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

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.

Chlorinated organophosphorus flame retardants-induced mitochondrial abnormalities and the correlation with progesterone production in mLTC-1cells.

Environmental monitoring data have indicated that three chlorinated organophosphorus flame retardants (Cl-OPFRs), including tris(2-chloroethyl)-phosphate (TCEP), tris(2-chloropropyl)-phosphate (TCPP), and tris(1,3-dichloro-2-propyl)-phosphate (TDCPP) are the predominant chemicals in various environmental matrices and exhibit reproductive endocrine disrupting activities. Currently, mitochondrial abnormality is a new paradigm for evaluating chemical-mediated cell dysfunction. However, a comprehensive correlation between these two aspects of Cl-OPFRs remains unclear. In this research, the effects of TCEP, TCPP, and TDCPP on progesterone production and mitochondrial impairment were investigated by using mouse Leydig tumor cells (mLTC-1). The half maximal inhibitory concentration (IC50) values at 48h exposure indicated that the rank order of anti-androgenic activity was TDCPP>TCPP. Whereas, TCEP exhibited elevation of progesterone production. At concentrations close to IC50 of progesterone production by TCPP and TDCPP, the elevation of intracellular reactive oxygen species (ROS), depletion of mitochondrial membrane potential (MMP), reduction of cellular adenosine triphosphate (ATP) content, and alteration of mitochondrial structures was observed. In addition, the expression of main genes related to progesterone synthesis was dramatically down-regulated by TCPP and TDCPP treatments. These results imply that the inhibition effect of TCPP and TDCPP on progesterone production might be related to mitochondrial damage and down-regulated steroidogenic genes.

Pre- and post-natal exposure of children to organophosphate flame retardants: A nationwide survey in France.

The use of organophosphate flame retardants (OPFRs) has been on the rise ever since many brominated flame retardants were banned, back in the 2000s. The objectives of this study are to describe the pre- and post-natal exposure of children to OPFRs, and to explore their possible determinants. A total of 259 children aged 3.5years and 388 mothers from the French ELFE mother-child cohort were included. Both pre- and post-natal exposure to OPFRs were assessed, using OPFR concentrations in the hair of pregnant women (in 2011) and their 3.5-year-old children (in 2014-2015) for 15 OPFRs, of which 9 were detected in>20% hair samples. The highest geometric means for pre-natal exposure were 272ng/g for tris(1-chloro-2-propyl) phosphate (TCPP), 69.7ng/g for ng/g for triphenyl phosphate (TPP) and 54.4ng/g for tris(1,3-dichloro-2-propyl) phosphate (TDCPP). The highest geometric means for post-natal exposure were 249.6ng/g for TCPP, 85.3ng/g for TDCPP and 83.8ng/g for 2-ethylhexyl diphenyl phosphate (EHDPP). Correlations were found between both pre-natal exposures, and between pre-and post-natal exposures. No correlation was however found between pre-and post-natal exposures for any given OPFR. Pre-natal exposure to the 9 OPFRs was associated with pre-natal exposure to polybrominated diphenyl ethers 209 (BDE209), and 47 (BDE47). Maternal BMI was associated with pre-natal exposure to OPFRs other than TBEP. Home renovation work prior to birth was also associated with pre-natal exposure to OPFRs, with the exception of EHDPP, tris(2-butoxyethyl) phosphate (TBEP) and triethyl phosphate (TEP). Determinants of post-natal exposure appeared more disparate across OPFRs; although both the type of flooring in children's rooms and pre-natal exposure to polybrominated diphenyl ethers seem to be associated with post-natal exposure. Lastly, higher socioeconomic status appeared to be associated with lower exposure for several (though not all) OPFRs. The high prevalence of exposure to OPFRs suggests the need for studies to assess the health effects of OPFRs exposure, particularly on children.

West African e-waste-soil assessed with a battery of cell-based bioassays

Soil samples randomly taken from major e-waste sites in West Africa (Nigeria, Benin and Ghana) were examined for an extensive range of organic contaminants. Cytotoxicity measurements and assessment of activation of xeno-sensing receptors from fish (Atlantic cod) were employed as a battery of in vitro biological assays to explore the quality and toxicity profile of West African e-waste soil. The concentrations of the measured contaminants of emerging concerns (CECs) and persistent organic pollutants (POPs) in the e-waste soil differs significantly from the reference soil with chemical profiles typically dominated by legacy polybrominated diphenyl ethers (PBDEs) (405.8 μgkg−1) and emerging organophosphate ester flame retardant tris (1-chloro-2-propyl) phosphate (TCPP) (404 μgkg−1), in addition to the short chain perfluorobutane sulfonate (PFBS) (275.3 μgkg−1) and perfluorobutanoate (PFBA) (16 μgkg−1). The study revealed that perfluorooctanoic acid (PFOA) occurred only in e-waste soil from Ghana and ranged from 2.6 to 5.0 μgkg−1. Overall, non-polar e-waste soil-derived extracts had a stronger effect on COS-7 cell viability than the polar extracts and elutriates. The highest receptor activation was observed with single polar and non-polar extracts from the Nigeria and Benin sites, indicating hotspots with Er-, PPARa- and Ahr-agonist activities. Thus, the results obtained with our battery of in vitro biological assays underscored these e-waste sites as remarkably polluted spots with complex toxicity profiles of great concern for human and environmental health.

The coupling between biological pump export and air-water exchange of organophosphate esters in a subtropical water environment

Organophosphate esters (OPEs) are well-known persistent organic pollutants with their ubiquitous environmental presence and adverse ecological and human health impacts. To study the transport and fate of OPEs in a subtropical environment, nine OPE compounds were analyzed in the gas phase (air samples), dissolved phase (water samples), and plankton samples collected over one year from or in the vicinity of an urban lake in Guangzhou, South China. The mean concentrations of ∑9OPEs were 2.93 ± 1.68 ng/m3 in the air, 455 ± 236 ng/L in the dissolved phase, 81.3 ± 41.2 ng/L in phytoplankton, and 4.79 ± 1.94 ng/L in zooplankton. Although the compositional profiles of OPEs varied among different media, tris (1-chloro-2-propyl) phosphate (TCPP) was the predominant OPE in most samples. Less hydrophobic OPEs such as TCPP and tris (2-chloroethyl) phosphate (TCEP) had lower bioaccumulation potential in the lake. The biological pump export played an important role in eliminating OPEs from the surface water, with fluxes ranging from 30.5 to 361 ng/m2/d. The more phytoplankton biomass in surface water, the greater the role of the biological pump. The fugacity fractions and air-water exchange fluxes suggested that TCPP and tris (1,3-dichloro-2-propyl) phosphate (TDCP) would enter the urban lake by gaseous deposition. Nevertheless, the lake acted as an important “secondary source” for TCEP and triphenyl phosphate (TPhP). The bio-pump might influence the air-water exchange processes of OPEs.

Multi-class organic pollutants in atmospheric particulate matter (PM2.5) from a Southwestern Europe industrial area: Levels, sources and human health risk

The occurrence of 50 multi-class pollutants comprising 18 polycyclic aromatic hydrocarbons (PAHs), 12 phthalate esters (PAEs), 12 organophosphorus flame retardants (OPFRs), 6 synthetic musk compounds (SMCs) and 2 bisphenols was studied in atmospheric particulate matter (PM2.5) samples collected at an industrial area focused on automotive manufacturing located at the Southwestern Atlantic European region (Vigo city, Spain) during 1-year period. Among all quantitated pollutants in PM2.5 samples, bisphenol A (BPA) was the most predominant with an average concentration of 6180 pg m−3, followed by PAHs comprising benzo(b+j)fluoranthene (BbF + BjF) and benzo(g,h,i)perylene (BghiP), accounting for 546 pg m−3 and 413 pg m−3 respectively. In addition, two OPFRs concerning tris(chloropropyl) phosphate (TCPP) and triphenyl phosphine oxide (TPPO) were the next following the concentration order, accounting for 411 pg m−3 and 367 pg m−3 respectively; being butyl benzyl phthalate (BBP) the most profuse PAE (56.1 pg m−3 by average). High relative standard deviations (RSDs) were observed during the whole sampling period, while statistically significant differences were only observed for PAHs concentrations during cold and warm seasons. Furthermore, some water-soluble ions and metal(oid)s were analysed in PM2.5 samples to be used as PM source tracers, whose concentrations were quite below the target levels set in the current legislation. Data obtained from principal component analysis (PCA) and PAHs molecular indices suggested a pyrogenic and petrogenic origin for PAHs, whereas occurrence of the remaining compounds seems to be attributed to resources used in the automotive industrial activity settled in the sampling area. Moreover, although a substantial anthropogenic source to PM2.5 in the area was observed, marine and soil resuspension contributions were also accounted. Finally, carcinogenic and non-carcinogenic risks posed by PM2.5-bound pollutants inhalation were assessed, being both averages within the safe level considering the whole period.

Organophosphate tri- and diesters in source water supply and drinking water treatment systems of a metropolitan city in China.

The water contaminations with organophosphate triesters (tri-OPEs) and diesters (di-OPEs) have recently provoked concern. However, the distributions of these compounds in natural water sources and artificial water treatment facilities are poorly characterized. A comprehensive study was therefore performed to measure their concentrations in a water source, a long-distance water pipeline, and a drinking water treatment plant (DWTP). Eight tri-OPEs and 3 di-OPEs were found to be widely distributed, with total concentrations in source water and pipelines ranging from 290.6 to 843.9ng/L. The most abundant pollutants were tris(1-chloro-2-propyl) phosphate (TCPP), triethyl phosphate, tri-n-butyl phosphate (TnBP), and diphenyl phosphate (DPhP). Di-OPEs appeared to be removed less efficiently in the DWTP than the parent tri-OPEs, and the elimination efficiencies of tri-OPEs were structure-dependent. Long-distance pipeline transportation had no significant effect on the distributions of tri- and di-OPEs. Statistical analysis suggested that the sources of di-OPEs and the corresponding tri-OPEs differed, as did those of DPhP and di-n-butyl phosphate. A risk analysis indicated that tri-OPEs present limited ecological risks that are mainly due to TnBP and TCPP, and that the human health risks of tri-OPEs are negligible. However, di-OPEs (especially DPhP) may increase these risks. Further studies on the risks posed by di-OPEs in aquatic environments are therefore needed.

Accumulations and equilibrium conditions of organophosphate esters (OPEs) in the indoor window film and the estimation of concentrations in air

The study of the fate of organophosphate esters (OPEs) in the interior environment is vital because of the growing use of OPEs. Organic films on glass are both sink and sources of indoor pollutants. Indoor window films have been employed as passive air samplers to collect OPEs in the indoor air. Nevertheless, little is known about the development and equilibrium condition of OPEs on indoor window films during the film formation process. In this study, the concentrations of twelve OPEs in indoor window films from different buildings on a university campus and the growth thickness of the films as a function of sampling time were investigated in different seasons. Ten out of the 12 OPEs were detected in window film with >50 % frequency. Tris (2-chloroethyl) phosphate (TCEP) and tris (1-chloro-2-propyl) phosphate (TCPP), which are chlorinated and toxic OPEs, were the dominant OPEs found in the winter. The majority of OPEs in window films exhibited linear growth patterns within 77 days. Temperature, humidity, ventilation, and seasonality all affected the concentrations of various OPEs in the window films. Low molecular weight OPEs, such as tri-n-butyl phosphate and TCEP, attained equilibrium between indoor air and window films within 49 or 77 days. The indoor air concentrations of OPEs were estimated from their film concentrations based on the theoretical approach for the passive air sampler. In winter, the predicted gas-phase air concentrations of OPEs (3.7 ng/m3 for TECP) were significantly lower than or comparable to summer (11 ng/m3, p < 0.05). To the best of our knowledge, this is the first attempt to combine uncertainty and sensitivity analysis to understand the behaviors of OPEs in indoor film and air.