Hexabromocyclododecane Isomers Research Articles

Occurrence of brominated flame retardants in household and car dust from the Czech Republic

The levels and profiles of 16 polybrominated diphenyl ethers congeners (PBDEs), three isomers of hexabromocyclododecane (HBCD) and other six “alternative” brominated flame retardants (BFRs) in dust collected in 25 Czech households and 27 car interiors were investigated. The Σ16 PBDEs contents varied widely with maximum concentrations reaching up to 5896 and 33728μg/kg in house and car dust, respectively. The highest concentrations of PBDEs were observed for BDE 209, which was found almost in all samples and exceeded concentrations of other PBDEs even by one order of magnitude. The profile and levels of Penta-, Octa-, and DecaBDE obtained within this study were comparable to those presented in other studies worldwide and confirmed lower contamination of dust from Europe compared to North America. From the group of “alternative” BFRs, suitable for commercial applications as an alternative to banned PBDEs, mainly decabromodiphenyl ethane (DBDPE) and HBCD were detected in the concentration ranges <20–3567 and <0.3–950μg/kg, respectively. γ-HBCD was dominating, forming up to 70% of ΣHBCD. Using the measured concentrations and estimates of dust ingestion rates it was estimated that toddlers had a higher exposure than adults for all compounds investigated.

Environmental fate of hexabromocyclododecane from a new Canadian electronic recycling facility

An electronics recycling facility began operation at the municipal landfill site for the City of Edmonton, Canada in March 2008 with the goal of processing 30,000 tonnes of electronic wastes per year. Of the many by-products from the process, brominated fire retardants such as hexabromocyclododecane (HBCD) can evolve off of e-wastes and be released into the environmental media. HBCD has been identified by many countries and international bodies as a chemical of concern because of its ability to bioaccumulate in the ecosystem. An evaluation of the potential emission of HBCD indicates that up to 500 kg per year may be released from a landfill and recycling facility such as that operating in Edmonton. A multimedia fugacity model was used to evaluate the dispersion and fate of atmospherically emitted HBCD traveling into surrounding agricultural land and forested parkland. The model indicates that the three isomers of HBCD partitioned into environmental media similarly. Much of the HBCD is lost through atmospheric advection, but it is also found in soil and sediment. Modeled air concentrations are similar to those measured at locations with a history of e-waste recycling. Since HBCD has been shown to bioaccumulate, the HBCD released from this source has the long-term potential to affect agricultural food crops and the park ecosystem.

Hexabromocyclododecanes in surface sediments and a sediment core from Rivers and Harbor in the northern Chinese city of Tianjin

In the present study, hexabromocyclododecanes (HBCDs) were investigated in the sediment from Haihe River (HR), Dagu Dainage Canal (DDC) and Tianjin Harbor (TH) at Bohai Bay using a total of 51 samples of surface sediments and a sediment core collected from May to September in 2010, and its diastereomer- and enantiomer-specific profiles were analyzed. The concentration of total HBCDs were generally high, with mean value and ranges of 31.0 and 1.35–634ngg−1dw, respectively. The contamination followed the order of TH>DDC>HR. Higher levels (up to 634ngg−1dw) occurred in the lower reach of HR and DDC located in an industrial area of Tianjin. This is the first time to report so high concentration of HBCDs in sediment in Southeast Asia. The γ-diastereomer dominated in most samples (44 out of 51), and this is in agreement with the diastereomer distribution pattern in industrial products, while α-HBCD was the dominant diastereomer in the other seven samples. However, only few samples exhibited γ-diastereomer ratio similar to that (75–89%) in technical products, indicating the inter-transformation and variable degradation of the different isomers. The high ratio of γ-diastereomer could be used as an indicator for fresh contamination input. Enantiomeric factors (EFs) of HBCD isomers in most of the samples were statistically different from technical products (p<0.05), showing a trend of more easily enrichment of the (−)-HBCD-enantiomer compared to the (+)-HBCD-enantiomer. The δ- and ε-diastereomers were frequently detected but at low level. The HBCDs in the sediment core showed several peaks, and the greatest value occurred in 2005, when a plastic manufacture plant using HBCD was set up nearby.

Hexabromocyclododecane in terrestrial passerine birds from e-waste, urban and rural locations in the Pearl River Delta, South China: Levels, biomagnification, diastereoisomer- and enantiomer-specific accumulation

Diastereoisomers and enantiomers of hexabromocyclododecane (HBCD) were determined in muscle and stomach contents of three terrestrial passerine birds from e-waste, urban and rural locations in South China. The highest HBCD concentration was found at the urban site, followed by the e-waste site, suggesting that HBCD was linked to urbanization and industrialization, as well as e-waste recycling activities. Trophic magnification for α-HBCD was observed in the terrestrial food chain. Diastereisomeric pattern in birds showed the predominance of α-isomer, with a minor contribution of γ-isomer. The enantiomeric analysis revealed a preferential enrichment of (−)-α-HBCD and (+)-γ-HBCD. The similarity in enantiomeric fractions of HBCD isomers between muscle and stomach contents of birds suggested that dietary uptake may be responsible for the observed nonracemic distribution of HBCD isomers in the studied birds although in vivo enantioselective biotic processes cannot be ruled out.

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.

Hexabromocyclododecanes (HBCDs) in marine fishes along the Chinese coastline

This study reports concentrations of hexabromocyclododecanes (HBCDs) in two species of marine fish, large yellow croaker (Pseudosciaenacrocea) and silver pomfret (Pampusargenteus) (n=46), from nine Chinese coastal cities (Dalian, Tianjin, Qingdao, Shanghai, Zhoushan, Wenzhou, Fuzhou, Quanzhou and Xiamen). HBCDs were detectable in all samples analyzed, indicating ubiquitous contamination of these compounds in the Chinese coastal environment. The average total HBCD concentration was 3.7ngg−1 lipid weight (range: 0.57–10.1ngg−1 lipid weight), which is relatively lower than other regions of the world, especially Europe, where HBCDs are intensively used. Among the three individual HBCD isomers (α-, β- and γ-HBCD) in all fish samples, the α-isomer showed a remarkable predominance (from 87.5% to 100% of total contribution), indicating its higher bioaccumulative potential. Geographically, the highest HBCD level present in fish was found in Dalian in northern China, and the lowest occurred in Wenzhou. Estimated daily intakes of HBCDs via fish consumption for the Chinese population were 0.004–1.00ngkgbody weight−1d−1. These exposure levels were much lower than the effect levels.

Determinations of hexabromocyclododecane (HBCD) isomers in channel catfish, crayfish, hen eggs and fish feeds from China by isotopic dilution LC–MS/MS

HBCD is widely used brominated flame retardant, which is increasingly reported in the environment. A new isotopic dilution LC–MS/MS method was developed to determine three HBCD isomers, α-, β- and γ-HBCD in channel catfish, crayfish, hen eggs and fish feeds in this study, and especially for the first time HBCD isomers composition in crayfish, hen eggs and fish feeds. Soxhlet extractor and GPC cleanup were used, some important steps and crucial parameters were modified and intensified compared with other literatures, and LC and MS/MS conditions were optimized. The limits of quantitation values of 0.01, 0.005 and 0.005 ng g −1 wet weight in channel catfish and crayfish were calculated for three HBCD isomers, respectively; so did 0.1, 0.05 and 0.05 ng g −1 wet weight in eggs and 0.2, 0.1, 0.1 ng g −1 wet weight in fish feeds. Recoveries of α-HBCD, β-HBCD and γ-HBCD were ranged between 75% and 105% for these productions at medium and high-level spiked samples, and between 60% and 85% at low-level spiked samples. The established methods were therefore suitable for the determinations of three HBCD isomers in these productions at trace contamination levels. Moreover, thirty commercial channel catfish, crayfish, hen eggs and fish feeds samples collected from local markets, and thirty home-produced hen eggs from private owners in Hubei province of China, were analyzed to determine whether these productions were contaminated by HBCD. Using the established methods, HBCD emerged in 4 of 30 fish feeds and 3 of 30 home-produced eggs, and in low-ng g −1 wet weight.

Several current-use, non-PBDE brominated flame retardants are highly bioaccumulative: Evidence from field determined bioaccumulation factors

With the phaseout of brominated flame retardants (BFRs) polybrominated diphenyl ethers (PBDEs), some non-PBDE BFRs have prompted to be alternatives to the discontinued PBDEs. To assess the bioaccumulation potential of these chemicals, field bioaccumulation factors (BAFs) for several non-PBDE BFRs including hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), pentabromotoluene (PBT), pentabromoethylbenzene (PBEB), and hexabromobenzene (HBB), were determined in the aquatic species from a natural pond in an electronic waste recycling site in South China. The log BAFs ranged 2.58–6.01, 3.24–5.58, 3.44–5.98, 2.85–5.98, 3.32–6.08, 2.04–4.77, 2.72–4.09 and 3.31–5.54 for α-HBCD, β-HBCD, γ-HBCD, ∑ HBCDs, BTBPE, PBT, PBEB, and HBB, respectively. The log BAF values for HBCD isomers, BTBPE, and HBB were greater than 3.7 (corresponding BAF value 5000) in most of the investigated species, demonstrating their highly bioaccumulative properties. α-, β-, and γ-HBCDs, BTBPE, and HBB appeared comparable or had even greater BAFs compared to PBDE congeners with similar K OW, suggesting that these BFRs may have a potentially high environmental risk. The BAFs for the given BFR compound were largely variable between species, due to the species-specific feeding ecology, trophic level, and metabolic capacity for these pollutants. Positive linear relationships between log BAF and log K OW ( r 2 = 0.59, p = 0.04), and molecular weight ( r 2 = 0.54, p = 0.06) of non-PBDE BFRs were observed in the species with low trophic level (Chinese mysterysnail), suggesting that the chemical's physicochemical properties also played key roles in the bioaccumulation processes.

Sustained production of Reelin-expressing interneurons in the hippocampal dentate hilus after developmental hypothyroidism in rats

Fire incidents have decreased significantly over the last 20 years due, in part, to regulations requiring addition of flame retardants (FRs) to consumer products. Five major classes of brominated flame retardants (BFRs) are hexabromocyclododecane isomers (HBCDs), tetrabromobisphenol-A (TBBPA) and three commercial mixtures of penta-, octa- and deca-polybrominated diphenyl ether (PBDE) congeners, which are used extensively as commercial FR additives. Furthermore, concentrations of PBDEs have been rapidly increasing during the 1999s in human breast milk and a number of endocrine effects have been reported. We used the H295R human adrenocortical carcinoma cell line to assess possible effects of some of these BFRs (PBDEs and several of their hydroxylated (OH) and methoxylated (CH3O) metabolites or analogues), TBBPA and brominated phenols (BPs) on the combined 17α-hydroxylase and 17,20-lyase activities of CYP17. CYP17 enzyme catalyzes an important step in sex steroidogenesis and is responsible for the biosynthesis of dehydroepiandrosterone (DHEA) and androstenedione in the adrenals. In order to study possible interactions with BFRs, a novel enzymatic method was developed. The precursor substrate of CYP17, pregnenolone, was added to control and exposed H295R cells, and enzymatic production of DHEA was measured using a radioimmunoassay. In order to avoid pregnenolone metabolism via different pathways, specific chemical inhibitor compounds were used. None of the parent/precursor BFRs had a significant effect (P < 0.05) on CYP17 activity except for BDE-183, which showed significant inhibition of CYP17 activity at the highest concentration tested (10 μM), with no signs of cytotoxicity as measured by mitochondrial toxicity tests (MTT). A strong inhibition of CYP17 activity was found for 6-OH-2,2′,4,4′-tetrabromoDE (6-OH-BDE47) with a concentration-dependent decrease of almost 90% at 10 μM, but with a concurrent decrease in cell viability at the higher concentrations. Replacement of the 6-OH group by a 6-CH3O group eliminated this cytotoxic effect, but CYP17 activity measured as DHEA production was still significantly inhibited. Other OH- or CH3O-PBDE analogues were used to elucidate possible structural properties behind this CYP17 inhibition and associated cytotoxicity, but no distinct structure activity relationship could be determined.These in vitro results indicate that OH and CH3O-PBDEs have potential to interfere with CYP17 activity for which the in vivo relevance still has to be adequately determined.

Altered thyroxine metabolism in rainbow trout ( Oncorhynchus mykiss) exposed to hexabromocyclododecane (HBCD)

Hexabromocyclododecane (HBCD) is an additive flame retardant used in consumer and industrial applications. Our earlier work suggested that fish exposed to HBCD exhibited an increase in the rate of turnover of thyroxine (T4), the precursor molecule to the active thyroid hormone triiodothyronine (T3). To examine this further, juvenile rainbow trout were held in the laboratory and fed diets containing environmentally relevant concentrations of the individual α, β or γ isomers. Thirty-two days after feeding began, 20 fish from each group were gavaged with gelatin containing 1 μCi [ 125I]-T4. Uptake of [ 125I]-T4 from the gut was low and recoveries of the initial [ 125I]-T4 were <10% after 2 d and <3% and <2% after 6 and 14 d respectively, with no differences among groups. However, measurements of the labeled T4 in tissues 2, 4, 6 and 14 d after gavage showed that tissue disposition and elimination rates of the hormone were altered by HBCD. In particular, on day 14 after gavage feeding, there was significantly lower radioactivity in the thyroid of fish exposed to the HBCD isomers relative to the reference group. This implies that either there was lower iodide uptake by the gland in fish exposed to HBCD or that the rate of thyroid hormone turnover in HBCD treated fish was elevated. There was also a significantly higher type II outer ring deiodinase enzyme activity in livers of fish exposed to the β and γ isomers. Taken together, these results indicate that HBCD can potentially impact the thyroid system of fish.

Determination of hexabromocyclododecane isomers in sewage sludge by LC‐MS/MS

A method has been developed to determine alpha, beta and gamma diastereoisomers of hexabromocyclododecane (HBCD), a brominated flame retardant, in sewage sludge, based on the ultrasonic-assisted extraction (UAE) of samples with dichloromethane-ACN (1:1) and the subsequent clean-up of extracts by dispersive solid phase extraction with primary-secondary amine. Levels of HBCD diastereoisomers were determined by LC coupled with ESI MS/MS. Evaluation of the matrix effect showed a high ion suppression for all the diastereoisomers studied, which was counteracted by using a mixture of labelled HBCD diastereoisomers as internal standards. This method yielded recoveries in the range of 79.6-112.5% with SDs equal or lower than 9.1 The limits of detection were 0.3 ng/g for alpha- and beta-HBCD and 0.2 ng/g for gamma-HBCD. The developed method was successfully applied to 19 sludge samples collected from the province of Madrid (Spain). In most of the samples, beta-HBCD was below the method detection limit, whereas alpha- and gamma-HBCD were quantified in all of the sludge samples, and gamma-HBCD was the predominant diastereoisomer in 63% of the analyzed samples and alpha-HBCD predominated in the rest.

Exposure to Hexabromocyclododecanes (HBCDs) via Dust Ingestion, but Not Diet, Correlates with Concentrations in Human Serum: Preliminary Results

BackgroundHexabromocyclododecane (HBCD) is a high-production-volume chemical used as flame retardant in polystyrene insulation and textiles. Because it is not chemically bound to the polymer, HBCD can migrate into the environment, contaminating indoor dust and foodstuff.ObjectivesWe examined for the first time the relationship between combined exposure to three HBCD isomers (∑HBCDs) via ingestion of food (duplicate diets) and indoor dust and HBCD concentrations in serum for 16 Belgian adults (20–25 years of age). We also determined the chiral signatures of HBCDs to advance understanding of source-to-human enantioselective degradation and/or metabolism.MethodsConcentrations and chiral signatures of α-, β-, and γ-HBCD in duplicate diets, dust, and serum were measured by liquid chromatography/tandem mass spectrometry.ResultsDietary intakes of ∑HBCDs were 1.2–20 ng/day (average, 7.2 ng/day), whereas those estimated under average (20 mg dust/day) and high (50 mg dust/day) dust ingestion scenarios were 1.1–15 ng/day (average intake, 3.2 ng/day) and 2.8–38 ng/day (average intake, 8.0 ng/day), respectively. Concentrations of ∑HBCDs measured in blood serum were < 0.5 to 11 ng/g lipid weight (lw) (average, 2.9 ng/g lw). γ-HBCD dominated in food, whereas α-HBCD dominated in dust and was the sole isomer in serum. Although exposure via dust ingestion correlated significantly (p < 0.01) with concentrations in serum, no such correlation was evident with dietary exposure (p > 0.1). Although no enantioselective enrichment was detected in either dust or diet, substantial enrichment of (−)α-HBCD was observed in serum.ConclusionsSerum concentrations of HBCDs were correlated with the exposure via dust, but not via dietary ingestion. The enrichment of the (−)α-HBCD enantiomer in humans appears to be due to in vivo enantioselective metabolism/excretion rather than ingestion of dust or diet.

Trophodynamics of Some PFCs and BFRs in a Western Canadian Arctic Marine Food Web

The trophodynamics of per- and polyfluorinated compounds and bromine-based flame retardants were examined in components of a marine food web from the western Canadian Arctic. The animals studied and their relative trophic status in the food web, established using stable isotopes of nitrogen (delta15N), were beluga (Delphinapterus leucas) > ringed seal (Phoca hispida) > Arctic cod (Boreogadus saida) > Pacific herring (Clupea pallasi) approximately equal to Arctic cisco (Coregonus autumnalis) > pelagic amphipod (Themisto libellula) > Arctic copepod (Calanus hyperboreus). For the brominated diphenyl ethers, the lipid adjusted concentrations of the seven congeners analyzed (Sigma7BDEs: -47, -85, -99, -100, -153, -154, and -209) ranged from 205.4 +/- 52.7 ng/g in Arctic cod to 2.6 +/- 0.4 ng/g in ringed seals. Mean Sigma7BDEs concentrations in Arctic copepods, 16.4 ng/g (n = 2, composite sample), were greater than those in the top trophic level (TL) marine mammals and suggests that (i) Arctic copepods are an important dietary component that delivers BDEs to the food web and (ii) because these compounds are bioaccumulative, metabolism and depletion of BDE congeners in top TL mammals is an important biological process. There were differences in the concentration profiles of the isomers of hexabromocyclododecane (HBCD) in the food web. The most notable difference was observed for beluga, where the alpha-isomer was enriched (accounting for approximately 90% of the SigmaHBCD body burden), relative to its primary prey species, Arctic cod, where the alpha-isomer accounted for only 20% of the SigmaHBCD body burden (beta: 4% and gamma: 78%). For the C8-C11 perfluorinated carboxylic acids, the trophic magnification factors (TMFs) were all greater than unity and increased with increasing carbon chain length. PFOS and its neutral precursor, PFOSA, also had TMF values greater than one. There were also pronounced differences in the PFOSA to PFOS ratio in ringed seal (0.04) and in beluga (1.4) and suggests that, in part, there are differences in the efficacy of biotransforming PFOSA by whale and seal top predators that both preferentially feed on Arctic cod.

Evaluation of hexabromocyclododecane in fish and marine mammal oil supplements

We analyzed the dietary fish and marine mammal oil supplements purchased from Japanese markets for hexabromocyclododecane (HBCD); 20 brands were analyzed by liquid chromatography–tandem mass spectrometry (LC/MS/MS). HBCD was detected in 15 of 22 samples, and the concentrations of all the HBCD isomers (α, β, and γ) ranged from <0.9 to 67 ng/g lipid weight. α-HBCD was the dominant residue among the HBCD isomers. However, the composition of HBCD isomers varied according to the sample type. We found that 1 sardine oil brand and 2 shark liver oil brands extracted from fish captured in seawater around Japan contained relatively high levels of HBCD, indicating that both the surface and deep seawaters around Japan may have been contaminated with HBCD.

In vitro effects of brominated flame retardants and metabolites on CYP17 catalytic activity: A novel mechanism of action?

Fire incidents have decreased significantly over the last 20 years due, in part, to regulations requiring addition of flame retardants (FRs) to consumer products. Five major classes of brominated flame retardants (BFRs) are hexabromocyclododecane isomers (HBCDs), tetrabromobisphenol-A (TBBPA) and three commercial mixtures of penta-, octa- and deca-polybrominated diphenyl ether (PBDE) congeners, which are used extensively as commercial FR additives. Furthermore, concentrations of PBDEs have been rapidly increasing during the 1999s in human breast milk and a number of endocrine effects have been reported. We used the H295R human adrenocortical carcinoma cell line to assess possible effects of some of these BFRs (PBDEs and several of their hydroxylated (OH) and methoxylated (CH(3)O) metabolites or analogues), TBBPA and brominated phenols (BPs) on the combined 17alpha-hydroxylase and 17,20-lyase activities of CYP17. CYP17 enzyme catalyzes an important step in sex steroidogenesis and is responsible for the biosynthesis of dehydroepiandrosterone (DHEA) and androstenedione in the adrenals. In order to study possible interactions with BFRs, a novel enzymatic method was developed. The precursor substrate of CYP17, pregnenolone, was added to control and exposed H295R cells, and enzymatic production of DHEA was measured using a radioimmunoassay. In order to avoid pregnenolone metabolism via different pathways, specific chemical inhibitor compounds were used. None of the parent/precursor BFRs had a significant effect (P < 0.05) on CYP17 activity except for BDE-183, which showed significant inhibition of CYP17 activity at the highest concentration tested (10 muM), with no signs of cytotoxicity as measured by mitochondrial toxicity tests (MTT). A strong inhibition of CYP17 activity was found for 6-OH-2,2',4,4'-tetrabromoDE (6-OH-BDE47) with a concentration-dependent decrease of almost 90% at 10 muM, but with a concurrent decrease in cell viability at the higher concentrations. Replacement of the 6-OH group by a 6-CH(3)O group eliminated this cytotoxic effect, but CYP17 activity measured as DHEA production was still significantly inhibited. Other OH- or CH(3)O-PBDE analogues were used to elucidate possible structural properties behind this CYP17 inhibition and associated cytotoxicity, but no distinct structure activity relationship could be determined. These in vitro results indicate that OH and CH(3)O-PBDEs have potential to interfere with CYP17 activity for which the in vivo relevance still has to be adequately determined.

Distribution and transportability of hexabromocyclododecane (HBCD) in the Asia-Pacific region using skipjack tuna as a bioindicator

The geographical distribution of hexabromocyclododecane (HBCD) was investigated through analysis of muscle tissue of skipjack tuna (Katsuwonus pelamis) collected from offshore waters of Asia-Pacific region (Japan, Taiwan, Philippines, Indonesia, Seychelles, Brazil, Japan Sea, East China Sea, South China Sea, Indian Ocean and North Pacific Ocean). HBCD was detected in almost all samples analyzed (<0.1 to 45ng/g lipid weight basis), indicating widespread presence of this compound in the marine environment. Elevated concentrations of HBCD were found in skipjack tuna from areas around Japan, which have the larger modern industrial/urban societies, and implicated these areas as primary regional sources. All three individual HBCD isomers (α-, γ- and β-HBCD) were detected in almost all samples; the percentage contribution of the α-isomer to total HBCD increased with increasing latitude. The estimated empirical 1/2 distance for α-HBCD was 8500km, which is one of the highest atmospheric transportability among various halogenated persistent organic pollutants (POPs).

Distribution of hexabromocyclododecane in Detroit River suspended sediments

The distribution of hexabromocyclododecane (HBCD) isomers (α, β and γ) was determined in Detroit River suspended sediments using liquid chromatography tandem mass spectrometry (LC/MS/MS). Individual isomers of HBCD were measured at concentrations ranging from <0.025 to 1.9 ng/g (dry wt.) for the α-isomer, <0.025 to 0.28 ng/g for the β-isomer, and <0.025 to 2.3 ng/g for the γ-isomer. Concentrations of total HBCD ranged from <0.075 to 3.7 ng/g. Roughly two-thirds of HBCD profiles in suspended sediments were dominated by the γ-isomer, and were similar to profiles of commercial technical mixtures. Profiles in the remaining samples were dominated by the α-isomer. The β-isomer was consistently detected at substantially lower levels than the other isomers; this isomer is a minor constituent in the commercial technical mixtures. Seasonal sampling showed significant shifts in the relative ratios of the HBCD isomers. The spatial distribution of HBCD in the Detroit River was similar to other persistent organic pollutants (e.g., PCBs), and showed a strong association with urban/industrial activities in the watershed. However, the highest HBCD concentrations (2.6–3.7 ng/g) were associated with areas of contemporary industrial activity, and were much lower than maximum concentrations of PCBs (2.2 μg/g) found in areas of the Detroit River associated with historical industrial activity.

Determination of HBCD, PBDEs and MeO-BDEs in California sea lions ( Zalophus californianus) stranded between 1993 and 2003

Blubber samples from male California sea lions ( Zalphophus californianus) stranded between 1993 and 2003 were analyzed for 27 polybrominated diphenyl ether (PBDE) congeners, three isomers of hexabromocyclododecane (HBCD) and 14 methoxylated polybrominated diphenyl ether (MeO-BDE) congeners. Total PBDEs ranged from 450 ng/g to 4740 ng/g wet mass and total HBCD ranged from <0.3 ng/g to 12 ng/g wet mass. The concentration of HBCD increased from 0.7 ng/g to12.0 ng/g wet mass in sea lion blubber between 1993 and 2003. However, no significant temporal trend was observed for any of the other brominated compounds over this 10 year period. Only one of the 14 MeO-BDE congeners was detected in the blubber samples, 6-methoxy-2,2′,4,4′-tetrabromodiphenyl ether (6-MeO-BDE 47), and concentrations ranged from <0.2 ng/g to 12 ng/g wet mass. A bromo-, chloro-heterocyclic compound, 1,1′-dimethyl-tetrabromo-dichloro-2,2′-bipyrrole (DBP-Br 4Cl 2), previously reported in marine species along the Pacific coast, was also identified in the sea lion blubber. DBP-Br 4Cl 2 ranged from 44 ng/g wet mass to 660 ng/g wet mass and was present at concentrations rivaling the dominant PBDE congener, BDE 47 (2,2′,4,4′-tetrabromodiphenyl ether). Concentrations of DBP-Br 4Cl 2 were positively correlated with 6-MeO-BDE 47 ( r = 0.7; p < 0.05). Both of these compounds have been identified in marine algae and sponges, and studies suggest they are both produced from natural sources. This study demonstrates that brominated compounds from both anthropogenic and biogenic sources can accumulate to similar levels in marine mammals. In addition, HBCD concentrations appear to be increasing in California sea lion populations, whereas PBDE concentrations, between 1993 and 2003, were highly variable.

Refinements to the diastereoisomer‐specific method for the analysis of hexabromocyclododecane

The emergence of hexabromocyclododecane (HBCD) as a bromine-based flame retardant of concern is partly attributable to recent measurements on the environmental occurrence of the individual diastereoisomers (alpha, beta and gamma). These measurements were fuelled by a newly developed liquid chromatography/tandem mass spectrometric (LC/MS/MS)-based analytical method. However, in the course of our recent studies on the environmental fate and behaviour of the diastereoisomers of HBCD, some interesting features of the LC/MS/MS method became apparent. For example, the ion signal of the native ions was found to be dependent on the final extract volume. This was true for both biotic and sediment samples and was found to arise from the suppression of the ion signal due to endogenous material in the extracts that escape clean-up. We have also found differences in the stability of the diastereoisomers in different solvents. If left unaccounted for, both factors can compromise analytical measurement data. By way of a series of controlled experiments conducted at our two laboratories [Department of Fisheries & Oceans Canada (DFO) and Environment Canada (EC)], we illustrate these features and demonstrate that use of newly synthesized labelled HBCD isomers [(13-carbon (13C) and deuterium (d18)] can minimize and often circumvent matrix-related effects.