Hexabromocyclododecane Diastereoisomers Research Articles

Different Cytotoxicity Induced by Hexabromocyclododecanes on Mouse Neuroblastoma N2a Cells via Oxidative Stress and Mitochondrial Apoptotic Pathway.

Hexabromocyclododecane (HBCD) is widely used in polystyrene foams, building materials, and electrical equipment as a brominated flame retardant (BFR) and persists in the environment and human body matrix. It has attracted increased attention since its neuroendocrine disorder effects have been observed in humans and animals. However, studies evaluating the neurotoxicity of HBCD diastereoisomers and the potential mechanisms involved are still limited. In this study, we compared the cytotoxicity induced by the three HBCD diastereoisomers (i.e., α-, β-, and γ-HBCD) in N2a cells and further investigated the underlying molecular mechanism. Our results showed that HBCD diastereoisomers decreased cell viability in the order of β-HBCD > α-HBCD > γ-HBCD. Moreover, α-HBCD and β-HBCD exposure led to different degrees of cell cycle disruption and oxidative stress of N2a cells, implying that oxidative stress-mediated differential cytotoxicity of HBCD diastereoisomers. The expressions of caspases and Bcl-2 were differentially regulated by α-HBCD and β-HBCD, suggesting that the mitochondrial apoptosis pathway may be critical in HBCDs-mediated N2a cell toxicity. Therefore, our studies provided novel evidence for the underlying mechanisms of the distinct cytotoxicity of HBCD diastereoisomers.

The distribution and metabolism of hexabromocyclododecane isomers varies in the tissues of Nibea albiflora

Hexabromocyclododecanes (HBCDs), as brominated flame retardants, have increasingly drawn concern due to their detection in various marine organisms in recent years. The present test investigated the selective accumulation, depuration, and bioisomerization of HBCDs in different tissues and organs of Nibea albiflora, as well as the genetic metabolic behavior of HBCDs between parents and offspring. In a semi-static water environment, N. albiflora were exposed to individual HBCD diastereoisomers (α-HBCD, β-HBCD, or γ-HBCD) at a concentration of 0.4 μg/L for bioaccumulation, followed by clean food for depuration. During the exposure period, the highest concentrations of these HBCDs were observed in the intestine and gill of N. albiflora. α-HBCD was detected in all exposure groups, suggesting that both β-HBCD and γ-HBCD could be bioisomerized to α-HBCD in N. albiflora. In addition, there was no bioisomerization of α-HBCD to either β-HBCD or γ-HBCD, and there was no bioisomerization between β-HBCD and γ-HBCD. The half-lives (t1/2) were variable among different diastereoisomers, following an order of α-HBCD > γ-HBCD > β-HBCD. The most rapid depuration rate of HBCDs was discovered in the liver while muscle showed the least. Additionally, prior to spawning, the parent fish were exposed to contaminated feed (silkworms sprayed with 200 μL of a 30 μg/mL HBCD solution) for 6 days. By comparing the HBCDs concentrations in the maternal gonad, fertilized eggs, hatching eggs, larvae, and juveniles, it was determined that the maternal transfer coefficients for HBCDs were approximately 1, indicating dynamic equilibrium of HBCDs throughout the process from maternal tissue to progeny development. Differences in HBCDs pattern between organs observed in the experiment support a proposal of an organ-specific diastereomer accumulation.

Occurrence of hexabromocyclododecanes (HBCDs) and tetrabromobisphenol A (TBBPA) in indoor dust from different microenvironments: levels, profiles, and human exposure.

The levels and distributions of hexabromocyclododecane diastereoisomers (HBCDs) (including α, β, and γ-HBCD) and tetrabromobisphenol A (TBBPA) were investigated in indoor dust from bedrooms and offices. HBCDs diastereoisomers were the most abundant compounds in the dust samples, and the concentrations of ∑HBCDs in the bedrooms and offices ranged from 10.6 to 290.1ng/g and 17.6 to 1521.9ng/g, respectively. The concentrations of target compounds in the offices were generally higher than those in the bedrooms, probably due to the presence of more electrical equipment in the offices. In this study, highest levels of target compounds were all found in the electronics. In the bedrooms, the highest mean level of ∑HBCDs was found in air conditioning filter dust (118.57ng/g), while the personal computer table surface dust showed the peak mean concentrations of ∑HBCDs (290.74ng/g) and TBBPA (539.69ng/g) in the offices. Interestingly, a significantly positive correlation was observed between the concentrations of ∑HBCDs in windowsills and beddings dust in the bedrooms, suggesting beddings was one of the crucial sources of ∑HBCDs in the bedrooms. The high dust ingestion values of ∑HBCDs and TBBPA were 0.046 and 0.086ng/kgbw/day for adults, while 0.811 and 0.04ng/kgbw/day for toddlers, respectively. The high dermal exposure values of ∑HBCDs were 0.026 and 0.226ng/kgbw/day for adults and toddlers, respectively. Except for dust ingestion, other human exposure pathways (such as the dermal contact with beddings and furniture) should be paid attention.

Extruded polystyrene microplastics as a source of brominated flame retardant additives in the marine environment: long-term field and laboratory experiments

Microplastics (MPs) in the environment have become a global concern, not only for the physical effects of the plastic particles themselves but also for being vectors of chemical additives. In this context, little is known about the ability of MPs, particularly extruded polystyrene microplastics (XPS-MPs), to release organic chemical additives in the marine environment. In this study, a series of field and laboratory experiments were carried out to determine the leaching behaviour of organic additives including brominated flame retardants from XPS-MPs into seawater. The conducted experiments confirmed a rapid release of bisphenol A (BPA), 2,4,6-tribromophenol (TBP), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane diastereoisomers (α-, β-, and γ-HBCDD) from the studied MPs followed by a slower rate of release over time. The effects of environmental factors on the leaching rates of these additives were also examined. Increasing Dissolved Organic Matter (DOM) concentrations and the temperature of the seawater enhanced the release of additives by increasing their solubility and polymer flexibility. In contrast, pH tested at 7, 7.5 and 8 was found to have a minor effect on additives leaching; and salinity negatively affected the leaching rate likely due to their reduced solubility and reduced diffusion from the MPs. The present study provides empirical evidence of the behaviour of XPS-MPs as a source of organic additives in the marine environment that merit further investigation.

A comprehensive evaluation of factors affecting the reactivity of FeS towards hexabromocyclododecane diastereoisomers

Reactivity of iron sulfide (FeS) towards hexabromocyclododecane (HBCD) was explored under conditions of varying temperature, pH, inorganic ion and dissolved organic matter (DOM) in this study. Results show that the reduction of HBCD by FeS has an activation energy of 29.2 kJ mol−1, suggesting that the rate-limiting step in the reduction was a surface-mediated reaction. The reduction of HBCD by FeS was a highly pH-dependent process. The optimal rate for HBCD reduction by FeS was observed at a pH of 6.2. All the tested inorganic ions suppressed the reduction of HBCD by FeS. XPS analysis confirmed that both Fe(II)-S and bulk S(-II) on FeS surface could be impacted by solution pH and inorganic ions and were responsible for the regulation of HBCD reduction. Some DOMs (i.e., fulvic acid, humic acid, salicylic acid, catechol and sodium dodecyl sulfate) were found to hinder the reduction via competing with HBCD for active sites on FeS surface. However, the presence of 2,2′-bipyridine, triton X-100 and cetyltrimethyl ammonium bromide was able to significantly enhance the rate of HBCD reduction by 5.8, 9.0 and 20 times, respectively. Different factors could influence the reduction efficiency of HBCD diastereoisomers to different extent, but not the reaction orders of HBCD diastereoisomers (α-HBCD < γ-HBCD < β-HBCD). Moreover, FeS could completely remove HBCD diastereoisomers in sediments with multiple factors within 9 d reaction. Our results contribute to give a better understanding on the performance of FeS towards HBCD under real and complex conditions and facilitate the application of FeS in remediation sites.

Probing the Mechanism of Hepatotoxicity of Hexabromocyclododecanes through Toxicological Network Analysis.

The prediction and mechanism analysis of hepatotoxicity of contaminants, because of their various phenotypes and complex mechanisms, is still a key problem in environmental research. We applied a toxicological network analysis method to predict the hepatotoxicity of three hexabromocyclododecane (HBCD) diastereoisomers (α-HBCD, β-HBCD, and γ-HBCD) and explore their potential mechanisms. First, we collected the hepatotoxicity related genes and found that those genes were significantly localized in the human interactome. Therefore, these genes form a disease module of hepatotoxicity. We also collected targets of α-, β-, and γ-HBCD and found that their targets overlap with the hepatotoxicity disease module. Then, we trained a model to predict hepatotoxicity of three HBCD diastereoisomers based on the relationship between the hepatotoxicity disease module and targets of compounds. We found that 593 genes were significantly located in the hepatotoxicity disease module (Z = 11.9, p < 0.001) involved in oxidative stress, cellular immunity, and proliferation, and the accuracy of hepatotoxicity prediction of HBCD was 0.7095 ± 0.0193 and the recall score was 0.8355 ± 0.0352. HBCD mainly affects the core disease module genes to mediate the adenosine monophosphate-activated kinase, p38MAPK, PI3K/Akt, and TNFα pathways to regulate the immune reaction and inflammation. HBCD also induces the secretion of IL6 and STAT3 to lead hepatotoxicity by regulating NR3C1. This approach is transferable to other toxicity research studies of environmental pollutants.

Spatial distribution, source identification, and anthropogenic effects of brominated flame retardants in nationwide soil collected from South Korea.

Soil samples were collected at 61 sites of the national monitoring network for persistent organic pollutants (POPs) in South Korea. The target compounds were brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), hexabromocyclododecanes (HBCDDs), and tetrabromobisphenol A (TBBPA). The mean concentrations of Σ27 PBDEs, Σ3 HBCDDs, and TBBPA in soil were 222, 17.2, and 4.4ng/g, respectively, but PBBs were not detected. Industrial sites had statistically higher BFR concentrations than suburban sites but no significant difference compared with urban sites. The commercial deca-BDE mixtures were the most likely source of PBDE contamination in the soil samples, with the minor influence of commercial penta-BDE and octa-BDE mixtures. The profiles of HBCDDs in most soil samples differed from those in the powder types of technical HBCDD mixtures, indicating that they are affected by the HBCDDs contained in commercial products and the conversion of HBCDD diastereoisomers (γ-HBCDD to α-HBCDD) in the environment. The concentrations of Σ27 PBDEs, Σ3 HBCDDs, and TBBPA were significantly correlated with population density, gross domestic product, and the number of companies (p<0.01), indicating a direct impact of anthropogenic activities. Significant correlations among BFRs were determined (0.63<r<0.74, p<0.01), suggesting that these pollutants had similar sources. Relatively good correlations (0.44<r<0.98, p<0.01) between BDE-209 and other light BDEs (except for BDE-71, -77,-126,-156, and-205) might result from the degradation of heavy BDEs under anaerobic and natural sunlight conditions. To the best of our knowledge, this study provides the most comprehensive soil monitoring data for various BFRs in South Korea. Furthermore, it is the first report on soil contamination by deca-BDE, HBCDDs, and TBBPA in South Korea.

Enantiomeric fraction of hexabromocyclododecanes in foodstuff from the Belgian market

Diet is considered a major route of human exposure to hexabromocyclododecane, a chiral environmental contaminant. A previous study reported on the occurrence of hexabromocyclododecane diastereoisomers in food items of animal origin collected in Belgium. The present study reports further results on corresponding enantiomeric fractions of the same samples. None of the samples could be considered as racemic for the α-isomer suggesting that foodstuff contamination occurred prior to death of the corresponding producing animal and was not the result of the food item being in contact with technical HBCDD. Non-racemic chiral signatures were also observed for β- and γ-isomers. We conclude that, depending on their dietary habits, different individuals might be overall exposed to non-racemic profiles. Considering that toxicological effects are enantiomer-dependent, this could modulate potential adverse effects.

State of the art in the analysis of brominated flame retardants in biota and sediment: insights from the characterisation of two new certified reference materials

The Joint Research Centre (JRC) of the European Commission has recently released two new Certified Reference Materials (CRMs) for the analysis of brominated flame retardants (BFRs): the freshwater sediment ERM-CC537a and the fish tissue ERM-CE102. The production of these CRMs responds to the need of expanding the offer of quality assurance/quality control tools for the analysis of BFRs in the fields of environmental analysis and food control, especially for compliance purposes. The sediment ERM-CC537a carries certified values for polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) diastereoisomers in the μg/kg range (dry mass), while the fish tissue ERM-CE102 is certified for PBDEs in the ng/kg range (wet weight). ERM-CC537a is the first reference material ever available with certified values for α-, β- and γ-HBCDD. The assignment of the certified values was performed via an intercomparison of expert laboratories. The evaluation of the data confirms the improving trend, observed in recent years, regarding the comparability of PBDE measurement results. The relative standard deviation (RSD) among laboratories is slightly better for the fish material (8–11%) compared to the sediment (9–15%), despite lower mass fractions in the biota matrix. The RSD of HBCDD data (17%) reveals that they are more challenging analytes. The average measurement uncertainty declared by the participants is about 30%, but an in-depth analysis of their performance reveals that it should be feasible to reduce the uncertainty budget.

Halogenated flame retardants in atmospheric particles from a North African coastal city (Bizerte, Tunisia): Pollution characteristics and human exposure

In the present study, atmospheric particle samples were collected between September 2015 and February 2016 from Bizerte city (Tunisia) to investigate the occurrence, potential sources and impacts of a range of flame retardants (FRs), including hexabromocyclododecane diastereoisomers (HBCDDs), new halogenated flame retardants (NHFRs), as well as methoxylated polybrominated diphenyl ethers (MeO-BDEs). Among 19 examined compounds, 9 congeners (α-HBCDD, β-HBCDD, γ-HBCDD, HBB, DBDPE, syn-DP, anti-DP, 2′-MeO-BDE-68 and 6-MeO-BDE-47) were detected in atmospheric particles at different levels and frequencies. Overall, the average concentration of NHFRs (1.53 pg m−3) was 1.5 and 51 folds higher than that of HBCDDs (1.04 pg m−3) and MeO-BDEs (0.03 pg m−3), respectively. By comparison with other areas of the world, NHFRs and HBCDDs in Bizerte were at medium pollution level, while MeO-BDEs were at lower levels. No significant correlations were found between NHFR, HBCDD and MeO-BDE concentrations, suggesting different sources related on one hand to the biogenic origin of MeO-BDE, and on the other hand to various types and utilisations of imported NHFR- and HBCDD-containing products, as Tunisia does not manufacture FRs. DP and HBCDD diastereoisomer profiles appeared to be divergent from their commercial products, pointing out that a complex degradation or stereoselective transformation processes occurring in ambient air around Bizerte city. The estimated daily human exposure dose (DED) to particle-bound HBCDDs, NHFRs and MeO-BDEs via outdoor air inhalation was generally at low levels. Hence, this study reports for the first time the occurrence and potential impact of HBCDDs, NHFRs and MeO-BDEs in atmospheric particles from North Africa.

Distribution, diastereomer-specific accumulation and associated health risks of hexabromocyclododecanes (HBCDs) in soil-vegetable system of the Pearl River Delta region, South China

The distribution and diastereomeric profiles of hexabromocyclododecanes (HBCDs, identified as persistent organic pollutants) in soil-vegetable system of open fields remain unknown. In this study, three main HBCD diastereoisomers (α-, β-, and γ-HBCDs) were analyzed in paired soil and vegetable samples from vegetable farms in four cities (Guangzhou, Jiangmen, Huizhou, Foshan) of the Pearl River Delta region, Southern China. The sum concentrations of the three diastereoisomers (∑HBCDs) in soils varied from 0.99 to 18.4 ng/g (dry weight) with a mean of 5.77 ng/g, decreasing in the order of Jiangmen > Guangzhou > Huizhou > Foshan. The distributions of HBCDs in both soil and vegetable were diastereomer-specific, with γ-HBCD being predominant. The ∑HBCDs in vegetables ranged from 0.87 to 32.7 ng/g (dry weight) with a mean of 16.6 ng/g, generally higher than those of the corresponding soils. Thus bioconcentration factors (BCFs, the ratio of contaminant concentration in vegetable to that in soil) of HBCDs were generally greater than 1.0, implying higher accumulation in vegetable. The estimated daily intake (EDI) of ΣHBCDs via consumption of vegetables varied from 0.26 to 9.35 ng/kg bw/day with a mean of 3.60 ng/kg bw/day for adults and from 0.32 to 11.5 ng/kg bw/day with a mean of 4.41 ng/kg bw/day for Children, far lower than the oral reference dose (RfD, 2 × 105 ng/kg bw/day) proposed by US National Research Council. These results suggest that HBCD in the vegetables posed low health risk for the local population. These data are the first report on HBCD occurrence and health risk in soil-vegetable system of open fields.

Diastereoisomer-specific neurotoxicity of hexabromocyclododecane in human SH-SY5Y neuroblastoma cells

Hexabromocyclododecane (HBCD) is a widely applied brominated flame retardant (BFR) and is regarded as a persistent organic pollutant. It has been found in human tissues and has the potential to cause neurological disorders. However, our understanding of HBCD neurotoxicity at the diastereoisomer level remains lacking. Here, we investigated the neurotoxicity of three HBCD diastereoisomers, i.e., α-, β-, and γ-HBCD, in SH-SY5Y human neuroblastoma cells. Results showed that the HBCD diastereoisomers decreased cell viability, increased lactate dehydrogenase (LDH) release, and impaired cytoskeleton development. Typical morphological features and apoptosis rates showed that the HBCD diastereoisomers induced SH-SY5Y cell apoptosis. The expression levels of several cell apoptosis-related genes and proteins, including Bax, caspase-3, caspase-9, cytochrome c, Bcl-2, and X-linked inhibitor of apoptosis (XIAP), as well as the cell cycle arrest, DNA damage, adenosine triphosphate (ATP) consumption, reactive oxygen species (ROS) levels, and intracellular calcium ion (Ca2+) levels, were examined. Results showed that the HBCD diastereoisomer neurotoxicity was ranked β-HBCD > γ-HBCD > α-HBCD. The cell apoptosis and caspase expression levels of the three HBCD diastereoisomers followed the same order, suggesting that caspase-dependent apoptosis may be one mechanism responsible for the structure-selective HBCD diastereoisomer neurotoxicity. The levels of intracellular Ca2+ and ROS increased significantly. The ROS levels were ordered β-HBCD > γ-HBCD > α-HBCD, whereas those of intracellular Ca2+ were γ-HBCD > β-HBCD > α-HBCD. Thus, ROS may be a key factor regulating the neurotoxicity of HBCD diastereoisomers. To the best of our knowledge, this is the first study to report on the diastereoisomer-specific toxicity of HBCD in human neural cells and on the possible mechanisms responsible for the selective neurotoxicity of HBCD diastereoisomers.

Different biotransformation of three hexabromocyclododecane diastereoisomers by Pseudomonas sp. under aerobic conditions

To date, the aerobic biodegradation of hexabromocyclododecanes (HBCDs) by HBCD-degrading bacteria has largely been studied via a mixture of all diastereoisomers. To improve the understanding of the degradation process of different diastereoisomers, we established an optimized method for isolating three diastereoisomers (α-, β-, and γ-HBCD) by high-performance liquid chromatography (HPLC) with a C18 column. One pure bacterial strain, Pseudomonas sp. strain GJY, was isolated with excellent HBCD biodegradation activity. At 30 °C, pH 7.0, and an initial HBCD concentration of 1 mg/L, the biodegradation rates of α-, β-, and γ-HBCDs were 85.38%, 82.64%, and 75.50% after 8 days of aerobic incubation, respectively. Only the enrichment of (+)γ-HBCD was observed, and no enantioselectivity was found in α- and β-HBCD. Finally, the metabolites were determined from a full scan, precursor ion scan, and product ion scan by UPLC–MS/MS. PBCDe, TeBCDe, DBCDi, PBCD-ols, TeBCDe-ols, and TrBCD-triols were the main products, and they exhibited differences in the three diastereoisomers. Interestingly, no aerobic hydroxylation product of HBCD, such as HBCD-ols and HBCD-diols, was identified in any of the degradation processes. In consideration of these products, the main degradation pathways of the three diastereoisomers were proposed.

Bioaccumulation and translocation of tetrabromobisphenol A and hexabromocyclododecanes in mangrove plants from a national nature reserve of Shenzhen City, South China

Brominated flame retardants (BFRs) such as tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs) are of ecological concern due to their ubiquitous presence and adverse effects. There is a paucity of data on environmental fate of such compounds in mangrove wetlands, which are unique ecosystems in coastal intertidal areas and act as natural sinks for many pollutants. In this study, mangrove plants and sediments were collected from an urban nature reserve in South China to investigate bioaccumulation and translocation of TBBPA and HBCDs. The mean (range) concentrations of TBBPA and ΣHBCD in roots, stems and leaves were 67 (<MDL-999), 174 (0.73–1105) and 20 (0.59–250) pg/g dry weight (dw), and 329 (15.6–2234), 766 (32.9–3255) and 298 (19.9–1520) pg/g dw, respectively. Tissue-specific accumulations were observed, varying with plant species and compounds. HBCD diastereoisomer patterns were similar for all plant species. γ-HBCD was the major diastereoisomer in roots, while α-HBCD dominated in stems and leaves. The predominance of α-HBCD in aboveground tissues may be ascribed to diastereoisomer-specific translocation, isomerization and/or metabolization in mangrove plants. Preferential enrichment of (−)-α-, (−)-β- and (+)-γ-HBCDs was found in all mangrove plant tissues, suggesting the enantioselectivity for HBCDs in mangrove plants. Translocation factors (log TF, root to stem) of HBCD diastereoisomers and log Kow were negatively correlated (p = 0.03), indicating passive translocation of HBCDs, driven by water movement during transpiration. Sediment-root bioaccumulation factors and log TFs (stem to leaf) both showed no obvious correlation with log Kow of HBCD diastereoisomers. These results reflected the complex behavior of HBCDs in mangrove plants, which have not been sufficiently captured in laboratory-based studies of plant contaminant accumulation.

Diastereoisomer-Specific Biotransformation of Hexabromocyclododecanes by a Mixed Culture Containing Dehalococcoides mccartyi Strain 195.

Hexabromocyclododecane (HBCD) stereoisomers may exhibit substantial differences in physicochemical, biological, and toxicological properties. However, there remains a lack of knowledge about stereoisomer-specific toxicity, metabolism, and environmental fate of HBCD. In this study, the biotransformation of (±)α-, (±)β-, and (±)γ-HBCD contained in technical HBCD by a mixed culture containing the organohalide-respiring bacterium Dehalococcoides mccartyi strain 195 was investigated. Results showed that the mixed culture was able to efficiently biotransform the technical HBCD mixture, with 75% of the initial HBCD (∼12 μM) in the growth medium being removed within 42 days. Based on the metabolites analysis, HBCD might be sequentially debrominated via dibromo elimination reaction to form tetrabromocyclododecene, dibromocyclododecadiene, and 1,5,9-cyclododecatriene. The biotransformation of the technical HBCD was likely diastereoisomer-specific. The transformation rates of α-, β-, and γ-HBCD were in the following order: α-HBCD > β-HBCD > γ-HBCD. The enantiomer fractions of (±)α-, (±)β-, and (±)γ-HBCD were maintained at about 0.5 during the 28 days of incubation, indicating a lack of enantioselective biotransformation of these diastereoisomers. Additionally, the amendment of another halogenated substrate tetrachloroethene (PCE), which supports the growth of strain 195, had a negligible impact on the transformation patterns of HBCD diastereoisomers and enantiomers. This study provided new insights into the stereoisomer-specific transformation patterns of HBCD by anaerobic microbes and has important implications for microbial remediation of anoxic environments contaminated by HBCD using the mixed culture containing Dehalococcoides.

Hexabromocyclododecanes in breast milk from residents in Shenzhen, China: Implications for infant exposure

Hexabromocyclododecanes (HBCDs) are widely used as flame retardants for various products and have become ubiquitous pollutants in environmental media. However, little is known about HBCD exposure for humans, especially in China. This study aimed to investigate the levels and profiles of hexabromocyclododecanes (HBCDs) in human breast milk and to estimate the daily HBCD intake for infants in Shenzhen, China. Levels of the HBCD diastereoisomers α-, β-, and γ-HBCD in 180 breast milk samples collected from primiparas in Shenzhen were measured. The concentrations of α-, β-, and γ-HBCD (ΣHBCDs) ranged within 0.103–15.1ng/g lipid and had a median of 1.82ng/g lipid. ΣHBCDs levels in milk in the present study are comparable to those in milk from other countries and regions but are markedly higher than those for most populations in other regions of China. Among the diastereoisomers, α-HBCD was predominant, accounting for 97.6% of the concentration of ΣHBCDs. The estimated daily intake of ΣHBCDs via breast milk for infants in Shenzhen ranged from 0.481 to 100ng/kgbw/day with a median of 8.40ng/kgbw/day, however, which was unlikely to raises a health concern based on the margin of exposure (MOE) approach. The duration of residence was found to have a significant positive correlation with the HBCD levels in the human breast milk (p<0.05). To our knowledge, this is the first report on HBCD levels in breast milk from Shenzhen residents.

Rapid and simultaneous determination of tetrabromobisphenol A and hexabromocyclododecane diastereoisomers in soil by matrix solid-phase dispersion with bamboo charcoal as dispersive adsorbent

A rapid and simple analytical method based on matrix solid-phase dispersion combined with liquid chromatography coupled with tandem mass spectrometry has been developed by using bamboo charcoal as a dispersive adsorbent to simultaneously determine tetrabromobisphenol A (TBBPA) and hexabromocyclododecane diastereoisomers (HBCDs) in soil. The factors influencing the performance of the proposed method were investigated and optimized in detail, and the matrix effects were evaluated. Under optimum conditions, the proposed method showed good linearity within the range of 0.8–80 ng g−1 and limits of detection of 4–75 pg g−1 (S/N = 3). The satisfactory recoveries of TBBPA ranging from 72.8% to 92.5% and HBCDs ranging from 76.8% to 102.2% were obtained with relatively standard deviation (RSD) ranging from 3.4% to 9.8%. The proposed method has been successfully applied to analyze TBBPA and HBCDs in actual soil samples from the Yellow River Delta in China.

Transport of Hexabromocyclododecane (HBCD) into the soil, water and sediment from a large producer in China

Hexabromocyclododecane (HBCD) is used as a flame retardant with extensive industrial applications, which is mainly produced at facilities on the coast of China. Radially distributed soil samples and equidistant paired water and sediment samples were taken around one of the biggest HBCD production enterprises to reflect its environmental behavior via air deposition and wastewater discharge of HBCD diastereoisomers (α-, β- and γ-HBCD). Worldwide high concentrations of HBCD (11,700ng/g in the soil, 5080ng/L in the water and 6740ng/g in the sediment) were detected in these environmental samples. Concentrations dropped by two orders of magnitude over several kilometers distance from the plant. The diastereoisomer pattern varied in the three environmental compartments examined, such that γ-HBCD was the predominant diastereoisomer in the soil and sediment whilst α- and γ-HBCD shared the predominance in the water. The mass inventories of HBCD in the local soil and sediment were estimated to be 5006kg and 30kg respectively, suggesting that soil was the major sink of HBCD in the production area. As for the soil, the environmental burdens in the areas with radiuses of 2, 4 and 6km were 3210, 3770 and 4590kg respectively.

Simultaneous liquid chromatography–tandem mass spectrometry analysis of brominated flame retardants (tetrabromobisphenol A and hexabromocyclododecane diastereoisomers) in French breast milk

TBBPA and HBCDs are the two classes of flame retardants that are still allowed for use by the European Commission. In May 2013, HBCDs were listed as Persistent Organic Pollutants under the Stockholm Convention, and they were banned with an exemption on EPS/XPS for cavity wall insulation. This study describes the development and optimisation of a rapid LC-ESI-MS/MS method using isotopic dilution quantification including a simplified extraction step using a mixture of solvents and sulphuric acid hydrolysis followed by the one-shot analysis of TBBPA and each of the α-, β- and γ-HBCD diastereoisomers. The limits of detection and quantification (LOD and LOQ) were 0.5 and 2.5 ng g−1 (lipid weight, lw) for TBBPA and HBCD diastereoisomers, respectively. The method was applied to analyse 106 samples of individual mature breast milk. TBBPA was quantified in 42% of these samples within a range of <LOQ to 15.1 ng g−1 lw. HBCD diastereoisomers were quantified in 8%, 3% and 3% of the collected samples for α-, β- and γ-HBCDs, respectively. The α-form was predominant in each quantifiable breast milk sample. The rapid newly developed LC-MS/MS method appears to be suitable for simultaneously analysing and quantifying TBBPA and HBCDs (three isomers) in human breast milk with the aim of establishing BFR multi-contamination profiles of breast milk samples.

Fate and adverse effects of hexabromocyclododecane diastereoisomers (HBCDDs) in a soil-ryegrass pot system

This study explored the fate and adverse effects of 3 main hexabromocyclododecane diastereoisomers (α-, β-, and γ-HBCDDs) in a soil pot system planted with ryegrass (Lolium perenne L.) using a short-term (8 weeks) experiment. At the end of the experiment, soil urease activity in planted spiked soil increased and catalase activity decreased; while there was no obvious change in sucrase and peroxidase activities. HBCDDs mainly accumulated in the root of ryegrass, with root concentration factors (RCF) in the range of 1.46–4.43 and only a small part was transferred to the stem (SCF: 0.198–0.305) and leaf (LCF: 0.042–0.062). The concentration factors varied for different HBCDD diastereoisomers, being in the order of α- > β- > γ-HBCDD for all tissues, indicating preferential accumulation of α-HBCDD in ryegrass tissues. Moreover, the enantiomeric analysis revealed an enrichment of (+)-α-, (−)-β- and (+)-γ-HBCDD enantiomers in ryegrass tissues. β- and γ-HBCDDs (up to 1.90% and 4.11%, respectively) were transformed to aα-HBCDD in ryegrass, while no isomerization product from α-HBCDD was found. Hydroxylated HBCDDs metabolites, such as monoOHHBCDDs and diOHHBCDDs were found in ryegrass tissues for the first time.