PM2.5-Bound Organophosphate Flame Retardants in Hong Kong: Occurrence, Origins, and Source-Specific Health Risks.

Organophosphate flame retardants (OPFRs) are emerging organic pollutants in PM2.5, which have caused significant public health concerns in recent years, given their potential carcinogenic and neurotoxic effects. However, studies on the sources, occurrence, and health risk assessment of PM2.5-bound OPFRs in Hong Kong are lacking. To address this knowledge gap, we characterized 13 OPFRs in one-year PM2.5 samples using gas chromatography-atmospheric pressure chemical ionization tandem mass spectrometry. Our findings showed that OPFRs were present at a median concentration of 4978 pg m-3 (ranging from 1924 to 8481 pg m-3), with chlorinated OPFRs dominating and accounting for 82.7% of the total OPFRs. Using characteristic source markers and positive matrix factorization, we identified one secondary formation and five primary sources of OPFRs. Over 94.0% of PM2.5-bound OPFRs in Hong Kong were primarily emitted, with plastic processing and waste disposal being the leading source (61.0%), followed by marine vessels (14.1%). The contributions of these two sources to OPFRs were more pronounced on days influenced by local pollution emissions (91.9%) than on days affected by regional pollution (44.2%). Our assessment of health risks associated with human exposure to PM2.5-bound OPFRs indicated a low-risk level. However, further source-specific health risk assessment revealed relatively high noncarcinogenic and carcinogenic risks from chlorinated OPFRs emitted from plastic processing and waste disposal, suggesting a need for more stringent emission control of OPFRs from these sources in Hong Kong.

Industrial Production of Organophosphate Flame Retardants (OPFRs): Big Knowledge Gaps Need to Be Filled?

Since the phase-out of traditional halogenated flame retardants (HFRs), interests of research are gradually being shifted to organophosphate flame retardants (OPFRs), and this can be reflected by the increasing number of publications on OPFRs year by year. Here, an extensive survey is conducted in an attempt to generate a list of OPFRs that are being produced in factories, and to investigate the annual production volume (APV). This survey suggests that at least n = 56 OPFR monomers and n = 62 OPFR mixtures are being currently produced in 367 factories around the world, and 201 out of them are in Mainland China. APV of OPFRs was estimated as 598,422 metric tons, and this number could be underestimated due to the limitation of available information. We also notice that current researches are confined to a limited number of OPFRs, especially for OP esters (OPEs), and other OPFRs with different structures from OPEs has been rarely studied. Based on all the collected datasets, we provide five recommendations for how to proceed with future research to more comprehensively understand the currently-produced OPFRs in the environment.

Effects of tris(2-chloroethyl) phosphate exposure on chicken embryos in a shell-less incubation system.

Tris(2-chloroethyl) phosphate (TCEP) is an organophosphate flame retardant that used in textiles, industrial materials, and furniture to delay the spread of fire after ignition. TCEP has been detected in the tissues and eggs of fish and birds. However, there are no studies regarding the effects of TCEP on avian embryos. In the present study, we investigated the developmental toxicity of TCEP exposure on chicken embryos in a shell-less incubation system, which enables in situ observation. Chicken embryos were treated with graded doses of TCEP (50, 250, and 500 nmol/g egg) on incubation day 0. The survival rate, morphological biometrics, heart rate, and length and branch number of extraembryonic blood vessels were measured on incubation days 3-9. Survival rates were reduced from incubation day 3 and were significantly decreased until day 9. Body length, head + bill length and eye diameter were significantly reduced by TCEP exposure. Regarding skeletal effects, spine length was decreased in a dose-dependent manner on day 9. Body weight on day 9 significantly reduced in all TCEP treatment groups. These results suggest that TCEP exposure to >50 nmol/g egg retards development in chicken embryos. TCEP exposure to 500 nmol/g egg significantly increased heart weight to body weight ratio in the embryos. More than 250 nmol/g egg of TCEP significantly reduced the heart rate of embryos in the early developmental stage. The formation of extraembryonic blood vessels and the number of erythrocytes were significantly reduced even with 50 nmol/g egg of TCEP. These findings suggest that TCEP exposure specifically affects the cardiovascular system in chicken embryos, which leads to developmental delay. The results of this study also demonstrate that the shell-less incubation system can be used to continuously monitor the effects of chemicals on developing avian embryos.

Multivariate optimization of a microextraction by packed sorbent-programmed temperature vaporization-gas chromatography-tandem mass spectrometry method for organophosphate flame retardant analysis in environmental aqueous matrices.

In this work, organophosphate ester flame retardant (OPFRs) assay in environmental waters was addressed by using microextraction by packed sorbent (MEPS) and gas chromatography-tandem mass spectrometry (GC-MS/MS). Ten OPFRs with different physicochemical properties were taken into account as target compounds for a comprehensive method evaluation. Five MEPS cartridges (i.e., C2, C8, C18, Silica, and DVB) and seven solvents (i.e., methanol, ethyl acetate, methyl tert-butyl ether, hexane, acetonitrile, dichloromethane, and trichloromethane) were surveyed. The analysis was performed by using a gas chromatograph equipped with a programmed temperature vaporization injector (PTV). Univariate and multivariate approaches were exploited in order to optimize the parameters affecting the MEPS extraction and the PTV injection of the analytes into the gas chromatographic system. The optimal working conditions were achieved using DVB as sorbent material and acetonitrile as elution solvent. Internal standard calibration was carried out using TBP-d27 and TCEP-d12. Satisfactory values of accuracy and precision were generally obtained as well as limit of detection (2.7-99 pg/mL for tap water; 2.9-97 pg/mL for river water; 3-107 pg/mL for wastewater) and limit of quantification (0.01-0.2 ng/mL). The proposed protocol was evaluated on real case scenarios by analyzing tap water, river water and simulated wastewater samples. The developed method is not only eco-friendly due to the low use of organic solvents but also simple and automatable since the MEPS extraction procedure can be implemented in the autosampler routine. Graphical abstract The steps of the analytical protocol.

Bioactivity assessment of organophosphate flame retardants via a dose-dependent yeast functional genomics approach.

Organophosphate flame retardants (OPFRs) have been widely detected in multiple environment media and have many adverse effects with complex toxicity mechanisms. However, the early molecular responses to OPFRs have not been fully elucidated, thereby making it difficult to assess their risks accurately. In this work, we systematically explored the point of departure (POD) of biological pathways at genome-wide level perturbed by 14 OPFRs with three substituents (alkyl, halogen, and aryl) using a dose-dependent functional genomics approach in Saccharomyces cerevisiae at 24 h exposure. Firstly, our results demonstrated that the overall biological potency at gene level (PODDRG20) ranged from 0.013 to 35.079 µM for 14 OPFRs, especially the tributyl phosphate (TnBP) exhibited the strongest biological potency with the least PODDRG20. Secondly, we found that structural characteristics of carbon number and logKow were significantly negatively correlated with POD, and carbon number and logKow also significantly affected lipid metabolism associated processes. Thirdly, these early biological pathways of OPFRs toxification were found to be involved in lipid metabolism, oxidative stress, DNA damage, MAPK signaling pathway, and amino acid and carbohydrate metabolism, among which the lipid metabolism was the most sensitive molecular response perturbed by most OPFRs. More importantly, we identified one resistant mutant strain with knockout of ERG2 (YMR202W) gene participated in steroid biosynthesis pathway, which can serve as a key yeast strain of OPFRs toxification. Overall, our study demonstrated an effective platform for accurately assessing OPFRs risks and provided a basis for further green OPFRs development.

Analysis, occurrence and removal efficiencies of organophosphate flame retardants (OPFRs) in sludge undergoing anaerobic digestion followed by diverse thermal treatments.

Organophosphate flame retardants (OPFRs) are a complex group of contaminants to deal with in sewage sludge, as currently there is a lack of robust analytical methods to measure them and management strategies to remove them. To facilitate quantifications of the occurrence of OPFRs in sludge and to establish their removal efficiencies (REs%) during thermal treatments, a simple, reliable, and rapid sample preparation methodology was developed for the determination of 21 OPFRs in diverse sludge, ash and biochar matrices. Matrix-solid phase dispersion (MSPD) tailored to ultra-performance liquid chromatography (UPLC) coupled to tandem mass spectrometry (MS/MS) was applied. Under optimal conditions, 0.5 g of freeze-dried sample were dispersed in 2 g of Bondesil C18, and 1.5 g of deactivated florisil were used as clean-up sorbent. The target analytes were extracted with 5 mL of acetone. The obtained extract was ready for analysis within 20 min without the need of any further treatment. The proposed methodology was assessed, providing absolute recoveries (Abs%) ranging from 50.4 to 112 % with good method repeatability (RSDs <17.9 %). Method limits of quantification ranged from 0.10 to 14.0 ng g-1 dry weight (d.w.). The optimized methodology was applied to raw-, digested-, combusted and pyrolyzed sludge samples collected from different waste treatment plants located in Norway, where 16 out of 21 OPFRs were detected in digested sludge samples up to 2186 ng g-1 (d.w.; sum concentration of OPFRs). Diverse thermal treatments of combustion and dry pyrolysis were assessed for the removal of OPFRs from sludge. Combustion at 300 °C reduced the concentrations of OPFRs by 98 % (in the ashes formed), whereas pyrolysis at temperatures >500 °C effectively removed the OPFRs in the produced biochar. Thermal treatments, in particularly dry pyrolysis, showed potential for achieving zero pollution management and recycling of OPFR contaminated sludge.

Urinary levels of organophosphate flame retardants metabolites in a young population from Southern Taiwan and potential health effects.

Background: Organophosphate flame retardants (OPFRs) are widely distributed in the environment and their metabolites are observed in urine, but little is known regarding OPFRs in a broad-spectrum young population from newborns to those aged 18 years. Objectives: Investigate urinary levels of OPFRs and OPFR metabolites in Taiwanese infants, young children, schoolchildren, and adolescents within the general population. Methods: Different age groups of subjects (n=136) were recruited from southern Taiwan to detect 10 OPFR metabolites in urine samples. Associations between urinary OPFRs and their corresponding metabolites and potential health status were also examined. Results: The mean level of urinary Σ10 OPFR in this broad-spectrum young population is 2.25 µg/L (standard deviation (SD) of 1.91 µg/L). Σ10 OPFR metabolites in urine are 3.25 ± 2.84, 3.06 ± 2.21, 1.75 ± 1.10, and 2.32 ± 2.29 µg/L in the age groups comprising of newborns, 1-5 year-olds, 6-10 year-olds, and 11-18 year-olds, respectively, and borderline significant differences were found in the different age groups (p=0.125). The OPFR metabolites of TCEP, BCEP, DPHP, TBEP, DBEP, and BDCPP predominate in urine and comprise more than 90% of the total. TBEP was highly correlated with DBEP in this population (r=0.845, p<0.001). The estimated daily intake (EDI) of Σ5OPFRs (TDCPP, TCEP, TBEP, TNBP, and TPHP) was 2,230, 461, 130, and 184 ng/kg bw/day for newborns, 1-5 yr children, 6-10 yr children, and 11-17 yr adolescents, respectively. The EDI of Σ5OPFRs for newborns was 4.83-17.2 times higher than the other age groups. Urinary OPFR metabolites are significantly correlated with birth length and chest circumference in newborns. Conclusion: To our knowledge, this is the first investigation of urinary OPFR metabolite levels in a broad-spectrum young population. There tended to be higher exposure rates in both newborns and pre-schoolers, though little is known about their exposure levels or factors leading to exposure in the young population. Further studies should clarify the exposure levels and factor relationships.

Investigating the associations between organophosphate flame retardants (OPFRs) and fine particles in paired indoor and outdoor air: A probabilistic prediction model for deriving OPFRs in indoor environments.

Contaminants of emerging concern such as organophosphate flame retardants (OPFRs) are associated with atmospheric fine particles (PM2.5), which pose the greatest health risk in the world. However, few surveys have explored the interaction between PM2.5 and OPFRs in residential paired indoor/outdoor environments. 11 priority OPFRs and PM2.5 were investigated across 178 paired indoor and outdoor air samples taken from 89 children's households in southern Taiwan, across cold and warm seasons. This involved exploring their associations with building characteristics, interior materials, and human activities. We developed a probabilistic predictive model for indoor OPFRs based on the indoor/outdoor (I/O) ratio of contaminants and an air quality index. The significant associations of paired indoor/outdoor OPFRs and PM2.5 were explored. The indoor level of OPFRs was greater than that of outdoor households, contrasting with PM2.5. The I/O OPFRs ratio was higher than 1 (except for TEHP, EHDPP, and TCP), which suggests that the sources of OPFRs were primarily emitted from indoors. Indoor TCEP was significantly positively associated with indoor and outdoor PM2.5. The OPFR level detected in apartments was higher than in houses due to the greater decoration, furniture and electronic devices. However, this was not the case for PM2.5. TCIPP was the dominant compound in paired indoor and outdoor air. The indoor OPFR predictive model obtained a high accuracy with an R2 value of 0.87. The material used in mattresses, the use of purifiers and heaters, and the total material area were the main influencing factors for indoor OPFRs in households. These findings could provide important evidence of the interaction between paired indoor/outdoor OPFRs and PM2.5 and interior equipment in different building types. In addition, it could prevent the potential risks posed by indoor/outdoor air pollutants and eliminate OPFR emissions through the selection of better construction and building materials.

Spatial distribution and risk assessment of 11 organophosphate flame retardants in soils from different regions of agricultural farmlands in mainland China.

The occurrence and distribution of organophosphate flame retardants (OPFRs) in nationwide farmland soils of mainland China are rarely measured. The current study was the first to collect 325 farmland soil samples from 109 cities throughout mainland China. Ten organophosphate esters (OPEs), including alkyl-OPEs, Cl-OPEs, and aryl-OPEs, together with an organophosphate intermediates (TPPO), were determined. The results indicated that ΣOPFRs ranged from 2.41 ng/g to 35.8 ng/g dry weight (dw), and ΣOPFRs in northeastern and southern China were significantly (p < 0.01) higher than those in northwestern and central China. Alkyl-OPEs and Cl-OPEs served as the main components of OPEs, and the novel aryl-OPEs showed the highest detection frequency (> 92 %). Principal component analysis (PCA) was employed to identify the different sources of OPEs, in which atmospheric deposition, irrigation, or direct release of plastic mulch acted as the main input routes in farmland soils. The potential risks of OPFRs were assessed through soil ingestion exposure and ecotoxicological impacts. Our results showed that direct exposure to farmland soils had no high risks to the human body and ecological environments. This study provides new evidence for further understanding the spatial distributions and contamination status of OPFRs in farmland soils throughout mainland China.

ERK/p38/ROS burst responses to environmentally relevant concentrations of diphenyl phosphate-evoked neutrophil extracellular traps formation: Assessing the role of autophagy.

Organophosphorus compounds were proposed to impair immune surveillance and increase the total burden of pathogens. However, scarce attention has been paid to the effects of organophosphate flame retardants (OPFRs) on neutrophils. Previous literature outlined that neutrophil extracellular traps (NETs) death (NETosis) is associated with autophagy-related signaling. Here we found that 20 µM diphenyl phosphate (DPHP) could promote NETs formation via assessing markers of NETs and the morphological changes. Concurrently, flow cytometry and western blot analysis revealed that DPHP-triggered NETs formation was associated with reactive oxygen species (ROS) burst and activation of extracellular signal-regulated kinase (ERK) and p38. Additionally, the results revealed that autophagy occurred in DPHP-triggered NETs formation, manifested as enhanced LC3B protein expressions and reduced p62 protein expressions. Mechanism dissection revealed that inhibition of autophagy by 3-methyladenine (3-MA) alleviated the ROS burst and subsequent NETosis caused by DPHP. Conversely, autophagy enhancer Rapamycin (Rapa) augmented the above effects of DPHP, including the generation of ROS and NETosis. Collectively, these data suggested ERK/p38 signaling and ROS burst might be an important cause of DPHP-triggered NETs formation, while suppression of excessive autophagy could rescue these actions. These observations provided a theoretical basis for the treatment and prevention of OPFRs-induced immunotoxicity.

Assessment of triphenyl phosphate (TPhP) exposure to nail salon workers by air, hand wipe, and urine analysis.

Triphenyl phosphate (TPP or TPhP) is commonly used as an additive plasticizer or organophosphate flame retardant (OPFR) in consumer products including nail polish. We evaluated exposure to TPhP from 12 nail salon technicians working at four nail salons located in California over a period of two work days. Bulk samples of 15 nail polishes and other nail products were collected. Study participants also provided two personal air samples, two hand wipe samples (pre- and post-shift on day two), and two urine samples (pre-shift day one and post-shift day two). The geometric mean (GM) of TPhP air sampling concentrations was 7.39 ng/m3. Post-shift TPhP hand wipe concentrations (GM 1.35 µg/sample) were significantly higher (p = 0.024) than pre-shift hand wipe concentrations (GM 0.29 µg/sample). Diphenyl phosphate (DPP or DPhP), a urinary metabolite of TPhP used in this study as a biomarker of exposure, was detected in all post-shift urine samples and 75% of urine pre-shift samples. DPhP post-shift concentrations (GM 1.35 µg/g creatinine) were significantly higher than pre-shift concentrations (GM 0.84 µg/g creatinine; p = 0.012). In addition, DPhP post-shift concentrations were correlated with TPhP post-shift hand wipe concentrations, suggesting dermal contact may be a relevant exposure pathway for nail salon workers.

Characterizing exposures to flame retardants, dioxins, and furans among firefighters responding to controlled residential fires.

Firefighters may encounter items containing flame retardants (FRs), including organophosphate flame retardants (OPFRs) and polybrominated diphenyl ethers (PBDEs), during structure fires. This study utilized biological monitoring to characterize FR exposures in 36 firefighters assigned to interior, exterior, and overhaul job assignments, before and after responding to controlled residential fire scenarios. Firefighters provided four urine samples (pre-fire and 3-h, 6-h, and 12-h post-fire) and two serum samples (pre-fire and approximately 23-h post-fire). Urine samples were analyzed for OPFR metabolites, while serum samples were analyzed for PBDEs, brominated and chlorinated furans, and chlorinated dioxins. Urinary concentrations of diphenyl phosphate (DPhP), a metabolite of triphenyl phosphate (TPhP), bis(1,3-dichloro-2-propyl) phosphate (BDCPP), a metabolite of tris(1,3-dichloro-2-propyl) phosphate (TDCPP), and bis(2-chloroethyl) phosphate (BCEtP), a metabolite of tris(2-chloroethyl) phosphate (TCEP), increased from pre-fire to 3-hr and 6-hr post-fire collection, but only the DPhP increase was statistically significant at a 0.05 level. The 3-hr and 6-hr post-fire concentrations of DPhP and BDCPP, as well as the pre-fire concentration of BDCPP, were statistically significantly higher than general population levels. BDCPP pre-fire concentrations were statistically significantly higher in firefighters who previously participated in a scenario (within the past 12 days) than those who were responding to their first scenario as part of the study. Similarly, firefighters previously assigned to interior job assignments had higher pre-fire concentrations of BDCPP than those previously assigned to exterior job assignments. Pre-fire serum concentrations of 2,3,4,7,8-pentachlorodibenzofuran (23478-PeCDF), a known human carcinogen, were also statistically significantly above the general population levels. Of the PBDEs quantified, only decabromodiphenyl ether (BDE-209) pre- and post-fire serum concentrations were statistically significantly higher than the general population. These results suggest firefighters absorbed certain FRs while responding to fire scenarios.

Associations between the exposure to organophosphate flame retardants during early pregnancy and the risk of spontaneous abortion based on metabolomics combined with tandem mass spectrometry.

BACKGROUND: As potential substitutes for polybrominated diphenyl ethers (PBDEs), organophosphate flame retardants (OPFRs) have been frequently detected in the environment. They have been suggested to impair fetal growth and development in toxicological studies. However, there are few studies on their maternal effects before or during early pregnancy. METHODS: This study was designed to investigate whether exposure to OPFRs before or during early pregnancy is associated with the risk of spontaneous abortion (SAB), using a nested case-control design based on the case data from clinical examinations in Shanghai, China. A total of 110 cases from this cohort project in 2019-2020 were included. The concentrations of OPFRs in maternal urine samples collected in early pregnancy were determined using Ultra high performance liquid chromatography- triple quadrupole mass spectrometer (UHPLC-MS/MS), and pregnancy outcomes were extracted from the medical records. Meanwhile, ultra high performance liquid chromatography time-of-flight mass spectrometer (UHPLC-Q-TOF/MS)-based metabonomics was used to obtain urine metabolic profiles of 110 women in early pregnancy. RESULTS: According to the quantitative results, the content of bis(1-chloro-2-propyl)phosphate (BCIPP) in urine was significantly different between the SAB patients and the healthy pregnant women. Besides, metabolic profile analysis showed a significant difference in the urine metabolism profile in early pregnancy between SAB cases and controls. Twenty-five different metabolites were screened out, which showed different degrees of correlation with the urinary BCIPP concentration. CONCLUSIONS: Based on these results, it suggests that there may be a certain correlation between BCIPP concentration in the urine and the risk of SAB from a metabolomics perspective, and its effect may be related to the metabolism of tryptophan and fatty acids.

Spatiotemporal distribution and mass loading of organophosphate flame retardants (OPFRs) in the Yellow River of China (Henan segment).

During three sampling periods in 2014, systematic investigations were conducted into contamination profiles of ten organophosphate flame retardants (OPFRs) in both suspended particulate phase and water phase in the Yellow River (Henan Area). This research shows that OPFRs exist at lower concentrations in the suspended phase than in the water phase. The median concentration of 10 OPFRs (∑10OPFRs) in the suspended particulate phase was 62.5 ng/g (fluctuating from ND to 6.17 × 103 ng/g, dw), while their median concentration in the water phase was 109 ng/L (fluctuating from 35.6 to 469 ng/L). Among the selected 10 OPFRs, triethylphosphate (TEP), tris(1-chloro-2-propyl) phosphate (TCPP), and tris(2-chloroethyl) phosphate (TCEP) were the predominant compounds in the water phase (occupying 91.6% of the ∑10OPFRs), while TCPP, TCEP, and tri-o-tolyl phosphate (o-TCP) were the most common in the suspended particulate phase, accounting for 90.1% of the ∑10OPFRs. Across the three sampling periods, there was no significant seasonable variation for OPFRs either in the water phase or in the suspended particulate phase, except for TCEP and TCPP in the water phase. Compared with research findings relating to concentrations of OPFRs around China and abroad, the OPFRs of the Yellow River (Henan Area) in the water phase were at a moderate level. Suspended particles (SS) had a very important impact on the transportation of OPFRs in the studied area, with about 83.9% of ∑10OPFRs inflow attributed to SS inflow and about 81.7% of ∑10OPFRs outflow attributed to SS outflow. The total annual inflow and outflow of OPFRs were 7.72 × 104 kg and 6.62 × 104 kg in the studied area, respectively.

A review on organophosphate flame retardants in indoor dust from China: Implications for human exposure.

To investigate the status of organophosphate flame retardants (OPFRs) in indoor dust in China, published scientific studies were systematically collected and analyzed. The analysis revealed large variations among microenvironments, including offices (median: 14.59 µg/g) and e-waste workshops (median: 13.36 µg/g), with high levels of OPFRs contamination. Chlorinated organophosphate ester flame retardants (Cl-OPFRs) were the dominant OPFRs (52-75%) in most indoor dust samples; however, in e-waste workshops, aryl- and alkyl-OPFRs were the most abundant. As an alternative flame retardant to polybrominated diphenyl ethers (PBDEs), OPFRs concentrations have increased in recent years in indoor environments in China. Urban sources are of greatest concern: Shanghai (mean: 13.54 µg/g), Guangzhou (mean: 10.76 µg/g), and Beijing (mean: 9.37 µg/g) have high ΣOPFRs contamination levels in indoor dust. Compared to other countries, the OPFRs concentrations in indoor dust in all studied microenvironments from China (median: 8.81 µg/g) were low. The estimated daily intakes of ΣOPFRs by dust ingestion for adults and children were 2.12 and 11.06 ng/kg/body weight/day (average), respectively. Human exposure to OPFRs through the accidental intake of indoor dust does not pose a direct health risk to the Chinese population. However, indoor dust ingestion is an important route for human exposure to OPFRs.

Differential exposure to organophosphate flame retardants in mother-child pairs.

BACKGROUND: Humans are ubiquitously exposed to flame retardants, including organophosphate esters (OPEs), through direct contact with consumer products or exposure through household dust. Children are at increased risk because of their proximity to dust, hand-to-mouth activity, and the importance of childhood as a critical period in neurodevelopment. OBJECTIVES: To quantify differences in exposure levels between mothers and children (three to six years of age), we analyzed urinary metabolites of OPEs. We additionally assessed the ability of silicone wristbands (measuring ambient exposure) to predict urinary metabolite concentrations. METHODS: We selected 32 mother and child dyads from an existing cohort. Participants provided baseline urine samples and wore wristbands for one week. After the first week, they returned their wristbands and provided a second urine sample. During the second week, participants wore a second wristband that they returned at the end of week two with a third and final urine sample. RESULTS: We found significantly higher levels of bis(1,3-dichloro-2-propyl) phosphate (BDCIPP) (p < 0.001) and lower levels of bis(1-chloro-2-isopropyl) 1-hydroxy-2-propyl phosphate (BCIPHIPP) (p < 0.001) in children's urine samples compared to mothers' samples at baseline. We found that triphenylphosphate (TPHP), tris(1,3-dichloroisopropyl) phosphate (TDCIPP), and tris(1-chloro-2-propyl) phosphate (TCIPP) measured in wristbands predicted their respective metabolite levels in urine. CONCLUSION: Children had higher levels than mothers for two of six flame retardant metabolites measured in urine. Generally, wristband measurements positively predicted internal dose. As little is known about the health effects of OPEs on child development, future research is needed to determine the impact of differential exposure.

The critical factors affecting typical organophosphate flame retardants to mimetic biomembrane: An integrated in vitro and in silico study.

Organophosphate flame retardants (OPFRs) have been reported to induce cytotoxicity in a structure-dependent manner. The toxic effects may be due to the damage of biomembrane integrity and/or the interference of membrane signal pathway. In this study, the damages of fifteen typical OPFRs (chlorinated phosphates, alkyl phosphates, aryl phosphates, and alkoxy phosphates) to mimetic biomembrane were determined by the electrochemical impedance spectroscopy (EIS). The molecular structure descriptors that characterized the action mechanisms were screened by stepwise regression. The six molecular descriptors (MATS7e, DLS_05, Mor19m, Mor22v, Mor12v and MATS8m) were screened to study the actions between OPFRs and mimetic biomembrane. A quantitative structure-activity relationship (QSAR) model was developed by the partial least squares (PLS) method. Statistical results indicated that the QSAR model had good robustness and mechanism interpretability. The distribution of atomic electronegativities (MATS7e) and atomic masses in three dimensional spaces (Mor19m) were the key factors influencing the actions between OPFRs and simulated biofilms. The compounds with strong electron-withdrawing property could invade the inner layer of membrane and destroy its integrity. High levels of steric hindrance could impair the damage capacity caused by electronegativity. Moreover, drug-like index (DLS_05), spatial structures of particle (Mor22v, Mor12v) and atomic masses (MATS8m) also affected the actions. The results revealed the mechanism of the actions of OPFRs with simulated biofilms and elucidated the key structural characteristics affecting the actions of OPFRs, which could provide theoretical basis for ecological risk assessment of OPFRs.

Biological effects of tris (1-chloro-2-propyl) phosphate (TCPP) on immunity in mussel Mytilus galloprovincialis.

Organophosphate flame retardants (OPFRs) are increasingly produced and used as alternatives of brominated flame-retardants (BFRs) and have become emerging marine environmental contaminants. So far, however, little is known regarding the biological effects of OPFRs in marine organisms. In this study, the biological effects of one of the most abundant OPFRs, tris (1-chloro-2-propyl) phosphate (TCPP), on the immunity in mussel Mytilus galloprovincialis were characterized by testing the reactive oxygen species, apoptosis, antioxidant system and immunity related gene expressions. Results indicated that both TCPP exposures (10 and 100 nmol L-1) significantly (p < 0.01) enhanced reactive oxygen species production and the high dose of TCPP induced more apoptosis and oxidative stress in mussel hemocytes. TCPP also induced an obvious hormesis phenomenon (low dose inhibition and high dose stimulation) in mussel hemocytes, as indicated by the gene expression profiles of caspase 8 and mytimacin. The down-regulated gene expression levels of lysozymes suggested that both TCPP exposures inhibited the innate immunity in mussel M. galloprovincialis. The significantly (p < 0.01) increased gene expression levels of TLR, galectin, PGRP and LITAF demonstrated that TCPP induced dose-dependent immune stress in mussels. Overall, this work suggested that TCPP could influence the immune system in marine mussel M. galloprovincialis.

Examination of technical mixtures of halogen-free phosphorus based flame retardants using multiple analytical techniques.

The application of phosphorus based flame retardants as replacements for commonly used halogenated flame retardants has been gaining interest due to the possibility that these compounds may have a less significant impact on human and environmental health. Unfortunately, little is known about the chemical compositions of many of the technical products (which often are mixtures) and a single separation technique for concurrent analysis of these types of compounds has not been identified. This paper reports the results of an investigation into the constituents of three halogen free organophosphate flame retardants (OPFRs), resorcinol bis(diphenyl phosphate) (RDBPP), bisphenol A bis(diphenyl phosphate) (BPA-BDPP), and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The major components of commercial samples of RDBPP and BPA-BDPP were isolated by preparative TLC and characterized by NMR. A commercial sample of DOPO was found to be essentially pure, but its analysis is complicated by the fact that it can exist in ring-open and ring-closed forms. With the structures of the components confirmed by NMR, multiple analytical separation techniques (gas chromatography (GC), liquid chromatography (LC), and packed column supercritical fluid chromatography (pSFC)) were investigated for the analysis of these three technical products. Packed column supercritical fluid chromatography allows the separation of the components of all three OPFRs, including the two forms of DOPO, in a single run.