Exposure to brominated and organophosphate ester flame retardants in U.S. childcare environments: Effect of removal of flame-retarded nap mats on indoor levels.

We assessed exposure to 39 brominated and 16 organophosphate ester flame retardants (FRs) from both dust and indoor air at seven childcare centres in Seattle, USA, and investigated the importance of nap mats as a source of these chemicals. Many childcare centres serving young children use polyurethane foam mats for the children's naptime. Until recently, the vast majority of these mats sold in the United States contained flame-retarded polyurethane foam to meet California Technical Bulletin 117 (TB117) requirements. With the 2013 update of TB117, allowing manufacturers to meet flammability standards without adding FRs to filling materials, FR-free nap mats have become widely available. We conducted an intervention study by actively switching out FR-treated nap mats with FR-free nap mats and measuring FR levels in indoor air and dust before and after the switch-out. The predominant FRs found in dust and indoor air were 2-ethylhexyl tetrabromobenzoate (EHTBB) and tris(1-chloro-2-propyl) phosphate (TCIPP), respectively. Nap mat samples analysed from four of the six centres contained a Firemaster® mixture, while one mat was predominantly treated with tris(1,3-dichloroisopropyl) phosphate (TDCIPP) and the other contained no detectable target FRs. After replacement, there was a significant decrease (p = 0.03-0.09) in median dust concentrations for bis(2-ethylhexyl) tetrabromophthalate (BEHTBP), EHTBB, tris(4-butylphenyl) phosphate (TBPP), and TDCIPP with reductions of 90%, 79%, 65%, and 42%, respectively. These findings suggest that the nap mats were an important source of these FRs to dust in the investigated childcare environments and that a campaign of swapping out flame-retarded mats for FR-free ones would reduce exposure to these chemicals. While calculated exposure estimates to the investigated FRs via inhalation, dust ingestion, and dermal absorption were below established reference dose values, they are likely underestimated when considering the toddlers' direct contact to the mats and personal cloud effects.

Stubbings WA ，Schreder ED ，Thomas MB ，Romanak K ，Venier M ，Salamova A ... -  《-》

Halogenated flame-retardant concentrations in settled dust, respirable and inhalable particulates and polyurethane foam at gymnastic training facilities and residences.

Halogenated flame-retardants (FRs) are used in a wide array of polymer-containing products. Animal studies and structure-activity modeling exercises suggest that FR exposure may result in detrimental toxicological effects. Workers with extended contact with such polymers (e.g., electronic dismantlers, carpet installers and aircraft personnel) have previously been observed to exhibit elevated body burdens of FRs, e.g., polybrominated diphenyl ethers (PBDEs). Recently, elevated PBDE blood levels were also reported in a non-occupational exposure group, gymnasts. These levels were hypothesized to be related to the large volumes of FR-treated polyurethane foam in gymnastics facilities. To further our understanding of workers' potential exposure, we analyzed FR concentrations in indoor dust and size-fractionated air particulates (respirable (<4 μm) and inhalable (>4 μm)) from gymnastic studios. Values were compared to samples from the homes of coaches employed at these facilities. Polyurethane foam blocks (i.e., pit foam) were also analyzed to characterize potential FR sources. FRs examined included those used to flame-retard polyurethane foam: 8 PBDE congeners, two brominated components of Firemaster 550 (2-ethylhexyl 2, 3, 4, 5-tetrabromobenzoate (TBB) and bis(2-ethylhexyl) 3, 4, 5, 6-tetrabromophthalate (TBPH)) and three chlorinated organophosphates (tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP) and tris(1,3-dichloro-2-propyl) phosphate (TDCPP)). Several additional FRs not used in polyurethane were also evaluated. These have also been detected in indoor dust and air and may also lead to adverse health effects. These include: BDE-183 and its replacement product (1, 2-bis(2, 4, 6-tribromophenoxy) ethane (BTBPE), two congeners of the deca-BDE formulation (BDE-206, -209) and their replacement decabromodiphenyl ethane (DBDPE) and hexabromocyclododecane (α-, β-, γ-HBCD), and tetrabromobisphenol-A (TBBPA)). Pit foam contained multiple FRs at cumulative concentrations of 12,100 to 25,800 μg g(-1), or 1.2% to 2.6% by weight. TBB and TBPH were the most abundant FRs detected, followed by TDCPP and several PBDEs. The mean total FR burden detected at the gyms was 8.6-fold higher (574 μg g(-1)) than that observed in the house dust samples (66.8 μg g(-1)). However, the polyurethane additives TBB and TDCPP were the only FRs that exhibited significantly greater levels (P<0.05) in gym than house dust. Mean levels of five FRs (BDE-99, -100, -153, -209 and TDCPP) were also higher in respirable particulates from the gyms than the homes and four FRs (BDE-47, TBB, TBPH and DBDPE) were higher at the homes than the gyms; these differences were not significant (P>0.05). Several additional FRs were detected in inhalable particulates; mean levels of BDE-66, -206 and TCPP were higher in the homes and BDE-47, -85, -99, -100, -153, -209, TBB, TBPH, and TDCPP were higher at the gyms. But, only the polyurethane additives i.e., BDE-100, TBB and TDCPP were significantly greater (P<0.05) in inhalable particulates from the gyms than at the homes. In conclusion, polyurethane foam collected from gymnastic studios exhibited a variety of FR compositional signatures; likely reflective of changes in FR usage over time and by different manufacturers. FR concentrations and compositional signatures also differed between settled dust, respirable and inhalable particulates between the gyms and homes. Concentrations of FRs used in polyurethane foam were higher in gym air and dust compared to homes, particularly TBB and TDCPP - which were also the primary FRs detected in the pit foam samples. Although these results should be interpreted with caution, as the sample size was small, these findings do suggest that FR concentrations observed in dust and air particulates from the gymnastic studios are further evidence that individuals frequenting these environments are at greater risk for exposure to these polymer additives.

La Guardia MJ ，Hale RC 《-》

Occurrence and human exposure to brominated and organophosphorus flame retardants via indoor dust in a Brazilian city.

Indoor dust is considered an important human exposure route to flame retardants (FRs), which has arised concern due the toxic properties of some of these substances. In this study, ten organophosphorus flame retardants (OPFRs), eight polybrominated diphenyl ethers (PBDEs) and four new brominated flame retardants (NBFRs) were determined in indoor dust from different places in Araraquara-SP (Brazil). The sampled places included houses, apartments, offices, primary schools and cars. The analysis of the sample extracts was performed by gas chromatography coupled to mass spectrometry and two ionization techniques were used (electron ionization - EI; electron capture negative ionization - ECNI). OPFRs were the most abundant compounds and tris(2-butoxyethyl) phosphate (TBOEP), tris(phenyl) phosphate (TPHP), tris(1,3-dichloroisopropyl) phosphate (TDCIPP) and tris(2-chloroisopropyl) phosphate (TCIPP) were present at the highest concentrations. Among the brominated FRs, the most ubiquitous compounds were BDE-209, bis(2-ethylhexyl) tetrabromophthalate (BEH-TEBP) and decabromodiphenyl ethane (DBDPE). Statistical analysis revealed that there were differences among dust typologies for TBOEP, TDCIPP, ethylhexyl diphenyl phosphate (EHDPHP), BDE-209, 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (EH-TBB), BEH-TEBP and DBDPE, which were attributed to different construction materials in each particular environment and to the age of the buildings. The highest levels of brominated FRs were observed in offices, TBOEP was at high concentration in primary schools, and TDCIPP was at high concentration in cars. A preliminary risk assessment revealed that toddlers were exposed to TBOEP levels higher than the reference dose when considering the worst case scenario. The results obtained in this study showed for the first time that although Brazil does not regulate the use of FRs, these substances are present in indoor dust at levels similar to the observed in countries that have strict fire safety standards, and that humans are exposed to complex mixtures of these contaminants via indoor dust.

Cristale J ，Aragão Belé TG ，Lacorte S ，Rodrigues de Marchi MR ... -  《-》

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.

Brits M ，Brandsma SH ，Rohwer ER ，De Vos J ，Weiss JM ，de Boer J ... -  《-》

Legacy and emerging organophosphοrus flame retardants in car dust from Greece: Implications for human exposure.

Organophosphorus flame retardants (PFRs) and emerging PFRs (ePFRs) are two groups of compounds used as replacements for brominated flame retardants (BFRs). They have already been detected in indoor dust (mainly in homes and offices). To date, few studies investigated the occurrence of FRs in car dust and the information of possible health risks is still limited. The present study reports on the investigation of the levels and profiles of eight target PFRs: tris(2-ethylhexyl) phosphate (TEHP), tris(2-chloroethyl) phosphate (TCEP), tris(2-butoxyethyl) phosphate (TBEP), triphenyl phosphate (TPHP), 2-ethylhexyl diphenyl phosphate (EHDPHP), tris(1-chloro-2-propyl) phosphate (TCIPP), tri cresyl phosphate (TCP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and four target ePFRs; 2,2-bis(chloromethyl)propane-1,3-diyltetrakis(2-chloroethyl)bisphosphate (V6), isodecyl diphenyl phosphate (iDDPHP), resorcinol bis(diphenylphosphate) (RDP) and bisphenol A-bis(diphenyl phosphate) (BDP) in car dust from Greece. The samples were collected from the interior of 25 private cars in Thessaloniki, Greece, with different years of manufacture (1997-2015) and continents of origin. After ultrasonic extraction and Florisil fractionation, the PFR analysis was carried out by GC-EI/MS, whereas the ePFRs were analyzed by LC-MS/MS. Levels of Σ8PFRs varied from 2000 to 190,000 ng g-1, with mean and median concentrations of 20,000 and 11,500 ng g-1, respectively. The concentrations of Σ4ePFRs ranged from 44 to 8700 ng g-1, with mean and median values at 1100 and 190 ng g-1, respectively. Estimations of human exposure showed that toddlers are more exposed than adults to both PFRs and ePFRs. Yet, the intake via dust ingestion and dermal absorption was several orders of magnitude lower than the corresponding reference doses.

Christia C ，Poma G ，Besis A ，Samara C ，Covaci A ... -  《-》