Concentrations Of Hexabromocyclododecane Research Articles

Inventorization and ecological risk assessment of tetrabromobisphenol A and hexabromocyclododecane in sediments from Guangdong coastal area of South China Sea

Brominated flame retardants (BFRs) exhibit excellent flame retardant properties and are widely used in various industries. Among the common BFRs, tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCDs) pose substantial ecological and human health risks due to their extensive application and long-range transport. This study established 131 sample collection sites along the coast of the South China Sea (SCS) in Guangdong Province to assess the concentration, distribution, inventory, and ecological risk of TBBPA and HBCDs in surface sediments. The concentrations of TBBPA in SCS sediments ranged from < limit of detection (LOD) to 80 μg/kg dry weight (dw), and those of HBCDs from < LOD to 18 μg/kg dw. The diastereoisomers of HBCDs (α-, β-, and γ-HBCD) in the sediment samples accounted for 36 %, 13 %, and 51 %, respectively. Human activities, particularly those associated with nearby electronic waste disassembly and textile and garment industries, considerably influenced the dispersion of TBBPA and HBCDs. The inventories of TBBPA and HBCDs in Guangdong Province's SCS were estimated to be 3.2 × 105 kg and 7.2 × 104 kg, respectively. The average risk quotient values ranged from <0.01 to 0.016, indicating a low to negligible environmental risk. This study provides deeper insights into the distribution and scientific significance of HBCDs and TBBPA in SCS sediment samples, elucidates the current state of BFR contamination, and offers recommendations for future research on environmental safety and human health in the region.

Co-metabolic degradation and metabolite detection of hexabromocyclododecane by Shewanella oneidensis MR-1.

Hexabromocyclododecane (HBCD) is a widely used brominated flame retardant; however, it is a persistent organic pollutant as well as affects the human thyroid hormones and causes cancer. However, the degradation of HBCD has received little attention from researchers. Due to its bioaccumulative and hazardous properties, an appropriate strategy for its remediation is required. In this study, we investigated the biodegradation of HBCD using Shewanella oneidensis MR-1 under optimized conditions. The Box-Behnken design (BBD) was implemented for the optimization of the physical degradation parameters of HBCD. S. oneidensis MR-1 showed the best degradation performance at a temperature of 30 °C, pH 7, and agitation speed of 115 rpm, with an HBCD concentration of 1125 μg/L in mineral salt medium (MSM). The strain tolerated up to 2000 μg/L HBCD. Gas chromatography-mass spectrometry analysis identified three intermediates, including 2-bromo dodecane, 2,7,10-trimethyldodecane, and 4-methyl-1-decene. The results provide an insightful understanding of the biodegradation of HBCD by S. oneidensis MR-1 under optimized conditions and could pave the way for further eco-friendly applications. KEY POINTS: • HBCD biodegradation by Shewanella oneidensis • Optimization of HBCD biodegradation by the Box-Behnken analysis • Identification of useful metabolites from HBCD degradation.

A Review of Distribution and Profiles of HBCD in Different Environmental Media of China.

Hexabromocyclododecane (HBCD) is the most important flame retardant that has been used in Expanded Polystyrene foam and Extruded Polystyrene foam in the past forty years across the world. China was the major producer and user of HBCD, and the total HBCD production was about 0.3 million tons. Although HBCD was completely banned in China in 2021 because of its long-range transport, bioaccumulation and toxicity, there is still a lot of residue in the environment. Therefore, we reviewed multiple studies concerning the distribution of HBCD in diverse environmental matrices, such as in the air, dust, soil, water, sediment, and biota. Results revealed that HBCD levels in different environments in China present geographical variation and were at a high level compared with other countries. In all environmental media, relatively high HBCD concentrations have been found in industrial and urban areas. Industrialization and urbanization are two important factors that influence the concentration and distribution of HBCD in the environment. In terms of isomer, γ-HBCD was the dominant isomer in soil, water, and sediment, while in the biota α-HBCD was the predominant isomer.

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 &amp;gt; γ-HBCD &amp;gt; 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.

Hexabromocyclododecane (HBCD) induced PANoptosis of chondrocytes via activation of the NLRP3 inflammasome and decreased the exercise ability of mice in vivo

Hexabromocyclododecane (HBCD) is a persistent organic pollutant (POP). HBCD is found in the blood and tissues of most populations and causes a range of toxicological damage to tissues and cells. However, the toxicological effects of HBCD on chondrocytes are not fully understood. Here, we evaluated the toxicological effects of HBCD on chondrocytes and cartilaginous tissue. For this, a model of primary cartilage cells was established. Chondrocytes were exposed to different concentrations of HBCD. Western blot, indirect immunofluorescence, ELISA and other biochemical experiments were performed to analyze the toxicological effects of HBCD on chondrocytes/articular cartilage tissue. Cell proliferation assays showed that HBCD caused a reduction in the proliferative capacity of chondrocytes, and further work indicated that HBCD induces chondrocyte death. Further experiments demonstrated that HBCD caused an inflammatory response in chondrocytes by evaluating the levels of inflammatory factors. We found that HBCD led to PANoptosis in chondrocytes by detecting panapoptosis-related marker molecules, and experimental data indicated that apoptosis markers (cleaved caspase-3/7), pyroptosis markers (caspase-1/GSDMD-N) and necroptosis markers (pMLKL/RIPK3) were upregulated after HBCD treatment. Subsequent experiments illustrated that HBCD activated the DAMP sensor NLRP3, which then mediated ZBP1-induced PANoptosis. In the in vivo model, the experimental animals were administered HBCD at 25, 50 and 100 µg/kg/week for 15 weeks. We found that HBCD led to an inflammatory response in articular cartilage tissue. The safranin O-fast green assay showed a certain degree of damage to cartilage tissue under HBCD treatment. Furthermore, HBCD resulted in an increase in MMP13 expression and a downregulation of COL2 expression in chondrocytes/cartilaginous tissues. HBCD decreased the exercise ability of mice in vivo. These data indicate that HBCD leads to chondrocyte damage. In summary, this study lays the foundation for further exploration of the toxicological effects of HBCD on bone and joints.

Spatial distribution, conversion, and ecological risk assessment of hexabromocyclododecanes in the sediments of black-odorous urban rivers nationwide in China

Hexabromocyclododecanes (HBCDs) have become a global pollution problem, particularly in China—a major producer and user of HBCDs. However, little is known about the HBCD pollution status in urban rivers nationwide in China. In this study, we comprehensively investigated the pollution characteristics of HBCDs in 173 sediment samples from black-odorous urban rivers across China. Total HBCD concentrations ranged from not-detected to 848 ng/g dw, showing significant differences among the various sampling cities, but generally increasing from west to east China. This distribution pattern of HBCDs was strongly associated with the local industrial output, gross domestic product, and daily wastewater treatment capacity. α-HBCD was the predominant diastereoisomer in most sediments, with an average proportion of 63.8 ± 18.8 %, followed by γ-HBCD (23.8 ± 19.5 %) and β-HBCD (12.4 ± 6.49 %), showing a significant increase of the α-HBCD proportions relative to those in HBCD commercial mixtures and an opposite trend for that of γ-HBCD. These results suggested that HBCDs might undergo isomerization from γ- to α-HBCD and biotic/abiotic degradation with preference for γ-HBCD. Of these conversions, the microbial degradation of HBCDs was further verified by the preferential transformation of (−)-α-, (+)-β-, and (−)-γ-HBCDs and the detection of HBCD-degrading bacteria, including Dehalococcoides, Bacillus, Sphingobium, and Pseudomonas. A risk assessment indicated that HBCDs pose low to moderate risks to aquatic organisms in most black-odorous urban river sediments.

Effects of hexabromocyclododecane and polyethylene microplastics on soil bacterial communities

Hexabromocyclododecane (HBCD) and polyethylene (PE) microplastic are ubiquitous pollutants, and knowledge about the effects of HBCD and PE pollution on soil bacterial communities remains obscure. In this study, the effects of different HBCD and PE concentrations and combined HBCD and PE exposure on the diversity, composition, and function of agricultural soil bacterial communities over 4 months were systematically examined for the first time. Generally, soil bacterial communities were influenced in both the 1-month and 4-month scenarios through HBCD and PE separately as well as combined exposure. After 4 months of exposure, PE and combined exposure significantly affected soil bacterial alpha diversity, however, low concentration of HBCD showed no apparent influence. 1-month and 4-month HBCD, PE, and combined exposure significantly influenced bacterial beta diversity. Compared with 1 month of exposure, HBCD, PE, and combined exposure demonstrated remarkable influences on soil bacteria after 4 months of exposure, especially on Nitrospirae, Elusimicrobia, Rokubacteria at the phylum level, and on MND1, Ruminiclostridium, Lysobacter, Anaeromyxobacter, Alistipes, WCHB1 at the genus level. The bacterial function analysis indicated that amino acid metabolism, carbohydrate metabolism, and membrane transport were the three predominant enriched bacterial functions after 1-month and 4-month HBCD and PE exposure. This research provides a comprehensive grasp of the effects of HBCD and PE pollution on soil microbial communities, which could have a beneficial impact on future soil pollution control.

Rising concentrations of polybrominated diphenyl ethers (PBDEs) in Nigerian foodstuffs despite global restrictions

The presence of brominated flame retardants (BFRs) in foodstuffs of African origin is poorly understood. To fill this gap, animal-derived food samples comprising 13 different items originally from Nigeria were obtained in 2021, and concentrations of novel brominated flame retardants (NBFRs), polybrominated diphenyl ethers (PBDEs), and hexabromocyclododecane (HBCDD) were measured. Arithmetic mean concentrations of NBFRs, PBDEs, and HBCDD in Nigerian foodstuffs were 2.1 ng/g (18 ng/g lipid weight (lw)), 1.3 ng/g (9.2 ng/g lw), and 0.42 ng/g (2.8 ng/g lw), with median concentrations of 1.7 ng/g (14 ng/g lw), 1.1 ng/g (8.2 ng/g lw), and <0.34 ng/g (<3.3 ng/g lw), respectively. Higher concentrations of NBFRs than of PBDEs and HBCDDs in Nigerian foodstuffs likely reflect use of NBFRs as substitutes for legacy BFRs in Nigeria. Comparison with previous dietary studies reveals rising concentrations of PBDEs in Nigerian foodstuffs in recent years with associated rises in dietary exposure, possibly due to active domestic use of PBDEs in Nigeria. Reassuringly, comparison of our exposure estimates with health-based limit values suggests adverse health effects of dietary intake of BFRs by Nigerians are unlikely to occur.

Brominated flame retardants in surface sediment from Western Guangdong, South China: Occurrence, distribution and toxicity in Caenorhabditis elegans

Sediment is the ultimate sink of environmental pollutants. A total of 128 surface sediment samples were collected from 8 rivers and 3 reservoirs in Maoming City, Guangdong Province. This study assessed the content and distribution of brominated flame retardants in sediments. The acute toxicity effects of tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCDs) in sediments were evaluated using Caenorhabditis elegans as model organisms. The concentration of TBBPA in sediments ranged from not detected (ND) to 12.59 µg/kg and was mainly distributed in the central area, which was affected by the emission of TBBPA from residential and factory. The concentration of HBCDs ranged from ND to 6.31 µg/kg, and the diastereoisomer distribution was consistent, showing a trend close to the South China Sea. The composition pattern of HBCDs in the surface sediments from rivers were 41.73%–62.33%, 7.89%–25.54%, and 18.76%–40.65% for α-, β-, and γ-HBCD, respectively, and in the sediments from reservoirs were 26.15%–45.52%, 7.44%–19.23%, and 47.04%–61.89% for α-, β-, and γ-HBCD, respectively. When the sum of concentrations of TBBPA and HBCD in sediments were above high levels, reactive oxygen species in nematodes significantly increased, resulting in an oxidative stress response. Intestinal permeability was also enhanced, causing intestinal damage. In addition, in terms of this study, TBBPA had a greater impact on biotoxicity compared to HBCDs, and more attention should be paid to the toxic effects of the river ecosystem organisms in Maoming City, Guangdong Province. This study can complement the pollution database in the study area and provide basic data for pollution control.

Spatial and temporal change of tetrabromobisphenol A and hexabromocyclododecane in mangrove sediments from the Pearl River Estuary, South China

Spatial and temporal trends of tetrabromobisphenol (TBBPA) and hexabromocyclododecane (HBCD) in mangrove sediments from the Pearl River Estuary (PRE) in South China were evaluated. Concentrations of TBBPA and HBCD in mangrove sediments ranged from 0.23 to 13.3 and 0.36 to 54.7 ng g−1 dry weight. The highest TBBPA concentration was seen in Guangzhou mangrove wetland near a dockyard and a ferry terminal where TBBPA is utilized in the coatings for the shipbuilding industry. The rapid development of building might elucidate the higher concentrations of HBCD in Shenzhen mangrove sediments. γ-HBCD and α-HBCD was the two main diastereoisomer of HBCD in mangrove sediments with contributions of 56.1 % and 34.0 %. Sediments from the three PRE mangrove ecosystems were selectively enriched for (−)-γ-HBCD. TBBPA concentrations in mangrove sediments from Guangzhou rose during 2012–2015 and declined from 2015 to 2021. HBCD concentrations in the PRE mangrove sediments exhibited an increasing trend from 2012 to 2021.

Spatial distribution, source, and ecological risk of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in Jiaozhou Bay, China

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) are commonly found in the environment as components of brominated flame retardants. Due to their potential impact on human health and wildlife, it is imperative to closely monitor and manage their levels in the environment. This study investigated the spatial distribution, sources, and ecological risks of PBDEs and HBCDs in Jiaozhou Bay (JZB), a large bay situated on the eastern coast of China. The results showed that PBDE concentrations ranged from not detected (ND) to 7.93 ng/L in the water and ND to 65.76 ng/g in the sediment, while HBCD concentrations ranged from ND to 0.31 ng/L in the water and ND to 16.63 ng/g in the sediment. Furthermore, we observed significantly higher concentrations of PBDEs and HBCDs in the inner JZB compared to the outer JZB. Our source apportionment analysis showed that PBDEs primarily originated from the production and debromination of BDE-209, as well as the emission of commercial PeBDEs, whereas HBCDs in sediments mostly stemmed from anthropogenic activities and river input. Finally, our eco-logical risk assessment highlighted the need for continuous monitoring of PBDEs in JZB sediments. Overall, our study aims to provide valuable assistance for the environmental management of the JZB bay area, which is characterized by a complex net-work of rivers and a thriving economy.

Human health risk assessment from exposure to multiple sources of Hexabromocyclododecanes (HBCDs) in Taiwan

Hexabromocyclododecanes (HBCDs) are endocrine-disrupting and persistent organic compounds commonly used in consumer products such as styrofoam, fire-resistant curtains, construction, aquaculture products, and food containers. Humans can expose to HBCD via dermal, ingestion, and inhalation routes; however, the inhalation exposure to HBCDs is not well characterized, especially for the size-segregated particles, which could quickly deposit into the respiratory system. In this study, we systematically characterized the dermal and inhalation exposures and performed an aggregate risk assessment of HBCDs in Taiwan. Sampling sites were selected considering the traffic or industrial contribution for air (n = 2, Sanchung, and Taichung) and soil sampling (n = 19, near the industrial zones). The quantitative analysis of HBCDs in extracted samples was achieved using LC–MS/MS. Our results showed that the concentrations of total HBCDs ranged from 0.1 to 6.6 pg m−3 in the particulate matter samples and 0.63 to 187 μg kg−1 in soil samples, where γ-HBCD was the dominant species, followed by α-HBCD and β-HBCD. The total HBCDs in the finest particles (i.e., particle size below 0.49 μm) ranged from N.D. to 1.5 pg m−3. However, no consistent trend was observed for the isomer distribution of HBCDs among air samples. Furthermore, the margin of exposure was the lowest through the ingestion pathway (5152 to 22555) and the highest through the inhalation pathway (6.71 × 105 to 2.09 × 107), showing that HBCD-induced health risk can predominantly attribute to ingestion exposure. Nevertheless, the traffic and industrial contribution of inhalable HBCD deserves further studies.

Novel Brominated Flame Retardants in Dust from E-Waste-Dismantling Workplace in Central China: Contamination Status and Human Exposure Assessment.

Novel brominated flame retardants (NBFRs) have been widely used as alternatives to legacy BFRs. However, information on the contamination status and human exposure risks of electronic waste (e-waste)-derived NBFRs in the e-waste workplace is limited. In this study, six NBFRs and the legacy BFRs, hexabromocyclododecanes (HBCDs), were analyzed in 50 dust samples from an e-waste-dismantling workplace in Central China. The dust concentration of NBFRs in e-waste-dismantling workshops (median, 157-169 ng/g) was found to be significantly higher than those in an outdoor environment (17.3 ng/g) (p &lt; 0.01). Differently, the highest median concentration of HBCDs was found in dust from the dismantling workshop for cellphones and computers (367 ng/g) among studied areas. The bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (BEHTBP) was the predominant compound, which contributed 66.0-88.0% of measured NBFR concentrations. NBFRs might originate from plastic and rubber materials in wastes based on the correlation and principal component analysis. Moreover, the total estimated daily intakes (average scenario) of NBFRs were calculated at 2.64 × 10-2 ng/kg bw/d and 2.91× 10-2 ng/kg bw/d for the male and female dismantling workers, respectively, via dust ingestion, inhalation, and dermal contact pathways, which were lower than the reference dose values, and thus indicated a limited human exposure risk for NBFRs at the current level. Although the dust concentrations and daily intakes of NBFRs were still lower than those of other emerging pollutants (e.g., organophosphate and nitrogenous flame retardants) measured in the same sampling set, the elevated levels of NBFRs suggested the progressive BFR replacement process in China, which deserves more attention regarding their adverse effects on both the environment and human health.

Expanded polystyrene buoys as an important source of hexabromocyclododecanes for aquatic ecosystem: Evidence from field exposure with different substrates

The production and use of hexabromocyclododecanes (HBCDs) have been strictly limited due to their persistence, toxicity and bioaccumulation. However, the release of HBCDs from related products and wastes would continue for a long time, which may cause many environmental problems. In this study, we investigated the occurrence and distribution of HBCDs and microplastics (MPs) in aquatic organisms inhabiting different substrates. HBCDs were measurable in the seawater, sediment, expanded polystyrene (EPS) substrates and organism samples. Mostly, the concentrations of HBCDs in organisms inhabiting EPS buoys were significantly higher than those of the same species inhabiting other substrates. Meanwhile, the diastereomeric ratio (α/γ) of HBCDs in organisms inhabiting EPS buoys was closer to that in EPS buoys. The fugacity values of HBCDs in EPS buoys were much higher than those in other media, implying that HBCDs can be transferred from EPS buoys to other media. Additionally, MPs derived from EPS buoys would be mistaken as food and ingested by aquatic organisms. The transfer of HBCDs from EPS buoys to aquatic organisms can be achieved by aqueous and dietary exposures. In combination, the contribution of MP ingestion to HBCDs for aquatic organisms should be very limited. These results supported EPS buoys as an important source of HBCDs for the aquatic ecosystem. To effectively control HBCDs pollution, it is necessary to discontinue or reduce the use of EPS buoys.

Temporal trends in concentrations of brominated flame retardants in UK foodstuffs suggest active impacts of global phase-out of PBDEs and HBCDD

Global restrictions on use of legacy brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) have generated demand for novel BFRs (NBFRs) as substitutes. Our research group has previously reported decreased concentrations of PBDEs and HBCDD and increased concentrations of NBFRs in UK indoor environments, suggesting that restrictions on PBDEs and HBCDD are exerting an impact. In this study, we analysed UK foodstuffs collected in 2020–21 and compared the BFR concentrations found with those found in similar samples collected in 2015 to investigate whether similar trends in BFR concentrations would be observed. Concentrations of PBDEs and HBCDD isomers detected in our samples had declined by 78–92 % and 59–97 % since the 2015 study, respectively. Moreover, concentrations of NBFRs (dominated by 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE or TBE), and bis(2-ethyl hexyl) tetrabromophthalate (BEH-TEBP or TBPH)) in UK foodstuffs increased significantly (28–1400 %) between 2015 and 2020–21. Combined, these findings suggest that restrictions on use of PBDEs and HBCDD have had a discernible impact on concentrations of these legacy BFRs and their NBFR replacements in UK foodstuffs. Interestingly, given recent reports of a significant increase in concentrations of decabromodiphenyl ethane (DBDPE) in UK house dust between 2014 and 2019, a significant decline (70–84 %) in concentrations of DBDPE was observed in UK foodstuffs.

Maternal Transfer and Apical and Physiological Effects of Dietary Hexabromocyclododecane Exposure in Parental Fathead Minnows (Pimephales promelas).

Hexabromocyclododecane (HBCD) is a persistent organic pollutant that has been characterized as an endocrine disruptor, undergoes maternal transfer, and hinders development and growth in oviparous organisms. The present study examined the apical effects of dietary HBCD (11.5, 36.4, 106 mg/kg, wet wt) on adult fathead minnow exposed for 49 days and the subsequent accumulation and maternal transfer kinetics in adult tissue and eggs, respectively. Exposed adults displayed a significant increase in egg production in the medium treatment group, but no other significant effects were noted. Maternal transfer of dietary HBCD had a similar egg-to-muscle ratios (EMR) in the low and medium treatment groups (1.65 and 1.27 [wet wt], respectively). However, the high treatment group deviated from other treatments with an EMR of 4.2 (wet wt), potentially due to differences in total lipid content in food and/or reaching diffusion/lipid saturation limits in adult tissue, resulting in lower accumulation in the adult muscle tissue. A positive correlation was observed between egg HBCD concentration and time of exposure, which indicates that maternal transfer of HBCD is of concern in fish, and further studies should be conducted to fully elucidate the potential adverse effects that may be observed in the early life stage of oviparous organisms. Environ Toxicol Chem 2023;42:143-153. © 2022 SETAC.

Progress in sample pretreatment and detection methods of hexabromocyclododecanes

作为一种常见的溴代阻燃剂,六溴环十二烷(HBCDs)因具备持久性、长距离迁移性、生物蓄积性和高毒性,于2013年被列入《斯德哥尔摩公约》。因此,环境样品中HBCDs污染水平的准确分析和严格控制对完善环境监管长效机制至关重要。然而,实际样品中HBCDs的定性定量分析正面临着基质复杂、目标物含量低等问题。尤其,HBCDs在高温环境及特定有机溶剂中易降解,会产生异构体,提高了分析难度。该综述简述了HBCDs的理化性质、毒性危害和标准限制,重点围绕不同基质中HBCDs的样品前处理和仪器检测两方面进行了总结。论文内容引用2000~2022年的70余篇源于科学引文索引(SCI)与中文核心期刊中的相关论文。总结归纳了固体和液体样品中HBCDs分析的前处理技术,包括索式提取、超声辅助萃取、加速溶剂萃取、超临界流体萃取、液液萃取、分散液液微萃取、固相萃取、分散固相萃取和固相微萃取等,介绍了气相色谱、液相色谱和色谱-质谱联用技术等仪器检测方法在HBCDs分析中的应用。通过综述近期相关研究,侧面表明HBCDs的分析方法研究发展迅速,但也面临一些挑战,如样品前处理步骤繁琐、耗时长、样品量和有机溶剂用量大等问题。最后,对新型样品前处理技术在HBCDs分析中的应用进行了展望。

Tetrabromobisphenol A and hexabromocyclododecanes in sediments from fishing ports along the coast of South China: Occurrence, distribution and ecological risk.

Tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDDs) have attracted extensive attention due to their strong persistence and toxicity. However, little has been known about their pollution status in fishing ports, which are typical sinks of land-sourced pollutants. In this study, we investigated the occurrence, distribution and ecological risk of TBBPA and HBCDDs in sediments from fishing ports along the coast of South China. The concentrations of TBBPA and ΣHBCDD (sum of α-, β-, and γ-HBCDD) in the fishing-port sediments were in the ranges of 0.02-21.5ng/g dw and 1.06-14.1ng/g dw, respectively. γ-HBCDD was the predominant diastereoisomer in most fishing-port sediments. The enantiomeric analysis indicated a preferential enrichment of (-)-enantiomers for α-, β-, and γ-HBCDD. The geographical location of fishing ports is a significant determinant of distribution for TBBPA and HBBCDs. The concentrations of TBBPA and HBCDDs in fishing-port sediments were strongly associated with local population density, but weakly correlated with total organic carbon content of the sediment. The mass inventories of TBBPA and ΣHBCDD were estimated to be 77.0ng/cm2 and 141ng/cm2, respectively. The ecological risk assessment demonstrated that TBBPA and HBCDDs in fishing-port sediments exhibited low risks to marine organisms. This study contributes to the understanding pollution situation of fishing ports, and provides a reference for environmental safety assessment and environmental pollution control.

Exposure, risk and predictors of hexabromocyclododecane and Tetrabromobisphenol-A in house dust from urban, rural and E-waste dismantling sites in Thailand.

In this study, for the first time, we determined concentrations of hexabromocyclododecane (HBCDD) and tetrabromobisphenol-A (TBBPA) in house dust and estimated human exposure to these substances in houses located in an e-waste dismantling site and in urban and rural residential areas of Thailand. The median HBCDD concentration in urban residential houses (2.10ngg-1) was similar to that in houses in an e-waste dismantling site (2.05ngg-1, p>0.05) and slightly higher than that in rural residential houses (1.11ngg-1, p>0.05). In contrast, significantly higher TBBPA concentrations were present in house dust from an e-waste dismantling site (median=720ngg-1; range=44-2300ngg-1) compared to those in urban (68.6ngg-1; 3.5-300ngg-1, p<0.001) and rural residential areas (17ngg-1; 2.0-201ngg-1, p<0.001). TBBPA concentrations increased with the increasing presence of electronic devices and a decreasing distance to the e-waste dismantling site. These results suggest that e-waste dismantling activities may contribute to TBBPA contamination of house dust. The median estimated daily intake (EDI) of HBCDD and TBBPA through dust ingestion for toddlers exceeded that for children and adults. However, EDI values for HBCDD and TBBPA from all age groups were below the oral reference dose guideline value suggested by the US National Research Council and National Toxicology Program (NTP).

Halogenated flame retardants in Irish waste polymers: Concentrations, legislative compliance, and preliminary assessment of temporal trends

Halogenated flame retardants (HFRs) were measured in 470 waste plastic articles from Ireland between 2019 and 2020. We identified articles containing concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), and tetrabromobisphenol-A (TBBP-A) exceeding European Union limits. Enforcement of existing limits of 1000 mg/kg will render an estimated 3.1% (2800 t) of articles in the waste categories studied unrecyclable, increasing to: 4.0, 4.9, and 5.6% if limits were reduced to 500, 200, and 100 mg/kg respectively. Meanwhile, enforcing limits of 1,000, 500, 200, and 100 mg/kg will respectively remove 78, 82, 84, and 85% of PBDEs, HBCDD, and TBBP-A present in such waste. Other FRs targeted were detected infrequently and predominantly at very low concentrations. However, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) was detected in 3 display/IT product samples at 14,000 to 32,000 mg/kg, indicating elevated concentrations of FRs used as alternatives to PBDEs and HBCDD, will likely increase in future. Comparison with data for Ireland in 2015–16, revealed concentrations and exceedances of limits for PBDEs, HBCDD, and TBBP-A were similar or have declined. For end-of-life vehicle fabrics and foams, HBCDD and ΣPBDE concentrations declined significantly (p < 0.05) since 2015–16. Moreover, ΣPBDE concentrations in waste small domestic appliances are significantly lower in 2019–20, with a similarly significant decline for TBBP-A in waste IT and telecommunications articles. In contrast, HBCDD concentrations in waste extruded polystyrene increased significantly between 2015–16 and 2019–20. For other waste categories studied, no statistically significant temporal trends are evident (p > 0.05). Fewer samples exceeded PBDE and HBCDD limits in 2019–20 (7.8%) than 2015–16 (8.7%), while exceedances for TBBP-A fell from 2.4% in 2015–16 to 0.57% in 2019–20. While comparison between the 2015–16 and 2019-20 datasets provide a preliminary indication of changes, further monitoring is required if the impact of legislation designed to eliminate HFRs from the waste stream is to be fully evaluated.