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 ... -  《-》

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 ... -  《-》

Legacy and alternative flame retardants in Norwegian and UK indoor environment: Implications of human exposure via dust ingestion.

Indoor dust has been acknowledged as a major source of flame retardants (FRs) and dust ingestion is considered a major route of exposure for humans. In the present study, we investigated the presence of PBDEs and alternative FRs such as emerging halogenated FRs (EHFRs) and organophosphate flame retardants (PFRs) in indoor dust samples from British and Norwegian houses as well as British stores and offices. BDE209 was the most abundant PBDE congener with median concentrations of 4700ngg-1 and 3400ngg-1 in UK occupational and house dust, respectively, 30 and 20 fold higher than in Norwegian house dust. Monomeric PFRs (m-PFRs), including triphenyl phosphate (TPHP), tris(chloropropyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) dominated all the studied environments. To the best of our knowledge, this is the first report of isodecyldiphenyl phosphate (iDPP) and trixylenyl phosphate (TXP) in indoor environments. iDPP was the most abundant oligomeric PFR (o-PFR) in all dust samples, with median concentrations one order of magnitude higher than TXP and bisphenol A bis(diphenyl phosphate (BDP). iDPP and TXP worst-case scenario exposures for British workers during an 8h exposure in the occupational environment were equal to 34 and 1.4ngkgbw-1day-1, respectively. The worst-case scenario for BDE209 estimated exposure for British toddlers (820ngkgbw-1day-1) did not exceeded the proposed reference dose (RfD) (7000ngkgbw-1day-1), while exposures for sum of m-PFRs (Σm-PFRs) in British toddlers and adults (17,900 and 785ngkgbw-1day-1 respectively) were an order of magnitude higher than for Norwegian toddlers and adults (1600 and 70ngkgbw-1day-1).

Kademoglou K ，Xu F ，Padilla-Sanchez JA ，Haug LS ，Covaci A ，Collins CD ... -  《-》

Phosphorus flame retardants: properties, production, environmental occurrence, toxicity and analysis.

Since the ban on some brominated flame retardants (BFRs), phosphorus flame retardants (PFRs), which were responsible for 20% of the flame retardant (FR) consumption in 2006 in Europe, are often proposed as alternatives for BFRs. PFRs can be divided in three main groups, inorganic, organic and halogen containing PFRs. Most of the PFRs have a mechanism of action in the solid phase of burning materials (char formation), but some may also be active in the gas phase. Some PFRs are reactive FRs, which means they are chemically bound to a polymer, whereas others are additive and mixed into the polymer. The focus of this report is limited to the PFRs mentioned in the literature as potential substitutes for BFRs. The physico-chemical properties, applications and production volumes of PFRs are given. Non-halogenated PFRs are often used as plasticisers as well. Limited information is available on the occurrence of PFRs in the environment. For triphenyl phosphate (TPhP), tricresylphosphate (TCP), tris(2-chloroethyl)phosphate (TCEP), tris(chloropropyl)phosphate (TCPP), tris(1,3-dichloro-2-propyl)phosphate (TDCPP), and tetrekis(2-chlorethyl)dichloroisopentyldiphosphate (V6) a number of studies have been performed on their occurrence in air, water and sediment, but limited data were found on their occurrence in biota. Concentrations found for these PFRs in air were up to 47 μg m(-3), in sediment levels up to 24 mg kg(-1) were found, and in surface water concentrations up to 379 ng L(-1). In all these matrices TCPP was dominant. Concentrations found in dust were up to 67 mg kg(-1), with TDCPP being the dominant PFR. PFR concentrations reported were often higher than polybrominated diphenylether (PBDE) concentrations, and the human exposure due to PFR concentrations in indoor air appears to be higher than exposure due to PBDE concentrations in indoor air. Only the Cl-containing PFRs are carcinogenic. Other negative human health effects were found for Cl-containing PFRs as well as for TCP, which suggest that those PFRs would not be suitable alternatives for BFRs. TPhP, diphenylcresylphosphate (DCP) and TCP would not be suitable alternatives either, because they are considered to be toxic to (aquatic) organisms. Diethylphosphinic acid is, just like TCEP, considered to be very persistent. From an environmental perspective, resorcinol-bis(diphenylphosphate) (RDP), bisphenol-A diphenyl phosphate (BADP) and melamine polyphosphate, may be suitable good substitutes for BFRs. Information on PFR analysis in air, water and sediment is limited to TCEP, TCPP, TPhP, TCP and some other organophosphate esters. For air sampling passive samplers have been used as well as solid phase extraction (SPE) membranes, SPE cartridges, and solid phase micro-extraction (SPME). For extraction of PFRs from water SPE is recommended, because this method gives good recoveries (67-105%) and acceptable relative standard deviations (RSDs) (<20%), and offers the option of on-line coupling with a detection system. For the extraction of PFRs from sediment microwave-assisted extraction (MAE) is recommended. The recoveries (78-105%) and RSDs (3-8%) are good and the method is faster and requires less solvent compared to other methods. For the final instrumental analysis of PFRs, gas chromatography-flame photometric detection (GC-FPD), GC-nitrogen-phosphorus detection (NPD), GC-atomic emission detection (AED), GC-mass spectrometry (MS) as well as liquid chromatography (LC)-MS/MS and GC-Inductively-coupled plasma-MS (ICP-MS) are used. GC-ICP-MS is a promising method, because it provides much less complex chromatograms while offering the same recoveries and limits of detection (LOD) (instrumental LOD is 5-10 ng mL(-1)) compared to GC-NPD and GC-MS, which are frequently used methods for PFR analysis. GC-MS offers a higher selectivity than GC-NPD and the possibility of using isotopically labeled compounds for quantification.

van der Veen I ，de Boer J 《-》

Organophosphorus flame retardants (PFRs) and plasticizers in house and car dust and the influence of electronic equipment.

All nine PFRs studied were detected in house and car dust from the Netherlands with the exception of tris(butyl) phosphate (TNBP) and tris(isobutyl) phosphate (TIBP) in car dust. Tris(2-butoxyethyl) phosphate (TBOEP, median 22 μg g(-1)) was dominant in house dust collected around and on electronics followed by tris(2-chloroisopropyl) phosphate (TCIPP, median 1.3 μg g(-1)), tris(2-chloroethyl) phosphate (TCEP, median 1.3 μg g(-1)) and tris(phenyl) phosphate (TPHP, median 0.8 μg g(-1)). Levels of TPHP and tris(methylphenyl) phosphate (TMPP, also known as TCP) in house dust on electronics were significantly higher than in house dust collected around electronics, suggesting that electronic equipment has limited contribution to the PFR levels in house dust, with the exception of TPHP and TMPP. Car dust was dominated by tris(1,3-dichloroisopropyl) phosphate (TDCIPP) with the highest levels found in dust collected from the car seats (1100 μg g(-1)). The mean TDCIPP and TCIPP levels observed in car dust were significantly higher than the levels observed in dust collected around electronics. Significantly higher mean TMPP levels in dust taken from car seats were found compared to dust collected around the equipment (p<0.05). This is probably influenced by the use of TDCIPP, TCIPP in polyurethane foam (car seats) and the use of TMPP as plasticizer in car interiors. Worldwide four PFR patterns were observed in house dust. The PFR pattern in the Netherlands of TDCIPP, TMPP, TCEP, TCIPP and TPHP in house dust is comparable to the pattern found in six other countries, which may point to identical sources of these PFRs in the indoor environment. However, the PFR levels between the countries and within countries showed high variation.

Brandsma SH ，de Boer J ，van Velzen MJ ，Leonards PE ... -  《-》