Concentrations Of Organophosphorus Flame Retardants Research Articles

Organophosphorus flame retardants in the Qiantang River of China: occurrence, source and ecological risk assessment.

In recent years, the prevalence and danger of organophosphorus flame retardants (OPFRs) have drawn attention from all around the world. This study examined twenty-five OPFRs observed in water and sediment samples from the Qiantang River in eastern China, as well as their occurrence, spatial distribution, possible origins, and ecological hazards. All the 25 OPFRs were detected in water and sediment samples. The levels of Σ25OPFRs in water and sediment were 35.5-192ng/L and 8.84-48.5ng/g dw, respectively. Chlorinated OPFRs were the main contributions in water, whereas alkyl-OPFRs were the most common congeners found in sediment. Spatial analysis revealed that sample locations in neighboring cities had somewhat higher water concentrations of OPFRs. Slowing down the river current and making the reservoir the main sink of OPFRs, the dam can prevent OPFRs from moving via the Qiantang River. Positive matrix factorization indicated that plasticizer in polyvinyl chloride, polyester resins, and polyurethane foam made the greatest contributions in water, whereas polyurethane foam and textile were the predominant source in sediment. Analysis of sediment-water exchange of OPFRs showed that twelve OPFRs in sediments can re-enter into the water body. The risk quotients showed the ecological risk was low to medium, but trixylyl phosphate exposures posed high ecological risk to aquatic organisms.

Reproductive toxicology of environmental endocrine-disrupting chemicals in women: a cohort study protocol.

Introduction: Epidemiological evidence over the last few decades has consistently shown that exposure to endocrine-disrupting chemicals (EDCs) is associated with adverse reproductive health outcomes, including male and female infertility, poor-pregnancy outcomes, and increased risk of diseases in childhood and beyond. To investigate the effects of EDCs and lifestyle on all aspects of reproduction (including early oocyte development, fertilization, embryo development, embryo implantation, abortion, and preterm birth). Methods: We performed this cohort study on patients receiving in vitro fertilization (IVF) treatment. Biological samples including urine, serum, follicular fluid, semen, fetal tissue, decidua, and placenta, were obtained. Results: By studying the correlations between reproductive outcomes and environmental pollutant exposure and lifestyle, we determined the toxicological mechanisms and health effects of EDCs on female reproductive health. We found that higher concentrations of per- and polyfluoroalkyl substances were correlated with polycystic ovary syndrome (PCOS). Using specific biomarkers, we also detected the concentrations of organophosphorus flame retardants (OPFRs) in urine and found that OPFRs may disrupt hormone homeostasis. Discussion: All of these results reveal EDCs may disrupt female reproduction.

Occurrence and seasonal variations of organophosphate flame retardants in air and dust from college microenvironments at Qingdao, China: Implications for student's exposure and risk assessment

Organophosphate flame retardants (OPFRs) are widely used as alternatives to brominated flame retardants in a variety of consumer products and their consumption has continuously increased in recent years. However, their concentrations and human exposures in indoor microenvironments, particularly in a university environment, have received limited attention. In this study, the concentrations and seasonal variations of 15 OPFRs were assessed in typical microenvironments of two universities, including dormitories, offices, public microenvironments (PMEs: classroom, dining hall, gymnasium and library), and laboratories on the northern coast of China.Analysis of the OPFRs in both air and dust samples indicated widespread distribution in college campuses. The average concentration of ∑15OPFRs in the winter (12,774.4 ng/g and 5.3 ng/m3 for dust and air, respectively) was higher than in the summer (2460.4 ng/g and 4.6 ng/m3 for dust and air, respectively). The dust and air samples collected from PMEs and laboratories exhibited higher concentrations of OPFRs, followed by offices and dormitories. An equilibrium was reached between dust and air in all collected microenvironments. The daily intakes of OPFRs were significantly lower than the reference dose. Dust ingestion was the primary intake pathway in the winter, while inhalation and dust ingestion were the main intake pathways in the summer. The non-carcinogenic hazard quotients fell within the range of 10−7–10−3 in both the summer and winter, which are below the theoretical risk threshold. For the carcinogenic risk, the LCR values ranged from 10−10 to 10−8, indicating no elevated carcinogenic risk due to TnBP, TCEP, and TDCP in indoor dust and air.

Organophosphorus flame retardants in fish from the middle reaches of the Yangtze River: Tissue distribution, age-dependent accumulation and ecological risk assessment

Two fish species from the middle reaches of the Yangtze River, China, were sampled to investigate the occurrence, tissue distribution, age-dependent accumulation and ecological risk assessment of 24 organophosphorus flame retardants (OPFRs). Seventeen OPFRs were detected in tissue samples with a total concentration ranging from not detected (ND) to 1092 ng g−1 dw. Cl-OPFRs were predominant in all tissues (mean: 145 ng g−1 dw, median: 72.9 ng g−1 dw) and the concentrations of OPFRs in brain were the greatest (crucian carp: 525 ng g−1 dw, silver carp: 56.0 ng g−1 dw) compared with the other three organs (e.g., liver, muscle and gonad). Furthermore, the total concentrations of OPFRs in crucian carp tissues were significantly greater than those in silver carp (P < 0.01). Age-dependent accumulation of OPFRs was observed in the two fish species, but the accumulation profiles in the two fish species were different. Ecological risk assessment demonstrated that both fish species were at medium to high risk, and TDCIPP was a main contributor (>50%).

Occurrence, distribution, and ecological risk of organophosphorus flame retardants and their degradation products in water and upper sediment of two urban rivers in Shenzhen, China.

Organophosphorus flame retardants (OPFRs) are widely used in various industrial manufacturing processes; thus, their environmental impact in agglomerated industrial areas is of great concern. In this study, seventeen kinds of OPFRs and five kinds of organophosphate diesters (Di-OPs) in water and upper sediment samples from two urban rivers in the agglomerated industrial area of Shenzhen city, China, were investigated. The results showed that the total concentrations of detectable OPFRs ranged from 3438.83 to 12,838.87ng/L with an average of 6494.94ng/L in water samples and from 47.16 to 524.46ng/g (dry weight, dw) with an average of 181.48ng/g dw in sediment. The values were higher than those in other rivers worldwide. Tris(2-chloroethyl) phosphate (TCEP) is the predominant OPFRs in water and upper sediment, up to 10,664.23ng/L in water and 414.12ng/g dw in sediment. The total concentration of OPFRs of sediment samples in the Maozhou River was around twice as high as in the Guanlan River. The results indicated that the level of OPFRs was associated with the industrial activity intensity. Di-OPs exhibited lower concentrations than their parent compounds, and can be attributed to the degradation/metabolism of their parent compounds in the river. The sediment-water partition of OPFRs is significantly correlated with their log Kow values. Risk assessment revealed moderate ecological risks posed by OPFRs in water to aquatic organisms. The present study revealed the pollution status of OPFRs in rivers from agglomerated industrial and residential areas.

Contaminant occurrence, spatiotemporal variation, and ecological risk of organophosphorus flame retardants (OPFRs) in Hangzhou Bay and east China sea ecosystem.

Occurrence, spatiotemporal variation, sources, and ecological risks of 20 organophosphorus flame retardants (OPFRs) in water and sediments from Hangzhou Bay (HZB) and its adjacent East China Sea (ECS) were investigated in this study. The concentrations of OPFRs (∑OPFR) in water ranged from 0.51ng/L to 885ng/L, with chlorinated OPFRs having the highest value. For sediments, ∑OPFR ranged from 2.93ng/g, dry weight (dw) to 37.8ng/g, dw. The ∑OPFR in the water and sediments of HZB in summer was significantly (p<0.05) higher than that in autumn. Additionally, the pollution of OPFRs in HZB was higher than that in ECS, and the high-concentration areas appeared in the north and south banks of HZB and near the coast of ECS. Principal component analysis-multiple linear regression showed that the OPFRs in this region were mainly from industrial products (e.g., polyurethane foam/paint/coating/textiles/product processing). In terms of aquatic environments, ecological risks were in a low (∑RQs<0.1) to moderate (0.1<∑RQs<1) level, with regard to median exposure levels, a moderate risk (0.1<∑RQs<1) was found in the sediments during autumn. This study can provide new insights into the OPFR pollution characteristic and ecological risk in a specific eco-environment.

Comparison of the extractability of organophosphorus flame retardants in landfill media using organic and green solvents

Organic solvents are mainly used in the extraction of organophosphorus flame retardants (OPFRs) because of their availability and having been tested as good extracting solvents for most environmental pollutants. However, organic solvents are toxic, flammable, and costly. Hence, there is an ongoing quest for less hazardous chemicals such as green deep eutectic solvents (DES) that are cheap, recyclable, non-toxic and degradable in the environment, which can be used to extract organic pollutants such as OPFRs in environmental samples. This study assessed the extractability of OPFRs in municipal landfill leachate and sediment, using organic solvents and DES. Of the fourteen targeted OPFRs, 11 (80%) and 7 (50%) were detected in the leachate and sediment samples, using hexane; whereas 14 (100%) and 13 (90%) OPFRs were detected in the same order of samples using DES. The concentrations of OPFRs obtained for the leachate using optimum organic and DES ranged from below the limit of quantification (< LOQ)—516 ± 8.10 ng/L and < LOQ—453 ± 8.10 ng/L respectively. Correspondingly, the concentrations of OPFRs in sediment samples ranged from < LOQ—135 ± 2.89 ng/g dw and < LOQ—395 ± 2.24 ng/g dw, respectively. The results from this study, therefore, highlight the potential of DES to extract more OPFR from complex matrices such as landfill leachate and sediment. This finding infers that green hydrophilic DES can serve as good replacement for organic solvents such as hexane in liquid–liquid extraction (LLE) and solid–liquid extraction (SLE) techniques for landfill leachate and sediment.

Mesoscale cycling of organophosphorus flame retardants (OPFRs) in the Bohai Sea and Yellow Sea biotic and abiotic environment: A WRF-CMAQ modeling

Rapid urbanization and industrialization in the eastern seaboard region of China enhance the widespread use of organophosphorus flame retardants (OPFRs). The present study set up a coupled WRF-CMAQ-SMOKE and multi-compartment exchange modeling framework to assess the environmental fate and cycling of OPFRs and their contamination in the Bohai and Yellow Seas' marine food web. The framework predicts meteorological conditions, optimized air emissions, and concentrations of OPFRs in air, seawaters, marine sediment, and the food web. The model was implemented to simulate the temporal and spatial fluctuations of Tris (2-chloroisopropyl) phosphate (TCPP), the most dominant congener of OPFRs in China, in the Bohai and the Yellow Sea ecosystems on a spatial resolution of 10 km. Results revealed the effects of source proximity, atmospheric transport and deposition, and the changes in meteorology on TCPP's temporal-spatial distribution across different areas of coastal waters. The model also captures TCPP levels in commercial fish species in the Bohai Sea. The detailed temporal-spatial characteristics of TCPP with the mesoscale resolution provide useful information and a new tool for the environmental and health consequences of mariculture, urban and industrial emission mitigation in coastal regions for emerging chemicals, and fishery industry development.

Bioaccumulation of organophosphorus flame retardants in the marine mussel Mytilus galloprovincialis

The bioaccumulation and depuration of seven organophosphorus flame retardants (OPFRs) in marine mussel Mytilus galloprovincialis were studied. OPFRs showed to be bioavailable in aquatic environments. When mussels are exposed to environmentally relevant concentrations of OPFRs, uptake kinetics fit well to a first-order model with a single compartment; in contrast depuration rates were generally underestimated by that model, most likely because it does not take into account the biotransformation of OPFRs by the organisms. The highest bioaccumulation rates were observed for tricresyl phosphate (TCrP), triphenyl phosphate (TPhP) and 2-ethylhexyldiphenylphosphate (EHDPP). This could be due to the presence of aryl groups in these compounds, their low solubility in water, and their affinity for fat tissues. According to these findings TCrP, with a BCF value of 4042 L kg−1 wet weight, should be classified in environmental regulations as an accumulative chemical.

Gridded emission inventory of organophosphorus flame retardants in China and inventory validation

The bioaccumulation and adverse effects of organophosphorus flame retardants (OPFRs) on human health have become a global concern. China produces the largest amount of OPFRs globally and has the highest global market share. However, little is known about its emission level and environmental cycling, thereby causing uncertainties in the assessment of the environmental and health impacts of OPFRs. We developed a gridded annual OPFRs emission inventory at 1/4° longitude by 1/4° latitude resolution over China from 2014 to 2018. The results show that the annual OPFRs emissions increased from approximately 670 tons/yr in 2014 to 1000 tons/yr in 2018 in China. Higher OPFR emissions were identified in Jiangxi, Shandong, Beijing-Tianjin-Hebei (BTH), Yangtze River Delta (YRD), and Pearl River Delta (PRD). In total, 2400 tons of OPFRs were released into the atmosphere during the multi-year period, in which production accounting for 56.6% of total OPFR emissions in China. An atmospheric transport model, the Canadian Model for Environmental Transport of Organochlorine Pesticides (CanMETOP), was employed to verify the gridded emission inventory and elucidate the atmospheric environmental fate of OPFRs. Modeled OPFRs in the air and soil agreed reasonably well with observed data, suggesting that the developed inventory was, to a large extent, reliable. The modeled atmospheric and surface soil concentrations of OPFRs across China ranged from 0 to 119 ng/m3 and 0 to 428 ng/g, respectively. East China is subjected to more intense OPFR contamination than the rest of the country. The results provide a valuable dataset and assessment of OPFRs, which may aid policy-makers and the scientific community in developing emission control strategies and evaluating the health and environmental consequences of OPFRs in China.

Ornamental houseplants as potential biosamplers for indoor pollution of organophosphorus flame retardants

We investigated the occurrence, compositions, and partitioning behaviors of organophosphorus flame retardants (OPFRs) in indoor dust, air, and ornamental plants in Dalian, China, to evaluate the possibility of using houseplants as indoor biosamplers of OPFRs. The mean concentrations of OPFRs in the indoor air, dust, and plant samples were 14.9 ng/m3, 18,000 ng/g, and 345 ng/g, respectively. Tris(2-chloroisopropyl) phosphate (TCIPP) was the dominant congener in all kinds of samples. Significant correlation was found between the concentrations of tris(1,3-dichloroisopropyl) phosphate (TDCIPP) in indoor air and plants, suggesting that ornamental plant can be used as a sentinel for certain OPFRs in the indoor air. We developed a predictive model to assess the partitioning coefficients of OPFRs between indoor air and plant. The lipid content in leaf cuticle instead of leaf organic matter was used to improve the accuracy and reliability of this assessment. Using this model, we can estimate the OPFR concentrations in the indoor air based on their concentrations measured in the corresponding indoor plant. The estimated air concentrations were generally comparable with the measured concentrations, especially for those with octanol-air partition coefficient log Koa <11.6. Indoor plants can also provide a more holistic understanding of OPFR occurrence within a home due to the relatively long-term air-foliage partitioning. The results suggest that under certain conditions indoor ornamental plants have the potential to be used as the biosamplers of OPFRs in the indoor environment due to their convenience and low-cost.

Determination of organophosphorus flame retardants in textile wastewater by dispersive liquid-liquid microextraction based on solidification of floating organic drop followed by ultra-high performance liquid chromatography-tandem mass spectrometry

A rapid method for the determination of five organophosphorus flame retardants (OPFRs) in textile wastewater was established by dispersive liquid-liquid microextraction (DLLME) based on solidification of floating organic drop (SFO) coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The analytes were extracted from the water samples by SFO-DLLME, which was performed using a mixture of an extraction solvent that was less dense than water, 1-undecanol, and a dispersive solvent, methanol. The influences of the SFO-DLLME parameters on the extraction efficiencies were studied. 1-Undecanol (extraction solvent, 400 μL) and methanol (dispersive solvent, 300 μL) were added to textile wastewater (containing 2 g NaCl) with pH between 6 and 9, and the solution was shaken for 2 min. Under optimum conditions, the linear ranges of the proposed method were from 2 μg/L to 100 μg/L with correlation coefficients (R2) above 0.99 for all the analytes. The limits of detection (S/N=3) ranged from 2 μg/L to 5 μg/L. The precision of the method was evaluated in terms of repeatability; the relative standard deviations varied from 2.7% to 11.2% (n=6). The relative recoveries ranged from 71.6% to 117.6% for all analytes. Only 3 of the 11 selected samples were tested positive for OPFRs, and the total concentrations of OPFRs in them were in the range of 2.6-3.4 μg/L. Hence, this method is accurate, environmentally friendly, fast, and convenient for the routine analysis of OPFRs in textile wastewater.

Characterization of residential household dust from Shanghai by particle size and analysis of organophosphorus flame retardants and metals

BackgroundPhysical and biological properties of dust particles might affect the availability and distribution of chemicals associated to indoor dust; however it has not been adequately examined. In this study, household dust from Shanghai was fractionated into five particle sizes and size distribution, morphology, surface area, organic matter, microorganisms, elemental composition, metals and organophosphorus flame retardants (OPFRs) compositions were characterized. Also, household dust samples from Stockholm that has previously been characterized were included in the analysis of OPFRs for comparison.ResultsThe respirable fraction had a yield of 3.3% in mass percentage, with a particle size of 2.22 ± 2.04 µm. As expected, both metals and OPFRs concentrations increased with decreased particle size. Al and Fe dominated (66–87%) followed by the concentrations of Zn (5–14%) and Ga (1.8–5%) of the sum of 16 metals in the dust. The concentrations of OPFRs in Shanghai dust ranged from 5.34 to 13.7 µg/g (median: 7.21 µg/g), compared to household dust from Stockholm that ranged from 16.0 to 28.3 µg/g (median: 26.6 µg/g). Tris(2-chloroisopropyl) phosphate (TCIPP) and tris(2-chloroethyl) phosphate (TCEP) dominated in Shanghai dust samples while tris(2-butoxyethyl) phosphate (TBOEP) dominated in dust from Stockholm homes.ConclusionThe results showed that mass percentage for each particle size fraction was not evenly distributed. Furthermore, the particle-bound microorganisms and OPFRs increased with decreased particle size, whereas metals had the highest concentrations at specific dust sizes. Therefore, it is essential to select the proper particle size in order to assess any specific human exposure study to indoor pollutants.

Seasonal trends of legacy and alternative flame retardants in river water in a boreal catchment.

Boreal forests store large amounts of atmospherically deposited (semi-)persistent organic pollutants (POPs). The terrestrial POPs may be exported to streams and rivers through processes that are heavily impacted by seasonality. In this screening study, concentrations of 4 legacy and 45 alternative flame retardants (FRs) were determined in the dissolved and particulate phase in streams within a relatively pristine boreal catchment in northern Europe (Krycklan Catchment Study; 3 sites) and in rivers more impacted by human activities further downstream towards the Baltic Sea (3 sites). The sampling included the main hydrological seasons (snow-free, snow-covered, and spring flood) and was conducted during two consecutive years (2014-2016). Of the 49 analyzed FRs, 11 alternative halogenated FRs (HFRs), 13 alternative organophosphorus FRs (OPFRs), and 4 legacy polybrominated diphenyl ethers (PBDEs) were detected in at least one sample. The average bulk (dissolved + particulate) concentrations of ∑FRs (including all sites) were highest for ∑HFRs (38 ± 70 ng L-1), followed by the ∑OPFRs (3.9 ± 4.9 ng L-1) and the ∑PBDEs (0.0040 ± 0.016 ng L-1). Bulk concentrations of HFRs, OPFRs, and PBDEs were highly variable with season and sampling location, e.g., during spring flood, bulk concentrations were up to 600 times, 3.7 times, and 4.9 times higher for HFRs, OPFRs and PBDEs, respectively, than during periods of lower flow. Bulk concentrations of ∑OPFRs, were elevated at all sites ~6 days before the actual start of the spring flood in 2015, suggesting that hydrophobicity fractionation had occurred within the snowpack. Similar to previous studies of other POPs in the same headwater catchment, there was a general trend that levels of ∑FRs were higher at the mire site than at the forested site. Annual fluxes of FRs were found to be ~15 times higher downstream the city of Umeå compared to at the outlet of the pristine catchment. This study should be regarded as a screening study considering the large number of diverse FRs analyzed and variability in the results.

Brominated and organophosphorus flame retardants in South African indoor dust and cat hair

Flame retardants (FRs), such as brominated flame retardants (BFRs) and organophosphorus flame retardants (OPFRs), are diverse groups of compounds used in various products related to the indoor environment. In this study concentrations of eight polybrominated diphenyl ethers (PBDEs), two alternative BFRs and ten OPFRs were determined in indoor dust (n = 20) and pet cat hair (n = 11) from South Africa. The OPFRs were the major FRs, contributing to more than 97% of the total FR concentration. The median Ʃ10OPFRs concentrations were 44,800 ng/g in freshly collected dust (F-dust), 19,800 ng/g in the dust collected from vacuum cleaner bags (V-dust), and 865 ng/g in cat hair (C-hair). Tris(1-chloro-2-propyl) phosphate (TCIPP) was the dominant OPFR in the dust samples with median concentrations of 7,010 ng/g in F-dust and 3,590 ng/g in V-dust. Tris(2-butoxyethyl) phosphate (TBOEP) was the dominant OPFR in C-hair, with a median concentration of 387 ng/g. The concentrations of Ʃ8PBDEs were higher in F-dust than in V-dust. BDE209 was the dominant BFR in all three matrices. Bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (BEH-TEBP) and 2-ethylhexyl-2,3,4,5- tetrabromobenzoate (EH-TBB) showed notable contributions to the BFR profile in cat hair. A worst-case dust exposure estimation was performed for all analytes. The estimated TCIPP daily intake through dust ingestion was up to 1,240 ng/kg bw for toddlers. The results indicate that OPFRs are ubiquitous in South African indoor environment. Indoor dust is a major source of human exposure to environmental contaminants. This can for example occur through hand-to-mouth contact of toddlers, and is an important route of exposure to currently used FRs accumulated on dust particles. The presence of FRs, in particular high concentrations of OPFRs, suggests that children and indoor pet cats may have greater exposure to FRs than adults.

Polyurethane heat preservation materials: The significant sources of organophosphorus flame retardants

The concentrations and compositions of organophosphorus flame retardants (OPFRs) in various heat preservation materials from different brands and types in China were investigated, as well as their OPFR burdens and emission amounts. The average concentrations of ΣOPFRs were 41.4 ± 10.2, (7.1 ± 4.0) × 104, and 56.3 ± 19.3 μg/g in phenolic foams (PF), polyurethane foams (PUR), and extruded polystyrene boards (XPS), respectively. OPFRs in the PUR materials were ∼3 orders of magnitude higher than those in the other two materials, suggesting that organophosphate esters were added as flame retardants (FRs) in the PUR materials. Obvious variations in the concentrations and compositions of OPFRs were discovered in those heat preservation materials due to their material types, brands, and fire-ratings, as well as contaminations. TCIPP was the most dominant OPFR with a range from 22.3 (in PF) to 6.73 × 104 (in PUR) μg/g, which emphasized that TCIPP was the most commonly used flame retardant additives in China. Based on the OPFR concentrations, OPFR emission rates, and application amounts of heat preservation materials, we calculated the total burdens of OPFRs in those materials and their emission amounts in China. The potential total burden of OPFRs in the completed new buildings of China in 2017 was estimated to be ∼(2.37 ± 1.11) × 104 t, while the total emission of OPFRs from those new materials was ∼3.19 ± 1.65 t/y. As significant sources of OPFRs, the heat preservation materials used in exterior or interior walls may pose potential health risks to humans.

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 5780.0ngL-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 45.2ng/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.

Occurrence, distribution and ecological risk assessment of organophosphorus flame retardants and plasticizers in sediment samples along the Vaal River catchment, South Africa

Abstract The occurrence, distribution and ecological risk assessment of twelve (12) organophosphorus flame retardants (OPFRs) were investigated in sediments from the Vaal River, South Africa. Six halogenated OPFRs [tris-(2-chloroethyl) phosphate (TCEP), three isomers of tris-(chloropropyl) phosphate (TCiPPs), tris-(1, 3-dichloro-2-propyl) phosphate (TDCiPP) and tris-(2, 3 dibromopropyl) phosphate (TDBPP)] and six non-halogenated OPFRs [tris-(n-butyl) phosphate (TBP), tris-(phenyl) phosphate (TPhP), tris-(butyl ethoxy) phosphate (TBOEP), tris-(2-ethylhexyl) phosphate (TEHP), diphenyl- 2-ethylhexyl phosphate (DPEHP) and tris-(m-cresyl) phosphate (m-TCP)] were detected in this study. The concentrations of twelve OPFRs in total (Σ12OPFRs) ranged from 68 to 278 ng g−1 dry weight (dw) with the mean and median of 138 and 120 ng g−1; respectively. The non-halogenated OPFRs showed more abundances than the halogenated OPFRs with TDBPP, TBP, and TBOEP the most abundant compounds. Generally, concentrations of OPFRs in more urbanized region were higher than those in less urbanized regions. When the concentrations of OPFRs and total organic carbon (TOC) were correlated, a moderate and significant correlation (p 1) while TBOEP, TPhP, and TBP posed medium risk (0.1

Targeted and non-target screening of persistent organic pollutants and organophosphorus flame retardants in leachate and sediment from landfill sites in Gauteng Province, South Africa

In the present study, target analysis and a non-target screening method were employed to investigate the degree of contamination of landfill sediment and leachate in Gauteng Province, South Africa. Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), organochlorinated pesticides (OCPs) and organophosphorus flame retardants (OPFRs) were extracted from sediment and leachate samples using solid-liquid extraction and liquid-liquid extraction methods, respectively; and analysed by target analysis using gas chromatography mass spectrometry (GC–MS). Targeted PBDEs were all detected in sediment samples. However, PCBs, CB 52 and CB 101 were below the quantification limit (LOQ) in the sediment samples. The concentrations of OCPs measured ranged from 0.09 ng/g dw (α-HCH) to 5.29 ng/g dw (pp-DDE) in Marie Louis, and from 0.14 ng/g dw (α-HCH) to 11.3 ng/g dw (γ-HCH) in Hatherly, with an average mass fraction of 1.0 (±2.0, SD) ng/g dw in Marie Louis and 2.0 (±3.0, SD) ng/g dw in Hatherly. Among the OPFRs, TnPP, TPTP, T35DMPP and TBPP were below the LOQ in both leachate and sediment samples. Overall, high concentrations of TDCIPP and TCIPP were obtained in both media, ranging from 226 to 14,500 ng/L and 52.0–13,800 ng/L and from 19.6–741 ng/g dw and 32.8–1240 ng/g dw in leachate and sediment, respectively. The high concentrations of certain OPFRs suggest that these may have replaced both PCBs and PBDEs in consumer products currently imported into South Africa. Common compounds identified by non-target screening with high-resolution mass spectrometry of leachate were diethyl [2‑(1, 3‑dioxolan‑2‑yl) ethyl] malonate (C12H20O6) and 4‑(benzyloxy) cyclohexanone (C13H20O2). These compounds are possibly associated with plasticizers used in the production of plastic and plastic coatings.

Novel Method for in Situ Monitoring of Organophosphorus Flame Retardants in Waters.

Widespread use of organophosphorus flame retardants (OPFRs) and their ubiquity in water results in the need for a robust and reliable monitoring technique to better understand their fate and environmental impact. In situ passive sampling using the diffusive gradients in thin-films (DGT) technique provides time-integrated data and is developed for measuring OPFRs here. Ultrasonic extraction of binding gels in methanol provided reliable recoveries for all tested OPFRs. Diffusion coefficients of TCEP, TCPP, TDCPP, TPrP, TBP, and TBEP in the agarose diffusive gel (25 °C) were obtained. The capacity of an HLB binding gel for OPFRs was >115 μg per disc, and the binding performance did not deteriorate with time up to 131 days. DGT performance is independent of typical environmental ranges of pH (3.12-9.71), ionic strength (0.1-500 mmol L-1), and dissolved organic matter (0-20 mg L-1), and also of diffusive layer thickness (0.64-2.14 mm) and deployment time (3-168 h). Negligible competition effects between OPFRs was found. DGT-measured concentrations of OPFRs in a wastewater treatment plant (WWTP) effluent (12-16 days) were comparable to those obtained by grab sampling, further verifying DGT's reliability for measuring OPFRs in waters.