Enantiomer-specific Accumulation Research Articles

Hexabromocyclododecanes in surface soil-maize system around Baiyangdian Lake in North China: Distribution, enantiomer-specific accumulation, transport, temporal trend and dietary risk

This study investigated the occurrence of hexabromocyclododecanes (HBCDs) in soil-maize system around Baiyangdian Lake. The total concentration of ΣHBCDs was in the order of industrial area > residential area > marginal area > Fuhe River estuary in soil. γ-HBCD was predominated in soils, roots and stems, while α-HBCD was the main diastereoisomer in leaves and kernels. Concentration of ΣHBCDs and three diastereoisomer concentrations in soils were significantly reduced and remained low level from 2018 to 2019. Selectivity enrichment of (+)α- and (-)γ-HBCD was found in soils, roots, stems and leaves, whereas only (+)β-HBCD dominated in stems. Most of the total root bioaccumulation factors (ΣRCFs) were less than 1.0, but no significant correlation was showed between translocation factors (TFs) and log Kow. RCFs and TFs of enantiomers suggested (-)β- and (-)γ-HBCD were easily translocated from soil to roots, while (+)α-, (-)β- and (-)γ-HBCD tended to translocate from stems to leaves. Estimated daily intake (EDI) and of ΣHBCDs, diastereoisomers and enantiomers were all lower than the threshold value, while the Calculated margins of exposure (MOE) were well above the threshold value, which demonstrate the safe consumption of Maize around Baiyangdian Lake.

The release and earthworm bioaccumulation of endogenous hexabromocyclododecanes (HBCDDs) from expanded polystyrene foam microparticles

Hexabromocyclododecanes (HBCDDs) are common chemical additives in expanded polystyrene foam (EPS). To evaluate the bioaccumulation potential of endogenous HBCDDs in EPS microparticles by earthworms, two ecologically different species of earthworms (Eisenia fetida and Metaphire guillelmi) were exposed to soil added with EPS microparticles of different particle sizes (EPS2000, 830–2000 μm and EPS830, <830 μm). To clarify the accumulation mechanisms, leaching experiments using EPS microparticles in different solutions were conducted. After exposure to EPS microparticles-amended soils (S-EPS) for 28 d, the total concentrations of HBCDDs reached 307–371 ng g−1 dw in E. fetida and 90–133 ng g−1 dw in M. guillelmi, which were higher than those in earthworms exposed to the soil that was artificially contaminated with a similar level of HBCDDs directly (ACS). The accumulation of HBCDDs in earthworms was significantly influenced by EPS microparticles' size and earthworms' species. The total concentrations of HBCDDs in earthworms' cast were significantly higher than the theoretical concentration of HBCDDs in S-EPS, which suggested that EPS microparticles can be ingested by earthworms. The release rate of HBCDDs from EPS5000 (2000–5000 μm) into water-based solutions (<1%) after a 3.5-h incubation was far lower than that into earthworm digestive fluid (7%). These results illustrated that the ingestion of EPS microparticles and consequent solubilization of HBCDDs by digestive fluid play an important role in the accumulation of HBCDDs contained in EPS microparticles in earthworms. After a 28-d incubation with the soil solution, 4.9% of the HBCDDs was accumulatively leached from the EPS5000, which indicated that HBCDDs can be released from EPS microparticles to soil environment, and then accumulated by earthworms. Moreover, similar to those exposed to ACS, the diastereoisomer- and enantiomer-specific accumulation of HBCDDs in earthworms occurred when exposed to S-EPS. This study provides more evidence for the risk of microplastics to the soil ecosystem.

Enantiomer-specific accumulation and depuration of α-hexabromocyclododecane (α-HBCDD) in chicken (Gallus gallus) as a tool to identify contamination sources

A LC-ESI(−)-HRMS method dedicated to the analysis of 6 HBCDD enantiomers at trace levels in animal matrices was developed, using a cellulose based stationary phase with a particle size of 2.5 μm. This method was applied to a sample set derived from a kinetic study of α-HBCDD previously conducted in fast- and slow-growing chickens (Gallus gallus domesticus, n = 49, plus controls), in order to study the enantiomer specific accumulation and depuration of α-HBCDD in various tissues. Regarding abdominal adipose tissue, muscle and liver, the average enantiomeric fractions of α-HBCDD (EFα) for continuously exposed groups ranged between 0.434 and 0.467, with standard deviations below 0.014, showing a significant enrichment in (−)α enantiomer even accentuated for slow growing individuals during depuration with EFα reduced by about 0.020. Similar trends were observed for pooled plasma. Then, EFα of circulating plasma α-HBCDD appeared to closely reflect EFα in storage tissues and liver, suggesting some equilibrium. The racemic elimination of α enantiomer in excreta during the contamination phase indicated that no preferential gastrointestinal absorption took place. By contrast, preferential excretion of (−)α-HBCDD from the circulating compartment to the intestinal lumen occurred during the depuration. Finally, the method was applied to samples collected in three chicken farms, selected for total HBCDD levels in muscle in the ng/g range, as a tool to determine whether the contamination occurred ante- or post-mortem, according to the chiral signature. Ante-mortem contamination was hypothesised for 2 farms, with feed being excluded as contamination source.

Experimental and Theoretical Evidence for Diastereomer- and Enantiomer-Specific Accumulation and Biotransformation of HBCD in Maize Roots.

Diastereomer- and enantiomer-specific accumulation and biotransformation of hexabromocyclododecane (HBCD) in maize (Zea mays L.) were investigated. Molecular interactions of HBCD with plant enzymes were further characterized by homology modeling combined with molecular docking. The (-)α-, (-)β-, and (+)γ-HBCD enantiomers accumulated to levels in maize significantly higher than those of their corresponding enantiomers. Bioisomerization from (+)/(-)-β- and γ-HBCDs to (-)α-HBCD was frequently observed, and (-)γ-HBCD was most easily converted, with bioisomerization efficiency of 90.5 ± 8.2%. Mono- and dihydroxyl HBCDs, debrominated metabolites including pentabromocyclododecene (PBCDe) and tetrabromocyclododecene (TBCDe), and HBCD-GSH adducts were detected in maize roots. Patterns of hydroxylated and debrominated metabolites were significantly different among HBCD diastereomers and enantiomers. Three pairs of HBCD enantiomers were selectively bound into the active sites and interacted with specific residues of maize enzymes CYP71C3v2 and GST31. (+)α-, (-)β-, and (-)γ-HBCDs preferentially bound to CYP71C3v2, whereas (-)α-, (-)β-, and (+)γ-HBCDs had strong affinities to GST31, consistent with experimental observations that (+)α-, (-)β-, and (-)γ-HBCDs were more easily hydroxylated, and (-)α-, (-)β-, and (+)γ-HBCDs were more easily isomerized and debrominated in maize compared to their corresponding enantiomers. This study for the first time provided both experimental and theoretical evidence for stereospecific behaviors of HBCD in plants.

Diastereomer- and enantiomer-specific accumulation, depuration, bioisomerization, and metabolism of hexabromocyclododecanes (HBCDs) in two ecologically different species of earthworms

In this study, two ecological types of earthworms were exposed to soil samples that were artificially contaminated with individual hexabromocyclododecane (HBCD) diastereomers (α-, β-, and γ-HBCDs) to investigate the bioaccumulation, depuration, enantiomer selectivity and isomerization of HBCDs in earthworms. The uptake rate constant (ku), bioaccumulation factor (BAF), biota soil accumulation factor (BSAF), and half-life (t1/2) for the α-HBCD were the highest among the three diastereomers. The bioaccumulation parameters of the three diastereoisomers differed between the two ecologically different species of earthworms. The BSAF values of α- and γ-HBCDs were substantially higher in Eisenia fetida than those in Metaphire guillelmi, with the higher lipid and protein contents in E. fetida as the primary reason for this difference. The other processes, such as uptake, depuration, metabolism and isomerization, also differed between the two species and led to a difference in the bioaccumulation of β-HBCD. The β- and γ-HBCDs were bioisomerized to α-HBCD in the earthworms, but to a greater extent in E. fetida. The highest BSAF, t1/2 of α-HBCD and the bioisomerization of β- and γ-HBCDs to α-HBCD might explain in part why α-HBCD was the dominant isomer in biota samples. Most of the enantiomer fractions (EFs) for the three HBCD diastereoisomers in the earthworms were different from those in standard samples (p<0.05), indicating that enantiomer selectivity occurred. Moreover, the trends and extent of the enantioselectivity were different between the two species. Additionally, the EFs of α-HBCD that was bioisomerized from β- or γ-isomers were also different from those in the standards (p<0.05), which likely reflect the integration of several processes, such as enantioselective isomerization and the subsequent selective metabolism of the produced α-HBCD or selective excretion of the enantiomers.

Enantiomer-specific accumulation, depuration, metabolization and isomerization of hexabromocyclododecane (HBCD) diastereomers in mirror carp from water

Until now, the bioaccumulation of hexabromocyclododecanes (HBCDs) in aquatic organisms has been studied only via dietary exposure. To better understand the environmental fate of HBCDs, we conducted a bioaccumulation test by exposing mirror carp to three HBCD diastereomers in water during 30d of accumulation and 30d of depuration according to Organization for Economic Co-operation and Development (OECD) Test Guidelines 305 (Bioaccumulation in Fish: Aqueous and Dietary Exposure). We found that the BCFKL values (bioconcentration factor calculated from kinetic data and adjusted to lipid content) of α-HBCD in different tissues of the carp were in the range of (3.07–4.52)×104, much higher than those of β-HBCDs (1.03–1.90×103) and γ-HBCD (0.95–1.73×103), as was true of t1/2. The order of BCFK for α-, β- and γ-HBCD in different tissues was viscera>gill>skin>muscle. β-HBCD and γ-HBCD were transformed to α-HBCD, with 50.0–92.9% and 96.2–98.6% bioisomerization efficiencies by the end of the experiment, respectively. No isomerization product from α-HBCD was found. Selective enrichment of the (+) α- and γ-HBCD was found, whereas β-HBCD did not show significant enantioselectivity. New metabolites such as tetrabromocyclododecene (TBCDe), tribromocyclododecadiene (TriBCDi) and tribromocyclododecatriene (TriBCDie) were found in mirror carp for the first time under multiple reaction monitoring (MRM) mode.

Species-specific bioaccumulation of polybrominated diphenyl ethers, hexabromocyclododecan and dechlorane plus in biota: A review

Polybrominated diphenyl ethers (PBDEs), hexabromocyclododecans (HBCDs) and dechlorane plus (DPs) are ubiquitous contaminants that are found in numerous matrices around world. They have been proven to be environmentally persistent, bioaccumulative, and toxic to biota, and subject to long-range transport. Technical PBDE mixtures consist of congeners with different bromine content. HBCDs were consisting of three diasteroisomers (α-, β- and γ-HBCD) and these three isomers are chiral and occur as racemates in technical mixtures. Commercially available DP is a mixture of two stereo isomers: syn -DP and anti -DP. Inter- and intra-species differences on bioaccumulation of PBDEs, HBCDs, and DPs were observed in wildlife which could be attributed to species-specific differences in habitat, diet, contaminant metabolism, absorption and execution as well as different physical and chemical properties among different chemicals. The congener-specific accumulation for PBDEs, the diadtereoisomer and enantiomer-specific accumulation for HBCDs, and the isomer-specific accumulation for DPs in biota indicated the bioaccumulation of these three types of contaminants in biota are very complex processes. This review summarizes the species-specific bioaccumulation of PBDEs, HBCDs, and DPs in biota and analyzes the potential causes for this observation. The currently existing problems and needs for further research are also discussed.

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.

Enantiomer-specific accumulation of hexabromocyclododecanes in eggs of predatory birds

The diastereomeric composition of hexabromocyclododecane (HBCD) in eggs of peregrine falcon ( Falco peregrinus), white-tailed sea eagle ( Haliaeetus albicilla), guillemot ( Uria aalge) and common tern ( Sterna hirundo) as well as the guillemots’ main prey, herring ( Clupea harengus) was determined by reversed-phase chromatography with triple-stage quadrupole mass spectrometric detection (LC–MS–MS). α-HBCD was the predominant diastereomer in all bird species, while in herring, γ-HBCD made a substantial contribution. Two, as yet unidentified diastereomers, were detected in common tern egg. The α-, β- and γ-HBCD (+) and (−) enantiomers were separated using a chiral stationary phase. The enantiomer fractions for α-HBCD differed substantially between different bird species as well as between guillemot and its prey, herring. Total HBCD levels determined by LC–MS–MS were comparable to those previously obtained by GC–MS.

Hexabromocyclododecane in Marine Species from the Western Scheldt Estuary: Diastereoisomer- and Enantiomer-Specific Accumulation

Hexabromocyclododecane (HBCD) is a widely used brominated flame retardant, which is increasingly reported in the environment. Here, we report on the diastereomeric and, for the first time, on the enantiomeric composition of HBCD in muscle and liver of several fish species caught in the Western Scheldt Estuary (The Netherlands). The total HBCD content (sum of alpha-, beta-, and gamma-diastereoisomers), as well as the distribution of diastereoisomers and enantiomers, varied between the species. The levels of total HBCD (9-1110 ng/g lipid weight) found in fish tissues were higher than those measured in fish from European rivers with no known point sources of HBCD but lower than in fish samples collected near factories producing or using HBCD. The concentrations of total HBCD expressed on a lipid weight basis were higher in liver than in muscle for bib and whiting, while in sole, HBCD had no preferential distribution between the tissues. A similar pattern for liver and muscle distribution was already observed for polybrominated diphenyl ethers (PBDEs) in these species. The alpha-HBCD diastereoisomer was most abundant in all fish samples with a higher contribution to the total HBCD levels in liver compared to muscle for bib and whiting. The gamma-HBCD diastereoisomer accumulated less in liver than in muscle of sole, bib, and whiting. For the first time, enantiomer fractions were determined for HBCD diastereoisomers in liver of three fish species and in muscle of two fish species. A significant enrichment of the (+) alpha-HBCD enantiomer was found in whiting and bib liver samples. A high enantioselectivity has also been seen for the gamma-HBCD diastereoisomer in whiting liver.

Enantiomer-specific accumulation of PCB atropisomers in the bowhead whale (Balaena mysticetus).

Blubber (n = 40) and liver (n = 20) samples from the bowhead whale (Balaena mysticetus) were collected during the 1997-1998 Native (Inuit) subsistence harvests in Barrow, AK. Bowhead tissues and zooplankton were analyzed for polychlorinated biphenyl (PCB) concentrations and the enantiomeric fractions (EFs) of eight chiral PCB congeners (PCB-91, 95, 135, 136, 149, 174, 176, and 183) to quantify the enantiomer-specific accumulation of PCBs in this cetacean. PCB concentrations in bowhead blubber were low (mean +/- 1 SE: 610 +/- 54 ng g(-1) lipid) relative to other cetaceans. The accumulation of several chiral PCBs (PCB-91, 135, 149, 174, 176, and 183) in bowhead blubber was enantiomer-specific relative to bowhead liver and zooplankton, suggesting that biotransformation processes within the bowhead whale are enantioselective. The EFs for PCB-95 and 149 were significantly correlated with body length in male and female whales, while EFs for PCB-91 correlated with length in males only. Despite evidence for enantioselective biotransformation, all three congeners bioaccumulated in the bowhead relative to PCB-153. Results suggest that enantioselective accumulation of PCB-91, 95, and 149 is influenced by PCB concentrations, age, and/or the modification of an uncharacterized stereoselective process (or processes) during sexual maturity.