Compound degraded:Hexabromocyclododecane (HBCD)

General Description (About POP compound)

Hexabromocyclododecane (HBCD) is a solid, white powder that is used as a flame retardant additive for thermoplastic polymers. Its principal use is in expanded polystyrene foams and other styrene resins. It may also be used in latex binders, unsaturated polyesters, and polyvinyl chloride wire, cable, and textile coatings. When used in textiles, it is applied as a back coating to the fabric, encapsulated in a polymer matrix. Textile applications include residential and commercial furniture, up-holstery seating in transportation, draperies, and wall coverings

Biodegradation pathway

Publications

Abstract Title Authors Article Link
In this study, two pure strains, named HBCD-1 and HBCD-2, were isolated from a continuous anaerobic reactor over 300-days acclimation, which processed high capability of biodegrading Hexabromocyclododecane. Both of the two strains degraded HBCD diastereomers in different extents, especially strain HBCD-1, which interestingly degraded ?-HBCD effectively. All of the degrading results were well fitted with the first-order kinetics model. By morphological observation and 16S rRNA gene sequence analysis, the strain HBCD-1 showed highest similarity with Achromobacter sp. Under the optimal culturing conditions of 30 °C, pH 7 and the initial HBCD concentration of 500 ?g/L, the biodegradation rate of HBCD-1 reached 90% after 8 days treatment. Moreover, during the biodegradation process by HBCD-1 strain, the concentration of bromide ion was lower than the theoretical value. Finally, 4 metabolites were determined by liquid chromatography–tandem mass spectrometry (LC–MS/MS), as well as a biodegradation pathway was proposed. Study of novel pure culture HBCD-1, effectively degrading Hexabromocyclododecane, isolated from an anaerobic reactor Peng at el., 2015 Link
In a previous study the biodegradation of hexabromocyclododecane (HBCD) was reported to occur under realistic environmental concentrations in soils and freshwater aquatic sediments with biotransformation half-lives ranging from approximately 2 days to 2 months. In this study we extend our knowledge as to the environmental behavior of HBCD with respect to the fate of the three major diastereomers of HBCD (?, ?, and ?) as well as to the identification of major intermediate metabolites formed during degradation. Substantial biological transformation of the ?-, ?-, and ?-[14C]HBCD diastereomers was observed in wastewater (i.e., digester) sludge and in freshwater aquatic sediment microcosms prepared under aerobic and anaerobic conditions. Concomitant with the loss of [14C]HBCD in these matrixes there was a concurrent production of three [14C]products. Using a combination of high performance liquid chromatography atmospheric pressure photoionization mass spectrometry and gas chromatography electron impact ionization mass spectrometry these metabolites were identified as tetrabromocyclo- dodecene, dibromocyclododecadiene, and cyclododeca- triene. We propose that HBCD is sequentially debrominated via dihaloelimination where at each step there is the loss of two bromines from vicinal carbons with the subsequent formation of a double bond between the adjacent carbon atoms. These results demonstrate that microorganisms naturally occurring in aquatic sediments and anaerobic digester sludge mediate complete debromination of HBCD. Biodegradation and Product Identification of [14C]Hexabromocyclododecane in Wastewater Sludge and Freshwater Aquatic Sediment Davis et al., 2006 Link
The persistent organic pollutant, brominated flame retardant, hexabromocyclododecane (HBCD), identified as an emerging contaminant has been detected in various environmental matrix. The increased level of this toxic organic compound in the environment has been associated with serious human health risks. The results obtained from this study revealed that various Rhodopseudomonas palustris strains isolated from paddy soil in Taiwan possessed good HBCD biodegradation capability when they were cultured aerobically. Among these strains, YSC3 was considered as one of the most potential isolates for HBCD degradation. The optimum HBCD biodegradation occurred at neutral pH and at 35 °C in all our pH and temperature tests at an initial HBCD concentration of 1 ppm. HBCD degradation kinetics generally decreased with the increase of initial HBCD concentration. The study also suggested that the cultivation temperature played a vital role on YSC3 for its initiation of cellular HBCD degradation. The relative-molar ratio of the released bromide ions during the biodegradation of HBCD was observed in the range between 1 and 3.5, suggesting that the debromination reactions occurred. Concomitant with the loss of HBCD, there was a concurrent production of two metabolites, pentabromocyclododecanol and pentabromocyclododecene, which were determined by liquid chromatography and mass spectrometry techniques. On the basis of the obtained results, the possible biodegradation pathways were also proposed in this study. Biodegradation of hexabromocyclododecane by Rhodopseudomonas palustris YSC3 strain: A free-living nitrogen-fixing bacterium isolated in Taiwan Chang et al., 2020 Link
The potential toxicity of hexabromocyclododecane (HBCD), its persistence in the environment, and its high bioaccumulation characteristics pose a need to remediate HBCD in the environment. Bacillus cereus and B. subtilis species complexes we isolated from Taiwan soil are capable of degrading HBCD. B. cereus can degrade HBCD with a half-life only 0.911 days. The highest efficiency of HBCD degradation by B. cereus was achieved at pH 7.0, 35 °C, and 0.10 ppm HBCD. The removal mechanism of HBCD by B. cereus is debromination and its pathway was proposed. The addition of surfactant Tween 60 improved HBCD removal but the addition of CaO2, slow-releasing oxygen, did not. These findings can facilitate the bioremediation of HBCD in the environment. Efficient hexabromocyclododecane-biodegrading microorganisms isolated in Taiwan Chou et al., 2021 Link
Bacterial evolution has resulted in the appearance of several Sphingomonadacea strains that gained the ability to metabolize hexachlorocyclohexanes (HCHs). HCHs have been widely used as pesticides but were banned under the Stockholm Convention on persistent organic pollutants (POPs) in 2009. Here we present evidence for bacterial transformation reactions of hexabromocyclododecanes (HBCDs), which are structurally related to HCHs. HBCDs were used as flame retardants. They are now also considered as POPs and their production and use is restricted since 2013. Racemic ?-, ?-, and ?-HBCDs and their mixture were exposed to Sphingobium chinhatense IP26 in resting cell assays in parallel to ?-HCH. All HBCD stereoisomers were converted with (?)?-HBCD being the best and both ?-HBCD enantiomers the poorest substrates. HBCD conversion rates were 27–430 times slower than that of ?-HCH. Three generations of hydroxylated transformation products were observed, 7 pentabromocyclododecanol isomers (PeBCD-ols), 11 tetrabromocyclododecadiols (TeBCD-diols) and 3 tribromocyclododecatriols (TrBCD-triols). The conversion of (+)?-, (?)?- and (?)?-HBCD was faster than those of their enantiomers. Therefore the respective enantiomeric excess increased to 3 ± 1%, 36 ± 1% and 6 ± 2% during 48 h of bacterial exposure. PeBCD-ols appeared first, followed by TeBCD-diols and TrBCD-triols indicating stepwise hydrolytic dehalogenation reactions. In conclusion, severe HCH pollution at geographically distinct dumpsites triggered bacterial evolution to express enzymes transforming such compounds. We used S. chinhatense IP26 bacteria to transform structurally related HBCDs, also regulated under the Stockholm Convention. Such bacteria might be useful for bioremediation but the toxicity of the numerous transformation products observed must be assessed in advance. Biotransformation of hexabromocyclododecanes with hexachlorocyclohexane-transforming Sphingobium chinhatense strain IP26 Heeb et al., 2017 Link
Hexabromocyclododecanes (HBCDs) are the second-most widely used brominated flame retardants. They cause inappropriate antidiuretic hormone syndrome and can induce cancer. However, little information is available about bacterial degradation of HBCDs. In this study, HBCDs (?-, ?- and ?-HBCD) degrading strain Pseudomonas aeruginosa HS9 was isolated, identified, and characterized. The strain HS9 could remove 69% (± 0.05%) of 1.7?mg/L HBCDs in 14 days. Based on identification of metabolites, this bacterium could oxidize HBCDs by two pathways. In the first, HBCDs are sequentially debromized to tetrabromocyclododecene, dibromocyclododecadiene, and then debromized once more to cis, trans, trans-1, 5, 9-cyclododecatriene (CDT). After that, CDT is then oxidized to 1,2-epoxy-5,9-cyclododecadiene. The second identified pathway is a simultaneous debrominating and hydroxylating process based on the detection of 2,5,6,9,10-pentabromocyclododecanols, which were newly identified. The strain’s effects on plant-maize growth were tested and bioremediation evaluation trials were performed. The addition of strain HS9 could decrease HBCDs of 4.08?mg/g (87.6% removed) and 0.1?mg/g (25% removed) in soil and plants, respectively. Microbial diversity analysis shows that the addition of strain HS9 can promote the abundance of plant-beneficial bacteria, such as Methylobacillus, Nitrosomonas, Plancoccus, Bacillus, and Rhodococcus. The results provide insights for the bioremediation of HBCDs-contaminated soils. The HBCDs biodegradation using a Pseudomonas strain and its application in soil phytoremediation Huang et al., 2019 Link
Hexabromocyclododecanes (HBCDs) are widely used brominated flame retardants that cause antidiuretic hormone syndrome and even induce cancer. However, little information is available about the degradation mechanisms of HBCDs. In this study, genomic and proteomic analyses, reverse transcription-quantitative PCR, and gene knockout assays reveal that a cytochrome P450-encoding gene is responsible for HBCD catabolism in Pseudomonas aeruginosa HS9. The CO difference spectrum of the enzyme CYP168A1 was matched to P450 characteristics via UV visibility. We demonstrate that the reactions of debromination and hydrogenation are carried out one after another based on detection of the metabolites pentabromocyclododecanols (PBCDOHs), tetrabromocyclododecadiols (TBCDDOHs), and bromide ion. In the 18O isotope experiments, PBCD18OHs were only detected in the H218O group, proving that the added oxygen is derived from H2O, not from O2. This study elucidates the degradation mechanism of HBCDs by Pseudomonas. IMPORTANCE Hexabromocyclododecanes (HBCDs) are environmental pollutants that are widely used in industry. In this study, we identified and characterized a novel key dehalogenase, CYP168A1, that is responsible for HBCD degradation from Pseudomonas aeruginosa strain HS9. This study provides new insights into understanding biodegradation of HBCDs. Hexabromocyclododecanes Are Dehalogenated by CYP168A1 from Pseudomonas aeruginosa Strain HS9 Huang et al., 2021 Link
Hexabromocyclododecanes (HBCDs), a new sort of brominated flame retardants (BFRs), are globally prevalent and recalcitrant toxic environmental pollutants. HBCDs have been found in many environmental media and even in the human body, leading to serious health concerns. HBCDs are biodegradable in the environment. By now, dozens of bacteria have been discovered with the ability to transform HBCDs. Microbial debromination of HBCDs is via HBr-elimination, HBr-dihaloelimination, and hydrolytic debromination. Biotic transformation of HBCDs yields many hydroxylated and lower brominated compounds which lack assessment of ecological toxicity. Bioremediation of HBCD pollution has only been applied in the laboratory. Here, we review the current knowledge about microbial debromination of HBCDs, aiming to promote the bioremediation applied in HBCD contaminated sites. Microbial debromination of hexabromocyclododecanes Yuyang et al., 2021 Link
Hexabromocyclododecane (HBCD) is one of the most frequently used brominated flame retardants (BFRs) in the industries nowadays. Despite being listed as persistent organic pollutant (POP), it is still in use until 2025. Because of its bio-accumulative and toxic characteristics, the applicable remediation approach is required. The aim of this study is to identify the microbial community from soil with HBCD degradation ability. The soil suspension and soil samples from Chiang Chun Soil and River Bank Soil showed to degrade HBCD by 60% 4 days after treatment, the debromination ratio was around 60%, and the total HBCD removal ratio reached 70% and 77.9%, respectively. The HBCD debromination metabolites, and oxidation metabolites were identified by GC–MS. The microbial taxonomic diversity was observed with DGGE approach to evaluate the effect of HBCD of microbial community. Bacillus spp. and Clostridium spp. were identified as the dominant microbes in the Chiang Chun Soil, but the amount of Bacillus spp. were showed to be affected by HBCD. In conclusion, HBCD could be removed by the microbial consortium in soil under aerobic culturing condition by various metabolic pathways. Aerobic degradation and the effect of hexabromocyclododecane by soil microbial communities in Taiwan Li et al., 2020 Link