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Semi-volatile organic compounds (SVOCs), such as phthalates and organophosphate flame retardants (OPFRs), are used in plastic products and electrical and electronic applications as plasticisers or flame retardants. There has been a growing concern that exposure to SVOCs can have an adverse impact on human health. Several large-scale epidemiological studies employ the sampling of house dust using household vacuum cleaners as the standard method. However, in this method, house dust samples might be contaminated by flame retardants and plasticisers because of the presence of these chemicals in the plastic materials of cleaners. Therefore, this study aimed to develop a low-cost, easy-to-distribute sampling method to collect house dust using a mop and analyse OPFRs, phthalate esters, and alternative plasticisers in house dust. Our findings show that the proposed mop sampling method can be easily distributable and lower contamination from a sampling tool. Moreover, the proposed house dust sampling method is extremely useful for a large-scale survey such as a cohort study. [ABSTRACT FROM AUTHOR]

Organophosphorus flame retardants (PFRs) are a class of flame retardants and environmental pollutants with various biological effects. Recentstudies have evidenced activation of some PFRs by human CYP enzymes (including CYP2E1) for genotoxic effects. However, the activity of CYPs in fish species toward PFR metabolism remains unclear. This study was aimed on comparing the metabolism of triphenyl phosphate (TPHP) and 4-OH-TPHP in human, rat, and common carp, and the involvement of human CYP2E1 and its orthologs in the metabolism, by using fomepizole (4-MP, CYP2E1 inhibitor) as a modulator, in silico molecular docking and dynamics analyses. The rate of TPHP metabolism was apparently faster with human and rat, microsomes than with fish microsomes, the major metabolites were phosphodiester and hydroxylated phosphate, with 30–80 % of TPHP forming unidentified metabolites in the system of each species. 4-OH-TPHP was readily metabolized by both human and rat microsomes, whereas it was hardly metabolized in carp assays. Meanwhile, with 4-MP the transformation of TPHP to 4-OH-TPHP was enhanced in the human/rat systems while suppressed in the carp system. Moreover, the formation of unidentified metabolites in human and rat systems was mostly inhibited by 4-MP. Through molecular dynamics analysis TPHP and its primary metabolites showed high affinity for human and rat CYP2E1, as well as the carp ortholog (CYP2G1-like enzyme), however, the 4-OH-TPHP bond to the latter was too far from the heme to permit a biochemical reaction. This study suggests that the metabolism/activation of TPHP might be favored in mammals rather than carp, a fish species.

Organophosphorus flame retardants (OPFRs) have been widely used in polymeric materials owing to their flame retardant and plasticizing effects. Investigating the fragmentation pathway of OPFRs is of great necessity for further discovering and identifying novel pollutants using orbitrap-based high-resolution mass spectrometry (HRMS). A total of 25 OPFRs, including alkyl, halogenated, and aromatic types, were analyzed in this study. The fragmentation pathways of the OPFRs were investigated using orbitrap-based HRMS with high-energy collision dissociation (HCD) in positive mode. The major fragmentation pathways for the three types of OPFRs are greatly affected by the substituents. In detail, the alkyl and halogenated OPFRs underwent three McLafferty hydrogen rearrangements, wherein the substituents were gradually cleaved to form the structurally stable [H4PO4]+ (m/z = 98.9845) ions. In contrast, the aromatic OPFRs would cleave not only the C-O bond but also the P-O bond, depending on the substituents, to form fragment ions such as [C6H7O]+ (m/z = 95.0495) or [C7H7]+ (m/z = 91.0530), among others. Using HRMS improved the accuracy of fragment ion identification, and the pathway became more evident. These fragmentation laws can provide identification information in pollutant screening work and theoretical references for the structural characterization of compounds with diverse substituent structures. [ABSTRACT FROM AUTHOR]

In this paper, 1 m³ climate chamber method and GC-MS were used to quantitatively analyze the content level changes of five organophosphorus flame retardants in pollution sources, and the average concentration of OPEs in the air was 110 ng/m3 based on calculation, in which tris-(2-chloroisopropyl) phosphate (TCPP) was the main pollutant. Moreover, the health risk assessment of one organophosphorus flame retardants in laminate flooring was evaluated, of which the non-carcinogenic risk and carcinogenic risk were at a low level. [ABSTRACT FROM AUTHOR]

The sustainable development of innovative eco-friendly multifunctional nanocomposites, possessing superior characteristics, is a noteworthy topic. Novel semi-interpenetrated nanocomposite films based on poly(vinyl alcohol) covalently and thermally crosslinked with oxalic acid (OA), reinforced with a novel organophosphorus flame retardant (PFR-4) derived from co-polycondensation in solution reaction of equimolar amounts of co-monomers, namely, bis((6-oxido-6H-dibenz[c,e][1,2]oxaphosphorinyl)-(4-hydroxyaniline)-methylene)-1,4-phenylene, bisphenol S, and phenylphosphonic dichloride, in a molar ratio of 1:1:2, and additionally doped with silver-loaded zeolite L nanoparticles (ze-Ag), have been prepared by casting from solution technique. The morphology of the as prepared PVA-oxalic acid films and their semi-interpenetrated nanocomposites with PFR-4 and ze-Ag was investigated by scanning electron microscopy (SEM), while the homogeneous distribution of the organophosphorus compound and nanoparticles within the nanocomposite films has been introspected by means of energy dispersive X-ray spectroscopy (EDX). It was established that composites with a very low phosphorus content had noticeably improved flame retardancy. The peak of the heat release rate was reduced up to 55%, depending on the content of the flame-retardant additive and the doping ze-Ag nanoparticles introduced into the PVA/OA matrix. The ultimate tensile strength and elastic modulus increased significantly in the reinforced nanocomposites. Considerably increased antimicrobial activity was revealed in the case of the samples containing silver-loaded zeolite L nanoparticles. [ABSTRACT FROM AUTHOR]

The inhibitory effect of dimethyl methylphosphonate (DMMP) on coal spontaneous combustion was investigated. The influence of DMMP on the thermal mass loss and thermal properties in the coal oxidation process was analyzed by synchronous thermal analysis. A DMMP inhibitor concentration of 10% provided the best inhibitory effect on coal oxidation. Addition of DMMP increased the coal ignition temperature by approximately 33°C, the burnout temperature by approximately 63°C, and the initial exothermal temperature by approximately 12°C. It also reduced the total heat release of the coal oxidation process by approximately 1200 J/g. Kinetic analysis of raw coal and DMMP-treated coal showed that DMMP exerted physical inhibition by blocking contact between coal and oxygen in the low-temperature oxidation stage. In the high-temperature oxidation stage, the chemical inhibition effect of DMMP was enhanced and the activation energy increased significantly (approximately 54.79 kJ/mol). Gas phase analysis indicated that DMMP could reduce oxygen consumption and CO emission during the coal oxidation process. On the basis of the above results and quantum chemical analysis, a mechanism for DMMP suppression of coal spontaneous combustion was proposed. This study provides reference data for prevention of coal spontaneous combustion and development of new inhibitors. [ABSTRACT FROM AUTHOR]

Organophosphorus flame retardants (PFRs) are a class of flame retardants and environmental pollutants with various biological effects. Recentstudies have evidenced activation of some PFRs by human CYP enzymes (including CYP2E1) for genotoxic effects. However, the activity of CYPs in fish species toward PFR metabolism remains unclear. This study was aimed on comparing the metabolism of triphenyl phosphate (TPHP) and 4-OH-TPHP in human, rat, and common carp, and the involvement of human CYP2E1 and its orthologs in the metabolism, by using fomepizole (4-MP, CYP2E1 inhibitor) as a modulator, in silico molecular docking and dynamics analyses. The rate of TPHP metabolism was apparently faster with human and rat, microsomes than with fish microsomes, the major metabolites were phosphodiester and hydroxylated phosphate, with 30–80 % of TPHP forming unidentified metabolites in the system of each species. 4-OH-TPHP was readily metabolized by both human and rat microsomes, whereas it was hardly metabolized in carp assays. Meanwhile, with 4-MP the transformation of TPHP to 4-OH-TPHP was enhanced in the human/rat systems while suppressed in the carp system. Moreover, the formation of unidentified metabolites in human and rat systems was mostly inhibited by 4-MP. Through molecular dynamics analysis TPHP and its primary metabolites showed high affinity for human and rat CYP2E1, as well as the carp ortholog (CYP2G1-like enzyme), however, the 4-OH-TPHP bond to the latter was too far from the heme to permit a biochemical reaction. This study suggests that the metabolism/activation of TPHP might be favored in mammals rather than carp, a fish species. • The biotransformation rate of TPHP was faster in mammals than in carp. • 4-OH-TPHP can be metabolized in mammal, but it is hardly metabolized in carp. • The formation of 4-OH-TPHP from TPHP can be mediated by carp CYP2E1-orthologs. • Most unidentified metabolites in mammalian assays were mediated by CYP2E1. • TPHP and its products have a high affinity for CYP2E1/CYP2G1-like in silico. [ABSTRACT FROM AUTHOR]

While the cardiovascular system is a primary target of organophosphorus flame retardants (OPFRs), particularly aryl-OPFRs, it is still exclusive whether the diisodecyl phenyl phosphate (DIDPP), widely used and broadly present in the environment at high concentrations, elicits atherosclerosis effects. Liver X receptors (LXRs) play a direct role in regulating the formation of atherosclerotic lesions. This study was the first to demonstrate that DIDPP acts as an LXRα ligand and functions as an LXRα antagonist with a half-maximal inhibitory concentration of 16.2 μM. We showed that treatment of an in vitro macrophage model with 1 to 10 μM of DIDPP resulted in the downregulation of direct targets of LXRα, namely ABCA1, ABCG1 and SR-B1, thereby leading to a 7.9–13.2 % reduction in cholesterol efflux. This caused dose-dependent, 24.1–43.1 % increases in the staining intensity of foam cells in the macrophage model. This atherosclerotic effect of DIDPP was proposed to be due to its antagonism of LXRα activity, as DIDPP treatment did not alter cholesterol influx. In conclusion, the findings of this study demonstrate that exposure to DIDPP may be a risk factor for atherosclerosis due to the LXRα-antagonistic activity of DIDPP and its ubiquity in the environment. [Display omitted] • DIDPP was identified as a LXRα antagonist in drinking water. • DIDPP markedly hinders cholesterol efflux from macrophages due to its LXRα transcriptional activity. • DIDPP significantly stimulates foam cell formation. [ABSTRACT FROM AUTHOR]

Biotransformation of organophosphorus flame retardants (OPFRs) mediated by cytochrome P450 enzymes (CYPs) has a potential correlation with their toxicological effects on humans. In this work, we employed five typical OPFRs including tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), tris(1-chloro-2-propyl) phosphate (TCIPP), tri(2-chloroethyl) phosphate (TCEP), triethyl phosphate (TEP), and 2-ethylhexyl diphenyl phosphate (EHDPHP), and performed density functional theory (DFT) calculations to clarify the CYP-catalyzed biotransformation of five OPFRs to their diester metabolites. The DFT results show that the reaction mechanism consists of Cα-hydroxylation and O-dealkylation steps, and the biotransformation activities of five OPFRs may follow the order of TCEP ≈ TEP ≈ EHDPHP > TCIPP > TDCIPP. We further performed molecular dynamics (MD) simulations to unravel the binding interactions of five OPFRs in the CYP3A4 isoform. Binding mode analyses demonstrate that CYP3A4-mediated metabolism of TDCIPP, TCIPP, TCEP, and TEP can produce the diester metabolites, while EHDPHP metabolism may generate para-hydroxyEHDPHP as the primary metabolite. Moreover, the EHDPHP and TDCIPP have higher binding potential to CYP3A4 than TCIPP, TCEP, and TEP. This work reports the biotransformation profiles and binding features of five OPFRs in CYP, which can provide meaningful clues for the further studies of the metabolic fates of OPFRs and toxicological effects associated with the relevant metabolites. [ABSTRACT FROM AUTHOR]

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Tris(1,3-dichloro-2-propyl)phosphate (TDCIPP) is an organophosphorus flame retardant that is an alternative to brominated flame retardants. Although TDCIPP can adversely affect human health, information about its effects on immune and allergic responses is scarce. We aimed to investigate the effects of dietary exposure to TDCIPP using less than the human tolerable daily intake (TDI) in allergic asthmatic mice. Male C3H/HeJSlc mice were fed a chow diet containing TDCIPP equivalent to 0.02 μg/kg/day (low; L), 0.2 μg/kg/day (medium; M), or 2 μg/kg/day (high; H) and were intratracheally administered ovalbumin (OVA, 1 μg/animal) every 2 weeks from 5 to 11 weeks of age. In OVA-treated mice, TDCIPP-H exposure tended to enhance pulmonary inflammation compared with vehicle exposure. TDCIPP dose-dependently decreased mRNA level of G protein-coupled estrogen receptor (GPER) in the lungs with or without OVA. OVA + TDCIPP-H treatment tended to increase the total cell number and promoted CD4+ cell activation compared with OVA alone treatment in mediastinal lymph nodes. In splenocytes, an increase in the fraction of Breg cells, but not of total B and T cells, and an increase in IL-5 in cell culture supernatants following OVA re-stimulation in OVA + TDCIPP-H-treated mice was observed compared with OVA-alone-treated mice. Moreover, OVA + TDCIPP-H exposure decreased Gr-1 expression in bone marrow (BM) cells. These results suggested that dietary exposure to TDCIPP at TDI level slightly enhances allergic diseases, such as allergic asthma, via GPER regulation at inflamed sites and secondary lymphoid tissue and BM cell alternations. [ABSTRACT FROM AUTHOR]

The fate of organophosphorus flame retardants（PFRs）in polished rice during the cooking process was examined. After adding PFRs to polished rice（500 ng/g）, the rice was washed with water and cooked in a rice cooker. Among the seven kinds of PFRs, approximately 68--86% of the PFRs residues were removed after washing with water three times. In the first washing with water, approximately 50--70% of the PFRs residues were removed from rice. By the subsequent heating in an electric rice cooker or in a microwave rice cooker, the removal rates of PFRs in the cooked rice were 74--94 and 78--96%, respectively. The removal rates in musenmai （500 ng/g） which need not to wash before cooking were lower than those in the washed rice. In the cooked musenmai, 10--50% of the PFRs residues were removed after heating in the electric rice cooker, and 10--70% were removed in the microwave rice cooker. The washing process is effective to reduce the intake of PFRs from rice. [ABSTRACT FROM AUTHOR]

In order to clarify the actual situation of indoor pollution to polished rice with organophosphorus flame retardants (PFRs) which are ubiquitous in the indoor environment, the pollution of PFRs to polished rice stored in a house for a week was investigated. The survey covered 64 ordinary families in the Osaka region. We analyzed six typical PFRs in 37 rice samples in 2015, and ten typical PFRs in 27 rice samples in 2016. Polished rice was homogenized with acetone-hexane and defatted by hexane-acetonitrile partition. Quantitative analysis for PFRs was performed by GC-FPD. The detection frequency of PFRs in the rice samples was 35/37 in 2015 and 27/27 in 2016. The highest values were 160 ng/g for TCEP, 500 ng/g for TCIPP and 430 ng/g for TBEP. The concentration ratio of each detected PFR in the polished rice samples was different in each house. In the analysis of 16 polished rice samples which were stored in the home, PFRs were detected in ten samples regardless of the storage methods. PFRs were detected from 12 out of 16 commercial brown rice samples. This result suggested that they were polluted during distribution and storage process of them. [ABSTRACT FROM AUTHOR]

Abstract Twelve organophosphorus flame retardants (PFRs) were detected in the muscle of 3 species of fish, mud carp (Cirrhinus molitorella), tilapia (Tilapia nilotica), and plecostomus (Hypostomus plecostomus), from rivers in the Pearl River Delta (PRD) region. The total concentrations of PFRs in the mud carp, tilapia, and plecostomus ranged from 2.3 to 16, 3.4 to 16, and 3.5 to 30 ng/g wet weight (ww), respectively. Generally, tris(2-ethylhexyl) phosphate (TEHP), tris (2-chloro-isopropyl) phosphate (TCPP), tris (2-chloroethyl) phosphate (TCEP), and tri-n-butyl phosphate (TnBP) were the dominant compounds of the PFRs, collectively accounting for up to 90% of the total PFR levels. Concentrations of PFRs were significantly higher in the plecostomus than in the mud carp and tilapia (p < 0.05), which could be explained by differences in habitat and feeding habits of the fish species. High concentrations of PFRs were found mainly in the Guangzhou section of the Pearl River (site P1, P2, and P3) and site B3, which was similar to our previous study of PFRs in sediment from the Pearl River Delta, indicating a relatively high level of PFRs pollution in these regions. The estimated daily intake (EDI) of total PFRs from consumption of fish was 17 ng/kg bw/day to 98 ng/kg bw/day for adults and children, which was three to four orders of magnitude lower than reference dose values. Graphical abstract Unlabelled Image Highlights • Levels of ∑12PFRs in fish from the PRD ranged from 2.3 to 30 ng/g ww. • High PFRs level was found mainly in the Guangzhou section of the Pearl River and site B3. • TEHP, TCPP, TCEP, and TnBP were the dominant compounds of the PFRs in the PRD. • The concentrations of PFRs were significantly higher in the plecostomus than in the mud carp and tilapia (p < 0.05). • All the PFR EDIs were far below the established corresponding RfD values. [ABSTRACT FROM AUTHOR]

Tris (1,3-dichloro-2-propyl) phosphate (TDCPP) is the most widely used organophosphorus flame retardant, which is now used instead of polybrominated diphenyl ethers (PBDEs). TDCPP has frequently been detected in inorganic environmental matrices, such as soil, water and air as well as biota. In vitro effects of TDCPP on cells had not been previously elucidated. Therefore, in the present study, cytotoxicity, DNA damage, cell cycle distribution, apoptosis caused by TDCPP was studied in RAW264.7 macrophage cells. TDCPP reduced viability of RAW264.7 cells in a concentration-dependent manner and caused damage to DNA that was detected by use of the comet assay and caused up-regulation of the level of γ-H2AX. TDCPP increased the intracellular reactive oxygen species (ROS) level in RAW264.7 cells up to 1.44-fold compared to the control group at 12 hr. Percentages of cells in G1 and G2 phases of the cell cycle were dose-dependently greater in cells exposed to TDCPP. TDCPP significantly down-regulated expression of CDK-4, Cyclin D1, Cyclin B1, CDC-2, which are regulators of G1 and G2 phases of the cell cycle. These results demonstrated that TDCPP is cytotoxic and damages DNA in RAW264.7 cells, which resulted in arrest of the cell cycle at G1 and G2 phases and resulted in apoptosis, suggest the necessity to evaluate the effects of TDCPP on the immune system at the cellular level. [ABSTRACT FROM AUTHOR]

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. [Display omitted] • Water hyacinth root can efficiently absorb OPEs via passive diffusion pathways. • The passive diffusion of OPEs is facilitated by anion channels and/or aquaporins. • Hydrophilicity is the decisive factor for OPE transfer in tissue/subcellular part. • OPEs can be degraded to diesters that are more soluble and acropetal-transferrable. • OPE exposure imposes certain effect on plant growth and rhizospheric microorganism. [ABSTRACT FROM AUTHOR]

Fire safety of polyurethanes (PUs) has limited their further practical applications. To address this problem, we designed novel phosphorus-based flame retardants (P-FR) by incorporating aryl (Ar) groups via Kabachnik–Fields reaction, realizing π–π interaction-reinforced Ar2 and Ar5. Total heat release and peak heat release rate of PU/Ar5, whose flame-retardancy-index of 5.02 due to reduced combustion time, decreased 23.24 and 9.23 %, respectively, compared with neat PU. Moreover, UL94 rating for PU/Ar5 was improved from V-2 to V-0. These results demonstrate that Ar5 effectively generate a barrier effect that blocks oxygen, fuel, and heat. Sluggish mobility and phase transition are responsible for such enhancement due to a delay effect with the existence of π–π interactions and steric hindrance. Encouragingly, tensile strength and toughness of PU/Ar5 were greatly improved by 1345.8 and 670.3 %, respectively, compared with neat PU. We believe that this study could provide a promising method for introducing specific function to flame retardants to enhance fire safety and mechanical properties of composites. [Display omitted] • Ar–P–N flame retardant (Ar5) was synthesized using Kabachnik–Fields reaction. • Synergetic effects of Ar5 and flame retardancy mechanism of aryl were identified. • Flame retardancy index of PU/Ar5 increased due to the reduced combustion time. • PU/Ar5 composite exhibited significantly improved tensile strength and toughness. • Modified-flame retardancy index was introduced with time-to-extinction factor. [ABSTRACT FROM AUTHOR]

In the past decade, organophosphate esters (OPEs) undergo rapid increase in production and use. Meanwhile, owing to their additive property, OPEs exhibit liability to escape from related products and therefore ubiquity in various environments. Moreover, numerous researches verify their bioavailability and negative effects on biota and human, hence their occurrence and associated risks have caught much concern, particularly those in aquatic systems. So far, however, OPEs in water are generally investigated as a whole, their phase distribution and behavior in waterbodies are incompletely characterized. We examined 25 OPEs in water (including dissolved and particulate phases), sediment, and sediment core samples from the Lian River, which flows through the Guiyu e-waste recycling zone and Shantou specific economic zone in South China. Compared to most global waterbodies, the Lian River showed high or ultrahigh OPE levels in both water and sediments, particularly in the reaches surrounded by e-waste recycling and plastic-related industries, which were the top two greatest OPE sources. Non-industrial and agriculture-related anthropogenic activities also contributed OPEs. Sediment core data suggested that OPEs have been present in waters in Guiyu since the 1960s and showed a temporal trend consistent with the local waste-recycling business. The phase distribution of OPEs in the Lian River was significantly correlated with their hydrophobicity and solubility. Owing to their wide range of physicochemical properties, OPE congeners showed significant percentage differences in the Lian River water and sediments. Generally, OPEs in water reflect their dynamic real-time inputs, while those in sediment signify their accumulative deposition, which is another cause of their phase distribution disparities in the Lian River. The physicochemical parameters of OPEs first imposed negative and then positive influences on their dissolved phase-sediment distribution, indicating the involvement of both the adsorption of dissolved OPEs and the deposition of particle-bound OPEs. [Display omitted] • OPEs showed both high levels but diverse profiles in the river water and sediments. • E-waste recycling and plastic-related industries were the top two OPE sources. • Temporal trend of OPEs in Guiyu waters matched the local waste recycling history. • Phase distribution of OPEs in the river was controlled by their K OW and solubility. • Sediment OPEs were contributed by both their dissolved and particle-bound forms. [ABSTRACT FROM AUTHOR]

The sea urchin (Paracentrotus lividus) was used to test the effects of one of the most abundant flame retardant additives for plastics, tris (1-chloro-2-propyl) phosphate (TCPP), and the synthetic hormone ethinylestradiol (EE2) on gametogenesis and gonad development of adults. With this aim, 403 individuals of both sexes were exposed to TCPP concentrations ranging from 0.2 to 10 µg/L, EE2 (0.01 µg/L), seawater and solvent controls for 7 and 28 days. EE2 and TCPP exposure did not cause histological damage in the gonads. Some evidence of estrogenic effects of TCPP within the µg/L range and EE2 within the ng/L range is reported. Females exposed to 1 µg/L TCPP for 7 days showed a significant increase in gonad development assessed as gametogenic stage, females exposed to 10 µg/L TCPP showed increased gonad development both in terms of weight (Gonad Index, GI, at both 7 and 28 days) and maturation (Pixelar Index, PI), and females exposed to 10 ng/L EE2 showed increased PI after 28 days exposure. Male sea urchins exposed to both TCPP and EE2 for 7 days showed increased frequencies of low development gonad stage. However, the patterns of response are affected by the high inter-individual variability, the differing initial stage of the gonad, as well as the dosage administered.

Alternative flame retardants (FRs) have now replaced legacy FRs (such as polybrominated diphenyl ethers, PBDEs), but little is known about their fate in the aquatic environment. In this study, a range of legacy FRs ( n = 10) and alternative FRs, including halogenated FRs (HFRs, n = 32) and organophosphorus FRs (OPFRs, n = 19), were screened in water samples collected from 23 rivers covering the whole latitudinal range of Sweden. Of the 61 targeted FRs, 26 were detected in at least one of the river samples, with ΣFR concentrations ranging up to 170 ng L − 1 (mean 31 ± 45 ng L − 1 ). In general, higher concentrations and a larger variety of FRs were detected in southern Sweden (ΣFR = 60 ± 56 ng L − 1 ) compared with the north (ΣFR = 9.0 ± 16 ng L − 1 ). In the south, HFRs were dominant, constituting on average 59% of ∑ FRs, whereas in the north, OPFRs were dominant, constituting on average 82% of ∑ FRs. This difference was best explained by higher population density in the south. The total daily flux of FRs into the Baltic Sea was estimated to be ~ 31 kg and comprised mainly tetrabromobisphenol-A (TBBPA), 3,4,5,6-tetrabromophthalic anhydride (TEBP-Anh), and 2,4,6-tribromophenol (TBP). To the best of our knowledge, this is the first report of environmental occurrence of TEBP-Anh, which was detected in two rivers and is suggested to originate from airports located near the sampling sites. [ABSTRACT FROM AUTHOR]

Organophosphorus flame retardants (OPFRs) are frequently detected in aquatic environments and can potentially amplify the food chain, posing a potential risk to organisms. Marine invertebrates have primitive nervous systems to regulate behavior, but how they respond to OPFRs that are potentially neurotoxic substances is unclear. This study assessed changes in the feeding behavior of rotifer Brachionus plicatilis exposed to alkyl OPFRs tributyl phosphate (TnBP) (0.376 nM, 3.76 and 22.53 µM) to elucidate the mechanism of behavioral toxicity. TnBP at 22.53 μM reduced the ingestion and filtration rates of rotifers for Chlorella vulgaris and Phaeocystis globosa in a 24-h test and altered rotifer- P. globosa population dynamics in 15-d coculture. Ciliary beat frequency was also reduced, and the expression of genes encoding the cilia axoneme was downregulated. TnBP could inhibit rotifer acetylcholinesterase activity by binding this protein and reduce the expression of the exocytotic membrane protein syntaxin-4, suggesting a disorder in nervous regulation of cilia beat. Moreover, TnBP induced abnormal shape and dysfunction of mitochondria, which caused insufficient energy required for ciliary movement. This study revealed diverse neurotoxicity mechanisms of TnBP, particularly as a potentially competing acetylcholinesterase ligand for aquatic invertebrates. Our research also provides a meaningful reference for OPFR-induced behavioral toxicity assessments. [Display omitted] • TnBP at environmental level reduced the control ability of rotifers over P. globosa. • The downregulation of some axonemal genes led to a slow CBF of rotifer. • TnBP could bind to the pocket of rotifer AChE protein and inhibited its activity. • TnBP inhibited the SNARE expression of B. plicatilis. • TnBP interfered with the mitochondrial dynamics and autophagy of rotifer. [ABSTRACT FROM AUTHOR]

The widespread, persistent and toxic organophosphorus esters (OPEs) have become one category of emerging environmental contaminants. Thus, it is in urgent need to develop a cost-effective and safe treatment technology for OPEs control. The current study is a comprehensive attempt to use UV/TiO 2 heterogeneous photocatalysis for the degradation of a water dissolved OPEs, tris(2-chloroethyl) phosphate (TCEP). A pseudo-first order degradation reaction with a k obs of 0.3167 min −1 was observed, while hydroxyl radical may be the dominating reactive oxidative species. As the reaction proceeded, TCEP was transformed to a series of hydroxylated and dechlorinated products. The degradation efficiency was significantly affected by pH value, natural organic matters and anions, implying that the complete mineralization of TCEP would be difficult to achieve in actual water treatment process. Based on the proteomics analysis regarding the metabolism reactions, pathways and networks, the significant activation of transmembrane transport and energy generation in Escherichia coli exposed to preliminary degrading products suggested that they can be transported and utilized through cellular metabolism. Furthermore, the descending trend of stress resistance exhibited that the toxicity of products was obviously weakened as the treatment proceeded. In conclusion, hydroxylation and dechlorination of TCEP with incomplete mineralization were likewise effective for its detoxification, indicating that UV/TiO 2 will be an alternative treatment method for OPEs control. [ABSTRACT FROM AUTHOR]

Twelve organophosphorus flame retardants (PFRs) were identified in the sediments and the sediment core collected from the rivers and the estuary in the Pearl River Delta, with the aim of investigating their spatial and vertical distributions. The concentrations of PFRs ranged from 8.3 to 470 ng/g dry weight with high levels of PFRs in the urban area and the e-waste recycling region. Generally, TPhP, TCPP, TEHP, TCEP, and TBEP were the dominant compounds of the PFRs, the composition of which varied across the different regions, reflecting the different sources of PFRs. In the estuary, the PFRs mainly derived from the Xijiang River and the Shunde sections. Increased concentrations of halogen-containing PFRs have been observed in the upper layers of the sediment core. Conversely, relatively high concentrations of halogen-free PFRs were observed in the lower layers of the sediment core, indicating different usage patterns or environmental behaviors between the halogen and the non-halogen PFRs in the study area. [ABSTRACT FROM AUTHOR]

Highlights: [•] DART-MS/MS was firstly applied to quantity contaminant in environmental water. [•] A rapid ISTD method was developed to quantify trimethyl phosphate (TMP) in sewage. [•] TMP was detected in environmental water at the level of ng/mL. [Copyright &y& Elsevier]

Occurrence, distribution, and potential ecological risks of ten organophosphate esters (OPEs) and nine synthetic musks (SMs) were investigated in sediments from the Yangtze River Estuary (YRE) and adjacent East China Sea (ECS). The total concentrations of OPEs in the surface sediments ranged from 0.977 to 19.0 ng/g dry weight (dw) with tris(2-chloro-propyl) phosphate being the dominant component. Total concentrations of SMs ranged from 0.176 to 7.25 ng/g dw, with 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyran and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene as the dominant SMs. Higher sedimentary concentrations of ΣOPEs and ΣSMs were found in the river mouths of the YRE, inter face of Hangzhou Bay, and mud area of the ECS; the results suggested that terrestrial discharge might be the main source of OPEs and SMs in the studied region. Risk assessment revealed that low ecological risks were posed by OPEs, and limited to low ecological risks were posed by SMs. [Display omitted] • OPEs and synthetic musks were mainly accumulated in mud area adjacent to YRE. • TCPP and TCEP were the two most abundant OPEs compounds in sediment. • HHCB and AHTN were the main fragrance posed limited- low ecological risks. • Low ecological risks from cumulative exposure of OPEs are mainly from TCPP. [ABSTRACT FROM AUTHOR]

Abstract: The aim of this study was to investigate the thermal degradability, and in particular, the thermal degradation mechanism of organophosphorus flame-retardant poly(methyl methacrylate) (PMMA). For this purpose thermogravimetry and direct pyrolysis mass spectrometry analyses were used. Release of diethylphosphinic acid, melamine, and several products involving Al–O–P and N–P linkages were detected from the organophosphorus additive containing aluminium diethylphosphinate, melamine polyphosphate and zinc borate. When incorporated in PMMA, reactions of diethylphosphinic acid, melamine and/or their derivatives with the ester group affected the decomposition pathways by generation of (C2H5)2POOCH3 and HNCO at relatively high temperatures. [Copyright &y& Elsevier]

The flame resistant finishing of silk fabric is still a challenge because most of the available treatment methods usually result in insufficient laundering durability. In this paper, a vinyl phosphorus-based monomer diethyl-2-(methacryloyloxyethyl) phosphate (DEMEP) was applied onto silk fabrics by graft copolymerization technique using potassium persulfate as an initiator. FT-IR spectra and amino analysis showed the evidence of the reaction between DEMEP and silk. The silk fabrics treated with DEMEP have excellent self-extinguishing property when the DEMEP add-on is over 50 % wt of silk fabrics. The LOI of treated samples is at least 28 % when the weight gain is 10 %. After being subjected to 30 hand wash cycles, DEMEP treated silk fabric can still pass the vertical flammability test. Thermal gravimetric (TGA) and differential thermal analysis (DTA) were applied to explore the thermal decomposition of silk fabrics treated with DEMEP. The initial decomposition temperature of silk fabric treated with DEMEP was shifted to a lower temperature. And at the end of decomposition at 700 °C, the char residue of silk fabric treated with DEMEP was higher than that of the control sample. [ABSTRACT FROM AUTHOR]

The sea urchin (Paracentrotus lividus) was used to test the effects of one of the most abundant flame retardant additives for plastics, tris (1-chloro-2-propyl) phosphate (TCPP), and the synthetic hormone ethinylestradiol (EE2) on gametogenesis and gonad development of adults. With this aim, 403 individuals of both sexes were exposed to TCPP concentrations ranging from 0.2 to 10 µg/L, EE2 (0.01 µg/L), seawater and solvent controls for 7 and 28 days. EE2 and TCPP exposure did not cause histological damage in the gonads. Some evidence of estrogenic effects of TCPP within the µg/L range and EE2 within the ng/L range is reported. Females exposed to 1 µg/L TCPP for 7 days showed a significant increase in gonad development assessed as gametogenic stage, females exposed to 10 µg/L TCPP showed increased gonad development both in terms of weight (Gonad Index, GI, at both 7 and 28 days) and maturation (Pixelar Index, PI), and females exposed to 10 ng/L EE2 showed increased PI after 28 days exposure. Male sea urchins exposed to both TCPP and EE2 for 7 days showed increased frequencies of low development gonad stage. However, the patterns of response are affected by the high inter-individual variability, the differing initial stage of the gonad, as well as the dosage administered. [ABSTRACT FROM AUTHOR]

Graphene oxide (GO), a novel two-dimension carbon nanomaterial, has showed tremendous potential for utilization in intelligent manufacturing and environmental protection. In parallel, tris(1,3–dichloro–2–propyl) phosphate (TDCIPP) is widely distributed in the water environment and represents a great threat to ecosystem health. However, the related knowledge remained absent regarding the impact of GO on the biological risks of TDCIPP. Herein, GO significantly reduced the mortality and malformation rates of zebrafish induced by TDCIPP maximumly by 28.6% and 41.8%, respectively. Decreased mitochondrial respiratory chain (MRC) enzyme and ATP activity induced by TDCIPP were mitigated by GO. Integrating proteomics and metabolomics revealed TDCIPP obviously induced the downregulation of the proteins and metabolites involved in the cytoskeleton, mitochondrial function, carbohydrate and amino acid metabolism, and the TCA cycle, but the alterations were attenuated by GO. GO primarily promoted MRC activity, carbohydrate metabolism, and fatty acid β–oxidation, thus activating the energy metabolism of zebrafish and leading to antagonistic effects on the developmental toxicity of TDCIPP. These results provide a novel view on the co–exposure of GO with other pollutants and promote the reconsideration of the environmental risks of GO. Unlabelled Image • GO reduced the mortality and malformation rate of zebrafish induced by TDCIPP. • GO relieved the mitochondria damage and MRC enzyme inhibition induced by TDCIPP. • GO co-exposure promoted the carbohydrate metabolism and fatty acid β–oxidation. • GO activated the energy metabolism leading to the antagonistic toxicity with TDCIPP. [ABSTRACT FROM AUTHOR]

Water, sediment, and wild aquatic species were collected from an electronic waste (e-waste) polluted pond in South China. This study aimed to investigate the bioaccumulation, tissue distribution, and trophic transfer of organophosphorus flame retardants (PFRs) in these aquatic organisms. The concentrations of PFRs detected in the analyzed organisms were between 1.7 and 47 ng/g wet weight (ww). Oriental river prawn and snakehead exhibited the highest and lowest levels, respectively. Tri- n -butyl phosphate (TnBP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCPP) and triphenyl phosphate (TPhP) were dominant contaminants, accounting for approximately 86% of the total sum. The mean values of bioaccumulation factors (BCFs) and logarithmic biota-sediment accumulation factors (log BSAFs) for individual PFRs varied from 6.6 to 1109 and from −2.0 to 0.41, respectively. Both log BCFs and log BSAFs of PFRs were significantly and positively correlated with their octanol-water partitioning coefficient (log K OW). The concentrations of PFRs in tissues of large mud carp and snakehead were significantly and positively correlated with the lipid content (each p < 0.05) and the liver, kidney, and gill exhibited high PFR levels. When the concentration was expressed on a lipid basis, liver exhibited the lowest level, indicating the probable effects of metabolism. Significantly positive correlation was also found between lipid content and total PFR concentration in muscle of all aquatic organisms, given the strong correlation between lipid content and the concentration of TnBP. Trophic magnification factors (TMF) of TnBP and TPhP were lower than 1 (0.57 and 0.62), indicating that these PFRs undergo trophic dilution in this aquatic food web. Image 1 • PFR bioaccumulation exhibited species-specific profiles. • TnBP, TCEP, TCPP, and TPhP were generally the dominant PFRs. • Log BCFs and log BSAFs were significantly correlated with log K OW. • PFR level was positively correlated with lipid content for a given species. • Trophic dilution for TnBP and TPhP were found in the aquatic food web. The present study revealed the bioaccumulation and biomagnification potentials of PFRs in aquatic organisms and provided basic data for the internal exposure of PFRs in organisms. [ABSTRACT FROM AUTHOR]

The fate of organophosphorus flame retardants (PFRs) in polished rice during the cooking process was examined. After adding PFRs to polished rice (500 ng/g), the rice was washed with water and cooked in a rice cooker. Among the seven kinds of PFRs, approximately 68-86% of the PFRs residues were removed after washing with water three times. In the first washing with water, approximately 50-70% of the PFRs residues were removed from rice. By the subsequent heating in an electric rice cooker or in a microwave rice cooker, the removal rates of PFRs in the cooked rice were 74-94 and 78-96%, respectively. The removal rates in musenmai (500 ng/g) which need not to wash before cooking were lower than those in the washed rice. In the cooked musenmai, 10-50% of the PFRs residues were removed after heating in the electric rice cooker, and 10-70% were removed in the microwave rice cooker. The washing process is effective to reduce the intake of PFRs from rice.

In order to clarify the actual situation of indoor pollution to polished rice with organophosphorus flame retardants (PFRs) which are ubiquitous in the indoor environment, the pollution of PFRs to polished rice stored in a house for a week was investigated. The survey covered 64 ordinary families in the Osaka region. We analyzed six typical PFRs in 37 rice samples in 2015, and ten typical PFRs in 27 rice samples in 2016. Polished rice was homogenized with acetone-hexane and defatted by hexane-acetonitrile partition. Quantitative analysis for PFRs was performed by GC-FPD. The detection frequency of PFRs in the rice samples was 35/37 in 2015 and 27/27 in 2016. The highest values were 160 ng/g for TCEP, 500 ng/g for TCIPP and 430 ng/g for TBEP. The concentration ratio of each detected PFR in the polished rice samples was different in each house. In the analysis of 16 polished rice samples which were stored in the home, PFRs were detected in ten samples regardless of the storage methods. PFRs were detected from 12 out of 16 commercial brown rice samples. This result suggested that they were polluted during distribution and storage process of them.

A critical challenge in environmental remediation is the design of adsorbents with proper pore size for the removal of organic pollutants. Three covalent organic frameworks (COFs) with different pore sizes were successfully prepared by a room-temperature solution-suspension method and used to remove a typical aryl-organophosphorus flame retardant [triphenyl phosphate (TPhP)] from aqueous solution. The prepared COFs showed strong acid resistance and thermal stability. The 1,3,5-triformylphloroglucinol (TFP) reacted with benzidine (BD) (COF2) and exhibited the highest sorption capacity for TPhP, followed by the reaction of TFP and 4,4″-diamino- p-terphenyl (DT) (COF3), and the reaction of TFP and p-phenylenediamine (COF1). Their adsorption equilibriums were achieved within 12 h, and COFs with a larger pore size have higher initial sorption rate but longer time to reach sorption equilibrium. According to the Langmuir fitting, the maximum sorption capacities of three COFs for TPhP were 86.1, 387.2, and 371.2 mg/g, respectively. The density functional theory calculation verified that COF1 with a small pore size prevents TPhP molecules from entering the pores, resulting in extremely low sorption capacity, whereas a relatively too large pore size (COF3) will decrease the sorption energy, which is also not conducive to the adsorption of TPhP. Moreover, the prepared COFs can selectively adsorb TPhP in the presence of coexisting compounds and had high removal of TPhP from actual municipal wastewater, showing a promising application potential for selective removal of micropollutants from water by precisely controlling the COF structure.