Tris(2-chloroisopropyl) Phosphate Research Articles

Human Exposure to Chlorinated Organophosphate Ester Flame Retardants and Plasticizers in an Industrial Area of Shenzhen, China.

Human exposure to organophosphate esters (OPEs) is more pervasive in industrial areas manufacturing OPE-related products. OPE exposure is of great concern due to its associations with adverse health effects, while studies on OPE exposure in industrial districts are scarce. This study aimed to assess human exposure to OPEs in a typical industrial area producing large amounts of OPE-related products in Shenzhen, China. Tris (2-chloroethyl)-phosphate (TCEP), tris (2-chloroisopropyl) phosphate (TCPP) and other common OPEs were analyzed in urine (n = 30) and plasma (n = 21) samples. Moreover, we measured five OPE metabolites (mOPEs) in plasma samples (n = 21). The results show that TCPP and TCEP are dominant compounds, with moderate to high levels compared with those reported in urine and plasma samples from other regions. In addition, di-n-butyl phosphate (DnBP) and diethyl phosphite (DEP) were frequently detected in plasma samples and could be considered as biomarkers. Risk assessment revealed a moderate to high potential health risk from TCEP exposure. Our results provide basic data for human exposure to OPEs in industrial areas and call for the prevention and mitigation of industrial chlorinated OPE pollution.

A natural environmental chamber study on the emissions and fate of organophosphate esters in the indoor environment

In this study, we investigated the emission and fate of 9 organophosphate esters (OPEs) from a natural environment chamber, in which three environment matrices (i.e., air, dust, and window film samples) as well as three decoration materials (i.e., laminate flooring, latex paint, and nonwoven paper) were collected within gradient variation of room temperature and relative humidity. ΣAlkyl-OPEs and ΣCl-OPEs were the predominant classes in the three environment matrices, accounting – on average – for 98.7%, 99.8% and 99.3% of ΣOPEs in indoor dust, air and window film, respectively. TBOEP was the most abundant OPE in air, dust, and laminate flooring, respectively, while tris (2-chloro-isopropyl) phosphate (TCIPP) and tris (1,3-dichloro-2-propyl) phosphate (TDCIPP) in nonwoven paper and latex paint, respectively. The results showed that higher room temperature expedited the emission of OPEs to indoor air. However, the room temperature and relative humidity had no effect on the levels of OPEs in dust. The OPEs equilibrium time in indoor environment may be dependent on room temperature and relative humidity. The area specific emission rates (SERs) of the three materials were calculated, and an optimal expression based on the concept of mass balance model was constructed, preliminarily revealing a general relationship between OPEs source and sink effects in indoor environment.

Exposure of e-waste dismantlers from a formal recycling facility in Spain to inhalable organophosphate and halogenated flame retardants

Concentration levels of 16 organophosphate esters (OPEs) and 18 halogenated flame retardants (HFRs) were measured in airborne fine particulate matter (PM2.5) from an e-waste dismantling facility in Catalonia (Spain) to assess their occurrence, profiles and potential health risks. Three different areas from the facility were studied, including an area for cathodic ray-tube (CRT) TV dismantling, a grinding area, and the outdoor background. OPEs and HFRs were detected in all samples, with concentrations between 10.4 and 110 ng/m3 for OPEs and from 0.72 to 2213 ng/m3 for HFRs. The compounds with highest concentrations in both working areas were triphenyl phosphate (TPHP) and tris(2-chloroisopropyl) phosphate (TCIPP) for OPEs and decabromodiphenyl ether (BDE-209) for HFRs. Higher concentration levels were found in the CRT area compared to the grinding one, probably due to the lower ventilation and different types of e-waste being processed. OPEs were also detected in the solid e-waste from the facility, highlighting the need to evaluate pollutant levels in e-waste before proceeding to its re-use. Estimated daily intakes via inhalation during workday were calculated, as well as carcinogenic and non-carcinogenic health risks, these being 25 and 50 times lower than threshold risk values in the worst cases, respectively. However, this calculated risk only considers the workday exposure via inhalation, while other routes of exposure (e.g., ingestion, dermal) could bring these values closer to threshold values.

Fire-retardant and smoke-suppressant rigid polyurethane foam composites

PurposeThe purpose of this paper is the production of fire retardant and smoke suppressant rigid polyurethane foam (RPUF) with lower toxicity by using several fire-retardant combinations.Design/methodology/approachFire-retardant additives with cooling effect, barrier ash formation effect, gas-phase inhibition effect and smoke suppressant effect combined to produce an optimum outcome on RPUF. The additive amount and burning time correlation were studied to find out the minimum amount of fire-retardant to obtain fire-retardant polyurethane foam.FindingsZinc borate powder was coated with 1.5 wt % of stearic acid and hydroxy stearic acid. Polyammonium diborates (PABs) were synthesized and used as a fire-retardant and smoke suppressant for rigid PU foam. Fire-retardant rigid polyurethane foams (FR-RPUF) composites formed by using several combinations of zinc borate, aluminum trihydroxide, trischloroisopropyl phosphate (TCPP), PABs, zinc borate coated with stearic acid and hydroxy stearic acid. Produced FR-RPUF were horizontal burning grade, and burning time was in the range of 1–10 s.Research limitations/implicationsThere were limitations during the mixing of fire-retardant powders with polyol due to the high viscosity of the mixture.Practical implicationsFR-RPUF foam with lower toxicity can be produced industrially with these fire-retardant combinations.Social implicationsFR-RPUF could be produced by using non-toxic additives. During a fire, these additives do not evolve toxic gases. The TCPP content of RPUF foam was reduced, and fire-retardant PU with lower toxicity was produced.Originality/valueCoated zinc borate and the combinations of the fire-retardants were successful in producing non-toxic fire-retardant and smoke suppressant PU foam.

Mesoscale cycling of organophosphorus flame retardants (OPFRs) in the Bohai Sea and Yellow Sea biotic and abiotic environment: A WRF-CMAQ modeling

Rapid urbanization and industrialization in the eastern seaboard region of China enhance the widespread use of organophosphorus flame retardants (OPFRs). The present study set up a coupled WRF-CMAQ-SMOKE and multi-compartment exchange modeling framework to assess the environmental fate and cycling of OPFRs and their contamination in the Bohai and Yellow Seas' marine food web. The framework predicts meteorological conditions, optimized air emissions, and concentrations of OPFRs in air, seawaters, marine sediment, and the food web. The model was implemented to simulate the temporal and spatial fluctuations of Tris (2-chloroisopropyl) phosphate (TCPP), the most dominant congener of OPFRs in China, in the Bohai and the Yellow Sea ecosystems on a spatial resolution of 10 km. Results revealed the effects of source proximity, atmospheric transport and deposition, and the changes in meteorology on TCPP's temporal-spatial distribution across different areas of coastal waters. The model also captures TCPP levels in commercial fish species in the Bohai Sea. The detailed temporal-spatial characteristics of TCPP with the mesoscale resolution provide useful information and a new tool for the environmental and health consequences of mariculture, urban and industrial emission mitigation in coastal regions for emerging chemicals, and fishery industry development.

Organophosphate flame retardants induce oxidative stress and Chop/Caspase 3-related apoptosis via Sod1/p53/Map3k6/Fkbp5 in NCI-1975 cells

Organophosphate flame retardants (OPFRs) have been ubiquitously detected in dust and air which could cause damage to human health through inhalation. Currently the understanding of their adverse effects and potential mechanisms on the lung are still limited. In this study, human non-small cell lung cancer cell line NCI-H1975 was used to investigate the cytotoxicity, oxidative stress, cellular apoptosis of 9 typical OPFRs with concentrations varied from 0 to 200 μM, and their toxic mechanism associated with molecular structure was compared. After 72 h, tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) displayed the highest cytotoxicity, followed by 2-ethylhexyl diphenyl phosphate (EHDPP), tris(2-butoxyethyl) phosphate (TBOEP) and tris(2-chloroisopropyl) phosphate (TCIPP), while tris(2-chloroethyl) phosphate (TCEP) and tris(2-ethylhexyl) phosphate (TEHP) exhibited the least suppression on cell viability. These results indicated that the variation of cytotoxicity on OPFRs could only be partially explained by their ester linkage. Moreover, the overexpression of intracellular reactive oxygen species (ROS), free Ca2+ and cellular apoptosis suggested that exposure to OPFRs can lead to apoptosis related to oxidative stress. Six genes associated with oxidative stress and apoptosis were upregulated dramatically compared with the control, demonstrating OPFRs induced Chop/Caspase 3-related apoptosis by activating Sod1/p53/Map3k6/Fkbp5 expression in NCI-H1975 cells. This is the first study to investigate cytotoxicity and related mechanism on commonly-used OPFRs in NCI-H1975 cells.

Degradation of organophosphorus flame retardants in heterogeneous photo-Fenton system driven by Fe(III)-based metal organic framework: Intermediates and their potential interference on bacterial metabolism

Organophosphorus flame retardants (OPFRs) have been regarded as one of the most rebarbative classes of emerging contaminants due to their persistence and toxicity. In the current study, Fe-based metal organic framework (MIL-88A) was synthesized and employed as photo-Fenton catalyst for the degradation of tris-(2-chloroisopropyl) phosphate (TCPP), a typical representative of OPFRs. The observations indicated that visible light could boost the reduction of ≡FeIII to ≡FeII in Fe–O clusters of MIL-88A during the photo-Fenton system and consequently induce the transformation of H2O2 to OH, which realized efficient degradation of TCPP. Due to the excellent function of MIL-88A, the effective pH application range of photo-Fenton system was extended in comparison with traditional Fenton system. The degradation efficiency of TCPP was visibly influenced in presence of humic acid (HA). MIL-88A exhibited a commendable reusability and stability after 3 times cycle. As the photo-Fenton reaction proceeded, TCPP was disintegrated to several kinds of carboxylated, dechlorinated and hydroxylated products. The observations of metabolomics endorsed that the interference of intermediate products mixture on E. coli weakened to a certain extent. In conclusion, carboxylation, dechlorination, hydroxylation and oxidation of TCPP were likewise effective for its detoxification, revealing that heterogeneous photo-Fenton system driven by Fe-based metal organic framework will be an attractive and safe treatment technique for OPFRs control.

Amino-functionalized MIL-88B as heterogeneous photo-Fenton catalysts for enhancing tris-(2-chloroisopropyl) phosphate (TCPP) degradation: Dual excitation pathways accelerate the conversion of [tbnd]FeIII to [tbnd]FeII under visible light irradiation

In this work, the amino-functionalized metal-organic frameworks (MIL-88B-NH2) was synthesized, characterized and used as heterogeneous photo-Fenton catalyst for tris-(2-chloroisopropyl) phosphate (TCPP) degradation. The photo-Fenton activity of MIL-88B-NH2 was investigated on the basis of influence factors, such as initial pH and TCPP concentration, and coexisting impurities. The results revealed that MIL-88B-NH2+H2O2+Vis system exhibited a satisfactory degradation efficiency of TCPP (almost 100%) within 60 min accompanied by a good reusability. Noticeably, the degradation kinetics constant of TCPP by MIL-88B-NH2+H2O2+Vis system was 0.086 min−1, which was visibly higher than that of MIL-88B+H2O2+Vis system (0.021 min−1) since the addition of amino-functionalized organic linker inhibiting the recombination rate of the photo-generated electron-hole pairs and improving the visible light response. Combined with the characterization, the conversion of FeIII to FeII could be accelerated by the photo-generated electron from the excitation of Fe-O clusters and NH2 functionalities, which strengthened the decomposition of H2O2 and formed plenty •OH. Simultaneously, six steady products were validated and potential degradation pathways of TCPP were proposed. It was anticipated that MIL-88B-NH2 could be considered as a desirable and alternative candidate in the application of heterogeneous photo-Fenton reaction to control the environmental risks caused by organophosphate flame retardants (OPFRs).

Occurrence, potential sources and risks of organophosphate esters in the high-elevation region, Tibet, China

Organophosphate esters (OPEs) are widely used flame retardants that are frequently released into the environment, causing potential harm to humans and ecosystems. Tibet is located on the Tibetan Plateau, known as the “roof of the world”, but the occurrence of OPEs in Tibet remains unclear. This is the first report of the occurrence, potential sources and risks of 12 OPEs in water, soil, sediment and snow from Xainza, a typical town at high-elevation in Tibet (average elevation = 4700 m). Ten OPEs were observed, with ∑OPE concentrations of 46.45–1744.73 ng/L in surface water, 29.74–73.85 ng/g in soil, and 13.30–32.23 ng/g in sediment. Moreover, the mean ∑OPE concentration in snow was 413.90 ng/L. Tris (2-chloroethyl) phosphate (TCEP) and tris (2-chloroisopropyl) phosphate (TCPP) were the main OPEs in surface water and snow, while 2-ethylhexyl diphenyl phosphate (EHDPP) was dominant in soil and sediment. Local human activities and long-distance atmospheric transport may be the main sources of OPEs in Xainza. The assessment of ecological risk indicated that EHDPP in soil poses potential risk. The occurrence of OPEs in Xainza showed that more attention should be paid to persistent organic pollutants in high-elevation regions.

Occurrence and distribution of organophosphate flame retardants in the typical soil profiles of the Tibetan Plateau, China

The urbanization and development of Tibetan Plateau (TP) probably results in a significant contamination of organic pollutants, such as organophosphate flame retardants (OPFRs). However, there is a lack of monitoring and evaluation of their occurrence and risks in the soil of TP. We investigated the concentrations, vertical distributions, potential sources, and ecological risks of OPFRs in soil profiles from four regions of TP, China. The total concentrations of OPFRs in all soil samples ranged from 1.35 to 126 ng/g with a median of 12.6 ng/g. Relatively high concentrations were discovered in the top soils from Lhasa, suggesting a rising contamination around cities of TP due to anthropogenic disturbance. Tri-n-butyl phosphate (TNBP) was the dominant OPFRs followed by tris(2-chloroethyl) phosphate (TCEP). Vertical distribution of ΣOPFRs was discovered, especially at site Lhasa. Source apportionment based on principle component analysis and correlation analysis suggests that OPFRs in the TP soil mainly originate from atmospheric transport, while some OPFRs in the top soil may be also influenced by nearby sources. The vertical distributions of OPFRs in soil may be influenced by both soil and chemical properties, as well as their use. The ecological risk quotients (RQs) of 6 OPFRs in the TP soil were calculated, and most of their ecological risks were relatively low or negligible. However, for the worst-case scenario calculated by the 95th percentile concentrations, TNBP and tris(2-chloro-isopropyl) phosphate (TCIPP) at site Lhasa and cresyl diphenyl phosphate (CDP) at site Nagri had moderate risks. More attentions should be paid to the Tibetan Plateau in the future due to the rising ecological risks of OPFRs, especially to the areas around cities.

Textile Washing Conveys SVOCs from Indoors to Outdoors: Application and Evaluation of a Residential Multimedia Model.

Indoor environments have elevated concentrations of numerous semivolatile organic compounds (SVOCs). Textiles provide a large surface area for accumulating SVOCs, which can be transported to outdoors through washing. A multimedia model was developed to estimate advective transport rates (fluxes) of 14 SVOCs from indoors to outdoors by textile washing, ventilation, and dust removal/disposal. Most predicted concentrations were within 1 order of magnitude of measurements from a study of 26 Canadian homes. Median fluxes to outdoors [μg·(year·home)-1] spanned approximately 4 orders of magnitude across compounds, according to the variability in estimated aggregate emissions to indoor air. These fluxes ranged from 2 (2,4,4'-tribromodiphenyl ether, BDE-28) to 30 200 (diethyl phthalate, DEP) for textile washing, 12 (BDE-28) to 123 200 (DEP) for ventilation, and 0.1 (BDE-28) to 4200 (bis(2-ethylhexyl) phthalate, DEHP) for dust removal. Relative contributions of these pathways to the total flux to outdoors strongly depended on physical-chemical properties. Textile washing contributed 20% tris-(2-chloroisopropyl)phosphate (TCPP) to 62% tris(2-butoxyethyl)phosphate (TBOEP) on average. These results suggest that residential textile washing can be an important transport pathway to outdoors for SVOCs emitted to indoor air, with implications for human and ecological exposure. Interventions should try to balance the complex tradeoff of textile washing by minimizing exposures for both human occupants and aquatic ecosystems.

Monitoring Human Exposure to Organophosphate Esters: Comparing Silicone Wristbands with Spot Urine Samples as Predictors of Internal Dose.

Silicone wristbands present a noninvasive exposure assessment tool and an alternative to traditional biomonitoring; however, questions about their utility remain as validation studies are limited. We sought to determine if wristbands provide quantitative estimates of internal organophosphate ester (OPE) exposure. We evaluated internal dose by measuring metabolite masses excreted in 24-hour urine samples collected over five days among ten adults. We compared internal dose to OPE concentrations in paired wristbands worn during collection and, as a comparison, evaluated metabolite levels in spot urine samples. Three of six OPE metabolites evaluated were detected in >98% of urine samples, and 24 of 34 assessed OPEs were detected in at least one wristband. OPE uptake in wristbands was linear over time (range=0.54-61.8 ng/g/day). OPE concentrations in spot urine and wristbands were not correlated with total diphenyl phosphate (DPHP) excreted in urine, which may be due to the range of possible DPHP parent compounds or dietary exposure. However, for tris-(1,3-dichloro-2-propyl)phosphate (TDCIPP) and tris-(2-chloroisopropyl)phosphate (TCIPP), wristbands and spot urine samples were both moderately to strongly correlated with internal dose (all rs>0.56 and p<0.1), suggesting both perform well as integrated exposure estimates. Given the potential advantages of silicone wristbands, further studies investigating additional compounds are warranted.

Presence of organophosphate flame retardants (OPEs) in different functional areas in residential homes in Beijing, China

The production and application of organophosphate esters (OPEs) have dramatically increased in recent years due to their use as a replacement for brominated flame retardants. In this study, 13 OPEs (Σ13OPEs) were analyzed in indoor air samples from kitchens and living rooms in 14 residential homes in Beijing, China. The concentrations of Σ13OPEs in kitchen air samples (mean: 13 ng/m3) were significantly (p < 0.05) higher than in living room air samples (5.0 ng/m3). In addition, paired window surface organic film samples were collected and analyzed to investigate film-air partitioning, exhibiting a mean concentration of Σ13OPEs of 4100 ng/m2. The congener profiles showed that tris(2-chloroisopropyl) phosphate (TCPP) was the predominant compound in both window film samples (48%) and the corresponding indoor air sample (56%). The estimated daily intakes (EDI) of OPEs via indoor air inhalation were 2.8 and 1.4 ng/kg/day for infants and adults, respectively, both of which are below the reference dose values (RfDs). Overall, these findings indicate that OPEs in the indoor air environment of residential homes in Beijing are not likely to pose a health risk to the general population.

Hepatic Gene Expression Profiling of Atlantic Cod (Gadus morhua) Liver after Exposure to Organophosphate Flame Retardants Revealed Altered Cholesterol Biosynthesis and Lipid Metabolism.

Since the phasing out and eventual ban on the production of organohalogen flame retardants, the use of organophosphate flame retardants (OPFRs) has increased rapidly. This has led to the detection of OPFRs in various environments including the Arctic. Two of the most prevalent OPFRs found in the Arctic are tris(2-chloroisopropyl) phosphate (TCPP), and 2-ethylhexyl diphenyl phosphate (EHDPP). The impacts of exposure to OPFRs on Arctic organisms is poorly understood. The objective of the present study was to determine the effects of exposure to TCPP, EHDPP, and a mixture of OPFRs on gene expression patterns in Atlantic cod, Gadus morhua. Precision-cut liver slices from Atlantic cod in vitro were exposed to either TCPP or EHDPP alone or in a mixture and sampled at 2 different time points to quantify gene expression patterns using RNA sequencing. We exposed the liver slices to 2 concentrations of TCPP and EHDPP, one of which was chosen based on the levels found in the Arctic environment. The RNA sequencing results demonstrated differential expression of hundreds of genes in response to exposure. The genes representing cholesterol biosynthesis and lipid metabolism pathway were significantly enriched in all the treatment groups. Almost all the cholesterol biosynthesis genes were significantly down-regulated in response to OPFR exposure. The effects on these pathways could involve various physiological processes including reproduction, growth, and behavior as well as adaptation to changing temperatures. Membrane fluidity is an important adaptive mechanism among aquatic organisms. Altered cholesterol homeostasis could have long-term consequences by altering the adaptive potential of aquatic organisms to changing water temperatures, particularly those living in polar environments. These results suggest that OPFRs could have unique effects on the organisms living in the Arctic compared with other environments. Further studies are needed to understand the long-term impacts of exposure to environmentally realistic concentrations using laboratory and field-based studies. Environ Toxicol Chem 2021;40:1639-1648. © 2021 SETAC.

Spatial distribution and air−water exchange of organophosphate esters in the lower Great Lakes

Organophosphate esters (OPEs) have been detected at elevated concentrations in the Great Lakes region, dwarfing other flame retardants, such as polybrominated diphenylethers (PBDEs), as chemicals of emerging concern (CECs). This prompted us to deploy polyethylene (PE) passive samplers in air and water column of the lower Great Lake region (Lake Erie and Lake Ontario) to detect gaseous and dissolved OPEs, evaluate their occurrence and spatial distribution, and estimate their air-water gas exchange fluxes. The median concentration of the total dissolved and gaseous phase OPEs detected (Σ9OPEs) were 95 ng L−1 and 404 pg m−3, respectively, during April–November 2014. Gaseous and dissolved concentrations were dominated by chlorinated compounds, in particular (tris(2-chloroethyl) phosphate (TCEP) and tris(2-chloroisopropyl) phosphate (TCPP), while tri-n-butyl phosphate (TnBP) was the dominant non-chlorinated OPEs in both media. Decreasing concentration gradients from shoreline/nearshore to offshore sites for both gaseous and aqueous OPEs reflect anthropogenic influence from the adjacent rural and urban regions. The partial dependence of gaseous OPEs on temperature indicate the importance of volatilization from local sources, fresh emissions as well as advection from distant sources to air. Almost all OPEs underwent net gas-phase deposition to the lakes, dominated by TCEP and TCPPs with median fluxes of −3980 ng/m2/day and −1320 ng/m2/day; the exception was TnBP, which underwent volatilization with the median fluxes of 1980 ng/m2/day. For all air-water pairs, the gaseous diffusive fluxes were 2–4 orders of magnitude greater than the estimated particle dry deposition fluxes.

Enhanced tris-(2-chloroisopropyl) phosphate degradation through ultraviolet driven peroxymonosulfate process: Kinetics, mechanism, residual toxicity assessment of intermediates products by proteomics

Tris-(2-chloroisopropyl) phosphate (TCPP), one of emerging organic pollutants has aroused a growing concern due to its potential biotoxicity and persistence. Oxidation degradation of using SO4*− based AOPs was explored. A pseudo-first order kinetics reaction with the degradation rate constant at 0.1789 min−1 fitted the transformation of TCPP. SO4*− was the predominant oxidation species confirmed by scavenging assay. Five steady intermediates including C6H13Cl2O4P (m/z 251.0002), C3H8ClO4P (m/z 174.9922), C9H17Cl2O5P (m/z 307.0266), C9H17Cl2O6P (m/z 323.0217), C6H12ClO6P (m/z 247.0134) were screened by high resolution mass spectroscopy analysis. The influences of vital parameters, i.e., natural anions, pH value, humic acid (HA) and peroxymonosulfate (PMS) dose were tested. HA and alkaline conditions can significantly decreased the photocatalytic rate to inhibit removal efficiency. EE/O evaluation had also proved that a neutral condition and HA pretreatment were conductive to elevating removal efficiency and reducing energy consumption. Based on proteomics and metabolic network analysis, TCPP was effectively detoxified as its further transformation proceeded, which was proved by nucleotide metabolisms, citric acid metabolism, oxidative phosphorylation and amino acid biosynthesis. To summarize, an appropriate degradation of TCPP likewise are effective for its detoxification, indicating the feasibility and security of TCPP elimination using UV/PMS treatment.

Occurrence, spatiotemporal distribution, and ecological risks of organophosphate esters in the water of the Yellow River to the Laizhou Bay, Bohai Sea

Limited information is available on the spatiotemporal occurrence and ecological risks of organophosphate esters (OPEs) in coastal environments. 175 water samples were collected in Laizhou Bay (LZB) and its rivers and estuaries during spring and summer for the determination of 12 targeted OPEs. Total concentration of OPEs ranged from 234.4 to 2892.1 ng L−1 in the river and estuarine water and 87.6 to 969.4 ng L−1 in the bay water, with medians of 1015.8 and 296.8 ng L−1, respectively, showing that riverine inputs were the major sources of OPEs in the bay. Tris (2-chloroisopropyl) phosphate (TCIPP) and triethyl phosphate (TEP) were the most abundant OPEs, with median contributions of 47% and 36% in the bay water, respectively. The total concentration of OPEs was higher in the estuarine area of the Yellow River and the southwestern coast of the LZB under the influence of riverine OPE inputs and ocean currents. In addition, the concentrations of dominant OPE species were significantly higher in the surface water than in the bottom water. The concentrations of dominant OPE species were found to be significantly lower in summer than in spring, mainly due to both precipitation and seawater dilution effects. However, the concentrations of three minor OPE species were significantly higher in summer than in spring, probably because of their high usage in summer. TCIPP and TEP concentrations were significantly negatively correlated with salinity. The targeted OPEs posed low ecological risk in the bay and moderate ecological risk in the rivers and estuaries, which was mostly ascribed to the toxicity of tris (2-chloroethyl) phosphate (TCEP) and resorcinol-bis (diphenyl) phosphate (RDP) to algae. Priority should be given to TCIPP, TEP, TCEP, and RDP in the LZB due to their high concentrations and/or toxicity.

Occurrence of organophosphate esters in surface water and sediment in drinking water source of Xiangjiang River, China

In this study, we investigated the occurrence of organophosphate esters (OPEs) in the surface water and sediments of the Xiangjiang (XJ) River, a drinking water source of Changsha City. The total concentrations of five detected OPEs (Σ5OPEs) in surface water and tap water were 6.07–25.3 ng L−1 (average 14.9 ± 4.98 ng L−1), and 23.6 ng L−1, respectively, and four detected OPEs (Σ4OPEs) in sediments were 3.74–27.5 ng g−1 dw (average 12.1 ± 6.48 ng g−1 dw). Tris-2-chloroisopropyl phosphate (TCIPP) was the dominant contributor in water and sediment samples, accounting for over 40% of ΣOPEs. A particular flood event during July–August 2020 reduced the level of OPEs in river water, leading to generally uniform OPE concentrations in surface water and sediment samples from the upper, middle, and lower reaches of XJ. Principal component analysis-multiple linear regression (PCA-MLR) results indicated that the main sources of OPEs in the surface water and sediments of XJ were emissions of waste-water treatment plants and anthropocentric activities. The results of ecological and human health risk assessments indicated that all OPEs posed a low or negligible ecological risk for algae, daphnia, and fish, and negligible risk for human health. Interestingly, the concentration and human health risk of OPEs in a composite tap water sample was generally higher than those in river water samples, indicating possible OPE contamination from water treatment processes or transportation through pipe networks.

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.

Seasonal variation and affecting factors of organophosphate esters in particulate matter in air: a comparison between measured data and model predictions

Six organophosphate esters (OPEs) with different octanol-air partition coefficient (KOA) were measured from gas and particle samples collected from an urban area of Central China between June 2018 and May 2019. The highest concentration of total OPEs (∑6OPEs) in total suspended particle (TSP) were found in winter, followed by spring, autumn, and summer. ∑6OPEs showed significant positive correlation with TSP concentration (p < 0.01), significant negative correlation with temperature (p < 0.01), weak negative linear correlations with relative humility (p < 0.05), and no significant correlations with wind speed (p > 0.05). Although OPEs were not detected in polyurethane foams (PUFs), the poly-parameter linear free energy relationship model (pp-LFER) estimated particle fractions of OPEs (fpart pp-LFERg/p) were below 2.73% for Tris (2-chloroisopropyl) phosphate (TCIPP), Tris (chloroethyl) phosphate (TCEP), and Tributyl phosphate (TnBP); 67.8% for Triphenyl phosphate (TPhP); and above 99.6% for TBOEP and TCrP. The concentrations of particle-bound TPhP, TCrP, and TBOEP estimated by pp-LFER (Cpart pp-LFERg/p) were 0.19, 0.09, and 0.05 ng/m3, which were in good agreement with measurements. However, the estimated Cpart pp-LFERg/p of TCEP, TCIPP, and TnBP showed obvious differences with measured data. According to filter-air partitioning estimated by pp-LFER, the strong adsorption of gaseous OPEs to glass fiber filter (GFF) may be responsible to the underestimation. Besides, the weak adsorption of gaseous OPEs to PUF is likely to be another important reason for the discrepancy between measured and modeled results. Therefore, the risk assessment of gaseous OPEs should be of concern in the further research.