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.

Sex-specific effects of prenatal organophosphate ester (OPE) metabolite mixtures and adverse infant birth outcomes in the maternal and developmental risks from environmental and social stressors (MADRES) pregnancy cohort.

BACKGROUND: Organophosphate esters (OPEs) are used as flame retardants and plasticizers in various consumer products. Limited prior research suggests sex-specific effects of prenatal OPE exposures on fetal development. We evaluated overall and sex-specific associations between prenatal OPE exposures and gestational age (GA) at birth and birthweight for gestational age (BW for GA) z-scores among the predominately low-income, Hispanic MADRES cohort. METHODS: Nine OPE metabolite concentrations were measured in 421 maternal urine samples collected during a third trimester visit (GA = 31.5 ± 2.0 weeks). We examined associations between single urinary OPE metabolites and GA at birth and BW for GA z-scores using linear regression models and Generalized Additive Models (GAMs) and effects from OPE mixtures using Bayesian Kernel Machine Regression (BKMR). We also assessed sex-specific differences in single metabolite analyses by evaluating statistical interactions and stratifying by sex. RESULTS: We did not find significant associations between individual OPE metabolites and birth outcomes in the full infant sample; however, we found that higher bis(1,3-dichloro-2-propyl) phosphate (BDCIPP) was associated with earlier GA at birth among male infants (p = 0.04), and a nonlinear, inverted U-shape association between the sum of dibutyl phosphate and di-isobutyl phosphate (DNBP + DIBP) and GA at birth among female infants (p = 0.03). In mixtures analysis, higher OPE metabolite mixture exposures was associated with lower GA at birth, which was primarily driven by female infants. No associations were observed between OPE mixtures and BW for GA z-scores. CONCLUSION: Higher BDCIPP and DNBP + DIBP concentrations were associated with earlier GA at birth among male and female infants, respectively. Higher exposure to OPE mixtures was associated with earlier GA at birth, particularly among female infants. However, we saw no associations between prenatal OPEs and BW for GA. Our results suggest sex-specific impacts of prenatal OPE exposures on GA at birth.

Prenatal exposures to organophosphate ester metabolite mixtures and children's neurobehavioral outcomes in the MADRES pregnancy cohort.

BACKGROUND: Evidence suggests organophosphate esters (OPEs) are neurotoxic; however, the epidemiological literature remains scarce. We investigated whether prenatal exposures to OPEs were associated with child neurobehavior in the MADRES cohort. METHODS: We measured nine OPE metabolites in 204 maternal urine samples (gestational age at collection: 31.4 ± 1.8 weeks). Neurobehavior problems were assessed among 36-month-old children using the Child Behavior Checklist's (CBCL) three composite scales [internalizing, externalizing, and total problems]. We examined associations between tertiles of prenatal OPE metabolites (> 50% detection) and detect/non-detect categories (< 50% detection) and CBCL composite scales using linear regression and generalized additive models. We also examined mixtures for widely detected OPEs (n = 5) using Bayesian kernel machine regression. RESULTS: Maternal participants with detectable versus non-detectable levels of bis(2-methylphenyl) phosphate (BMPP) had children with 42% (95% CI: 4%, 96%) higher externalizing, 45% (-2%, 114%) higher internalizing, and 35% (3%, 78%) higher total problems. Participants in the second versus first tertile of bis(butoxethyl) phosphate (BBOEP) had children with 43% (-1%, 109%) higher externalizing scores. Bis(1-chloro-2-propyl) phosphate (BCIPP) and child sex had a statistically significant interaction in internalizing (p = 0.02) and total problems (p = 0.03) models, with 120% (23%, 295%) and 57% (6%, 134%) higher scores in the third versus first BCIPP tertile among males. Among females, detectable vs non-detectable levels of prenatal BMPP were associated with 69% higher externalizing scores (5%, 170%) while the third versus first tertile of prenatal BBOEP was associated with 45% lower total problems (-68%, -6%). Although the metabolite mixture and each CBCL outcome had null associations, we observed marginal associations between di-n-butyl phosphate and di-isobutyl phosphate (DNBP + DIBP) and higher internalizing scores (0.15; 95% CrI: -0.02, 0.32), holding other metabolites at their median. CONCLUSIONS: Our results generally suggest adverse and sex-specific effects of prenatal exposure to previously understudied OPEs on neurobehavioral outcomes in 36-month children, providing evidence of potential OPE neurotoxicity.

Inulin alleviates neuroinflammation and oxidative stress induced by perinatal 2-ethylhexyl diphenyl phosphate (EHDPHP) exposure in female mice and offspring.

Organophosphorus flame retardants (OPFRs), including 2-ethylhexyl diphenyl phosphate (EHDPHP), are prevalent in everyday life due to their broad usage in fields such as healthcare, electronics, industry, and sports. These compounds, added to polymers through physical mixing, can leach into the environment, posing a risk to humans through direct contact or the food chain. Despite known associations with health issues like endocrine disruption, neurotoxicity, and reproductive toxicity, the implications of perinatal EHDPHP exposure on both mothers and offspring are still unclear. This study aimed to investigate the neuroinflammatory effects of EHDPHP and the potential mitigating role of inulin. Pregnant C57 mice were administered either a corn oil control or an EHDPHP solution (300 µg/kg bw/d) from gestation day 7 (GD7) to postnatal day 21 (PND21). Concurrently, mice were provided either regular drinking water or water supplemented with 1% inulin. We found that EHDPHP significantly increased the serum levels of IL-1ß, IL-6, and MDA, but decreased SOD levels in both mothers and pups. These effects were reversed by inulin supplementation. RNA-sequencing revealed that EHDPHP induced inflammation and oxidative stress through the TLR4/NF-κB pathway, which was mitigated by inulin. In conclusion, inulin ameliorated EHDPHP-induced neuroinflammation and oxidative stress in both mothers and offspring, highlighting its potential therapeutic role.

Organophosphate esters in inert landfill soil: A case study.

Organophosphate esters (OPEs) used as flame retardants and plasticizers are additives in building and construction materials, decorations, furniture, electronic equipment, among other applications. The presence of materials containing these substances in construction and demolition waste (CDW) from weak waste management practices can result in environmental contamination. In this study, OPEs' presence in soil samples collected from a CDW landfill in Brazil was evaluated. Soil samples were collected in areas adjacent to CDW from an inert landfill, and the samples were analysed by gas chromatography coupled to mass spectrometry. The OPEs were detected in all soil samples at quantifiable concentrations ranging from 21 to 251 ng g-1, and detected compounds were tris(phenyl) phosphate, tris(2-butoxyethyl) phosphate, tris(1,3-dichloroisopropyl) phosphate, tris(2-chloroisopropyl) phosphate and 2-ethylhexyl diphenyl phosphate. The presence of these compounds in a CDW landfill is probably due to the lack of control of the materials sent to and deposited in the landfill, which, results in part from the lack of sampling and screening systems that can help identify the presence of contaminants in the CDW waste stream. This is partially due to OPEs not being considered controlled compounds under current regulations, thus screening or separation for handling of OPEs at construction and demolition work sites is rare to non-existent. The data generated in this study reveals the need for improving CDW management to minimize, if not eliminate, environmental contamination by OPEs.

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.

Identifying Dermal Uptake as a Significant Pathway for Human Exposure to Typical Semivolatile Organic Compounds in an E-Waste Dismantling Site: The Relationship of Contaminant Levels in Handwipes and Urine Metabolites.

Dermal exposure to semivolatile organic compounds (SVOCs) has recently attracted widespread attention; understanding these exposures is particularly important for people whose skin is frequently exposed to different pollution surfaces. In this study, handwipes were collected from exposed occupational workers and local residents near a typical electronic waste (e-waste) dismantling area; urine samples were also sampled. The wipes were analyzed for three typical SVOCs: polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), and organophosphate flame retardants (OPFRs). The median levels of PAHs, OPFRs, and PBDEs in handwipes from e-waste dismantlers were 96.0, 183, and 238 ng, respectively. The analytes were higher in the handwipes collected from workers than those from residents, indicating that they were subjected to greater dermal exposure during primitive e-waste dismantling activities. Among the three SVOCs, the strongest correlation was found between triphenyl phosphate (TPhP) in handwipes and diphenyl phosphate (DPhP) in paired urine; the next strongest correlations were between PAHs and PBDEs and their corresponding urinary metabolites. The results showed that TPhP contributed the highest exposure to e-waste dismantlers via dermal exposure. Our research highlights the importance of dermal exposure to TPhP, which should be considered in future exposure risk assessments.

Assessing decontamination and laundering processes for the removal of polycyclic aromatic hydrocarbons and flame retardants from firefighting uniforms.

Firefighter uniforms protect firefighters from exposure to potentially harmful chemicals including a range of semi-volatile organic compounds (SVOCs). Contaminated uniforms can become a secondary source of firefighters' exposure to these chemicals. There is inconsistency on the removal efficiency of SVOCs during the cleaning, laundering and field decontamination of firefighting uniforms. Therefore, this study aims to assess how effective decontamination and laundering processes are in reducing firefighter uniforms as a vector for transport and exposure to SVOCs. Firefighters who had attended a controlled house fire and simulated container burns had their uniforms sampled pre- and post-laundering. Clean station wear was laundered with contaminated uniforms and after a load of contaminated uniforms to assess inter and intra load contamination. Surface wipes were collected from uniforms across 12 fire stations, after they had returned from a laundering provider. Concentrations of 13 polycyclic aromatic hydrocarbons (PAHs), six organophosphate flame retardants (OPFRs) and seven polybrominated diphenyl ethers (PBDEs) were measured in the collected samples. The concentrations of ∑13 PAHs in firefighters uniforms ranged between 0.063 and 43 µg g-1, while concentration of ∑6 OPFRs were between 0.061 and 90 µg g-1 with ∑7 PBDEs concentrations being measured between 0.00054 and 0.97 µg g-1.The highest concentrations of ∑13 PAHs were measured on the outer layers of gloves at an average of 19 µg g-1, with the highest ∑6 OPFRs concentrations being measured in the middle layers of gloves at an average of 31 µg g-1. The highest ∑7 PBDEs concentrations were measured on the shell layers of turnout jackets at 0.42 µg g-1. The significant reduction in ∑13 PAHs after laundering or decontamination was only found in 3 of the 16 sampled areas from firefighting uniforms. No significant differences were found in the between pre- and post-laundering concentrations of ∑6 OPFRs or ∑7 PBDEs in firefighting uniforms. The current laundering techniques do not appear to effectively remove PAHs, OPFRs and PBDEs at the measured concentrations from firefighters' uniforms. Further research is required to assess if chemical exposure though firefighting uniforms poses a health risk to firefighters and to develop methods for the removal of SVOCs from firefighting uniforms.

Interlaboratory comparison investigations (ICIs) and external quality assurance schemes (EQUASs) for flame retardant analysis in biological matrices: Results from the HBM4EU project.

The European Human Biomonitoring Initiative (HBM4EU) is coordinating and advancing human biomonitoring (HBM). For this purpose, a network of laboratories delivering reliable analytical data on human exposure is fundamental. The analytical comparability and accuracy of laboratories analysing flame retardants (FRs) in serum and urine were investigated by a quality assurance/quality control (QA/QC) scheme comprising interlaboratory comparison investigations (ICIs) and external quality assurance schemes (EQUASs). This paper presents the evaluation process and discusses the results of four ICI/EQUAS rounds performed from 2018 to 2020 for the determination of ten halogenated flame retardants (HFRs) represented by three congeners of polybrominated diphenyl ethers (BDE-47, BDE-153 and BDE-209), two isomers of hexabromocyclododecane (α-HBCD and γ-HBCD), two dechloranes (anti-DP and syn-DP), tetrabromobisphenol A (TBBPA), decabromodiphenylethane (DBDPE), and 2,4,6-tribromophenol (2,4,6-TBP) in serum, and four metabolites of organophosphorus flame retardants (OPFRs) in urine, at two concentration levels. The number of satisfactory results reported by laboratories increased during the four rounds. In the case of HFRs, the scope of the participating laboratories varied substantially (from two to ten) and in most cases did not cover the entire target spectrum of chemicals. The highest participation rate was reached for BDE-47 and BDE-153. The majority of participants achieved more than 70% satisfactory results for these two compounds over all rounds. For other HFRs, the percentage of successful laboratories varied from 44 to 100%. The evaluation of TBBPA, DBDPE, and 2,4,6-TBP was not possible because the number of participating laboratories was too small. Only seven laboratories participated in the ICI/EQUAS scheme for OPFR metabolites and five of them were successful for at least two biomarkers. Nevertheless, the evaluation of laboratory performance using Z-scores in the first three rounds required an alternative approach compared to HFRs because of the small number of participants and the high variability of experts' results. The obtained results within the ICI/EQUAS programme showed a significant core network of comparable European laboratories for HBM of BDE-47, BDE-153, BDE-209, α-HBCD, γ-HBCD, anti-DP, and syn-DP. On the other hand, the data revealed a critically low analytical capacity in Europe for HBM of TBBPA, DBDPE, and 2,4,6-TBP as well as for the OPFR biomarkers.

Organophosphorus flame-retardant tris(1-chloro-2-propyl)phosphate is genotoxic and apoptotic inducer in human umbilical vein endothelial cells.

Tris(1-chloro-2-propyl)phosphate (TCPP) is a chlorinated organophosphorus flame retardant (OPFR) widely used in consumer goods after the phaseout of brominated flame retardants (BFRs). TCPP can percolate into the indoor and outdoor dusts, leading to its detection in the human body fluids (urine, breast milk) and placenta. However, TCPP has not been studied so far for its toxicity in the human vascular system. Hence, we have used human umbilical vein endothelial cells (HUVECs) and exposed them to TCPP ranging from low to high (5-400 µM) concentrations for 24 h. Cytotoxicity analysis by MTT and NRU assays exhibited 15.27% and 20.56%, 21.67%, and 48.67% survival decline of cells only at 200 and 400 µM. Comet assay data showed DNA damage from 50 to 400 µM with Olive tail moment (OTM) values between 1.03 and 35.59, respectively. TCPP-exposed HUVECs exhibited 1.09 and 1.39-fold greater intracellular reactive oxygen species (ROS) at 25 and 400 µM, indicating oxidative stress. HUVEC mitochondrial membrane potential (ΔΨm) measurements showed 1.16 and 1.48-fold higher fluorescence of Rh123 dye at 25 and 400 µM, confirming mitochondrial dysfunction. Flow cytometric data demonstrated 5.1%-58.8% cells in SubG1 apoptotic phase at 5 and 400 µM TCPP. Our novel data revealed that TCPP is a genotoxic and apoptotic inducer, which may trigger alike responses in human vascular system. Overall, detailed in vivo studies are warranted on the transcriptional and translations effects of TCPP.

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.

Toxicity of tris(2-chloroethyl) phosphate in Daphnia magna after lifetime exposure: Changes in growth, reproduction, survival and gene transcription.

In recent years, with the elimination of brominated flame retardants (BFRs), the product volume of tris(2-chloroethyl) phosphate (TCEP), as a main substitute of BFRs, was increasing and frequently detected in natural waters. However, the current toxicological studies on TCEP were mainly focused on the partial life stage assessment of model animals, and thus it might underestimate the impact of TCEP on environmental risks. Therefore, the whole-life-stage effects of TCEP on growth, reproduction, survival and gene transcription in Daphnia magna (D. magna) were studied in this study after exposure to environmentally relevant or greater concentrations (500 or 5000 ng/L). It was found that chronic exposure to TCEP at environmental relevant or greater concentrations promoted growth of D. magna and the expressions of genes involved in the pathways associated with growth were significantly up-regulated. TCEP did not affect reproduction of D. magna, but the expressions of some genes screened in reproduction stage were significantly changed. Furthermore, the expressions of genes involved in two heart disease-related pathways were down-regulated at the death stage of D. magna after TCEP exposure for 62 days, suggesting that TCEP delayed the death of D. magna by retarding their heart senility.

The occurrence of PAHs and flame-retardants in air and dust from Australian fire stations.

Firefighters are exposed to a wide range of chemicals whilst on duty, including polycyclic aromatic hydrocarbons (PAHs), organophosphate flame-retardants (OPFRs), and polybrominated diphenyl ethers (PBDEs). These groups of chemicals are related to combustion emissions. PAHs are formed during combustion. OPFRs and PBDEs are flame-retardants and are inadvertently released during combustion. Exposure to these chemicals occurs when attending fire scenes, and firefighters can track these chemicals back into fire stations leading to further exposure. The objective of this study was to understand the concentrations of PAHs, OPFRs, and PBDEs in fire stations, to evaluate factors that affect chemical concentration, and to assess how air and dust could contribute to firefighters' relevant exposure risk. Concentrations of 13 PAHs, 9 OPFRs, and 8 PBDEs were quantified in fire station dust (n = 49) and air (n = 15) samples collected between November 2017 and February 2018. The median ∑13PAH concentration was 15 ng m-3 and 3.1 µg g-1 in air and dust, respectively, while the median ∑9 OPFR concentration was 56 ng m-3 in air and 84 µg g-1 in dust, and ∑8 PBDE had a median concentration of 0.78 ng m-3 in air and 26 µg g-1 in dust. The estimated daily intakes through dust and air for ∑13 PAHs, ∑9 OPFRs, and ∑8 PBDEs in firefighters were 3.6, 17, and 1.6 ng (kg body weight)-1 day-1, respectively. The worst-case estimated daily intakes were only 2% of the reference dose for individual chemicals. Pearson's correlations with chemical concentration for several PAHs, OPFRs, and PBDEs were found between the number of years since fire stations were last renovated, as well as the storage locations of firefighting ensembles. These results suggest chemicals are brought back to fire stations from fire scenes and that they are accumulating in fire stations. They also suggest soiled firefighting ensembles are a source of these chemicals in fire stations and that their proximity to the rest of the station determines the extent to which they contribute to chemical concentrations in fire stations.

In vitro oral and inhalation bioaccessibility of hydrophobic organic contaminants (HOCs) in airborne particles and influence of relevant parameters.

The bioaccessibility of environmental contaminants has been assessed widely using in vitro simulation; however, the physiological parameters used vary greatly. In this study, we assessed the influence of various physiological parameters and food material on the oral or inhalation bioaccessibility of PM2.5-bound hydrophobic organic contaminants (HOCs), including halogenated flame retardants (HFRs), organophosphorus flame retardants (OPFRs), and polycyclic aromatic hydrocarbons (PAHs). The results showed that physiologically based pepsin and pancreatin have a small influence on the HOC liberation from particles. The bioaccessibility increased dramatically when the bile salt concentrations exceeding the critical micelle concentration, and application of porcine bile salts probably lead to underestimated bioaccessibility. Protein and carbohydrates significantly increased the bioaccessibility of most HOCs, while a significant bioaccessibility reduction was caused by green tea. The bioaccessibility of most HOCs was not promoted by liquor under normal physiological condition, but was significantly promoted under fast condition. Long residence time of PM2.5 in the lung (15 days) would result in higher mobilization of PAHs into the lung fluid than short time (one day). However, the inverse time-dependence for OPFRs suggests degradation in the lung fluid. A mechanism of hydrolysis of organophosphorus ester is hypothesized, and the half lives ranged from 17 to 90 days.

Tris(1,3-dichloro-2-propyl)phosphate (TDCIPP) disrupts zebrafish tail fin development.

The flame retardant, tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), is one of the most developmentally toxic organophosphate flame retardants (OPFRs). However, few mechanistic studies on phenotypic malformation caused by TDCIPP have been conducted. This study investigates the molecular mechanism underlying abnormal tail fin development consistently observed in zebrafish embryos exposed to TDCIPP. The results show that the defects in the tail fin (e.g., bent spine, defective caudal fin, and damaged tip) were associated with altered expression of transcription factors. The significant up-regulation of mmp9 and, among insulin-growth factor (IGF) families, igfbp-1a and igfbp1b was observed, whereas alterations in the expression of cdx4, igf1a, ifg1b, igf2b, and vegaa regulating tail development were dependent on time points. In accordance with changes in mRNA gene expression, TDCIPP impaired vessel formation and disorganized muscle in transgenic Tg(fli-GFP) zebrafish larvae. Furthermore, we found that the overexpression of mmp9 caused by TDCIPP was not linked to igfbp-1. Overall, these findings demonstrate that TDCIPP disrupts the progression of tail fin development, accompanied by defects in vessel and muscle formation in developing zebrafish embryos.

Monitoring and exposure assessment of organophosphorus flame retardants in source and drinking water, Nanjing, China.

This study developed a new method to determine the residues of 13 organophosphorus flame retardants (OPFRs) in drinking water by gas chromatography-tandem mass spectrometry (GC-MS/MS) technique and investigated the chemical distribution in water samples from municipal plants along the Yangtze River in Nanjing. The linear calibration correlation coefficients R2 for all 13 OPFRs were at least 0.998 0. Three levels of spiked test were performed. Most of the recoveries were in the range of 80~120%, and the relative standard deviations (RSDs) for the 13 OPFRs were 2.1~17% (n = 6). Five OPFRs were 100% positively detected in the samples, and 3 OPFRs were positively detected in some samples. The concentrations of detected OPFR in the water ranged from 0.7 to 5780.0 ng L-1. The average concentrations of OPFRs in wet season were higher than those in dry season, and the contaminants mainly originated from the source water in the Yangtze River. The exposure assessments of individual and total OPFRs were investigated. The estimated daily intakes of total OPFRs via ingestion of drinking water reached up to 64.8 and 45.2 ng/kg bw/day in dry and wet season, respectively. This study demonstrates a profile of OPFR distribution in Nanjing municipal water and provides information on human exposure assessment via drinking water in the Nanjing District, China.

Assessment of organophosphate flame retardants in surface water and sediment from a freshwater environment (Yangtze River, China).

Organophosphate flame retardants (OPFRs) have been detected in the surface water, suspended sediments, and river sediments from the Yangtze River in China. A modified polar organic chemical integrative sampler (m-POCIS) was successfully used to quantify the OPFR concentrations in surface water. The OPFR concentrations estimated by the field m-POCIS at six sampling locations ranged from 8.99 to 112.45 ng/L with an average concentration of 47.04 ng/L. The OPFR concentrations in suspended sediments were related to the sediment particle size distribution. Chlorinated and alkyl OPFRs were the principle compounds in sediments, especially tris(2-chloroisopropyl) phosphate (TCPP) with concentrations of 3.37-29.65 ng/g. The relationship between the OPFR concentrations and total organic carbon (TOC) contents in sediments was examined. The results suggested that the OPFR concentrations were significantly correlated with the TOC contents. The primary OPFR transport mechanism in a freshwater environment occurs in surface water rather than sediment. This was evaluated by the logKow and field sediment-water partition coefficient (logKoc) values between the sediment and water. Finally, the various distributions and transport of OPFRs at the sampling sites indicated that human activities, agricultural production, and wastewater effluents from sewage plants have an important effect on the OPFR levels in a freshwater environment.

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.

Using silicone wristbands to evaluate preschool children's exposure to flame retardants.

Silicone wristbands can be used as passive sampling tools for measuring personal environmental exposure to organic compounds. Due to the lightweight and simple design, the wristband may be a useful technique for measuring children's exposure. In this study, we tested the stability of flame retardant compounds in silicone wristbands and developed an analytical approach for measuring 41 flame retardants in the silicone wristband in order to evaluate exposure to these compounds in preschool-aged children. To evaluate the robustness of using wristbands to measure flame retardants, we evaluated the stability of 3 polybrominated diphenyl ethers (BDEs), and 2 organophosphate flame retardants (OPFRs) in wristbands over 84 days and did not find any evidence of significant loss over time at either 4 or -20°C (p>0.16). We recruited a cohort of 92 preschool aged children in Oregon to wear the wristband for 7 days in order to characterize children's acceptance of the technology, and to characterize their exposure to flame retardants. Seventy-seven parents returned the wristbands for analysis of 35 BDEs, 4 OPFRs, and 2 other brominated flame retardants although 5 were excluded from the exposure assessment due to protocol deviations (n=72). A total of 20 compounds were detected above the limit of quantitation, and 11 compounds including 4 OPFRs and 7 BDEs were detected in over 60% of the samples. Children's gender, age, race, recruitment site, and family context were not significantly associated with returning wristbands or compliance with protocols. Comparisons between flame retardant data and socio-demographic information revealed significant differences in total exposures to both ΣBDEs and ΣOPFRs based on age of house, vacuuming frequency, and family context. These results demonstrate that preschool children in Oregon are exposed to BDEs that are no longer being produced in the United States and to OPFRs that have been used as an alternative to polybrominated compounds. Silicone wristbands were well tolerated by young children and were useful for characterizing personal exposure to flame retardants that were not bound to particulate matter.

Differential modulation of neuro- and interrenal steroidogenesis of juvenile salmon by the organophosphates - tris(2-butoxyethyl)- and tris(2-cloroethyl) phosphate.

Following the ban of polybrominated diphenyl ether (PBDEs) flame retardants under well-documented toxicity issues, organophosphate such as tris(2-butoxyethyl) phosphate (TBOEP) and tris(2-cloroethyl) phosphate (TCEP) were considered as potential substitutes. Although TBOEP and TCEP are consistently detected in the aquatic environment, there are few data about the possible toxicological effects of these compounds on aquatic organisms, including fish. In the present study, we have investigated the influence of TBOEP and TCEP on neuro- and interrenal steroidogenesis of juvenile Atlantic salmon (Salmo salar), after a seven-day exposure to four different concentrations (0 (control), 0.04, 0.2 and 1mg/L) of each compound. TBOEP and TCEP were diluted in Milli-Q water. The expression of genes involved in steroidogenesis (StAR, cyp19a, cyp19b, cholesterol side-chain cleavage enzyme (P450scc), 3ß-hydroxysteroid dehydrogenase (3ß-hsd), and 11ß-hydroxylase (cyp11ß)), were analyzed in the brain and head kidney using real-time PCR. Plasma 11-ketotestosterone (11-KT) analysis was performed using enzyme immunoassay (EIA). Our results showed that TBOEP accumulated more rapidly than TCEP in fish muscle tissue. Surprisingly, TBOEP produced less pronounced effects than TCEP on neural and interrenal steroidogenic responses, despite the observed rapid uptake and bioaccumulation pattern. Specifically, TBOEP produced significant and consistent concentration-specific alterations on neural- and interrenal steroidogenesis. Plasma levels of 11-KT were not significantly altered by any of the exposures. The increased expression of steroidogenic genes demonstrated in the present study could produce time-specific alterations in the production of glucocorticoids and steroid hormones that play integral roles in fish metabolism, stress responses and adaptation, sexual maturation, reproduction and migration with overt consequences on reproductive success and survival.