Chlorinated Organophosphate Flame Retardants Research Articles

Potential Adverse Outcome Pathways of Chlorinated Organophosphate Flame Retardants.

Chlorinated organophosphate flame retardants (Cl-OPFRs) are frequently detected chemicals in the environment and biological samples, yet there is a lack of systematic evaluation regarding the adverse effects and toxicological mechanisms of Cl-OPFRs. This study utilizes the adverse outcome pathway (AOP) framework to assess the health implications and mechanisms of Cl-OPFRs, identifying multi-system toxicity, with a particular emphasis on reproductive issues and the possible toxic mechanisms. These results enhance knowledge of the health hazards linked to Cl-OPFRs, supporting the creation of focused risk evaluations and suitable regulatory actions.

Organophosphate flame retardant TDCPP: A risk factor for renal cancer?

Tris (1,3-dichloro-2-propyl) phosphate (TDCPP), a chlorinated organophosphate flame retardants(OPFRs), is widely used in a range of plastic foams, resins, and latexes. It can be detected in human tissues, including urine, and milk. Recent research has suggested that TDCPP has neurotoxic, reproductive, and potentially carcinogenic. In our study, we proposed a novel method for predicting the gene associated with tumor-compound interactions. We firstly used The Comparative Toxicogenomics Database (CTD) and downloaded potentially interactive genes about TDCPP in renal carcinoma. Gene expression data and the corresponding clinical information of the Kidney renal clear cell cancer (KIRC) patients were obtained from The Cancer Genome Atlas database (TCGA). Data from normal people in The Genotype‐Tissue Expression (GTEx) databases was used to supplement the calculations. After being predicted by PharmMapper database, and validated by Gene Ontology and Kyoto Encyclopedia of Genes and Genomes, 25 genes were selected to construct protein-protein interaction network analysis. The prognostic value of these genes was evaluated with Kaplan-Meier analysis, and four interactive genes were selected. Gene set variation analysis and drug-target binding prediction proved the hub gene has a potential relationship with renal clear cell carcinoma. We then used the ChEA3 (Chip-X Enrichment Analysis, Version 3) database to predict the upstream of these interactive genes. Molecular docking was used to predict the binding of these transcription factors to TDCPP and interactive genes to TDCPP. Moreover, in cell lines and in vivo experiments demonstrated the cancer-promoting effect of TDCPP. The expression of the interactive genes was verified by qPCR and Western blot. Combining binding energy and qPCR results, we choose EPAS1 to verify its function in renal carcinoma cell lines. Our study provides a novel method to predict the potential interactive genes between TDCPP and renal cancer, which may reveal potential targets for the treatment and prevention of diseases.

Dermal uptake of chlorinated organophosphate flame retardants via contact with furniture fabrics; implications for human exposure

The chlorinated organophosphate flame retardants (Cl-PFRs): tris-(2-chloroethyl)-phosphate (TCEP), tris-(1-chloro-2-propyl)-phosphate (TCIPP) and tris-(1,3-dichloropropyl)-phosphate (TDCIPP), have been widely used in upholstered furniture despite their carcinogenic potential. Although Cl-PFRs are mainly added to furniture foam, they are present in the fabrics likely due to migration from the foam. While several studies have assessed human exposure to Cl-PFRs via different pathways, no information exists on dermal uptake of these chemicals through contact with fabrics. In the current study, dermal absorption of TCEP, TCIPP and TDCIPP from 3 UK domestic furniture fabrics was experimentally assessed for the first time using in vitro 3D-human skin equivalents (EpiSkin™) under different real-life exposure scenarios. Results revealed all 3 target Cl-PFRs were dermally bioavailable to varying degrees (3.5%–25.9% of exposure dose) following 24 h contact with the studied fabrics. Estimated permeability coefficients (KP, cm h−1) showed TCEP had the highest percutaneous penetration potential followed by TCIPP, then TDCIPP. Further investigation revealed human dermal uptake of Cl-PFRs can be influenced by several factors including: the specific physicochemical properties of the compound, the type of exposure matrix, the exposure dose and the degree of skin hydration at the point of contact. Exposure assessment revealed UK adults and toddlers can be exposed to 20.4 and 14.1 ng TCIPP/kg bw/day via contact with furniture fabrics in summer, which is higher than international average exposures via inhalation and dust ingestion for adults and dietary exposure for toddlers. Therefore, risk assessment studies for Cl-PFRs and future replacements should consider dermal contact with consumer products (e.g. furniture fabrics) as a potential significant human exposure pathway.

Legacy and emerging flame retardants (FRs) in the urban atmosphere of Pakistan: Diurnal variations, gas-particle partitioning and human health exposure

Atmospheric concentration of legacy (LFRs) and emerging flame retardants (EFRs) including 8 polybrominated diphenyl ethers (PBDEs), 6 novel brominated flame retardants (NBFRs), 2 dechlorane plus isomers (DP), and 8 chlorinated organophosphate flame retardants (OPFRs) were consecutively measured in eight major cities across Pakistan. A total of 96 samples (48 PM2.5 & 48 PUFs) were analyzed and the concentrations of ∑8PBDEs (gaseous+particulate) ranged between 40.8 and 288 pg/m3 with an average value of 172 pg/m3. ∑6NBFRs ranged between 12.0 and 35.0 pg/m3 with an average value of 22.5 pg/m3 while ∑8OPFRs ranged between 12,900–40,800 pg/m3 with an average of 24,700 pg/m3. Among the studied sites, Faisalabad city exhibited the higher concentrations of FRs among all cities which might be a consequence of textile mills and garment manufacturing industries. While analyzing the diurnal patterns, OPFRs depicted higher concentrations during night-time. The estimated risks of all groups of FRs from inhalation of ambient air were negligible for all the cities, according to USEPA guidelines. Nonetheless, our study is the first to report gaseous and particulate concentrations of FRs in air on a diurnal basis across major cities in Pakistan, offering insights into the atmospheric fate of these substances in urban areas in a sub-tropical region.

Mass defect filtering for suspect screening of halogenated environmental chemicals: A case study of chlorinated organophosphate flame retardants.

Organophosphate flame retardants (OPFRs) are a class of flame retardants widely found in environmental and biological matrices that have been extensively studied due to their adverse health effects in humans. OPFRs are loosely bound chemicals that can detach from treated products and be released into indoor and outdoor environments, where they have the potential to further undergo transformation and degradation processes, in particular the chlorinated OPFRs (Cl-PFRs). Their detection remains a moving target for analysts, and traditional targeted mass spectrometry methods are suitable only for those compounds with authentic standards. Mass defect filter (MDF) is a strategy to filter molecular features using thresholds applied to the mass defect value of a target ion or molecular feature of interest. We have developed an MDF strategy for the detection and tentative identification of twelve potential Cl-PFR transformation products in a study mixture of six known Cl-PFRs using MS/MS data acquired on a high-resolution mass spectrometer. Most compounds in the Cl-PFRs family share a ClO4 P group as a core structure, of which modification results in a significant shift in the exact masses of the resulting compounds but show only a minimal shift in their mass defects. Subsequently, the MDF strategy was employed to tentatively identify Cl-PFRs retrospectively in six human urine samples that had previously been analyzed. MDF in combination with product ion filtering for the characteristic [H2 O3 P]+ and [H4 O4 P]+ ions and neutral loss filtering for the characteristic Cn H2n-x Clx group resulted in revealing suspects and homologues in the Cl-PFRs family. Furthermore, the MDF of the product ions detected additional Cl-PFR-related compounds that differed significantly in the exact masses of both precursor and product ions but had minimal shift in the mass defects of product ions. The mass defect of one or more common product ions helped to detect a few Cl-PFR analogs that had not been identified by MDF of the core structure precursor ion. MDF helped to detect some Cl-PFRs present in lower concentrations, which went undetected without data filters. MDF also helped to detect chromatographic peaks for Cl-PFR homologues that are likely structural analogs that resulted from impurities and/or derivatives and transformation products. The methodology was applied to demonstrate and tentatively detect known and suspect Cl-PFRs in human urine samples retrospectively.

The adverse effect of TCIPP and TCEP on neurodevelopment of zebrafish embryos/larvae

Tris (1-chloro-2-propyl) phosphate (TCIPP) and tris (2-chloroethyl)phosphate (TCEP) are two widely used chlorinated organophosphate flame retardants (ClOPFRs), and have been frequently detected in various environmental media. Concern is now growing whether TCIPP and TCEP can cause neurotoxicity since they have similar chemical structure with organophosphorus pesticide. Therefore, in this study, zebrafish embryos (2–120 h post-fertilization [hpf]) were exposed to TCIPP or TCEP (0, 100, 500 or 2500 μg/L) or a model neurotoxicant, chlorpyrifos (CPF, 100 μg/L) to investigate the adverse effects and possible mechanisms of TCIPP and TCEP on neurodevelopment. Our results showed that CPF exposure resulted in developmental toxicity including decreased hatching, survival rates and increased malformation rates (e.g., spinal curvature) as well as behavior changes such as decreased locomotive activity in dark stimulation. In contrast, TCIPP and TCEP showed no significant effects on developmental parameters, but caused similar effects on locomotive activity at high concentration, indicating that although not as potent as CPF, TCIPP and TCEP may still cause adverse effects on neurodevelopment. Furthermore, our results suggest that TCIPP and TCEP showed no effects on acetylcholine content or AChE activity, which were considered as the main targets of CPF. However, TCIPP and TCEP exposure can significantly down-regulate the expression of selected genes and proteins related to neurodevelopment (e.g., mbp, syn2a, and α1-tubulin) similar as CPF did. Besides that, TCIPP and TCEP can also affect the transcription of shha and gap43, which were not affected by CPF, pointing out a complex mechanism underlying TCIPP and TCEP's neurodevelopmental toxicity. Overall, our results demonstrated that TCEP and TCIPP may have adverse effect on the neurodevelopment of zebrafish embryos/larvae, but the underlying mechanism is not via the inhibition of acetyl cholinesterase activity.

Assessing bioaccessibility and bioavailability of chlorinated organophosphorus flame retardants in sediments

The distribution of chlorinated organophosphate flame retardants (OPFRs) in sediments has been well documented, but the study about their bioavailability remains lacking. This study investigated the applicability of solid phase microextraction (SPME) fiber and Tenax extraction to predict the bioavailability of two chlorinated OPFRs: tri(2-chloroisopropyl) phosphate and tri(1,3-dichloro-2-isopropyl) phosphate, in sediments. Our results showed that both SPME fiber and Tenax extracted concentrations correlated significantly with the measured concentrations in the aquatic worm (Lumbriculus variegatus). We also measured the Tenax extracted concentrations at 6 and 24 h, and a strong linear relationship between these two time durations was found. In addition, the 6-h Tenax extracted concentrations also significantly correlated with the SPME fiber extracted concentrations, and the Tenax extracted concentrations were much higher than the SPME fiber extracted concentrations. These results demonstrate the efficiency of SPME and Tenax extraction methods to predict the bioavailability of chlorinated OPFRs in sediments, and it was found that the Tenax extraction is more promising than the SPME extraction.

In-vitro estimation of bioaccessibility of chlorinated organophosphate flame retardants in indoor dust by fasting and fed physiologically relevant extraction tests.

This paper reports the evaluation of in-vitro physiologically relevant extraction tests for ascertainment of the bioaccessible fractions of emerging flame retardants from indoor dust in the gastric and gastrointestinal compartments. Standardized bioaccessibility tests under both fasting (UBM-like test) and fed (FOREhST test) conditions simulating the macronutrient composition of an average child diet were harnessed for investigation of the oral bioaccessibility of chlorinated organophosphate esters, namely, tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP) and tris(1,3-dichloro-2-propyl) phosphate (TDCP), in household and automobile cabin dust samples with varying concentration levels of contaminants. Minimal processing of the biomimetic extracts (only protein precipitation using acetonitrile) was proven feasible by analysis with liquid chromatography-mass spectrometric detection (LC-MS/MS). An inversely proportional relationship was identified between log Kow and oral bioaccessibility concentrations for TCEP, TCPP and TDCP in both dust samples with maximum bioaccessibility fractions for TCEP within the range of 50-103%. Non-bioaccessible fractions were determined by matrix-solid phase dispersion. Limits of quantification of LC-MS/MS in surrogate digestive fluids ranging from 0.4-0.8ng/mL suffice for determination of freely dissolved fractions of the two less hydrophobic species. Our results indicate that lipophilic food commodities used under fed-state gastrointestinal extraction conditions do not increase availability of TCEP, TCPP and TDCP in body fluids, and therefore conservative conditions in human health risk explorations for the target moderately polar flame retardants might be obtained with simplified tests under fasting conditions. This also holds true for the UBM/FOREhST bioaccessibility data for SRM 2585 (organic contaminants in house dust). Estimated average daily intake doses for toddlers incorporating oral bioaccessibility data afforded body burdens for the three chlorinated alkyl phosphates of ca. 3000 to 700 times below reference dose values, which indicate that long-term exposure to chlorinated organophosphate esters via accidental ingestion of indoor dust does not pose health risks to toddlers.

Chlorinated organophosphate and “legacy” brominated flame retardants in UK waste soft furnishings: A preliminary study

The Furniture and Furnishings (Fire Safety) Regulations 1988 is the major driver for the use of chemical flame retardants (FRs) in soft furnishings marketed in the UK. While these regulations specify the level of flame retardancy required, they do not specify how such levels should be achieved. Consequently, it remains unclear which FRs are present in UK soft furnishings. This is important not only to help assess what FRs we may be exposed to currently, but which FRs are currently entering the waste stream with concomitant potential for release into the environment. To address this data gap, concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD) and a range of chlorinated organophosphate flame retardants (OPFRs) were measured in samples of domestic and office waste soft furnishings products entering the UK waste stream in 2011 and 2012. This preliminary study measured the FR content of: carpets (n = 4), curtains (n = 7), mattress fabrics (n = 2), furniture foam (n = 9), and furniture upholstery textiles (n = 10). Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) were not found at significant concentrations (below detection limits in most samples) in any of the twenty two analysed products. In contrast, 7 of the 9 furniture foam samples were treated with tris(2-chloroisopropyl)phosphate (TCIPP) at a mean concentration of 1.9% w/w, with another single foam sample containing tris(1,3-dichloroisopropyl)phosphate (TDCIPP) and tris(2-chloroethyl)phosphate (TCEP) at 1.1 and 0.5% respectively. By comparison, PBDE concentrations are within the range reported previously for UK indoor dust [18], rather than the percent by weight levels required to impart flame retardancy.

Occurrence and Concentrations of Halogenated Flame Retardants in the Atmospheric Fine Particles in Chinese Cities.

The concentrations of halogenated flame retardants (HFRs) in PM2.5 were monitored for one year at 10 urban sites in China during 2013-2014. This study investigated four classes of HFRs: nine polybrominated diphenyl ethers (PBDEs), six nonbromodiphenyl ether (BDE) brominated flame retardants, two dechlorane plus (DP) flame retardants, and three chlorinated organophosphate flame retardants (OPFRs). Extremely high concentrations of BDE-209 and DBDPE were observed in only one city (Guangzhou), which was a consequence of the intensive e-waste recycling and disposal operations in the Pearl River Delta. This result differed from the tris(monochloropropyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) distributions, which showed high concentrations in most cities, suggesting wide usage and large emissions in China in recent years. The highest TCPP and TCEP concentrations were observed in the summer, indicating that emission from local sources was an important factor controlling the levels in the air. This was not the case for BDE-209 and DBDPE, for which higher concentrations were found in winter. When bound to particulate matter due to low vapor pressure, these compounds may be more persistent in air, and temperature-dependent gas-particle partitioning was a key factor. Moreover, regional pollution and long-range transport had a significant influence on the seasonal distributions of BDE-209 and DBDPE, especially in cities (Guangzhou and Shanghai) close to electrical/electronic waste recycling sites. Residents in urban areas were exposed to higher levels of chlorinated OPFRs. This raises considerable concern, and an appropriate risk assessment is required.

Inhalation a significant exposure route for chlorinated organophosphate flame retardants

Chlorinated organophosphate flame retardants (ClOPFRs) are widely used as additive flame retardants in consumer products including furniture, children's products, building materials, and textiles. Tests of indoor media in homes, offices, and other environments have shown these compounds are released from products and have become ubiquitous indoor pollutants. In house dust samples from Washington State, U.S.A., ClOPFRs were the flame retardants detected in the highest concentrations. Two ClOPFRs, tris(1,3-dichloro-2-propyl)phosphate (TDCPP or TDCIPP) and tris(2-chloroethyl)phosphate (TCEP), have been designated as carcinogens, and there is growing concern about the toxicity of the homologue tris(1-chloro-2-propyl)phosphate (TCPP or TCIPP). In response to concerns about exposure to these compounds, the European Union and a number of U.S. states have taken regulatory action to restrict their use in certain product categories. To better characterize exposure to ClOPFRs, inhalation exposure was assessed using active personal air samplers in Washington State with both respirable and inhalable particulate fractions collected to assess the likelihood particles penetrate deep into the lungs. Concentrations of ∑ClOPFRs (respirable and inhalable) ranged from 97.1 to 1190 ng m−3 (mean 426 ng m−3), with TCPP detected at the highest concentrations. In general, higher levels were detected in the inhalable particulate fraction. Total intake of ClOPFRs via the inhalation exposure route was estimated to exceed intake via dust ingestion, indicating that inhalation is an important route that should be taken into consideration in assessments of these compounds.

Human dermal absorption of chlorinated organophosphate flame retardants; implications for human exposure

Tris-2-chloroethyl phosphate (TCEP), tris (1-chloro-2-propyl) phosphate (TCIPP) and tris-1,3-dichloropropyl phosphate (TDCIPP) are organophosphate flame retardants (PFRs) widely applied in a plethora of consumer products despite their carcinogenic potential. Human dermal absorption of these PFRs is investigated for the first time using human ex vivo skin and EPISKIN™ models. Results of human ex vivo skin experiments revealed 28%, 25% and 13% absorption of the applied dose (500ng/cm2, finite dose) of TCEP, TCIPP and TDCIPP, respectively after 24h exposure. The EPISKIN™ model showed enhanced permeability values (i.e. weaker barrier), that were respectively 16%, 11% and 9% for TCEP, TCIPP and TDCIPP compared to human ex vivo skin. However, this difference was not significant (P>0.05). Estimated permeability constants (Kp, cm/h) showed a significant negative correlation with log Kow for the studied contaminants. The effect of hand-washing on dermal absorption of PFRs was investigated. Washing reduced overall dermal absorption, albeit to varying degrees depending on the physicochemical properties of the target PFRs. Moreover, slight variations of the absorbed dose were observed upon changing the dosing solution from acetone to 20% Tween 80 in water, indicating the potential influence of the dose vehicle on the dermal absorption of PFRs. Finally, estimated dermal uptake of the studied PFRs via contact with indoor dust was higher in UK toddlers (median ΣPFRs=36ng/kgbwday) than adults (median ΣPFRs=4ng/kgbwday). More research is required to fully elucidate the toxicological implications of such exposure.

Flame retardant transfers from U.S. households (dust and laundry wastewater) to the aquatic environment.

Levels of flame retardants in house dust and a transport pathway from homes to the outdoor environment were investigated in communities near the Columbia River in Washington state (WA). Residential house dust and laundry wastewater were collected from 20 homes in Vancouver and Longview, WA and analyzed for a suite of flame retardants to test the hypothesis that dust collecting on clothing and transferring to laundry water is a source of flame retardants to wastewater treatment plants (WWTPs) and subsequently to waterways. Influent and effluent from two WWTPs servicing these communities were also analyzed for flame retardants. A total of 21 compounds were detected in house dust, including polybrominated diphenyl ethers (PBDEs), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB or EH-TBB), bis(2-ethylhexyl) 3,4,5,6-tetrabromophthalate (TBPH), 1,2-bis(2,4,6,-tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE), hexabromocyclododecane (HBCD or HBCDD), tetrabromobisphenol A (TBBPA), and three chlorinated organophosphate flame retardants (ClOPFRs), tris(1,3-dichloro-2-propyl)phosphate (TDCPP or TDCIPP), tris(1-chloro-2-propyl)phosphate (TCPP or TCIPP), and tris(2-chloroethyl)phosphate (TCEP). Levels ranged from 3.6 to 82,700 ng g(-1) (dry weight). Of the 21 compounds detected in dust, 18 were also detected in laundry wastewater. Levels ranged from 47.1 to 561,000 ng L(-1). ClOPFRs were present at the highest concentrations in both dust and laundry wastewater, making up 72% of total flame retardant mass in dust and 92% in laundry wastewater. Comparison of flame retardant levels in WWTP influents to estimates based on laundry wastewater levels indicated that laundry wastewater may be the primary source to these WWTPs. Mass loadings to the Columbia River from each treatment plant were by far the highest for the ClOPFRs and ranged up to 114 kg/yr for TCPP.

Atmospheric deposition of chlorinated organophosphate flame retardants (OFR) onto soils

This study highlights the influence of dry and wet deposition on concentrations of chlorinated organophosphate flame retardants (OFR) in soil. Soil samples were collected in 2010/11 during a period of snow falling to snow melting, a period of rainfall and a dry period. Snow and rainwater samples were also collected from the soil sampling site. Tris(2-chloroethyl)phosphate (TCEP), tris(2-chloroisopropyl)phosphate (TCPP) and tris(1,3-dichloro-2-propyl)phosphate (TDCP) were analysed in soil samples using a combination of Twisselmann extraction and solid-phase microextraction (SPME), followed by gas chromatography-mass spectrometry (GC-MS). SPME/GC-MS was applied to analyse TCEP, TCPP and TDCP in aqueous samples.Concentrations of TCEP were between 236 and 353ngL−1 in snow and 78 and 234ngL−1 in rain. TCPP concentrations were between 226 and 284ngL−1 in snow and 371 and 385ngL−1 in rain. In soil samples, concentrations ranged from 5.07 to 23.48ngg−1 dry weight (dwt) for TCEP and 5.66 to 19.82ngg−1 dwt for TCPP. Concentrations of TDCP in rainwater and snow samples were rather low (46 and 100ngL−1, respectively); concentrations of TDCP were below the limit of detection in soil samples.Snow melting caused enhanced soil concentrations of TCEP and TCPP, but greater effect of snow melting was observed for TCEP than for TCPP soil concentrations. No significant correlation between precipitation amounts and soil concentrations was observed. The influence of wet deposition on soil contents of TCEP and TCPP may be covered by volatilisation or by the mobility of both compounds in soil and their transport to deeper soil zones with seepage water. Snow was found to be a more efficient scavenger and transporter of chlorinated OFR into soil than rainwater. During dry weather, the soil concentrations of both compounds seemed to be driven mainly by air concentrations, which are determined by source emission strengths and photochemical degradation in the atmosphere.Values of calculated air concentrations were between 0.0034ngm−3 for TCEP and 0.99ngm−3 for TCPP. Total OFR specific loads were 3756ng m-2 day-1 within the first 24h and 3028ng m-2 day-1 within the next 24h. Fugacity calculations (0.011 to 0.103 for TCPP and 0.005 to 0.073 for TCEP) indicated net deposition from air to soil for both compounds.

Identification of Flame Retardants in Polyurethane Foam Collected from Baby Products

With the phase-out of PentaBDE in 2004, alternative flame retardants are being used in polyurethane foam to meet flammability standards. However, insufficient information is available on the identity of the flame retardants currently in use. Baby products containing polyurethane foam must meet California state furniture flammability standards, which likely affects the use of flame retardants in baby products throughout the U.S. However, it is unclear which products contain flame retardants and at what concentrations. In this study we surveyed baby products containing polyurethane foam to investigate how often flame retardants were used in these products. Information on when the products were purchased and whether they contained a label indicating that the product meets requirements for a California flammability standard were recorded. When possible, we identified the flame retardants being used and their concentrations in the foam. Foam samples collected from 101 commonly used baby products were analyzed. Eighty samples contained an identifiable flame retardant additive, and all but one of these was either chlorinated or brominated. The most common flame retardant detected was tris(1,3-dichloroisopropyl) phosphate (TDCPP; detection frequency 36%), followed by components typically found in the Firemaster550 commercial mixture (detection frequency 17%). Five samples contained PBDE congeners commonly associated with PentaBDE, suggesting products with PentaBDE are still in-use. Two chlorinated organophosphate flame retardants (OPFRs) not previously documented in the environment were also identified, one of which is commercially sold as V6 (detection frequency 15%) and contains tris(2-chloroethyl) phosphate (TCEP) as an impurity. As an addition to this study, we used a portable X-ray fluorescence (XRF) analyzer to estimate the bromine and chlorine content of the foam and investigate whether XRF is a useful method for predicting the presence of halogenated flame retardant additives in these products. A significant correlation was observed for bromine; however, there was no significant relationship observed for chlorine. To the authors knowledge, this is the first study to report on flame retardants in baby products. In addition, we have identified two chlorinated OPFRs not previously documented in the environment or in consumer products. Based on exposure estimates conducted by the Consumer Product Safety Commission (CPSC), we predict that infants may receive greater exposure to TDCPP from these products compared to the average child or adult from upholstered furniture, all of which are higher than acceptable daily intake levels of TDCPP set by the CPSC. Future studies are therefore warranted to specifically measure infants exposure to these flame retardants from intimate contact with these products and to determine if there are any associated health concerns.

Emerging pollutants in the North Sea in comparison to Lake Ontario, Canada, data

In the present study, the concentrations and fate of contaminants such as organophosphate flame retardants and plasticizers, musk compounds such as galaxolide (HHCB), tonalide (AHTN), musk ketone and musk xylene, the bactericide triclosan, as well as the metabolites HHCB-lactone and triclosan-methyl were compared in the aqueous phase of the German Bight (North Sea). The concentrations of these compounds were around 1 to 10 ng/L in nearshore areas, and the concentrations were lower in the more pristine areas. The highest concentrations were determined for tris-(2-chloro-isopropyl) phosphate in the North Sea with concentration exceeding 10 ng/L even for the offshore samples. The samples contained 1 to 20 ng/L chlorinated organophosphates, approximately 1 ng/L nonchlorinated organophosphates, and 0.3 to 3 ng/L fragrance compounds. Some samples from Lake Ontario (Canada) were analyzed in comparison. Per capita emissions were calculated for both regions. These emissions were compared and turned out to be very similar for the Canadian and German locations. For the North Sea, some observations concerning stability, dilution, and degradation, as well as sources of the respective substances, were performed. These data indicate that the chlorinated organophosphates and some musk fragrances exhibit half lives exceeding the residence times and thus can be considered to be persistent in this ecosystem. In the German Bight, the river Elbe is the dominating source for the more hydrophilic compounds, such as chlorinated organophosphate flame retardants, which are diluted only into the North Sea. However, for the more lipophilic compounds such as the musk fragrances, different input patterns as well as distribution patterns are relevant, though the river Elbe is still a major source of pollution to the German Bight of the North Sea. The data seem to indicate either relevant inputs further west of the sampling area or mobilization from the sediments.

Supercritical fluid extraction and chromatography—mass spectrometry of flame retardants from polyurethane foams

Four chlorinated organophosphate flame retardants present in polyurethane foams were analysed by supercritical fluid chromatography with flame-ionization detection and mass spectrometry. In addition, their amenability to gas chromatography was investigated. Real samples were analysed by using these techniques after on-line extraction with supercritical carbon dioxide. On-line quantitative extraction of the flame retardants from the polyurethane foams was investigated by using an external calibration.