Alin C. Dirtu

After the PBDE Phase-Out: A Broad Suite of Flame Retardants in Repeat House Dust Samples from California

Higher house dust levels of PBDE flame retardants (FRs) have been reported in California than other parts of the world, due to the state’s furniture flammability standard. However, changing levels of these and other FRs have not been evaluated following the 2004 U.S. phase-out of PentaBDE and OctaBDE. We analyzed dust collected in 16 California homes in 2006 and again in 2011 for 62 FRs and organohalogens, which represents the broadest investigation of FRs in homes. Fifty-five compounds were detected in at least one sample; 41 in at least 50% of samples. Concentrations of chlorinated OPFRs, including two (TCEP and TDCIPP) listed as carcinogens under California’s Proposition 65, were found up to 0.01% in dust, higher than previously reported in the U.S. In 75% of the homes, we detected TDBPP, or brominated “Tris,” which was banned in children’s sleepwear because of carcinogenicity. To our knowledge, this is the first report on TDBPP in house dust. Concentrations of Firemaster 550 components (EH-TBB, BEH-TEBP, and TPHP) were higher in 2011 than 2006, consistent with its use as a PentaBDE replacement. Results highlight the evolving nature of FR exposures and suggest that manufacturers continue to use hazardous chemicals and replace chemicals of concern with chemicals with uncharacterized toxicity.

Analytical developments and preliminary assessment of human exposure to organophosphate flame retardants from indoor dust

A new and efficient analytical method was developed and validated for the analysis of organophosphorus flame retardants (OPFRs) in indoor dust samples. This method involves an extraction step by ultrasonication and vortex, followed by extract clean-up with Florisil solid-phase extraction cartridges and analysis of the purified extracts by gas chromatography-mass spectrometry (GC-MS). Method recoveries ranged between 76 and 127%, except for volatile OPFRs, such as triethyl phosphate (TEP) and tri-(n-propyl) phosphate (TnPP), which were partially lost during evaporation steps. The between day precision on spiked dust samples was <14% for individual OPFRs, except for TEP, tri-iso-butyl phosphate (TiBP) and tri (2-butoxyethyl) phosphate (TBEP). Method limit of quantifications (LOQ) ranged between 0.02 μg/g (TnPP and tris(1-chloro-2-propyl phosphate (TCPP)) and 0.50 μg/g (TiBP). The method was further applied for the analysis of indoor dust samples taken from Flemish homes and stores. TiBP, TBEP and TCPP were most abundant OPFR with median concentrations of 2.99, 2.03 and 1.38 μg/g in house dust and of 1.04, 3.61, and 2.94 μg/g in store dust, respectively. The concentration of all OPFRs was at least 20 to 30 times higher compared to polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs). Estimated exposure to OPFRs from dust ingestion ranged for individual OPFRs between <1 and 50 ng/kg body weight for adults and toddlers, respectively. The estimated body burdens were 1000 to 100 times below reference dose (RfD) values, except for the scenario with high dust ingestion and high concentrations of TBEP in toddlers, where intake was only 5 times below RfD. Exposure of non-working and working adults to OPFRs appeared to be similar, but in specific work environments, exposure to some OPFRs (e.g. TDCPP) was increased by a factor >5.

Occurrence of alternative flame retardants in indoor dust from New Zealand: Indoor sources and human exposure assessment

Due to worldwide restrictions on polybrominated diphenyl ethers (PBDEs), the demand for alternative flame retardants (AFRs), such as organophosphate flame retardants (OPFRs), novel brominated FRs (NBFRs) and hexabromocyclododecanes (HBCDs), has recently increased. Little is known about human exposure to NBFRs and OPFRs and that their levels in dust have been scarcely evaluated worldwide. To increase the knowledge regarding these chemicals, we measured concentrations of five major NBFRs, ten OPFRs and three HBCD isomers in indoor dust from New Zealand homes. Dust samples were taken from living room floors (n=34) and from mattresses of the same houses (n=16). Concentrations (ngg(-1)) of NBFRs were: 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) (<2-175), decabromodiphenyl ethane (DBDPE) (<5-1430), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) (<2-2285) and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH) (<2-640). For OPFRs, concentrations (ngg(-1)) ranged between: tri-ethyl-phosphate (TEP) (<10-235), tri-n-butyl-phosphate (TnBP) (<20-7545), tris-(2-chloroethyl)-phosphate (TCEP) (<20-7605), tris-(1-chloro-2-propyl) phosphate (TCPP) (20-7615), tri-(2-butoxyethyl)-phosphate (TBEP) (50-27325), tris-(2,3-dichloropropyl)-phosphate (TDCPP) (20-16560), tri-phenyl-phosphate (TPhP) (20-35190), and tri-cresyl-phosphate (TCP) (<50-3760). HBCD concentrations fell in the range <2-4100ngg(-1). BTBPE, DBDPE, TBPH, TBEP, and TnBP showed significant positive correlation (p<0.05) between their concentrations in mattresses and the corresponding floor dust (n=16). These data were used to derive a range of plausible exposure scenarios. Although the estimated exposure is well below the corresponding reference doses (RfDs), caution is needed given the likely future increase in use of these FRs and the currently unknown contribution to human exposure by other pathways such as inhalation and diet.

Multi-residue method for the determination of brominated and organophosphate flame retardants in indoor dust

A new method was optimized for the simultaneous determination of several flame retardants (FRs) in indoor dust, namely polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), novel brominated flame retardants (NBFRs) and organophosphate ester flame retardants (OPFRs). The method was based on two previously validated analytical methods for NBFRs and OPFRs, which were combined in order to include even a large number of FRs. An ultrasonic extraction method and two-stage clean-up by adsorption chromatography was optimized using an indoor dust standard reference material (SRM 2584). The 1st cleanup step was essential for fractionation of analytes in the dust extracts, while the 2nd step was important for the further removal of interferences. Analysis of cleaned dust extracts was performed with gas chromatography electron impact ionization mass spectrometry for OPFRs, gas chromatography electron capture negative ionization mass spectrometry for PBDEs and NBFRs and liquid chromatography electrospray ionization tandem mass spectrometry for HBCDs. Method validation by matrix spiking demonstrated good accuracy ranging from 81 to 130%. Matrix effects were investigated by spiking sodium sulfate and dust with analyte standards. Typical recoveries ranged between 80 and 110% at both spiking levels, though occasional deviations were observed at low spiking concentrations. Precision between different days was generally below 24% relative standard deviation (RSD) at low concentrations and below 11% RSD at high concentrations. Method limits of quantification for BFRs ranged between 0.04 (BDE 28) and 17 ng/g (BDE 209), 6 ng/g for sum HBCDs, and for OPFRs between 10 (triphenyl phosphate) and 370 ng/g (tri-isobutyl phosphate). The method was applied to SRM 2585 and to a set of indoor dust samples from various countries. The newly developed method will be employed for the monitoring of human exposure via dust ingestion to phased-out and alternate FRs.

Levels and profiles of organochlorines and flame retardants in car and house dust from Kuwait and Pakistan: implication for human exposure via dust ingestion.

There are only few studies documenting indoor pollution in the Middle East and the Indian subcontinent. In present study, we have evaluated the occurrence of various organochlorines (OCs) and flame retardants (FRs) in dust from cars and houses of Pakistan and Kuwait. Polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), organophosphate FRs (PFRs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) were investigated in indoor dust from urban houses (N=15 per country) and cars (N=15 per country). PFRs were the major analytes in all four microenvironments, followed by PBDEs>NBFRs>OCPs>PCBs. For all classes of analytes, relatively lower levels were observed in car and house dust from Pakistan than Kuwait. Levels of ∑PBDEs, ∑NBFRs and ∑PFRs were higher in car dust, while ∑OCPs and ∑PCBs were higher in house dust from both countries. ∑PFRs occurred at average concentrations of 16,900, 87,900, 475, and 2500ng/g in Kuwaiti house and car, and Pakistani house and car dust, respectively. For both countries, the profiles of analytes in car dust were different from those in the house dust. Different exposure scenarios using 5th percentile, median, mean, and 95th percentile levels were estimated for adult, taxi drivers and toddlers. For Kuwaiti toddlers, assuming high dust intake and mean and 95th percentile concentrations, the values computed for ∑OCPs (1500ng/kg bw/day) were higher than RfD values, while for ∑PCBs (14.5ng/kg bw/day) it was only two-fold lower than the corresponding RfDs.

Inter-species differences for polychlorinated biphenyls and polybrominated diphenyl ethers in marine top predators from the Southern north Sea: Part 1. Accumulation patterns in harbour seals and harbour porpoises

Harbour porpoises (Phocoena phocoena) and harbour seals (Phoca vitulina) are two representative top predator species of the North Sea ecosystem. The median values of sum of 21 polychlorinated biphenyl (PCB) congeners and sum of 10 polybrominated diphenyl ether (PBDE) congeners were 23.1 microg/g lipid weight (lw) and 0.33 microg/g lw in blubber of harbour seals (n=28) and 12.4 microg/g lw and 0.76 microg/g lw in blubber of harbour porpoises (n=35), respectively. For both species, the highest PCB concentrations were observed in adult males indicating bioaccumulation. On the contrary, the highest PBDE concentrations were measured in juveniles, likely due to better-developed metabolic capacities with age in adults. A higher contribution of lower chlorinated and non-persistent congeners, such as CB 52, CB 95, CB 101, and CB 149, together with higher contributions of other PBDE congeners than BDE 47, indicated that harbour porpoises are unable to metabolize these compounds. Harbour seals showed a higher ability to metabolize PCBs and PBDEs.

Country specific comparison for profile of chlorinated, brominated and phosphate organic contaminants in indoor dust. Case study for Eastern Romania, 2010

We have evaluated the levels and specific profiles of several organohalogenated contaminants, including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and flame retardants (FRs), such as polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), novel brominated FRs (NBFRs), and organophosphate FRs (OPFRs), in 47 indoor dust samples collected in 2010 from urban locations from Iasi, Eastern Romania. The dominant contaminants found in the samples were OPFRs (median sum OPFRs 7890 ng/g). Surprisingly, OCPs were also measured at high levels (median 1300 ng/g). Except for BDE 209 (median 275 ng/g), PBDEs were present in dust samples at relatively low levels (median sum PBDEs 8 ng/g). PCBs were also measured at low levels (median sum PCBs 35 ng/g), while NBFRs were only occasionally detected, showing a low usage in goods present on the Romanian market. The results of the present study evidence the existence of a multitude of chemical formulations in indoor dust. FRs are usually associated to human exposure via ingestion of dust, but other chemicals, such as OCPs, are not commonly reported in such matrix. Although OCPs were found at comparable levels with OPFRs in Romanian dust, OCPs possess a higher risk to human health due to their considerably lower reference dose (RfD) values. Indeed, the OCP exposure calculated for various intake scenarios was only 2-fold lower than the corresponding RfD. Therefore, the inclusion of OCPs as target chemicals in the indoor environment becomes important for countries where elevated levels in other environmental compartments have been previously shown.

Brominated flame retardants and polychlorinated biphenyls in fish from the river Scheldt, Belgium.

Levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and polychlorinated biphenyls (PCBs) were measured in several fish species originating from the river Scheldt (Belgium). Five sampling locations were chosen in a highly industrialized area along the river, while two ponds in the vicinity of the river served as reference sites. The present study is a follow-up of a survey performed in 2000 which reported extremely high levels of PBDEs and HBCDs in eel (Anguilla anguilla) collected from the same region (Oudenaarde, Flanders). The sum of tri- to hepta-BDE congeners (2270+/-2260 ng/g lipid weight (lw), range 660-11500 ng/g lw) and total HBCDs (4500+/-3000 ng/g lw, range 390-12100 ng/g lw) were one order of magnitude higher than levels usually reported from freshwater systems, indicating the presence of point sources. In most samples, levels of total HBCDs were higher than those of PBDEs, probably due to the high density of factories using HBCD as an additive brominated flame retardant (BFR). The high values of HBCDs were confirmed by both gas- and liquid-chromatography-mass spectrometry. Although BFR levels were between the highest ever reported in freshwater ecosystems, PCBs could be detected at even higher concentrations (16000+/-14300 ng/g lw, range 3900-66600 ng/g lw), being among the highest levels recorded in Belgium. The inter-sampling site variation of PBDEs, HBCDs and PCBs was comparable. All locations presented similar PBDE congener profiles, with BDE 47 being the dominant congener, followed by BDE 100, BDE 99 and BDE 49, probably originating from the former use of the penta-BDE technical mixture. In order to estimate the impact of these point sources on human exposure, we further focussed on eels which showed a considerable decrease in the PBDE and HBCD levels between 2000 and 2006. Due to the wide span in concentrations between the different sampling locations, a variable contribution to the total human exposure through local eel consumption was estimated. The calculated daily intake ranged from 3 ng to 330 ng PBDEs/day for normal eel consumers, but was as high as 9800 ng PBDEs/day for anglers, which may be considered at risk.

Anthropogenic and naturally-produced organobrominated compounds in marine mammals from Brazil

Liver samples from 51 cetaceans, comprising 10 species, stranded between 1994 and 2006 in a highly industrialized and urbanized region in Southeast Brazil, were analyzed for polybrominated diphenyl ethers (PBDEs) and methoxylated-PBDEs (MeO-PBDEs). A concentration range of PBDEs (3-5960ng/g lw) similar to that observed in Northern Hemisphere dolphins was found. MeO-PBDE concentrations in continental shelf (CS) dolphins from Brazil are among the highest detected to date in cetaceans (up to 250microg/g lw). Higher SigmaMeO-PBDE concentrations were measured in CS and oceanic dolphins than in estuarine dolphins. The SigmaPBDE/SigmaMeO-PBDE ratio varied significantly ranging from a mean value of 7.12 to 0.08 and 0.01 for estuarine, CS and oceanic species, respectively. A positive correlation was observed between SigmaPBDE and year of stranding of male estuarine dolphins (Sotalia guianensis), which suggests temporal variation in the exposure. Placental transfer of organobrominated compounds was also evidenced in S. guianensis.

Persistent organic pollutants (POPs) in human milk: A biomonitoring study in rural areas of Flanders (Belgium)

To collect information on the concentrations of persistent organic pollutants (POPs) in the rural areas in Flanders (Belgium), 84 breastfeeding mothers were recruited in rural communities in East and West Flanders and Flemish Brabant in 2009-2010. Polychlorinated biphenyl (PCB) congeners, organochlorine pesticides, brominated flame retardants, perfluorinated compounds, polychlorinated dibenzodioxines and dibenzofurans, and dioxin-like PCBs were measured in individual milk samples and in a pooled milk sample, while some additional pollutants were only measured in the pooled sample. For most pollutants, the concentrations in this study were lower or comparable to the concentrations measured in the pooled Belgian sample of the WHO human milk study of 2006, except for the pesticides dichlorodiphenyltrichloroethane DDT (+25% for ΣDDT and metabolites) and trans-nonachlor (+94%), and for the brominated flame retardant hexachlorocyclododecane HBCD (+153%). Perfluorinated compounds were for the first time determined in human milk samples from Belgium and the concentrations were comparable to those from other European countries. Also, interesting associations were found between the concentrations of POPs measured in human milk and personal characteristics as well as dietary habits of the study population. PFOS en PFOA concentrations were significantly higher in milk of primiparous participants compared to mothers who gave birth to their second child. Lower brominated PBDE congeners increased with increasing BMI of the mothers (p=0.01 for BDE 47, p=0.02 for BDE 99 and p=0.02 for BDE 100). Participants consuming milk or dairy products daily had significant higher concentrations of ΣDDTs (p=0.03) and oxychlordane (p=0.047) in their human milk samples.