and further analyzed to accurately determine the concentrations of BEHPP and eight other OPEs, including tris(2-chloroethyl) phosphate (TCEP), tris(1,3-dichloro-isopropyl) phosphate (TDCIPP), triphenyl phosphate (TPHP), tris(2-butoxyethyl) phosphatetris (TBOEP), 2-ethylhexyl diphenyl phosphate (EHDPP), tris(2-ethylhexyl) phosphate (TEHP), 4-biphenylol diphenyl phosphate (BPDPP), and tris(2-biphenyl) phosphate (TBPHP). BEHPP was detected in all six functional areas (agricultural, scenic, commercial, industrial, and residential areas) of this region, and exhibited a high detection frequency of 67.4%, with a median concentration of 0.455 ng/g dry weight (DW range: nd-7.05 ng/g dw), regardless of the functional area. Samples from commercial, industrial, and residential areas contained significantly greater BEHPP concentrations than those from agricultural and scenic areas. Furthermore, strong and statistically significant correlations were observed between BEHPP and other OPE congeners, particularly for TEHP (r = 0.764, p < 0.001), TBOEP (r = 0.687, p < 0.001), and TPHP (r = 0.709, p < 0.001), indicating that BEHPP may have similar commercial applications and sources to these compounds in surface soil. Collectively, this study provides the first evidence of the presence of BEHPP in soil samples, and indicates that this emerging contaminant is widely distributed across all five functional areas of a typical region (South China).

Ornamental houseplants as potential biosamplers for indoor pollution of organophosphorus flame retardants

We investigated the occurrence, compositions, and partitioning behaviors of organophosphorus flame retardants (OPFRs) in indoor dust, air, and ornamental plants in Dalian, China, to evaluate the possibility of using houseplants as indoor biosamplers of OPFRs. The mean concentrations of OPFRs in the indoor air, dust, and plant samples were 14.9 ng/m3, 18,000 ng/g, and 345 ng/g, respectively. Tris(2-chloroisopropyl) phosphate (TCIPP) was the dominant congener in all kinds of samples. Significant correlation was found between the concentrations of tris(1,3-dichloroisopropyl) phosphate (TDCIPP) in indoor air and plants, suggesting that ornamental plant can be used as a sentinel for certain OPFRs in the indoor air. We developed a predictive model to assess the partitioning coefficients of OPFRs between indoor air and plant. The lipid content in leaf cuticle instead of leaf organic matter was used to improve the accuracy and reliability of this assessment. Using this model, we can estimate the OPFR concentrations in the indoor air based on their concentrations measured in the corresponding indoor plant. The estimated air concentrations were generally comparable with the measured concentrations, especially for those with octanol-air partition coefficient log Koa <11.6. Indoor plants can also provide a more holistic understanding of OPFR occurrence within a home due to the relatively long-term air-foliage partitioning. The results suggest that under certain conditions indoor ornamental plants have the potential to be used as the biosamplers of OPFRs in the indoor environment due to their convenience and low-cost.

Occurrence and risk assessment of organophosphate esters in urban rivers from Piracicaba watershed (Brazil).

Organophosphate esters (OPEs) are substances globally used as flame retardants and plasticizers that have been detected in all environmental compartments. This study aimed to evaluate the occurrence and sources of ten OPEs in the Piracicaba River Basin (Brazil). Twelve sampling sites were selected in five rivers with different pollution sources; six sampling campaigns were performed encompassing dry and wet seasons. ΣOPEs ranged from 0.12 to 6.2 μg L-1; the levels in urban areas were higher than in rural and non-urban areas, but no overall tendency concerning the seasonal effect on OPEs concentrations was observed. Tris(2-butoxyethyl) phosphate (TBOEP), tris(2-chloroisopropyl) phosphate (TCIPP), and tris(1,3-dichloroisopropyl) phosphate (TDCIPP) were the most abundant and frequently detected compounds. Nine OPEs were detected at higher concentrations in a site affected by effluents from textile industries. An acute toxicity test using Daphnia similis was performed for tris(2-ethylhexyl) phosphate (TEHP) for the calculation of a preliminary predicted no effect concentration (PNEC). The risk quotient (RQ) approach was applied and risk to aquatic environment related to TEHP levels was observed in areas adjacent to textile industries, but more toxicity studies are required for the determination of a more reliable PNEC.

Toddler behavior, the home environment, and flame retardant exposure

Toddlers are at increased risk of dust ingestion and subsequently flame retardant (FR) exposure because they often play close to the floor and mouth hands and objects. Exposure to some FRs have been associated to endocrine disruption and neurodevelopmental disorders. Previous research has shown higher FR concentrations in toddlers’ serum and urine, but which toddler-behaviors influence exposure levels remains to be determined. We investigated how toddler-behaviors are associated to FRs in hand wipes (HWs) and saliva. Fifty 8-18 month-old children from the Linking EDCs in maternal Nutrition to Child health study, were visited at home. The child’s behavior was observed and assessed using a questionnaire. Hand-to-object behavior frequency was associated with HW tris(chloroethyl) phosphate (TCEP), tris(1,3-dichloroisopropyl) phosphate (TDCIPP), tris(phenyl) phosphate, tris(methylphenyl) phosphate, and resorcinol bis(diphenyl phosphate) levels above the detection limit. Children playing with electronics multiple times per week had higher TDCIPP HW levels compared to children playing with electronics once per month or never (p = 0.032 and p = 0.046). Frequent mouth-to-object and frequent mouthing a pacifier were associated with lower TDCIPP (p = 0.019) and tris(2-chloroisopropyl) phosphate (TCIPP) HW levels, respectively (p = 0.002–0.019). Exposure estimates based on hand-to-mouth behavior did not exceed the available reference doses. This is the first study investigating toddler-behavior in relation to FR hand loadings. Although a range of behaviors was investigated, only a few showed a relation with FR HW levels, suggesting that toddler-behavior might not alone be responsible for the elevated FR levels in children. It is therefore important to explore other pathways including dermal absorption and inhalation.

Traditional and emerging organophosphate esters (OPEs) in indoor dust of Nanjing, eastern China: Occurrence, human exposure, and risk assessment

Here, fifteen OPEs were investigated in n = 50 floor dust samples collected from six types of indoor spaces in Nanjing, eastern China, in the year 2018. Ten OPEs, including tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), tris(1,3-dichloro-isopropyl) phosphate (TDCIPP), tris(2-ethylhexyl) phosphate (TEHP), tris(2-butoxyethyl) phosphate (TBOEP), 2-ethylhexyl-diphenyl phosphate (EHDPP), triphenyl phosphate (TPHP), tris(methyl-phenyl) phosphate (TMPP), 4-biphenylyl diphenyl phosphate (4-BPDP) and tris(2-biphenylyl) phosphate (TBPP), were detected in at least one of the analyzed samples (>method limits of quantification). Regardless of indoor spaces, EHDPP (34% of Σ8OPEs, mean: 1.43 μg/g) and TDCIPP (19%, 0.81 μg/g) were the ascendant OPEs in indoor floor dust. 4-BPDP and TBPP were detectable in indoor floor dust samples, but at relatively low detection frequencies with 2% and 10%, respectively. Various indoor microenvironments exhibited different pollution characteristics of OPEs. Floor dust collected from electronic product maintenance centers contained the richest OPE contaminants with highest mean Σ8OPEs concentration of 7.92 μg/g. On the basis of measured Σ10OPEs concentrations in dust sample, we estimated daily intake via floor dust ingestion to be 1.37, 0.75 and 1.24 ng/kg BW/day for electronic engineers, undergraduates, and graduate students under mean-exposure scenario, respectively. Overall, our study reported the occurrence of 4-BPDP and TBPP in environmental samples for the first time, and demonstrated that indoor floor dust ingestion exposure does values were far less than reference dosage values of oral toxicity proposed by United States Environmental Protection Agency (USEPA) Integrated Risk Information System.

Estimating renal and hepatic clearance rates of organophosphate esters in humans: Impacts of intrinsic metabolism and binding affinity with plasma proteins

The renal and hepatic clearance rates of organophosphate esters (OPEs) in humans were estimated. Six OPEs and their corresponding diester metabolites (mOPEs) were quantified respectively in 30 paired human plasma and urine samples collected in Hengshui, Hebei province, China. The renal clearance rate (CLrenal) of triphenyl phosphate (TPHP), tris(chloroethyl) phosphate (TCEP) and tris(1,3-dichloro-isopropyl) phosphate (TDCIPP) was estimated to be 68.9, 50.9 and 33.3 mL/kg/day, respectively, while it was not calculated for other three OPEs due to the low detection frequencies in human samples. To estimate the clearance rates of the target OPEs, hepatic clearance rates (CLh) of OPEs were extrapolated from their in vitro intrinsic clearance data in human liver microsomes (CLHLM). The calculated CLh values of TCEP and TDCIPP were comparable to their CLrenal, indicating that the in vitro extrapolation method was suitable for estimating the clearance rates of OPEs. The higher binding affinity of TDCIPP with plasma proteins could reduce its renal clearance. The estimated half-lives of Cl-OPEs in human were longer than those of the aryl- and alkyl-OPEs. This study provided a feasible in vitro method to predict the clearance and half-lives of OPEs in human, which is significant for their accurate health risk assessment.

Chlorinated phosphorus flame retardants exert oxidative damage to SMMC-7721 human hepatocarcinoma cells

Chlorinated phosphorus flame retardants are organic pollutants widely distributed in the environment. However, there is still a lack of understanding of the toxicity mechanism of chlorinated phosphorus flame retardants at the molecular level. Tris (1, 3-dichloroisopropyl) phosphate (TDCPP), tris (2-chloropropyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP) were used as typical representatives of chlorinated phosphorus flame retardants to evaluate their cytotoxicity as well as changes in the expression of the enzymes lactate dehydrogenase (LDH), superoxide dismutase (SOD), and catalase (CAT), which will be meaningful for an in-depth study of the toxicity mechanism of TDCPP, TCPP and TCEP. The results showed that the three chemicals reduced cell viability over a period of 24 h. The exposure increased extracellular levels of lactate dehydrogenase and decreased intracellular levels of superoxide dismutase and catalase in a concentration-dependent manner. Expression of the SOD and CAT genes were down-regulated indicating that the SMMC-7721 human hepatocarcinoma cells may experience oxidative damage as a result of exposure to the three chemicals. The expression of the Bax apoptosis protein was up-regulated and the Bcl-2 apoptosis protein was down-regulated, suggesting that the three chemicals may cause functional defects, damage the cell structure and promote apoptosis. The results from this study should provide the basis for a detailed investigation of the ecological toxicity of chlorinated phosphorus flame retardants.

Characterization and 16S rRNA gene-based metagenomic analysis of the organophosphorous flame retardants degrading consortium YC-BJ1

As flame retardants, organophosphate is recognized as a global environmental contaminant because of its wide application. This contaminant is hardly degradable by hydrolysis in the environment due to its special physicochemical properties. Therefore, it is of urgent needs to study the microbial degradation of organophosphate. Through continuous enrichment, we isolated one bacterial consortium, named YC-BJ1, from leachate of waste treatment plant in Beijing. The bacterial consortium YC-BJ1 could efficiently degrade 99.8% of triphenyl phosphate (TPhP) and 91.9% of tricresyl phosphate (TCrP) with the concentration of 100 mg/L within 4 days. Besides aryl phosphates, it could degrade chloro-phosphates, tris(1,3-dichloroisopropyl) phosphate (TDCPP) and tris(2-chloroethyl) phosphate (TCEP) by 16.5% and 22.0% respectively. The degradation of the consortium on TPhP was optimized through a broad range of temperature (15-40 ℃), pH (5.0-12.0) and salinity (0%-4%). 16S rRNA gene-based metagenomic analysis revealed that Hyphomicrobium (38.80%), Chryseobacterium (17.57%) and Sphingopyxis (17.46%) were the dominant genera of the consortium YC-BJ1. Compared with the reported organophosphorus flame retardants (OPFRs) degrading bacteria and microflora, the mixed microflora YC-BJ1 exhibited great advantages in degradation efficiency and environmental adaptability, demonstrating its wide application potential. The enrichment and isolation of highly efficient degrading flora can provide abundant microbial resources for the degradation of OPFRs and the bioremediation towards OPFRs-contaminated environments, and also lay a solid foundation for the exploration of its degradation mechanism.