Organophosphorus flame retardants in the European eel in Flanders, Belgium: Occurrence, fate and human health risk.

The present study investigated the levels, profiles and human health risk of organophosphorus flame retardants and plasticizers (PFRs) in wild European eels (Anguilla anguilla) from freshwater bodies in the highly populated and industrial Flanders region (Belgium). Yellow eels (n=170) were collected at 26 locations between 2000 and 2009 and for each site, muscle samples of 3-10 eels were pooled and analyzed (n=26). Muscle lipid percentages varied widely between 2.4% and 21%, with a median value of 10%. PFRs were detected in all pooled samples in the order of tris-2-chloroisopropyl phosphate (TCIPP)>triphenyl phosphate (TPHP)>2-ethylhexyl diphenyl phosphate (EHDPHP)>tris-2-butoxyethyl phosphate (TBOEP)>tris-2-chloroethyl phosphate (TCEP)>tris-1,3-dichloro-2-propyl phosphate (TDCIPP). The median sum PFR concentration for all 26 sites was 44 ng/g lw (8.4 ng/g ww), and levels ranged between 7.0 and 330 ng/g lw (3.5 and 45 ng/g ww). Levels and profiles of PFRs in eels showed that sampling locations and river basin catchments are possible drivers of spatial variation in the aquatic environment. Median PFR concentrations were lower than those of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs). No correlation was observed between the PFR concentrations and lipid contents, suggesting that the accumulation of PFRs is not primarily associated with lipids. Human exposure to PFRs, due to consumption of wild eels, seems to be of minor importance compared to other potential sources, such as inhalation and ingestion of indoor dust. Nevertheless, considering the very limited data available on PFRs in human dietary items and their expected increasing use after the phase out of PBDEs and HBCDs, further investigations on PFRs in biota and human food items are warranted.

Malarvannan G ，Belpaire C ，Geeraerts C ，Eulaers I ，Neels H ，Covaci A ... -  《-》

Tracing organophosphorus and brominated flame retardants and plasticizers in an estuarine food web.

Nine organophosphorus flame retardants (PFRs) were detected in a pelagic and benthic food web of the Western Scheldt estuary, The Netherlands. Concentrations of several PFRs were an order of magnitude higher than those of the brominated flame retardants (BFRs). However, the detection frequency of the PFRs (6-56%) was lower than that of the BFRs (50-97%). Tris(2-butoxyethyl) phosphate (TBOEP), tris(isobutyl) phosphate (TIBP) and tris(2-chloroisopropyl) phosphate (TCIPP) were the dominant PFRs in sediment with median concentrations of 7.0, 8.1 and 1.8 ng/g dry weight (dw), respectively. PFR levels in the suspended particular matter (SPM) were 2-12 times higher than that in sediment. TBOEP, TCIPP, TIBP, tris(2-chloroethyl) phosphate (TCEP) and tris(phenyl) phosphate (TPHP) were found in organisms higher in the estuarine food web. The highest PFR concentrations in the benthic food web were found in sculpin, goby and lugworm with median concentrations of 17, 7.4, 4.6 and 2.0 ng/g wet weight (ww) for TBOEP, TIBP, TCIPP and TPHP, respectively. Comparable levels were observed in the pelagic food web, BDE209 was the predominant PBDE in sediment and SPM with median concentrations up to 9.7 and 385 ng/g dw, respectively. BDE47 was predominant in the biotic compartment of the food web with highest median levels observed in sculpin and common tern eggs of 79 ng/g lipid weight (lw) (2.5 ng/g ww) and 80 ng/g lw (11 ng/g ww), respectively. Trophic magnification was observed for all PBDEs with the exception of BDE209. Indications of trophic magnification of PFRs were observed in the benthic food web for TBOEP, TCIPP and TCEP with tentative trophic magnification factors of 3.5, 2.2 and 2.6, respectively (p<0.05). Most of the other PFRs showed trophic dilution in both food webs. The relative high PFR levels in several fish species suggest high emissions and substantial exposure of organisms to PFRs in the Western Scheldt.

Brandsma SH ，Leonards PE ，Leslie HA ，de Boer J ... -  《-》

Dietary intake of phosphorus flame retardants (PFRs) using Swedish food market basket estimations.

The occurrence of eight phosphorus flame retardants (PFRs) was investigated in 53 composite food samples from 12 food categories, collected in 2015 for a Swedish food market basket study. 2-ethylhexyl diphenyl phosphate (EHDPHP), detected in most food categories, had the highest median concentrations (9 ng/g ww, pastries). It was followed by triphenyl phosphate (TPHP) (2.6 ng/g ww, fats/oils), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) (1.0 ng/g ww, fats/oils), tris(2-chloroethyl) phosphate (TCEP) (1.0 ng/g ww, fats/oils), and tris(1-chloro-2-propyl) phosphate (TCIPP) (0.80 ng/g ww, pastries). Tris(2-ethylhexyl) phosphate (TEHP), tri-n-butyl phosphate (TNBP), and tris(2-butoxyethyl) phosphate (TBOEP) were not detected in the analyzed food samples. The major contributor to the total dietary intake was EHDPHP (57%), and the food categories which contributed the most to the total intake of PFRs were processed food, such as cereals (26%), pastries (10%), sugar/sweets (11%), and beverages (17%). The daily per capita intake of PFRs (TCEP, TPHP, EHDPHP, TDCIPP, TCIPP) from food ranged from 406 to 3266 ng/day (or 6-49 ng/kg bw/day), lower than the health-based reference doses. This is the first study reporting PFR intakes from other food categories than fish (here accounting for 3%). Our results suggest that the estimated human dietary exposure to PFRs may be equally important to the ingestion of dust.

Poma G ，Glynn A ，Malarvannan G ，Covaci A ，Darnerud PO ... -  《-》

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 《-》

Exposure assessment of organophosphorus and organobromine flame retardants via indoor dust from elementary schools and domestic houses.

To assess the exposure of flame retardants (FRs) for school-children, organophosphorus flame retardants and plasticizers (PFRs) and organobromine flame retardants (BFRs) were determined in the indoor dust samples collected from elementary schools and domestic houses in Japan in 2009 and 2010. PFRs were detected in all the dust samples analyzed and the highest concentration of total PFRs was thousand-fold higher than that of BFRs. Among the PFRs, tris(butoxyethyl)phosphate (TBOEP) showed the highest concentration with a median (med.) of 270,000 ng g(-1) dry weight (3700-5,500,000 ng g(-1) dry weight), followed by tris(methylphenyl)phosphate (TMPPs)>triphenyl phosphate (TPHP)=tris(1,3-dichloro-2-propyl)phosphate (TDCIPP)=tris(2-chloroisopropyl)phosphate (TCIPP)=tris(2chloroethyl)phosphate (TCEP)>ethylhexyl diphenyl phosphate (EHDPP). Significantly higher concentrations of TBOEP, tri-n-butyl phosphate (TNBP), TPHP, TMPPs, and total-PFRs were found in dust samples from elementary schools than from domestic houses. It might be due to that higher concentrations of TBOEP (as leveling agent) were detected from the floor polisher/wax products collected in those elementary schools. On the other hand, significantly higher concentrations of TCEP, TCIPPs, and total chloroalkyl-PFRs were found in domestic houses than in elementary schools. Exposure assessments of PFRs via indoor dust from elementary schools and domestic houses were conducted by calculating the hazard quotient (HQ). Among PFRs, HQs for TBOEP exceeded 1 (higher than reference dose: RfD) and its highest value was 1.9. To reduce the intake of TBOEP by school-children, it is recommended that the use of floor polisher/wax containing TBOEP be reduced in schools.

Mizouchi S ，Ichiba M ，Takigami H ，Kajiwara N ，Takamuku T ，Miyajima T ，Kodama H ，Someya T ，Ueno D ... -  《-》