Tris(1-chloro-2-propyl) Phosphate Research Articles

A tiered toxicity testing strategy for assessing early life stage toxicity in estuarine fish (Mugilogobius chulae): A case study on tris (1-chloro-2-propyl) phosphate ester

The estuarine ecological environment faces significant threats from contaminants of emerging concern (CECs); yet, the risk posed by CECs to resident organisms remains poorly understood. Here, we employed tiered toxicity testing to investigate the adverse effects and potential mechanisms of tris (1-chloro-2-propyl) phosphate (TCPP) on the early life stages of an estuarine fish, Mugilogobius chulae. TCPP affected the development of M. chulae embryos, including survival, morphology, hatching, and behavior. A concentration-dependent transcriptomic analysis showed that TCPP disrupted 12 neurodevelopment-related KEGG pathways in M. chulae embryos, with five of the 30 % top-ranked pathways related to neurotransmitter signaling. Besides the cholinergic synapse signaling pathway, the glutamatergic signaling pathway (including NMDAR and AMPAR subtypes) may also mediate TCPP-induced neurodevelopmental toxicity. The NMDAR subtype GRIN2B was downregulated at high concentrations. Molecular dynamics simulations revealed a strong interaction between TCPP and GRIN2B, with TCPP binding to the residues Ile153 and Ile188. The results suggest that NMDARs play a crucial role in TCPP-induced neurodevelopmental toxicity toward M. chulae. AOP network analysis predicted that TCPP may impact cognitive functions and memory. Our study provides a novel testing strategy for identifying the mechanisms of toxicity of CECs, a crucial component of ecological risk assessment.

Regulation of Ocean Surface Currents and Seasonal Sea Ice Variations on the Occurrence and Transport of Organophosphate Esters in the Central Arctic Ocean.

Organophosphate esters (OPEs) have been observed in the remote Arctic Ocean, yet the influence of hydrodynamics and seasonal sea ice variations on the occurrence and transport of waterborne OPEs remains unclear. This study comprehensively examines OPEs in surface seawater of the central Arctic Ocean during the summer of 2020, integrating surface ocean current and sea ice concentration data. The results confirm significant spatiotemporal variations of the OPEs, with the total concentration of seven major OPEs averaging 780 ± 970 pg/L. Chlorinated OPEs, particularly tris(1-chloro-2-propyl) phosphate (TCPP), were dominant. The significant impact of hydrodynamics on the OPE transport is demonstrated by higher OPE concentrations in regions with strong surface currents, especially at the edge of the Beaufort Gyre and the confluence of the Beaufort Gyre and the Transpolar Drift. Furthermore, OPE levels were generally higher in drifting-ice-covered regions compared to ice-free regions, attributed to the volatilization of dissolved OPEs formerly trapped below the sea ice or newly released from melting snow and sea ice. Notably, TCPP decreased by only 19% in the ice-free area, while the more volatile triphenyl phosphate decreased by 63% compared with the partial ice region.

Occupational Exposure of On-Shift Ottawa Firefighters to Flame Retardants and Polycyclic Aromatic Hydrocarbons.

Firefighters can be exposed to complex mixtures of airborne substances, including hazardous substances released during structural fires. This study employed silicone wristbands (SWBs) as passive samplers to investigate potential exposure to polycyclic aromatic hydrocarbons (PAHs) and flame retardants (FRs). SWBs were deployed at different areas of four fire stations, in four truck cabins, and at an office control location; they were also donned outside the jackets of 18 firefighters who responded to fire calls. Overall, office areas had significantly lower PAHs than fire station areas. Vehicle bays and truck cabins had significantly higher concentrations of low molecular weight (LMW) PAHs than sleeping and living room areas. For organophosphate ester flame retardants (OPFRs), tri-n-butyl phosphate (TnBP) and tris(1-chloro-2-propyl) phosphate (TCPP) were detected in all the samples; 2-ethylhexyl diphenyl phosphate (EHDPP) was more frequently detected in the fire station areas. Triphenyl phosphate (TPP) concentrations were highest in the truck cabin and office areas, and tris(1,3-dichloro-2-propyl)phosphate (TDCPP) was highest in truck cabins. Thirteen of 16 PAHs and nine of 36 OPFRs were detected in all the SWBs worn by firefighters, and tris (2-butoxyethyl) phosphate (TBEP) was the predominant OPFR. Levels of LMW PAHs were significantly lower when firefighters did not enter the fire. LMW PAHs, HMW (high molecular weight) PAHs, and EHDPP were significantly elevated when heavy smoke was reported. This work highlights the potential for occupational exposure to PAHs and flame retardants in some fire station areas; moreover, factors that may influence exposure during fire suppression. Whilst firefighters' occupational exposure to PAHs is likely related to fire suppression and exposure to contaminated gear and trucks, exposure to OPFRs may be more related to their presence in truck interiors and electronics.

Monitoring of OPFRs in WWTPs: Unveiling environmental insights with high resolution mass spectrometry

Exploring the occurrence pattern of organophosphate flame retardants (OPFRs) in environmental samples has attracted increasing attention lately. In the conventional wastewater treatment plants (WWTPs), OPFRs are not sufficiently removed and therefore are discharged to the aquatic environment. However, concerns arise from their release regarding the potential risk posed to organisms. Consequently, closely monitoring this group of emerging contaminants, along with the evaluation of the associated ecological risk are matters of utmost importance. Given the aforementioned information, influents and effluents from two WWTPs (WWTP-A and WWTP-S) in Thessaloniki were gathered during a 36-month sampling initiative spanning from 2020 to 2023 in order to evaluate the occurrence and concentration levels of OPFRs. The collected samples underwent solid-phase extraction and then preceded to analysis with a Q Exactive Focus Orbitrap mass analyzer. In the present study, except for the implementation of the target analysis approach, removal efficiencies and mass loads were further calculated. TBEP (tris-2-butoxyethylphosphate) and TEP (triethyl phosphate) were detected in all influent samples (%DF = 100 %) in WWTP-A while in WWTP-S only TCPP (tris-1-chloro-2-propyl phosphate) was omnipresent. In effluents of both WWTPs, only TEP maintained the same detection frequency (%DF = 100 %). The highest mean concentration levels in WWTP-S influents were calculated for TEP (327 ng/L) followed by TCPP (277 ng/L) while in WWTP-A the highest mean concentrations in influents were detected for TCPP (405 ng/L) and TDCP (Tris(1,3-dichloro-2-propyl)phosphate) (124 ng/L). In effluents, the highest mean concentration was reported for TCPP, in both WWTPs, reaching 295 ng/L and 240 ng/L in WWTP-S and WWTP-A respectively. Generally, OPFRs exhibited low to moderate average removal efficiencies. Positive and negative removal efficiencies were also noticed during the monitoring campaign. The average mass load in WWTP-S was as high as 10.1 mg/day/1000 inhabitants and in WWTP-A, 11 mg/day/1000 inhabitants in effluents. Finally, different mathematical tools were employed for the assessment of the risk posed to algae, invertebrates and fish. For the toxicity assessment in these three trophic levels the worst-case scenario was taken into consideration. Generally, all the target analytes presented low or medium values in all trophic levels for acute and chronic toxicity.

Nano titanium dioxide alleviates the toxic effects of tris (2-chloropropyl) phosphate on the digestive gland and hemolymph of thick-shell mussel Mytilus coruscus

In the marine environment, nanoparticles play a role in adsorbing and catalytically degrading organic pollutants, thereby mitigating their toxic effects on aquatic organisms. This study aimed to investigate the impact of nano titanium dioxide (nTiO2) and tris (2-chloropropyl) phosphate (TCPP) on the hemolymph and digestive function of the thick-shell mussel Mytilus coruscus. Mussels were divided into a control group, a group exposed to TCPP alone, a group exposed to a combination of TCPP and 0.5 mg/L nTiO2, and a group exposed to a combination of TCPP and 1 mg/L nTiO2. After 14 days of exposure, oxidative stress responses, including superoxide dismutase (SOD) activity and malondialdehyde (MDA) content, immune defense responses, including acid phosphatase (ACP) and alkaline phosphatase (AKP) activities, and gene expression, including HSP70 expression, were measured in the hemolymph and digestive glands of the mussels. Compared to the control group, mussels solely exposed to 100 μg/L TCPP exhibited a significant reduction in SOD activity in the hemolymph. When TCPP was co-exposed with 0.5 mg/L nTiO2, there were significant increases in MDA content and AKP activity in both the digestive gland and hemolymph compared to the control group. Upon co-exposure of TCPP with 1 mg/L nTiO2, MDA content and AKP activity in the digestive gland significantly decreased, while SOD, ACP, and AKP activity in the hemolymph significantly increased and MDA content significantly decreased, returning to the control group levels. Furthermore, in the combined exposure, HSP70 gene expression significantly decreased as the nTiO2 concentration increased from 0.5 mg/L to 1 mg/L. In summary, TCPP impacted the hemolymph and digestive function of mussels, whereas a concentration of 1 mg/L nTiO2 effectively alleviated the toxic effects of TCPP. This study is crucial for assessing the ecological risks of nanoparticles and emerging organic pollutants in marine environments, and provides new insights into the interaction between nTiO2 and TCPP, as well as the influence of nTiO2 concentration on mitigating TCPP toxicity.

Integrated biomarker-based ecological risks assessment of tadpole responses to tris(2-chloroethyl) phosphate, tris(1-chloro-2-propyl) phosphate, and their combined environmental exposure

Tris(2-chloroethyl) phosphate (TCEP) and tris(1-chloro-2-propyl) phosphate (TCPP) are common chlorinated organophosphorus flame retardants (OPFRs) used in industry. They have been frequently detected together in aquatic environments and associated with various hazardous effects. However, the ecological risks of prolonged exposure to these OPFRs at environmentally relevant concentrations in non-model aquatic organisms remain unexplored. This study investigated the effects of long-term exposure (up to 25 days) to TCEP and TCPP on metamorphosis, hepatic antioxidants, and endocrine function in Polypedates megacephalus tadpoles. Exposure concentrations were set at 3, 30, and 90 μg/L for each substance, conducted independently and in equal-concentration combinations, with a control group included for comparison. The integrated biomarker response (IBR) method developed an optimal linear model for predicting the overall ecological risks of TCEP and TCPP to tadpoles in potential distribution areas of Polypedates species. Results showed that: (1) Exposure to environmentally relevant concentrations of TCEP and TCPP elicited variable adverse effects on tadpole metamorphosis time, hepatic antioxidant enzyme activity and related gene expression, and endocrine-related gene expression, with their combined exposure exacerbating these effects. (2) The IBR value of TCEP was consistently greater than that of TCPP at each concentration, with an additive effect observed under their combined exposure. (3) The ecological risk of tadpoles exposed to the combined presence of TCEP and TCPP was highest in China's Taihu Lake and Vietnam's Hanoi than in other distribution locations. In summary, prolonged exposure to environmentally relevant concentrations of TCEP and TCPP presents potential ecological risks to amphibian tadpoles, offering insights for the development of policies and strategies to control TCEP and TCPP pollution in aquatic ecosystems. Furthermore, the methodology employed in establishing the IBR prediction model provides a methodological framework for assessing the overall ecological risks of multiple OPFRs.

Community-level risk assessments on organophosphate esters in the sediments from the Bohai Sea of China based on multimodal species sensitivity distributions coupled with the equilibrium partitioning method

Organophosphate esters (OPEs), increasingly used as alternatives to brominated flame retardants, are ubiquitous in the global aquatic environment. Despite their potential toxicological impact on ecosystems, community-level risk assessments for OPEs in sediments remain scarce. This study investigated OPE occurrences and composition characteristics in the Bohai Sea's sediments and appraised both individual and joint ecological risks posed by characteristic OPE homologs using ten commonly used species sensitivity distribution (SSD) models, integrating acute-to-chronic conversion and phase equilibrium partitioning. OPEs were detected across all sediment samples, with total concentrations ranging from 0.213 ng/g dry weight (dw) to 91.1 ng/g dw. The predominant congeners included tri-n-butyl phosphate (TnBP), triisobutyl phosphate (TiBP), tri(2-ethylhexyl) phosphate, tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(1, 3-dichloro-2-propyl) phosphate (TDCIPP), and triphenylphosphine oxide. Best-fit SSD models varied among TnBP, TiBP, TCEP, TCPP, and TDCIPP, demonstrating Sigmoid, Burr III, Sigmoid, Burr III, and Burr III, respectively. The same parametric model demonstrated variability in the fitting process for different OPE congeners, which also happened to the fitting results of ten parametric models for the same specific characteristic congener, underscoring the necessity of employing multiple models for precise community-level risk assessments. Hazard concentrations for a 5% cumulative probability were 0.116 mg/L, 2.88 mg/L, 1.30 mg/L, 1.44 mg/L, and 1.85 mg/L for each respective congener. The resulting risk quotients (RQ) and overall hazard index (HI) were selected as criteria to assess the individual and joint ecological risks of OPEs in sediments from the Bohai Sea, respectively. RQ and HI were both below 0.1, indicating a low risk to the local ecosystems. Multi-model SSD analysis could provide refined data for community-level risk evaluation, offering valuable insights for the development of evidence-based environmental standards and pollution control strategies.

Phase change material microcapsules doped with phosphorus-based flame retardant filled titanium dioxide nanotubes for enhancing the energy storage and temperature regulation performance of buildings

Solar energy is not only a green alternative to fossil energy but also a candidate for future mainstream energy sources. To improve the efficiency and application range of solar energy, we investigated tris (1-chloro-2-propyl) phosphate (TCPP) modified titanium dioxide nanotubes (TNTs) doped phase change material microcapsules (p-t-MPCMs) to enhance the temperature regulation and flame retardancy of epoxy resin (EP) coatings. Transmission electron microscopy (TEM) and Fourier transform infrared (FTIR) spectroscopy determined the successful preparation of p-TNTs and p-t-MPCMs. Moreover, it was confirmed that the p-t-MPCMs had great thermal stability and reliability by the thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The p-t-MPCMs increased residual mass by 12.2 % at 600 ℃ while correcting the initial melting temperature of MPCMs by 1.0 ℃. Based on the principle of oxygen consumption, the heat release rate (HRR) of EP coatings containing the p-t-MPCMs (p-t-MPCM/EP) was reduced from 665.92 kW/m2 to 443.78 kW/m2, resulting in a total heat release reduction (THR) of 17.73 % tested by a conical calorimeter. Then the results of the miniature chamber model demonstrated that p-t-MPCM/EP had outstanding temperature control ability. In summary, the p-t-MPCMs expressed great potential in regulating building temperature timely and improving the fire safety of EP coatings.

Exposure to resorcinol bis (diphenyl phosphate) induces colonization of alien microorganisms with potential impacts on the gut microbiota and metabolic disruption in male zebrafish

Organophosphate esters (OPEs) have been demonstrated to induce various forms of toxicity in aquatic organisms. However, a scarcity of evidence impedes the conclusive determination of whether OPEs manifest sex-dependent toxic effects. Here, we investigated the effects of tris (1-chloro-2-propyl) phosphate (TCPP) and resorcinol bis (diphenyl phosphate) (RDP) on the intestines of both female and male zebrafish. The results indicated that, in comparison to TCPP, RDP induced more pronounced intestinal microstructural damage and oxidative stress, particularly in male zebrafish. 16S rRNA sequencing and metabolomics revealed significant alterations in the species richness and oxidative stress-related metabolites in the intestinal microbiota of zebrafish under exposure to both TCPP and RDP, manifesting gender-specific effects. Based on differential species analysis, we defined invasive species and applied invasion theory to analyze the reasons for changes in the male fish intestinal community. Correlation analysis demonstrated that alien species may have potential effects on metabolism. Overall, this study reveals a pronounced gender-dependent impact on both the intestinal microbiota and metabolic disruptions of zebrafish due to OPEs exposure and offers a novel perspective on the influence of pollutants on intestinal microbial communities and metabolism.

Global responses to tris(1-chloro-2-propyl) phosphate and tris(2-butoxyethyl) phosphate in Escherichia coli: Evidences from biomarkers, and metabolic disturbance using GC-MS and LC-MS metabolomics analyses

Tris(1-chloro-2-propyl) phosphate (TCPP) and tris(2-butoxyethyl) phosphate (TBEP) as pollutants of emerging concern have aroused the rising attention due to their potential risks on aquatic ecosystem and public health. Nevertheless, there is a lack of toxicological mechanisms exploration of TCPP and TBEP at molecular levels. Herein, the toxicity effects and molecular mechanism of them were fully researched and summarized on Escherichia coli (E.coli). Acute exposure to them significantly activated antioxidant defense system and caused lipid peroxidation, as proved by the changes of antioxidant enzymes and MDA. The ROS overload resulted in the drop of membrane potential as well as the downregulated synthesis of ATPase, endorsing that E. coli cytotoxicity was ascribed to oxidative stress damage induced by TCPP and TBEP. The combination of GC-MS and LC-MS based metabolomics validated that TCPP and TBEP induced metabolic reprogramming in E.coli. More specifically, the responsive metabolites in carbohydrate metabolism, lipids metabolism, nucleotide metabolism, amino acid metabolism, and organic acids metabolism were significantly disturbed by TCPP and TBEP, confirming the negative effects on metabolic functions and key bioprocesses. Additionally, several biomarkers including PE(16:1(5Z)/15:0), PA(17:1(9Z)/18:2(9Z,12Z)), PE(19:1(9Z)/0:0), and LysoPE(0:0/18:1(11Z)) were remarkably upregulated, verifying that the protection of cellular membrane was conducted by regulating the expression of lipids-associated metabolites. Collectively, this work sheds new light on the potential molecular toxicity mechanism of TCPP and TBEP on aquatic organisms, and these findings using GC-MS and LC-MS metabolomics generate a fresh insight into assessing the effects of OPFRs on target and non-target aquatic organisms.

A comprehensive investigation on both the combustion characteristic and electrochemical performance of lithium battery with flame retardant tris (2-chloropropyl) phosphate

Thermal failures of lithium batteries have become more and more critical for the further development of energy storage technologies. Adding flame retardant additives has been proven promising to improve safety. However, the electrochemical performance usually degrades with additives. It is important to balance flame retardancy and electrochemical performance. In this study, both the combustion characteristics and electrochemical performance of Tris (2-ChloroPropyl) Phosphate (TCPP) are investigated to seek its potential for application in practical batteries. A novel experimental setup as well as key parameters are proposed to quantificationally characterize the flame retardancy of TCPP. The experimental results indicate that only 5 wt% of TCPP additives can lengthen both the jet delay times and auto-ignition delay times of the electrolyte jets by 50.6 % and 38.1 %, indicating the excellent flame-retardant efficiency of TCPP. The lithium salt in the electrolytes also presents significant flame retardancy on the combustion of electrolyte jets, particularly lengthening the auto-ignition delay times by as high as 74.8 %. Tests on the electrochemical performance reveal that 5 wt% of TCPP additives have negligible impacts on the discharge capacity. The overall deterioration of the discharge retention ratio is less than 6.0 % during long-term and various C-rates cycling tests.

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.

From Bioresources to Thermal Insulation Materials: Synthesis and Properties of Two-Component Open-Cell Spray Polyurethane Foams Based on Bio-Polyols from Used Cooking Oil.

Open-cell spray polyurethane foams are widely used as highly efficient thermal insulation materials with vapor permeability and soundproofing properties. Unfortunately, for the production of commercial foams, mainly non-renewable petrochemical raw materials are used. The aim of this study was to determine the possibility of completely replacing petrochemical polyols (the main raw material used in the synthesis of polyurethanes, alongside isocyanates) with bio-polyols obtained from used cooking oils, classified as waste materials. The research consisted of three stages: the synthesis of bio-polyols, the development of polyurethane foam systems under laboratory conditions, and the testing of developed polyurethane spray systems under industrial conditions. The synthesis of the bio-polyols was carried out by using two different methods: a one-step transesterification process using triethanolamine and a two-step process of epoxidation and opening oxirane rings with diethylene glycol. The obtained bio-polyols were analyzed using gel chromatography and nuclear magnetic resonance spectroscopy. The developed polyurethane foam formulations included two types of fire retardants: halogenated tris(1-chloro-2-propyl) phosphate (TCPP) and halogen-free triethyl phosphate (TEP). In the formulations of polyurethane systems, reactive amine catalysts were employed, which become incorporated into the polymer matrix during foaming, significantly reducing their emission after application. The foams were manufactured on both a laboratory and industrial scale using high-pressure spray machines under conditions recommended by commercial system manufacturers: spray pressure 80-100 bar, component temperature 45-52 °C, and component volumetric ratio 1:1. The open-cell foams had apparent densities 14-21.5 kg/m3, thermal conductivity coefficients 35-38 mW/m∙K, closed-cell contents <5%, water vapor diffusion resistance factors (μ) <6, and limiting oxygen indexes 21.3-21.5%. The properties of the obtained foams were comparable to commercial materials. The developed polyurethane spray systems can be used as thermal insulation materials for insulating interior walls, attics, and ceilings.

Coating Composites Based on Polyurea Elastomers with Increased Fire Resistance and Their Use as Roofing Systems

This paper presents the results of tests on elastomer coatings based on polyurea–polyurethane formulation with increased fire parameters. Coatings modified with flame retardants: bis(phenylphosphate) resorcinol (RDP), trischloropropyl phosphate (TCPP), and aluminum hydroxide (ATH) were tested. Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA/DTG) were used to investigate the structure and thermal stability. The effectiveness of resorcinol bis(phenylphosphate) (RDP), tris chloropropyl phosphate (TCPP), and aluminum hydroxide (ATH) on heat release rate (HRR), smoke release rate (RSR), and oxygen consumption was evaluated using cone calorimetry. The cone calorimetry results were correlated with the mechanical properties of the coatings. The cone calorimetry analysis showed suitable organophosphorus flame retardant (FR) performance, significantly decreasing HRR and oxygen consumption. Additionally, 15% TCPP caused a reduction of HRR by over 50%, obtaining 211.4 kW/m2 and pHRR by over 55%, reaching 538.3 kW/m2. However, organophosphorus flame retardants caused a significant deterioration of mechanical properties simultaneously. Introducing a mixture of two FRs (RDP/TCPP) resulted in obtaining a coating with improved fire resistance and maintained good mechanical strength. The polyurea–polyurethane coating, modified with a mixture of two RDP/TCPP retardants (10:5), was simulated for the burning of roof systems. The result of the simulation was assessed positively. Thus, finally, it was confirmed that the proposed polyurea–polyurethane coating achieved the assumed flame retardant level.

Toxicology and carcinogenesis studies of an isomeric mixture of tris(chloropropyl) phosphate administered in feed to Sprague Dawley (Hsd:Sprague Dawley SD) rats and B6C3F1/N mice.

Tris(chloropropyl) phosphate (TCPP) is used as a flame retardant in textiles, furniture foam, and other related products. In addition, it is manufactured for use in construction materials, electronic products, paints, coatings, and adhesives. Several flame retardants, including structurally similar organohalogen compounds, have been removed from products in commerce due to toxicity concerns, and TCPP has been proposed as a replacement flame retardant for use in these products. An anticipated increase in use of TCPP has generated concerns for increased human exposure through oral, dermal, and inhalation routes; however, publicly available toxicity data are scarce. The U.S. Consumer Product Safety Commission therefore requested that the National Toxicology Program (NTP) form a research program on TCPP to conduct subchronic and chronic exposure studies in rats and mice for hazard identification and characterization information. Because TCPP is commercially available as an isomeric mixture, the NTP studies tested a commercial TCPP product containing four isomers commonly found in other commercial mixtures of TCPP: tris(1-chloro-2-propyl) phosphate (TCIPP; CASRN 13674-84-5), bis(2-chloro-1-methylethyl) 2-chloropropyl phosphate (CASRN 76025-08-6), bis(2-chloropropyl) 2-chloroisopropyl phosphate (CASRN 76649-15-5), and tris(2-chloropropyl) phosphate (CASRN 6145-73-9). Following procurement of TCPP, the percent purity of the four isomers was determined prior to conducting hazard characterization studies. (Abstract Abridged).

Occurrence and Risk of Organophosphate Flame Retardants in Multiple Urban Water of Beijing, China

Investigating the organophosphate flame retardants (OPFRs) concentration and attenuation in multiple water of Beijing would provide valuable insight into OPFR management and reduction; thus, 6 OPFRs were determined by solid phase extraction-high performance liquid chromatography-tandem mass spectrometry to explore the pollution characteristics, and ecological risk of OPFRs. The results showed that 5 OPFRs were detected with a concentration ranging from ND to 394.77 ng/L except for tris(2,3-dibromopropyl) phosphate (TDBP). The chloroalkyl phosphate was the main compound and tris(chloropropyl) phosphate (TCPP) was the most abundant OPFRs with the highest concentration. The concentration of aryl-OPFRs in surface water and groundwater was much lower than that of chlorinated ones, and the concentration of chlorinated OPFRs in surface water was higher than that in groundwater. The treatment effect of chlorinated OPFRs including TCPP, TCEP, and TDCPP in STPs was negative. Ecological risk assessment showed that low risk of OPFRs for the organisms (algae, crustacean, and fish).

Enhanced removal of organophosphate esters by iron-modified biochar with developed mesoporous: Performance and mechanism based on site energy distribution theory

Removing the widely concerned pollutant of organophosphate esters (OPEs) by agriculture waste biochar is an effective way to address the waste and pollutant problem simultaneously. In this work, an iron-modified coconut shell biochar (MCSB) was prepared by co-pyrolysis method and used to adsorb tris(2-chloroethyl) phosphate (TCEP) and tris(1-chloro-2-propyl) phosphate (TCPP), which were two typical OPEs. The attention was focused on comprehensively investigating the adsorption behaviors to study the adsorption mechanisms of TCEP and TCPP onto MCSB. With the development of mesoporous and formation of γ-Fe2O3 in MCSB, the adsorption equilibrium was quickly reached in 60 min with the Langmuir maximum adsorption capacities of 211.3 mg/g for TCEP and 223.7 mg/g for TCPP, respectively. Results of adsorption kinetics and isotherm showed the heterogeneous and multilayer of the adsorption process. Pore-filling interaction, the Lewis acid-base interaction, and the hydrophobic interaction were considered to drive the adsorption. And the site energy distribution theory was introduced to further reveal that the physisorption was the main adsorption mechanism, while the Lewis acid-base interaction was responsible for the differences in adsorption of TCEP and TCPP onto MCSB. Additionally, the excellent adsorption performances of MCSB in various circumstances and fixed-bed column experiments suggested that the MCSB would be a promising adsorbent for OPEs removal.

Genotoxic and Toxic Effects of The Flame Retardant Tris(Chloropropyl) Phosphate (TCPP) in Human Lymphocytes, Microalgae and Bacteria.

Tris(chloropropyl) phosphate (TCPP) is a characteristic and widely used organophosphorus flame retardant. TCPP is comprised of four isomers and the most abundant is tris(1-chloro-2-propyl) phosphate. TCPP can be released into the environment, with potential impacts on living organisms and humans due to its extensive industrial use. Aiming to assess the potential risks of TCPP on human health and the environment, its toxic and genotoxic effects-using organisms from different trophic levels, i.e., bacteria, green microalgae, and human cells-were investigated. TCPP exposure at nominal concentrations of 10, 20, 30 and 40 μg mL-1 was studied to identify the potential risk of inducing genotoxic effects in cultured human lymphocytes. Treatment with 30 and 40 μg mL-1 of TCPP induced marginally significant micronuclei (MN) frequencies as well as cytotoxic effects. Freshwater microalgae species treated with TCPP (0.5, 1, 10, 20 and 50 μg L-1) showed different growth rates over time. All the tested microalgae species were adversely affected after exposure to TCPP during the first 24 h. However, differences among the microalgae species' sensitivities were observed. In the case of the freshwater species, the most sensitive was found to be Chlorococcum sp. The marine algal species Dunaliella tertiolecta and Tisochrysis lutea were significantly affected after exposure to TCPP. The effects of TCPP on Aliivibrio fischeri that were observed can classify this flame retardant as a "harmful" compound. Our results suggest a potential risk to aquatic organisms and humans from the wide utilization of TCPP and its consequent release into the environment. These results highlight that further research should be conducted to investigate the effects of TCPP individually and in combination with other organophosphorus flame retardants in various organisms. In addition, the concern induced by TCPP points out that measures to control the introduction of TCPP into the environment should be taken.

Organophosphorus Flame Retardant TCPP Induces Cellular Senescence in Normal Human Skin Keratinocytes: Implication for Skin Aging.

Tris (1-chloro-2-propyl) phosphate (TCPP) is one of the most frequently detected organophosphorus flames in the environment. Continuous daily exposure to TCPP may harm human skin. However, little is known about the adverse effects of TCPP on human skin. In this study, we first evaluated the detrimental effects and tried to uncover the underlying mechanisms of TCPP on human skin keratinocytes (HaCaT) after 24 h exposure. We found that TCPP caused a concentration-dependent decrease in HaCaT cell viability after exposure to 1.56-400 μg/mL for 24 h, with an IC50 of 275 μg/mL. TCPP also promoted the generation of intracellular reactive oxygen species (ROS) and triggered DNA damage, evidenced by an increase of phosphorylated histone H2A.X (γH2A.X) in the nucleus. Furthermore, the cell cycle was arrested at the G1 phase at 100 μg/mL by upregulation of the mRNA expression of p53 and p21 and downregulation of cyclin D1 and CDK4 expression. Additionally, both the senescence-associated-β-galactosidase activity and related proinflammatory cytokine IL-1β and IL-6 were elevated, indicating that TCPP exposure caused cellular senescence may be through the p53-dependent DNA damage signal pathway in HaCaT cells. Taken together, our data suggest that flame-retardant exposure may be a key precipitating factor for human skin aging.

A scalable field study using leaves as a novel passive air sampler to evaluate the potential source of organophosphate esters in street dust

Organophosphate esters (OPEs) are widely used as flame retardants and plasticizers in industrial and commercial products. It is generally believed that OPEs in street dust mainly originate from road traffic and anthropogenic activities. The influence of atmospheric deposition is still unknown. In this study, leaves were employed as a novel passive air sampler to collect particle matters (PM) in 12 cities in the central province of Henan, China. Similar compositional profiles of OPEs were found in street dust and PM samples. The concentrations of individual OPEs in PM were 1–4 times higher than in street dust. Chlorinated OPEs concentration in PM shows a moderate correlation (r2 = 0.538, p < 0.01) with that in street dust. The concentration of alkyl OPEs in PM has a high correlation (r2 = 0.843, p < 0.01) with that in street dust. No significant correlation (r2 = 0.133, p = 0.132) was found on the aryl OPEs concentrations between street dust and PM. Spearman correlation reveals that the emission sources of tricresyl phosphate (TCrP) and triethyl phosphate (TEP) may be different from other OPEs in dust and PM samples. Principle component analysis (PCA) provides an appropriate explanation that tris (2-chloroethyl) phosphate (TCEP), triphenyl phosphate (TPhP), tris (chloropropyl) phosphate (TCPP), tributyl phosphate (TnBP), and TEP in street dust and PM may be emitted from the same sources, suggesting that PM has a significant influence on the occurrence of OPEs in street dust. The estimated dry deposition fluxes of particle-bound OPEs show a significant correlation (R2 = 0.969, p < 0.01) with OPEs concentrations in street dust, revealing that the input of atmospheric deposition could be a major source of OPEs in street dust.