Organohalogen compounds of emerging concern in Baltic Sea biota: Levels, biomagnification potential and comparisons with legacy contaminants.

While new chemicals have replaced major toxic legacy contaminants such as polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDT), knowledge of their current levels and biomagnification potential in Baltic Sea biota is lacking. Therefore, a suite of chemicals of emerging concern, including organophosphate esters (OPEs), short-chain, medium-chain and long-chain chlorinated paraffins (SCCPs, MCCPs, LCCPs), halogenated flame retardants (HFRs), and per- and polyfluoroalkyl substances (PFAS), were analysed in blue mussel (Mytilus edulis), viviparous eelpout (Zoarces viviparus), Atlantic herring (Clupea harengus), grey seal (Halichoerus grypus), harbor seal (Phoca vitulina), harbor porpoise (Phocoena phocoena), common eider (Somateria mollissima), common guillemot (Uria aalge) and white-tailed eagle (Haliaeetus albicilla) from the Baltic Proper, sampled between 2006 and 2016. Results were benchmarked with existing data for legacy contaminants. The mean concentrations for ΣOPEs ranged from 57 to 550 ng g-1 lipid weight (lw), for ΣCPs from 110 to 640 ng g-1 lw for ΣHFRs from 0.42 to 80 ng g-1 lw, and for ΣPFAS from 1.1 to 450 ng g-1 wet weight. Perfluoro-4-ethylcyclohexanesulfonate (PFECHS) was detected in most species. Levels of OPEs, CPs and HFRs were generally similar or higher than those of polybrominated diphenyl ethers (PBDEs) and/or hexabromocyclododecane (HBCDD). OPE, CP and HFR concentrations were also similar to PCBs and DDTs in blue mussel, viviparous eelpout and Atlantic herring. In marine mammals and birds, PCB and DDT concentrations remained orders of magnitude higher than those of OPEs, CPs, HFRs and PFAS. Predator-prey ratios for individual OPEs (0.28-3.9) and CPs (0.40-5.0) were similar or somewhat lower than those seen for BDE-47 (5.0-29) and HBCDD (2.4-13). Ratios for individual HFRs (0.010-37) and PFAS (0.15-47) were, however, of the same order of magnitude as seen for p,p'-DDE (4.7-66) and CB-153 (31-190), indicating biomagnification potential for many of the emerging contaminants. Lack of toxicity data, including for complex mixtures, makes it difficult to assess the risks emerging contaminants pose. Their occurence and biomagnification potential should trigger risk management measures, particularly for MCCPs, HFRs and PFAS.

Serum concentrations of legacy and emerging halogenated flame retardants in a Norwegian cohort: Relationship to external exposure.

Sixty-one serum samples from a Norwegian cohort were analyzed for 43 emerging and legacy halogenated flame retardants (HFRs). BDE-47, -153, -197 and -209 were detected in >56% of the samples with median concentrations of 0.23, 1.0, 0.64 and 1.5 ng/g lipid, respectively. BDE-49, -85, -99, -100, -154, -206, -207, -208 as well as HBB, syn- and anti-DDC-CO, OBTMPI, DBDPE, α-HBCDD and TBBPA were also detected in some serum samples (detection frequencies of 2-36%). Other tri-octaBDEs, TBP-AE, α- and ß-DBE-DBCH, BATE, pTBX, αß-TBCO, PBBz, TBCT, PBT, PBEB, DPTE, EH-TBB, BTBPE, BEH-TEBP, HCDBCO, ß- and γ-HBCDD were below the limits of detection (mLOD). Concentrations of individual BDE congeners detected in this study were within the range from previous European studies. Positive correlations were seen between concentrations of BDE-47 in dust and BDE-153 in serum, between BDE-153 in dust and BDE-153 in serum, and between BDE-153 masses in handwipes and BDE-47 concentrations in serum (Spearman's rank, 0.29 < r < 0.43). Associations between the number of phones/mobiles, numbers of electronic equipment per person in the home and the consumption of specific food categories (such as soups/spices/sauces and alcoholic beverages) with BDE-47 and -153 serum levels were confirmed by multivariate linear regression analyses. The measured median serum level of BDE-47 was slightly over-predicted by a factor of 5.5 whereas other BDE congeners were under-predicted by factors of 13-6000 when compared to serum concentrations predicted from external exposure media (inhalation, dermal uptake, dietary intake from duplicate diet and dust ingestion) using a simple one compartment pharmacokinetic (PK) model. BDE-153 was not detected and BDE-197 not analyzed in food so no dietary intake assessments for these could be made, which may partially explain the discrepancies between their measured and predicted serum concentrations. Overall, our results suggest that exposure via diet is the most important exposure pathway for BDE-47 and -209, with diet being responsible for more than 96% of the total daily intake of these two BDEs in the Norwegian cohort.

Mass balance study of brominated flame retardants in female captive peregrine falcons.

Little is known about brominated flame retardant (BFR) dynamics in birds, especially large molecules such as decabromodiphenyl ether (BDE-209). In particular, bioaccumulation from food and transfer dynamics to eggs are poorly understood. Therefore, an input-output mass balance study of tri-decaBDEs, DBDPE and HBCDD was performed in three female peregrine falcons from a captive breeding program by analyzing their naturally contaminated food (quail, chicken (cockerels)), plasma, feces and eggs. Predominant BFRs in cockerels and quail were BDE-209 and DBDPE, as well as HBCDD in quail. The predominant BFRs found in falcon plasma were BDE-209, -153 and -183, in eggs, HBCDD, BDE-209 and -153 and in feces, BDE-209. Mean absorption efficiencies (AE) for the tetra-octabrominated BDEs ranged from 84-100% and 70% for HBCDD. The AEs for BDE-206, -207, -208 and -209 varied due to the large variability seen for feces fluxes. All egg/plasma ratios for BDEs were similar and greater than one (range 1.1-2.7), including for BDE-209, indicating efficient transfer from females to the eggs. Excretion via egg-laying was approximately 6.0-29% of the initial, pre-breeding body burden of individual penta-decaBDE congeners, (15-45% for BDE-206). HBCDD was not detected in plasma but was found in eggs, also indicating efficient transfer and excretion via eggs. Input fluxes from food exceeded the output fluxes (feces, eggs) indicating considerable metabolism for tetra-octaBDEs, possibly also for the nona-decaBDEs and HBCDD. Bioaccumulation factors calculated from lipid weight concentrations in plasma and food (BAFp) were highest for BDE-208 (31), -153 (23), -209 (19) and -207 (16) and from eggs and food (BAFe), were highest for HBCDD (140), BDE-153 (41), -208 (42), BDE-207 (24) and BDE-209 (21). BAFe and BAFp values were below 10 for BDE-47, -99 and -100. For one falcon, egg results were available from three different years and estimated half-lives were 65 d (BDE-99), 624 d (BDE-153), 31 d (BDE-154), 349 d (BDE-183), 77 d (BDE-196) and 89 d (BDE-197).

Organohalogenated Flame Retardants and Organophosphate Esters in Office Air and Dust from Sweden.

A wide range of organohalogenated flame retardants (HFRs) and organophosphate esters (OPEs) were measured in air and floor dust from 10 offices in Stockholm, Sweden. Concentrations of ∑18 emerging HFRs, ∑21 legacy HFRs and ∑11 OPEs from the offices were found to be 420, 510, and 1600000 ng/g, respectively, in floor dust and 400, 15, and 160 000 pg/m3 respectively in active air samples. All targeted compounds were detected in dust except 2,3,5,6-tetrabromo- p-xylene (pTBX) indicating widespread application of a broad range of FRs in the Swedish offices while only 54% of targeted compounds were detected in indoor air. Estimated ∑OPE exposure in Swedish offices is 3-4 orders of magnitude higher than for ∑emerging HFRs and ∑legacy HFRs via all three different exposure routes in our study. Adult's estimated intakes of emerging and legacy HFRs and OPEs from office air and dust during working hours (30% of a day) are some orders of magnitude lower than the corresponding reference doses (RfD). However, in worst case exposure scenarios (maximum concentrations and high dust intake), the intake of tris(2-butoxyethyl) phosphate (TBOEP) was one-third of its RfD, which may be of potential concern if exposure is as high in other microenvironments.

Assessment of dermal exposure to halogenated flame retardants: Comparison using direct measurements from hand wipes with an indirect estimation from settled dust concentrations.

There are few studies estimating dermal exposure to halogenated flame retardants in adults. To fill this gap, sixty-one hand wipe samples were collected from a Norwegian adult cohort using gauze pads immersed in isopropanol. BDE-47, BDE-209, bis(2­ethyl­hexyl)­3,4,5,6­tetrabromophthalate (BEH-TEBP) and decabromodiphenylethane (DBDPE) were the most frequently detected chemicals. The highest median mass in hand wipes was that of sumEHFR (570 ng), followed by sumHBCDD (180 ng) and sumPBDE (2.9 ng). The high EHFR level was mainly driven by tetrabromobisphenol A (TBBPA) which accounted for 77% of the total mass. Positive and significant correlations were observed between FR levels in hand wipes and settled dust (0.26 < r < 0.56, p < 0.05), as well as between FR levels in hand wipes and the number of electronic consumer products at home (0.27 < r < 0.40, p < 0.05). Significant bivariate associations with number of laptops/tablets and phones/mobiles were further confirmed by multivariate linear regression analyses. Dermal exposure was estimated using the levels measured in handwipes. The estimated median dermal exposure was 2600, 840 and 6.2 pg/kg bw/d for sumEHFR, sumHBCDD and sumPBDE, respectively. Further, we compared these results with the dermal exposure as estimated indirectly by utilizing previously reported FR levels in settled dust collected from the residences of the same studied cohort. With the indirect approach, higher dermal exposures to sumPBDE but lower exposures to sumEHFR and sumHBCDD were observed compared to the direct dermal exposure estimated via hand wipes. Comparable exposure estimates between hand wipes and the indirect method were obtained for α­, ß­tetrabromoethylcyclohexane (DBE-DBCH), DBDPE, BDE-28, -35, -49, -99, -153, 154, and -183. For other individual HFRs, the exposure estimates obtained from the two approaches were significantly different (Mann-Whitney U test, p < 0.05). Both methods gave similar dermal exposure estimates for many individual FRs. However, it is important to be aware of the value and limitations of each method when using them to estimate human exposure.

Brominated Flame Retardants and Organophosphate Esters in Preschool Dust and Children's Hand Wipes.

Children spend a considerable part of their day in preschool, where they may be exposed to hazardous chemicals in indoor dust. In this study, brominated flame retardants (BFRs) and organophosphate esters (OPEs) were analyzed in preschool dust ( n = 100) and children's hand wipe samples ( n = 100), and diphenyl phosphate (DPHP) was analyzed in urine ( n = 113). Here we assessed children's exposure via dust, identified predictors for chemicals in dust, and studied correlations between different exposure measures. The most abundant BFRs in dust were decabromodiphenyl ether (BDE-209) and decabromodiphenyl ethane (DBDPE) found at median levels of 270 and 110 ng/g dust, respectively. Tris(2-butoxyethyl) phosphate (TBOEP) was the most abundant OPE, found at a median level of 79 000 ng/g dust. For all OPEs and some BFRs, there were significant correlations between the levels in dust and hand wipes. In addition, triphenyl phosphate (TPHP) in preschool dust was significantly correlated with the corresponding metabolite DPHP in children's urine. The levels of pentaBDEs in dust were higher in older preschools compared with newer, whereas levels of DBDPE were higher in newer preschools. Children's estimated intakes of individual BFRs and OPEs via preschool dust were below available health-based reference values. However, there are uncertainties about the potential health effects of some emerging BFRs and OPEs.

Human Exposure to Legacy and Emerging Halogenated Flame Retardants via Inhalation and Dust Ingestion in a Norwegian Cohort.

In this study, we estimated human exposure to polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs), and several emerging flame retardants (EFRs) via inhalation and dust ingestion. Sixty indoor stationary air samples, 13 personal air samples, and 60 settled dust samples were collected from a Norwegian cohort during winter 2013. PBDEs showed the highest median concentration in dust (1200 ng/g), followed by EFRs (730 ng/g) and HBCDDs (190 ng/g). The PBDE concentrations in dust were mainly driven by BDE-209 and those of EFRs by bis(2-ethylhexyl) tetrabromophthalate. EFRs predominated in stationary air samples, with 2-ethylhexyl 2,3,4,5-tetrabromobenzoate and 4-(1,2-dibromoethyl)-1,2-dibromocyclohexane having the highest median concentrations (150 and 25 pg/m3 (sum of α- and ß-isomers), respectively). Different profiles and concentrations were observed in personal air samples compared to the corresponding stationary air samples. In relation to inhalation exposure, dust ingestion appears to be the major exposure pathway to FRs (median total exposure 230 pg/kg bw/d, accounting for more than 65% of the total exposure) for the Norwegian cohort. The calculated exposure due to air inhalation was substantially lower when the stationary air concentrations were used rather than personal air concentrations (43 pg/kg bw/d versus 130 pg/kg bw/d). This suggests that other exposure situations (such as outdoors or in offices) contributed significantly to the overall personal exposure, which cannot be included by using only a stationary air sampling technique. The median and 95th percentile exposures for all target FRs did not exceed the reference dose.

Assessment of dietary exposure to organohalogen contaminants, legacy and emerging flame retardants in a Norwegian cohort.

Polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), emerging halogenated flame retardants (EHFRs) and organophosphate flame retardants (PFRs) were detected in 24h duplicate diet samples from a Norwegian cohort (n=61), with concentrations ranging from

Estimated intakes of brominated flame retardants via diet and dust compared to internal concentrations in a Swedish mother-toddler cohort.

Tri-decabrominated diphenyl ethers (tri-decaBDEs), isomer-specific hexabromocyclododecanes (HBCDs) and 14 emerging brominated flame retardants (EBFRs) were determined in Swedish market basket samples, two pooled breast milk samples and house dust collected in homes of first-time mothers. Daily dietary and dust intakes were estimated for the mothers and their toddlers and compared to previously reported levels in serum of both the mothers and toddlers and in feces of the toddlers (n=20). Diet was the main contributor for intake of ΣpentaBDE and α-tetrabromoethylcyclohexane (DBE-DBCH) for both mothers and toddlers. For ΣoctaBDE, ΣHBCD and pentabromobenzene (PBBz), dietary intake was more important for mothers while house dust ingestion was more important for toddlers. House dust was the main exposure route for ΣdecaBDE, decabromodiphenyl ethane (DBDPE), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB), bis(2-ethylhexyl)tetrabromophthalate (BEH-TEBP), bis(2,4,6-tribromophenoxy) ethane (BTBPE) and pentabromotoluene (PBT) for both mothers and toddlers. Significant correlations (Spearmans, α<0.05) were found between the mothers' BDE serum concentrations and their consumption of meat and fish while no correlations were found between BFR dietary intake and serum or feces concentrations in toddlers. Octa-decaBDE congener concentrations in serum and feces of toddlers were significantly correlated to those in house dust. BDE-207 and -208 concentrations in serum of mothers were significantly correlated with the nonaBDEs in house dust. The correlations between house dust and internal concentrations and comparison of the house dust and dietary contributions to the estimated daily intakes suggest that dust exposure plays a larger role for the octa-decaBDE body burden in toddlers than in their mothers.

Emerging flame retardants, PBDEs, and HBCDDs in indoor and outdoor media in Stockholm, Sweden.

Dust, indoor air, outgoing air from ventilation systems, outdoor air, and soil were sampled in and around Stockholm, Sweden during the winter and spring 2012. The concentrations of several emerging flame retardants (EFRs), polybrominated diphenyl ethers (PBDEs), and isomers of hexabromocyclododecane (HBCDD) were measured. The most commonly found EFR was 1,2-dibromo-4-(1,2 dibromoethyl)cyclohexane (TBECH or DBE-DBCH), which was found in nearly all indoor, ventilation, and outdoor air samples, most dust samples, but not in soil samples. Other frequently detected EFRs included pentabromotoluene (PBT), hexabromobenzene (HBB), 2,3,4,5-tetrabromo-ethylhexylbenzoate (EHTBB), 2,3,4,5-tetrabromo-bis(2-ethylhexyl) phthalate (BEH-TEBP), and decabromodiphenyl ethane (DBDPE). PBDE concentrations were significantly lower in air and dust samples compared to a previous study in Stockholm. In outdoor air, DBE-DBCH, PBT, EHTBB, DBDPE, and PBDEs showed an "urban pulse" with concentrations increasing as samples were taken in more urban areas compared to rural areas. These EFRs show similar environmental behavior as PBDEs. Higher brominated BDEs showed this same urban pulse in soil but lower brominated BDEs did not. Air-soil fugacity fractions were calculated, and these indicated that most compounds are undergoing net deposition from atmosphere to soil, with the higher brominated PBDEs furthest from equilibrium.

Feasibility study of feces for noninvasive biomonitoring of brominated flame retardants in toddlers.

This study investigated the feasibility of using feces as a noninvasive matrix to estimate serum concentrations of brominated flame retardants (BFRs) in toddlers for biomonitoring purposes. Tri- to decabrominated diphenyl ethers (tri-decaBDEs), isomer-specific hexabromocyclododecanes, and 16 emerging BFRs were determined in feces from 22 toddlers (11-15 months of age), and results were compared to previously analyzed matched serum samples. BDE-47, -153, -196, -197, -203, -206, -207, -208, and -209 were detected in the feces creating a matched data set (feces-serum, n = 21). Tetra-octaBDE concentrations were significantly higher (Student's paired comparisons t test, α = 0.05) in serum versus feces with BDE-153 having the highest mean difference between the sample matrices. BDE-209 was found in significantly higher concentrations in feces compared to serum. Significant correlations (Pearson's, α = 0.05) between congener-specific concentrations in feces and serum were found for all BDEs except BDE-197 and -203. The feces-serum associations found can be used to estimate serum concentrations of tetra-decaBDEs from feces concentrations and enable a noninvasive sampling method for biomonitoring BDEs in toddlers.

Brominated flame retardants in matched serum samples from Swedish first-time mothers and their toddlers.

Tri-decabrominated diphenyl ethers and 21 other flame retardants were determined in matched serum samples from 24 Swedish mothers (Uppsala county) and their toddlers (11-15 months of age). The median concentrations of individual polybrominated diphenyl ethers (PBDEs) ranged from 0.036 to 0.95 ng/g lipid in mothers and from 0.057 to 1.5 ng/g lipid in toddlers. BDE-209 was detected in all but one sample. BDE-153 was the predominant congener in the mothers while in toddlers, BDE-209 was found in the highest concentrations. The levels of BDE-47, -100, -207, -208, and -209 in toddlers were significantly higher (p < 0.05) than those in their mothers. Dechlorane Plus (anti- and syn-) and α- and ß-tetrabromoethylcyclohexane were detected in a few (2-4) serum samples from both mothers and toddlers. This study also reports concentrations of α-HBCD and eight emerging brominated flame retardants (EBFRs) in the standard reference material serum (SRM 1958, NIST). Lack of correlations between the matched serum samples indicate different exposure routes for octa-decaBDEs in mothers versus toddlers. Congener-to-congener correlations within the mother or toddler cohorts suggest diet as an important exposure pathway for tetra-nonaBDEs for mothers, breastfeeding as a predominant exposure pathway for tetra-hexaBDEs, and dust for octa-decaBDEs for toddlers.

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.

Clean-up method for determination of established and emerging brominated flame retardants in dust.

A clean-up method was developed to enable the determination of tri-decabrominated diphenyl ethers, isomer-specific hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), (2-ethylhexyl)tetrabromobenzoate (TBB), and bis(2-ethylhexyl)tetrabromophthalate (TBPH) in the same dust sample extract using reasonable amounts of solvents and without dividing the sample. After extraction, the sample was separated on a silica column into three fractions that were subsequently cleaned up individually. The polybrominated diphenyl ethers (PBDEs) and DBDPE were eluted in Fraction I, TBB, TBPH, and BTBPE in Fraction II, and HBCDs in Fraction III. Fractions I and II were analyzed using gas chromatography/mass spectrometry and Fraction III using liquid chromatography/mass spectrometry. The method gave good recoveries (60-120%), precise results using (13) C-labelled internal standards and was accurate when comparing results to certified values (PBDEs in NIST SRM 2585). The method was applied to dust samples from the Stockholm (Sweden) area. All the emerging brominated flame retardants (BFRs) studied, except BTBPE, were present in all the samples in quantifiable concentrations, often higher than the PBDEs. BTBPE was quantified in only one sample. It is evident that emerging BFRs are present in Swedish homes, and these compounds should be included in the BFR analyses of indoor environments.

Indoor air is a significant source of tri-decabrominated diphenyl ethers to outdoor air via ventilation systems.

Ventilation of indoor air has been hypothesized to be a source of PBDEs to outdoors. To study this, tri-decabrominated diphenyl ethers were analyzed in outgoing air samples collected inside ventilation systems just before exiting 33 buildings and compared to indoor air samples from microenvironments in each building collected simultaneously. Median ∑(10)PBDE (BDE- 28, -47, -99, -153, -183, -197, -206, -207, -208, -209) concentrations in air from apartment, office and day care center buildings were 93, 3700, and 660 pg/m(3) for outgoing air, and 92, 4700, and 1200 pg/m(3) for indoor air, respectively. BDE-209 was the major congener found. No statistically significant differences were seen for individual PBDE concentrations in matched indoor and outgoing air samples, indicating that outgoing air PBDE concentrations are equivalent to indoor air concentrations. PBDE concentrations in indoor and outgoing air were higher than published outdoor air values suggesting ventilation as a conduit of PBDEs, including BDE-209, from indoors to outdoors. BDE-209 and sum of BDE-28, -47, -99, and -153 emissions from indoor air to outdoors were roughly estimated to represent close to 90% of total emissions to outdoor air for Sweden, indicating that contaminated indoor air is an important source of PBDE contamination to outdoor air.

Decabromodiphenyl ethane and decabromodiphenyl ether in Swedish background air.

Decabromodiphenyl ethane (DPDPE) is a flame retardant that has been on the market for more than 20 years and is used as a replacement for decabromodiphenyl ether (BDE-209). Environmental data on DPDPE are scarce but for BDE-209, studies have shown that long-range transport in the atmosphere leads to contamination of remote regions. Given their similar physical-chemical properties, we hypothesized that this is also true for DPDPE. In this study we explored the European continent as a source for DBDPE by collecting air samples at a back-ground location in southern Sweden. Twelve samples with stable air mass back trajectories over the 24 h sampling period were analysed. BDE-209 and 5 polycyclic aromatic hydrocarbons (PAHs) were also included in the study. The concentration ranges of DBDPE and BDE-209 were similar, 0.077-7.9 and 0.093-1.8 pg m(-3) air, respectively. The highest concentrations were detected when the air originated from the European continent and the lowest during periods with rather stagnant air over southern Scandinavia. The concentrations of DBDPE and BDE-209 did not co-vary, indicating that there are different major sources of the two compounds. In air, the compounds measured in this study are predominantly associated with particles. PAHs in the atmosphere are known to originate primarily from combustion processes and their concentrations were highly correlated with several measures of atmospheric particle concentration, i.e. PM 10, PM 2.5, soot, and N 450 (number of particles in the size range approximately 420-450 nm). No clear correlations were found between the concentrations of DBDPE or BDE-209 and any of the measures of particle concentrations, indicating that the emissions of these are not related to the major sources of emissions of soot or small particles.

Temporal trends of polybrominated diphenyl ethers and hexabromocyclododecane in Swedish Peregrine Falcon (Falco peregrinus peregrinus) eggs.

A temporal trend study of brominated flame retardants in eggs from peregrine falcon (Falco peregrinus peregrinus), a terrestrial bird of prey, is presented. Eggs collected between 1974 and 2007 were analyzed for the major constituents of the Penta-, Octa- and Decabromodiphenyl ether technical products (BDE-47, -99, -100, -153, -183 and -209), and hexabromocyclododecane (HBCD). Concentrations of BDE-99, -100, -153, -183, -209 and HBCD increased from 1974 to 2000. After the early 2000s, BDE-99, -100, -153 and -183 concentrations decreased, whereas BDE-209 and HBCD concentrations continued to increase. No temporal trend was detected for BDE-47. Rates of increase also differed, with BDE-99 and -100 increasing 3-fold between the 1980s and mid-1990s, and BDE-153 and -183 increasing approximately 10-fold during the same period. The average yearly increase was 15% and 11% for BDE-209 and HBCD, respectively, based on log-linear regression trends. There is a change in BDE congener patterns over time, with a shift from the predominance of BDE-99 and -47 until the late 1980s, to BDE-153 becoming the predominant congener later on. BFR temporal trends in Swedish peregrine falcon eggs reflect European BFR usage patterns.

Environmental analysis of higher brominated diphenyl ethers and decabromodiphenyl ethane.

Methods for environmental analysis of higher brominated diphenyl ethers (PBDEs), in particular decabromodiphenyl ether (BDE209), and the recently discovered environmental contaminant decabromodiphenyl ethane (deBDethane) are reviewed. The extensive literature on analysis of BDE209 has identified several critical issues, including contamination of the sample, degradation of the analyte during sample preparation and GC analysis, and the selection of appropriate detection methods and surrogate standards. The limited experience with the analysis of deBDethane suggests that there are many commonalities with BDE209. The experience garnered from the analysis of BDE209 over the last 15 years will greatly facilitate progress in the analysis of deBDethane.

Polybrominated diphenyl ether congener patterns, hexabromocyclododecane, and brominated biphenyl 153 in eggs of peregrine falcons (Falco peregrinus) breeding in Sweden.

Previous analyses of 52 peregrine falcon (Falco peregrinus) eggs collected from two wild and one captive population in Sweden 1987 through 1999 were complemented by including additional polybrominated diphenyl ether (PBDE) congeners (BDE-35, -183, -184, -185, -196, -197, -203, and -207). In addition, 31 eggs not previously analyzed for hexabromocyclododecane (HBCD) and BDE-209 were analyzed for these. Geometric mean concentrations of BPBDEs, HBCD, and the hexabrominated biphenyl (BB-153) were 3,100, 140, and 81 ng/g of lipid weight for the southern population; 2,500, 110, and 84 ng/g of lipid weight for the northern population; and 47, not detected, and 8 ng/g of lipid weight for the captive population. The BDE congener pattern was dominated by BDE-153, -99, and -100. The results were used to investigate whether a difference in PBDE congener pattern could be distinguished between the two wild populations of peregrine falcons due to different diets, as the southern population preys mainly on birds belonging to the terrestrial food chain while the northern population preys more on aquatic birds. A multivariate t-test showed a subtle but significant (p < 0.001) difference in PBDE congener pattern between the two populations. However, our hypothesis that higher-brominated congeners of PBDEs would be present to a greater extent in the terrestrial food chain was not supported by principal component analysis. The average brood size for individual females from the southern population decreased with increasing concentrations of IPBDE in the eggs (log-linear regression p < 0.01).

Effect of sewage-sludge application on concentrations of higher-brominated diphenyl ethers in soils and earthworms.

Polybrominated diphenyl ethers (PBDEs), including octa-decaBDEs, were found in soil and earthworm samples collected in 2000 from three research stations (reference plots and sewage-sludge-amended plots) and two farms (reference and amended/flooded soils) in Sweden. Sewage-sludge amendment at the research stations increased concentrations of all BDE congeners 2- to 13-fold, with the highest increases for BDE-209. Concentrations 100-to 1000-fold higher were seen in contaminated soils at both farms. BDE-209 was the predominant congener in all soils. sigmaPBDE concentrations in worms ranged from 3.1 to 38 000 ng/g lipid weight and were correlated to soil concentrations, including the octa-decaBDEs. Biota-soil accumulation factors declined in the following order: TeBDE > PeBDE > HxBDE > OcBDE > NoBDE > DeBDE, and ranged from 0.3 to 2 for the octa-decaBDEs. Thus, higher-brominated PBDEs, including BDE-209, are bioavailable from soils and accumulate in earthworms, presenting an exposure pathway into the terrestrial food web. High levels found at one farm 20 years after the last use of PBDEs indicate high persistence of PBDEs in soils, including BDE-209. No evidence of photolytic debromination of BDE-209 in soils was seen.