S.H. Brandsma

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.

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.

Towards development of a rapid and effective non-destructive testing strategy to identify brominated flame retardants in the plastics of consumer products.

Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants (BFRs) once extensively used in the plastics of a wide range of consumer products. The listing of certain congeners that are constituents of commercial PBDE mixtures (including c-octaBDE) in the Stockholm Convention and tightening regulation of many other BFRs in recent years have created the need for a rapid and effective method of identifying BFR-containing plastics. A three-tiered testing strategy comparing results from non-destructive testing (X-ray fluorescence (XRF)) (n=1714), a surface wipe test (n=137) and destructive chemical analysis (n=48) was undertaken to systematically identify BFRs in a wide range of consumer products. XRF rapidly identified bromine in 92% of products later confirmed to contain BFRs. Surface wipes of products identified tetrabromobisphenol A (TBBPA), c-octaBDE congeners and BDE-209 with relatively high accuracy (>75%) when confirmed by destructive chemical analysis. A relationship between the amounts of BFRs detected in surface wipes and subsequent destructive testing shows promise in predicting not only the types of BFRs present but also estimating the concentrations present. Information about the types of products that may contain persistent BFRs will assist regulators in implementing policies to further reduce the occurrence of these chemicals in consumer products.

Dust Measurement of Two Organophosphorus Flame Retardants, Resorcinol Bis(diphenylphosphate) (RBDPP) and Bisphenol A Bis(diphenylphosphate) (BPA-BDPP), Used as Alternatives for BDE-209

Resorcinol bis(diphenylphosphate) (RBDPP) and bisphenol A bis(diphenylphosphate) (BPA-BDPP) are two halogen-free organophosphorus flame retardant (PFRs) that are used as an alternative for the decabromodiphenyl ether (Deca-BDE) technical mixture in TV/flatscreen housing and other electronic consumer products. In this study, dust samples were collected from various microenvironments in The Netherlands (houses, cars), Greece (houses), and Sweden (apartments, cars, furniture stores, electronics stores) and analyzed for RBDPP and BPA-BDPP. Additionally, the dust samples from The Netherlands were analyzed for decabromodiphenyl ether (BDE-209) for comparison and for TPHP, which is a byproduct in the RBDPP and BPA-BDPP technical products. BPA-BDPP was detected in almost all dust samples from The Netherlands, Greece, and Sweden. Highest concentrations were found in dust samples collected on electronic equipment from all three countries with BPA-BDPP levels ranging from <0.1 to 1300 μg/g and RBDPP levels from <0.04 to 520 μg/g. RBDPP and BPA-BDPP levels in dust collected further away from the electronics (source) were usually lower. BDE-209 levels in The Netherlands dust samples collected on and around the electronics were similar and much lower than the BPA-BDPP/RBDPP levels, indicating that the electronics were not the source of BDE-209. Strong positive correlations were found between TPHP concentrations and those of RBDPP (r = 0.805) and BPA-BDPP (r = 0.924), probably due to TPHP being a byproduct in commercial RBDPP and BPA-BDPP mixtures in electronics. To our knowledge, this is the first time that RBDPP and BPA-BDPP were detected in dust samples from Europe.

Dietary exposure of rainbow trout to 8:2 and 10:2 fluorotelomer alcohols and perfluorooctanesulfonamide: Uptake, transformation and elimination

The bioaccumulation of perfluorooctanesulfonamide (PFOSA) and two fluorotelomer alcohols (8:2 FTOH, 10:2 FTOH) by rainbow trout (Oncorhynchus mykiss) through dietary exposure, including depuration rates and metabolism was investigated. Concentrations in the spiked feed ranged from 10.9 μg g⁻¹ wet weight (wet wt) for PFOSA and 6.7 μg g⁻¹ wet wt for 8:2 FTOH to 5.0 μg g⁻¹ wet wt for 10:2 FTOH. Trout was fed at 1.5% body weight per day for 30 d and depuration was followed for up to 30 d following previously published dietary exposure protocols. Perfluorooctanesulfonate (PFOS) was the major perfluoroalkylsulfonate (PFSA) detected in fish following dietary exposure to PFOSA. Half-lives of PFOS and PFOSA were 16.9 ± 2.5 and 6.0 ± 0.4 d, respectively. A biomagnification factor (BMF) of 0.023 was calculated for PFOSA which indicates that dietary exposure to PFOSA does not result in biomagnification in the rainbow trout. PFOS had a BMF of 0.08. The fluorotelomer saturated acids (8:2 FTCA, 10:2 FTCA) and fluorotelomer unsaturated acids (8:2 FTUCA, 10:2 FTUCA) were the major products detected in rainbow trout following dietary exposure to 8:2 FTOH and 10:2 FTOH, respectively. Half-lives were 3.7 ± 0.4, 2.1 ± 0.5, 3.3, and 1.3 d for 10:2 FTCA, 10:2 FTUCA, 8:2 FTCA, and 8:2 FTUCA, respectively. Small amounts of perfluorooctanoate (PFOA) and perfluorodecanoate (PFDA) were also detected in the FTOH exposed fish.

Polybrominated diphenyl ether contamination levels in fish from the Antarctic and the Mediterranean Sea

Polybrominated diphenyl ethers (PBDEs) concentrations and congener profiles were evaluated in four species of Antarctic fish (Chionodraco hamatus, Chaempsocephalus gunnari, Gymnoscopelus nicholsi,Trematomus eulepidotes) and in one Mediterranean species (Tuna, Thunnus thynnus). The GC/MS-ECNI analysis revealed that average sigmaPBDE concentrations in Antarctic fish species ranged from 0.09 ng g(-1)wet weight (wet wt) in G. nicholsi to 0.44 ng g(-1)wet wt in C. gunnari. In Mediterranean tuna they were two or three orders of magnitude higher (15 ng g(-1)wet wt). The PBDE congener profiles differed between species; low brominated congeners prevailed in Antarctic species while in tuna tetra- and pentabromodiphenyl ethers were the most abundant congener groups (41% and 44%, respectively). These results showed that PBDE levels significantly correlated with the length of the fishes (r(2)=0.85, p<0.01) in C. hamatus, but not with the weight of the fish. Moreover, mean sigmaPBDE concentrations in tuna were statistically higher in females than in males (18 and 13 ng g(-1)wet wt, respectively; p<0.05), which was explained by the lower fat contents of the males that just had entered the spawning period. The results of this study confirm that PBDE contamination of the marine environment now occurs on a global scale.

Analysis of two alternative organophosphorus flame retardants in electronic and plastic consumer products: Resorcinol bis-(diphenylphosphate) (PBDPP) and bisphenol A bis (diphenylphosphate) (BPA-BDPP)

Following the phase-out of polybrominated diphenyl ethers (PBDEs), organophosphorus flame retardants (PFRs) are increasingly used as alternative flame retardants in many products. Data on the presence of two alternative PFRs in consumer products, resorcinol bis (diphenylphosphate) (PBDPP or RDP) and bisphenol A bis (diphenylphosphate) (BPA-BDPP or BDP) is still scarce or non-existing. In this study we propose a simple extraction method and analysis by liquid chromatography-atmospheric pressure chemical ionization (APCI) coupled to a high resolution time-of-flight mass spectrometry (TOF) for plastic consumer products. Detection limits were low enough for trace quantitation in plastic or electronic samples (0.001% and 0.002% w/w for PBDPP and BPA-BDPP, respectively). The APCI source provided better sensitivity and matrix effects than the commonly used ESI source for the analysis of these PFRs. Both PBDPP and BPA-BDPP were detected in 7 of the 12 products purchased in 2012 (at 0.002-0.3% w/w for PBDPP and 0.02-0.18% w/w for BPA-BDPP) while only PBDPP was found in 4 of the 13 products purchased before 2006 (0.005-7.8% w/w). In newly purchased products, PBDPP, BPA-BDPP and triphenyl phosphate (TPHP) were the most frequently detected PFRs. These results support the recent findings of our research group about high concentration levels of PBDPP and BPA-BDPP up to 0.5-1 mg g(-1) in house dust collected on electronic equipment and highlights the need for further research on these two novel PFRs.

Perfluoroalkyl compounds in relation to life‐history and reproductive parameters in bottlenose dolphins (Tursiops truncatus) from Sarasota Bay, Florida, USA

Perfluoroalkyl compounds (PFCs) were determined in plasma, milk, and urine of free-ranging bottlenose dolphins (Tursiops truncatus) from Sarasota Bay (FL, USA) during three winter and two summer capture-and-release programs (2002-2005). Plasma and urine samples were extracted using an ion-pairing method. Perfluoroalkyl compounds were extracted from milk samples using acetonitrile, and extracts were cleaned with graphitized nonporous carbon. All extracts were analyzed by high-performance liquid chromatography-tandem mass spectrometry. Mean seasonal sum of PFCs (sigma PFCs) detected in dolphin plasma ranged from 530 to 927 ng/g wet weight. No significant differences (p > 0.05) were found in concentrations between seasons, suggesting a constant exposure to PFCs. Overall, blubber thickness of dolphins did not correlate with PFC concentrations in plasma, suggesting an absence of PFC sequestration in blubber. Sexually immature calves (age, <10 years; mean sigma PFCs, 1,410 +/- 780 ng/ g wet wt) were significantly more contaminated (p < 0.001) than their mothers (mean sigma PFCs, 366 +/- 351 ng/g wet wt). The reproductive history of females had a significant role in the burden of PFC contamination; PFC concentrations in nulliparous females (females that have not been observed with calves) were significantly greater than those detected in uniparous females (females that have been observed with one calf), suggesting an off-loading of PFCs during or after parturition. To investigate this hypothesis, PFCs were analyzed in milk samples (n=10; mean sigma PFCs, 134 +/- 76.1 ng/g wet wt), confirming a maternal transfer of PFCs through lactation in dolphins. Results from the present study showed that young and developing bottlenose dolphins are highly exposed to PFCs. These chemicals also were detected in urine (mean sigma PFCs, 26.6 +/- 79 ng/g wet wt), indicating that the urinary system is an important pathway of PFC depuration in dolphins.

Wastewater analysis of Census day samples to investigate per capita input of organophosphorus flame retardants and plasticizers into wastewater

The use of organophosphate esters (PFRs) as flame retardants and plasticizers has increased due to the ban of some brominated flame retardants. There is however some concern regarding the toxicity, particularly carcinogenicity and neurotoxicity, of some of the PFRs. In this study we applied wastewater analysis to assess use of PFRs by the Australian population. Influent samples were collected from eleven wastewater treatment plants (STPs) in Australia on Census day and analysed for PFRs using gas chromatography coupled with mass spectrometry (GC-MS). Per capita mass loads of PFRs were calculated using the accurate Census head counts. The results indicate that tris(2-butoxyethyl) phosphate (TBOEP) has the highest per capita input into wastewater followed by tris(2-chloroisopropyl) phosphate (TCIPP), tris(isobutyl) phosphate (TIBP), tris(2-chloroethyl) phosphate (TCEP) and tris(1,3-dichloroisopropyl) phosphate (TDCIPP). Similar PFR profiles were observed across the Australian STPs and a comparison with European and U.S. STPs indicated similar PFR concentrations. We estimate that approximately 2.1 mg person(-1) day(-1) of PFRs are input into Australian wastewater which equates to 16 tonnes per annum.

Flame retardants: Dust – And not food – Might be the risk

Flame retardants (FRs) are used to delay ignition of materials such as furniture and electric and electronic instruments. Many FRs are persistent and end up in the environment. Environmental studies on flame retardants (FRs) took off in the late 1990s. Polybrominated diphenylethers (PBDEs) appeared to be bioaccumulative and were found in many organisms all over the world. When PBDEs were banned or their production voluntarily terminated, alternatives appeared on the market that often had similar properties or were of more concern due to their toxicity such as halogenated phosphorus-based FRs. Here we show that in spite of the ban on PBDEs more brominated FRs are being produced, an increasing number of other FRs is being applied and FR levels in our homes are much higher than in the outdoor environment. While nowadays we live in better isolated houses and sit in front of the computer or television, on flame retarded upholstery, we are at risk due to the toxic effects of a suite of FRs. The high exposure to these substances indoors calls for better risk assessments that include mixture effects.