Tris(2-chloroethyl) Phosphate Research Articles

Synergistic degradation of Tris (2-Chloroethyl) Phosphate (TCEP) by US/Fenton system: Experimental, DFT calculation and toxicity evaluation.

Organophosphorus esters (OPEs), exemplified by tris (2-chloroethyl) phosphate (TCEP), find extensive application in diverse industries such as construction materials, textiles, chemical manufacturing, and electronics, consequently resulting in an increased concentration of these compounds in industrial wastewater. The fundamental objective of this investigation was to examine the degradation of TCEP through the implementation of US/Fenton oxidation techniques in a solution. The findings revealed that the US/Fenton system effectively facilitated the degradation of TCEP, with the Chan kinetic model precisely elucidating the degradation process. Under optimized reaction conditions, the degradation efficiency of TCEP reached an impressive 93.18%. However, the presence of common co-existing aqueous substrates such as Cl-, HCO3-, H2PO4-, and HA hindered the degradation process. Bursting tests and electron paramagnetic resonance (EPR) studies affirmed ∙OH oxidation as the principal mechanism underlying TCEP degradation. Detailed degradation pathways for TCEP were established through the utilization of density-functional theory (DFT) calculations and GC/MS tests. Moreover, the ecotoxicological evaluation of TCEP and its intermediates was conducted using the Toxicity Estimation Software Tool (T.E.S.T.).

Experimental investigation on the combustion characteristics of electrolyte jets containing flame retardant tris (2-chloroethyl) phosphate

Abstract It is critical to well understand the combustion characteristics of the electrolytes inside lithium-ion batteries for safety concerns, particularly the electrolyte jet flames after thermal runaway. An electrolyte jet fire setup is developed in this study to investigate the combustion characteristics of electrolyte jets with the flame-retardant additive tris (2-chloroethyl) phosphate (TCEP) under high-temperature circumstances. Jet and ignition delay times and flammability are defined to characterize the flame-retardant effects. The fundamental parameters of self-extinguishing time and propagation rate are also measured for a comprehensive comparison. The experimental results show that the propagation of electrolyte flame at ambient temperature can be entirely stopped with 40 wt % of TCEP additives and 50 wt % can make the electrolyte nonflammable. Owing to the high boiling temperature and vaporization enthalpy of TCEP, more heat is required for the decomposition of electrolytes and TCEP mixtures, resulting in lower decomposition reaction rates and heat release rates. Thus, both the jet delay times and the ignition delay times significantly increase with the TCEP additives. Moreover, analyses on the spectrum of electrolyte jet flame reveal that the suppressing effects of TCEP on the combustion of electrolyte jets are operated by scavenging the OH radical and heat release.

Tris (2-chloroethyl) phosphate presence inhibits methane production from anaerobic digestion: Alterations in organic matter transformation, cell physiological status, and microbial community

Organophosphate flame retardants (OPFRs) are widely used in consumer products, leading to their unavoidable release into the environment, especially accumulation in anaerobic environments and posing potential risks. This study focused on Tris(2-chloroethyl) phosphate (TCEP), a representative OPFR, to investigate its effects on carbon transformation and methane production in anaerobic digestion. Increasing TCEP concentrations from control to 16 mg/L resulted in decreased cumulative methane yield (from 235.4 to 196.3 mL/g COD) and maximum daily methane yield (from 40.8 to 16.17 mL/(g COD·d)), along with an extended optimal anaerobic digestion time (from 15 to 20 days). Mechanistic analysis revealed TCEP binding to tyrosine-like proteins in extracellular polymeric substances, causing cell membrane integrity impairment. The TCEP-caused alteration of the physiological status of cells was demonstrated to be a significant contribution to the inhibited bioprocesses including acidogenesis, acetogenesis, and methanogenesis. Illumina Miseq sequencing showed TCEP decreasing the relative abundance of acidogens (58.8 % to 46.0 %) and acetogens (7.1 % to 5.0 %), partly shifting the methanogenesis pathway from acetoclastic to hydrogenotrophic methanogenesis. These findings enhance understanding of TCEP's impact on anaerobic digestion, emphasizing the environmental risk associated with its continued accumulation.

Trimester-specific effect of maternal co-exposure to organophosphate esters and phthalates on preschooler cognitive development: The moderating role of gestational vitamin D status

Organophosphate esters (OPEs) and phthalate acid esters (PAEs) are prevalent endocrine-disrupting chemicals (EDCs). Humans are often exposed to OPEs and PAEs simultaneously through multiple routes. Given that fetal stage is a critical period for neurodevelopment, it is necessary to know whether gestational co-exposure to OPEs and PAEs affects fetal neurodevelopment. However, accessible epidemiological studies are limited. The present study included 2, 120 pregnant women from the Ma'anshan Birth Cohort (MABC) study. The concentrations of tris (2-chloroethyl) phosphate (TCEP), 6 OPE metabolites and 7 PAE metabolites were measured in the first, second and third trimester using ultra-performance liquid chromatography-tandem mass spectrometry (LC-MS). Cognitive development of preschooler was assessed based on the Wechsler Preschool and Primary Scale of Intelligence-Fourth Edition (WPPSI-IV) of the Chinese version. Generalized estimating equations (GEEs), restricted cubic spline (RCS) and generalized additive models (GAMs) were employed to explore the associations between individual OPE exposure and preschooler cognitive development. The quantile-based g-computation (QGC) method was used to estimate the joint effect of PAEs and OPEs exposure on cognitive development. GEEs revealed significant adverse associations between diphenyl phosphate (DPHP) (β: −0.58, 95% CI: −1.14, −0.01), bis (2-butoxyethyl) phosphate(BBOEP) (β: −0.44, 95% CI: −0.85, −0.02), bis(1-chloro-2-propyl) phosphate (BCIPP) (β: −0.81, 95%CI: −1.43, −0.20) and full-scale intelligence quotient (FSIQ) in the first trimester; additionally, TCEP and bis(2-ethylhexyl) phosphate (BEHP) in the second trimester, as well as DPHP in the third trimester, were negatively associated with cognitive development. Through the QGC analyses, mixture exposure in the first trimester was negatively associated with FSIQ scores (β: −1.70, 95% CI: −3.06, −0.34), mono-butyl phthalate (MBP), BCIPP, and DPHP might be the dominant contributors after controlling for other OPEs and PAEs congeners. Additionally, the effect of OPEs and PAEs mixture on cognitive development might be driven by vitamin D deficiency.

Do the same chlorinated organophosphorus flame retardants that cause cytotoxicity and DNA damage share the same pathway?

Organophosphorus flame retardants (OPFRs) have been frequently detected with relatively high concentrations in various environmental media and are considered emerging environmental pollutants. However, their biological effect and underlying mechanism is still unclear, and whether chlorinated OPFRs (Cl-OPFRs) cause adverse outcomes with the same molecular initial events or share the same key events (KEs) remains unknown. In this study, in vitro bioassays were conducted to analyze the cytotoxicity, mitochondrial impairment, DNA damage and molecular mechanisms of two Cl-OPFRs. The results showed that these two Cl-OPFRs, which have similar structures, induced severe cellular and molecular damages via different underlying mechanisms. Both tris(2-chloroethyl) phosphate (TCEP) and tris(1-chloro-2-propyl) (TCPP) induced oxidative stress-mediated mitochondrial impairment and DNA damage, as shown by the overproduction of intracellular reactive oxygen species (ROS) and mitochondrial superoxide. Furthermore, the DNA damage caused by TCPP resulted in p53/p21-mediated cell cycle arrest, as evidenced by flow cytometry and real-time PCR. At the cellular and molecular levels, TCPP increased the sub-G1 apoptotic peak and upregulated the p53/Bax apoptosis pathway, possibly resulted in apoptosis associated with its stronger cytotoxicity. Although structurally similar to TCPP, TCEP did not induce mitochondrial impairment and DNA damage by the same KEs. These results provide insight into the toxicity of Cl-OPFRs with similar structures but different mechanisms, which is of great significance for constructing adverse outcome pathways or determining intermediate KEs.

Determination of potential dermal exposure rates of phosphorus flame retardants via the direct contact with a car seat using artificial skin

Dermal exposure to phosphorus flame retardants (PFRs) has received much attention as a major alternative exposure route in recent years. However, the information regarding dermal exposure via direct contact with a product is limited. In addition, in the commonly used dermal permeability test, the target substance is dissolved in a solvent, which is unrealistic. In this study, a dermal permeability test of PFRs in three car seats was performed using artificial skin. The PFR concentrations in the car seats are 0.12 wt% tris(2-chloroethyl) phosphate (TCEP), 0.030–0.25 wt% tris(2-chloroisopropyl) phosphate (TCPP), 0.15 wt% triphenyl phosphate (TPhP), 0.89 wt% cresyl diphenyl phosphate (CsDPhP), 0.074 wt% tricresyl phosphate (TCsP), and 0.46–4.7 wt% diethylene glycol bis [di (2-chloroisopropyl) phosphate (DEG-BDCIPP). The mean skin permeation rates for a contact time of 24 h are 14 (TCEP), 5.4–160 (TCPP), 0.67 (CsDPhP), 0.38 (TPhP), and 3.3–58 ng cm−2 h−1 (DEG-BDCIPP). The concentrations of TCsP in receptor liquid were lower than the limit of quantification at the contact time of 24 h. The skin permeation rates were significantly affected by the type of car seat (e.g., fabric or non-fabric). The potential dermal TCPP exposure rate for an adult via direct contact with the car seat during the average daily contact time (1.3 h), which was the highest value assessed in this study, was estimated to be 16,000 ng kg−1 day−1, which is higher than that related to inhalation and dust ingestion reported as significant exposure route of PFRs in previous studies. These facts reveal that dermal exposure associated with direct contact with the product might be an important exposure pathway for PFRs.

Novel method for rapid monitoring of OPFRs by LLE and GC–MS as a tool for assessing biodegradation: validation and applicability

Organophosphate flame retardants (OPFRs) are high-production volume chemicals widely present in environmental compartments. The presence of water-soluble OPFRs (tri-n-butyl phosphate (TnBP), tris(2-butoxyethyl) phosphate (TBEP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCPP), and triethyl phosphate (TEP)) in water compartments evidences the struggle of conventional wastewater treatment plants (WWTPs) to effectively eliminate these toxic compounds. This study reports for the first time the use of white-rot fungi as a promising alternative for the removal of these OPFRs. To accomplish this, a simple and cost-efficient quantification method for rapid monitoring of these contaminants’ concentrations by GC–MS while accounting for matrix effects was developed. The method proved to be valid and reliable for all the tested parameters. Sample stability was examined under various storage conditions, showing the original samples to be stable after 60 days of freezing, while post-extraction storage techniques were also effective. Finally, a screening of fungal degraders while assessing the influence of the glucose regime on OPFR removal was performed. Longer chain organophosphate flame retardants, TBP and TBEP, could be easily and completely removed by the fungus Ganoderma lucidum after only 4 days. This fungus also stood out as the sole organism capable of partially degrading TCEP (35% removal). The other chlorinated compound, TCPP, was more easily degraded and 70% of its main isomer was removed by T. versicolor. However, chlorinated compounds were only partially degraded under nutrient-limiting conditions. TEP was either not degraded or poorly degraded, and it is likely that it is a transformation product from another OPFR’s degradation. These results suggest that degradation of chlorinated compounds is dependent on the concentration of the main carbon source and that more polar OPFRs are less susceptible to degradation, given that they are less accessible to radical removal by fungi. Overall, the findings of the present study pave the way for further planned research and a potential application for the degradation of these contaminants in real wastewaters.Graphical

Degradation of organophosphate flame retardants by a consortium of bacterial strains isolated from the To Lich river, Hanoi

Organophosphate flame retardants (OPFRs) are degraded by a consortium of 10 bacterial strains isolated from the To Lich river, contaminated with OPFRs. The bacterial consortium is cultured in an A-Cl medium supplemented individually with OPFRs (10 mg/l), resulting in optical density at 600 nm ranging from 1 to 1.5. The consortium of 10 bacterial strains exhibits the ability to degrade tris(2-ethylhexyl) phosphate (TEHP) by 98.5 and 100% after two and three days of cultivation, respectively. Triethyl phosphate (TEP) is also degraded by 76.1 and 100% after two and five days of cultivation, respectively. The degradation efficiency of trimethyl phosphate (TMP), tris(2-chloroethyl) phosphate (TCEP), tris(1,3-dichloro-2-propyl) phosphate (TCDPP), and tributoxy ethyl phosphate (TBEP) is also in the range of 97 to 100% after four days of cultivation. In the experiment adding a mixture of 7 substances in OPFRs at a concentration of 10 mg/l for each compound, only TEHP is completely degraded after six days of cultivation. The degradation efficiency of other OPFRs increases from 93.2 to 100% after six days of cultivation. Comparing the degradation rates of OPFRs in both experiments, the results indicate that the cultures supplemented with each compound individually exhibit a faster degradation rate than when a mixture of OPFRs compounds is added.

Organophosphate esters in the urban atmosphere of Thessaloniki city, Greece

The occurrence of organophosphate esters (OPEs) in the atmosphere of the urban area of Thessaloniki city, Greece was studied. OPEs were determined in particulate matter (PM2.5) and precipitation during the period 2020–2021. ∑OPEs in rainwater ranged from 520 to 4719 ng L−11 (mean: 1662 ng L−1) with tris (2-butoxyethyl) phosphate (TBOEP) and tris (1-chloro-2-propyl) phosphate (TClPP) being the most abundant compounds. TBOEP and TClPP as well as triphenylphosphine oxide (TPPO) and tris (chloroethyl) phosphate (TCEP) were the dominant OPEs in PM2.5. Concentrations of ∑OPEs in PM2.5ranged from 2.82 to 13.3 ng m−3 (mean: 5.93 ng m−3). Wet deposition fluxes of OPEs were estimated and air mass back trajectories were used to elucidate possible source profiles. An overall low health risk for local population via inhalation of OPEs was revealed.

Thermally activated persulfate (TAP)-enhanced tris(2-chloroethyl) phosphate removal in real-world waters based on a response-surface approach as well as toxicological evaluation on its degradation products

As a typical organophosphorus flame retardant, tris(2-chloroethyl) phosphate (TCEP) is refractory in aqueous environment. The application of TAP is a promising method for removing pollutants. Herein, the removal of TCEP using TAP was rigorously investigated, and the effects of some key variables were optimized by the one-factor-at-a-time approach. To further evaluate the interactions among variables, the response surface methodology (RSM) based on central composite design was employed. Under optimized conditions (pH 5, [PS]0: [TCEP]0 = 500:1), the maximum removal efficiency (RE) of TCEP reached up to 90.6%. In real-world waters, the RE of TCEP spanned the range of 56%− 65% in river water, pond water, lake water and sanitary sewage. The low-concentration Cl- (0.1 mM) promoted TCEP degradation, but the contrary case occurred when the high-concentration Cl-, NO3-, CO32-, HCO3-, HPO42-, H2PO4-, NH4+ and humic acid were present owing to their prominently quenching effects on SO4•-. Both EPR and scavenger experiments revealed that the main radicals in the TAP system were SO4•- and •OH, in which SO4•- played the most crucial role in TCEP degradation. GC-MS/MS analysis disclosed that two degradation products appeared, sourcing from the replacement, oxidation, hydroxylation and water-molecule elimination reactions. The other two products were inferred from the comprehensive literature. As for acute toxicity to fish, daphnid and green algae, product A displayed the slightly higher toxicity, whereas other three products exhibited the declining toxicity as compared to their parent molecule. These findings offer a theoretical/practical reference for high-efficiency removal of TCEP and its ecotoxicological risk evaluation.

Matrix solid-phase dispersion extraction of organophosphorus flame retardants in soil based on response surface methodology

Organophosphorus flame retardants (OPFRs) are widely used in commercial products owing to their exceptional flame-retarding and plasticizing properties. However, OPFRs are also well recognized as emerging persistent organic pollutants (POPs) because of their environmental persistence, biological concentration, and potential toxicity. Thus, the accurate detection of OPFRs in environmental media is critical for analyzing their fate, transport, and ecological risk. However, very few OPFR detection methods are currently available, and the types of OPFRs detected may vary from site to site. In this study, matrix solid-phase dispersion extraction (MSPD), a simple, rapid, and versatile technique for preparing solid, semisolid, liquid, and viscous samples, was combined for the first time with gas chromatography-tandem mass spectrometry (GC-MS/MS) to analyze 10 OPFRs in soil, namely, tripropyl phosphate (TPrP), tri-n-butyl phosphate (TnBP), tri-iso-butyl phosphate (TiBP), tris(2-chloroisopropyl) phosphate (TCIPP), tris(2-chloroethyl) phosphate (TCEP), tris(1,3-dichloro-2-propyl) phosphate (TDCPP), triphenyl phosphate (TPHP), 2-ethylhexyl diphenyl phosphate (EHDPP), triphenylphosphine oxide (TPPO), and trimethylphenyl phosphate (TCP). The GC-MS/MS system was equipped with a Bruker-5MS capillary column coupled with a triple quadrupole mass spectrometer operated in multiple reaction monitoring (MRM) mode. Prior to detection, a mixed standard solution was fortified with 10 ng of13C-PCB208 as an internal standard. The optimal conditions under which MSPD could achieve high selectivity for OPFRs were determined. In addition, single-factor analysis was used to examine the influence of the sorbent (i. e., C18, PSA, Florisil, GCB, and multiwalled carbon nanotubes (MWCNTs)) as well as the dosage, type, and volume of the eluent on the extraction efficiency of the method for the 10 OPFRs. When GCB and ethyl acetate were used as the adsorbent and solvent, respectively, during elution, high extraction recoveries for the OPFRs were achieved. Optimization via response surface methodology (RSM) was adopted to further analyze the impact of three key factors, namely, the adsorbent dosage, eluent volume, and grinding time, as well as their interactions, on OPFR recoveries. Under the optimal conditions of 0.3 g of GCB as the adsorbent, 10 mL of ethyl acetate as the eluent, and 5 min of grinding time, the relative average recovery of the OPFRs was 87.5%. Furthermore, the 10 OPFRs showed good linear relationships under five concentration gradients, with correlation coefficients greater than 0.998. The limits of detection (LODs) and quantification (LOQs) were calculated as signal-to-noise ratios (S/N) of 3 and 10, respectively, and found to be in the ranges of 0.006-0.161 and 0.020-0.531 ng/g, respectively. The performance of the proposed method was verified by determining the recoveries and relative standard deviations (RSDs) of the OPFRs in soils spiked at low, medium, and high levels (10, 20, and 100 ng/g, respectively). The recoveries of the OPFRs ranged from 70.4% to 115.4%, with RSDs ranging from 0.7% to 6.7%. Compared with the conventional accelerated solvent extraction (ASE) method, MSPD presents higher efficiency, simpler operation, and less solvent requirements. The developed method was applied to determine OPFRs in soil samples collected from different sites in Suzhou, including an electronics factory, an auto-repair factory, a paddy field, and a school field. The results revealed that the contents of OPFRs in the soils from the electronics and auto-repair factories were significantly higher than those in the soils from the paddy and school fields. The main pollutants in the soil samples collected from the electronics and auto-repair factories were TCIPP, TPPO, TCEP, and TDCPP. Moreover, the contents of these compounds were 5.30, 4.44, 4.54, and 4.20 ng/g, in soils from the electronics factory and 2.70, 3.93, 7.60, and 5.04 ng/g, in soils from the auto-repair factory. To the best of our knowledge, this study is the first to determine high concentrations of TPPO in industrial soils. Thus, the combination of MSPD and GC-MS/MS adopted in this study can provide useful insights into the detection of the 10 OPFRs in soil.

Assessment of Daily Exposure to Organophosphate Esters through PM2.5 Inhalation, Dust Ingestion, and Dermal Contact.

Inhalation of airborne fine particulate matter (PM2.5), dust ingestion, and dermal contact with dust are important pathways for human exposure to different contaminants, such as organophosphate esters (OPE), compounds that are widely used as flame retardants and plasticizers. There are limited studies assessing the extent of the contamination of OPE in indoor airborne PM2.5. This study offers a novel approach by examining various indoor environments, such as homes, workplaces, and means of transport, where people typically spend their daily lives. The goal is to provide a comprehensive assessment of daily exposure to these pollutants. Both PM2.5 and dust samples were collected in order to determine the concentration levels of 17 different OPEs. Fifteen OPEs in PM2.5 and 16 in dust samples were detected. Concentration levels in indoor air ranged from 4.37 to 185 ng/m3 (median 24.4 ng/m3) and from 3.02 to 36.9 μg/g for the dust samples (median 10.2 μg/g). Estimated daily intakes (EDIs) of OPEs were calculated for adults, yielding median values of 3.97 ng/(kg bw × day) for EDIInhalation, 5.89 ng/(kg bw × day) for EDIDermal, and 1.75 ng/(kg bw × day) for EDIIngestion. Such levels lie below human health threshold risk limits, although in some cases they could be only 2 times below the threshold for carcinogenic risk, with a main contribution from tris(2-chloroethyl) phosphate (TCEP). Given this threshold proximity, additional exposure to these chemicals from other pathways, such as food ingestion, gas phase exposure, and/or inhalation of coarser particles (PM10-2.5), could therefore lead to health limit exceedances.

Multi-pathway exposure assessment of organophosphate flame retardants in a southern Chinese population: Main route identification with compound-specificity

In this study, we conducted comprehensive organophosphorus flame retardant (PFR) exposure assessments of both dietary and non-dietary pathways in a rural population in southern China. Skin wipes were collected from 30 volunteers. Indoor and outdoor air (gas and particles), dust in the houses of these volunteers, and foodstuffs consumed by these volunteers were simultaneously collected. The total PFR concentrations in dust, gas, and PM2.5 varied from 53.8 to 5.14 × 105 ng/g, 0.528 to 4.27 ng/m3, and 0.390 to 16.5 ng/m3, respectively. The forehead (median of 1.36 × 103 ng/m2) and hand (median of 920 ng/m2) exhibited relatively high PFR concentrations, followed by the forearm (median of 440 ng/m2) and upper arm (median of 230 ng/m2). The PFR concentrations in the food samples varied from 0.0700 to 10.9 ng/g wet weight in the order of egg > roast duck/goose and vegetable > pork > chicken > fish. Tris(1-chloro-isopropyl) phosphate (TCPP) was the main PFR in the non-diet samples, whereas the profiles of PFR individuals varied by food type. Among the multiple pathways investigated (inhalation, dermal exposure, dust ingestion, and food ingestion), dermal absorption and dust ingestion were the predominant pathways for tris(2-chloroethyl) phosphate (TCEP) and bisphenol A-bis(diphenyl phosphate) (BDP), respectively, whereas dietary exposure was the most important route for other chemicals.

Occurrence, source apportionment, and ecological risk assessment of organophosphate esters in surface sediment from the Ogun and Osun Rivers, Southwest Nigeria

Organophosphate esters (OPEs) are synthetic chemicals widely used as e.g., flame retardants and plasticisers in various consumer products. Due to the toxicity of OPEs in aquatic ecosystems, exposure of fauna and flora to these compounds is of potential concern. In this study, the concentrations, profiles, sources, and ecological risk of eight OPEs were investigated in the sediments from the two major rivers in southwest Nigeria. Concentrations of ∑OPEs in surface sediments were in the range 13.1 – 2110 ng/g dry weight (dw) (median: 378 ng/g dw) in the Ogun River and 24.7—589 ng/g dw (median: 174 ng/g dw) in the Osun River. These concentrations are broadly within the range of those reported in surface sediment in previous studies conducted in other locations around the world. Tris (2-butoxyethyl) phosphate (TBOEP) was the dominant OPE in the sediment samples with a median concentration of 337 and 126 ng/g dw for the Ogun and Osun Rivers respectively, while tri-n-butyl phosphate (TnBP) was not detected in any sample. Excluding TBOEP, the chlorinated organophosphate esters: tris(2-chloroethyl) phosphate (TCEP), tris(2-chloro-propyl) phosphate (TCIPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) were the dominant OPEs in the Osun River, while the aryl-OPEs: triphenyl phosphate (TPHP), 2-ethylhexyl diphenyl phosphate (EHDPP), and tri-m-tolyl phosphate (TMTP) were dominant in the Ogun River. Under a median exposure scenario, moderate ecological risk was predicted from exposure to TCIPP in the Osun River. In contrast, under a high exposure scenario, concentrations of TDCIPP (risk quotient, RQ = 5.33—5.37) constituted a high ecological risk in both rivers, with moderate risks observed for TBOEP (RQ = 0.022—0.18) and TCIPP (RQ = 0.097 – 0.16). Therefore, the risk to aquatic organisms from concomitant exposure to mixtures of OPEs in freshwater ecosystems requires further investigation.Graphical

Organophosphorus flame retardants and their metabolites in paired human blood and urine

Organophosphorus flame retardants (OPFRs) have been shown to be carcinogenic, neurotoxic, and endocrine disruptive, so it is important to understand the levels of OPFRs in human body as well as the modes of external exposure. In this study, we investigated the levels of 13 OPFRs and 7 phosphodiester metabolites in paired human blood and urine, as well as the influencing factors (region, age and gender), and studied the relationship between OPFRs and oxidative stress by urinary metabolites. We found that the concentrations of triphenyl phosphate (TPhP) and tris-(2-ethylhexyl) phosphate (TEHP) in the blood of urban populations were higher than those of rural populations, and that younger populations suffered higher TPhP and 2-ethylhexyl diphenyl phosphate (EHDPP) exposures than older populations. In addition, we found that tris-(2-chloroethyl) phosphate (TCEP), tributyl phosphate (TnBP), TPhP and EHDPP exposure induced oxidative stress. The results of the internal load principal component analysis indicated that dust ingestion, skin exposure, respiration and dietary intake may be the most important sources of TCEP, tris(2-butoxyethyl) phosphate (TBOEP), tri(2-chloroisopropyl) phosphate (TCIPP) and TEHP, respectively, and dust ingestion and skin exposure may be the main sources of TPhP for humans.

Study of the Spatiotemporal Variations, Source Determination, and Potential Ecological Risk of Organophosphate Esters in Typical Coastal Tourist Resorts in China

Investigation of the environmental occurrence and behavior of organophosphate esters (OPEs) is very important and is becoming a hot topic in the academic community. In this study, 12 targeted OPEs in the water and sediment from 19 coastal tourist resorts in the Shandong Peninsula in China were analyzed to show their concentrations, spatial variations, and potential ecological risks. The results showed that the total concentrations of OPEs (ΣOPEs) were in the range of 18.52–3069.43 ng/L in the water and 3.20–568.76 ng/g in the sediment. The dominant OPEs in the water and sediment were tris (2-chloroisopropyl) phosphate (TCIPP), tris (2-chloroethyl) phosphate (TCEP), and triethyl phosphate (TEP). The OPE concentrations in the water were ranked as dry season > normal season > wet season. The sewage treatment plants near tourist resorts were important contributors to the level of OPEs in the water. Triphenyl phosphate (TPHP), tri-n-butyl phosphate (TNBP), and resorcinol-bis(diphenyl)phosphate (RDP) had a relatively higher ecological risk than other OPEs in the water samples. Industrial emissions might be the main source of OPEs in the coastal tourist resorts of Shandong Peninsula in China. The results of this study verified that OPEs occur in the water and sediment of coastal tourist resorts, and more attention should be given to the existence of OPEs and the safety of aquatic environments near coastal tourist resorts.

Uptake mechanism, translocation, and transformation of organophosphate esters in water hyacinth (Eichhornia crassipes): A hydroponic study

Owing to their dominant wastewater origin, bioavailability, and toxicity, the occurrence and behavior of organophosphate esters (OPEs) in aquatic systems have attracted considerable attention over the past two decades. Aquatic plants can accumulate and metabolize OPEs in water, thereby playing an important role in their behavior and fate in waterbodies. However, their uptake, translocation and transformation mechanisms in plants remain incompletely characterized. We investigated the accumulation and transformation of OPEs in water hyacinth (Eichhornia crassipes) through a series of hydroponic experiments using three representative OPEs, tris(2-chloroethyl) phosphate (TCEP), tris(2-butoxyethyl) phosphate (TBEP), and triphenyl phosphate (TPP). These OPEs can not only be adsorbed onto and enter plant roots via passive diffusion pathways, which are facilitated by anion channels and/or aquaporins, but also can return to the solution when concentration gradients exist. After entry, hydrophilic TCEP showed a dominant distribution in the cell sap, strong acropetal transportability, and rapid translocation rate, whereas hydrophobic TPP was mostly retained in the root cell wall and therefore demonstrated weak acropetal transportability; TBEP with moderate hydrophilicity remained in the middle. All these OPEs can be transformed into diesters, which presented higher proportions in the cell sap and therefore have stronger acropetal transferability than their parent OPEs. TCEP exhibits the lowest biodegradability, followed by TPP and TBEP. These OPEs exerted apparent effects on plant growth, photosynthesis, and the diversity and composition of the rhizosphere microbial community.

Emerging and traditional organophosphate esters in office air from Hangzhou, East China: Seasonal variations, influencing factors and human exposure assessment

Eight emerging and six traditional organophosphate esters (OPEs) were investigated in office air from Hangzhou China with all the traditional OPEs and 5 out of 8 emerging OPEs detected. The median concentrations of ∑traditional OPEs and ∑emerging OPEs were 61,200 and 5.81 pg/m3, respectively. Butylphenyl diphenyl phosphate (BPDPP) and trisisopropyltrisphenyl phosphate (TIPPP) were observed for the first time in indoor air and Chinese office, respectively. The levels of ∑traditional OPEs decreased in the following order: summer > autumn > spring > winter. Conversely, no obvious trends were observed for emerging OPEs. ∑traditional OPEs (p < 0.001) and tri(chloroisopropyl) phosphate (TCIPP) (p < 0.01) concentrations were positively correlated with temperature. Interestingly, ∑emerging OPEs and the individual emerging OPEs analytes had no significant correlations with temperature (p > 0.05). ∑traditional OPEs, tris(2-chloroethyl) phosphate (TCEP) and TCIPP levels were significantly positively correlated with relative humidity (p < 0.05), while ∑emerging OPEs levels were negatively correlated with relative humidity (p < 0.05). Median intakes of traditional OPEs were estimated to be several orders of magnitude lower than the corresponding Reference Dose (RfD) values. The distinct environmental behaviors of emerging OPEs compared to traditional OPEs, coupled with the lack of established RfD values for them, underscore the need for their risk evaluations in future.

Environmentally relevant concentrations of tris (2-chloroethyl) phosphate (TCEP) induce hepatotoxicity in zebrafish (Danio rerio): a whole life-cycle assessment.

Tris (2-chloroethyl) phosphate (TCEP), a typical organophosphate flame retardant, is of increasingly great concern considering their ubiquitous presence in aquatic environments and potential ecotoxicity. The present work was aimed to investigate the potential growth inhibition and hepatic stress induced by whole life-cycle exposure to TCEP (0.8, 4, 20 and 100μg/L) in zebrafish. The results revealed that the body length, body mass and hepatic-somatic index (HSI) of zebrafish were significantly declined after exposure to TCEP for 120days. GPx activity and GSH content were increased in the liver of zebrafish treated with low concentrations (0.8 and 4μg/L) of TCEP, while exposure to high concentrations (20 and 100μg/L) of TCEP reduced antioxidative capacity and elevated lipid peroxidation (LPO) levels. Gene transcription analysis demonstrated that the mRNA levels of nrf2 were altered in a similar manner to the transcription of the downstream genes nqo1 and hmox1, suggesting that Nrf2-Keap1 pathway mediated TCEP-induced oxidative stress in zebrafish liver. In addition, TCEP exposure might alleviate inflammatory response through down-regulating transcription of inflammatory cytokines (il-1β, il-6 and inos), and induce apoptosis via activating the p53-Bax pathway. Moreover, whole life-cycle exposure to TCEP caused a series of histopathological anomalies in zebrafish liver. Overall, our results revealed that lifetime exposure to environmentally relevant concentrations of TCEP could result in growth retardation and induce significant hepatotoxicity in zebrafish.

Deriving seawater quality criteria of tris(2-chloroethyl) phosphate for ecological risk assessment in China seas through species sensitivity distributions

Tris(2-chloroethyl) phosphate (TCEP), one of the widely used organophosphorus flame retardants (OPFRs), has been frequently detected in the marine environment in the seas off China. The existing freshwater biotoxicity data are not suited to derivation of the seawater quality criteria of TCEP and evaluating the associated ecological risks. This study aimed at deriving water quality criteria (WQC) of TCEP for marine organisms based on species sensitivity distribution (SSD) approach using the acute toxicity data generated from multispecies bioassays and chronic toxicity data by converting acute data with the acute-to-chronic ratios (ACRs); the derived WQC were then used to evaluate the ecological risk for TCEP in China Seas. According to median effective concentration (EC50) and median lethal concentration (LC50), TCEP had a moderate or low toxicity to eight marine species selected, among which mysid Neomysis awatschensis (96h-LC50 of 39.65 mg/L) and green alga Platymonas subcordiformis (96-h EC50 of 395.42 mg/L) were the most sensitive and the most tolerant, respectively. The acute and chronic hazardous concentrations of TCEP for 5% of marine species (HC5) were estimated to be 29.55 and 2.68 mg/L, respectively. The short-term and long-term WQC were derived to be 9.85 and 0.89 mg/L, respectively. The risk quotient (RQ) values indicated that TECP at current levels poses a negligible risk to marine ecosystems in China. These results will provide valuable reference for the government to establish a seawater quality standard for TCEP.