Current-Use Brominated Flame Retardants in Water, Sediment, and Fish from English Lakes

Abstract

Concentrations are reported of hexabromocyclododecanes (HBCDs) and tetrabromobisphenol-A (TBBP-A) in water (n = 27), sediment (n = 9), and fish samples (n = 30) from nine English lakes. Seasonal variation in concentrations in water is minimal. Concentrations of TBBP-A range from 140 to 3200 pg L(-1) (water), 330 to 3800 pg g(-1) dry weight (sediment), and <0.29 to 1.7 ng g(-1) lipid weight (fish). Those of SigmaHBCDs range between 80 and 270 pg L(-1) (water), 880 and 4800 pg g(-1) dry weight (sediment), and 14 and 290 ng g(-1) lipid weight (fish). Aqueous concentrations of SigmaHBCDs and TBBP-A are significantly positively correlated, indicating a common source. Average +/-sigma(n) "freely-dissolved" phase proportions are 47 +/- 4.7% (SigmaHBCDs) and 61 +/- 2.9% (TBBP-A). Average field-derived bioaccumulation factors are 5900, 1300, 810, and 2100 for alpha-, beta-, gamma-, and SigmaHBCDs, respectively. Tetrabromocyclododecadienes are detected in all sediments, with pentabromocyclododecenes present in some. This suggests HBCD degrades via sequential loss of HBr. The delta-HBCD meso form was quantified in 43% of fish samples (1.0-11% SigmaHBCDs). Its absence from temporally and spatially consistent water and sediment samples suggests it is formed via bioisomerization. While HBCD chiral signatures are racemic in water and sediment, our data reveal enantiomeric enrichment of (-)alpha-HBCD and (+)gamma-HBCD in fish.

Levels, isomer profiles and chiral signatures of particle-bound hexabromocyclododecanes in ambient air around Shanghai, China

“…Janák et al (2005Janák et al ( , 2008 postulated the occurrence of d-HBCD in fish and piscivorous birds. Harrad et al (2009b) first confirmed its presence in 13 fish samples. But its source was unclear, although it was hypothesized to have arisen via bioisomerization (Harrad et al, 2009b).…”

“…Harrad et al (2009b) first confirmed its presence in 13 fish samples. But its source was unclear, although it was hypothesized to have arisen via bioisomerization (Harrad et al, 2009b).…”

“…Thermal rearrangement and photo-isomerization also occur between these three diastereomers, especially between g-and a-HBCDs (Harrad et al, 2009a;Heeb et al, 2008aHeeb et al, , 2008bKöppen et al, 2008). Moreover, enantiomers of the three diastereomers exhibited different enrichment in biota samples with non-racemic signatures (Abdallah and Harrad, 2011;Covaci et al, 2006;Eljarrat et al, 2009;Esslinger et al, 2011;Harrad et al, 2009bHarrad et al, , 2010He et al, 2010;Köppen et al, 2010;Peck et al, 2005;Tomy et al, 2008). Two meso forms d-HBCD and 3-HBCD have been found by Heeb et al (2005) in commercial HBCD in concentration of 0.5% and 0.3%, respectively.…”

Levels and distribution of hexabromocyclododecane (HBCD) in environmental samples near manufacturing facilities in Laizhou Bay area, East China

“…18 However, they were at the same level as in other freshwater fish, e.g., in crucian carp in South China (21-378 ng g À1 lw) 29 and in fish from English lakes (14-290 ng g À1 lw). 23 P HBCD concentrations varied significantly in the different aquatic species and tissues. Among the four species at the sampling site S19, loach exhibited the highest concentration of HBCD (128 ng g À1 lw), which was 18 times higher than that in silver carp (7.09 ng g À1 lw).…”

Current levels and composition profiles of PBDEs and alternative flame retardants in surface sediments from the Pearl River Delta, southern China: Comparison with historical data

“…A class of HFRs known as polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), and Dechlorane Plus (DP) have become a topic of great concern because of their widespread occurrence in the environment and potential adverse effects on humans and wildlife (Cetin and Odabasi, 2007;Qiu et al, 2007;Harrad et al, 2009;Covaci et al, 2011;Ali et al, 2012). The phase-out of technical pentaand octa-BDE mixtures in many regions worldwide has caused their manufacturers to seek alternatives to these products.…”