Organophosphate Flame Retardants Concentrations Research Articles

Different organophosphate flame retardant and metabolite concentrations in urine from male and female university students in Beijing and an assessment of exposure via indoor dust

Organophosphate flame retardants (OPFRs) have been found in human samples and associated with adverse health effects. In the present study, OPFR and dialkyl and diaryl phosphate (DAP) concentrations in human urine were determined and differences in the concentrations in urine from males and females were investigated. Urine samples from 22 male and 26 female university students, paired dust samples from the dormitories (13 each for males and females), and 10 dust samples from university teaching buildings were analyzed. The tri-o-cresyl phosphate (TOCP), tri-p-cresyl phosphate (TPCP), and tris(2-chloroisopropyl)phosphate (TCIPP) concentrations were significantly higher (p = 0.049, 0.023, and 0.027, respectively) in urine from the female students than in urine from the male students. Similar differences were found between males and females in terms of OPFR exposure and OPFR concentrations in urine for three-fourths of the OPFRs. Questionnaire answers and calculations indicated that disparities in OPFR concentrations in urine were mainly caused by females spending much more time than males in dormitories. Organophosphate flame retardants may pose degrees of health risk similar to those of polybrominated diphenyl ethers (PBDEs), and this must be considered when making decisions about controlling flame retardants. We are not aware of any previous studies that simultaneously monitor OPFRs and DAPs in human urine in China. Environ Toxicol Chem 2019;38:760-768. © 2019 SETAC.

Legacy and Currently Used Organic Contaminants in Human Hair and Hand Wipes of Female E-Waste Dismantling Workers and Workplace Dust in South China.

Legacy organic contaminants, such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), and several currently used organic contaminants, such as novel brominated retardants (NBFRs), organophosphate flame retardants (OPFRs), and Dechlorane Plus (DPs), were measured in the segmented hair and hand wipes of e-waste dismantling workers and in the dust from their workplace in an e-waste recycling site in South China to assess the accumulation and sources of organic contaminants in the hair shaft. The median concentrations of DPs, PBDEs, NBFRs, PCBs and OPFRs in hair samples were 23.5, 154, 156, 349, and 371 ng/g, respectively. A linear increase in organic contaminant concentrations was found along the hair shaft, with significant differences among each segment, while the age-related patterns were similar among the 7 hair segments. A linear relationship was found between the accumulation rates and the log KOW, indicating that the accumulation rates of organic contaminants along the hair shaft decreased with increasing log KOW values. Enantiomer fraction (EF) values of PCB-132 in distal segments were close to those in dust and air, while EFs in proximal segments were close to those in serum. The contributions of PCBs from external sources to hair increased with the distance from the scalp of hair segments, from 67.8% in 0-3 cm segments to 95.9% in 18-21 cm segments.

Organophosphate flame retardants in college dormitory dust of northern Chinese cities: Occurrence, human exposure and risk assessment

Organophosphate flame retardants (OPFRs) are widely added to consumer products and building materials, which may pose potential health risk to humans. But information on their contamination and human exposure in the indoor environment especially dormitories in northern China is rare. In this study, twelve OPFRs were investigated in college dormitory dust that collected from Harbin, Shenyang, and Baoding, in northern China. Indoor dust samples were also collected from homes and public microenvironments (PMEs) in Harbin for comparison. The median ∑OPFR concentrations in dormitory dust in Shenyang samples (8690 ng/g) were higher than those in Baoding (6540 ng/g) and Harbin (6190 ng/g). The median ∑OPFR concentrations in home dust (7150 ng/g) were higher than in dormitory and PME dust (5340 ng/g) in Harbin. Tris(2‑chloroethyl) phosphate (TCEP) and tris (2-chloroisopropyl) phosphate (TCIPP) were the most abundant chlorinated OPFRs, while triphenyl phosphate (TPHP) and tris(2‑butoxyethyl) phosphate (TBOEP) were the dominant non-chlorinated OPFRs. The daily intakes of ∑OPFR were estimated, with the median values for female students (2.45 ng/kg-day) higher than those for male students (2.15 ng/kg-day) while were similar to adults (2.45 ng/kg-day) in homes. The estimated daily intakes (EDI) of these OPFRs from indoor dust in Harbin were all below the recommended values. The calculated non-carcinogenic hazard quotients (10−8–10−3) from OPFRs were much lower than the theoretical risk threshold. Meanwhile, carcinogenic risk (CR) of tri‑n‑butyl phosphate (TNBP), TCEP, tris(2‑ethylhexyl) phosphate (TEHP), and tris(1,3‑dichloroisopropyl) phosphate (TDCIPP) were also estimated. The highest carcinogenic risk of TCEP for gender-specific and age-specific category range from 1.75 × 10−7 to 2.46 × 10−7 from exposure to indoor dust indicated a low potential carcinogenic risk for human exposure.

Organophosphate flame retardants in leachates from six municipal landfills across China

With the phasing out of brominated flame retardants, organophosphate flame retardants (OPFRs) have been widely used and further detected in multiple environmental media. However, municipal landfill leachates, an important source of contamination of OPFRs to aquatic environment, have not been fully understood, especially in a developing country like China. Thus, the occurrence, aqueous removal efficiency, environmental emission, and risk assessment of 10 OPFRs were investigated in leachates from six municipal landfills across China. The results indicated that except triethyl phosphate (TEP), the remaining 9 OPFRs were detected in both raw and final leachates with different frequencies higher than 33.3%. The range of total concentrations of OPFRs (ΣOPFRs) across China was 29.0–437 and 0.652–32.4 μg L−1 in raw and final leachates, respectively. Tris(2-chloroethyl) phosphate (TCEP) was the dominant species and accounted for 78.5% and 85.8% of average ΣOPFR concentration in raw and final leachates, respectively. This may be because TCEP is the most prevalently used OPFR in China. The overall aqueous removal efficiency of ΣOPFRs across China ranged from 57.7% to 99.8%. Tris(2-butoxyethyl) phosphate was the most removed species (98.8%), whereas TCEP was the least removed species (91.5%). The annual emissions of ΣOPFRs discharged into the aquatic environment from municipal landfills across China were estimated to be between 170 and 7094 g. Further risk assessment based on risk quotient values in the final leachates showed that most OPFRs posed negligible risk except TCEP (medium and high risk) and tributyl phosphate (medium risk).

Distributions of organophosphate flame retardants (OPFRs) in three dust size fractions from homes and building material markets

The distributions of organophosphate flame retardants (OPFRs) in various size fractions of indoor dust samples from homes (H; n = 18) and building material markets (B; n = 7) in the Rhine/Main region of Germany were investigated. Three particle size fractions (F1: 150–200 μm, F2: 63–150 μm, and F3: <63 μm) and bulk dust (BD) subsamples (<200 μm) of each sample were analyzed for 10 OPFRs. On average, the total OPFR concentrations (∑10OPFR) in bulk dust and all three size fractions from building material markets were 133, 153, 196, and 88.0 μg/g in subsamples B-BD, B-F1, B-F2, and B-F3. These concentrations were at least five times higher than those in bulk dust and all three size fractions from homes, with values of 19.3, 17.2, 19.5, and 18.7 μg/g for subsamples H-BD, H-F1, H-F2, and H-F3, respectively. Tris(2-chloroisopropyl)phosphate (TCIPP) was the dominant congener in dust from building material markets, contributing over 91% to the ∑10OPFR of B-BD and all particle size fractions. Meanwhile, both tris(2-butoxyethyl)phosphate (TBOEP) and TCIPP were abundant in dust from homes, respectively contributing 28%–41% and 31%–43% to the ∑10OPFR of H-BD and all particle size fractions. Most of the OPFR concentrations showed no consistent trend with particle size. However, TCIPP was more likely to be enriched in F2. Microscopic examination indicated that TCIPP in indoor dust mainly originated from abraded fragments of commercial products. In contrast, TBOEP accumulated in F3, related to direct transfer of floor-care products to fine dust particles. The concentrations of OPFRs were not significantly correlated with total organic carbon contents in any particle size fraction. However, evaluation of their mass contributions showed that more than 85% of OPFRs accumulated in particles smaller than 150 μm, indicating that this particle size fraction is most suitable for monitoring of OPFRs.

Combined toxicity of organophosphate flame retardants and cadmium to Corbicula fluminea in aquatic sediments

Organophosphate flame retardants (OPFRs), as alternatives to polybrominated biphenyl ethers (PBDEs), are frequently detected in various environmental matrices. Owing to urbanization and industrial pollution, co-contamination of OPFRs and heavy metals is ubiquitous in the environment. The toxicity of OPFRs in aqueous phase is a significant concern, but uncertainty still exists regarding the co-toxicity to benthic organisms of OPFRs and metals in sediments. Hence, we explored the physiological response of Corbicula fluminea to OPFRs and Cd in sediments. The results indicated that the antioxidant system in the clams was stimulated in the presence of OPFRs and Cd, and the oxidative stress increased with increasing concentrations of OPFRs. In contrast, the cytochrome P450 (CYP450) content and acetylcholinesterase (AChE) activity were reduced by exposure to both OPFRs and Cd. The cytochrome P450 4 family (CYP4) mRNA expression and OPFR toxicity were lower than those in previously reported experiments conducted in the water phase. Moreover, the expression levels of metallothionein (MT) and AChE mRNA decreased when OPFRs and Cd were present together. The highest integrated biomarker response (IBR) index (IBR = 15.41) was observed in the presence of 45 mg kg−1 Cd + 200 mg kg−1 OPFRs, rather than the 45 mg kg−1 Cd + 400 mg kg−1 OPFRs treatment (IBR = 9.48). In addition, CYP450 and AChE in the digestive glands of C. fluminea exhibited significant correlations with the concentration of the OPFR/Cd mixture (p < 0.01) and could be effective biomarkers for OPFR and Cd co-contamination. The results potentially contribute to more realistic predictions and evaluations of the environmental risks posed by OPFRs in aquatic sediments contaminated with heavy metals, particularly with respect to the risk to benthic organisms.

Developmental Exposure to Low Concentrations of Organophosphate Flame Retardants Causes Life-Long Behavioral Alterations in Zebrafish.

As the older class of brominated flame retardants (BFRs) are phased out of commercial use because of findings of neurotoxicity with developmental exposure, a newer class of flame retardants have been introduced, the organophosphate flame retardants (OPFRs). Presently, little is known about the potential for developmental neurotoxicity or the behavioral consequences of OPFR exposure. Our aim was to characterize the life-long neurobehavioral effects of 4 widely used OPFRs using the zebrafish model. Zebrafish embryos were exposed to 0.1% DMSO (vehicle control); or one of the following treatments; isopropylated phenyl phosphate (IPP) (0.01, 0.03, 0.1, 0.3 µM); butylphenyl diphenyl phosphate (BPDP) (0.003, 0.03, 0.3, 3 µM); 2-ethylhexyl diphenyl phosphate (EHDP) (0.03, 0.3, 1 µM); isodecyl diphenyl phosphate (IDDP) (0.1, 0.3, 1, 10 µM) from 0- to 5-days postfertilization. On Day 6, the larvae were tested for motility under alternating dark and light conditions. Finally, at 5-7 months of age the exposed fish and controls were tested on a battery of behavioral tests to assess emotional function, sensorimotor response, social interaction and predator evasion. These tests showed chemical-specific short-term effects of altered motility in larvae in all of the tested compounds, and long-term impairment of anxiety-related behavior in adults following IPP, BPDP, or EHDP exposures. Our results show that OPFRs may not be a safe alternative to the phased-out BFRs and may cause behavioral impacts throughout the lifespan. Further research should evaluate the risk to mammalian experimental models and humans.

Trace organic contaminants in urban runoff: Associations with urban land-use

Urban development has led to an increase in urban runoff, accompanied with a decrease in water quality during rain events. One of the major causes of the decrease in water quality is the presence of trace organic contaminants in urban runoff. However, little is known about the sources of organic contaminants in urban runoff, especially related to land-use and temporal trends in those associated land uses. The objective of this study was to assess the occurrence and concentration trends of organic contaminants for a high-density residential site and commercial strip site in Madison, WI. Flow-weighted samples of urban stormwater runoff, collected with an auto-sampler, were composited and analyzed, producing mean organic contaminants concentrations for each storm event. The contaminants, which include pesticides, flame retardants, polycyclic aromatic hydrocarbons, corrosion inhibitors, among others, were extracted and analyzed by gas chromatography coupled with mass spectrometry or liquid chromatography coupled with tandem mass spectrometry. There were 30 organic contaminants that had greater than 50% detections in at least one of the sites, and those organic contaminants did provide information on similarities and differences of organic contaminants in urban runoff derived from different land uses. The sum of the total measured pesticides showed no significant difference between sites; this was likely due to the considerable green space and associated pesticide use in both sites. However, there were higher total concentrations of organophosphate flame retardants and corrosion inhibitors in the residential site. The reason for this is unknown and will require follow-up studies; however, several hypotheses are presented. Conversely, there were higher total concentrations of polycyclic aromatic hydrocarbons in the commercial site; this is most likely due to higher vehicle traffic in the commercial site. These data show that land-use may be important in determining the composition and concentrations of trace organic contaminants in urban stormwater runoff.

Evaluation of the current contamination status of PFASs and OPFRs in South Korean tap water associated with its origin

We investigated the concentrations of perfluoroalkyl substances (PFASs) and organophosphate flame retardants (OPFRs) in 44 tap water samples, collected from eight major cities in South Korea served by four representative watersheds, to evaluate the water contamination status. The total concentrations of PFASs and OPFRs ranged from 1.44 to 224ng/L (median=11.9ng/L), and 74.0 to 342ng/L (median=151ng/L), respectively. The predominant compounds in tap water were perfluorohexane sulfonate (PFHxS), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), tris(2-chloroethyl) phosphate (TCEP), tris(chloroisopropyl) phosphate (TCIPP), and tris(2-butoxyethyl) phosphate (TBOEP). Tap water originating from the Nakdong River within an industrial complex showed a notably higher PFHxS proportion to total PFASs. In addition, significantly higher PFAS levels were found in river-originating tap water than in lake/reservoir-originating tap water (Mann-Whitney U test, p<0.05). Meanwhile, major OPFRs showed no clear difference in distribution by region, and no significant difference in major OPFR levels was observed according to tap water origin. Finally, the average human exposure via tap water consumption was estimated for PFASs (46.8ng/person/day) and OPFRs (254ng/person/day).

Semivolatile Organic Compounds (SOCs) in Fine Particulate Matter (PM2.5) during Clear, Fog, and Haze Episodes in Winter in Beijing, China

Few efforts have been made to elucidate the influence of weather conditions on the fate of semivolatile organic compounds (SOCs). Here, daily fine particulate matter (PM2.5) during clear, haze, and fog episodes collected in the winter in Beijing, China was analyzed for polycyclic aromatic hydrocarbons (PAHs), brominated flame retardants (BFRs), and organophosphate flame retardants (OPFRs). The total concentrations of PAHs, OPFRs, and BFRs had medians of 45.1 ng/m3 and 1347 and 46.7 pg/m3, respectively. The temporal pattern for PAH concentrations was largely dependent on coal combustion for residential heating. OPFR compositions that change during colder period were related to enhanced indoor emissions due to heating. The mean concentrations of SOCs during haze and fog days were 2-10 times higher than those during clear days. We found that BFRs with lower octanol and air partition coefficients tended to increase during haze and fog episodes, be removed from PM2.5 during clear episodes, or both. For PAHs and OPFRs, pollutants that are more recalcitrant to degradation were prone to accumulate during haze and fog days. The potential source contribution function (PSCF) model indicated that southern and eastern cities were major source regions of SOCs at this site.

Concentrations of organophosphate flame retardants and plasticizers in urine from young children in Queensland, Australia and associations with environmental and behavioural factors

In recent years, the production and usage volumes of organophosphate flame retardants (OPFRs) has increased substantially. Certain OPFRs are suspected reproductive toxins, carcinogenic, and neurotoxic. Insufficient information is available on human exposure pathways to these chemicals, particularly in Australia. We aim to assess the association between OPFR concentrations in the urine of children to environmental and behavioural risk factors. Concentrations of eight OPFRs and eleven metabolites were measured in the urine of 51 children, aged 3–29 months, in Southeast Queensland, Australia and compared to their behavioural and environmental risk factor data obtained by an online questionnaire. Of the 11 OPFR metabolites analysed, 55% were frequently detected in the majority (> 80%) of samples. The most frequently detected metabolite was bis(1,3-dichloroisopropyl) phosphate (BDCIPP) (detected in 100% of samples), followed by 1-hydroxy-2-propyl bis(1-chloro-2-propyl) phosphate (BCIPHIPP) (96%), diphenyl phosphate (DPHP) (94%) and bis(1-chloroisopropyl) phosphate (BCIPP) (86%). In multivariable modelling, age was positively associated with concentrations of bis(2-butoxyethyl) phosphate (BBOEP) and negatively associated with concentrations of BCIPP and BCIPHIPP. Other non-age related factors, including vacuuming frequency, hand-washing frequency and presence and number of some electrical appliances in the home were also associated with concentrations of OPFR metabolites.

Organophosphate flame retardants (OPFRs) in water and sediment: Occurrence, distribution, and hotspots of contamination of Lake Shihwa, Korea

Contamination by organophosphate flame retardants (OPFRs) is an emerging concern in aquatic environments. Concentrations of 18 OPFRs were measured in water and sediments collected from the artificial Lake Shihwa. OPFR concentrations in sediments measured in this study were the highest reported worldwide, implying severe OPFR contamination. The highest concentrations of OPFRs were found in creeks taken near industrial complexes, and OPFR concentrations decreased with increasing distance from creeks to inshore or offshore lake waters. On-going OPFR contamination by wastewater treatment plant (WWTP) discharge was evidenced by the clear decrease in OPFRs in water samples collected moving away from WWTP outfall. TBEP and TEP were dominant in water samples, while TDCPP and TCPP were dominant in sediment samples. Differences in contamination profiles with sample matrices are likely due to hydrophobicity of individual OPFRs. Non-parametric multidimensional scaling ordination showed that OPFR contamination was affected by pollution inflow and proximity to industrial complexes.

Assessment of organophosphate flame retardants in surface water and sediment from a freshwater environment (Yangtze River, China).

Organophosphate flame retardants (OPFRs) have been detected in the surface water, suspended sediments, and river sediments from the Yangtze River in China. A modified polar organic chemical integrative sampler (m-POCIS) was successfully used to quantify the OPFR concentrations in surface water. The OPFR concentrations estimated by the field m-POCIS at six sampling locations ranged from 8.99 to 112.45ng/L with an average concentration of 47.04ng/L. The OPFR concentrations in suspended sediments were related to the sediment particle size distribution. Chlorinated and alkyl OPFRs were the principle compounds in sediments, especially tris(2-chloroisopropyl) phosphate (TCPP) with concentrations of 3.37-29.65ng/g. The relationship between the OPFR concentrations and total organic carbon (TOC) contents in sediments was examined. The results suggested that the OPFR concentrations were significantly correlated with the TOC contents. The primary OPFR transport mechanism in a freshwater environment occurs in surface water rather than sediment. This was evaluated by the logKow and field sediment-water partition coefficient (logKoc) values between the sediment and water. Finally, the various distributions and transport of OPFRs at the sampling sites indicated that human activities, agricultural production, and wastewater effluents from sewage plants have an important effect on the OPFR levels in a freshwater environment.

Occurrence and distribution of organophosphate flame retardants (OPFRs) in soil and outdoor settled dust from a multi-waste recycling area in China

Distribution of 12 organophosphate flame retardants (OPFRs) was determined in soil and outdoor settled dust samples collected from a multi-waste (electronic, plastic, and rubber wastes and abandoned household-appliances and vehicles) recycling area, that encompassed different modes of operation i.e. open (ORS) and semi-closed recycling (SCRS). Among the twelve OPFRs analyzed, eleven were detected at a frequency of 75%–100% in all soil and dust samples. In soil samples, ΣOPFR concentrations were significantly higher at ORS (122–2100ng/g) than at SCRS (58.5–316ng/g) and nearby farmlands (37.7–156ng/g). The ΣOPFR concentrations in dust samples were higher than those in soil samples with spatial distribution similar to that observed for soil, decreasing from ORS (1390–42,700ng/g) to SCRS (914–7940ng/g). Tris(2-chloroisopropyl) phosphate (TCIPP) was the major OPFRs in both soil (<MDL–1370ng/g) and dust (39.9–16,300ng/g) samples. Chlorinated OPFRs [TCIPP, tris(1,3-dichloroisopropyl) phosphate (TDCIPP) and tris(2-chloroethyl) phosphate (TCEP)] and aryl-OPFRs [triphenyl phosphate (TPHP), tris(methylphenyl) phosphate (TMPP)] exhibited spatial difference between ORS and SCRS. Principle component analysis (PCA) of OPFR concentrations revealed that TCIPP, TDCIPP, TPHP, TMPP originated from similar sources. TMPP was assessed to pose eco-toxicological risk (risk quotient values: RQs) in the soil ecosystem. The median estimated daily intake (EDI) of OPFRs via soil and outdoor settled dust ingestion (based on average ingestion rate) was 3.14×10−1ng/kgbw/day for adults at ORS. Our results suggest that waste recycling is an important source of chlorinated- and aryl-OPFRs in the environment.

Measuring and modeling surface sorption dynamics of organophosphate flame retardants on impervious surfaces

Understanding the sorption mechanisms for organophosphate flame retardants (OPFRs) on impervious surfaces is important to improve our knowledge of the fate and transport of OPFRs in indoor environments. The sorption processes of semivolatile organic compounds (SVOCs) on indoor surfaces are heterogeneous (multilayer sorption) or homogeneous (monolayer sorption). In this study, we adopted simplified Langmuir isotherm and Freundlich isotherm in a dynamic sink model to characterize the sorption dynamics of OPFRs on impervious surfaces such as stainless steel and made comparisons between the two models through a series of empty chamber studies. The tests involve two types of stainless steel chambers (53-L small chambers and 44-mL micro chambers) using tris(2-chloroethyl)phosphate (TCEP) and tris(1-chloro-2-propyl)phosphate (TCPP) as target compounds. Our test results show that the dynamic sink model using Freundlich isotherm can better represent the sorption process in the empty small chamber. Micro chamber test results from this study show that the sink model using both simplified Langmuir isotherm and Freundlich isotherm can well fit the measured gas-phase concentrations of OPFRs. We further applied both models and the parameters obtained to predict the gas phase concentrations of OPFRs in a small chamber with an emission source. Comparisons between model predictions and measurements demonstrate the reliability and applicability of the sorption parameters.

Contamination Characteristics and Human Exposure to Organophosphate Flame Retardants in Road Dust from Suzhou City

The contamination levels and distribution characteristics of four organophosphate flame retardants (OPFRs) in 25 outdoor dust samples collected in Suzhou were quantitatively analyzed by gas chromatography-mass spectrometry (GC-MS). The exposure to OPFRs via ingestion and inhalation of dust were also estimated for adults, children, and professional street sweepers. Four types of OPFRs were detected in all dust samples at different levels; the total OPFRs concentrations ranged from non-detected (ND) to 8901.66 ng·g-1, with a median of 1039.21 ng·g-1. The concentrations of TCPP, TBEP, TDCPP, and TCEP were in the range of 0-6931.46, 0-2021.15, 0-788.44, and 0-62.16 ng·g-1, respectively. The daily intake of ∑OPEs under a high dust ingestion scenario was 125.68, 915.78, and 6314.16 pg·kg-1 for adults, children, and professional street sweepers, respectively. The estimated exposure of children to ∑OPEs was six times higher than that of adults. However, the daily intake of OPFRs via dust inhalation was 3.07E-02, 1.89E-02, and 1.54E-01 pg·kg-1 for adults, children, and professional street sweepers, respectively. These findings indicated that the occurrence of OPFRs in the dust poses a significant risk to children and professional street sweepers.

In situ calibration of polar organic chemical integrative samplers to monitor organophosphate flame retardants in river water using polyethersulfone membranes with performance reference compounds

Passive sampler is an innovative way of monitoring chemicals in different environmental. A modified polar organic chemical integrative sampler (m-POCIS) with a performance reference compound (PRC) was used to evaluate the concentrations of 8 organophosphate flame retardants (OPFRs) under field conditions. The m-POCIS was deployed for 15days under laboratory conditions and 21days under in situ conditions to determine the concentrations of OPFRs. The analytes were trapped in the sorbent and the microporous polyethersulfone (PES) membrane of the m-POCIS. Sampling rates (Rs) were determined for the studied compounds and ranged from 0.02±0.0003L/d (triphenylphosphine oxide, TPPO) to 0.24±0.021L/d (tripropyl phosphate, TPrP) in the laboratory. The membranes accumulation increased with usage and was correlated to the logKow. Among the tested compounds, tripentylphosphate (TPeP) and triphenylphosphate (TPhP) had the highest logKow values and were mostly detected in the membranes. This behavior resulted in a lag-phase, which was measured by extrapolating the data from the last third of the uptake phase (quasilinear) to the x-axis using a linear regression, before the compounds transferred into the sorbent. TPhP was the only compound with a lag-phase of 3.9days during the 15days experiment. Deuteratedtributyl phosphate (TBP-d27) and desisopropyl atrazine-d5 (DIA-d5) were identified through specific experiments as potential PRC. The results from the PRC calibrations suggested that DIA-d5 (ke (in situ)=0.075±0.0048day−1) can be used as a PRC for the evaluation of OPFRs using m-POCISs. The time-weighted average (TWA) concentrations estimated by the m-POCIS with or without a PRC were significantly correlated with the corresponding values determined from the grab samples. After the PRC calibration, the TWA concentrations of the tested OPFRs in an aquatic environment were lower than those estimated using the laboratory sampling rates (Rs). The m-POCIS with a PRC correction was a suitable tool for estimating OPFRs TWA concentrations in the Yangtze River.

Occurrence, Removal, and Environmental Emission of Organophosphate Flame Retardants/Plasticizers in a Wastewater Treatment Plant in New York State.

The occurrence and fate of 14 triester organophosphate flame retardants (OPFRs) and plasticizers and their two diester metabolites were investigated in a wastewater treatment plant (WWTP) in the Albany area of New York State. All target OPFRs were found in wastewater, with average concentrations that ranged from 20.1 ng/L for tris(methylphenyl) phosphate (TMPP) to 30 100 ng/L for tris(2-butoxyethyl)phosphate (TBOEP) in influents and from 7.68 ng/L for TMPP to 12 600 ng/L for TBOEP in final effluents. TBOEP was the dominant compound in influents (max: 69 500 ng/L) followed in decreasing order by tris(1-chloro-2-propyl)phosphate (TCIPP; max: 14 500 ng/L), bis(1,3-dichloro-2-propyl)phosphate (BDCIPP; max: 4550 ng/L), tris(1,3-dichloro-2-propyl)phosphate (TDCIPP; max: 3150 ng/L) and tris(2-chloroethyl)phosphate (TCEP; max: 8450 ng/L). The fraction of TMPP sorbed to suspended particulate matter (SPM) was 56.4% of the total mass in wastewater, which was the highest among the target chemicals analyzed. The average concentrations of OPFRs in sludge were between 4.14 ng/g dw for tripropyl phosphate (TPP) and 7290 ng/g dw for TBOEP; for ash, they were between 2.17 ng/g dw for TMPP and 427 ng/g dw for triphenyl phosphate (TPhP). The mass loadings of OPFRs into the WWTP ranged from 0.02 mg/day/person for TPP to 28.7 mg/day/person for TBOEP, whereas the emission from the WWTP ranged from 0.01 mg/day/person for 2-ethylhexyl diphenyl phosphate (EHDPP) to 5.12 mg/day/person for TCIPP. The removal efficiencies for OPFRs were slightly above 60% for TMPP, TBOEP, and tris(2-ethylhexyl)phosphate (TEHP) whereas those for other OPFRs were <40% (TPhP and BDCIPP) to negative values, suggesting incomplete removal in WWTPs.

Organophosphate Flame Retardants in House Dust from South China and Related Human Exposure Risks.

House dust associated with organic pollutants is not only a potential source of pollutants to the outdoor environment, but also a source to human exposure. The present study investigated the occurrence and concentrations of organophosphate flame retardants (OPFRs) in house dust collected from South China dwellings (n = 20). The results revealed a universal presence of most target OPFRs in house dust, with concentrations of ΣOPFRs ranging from 2.06 to 19.95μg/g. The median concentration of ΣOPFR (9.20μg/g) was one order of magnitude greater than that of polybrominated diphenyl ethers (0.80μg/g). The composition of OPFR chemicals in house dust was dominated by chlorinated OPFRs, such as tris(1,3-dichloro-2-propyl) phosphate (TDCPP) and tris(1-chloro-2-propyl) phosphate (TCPP). This compositional pattern was different from what has been reported in indoor dust from many other countries, where tris(2-butoxyethyl) phosphate (TBEP) was generally dominant. The daily intake of OPFRs by adults was estimated to be 1.6 and 4.2ng/kg body weight/day under average and high exposure scenarios, respectively, and 31.7 and 127ng/kg body weight/day for toddlers.

Organophosphate flame retardants in the indoor air and dust in cars in Japan.

The concentrations of organophosphate flame retardants (OPFRs) in the indoor air and dust were measured in 25 unoccupied cars in Japan. In the indoor air of the cars, most OPFRs were neither detected nor found at a concentration lower than the method quantification limit. The highest concentration (1500ngm-3) was obtained for tris(1-chloro-2-propyl) phosphate (TCIPP). By contrast, many OPFRs were detected in the dust samples collected from the interior of the cars. TCIPP and tris(2-ethylhexyl) phosphate (TEHP) were present at the highest concentrations at 390 μgg-1 (in dust from car seats) and 640μgg-1 (in dust from car floor mats), respectively. The highest median concentrations (35μgg-1 for car seats, 53μgg-1 for car floor mats) were obtained for tris(2-butoxyethyl) phosphate (TBOEP). According to the results of our exposure assessment, the typical exposures to OPFRs via inhalation in car cabins ranged from 9.0×10-4 to 7.8×10-1 ngkg-bw-1 day-1. The typical exposures to OPFRs via dust ingestion ranged from 9.2×10-4 to 8.8×10-1 ngkg-bw-1 day-1. We compared these results with the ref-erence doses for OPFRs and found that, based on cur-rent information about the toxicities of OPFRs, exposure to OPFRs in car cabins via inhalation and dust ingestion is unlikely to have adverse human health effects.