Hexabromocyclododecane Levels Research Articles

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.

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。

Microplastics and Brominated Flame Retardants in Freshwater Fishes From Italian Lakes: Implication for Human Health

Microplastics (MPs) and brominated flame retardants (BFRs) represent a synergic threat for aquatic environments and organisms' health status, with an additional concern over food quality and food security for species of commercial interest. In this study, the ingestion of MPs, levels of polybrominated diphenyl ethers (PBDEs), and hexabromocyclododecane (HBCDs) were assessed in organisms from two lakes of Central Italy, with the aims of exploring the bioavailability of these pollutants in freshwater environments, the possible translocation of MPs from digestive to edible tissues, and the relationship between MPs ingestion and bioaccumulation of BFRs. The fish Perca fluviatilis, Anguilla anguilla, Carassus auratus, and the crayfish Procambarus clarkii, all species commercialized for human consumption, were caught in Trasimeno Lake; moreover, P. fluviatilis and Rutilus rutilus were also sampled in Piediluco, a lake strongly influenced by industrial and anthropogenic activities, where fishing for commercial purpose is forbidden. With the exception of C. auratus which showed the highest frequency of MPs ingestion (75%), species from Piediluco Lake exhibited a more elevated percentage of organisms positive to MPs ingestion (45%) and higher levels of PBDEs and HBCDs (mean values of 343 and 792 pg/g, respectively, in P. fluviatilis; 445 and 677 pg/g, respectively, in R. rutilus) than Trasimeno species (25% frequency of MPs ingestion, mean values between 6 and 163 pg/g for PBDEs and 5-107 pg/g for HBCDs). Polyester fibers dominated among MP typologies, and a high occurrence of man-made natural fibers was recorded. The number of MPs extracted in the gastrointestinal tracts of fish and soft bodies of crayfishes positive to MPs ingestion ranged between 1 and 2, whereas no MPs were found in fish filets. Given these results, the risk related to human consumption of Trasimeno organisms appears very low, whereas further investigations are required to better elucidate the possible role of MPs pollution in modulating chemical bioaccumulation in edible tissues. This study contributed to assess both environmental quality and food safety, reinforcing the use of bioindicator species for monitoring plans, in accordance with European recommendations.

A nationwide survey of 20 legacy brominated flame retardants in indoor dust from China: continuing occurrence, national distribution, and implication for human exposure.

Despite the restrictions on polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDDs), these chemicals are still ubiquitous environmental pollutants. In this study, we measured the concentrations and profiles of 17 PBDE congeners and 3 HBCDD isomers in indoor dust samples collected from 23 provinces and cities across China. The summed concentrations of PBDEs (Σ17PBDEs) ranged from 4.19 to 817ng/g, with an average of 171 ± 184ng/g. BDE-209 was the most abundant congener. The concentrations of HBCDDs ranged from 6.65 to 1335ng/g, with an average of 236 ± 324ng/g. Unlike commercial HBCDD formulations, α-HBCDD was the predominant isomer in the indoor dust samples analyzed. Geographical distributions showed that the concentrations of PBDEs and HBCDDs varied significantly among different regions. Higher PBDE and HBCDD levels were observed in samples from eastern coastal and economically developed regions. Further, we estimated the daily intakes of PBDEs and HBCDDs through the routes of dust ingestion and dust dermal absorption for different age groups. Dust dermal absorption is an unneglectable exposure pathway to PBDEs and HBCDs for the Chinese population. Among the age groups, infants had the highest exposure via dust dermal absorption, and toddlers had the highest exposure via dust ingestion. Compared with the threshold values, the exposure doses of PBDEs and HBCDDs are unlikely to pose significant health concerns for both infants and adults in China. This is the first national survey of PBDEs and HBCDDs in indoor dust samples across China after the restriction.

Relative importance of aqueous leachate versus particle ingestion as uptake routes for microplastic additives (hexabromocyclododecane) to mussels.

Microplastic pollution is emerging as a global environmental issue, and its potential for transferring hazardous chemicals to aquatic organisms is gaining attention. Studies have investigated the transfer of chemicals, mainly sorbed chemicals, through ingestion of microplastics by organisms, but limited information is available regarding chemical additives and uptake via the aqueous route through plastic leaching. In this study, we compared two bioaccumulation pathways of the additive hexabromocyclododecane (HBCD) by exposing mussels (Mytilus galloprovincialis) to two different sizes of expanded polystyrene (EPS): inedible size (4.2-5.5 mm) for leachate uptake and edible size (20-770μm) for particle ingestion and leachate uptake. Over 10 days, the HBCD concentration increased significantly in mussels in the EPS exposure groups, indicating that EPS microplastic acts as a source of HBCD to mussels. The concentration and isomeric profiles of HBCD in mussels show that uptake through the aqueous phase is a more significant pathway for bioaccumulation of HBCD from EPS to mussels than particle ingestion. HBCD levels measured in EPS, leachate and exposed mussels from this study are environmentally relevant concentration. The fate and effects of chemical additives leached from plastic debris in ecosystem requires further investigation, as it may affect numerous environments and organisms through the aqueous phase.

BFRs (PBDEs and HBCDs) in freshwater species from Lake Trasimeno (Italy): The singular case of HBCDs in red swamp crayfish

Eighty-six samples belonging to five different species (crucian carp, Carassius carassius; European perch, Perca fluviatilis; tench, Tinca tinca; eel, Anguilla anguilla; red swamp crayfish, Procambarus clarkii) collected from Lake Trasimeno (Italy) were analyzed to assess polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) contamination. The Trasimeno is the largest Italian peninsular lake located in Umbria (Central Italy), in a rural area with low anthropogenic impact. All the samples were analyzed by an in-house developed analytical procedure involving a single sample preparation with dual detection: Gas- and Liquid-Chromatography coupled to tandem Mass Spectrometry (GC–MS/MS for PBDEs and LC-MS/MS for HBCDs). BFRs levels in crucian carp, tench and European perch were negligible and mostly below quantification limits (LOQs). In eel, the species with the higher fat content, PBDE sum (15 congeners) ranged from 0.269 to 0.916 ng/g w.w. BDE-47, -100 and -154 accounted for roughly 57%, 16% and 11% of the PBDE sum, respectively, while BDE-99 (usually one of the most abundant congeners in biota), only for 3%. HBCDs (sum of α-, β-, γ-isomers) were found between 0.157 and 1.14 ng/g w.w. with α- as predominant isomer (92% of the sum), followed by γ- (5%) and β- (2%). Peculiar was the contamination in red swamp crayfish characterized by negligible PBDEs and very high HBCDs levels with a singular contamination pattern. In female pools (n = 9) the mean HBCDs sum was 0.150 ng/g w.w., while in males higher concentrations were measured (mean = 2.77 ng/g w.w.). A significant correlation seems to exist between the contamination level and the seasonal cycle only in male crayfish. Interestingly, among the HBCDs, the γ-isomer was the highest (67% of the total) while α- contributes only for 20%.

Legacy and alternative halogenated flame retardants in Lake Geneva fish.

Legacy (i.e., polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD)) and alternative halogenated flame retardants (HFRs) were analyzed in 31 whole fish samples from Lake Geneva in 2018. Two fish species, namely, the burbot (Lota lota) and the roach (Rutilus rutilus), were selected, hypothetically representing different habitats, feeding behaviors, and different metabolic capacities. Roach (N= 20) and burbot (N= 11) displayed similar size and mass, but the latter species was overall leaner than the former. The sum of individual PBDE concentrations (0.54-9.86ngg-1 wet weight (ww)) was similar in both species, but the respective molecular profiles suggested contrasted metabolic capacities. HBCDD sum of isomer concentrations ranged from non-detected to 3.477ngg-1 (ww), also similar in both species. Both PBDEs and HBCDD levels were far below the threshold that indicates a risk to fish predators. Referring to previous surveys, which involved a wider range of species, PBDE concentrations have declined or are stable. HBCDD concentrations remained low, despite the PBDE ban, which could have fostered the consumption of other HFRs. The occurrence of alternative HFRs was also low for most compounds analyzed. Only dechloranes and decabromodiphenyl ethane (DBDPE) had detection rates above 50%. Dechloranes spanned a concentration range between 5 and 10 times the quantification limits (0.002 to 0.005ngg-1 wet weight), lower than DBDPE (< 0.005 to 2.89ngg-1 wet weight). Quality standards targeting biota are currently missing for these emerging chemicals.

Occurrence, distribution, and bioaccumulation of new and legacy persistent organic pollutants in an ecosystem on King George Island, maritime Antarctica

The occurrence and bioaccumulation of new and legacy persistent organic pollutants (POPs), organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), hexabromocyclododecanes (HBCDs), and Dechlorane Plus (DPs) and their related compounds (Dechloranes) in an ecosystem on King George Island, Antarctica are investigated. The new and legacy POPs were widely detected in the animal samples collected from Antarctica, which included Limpet, Antarctic cod, Amphipods, Antarctic icefish, Gentoo and Chinstrap penguins, Kelp gull, and South polar skua. The trophic magnification factors indicated that the levels of PCNs and HBCDs, as well as the legacy POPs, were magnified through the food web, whereas DPs might be diluted through the trophic levels contradicting the classification of Dechloranes as POPs. This is one of the first extensive surveys on PCNs, HBCDs, and Dechloranes, which provides unique information on the distribution and trophic biomagnification potential of the new and legacy POPs in the Antarctic region.

Hexabromocyclododecane in riverine and estuarine sediments from Osaka, Japan: spatial distribution and concentration variability within identical samples.

In this study, hexabromocyclododecane (HBCD) in riverine and estuarine sediments was investigated in Osaka, Japan. The mean total HBCD concentration detected in sediments ranged from < 0.50 to 130ngg-1 dry weight. This exceeded the ubiquitous HBCD contamination level found globally but was lower than that in areas affected by point sources, such as textile industries and expanded polystyrene plants. Sewage effluent was one of the suspected point sources of HBCD in the study area. The HBCD concentrations in sediments were highly dependent on certain factors, such as the location of the sampling site (proximity to possible emission sources), sediment properties (silt or sand), and organic substance content. The range of the diastereomer composition of α- and γ-HBCD was wider than that in other studies. Repeatability tests (n = 3) were conducted for all samples to assess the variability in the HBCD concentrations within identical sediment samples. Some variations were observed in the HBCD concentrations and diastereomer compositions within the repeatability test results at some sampling sites; nevertheless, the same samples were extracted and analyzed in triplicate. The bromine contents of the extracts of these samples were analyzed by X-ray fluorescence, and the results agreed well with those estimated from the LC-MS/MS results. From these results, it was confirmed that several sediment samples contained heterogeneously distributed HBCD. The risk characterization ratios (predicted environmental concentration/predicted no-effect concentration) of sites with high HBCD concentrations ranged from 0.1 to 1; thus, further information is required, and the sediment HBCD levels in this region should be continuously studied.

Assessment of Tetrabromobisphenol and Hexabromocyclododecanes exposure and risk characterization using occurrence data in foods

Tetrabromobisphenol A (TBBPA) and Hexabromocyclododecanes (HBCDs) are two of the most used BFRs and they have cumulated in the environment. TBBPA and HBCDs in food were determined and their risks were assessed. The analytical method used was validated in different food categories, and the performance parameters were acceptable based on the criteria of AOAC. Fish and cephalopods were contaminated with TBBPA higher than other foods, and fish contained higher levels of HBCDs than other foods. α-HBCD was the predominant diastereomer in fish and meat and had strong correlations with HBCDs in fish and cephalopods. HBCDs accumulated easier than TBBPA in food. People were exposed to TBBPA from 0.125 ng kg−1 b.w. day−1 to 0.284 ng kg−1 b.w. day−1 and HBCDs from 0.353 ng kg−1 b.w. day−1 to 1.006 ng kg−1 b.w. day−1 via food and air. Food mainly contributed to exposure to TBBPA and HBCDs and vegetables were the main contributors for exposure to TBBPA and HBCDs in food. MOEs for the whole population were over 100, and the risks of exposure to TBBPA and HBCDs from food and the environment were of low concern to public health.

Fate of Hexabromocyclododecane (HBCD), A Common Flame Retardant, In Polystyrene-Degrading Mealworms: Elevated HBCD Levels in Egested Polymer but No Bioaccumulation

As awareness of the ubiquity and magnitude of plastic pollution has increased, so has interest in the long term fate of plastics. To date, however, the fate of potentially toxic plastic additives has received comparatively little attention. In this study, we investigated the fate of the flame retardant hexabromocyclododecane (HBCD) in polystyrene (PS)-degrading mealworms and in mealworm-fed shrimp. Most of the commercial HBCD consumed by the mealworms was egested in frass within 24 h (1-log removal) with nearly a 3-log removal after 48 h. In mealworms fed PS containing high HBCD levels, only 0.27 ± 0.10%, of the ingested HBCD remained in the mealworm body tissue. This value did not increase over the course of the experiment, indicating little or no bioaccumulation. Additionally, no evidence of higher trophic level bioaccumulation or toxicity was observed when L. vannamei (Pacific whiteleg shrimp) were fed mealworm biomass grown with PS containing HBCD. Differences in shrimp survival were attributable to the fraction of mealworm biomass incorporated into the diet, not HBCD. We conclude that the environmental effects of PS ingestion need further evaluation as the generation of smaller, more contaminated particles is possible, and may contribute to toxicity at nanoscale.

Single sample preparation for brominated flame retardants in fish and shellfish with dual detection: GC-MS/MS (PBDEs) and LC-MS/MS (HBCDs).

An analytical method for the simultaneous determination of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in fish, shellfish and muscle of terrestrial animals was developed as an extension of a previously validated method for PBDE analysis. A single sample preparation based on QuEChERS-like extraction and a two-step clean-up, followed by a dual instrumental detection, was implemented. GC-MS/MS was used for PBDEs and LC-MS/MS for HBCDs. The method allows the quantification of fifteen PBDEs (28, 47, 49, 66, 77, 85, 99, 100, 138, 153, 154, 183, 197, 206, 209) and three HBCD isomers (α, β and γ), reaching 10 pg/g LOQs for all the analytes except BDE 206 and 209 (100 pg/g LOQ). The validated method was applied to the analysis of 12 fish and shellfish species (sole, spiny dogfish, smooth-hound, mackerel, swordfish, grey mullet, cod, anchovy, red mullet, Atlantic horse mackerel, tuna fish and mussel) collected in central Italian markets accounting for a total of 44 samples. Generally, ΣPBDEs showed higher concentration than ΣHBCDs except in the case of mussels in which ΣHBCDs > ΣPBDEs. Cod and smooth-hound are the least contaminated species among those analysed in the present study, whereas the highest brominated flame retardant (BFR) levels were found in spiny dogfish samples. The measured contamination levels were generally comparable to or lower than those already published in European studies. Literature data for HBCDs in European fish and shellfish were hard to find; therefore, PBDE and HBCD levels were also compared with European Environmental Quality Standard (EQS) in biota (Directive 2013/39/EU). EQSs for HBCDs are six orders of magnitude higher than those for PBDEs; therefore, while no exceedance was observed for the first, almost all the samples analysed for PBDEs were above EQSs. The presented preliminary data on PBDEs and HBCDs are among the first published in marine fish and shellfish commercialised in Central Italy. Graphical abstrac.

Serum measures of hexabromocyclododecane (HBCDD) and polybrominated diphenyl ethers (PBDEs) in reproductive-aged women in the United Kingdom

We investigated the serum concentrations of two brominated flame retardants (BFRs) – polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) –in 59 women aged between 23 and 42 from the United Kingdom. We also collected demographic data, including age, bodyweight and height in order to test for associations with BFR levels. Temporal and global differences were also assessed using previously published data.HBCDD was detected in 68% of samples with a mean concentration of 2.2 ng/g lipid (range = <0.3–13 ng/g lipid). The dominant stereoisomer was α-HBCDD with an average contribution of 82% (0–100%) towards ΣHBCDD, was followed by γ-HBCDD (average contribution = 17%). PBDEs were detected in 95% of samples with a mean ∑PBDE (sum of BDEs −28, −47, −99, −100, −153, −154 and −183) concentration of 2.4 ng/g lipid (range = <0.4–15 ng/g lipid). BDEs −153 and −47 were the dominant congeners, contributing an average of 40% and 37% respectively, to the average ΣPBDE congener profile.Data from this study suggests that HBCDD levels decrease with age, it also suggests a positive association between bodyweight and HBCDD levels, which likewise requires a large-scale study to confirm this. The data also show that 10 years after their European ban, PBDE body burden has begun to decrease in the UK. Whilst it is too early to draw any firm conclusions for HBCDDs, they appear to be following a similar pattern to PBDEs, with levels decreasing by a factor of >2.5 since 2010. Whilst the human body burden appear to be decreasing, both PBDEs and HBCDD are still consistently detected in human serum, despite legislative action limiting their production and use. This highlights the need to continuously assess human exposure and the effectiveness of policy aimed at reducing exposure.

The effects of prosperity indices and land use indicators of an urban conurbation on the occurrence of hexabromocyclododecanes and tetrabromobisphenol A in surface soil in South China

Hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) are legacy brominated flame retardants which are still produced and used in China. In this study, 187 surface soils from the Pearl River Delta (PRD) urban conurbation in China were collected, and the effects of urban conurbation development on the concentrations, distributions and human exposure risk of HBCDs and TBBPA were investigated. The concentration ranges of Σ3HBCD (sum of α-, β-, and γ-HBCD) and TBBPA in soil were below the limit of quantification (<LOQ) to 300 ng g−1 dry weight (dw) and < LOQ to 53.1 ng g−1 dw, respectively. Concentration levels of HBCDs and TBBPA in the PRD were affected both by distributions of land-use type and by the location of the city. Soils from residential areas contained the highest concentrations of Σ3HBCD (median: 1.75 ng g−1 dw) and TBBPA (1.92 ng g−1 dw) among all land-use types. In addition, soils from the central PRD had higher Σ3HBCD and TBBPA levels (0.46 and 0.90 ng g−1 dw) than those from the surrounding areas (0.17 and 0.07 ng g−1 dw). The concentrations of Σ3HBCD and TBBPA were highly correlated with urbanization level, population density, regional GDP and per capita income in all cities studied (p < 0.01), which indicates that the prosperity of the urban conurbation may play an important role in soil contamination of HBCDs and TBBPA in the PRD. Children living in residential areas had the highest estimated daily intakes of Σ3HBCD (7.09 pg kg−1 d−1) and TBBPA (7.76 pg kg−1 d−1), suggesting that people living in residential areas have a relatively higher exposure risk of HBCDs and TBBPA. This is a comprehensive study to report the effects of prosperity indices and land use indicators of an urban conurbation on the occurrence of HBCDs and TBBPA in soil in China.

Rat strain response differences upon exposure to technical or alpha hexabromocyclododecane

Hexabromocyclododecane (HBCD) is a brominated flame retardant which was recommended by a UN expert body under the Stockholm Convention to be eliminated from the global marketplace in 2011; however, due to its ability to persist in the environment, undergo long-range transport and bioaccumulate, it remains a concern for human health. The commercial mix of HBCD (T-HBCD) consists of α-HBCD, β-HBCD and γ-HBCD. Although the γ-HBCD (79%) isomer is the predominant isomer of T-HBCD, the most bioaccumulative isomer detected in mammals is the α-HBCD isomer. This study was undertaken to investigate three rat strains treated with commercial grade (technical) HBCD or HBCD enriched with the α isomer (A-HBCD) and to examine strain- and sex-related differences in response to exposure. Female Sprague Dawley (SD), Wistar (WI) and Fischer F344 (FI) rats were exposed for 28 days to either T-HBCD or A-HBCD in feed, at doses of 0, 250, 1250 and 5000 mg/kg diet. The FI rodent strain was found to be the most sensitive to effects of HBCD based on the greatest number of significantly affected endpoints which indicated that T-HBCD primarily affected liver and thyroid, resulting in multiple health effects. Consequently, male FI were included in the study and exposed to T- and A-HBCD. Histopathological data supports previously reported effects of HBCD on the thyroid and endocrine system although the effects in FI rats are significantly elevated compared to other strains. As with T-HBCD, liver and thyroid were found to be target organs of A-HBCD. Sex differences, specifically in tissue concentration levels, immune response parameters and in number and severity of thyroid and liver lesions, following exposure to either T- or A-HBCD were apparent, with treatment eliciting a greater response in males. Residue analysis revealed that α-HBCD is more bioaccumulative than γ-HBCD in all rodent strains, with levels of HBCD in animals treated with A-HBCD several fold higher for all tissues tested (7–11 fold at the highest dose). Thus, residue data supports the selective uptake (implies there are differences in bioavailability and/or bioaccumulation; is this the case or do certain isomers simply have a longer half-life) of specific isomers, with α-HBCD > γ-HBCD. Taken together, our study highlights the importance of selecting the most appropriate strain and of including both sexes in studies to ensure that sex-related differences in response to test chemical is taken into consideration. Moreover, ours is the first study to show the effects of a sub-acute exposure to a diet containing only HBCD enriched for the α isomer, which better represents the isomer ratios present in the biota due to bioaccumulation.

Tetrabromobisphenol A, hexabromocyclododecane isomers and polybrominated diphenyl ethers in foodstuffs from Beijing, China: Contamination levels, dietary exposure and risk assessment

Hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA) and polybrominated diphenyl ether (PBDEs) are three legacy brominated flame retardants (BFRs); however, they are still produced and used in China. In this study, these three BFRs were measured in commonly consumed animal-based and plant-based foodstuffs from Beijing, China, and the dietary intakes of these BFRs by adults in Beijing were estimated to assess the related health concerns. The median levels of TBBPA in animal-based foodstuffs ranged from <LOD to 8.03 ng/g lipid weight (lw), whereas those in all the plant-based food groups were lower than the LOD. The median levels of total HBCD in animal-based foodstuffs were from 1.14 to 5.65 ng/g lw, and α-HBCD was the predominant isomer. The median HBCD level in vegetables was 0.266 ng/g wet weight (ww), whereas γ-HBCD was the most abundant isomer. The median levels of total PBDEs in animal-based foodstuffs were from 3.22 to 13.7 ng/g lw, and BDE-209 was the most abundant congener, comprising a proportion of at least 85% of total PBDEs. The daily dietary intakes of TBBPA, HBCD and PBDEs for adults in Beijing were 2.52, 2.74 and 9.77 ng/kg body weight/day, respectively. Meat consumption was found to be the primary source of BFR dietary intake. A comparison between the calculated estimated daily intakes (EDIs) and the corresponding threshold reference values (TRVs) indicated that daily intake of BFRs via food consumption is unable to cause significant health risks. Likewise, the margin of exposures (MOEs) calculated following the European Food Safety Authority (EFSA) approach were far higher than the threshold, which also proved that the EDIs of BFRs are unlikely to raise significant health concerns.

Prenatal exposure to organohalogen compounds and children’s mental and motor development at 18 and 30 months of age

BackgroundOrganohalogen compounds (OHCs), i.e. polychlorinated biphenyls (PCBs, are wide-spread environmental pollutants known to be neurotoxic for the developing brain. The hydroxylated metabolites of PCBs, OH-PCBs, might be even more toxic due to their structure and interference with thyroid hormone metabolism. We found that prenatal exposure to OH-PCBs was associated with thyroid hormone metabolism at toddler age. Little, however, is known about the neurotoxicity of OH-PCBs in humans. ObjectivesTo determine whether prenatal background exposure to OHCs has an effect on mental and motor development in children at the age of 18 and 30 months. MethodsOne hundred and eighty-one healthy mother-infant pairs were included in this observational study performed in the Netherlands. We measured maternal pregnancy levels of PCB-153 and three OH-PCBs. In one part of the cohort we measured another nine PCBs and three OH-PCBs and in the other part we measured five brominated diphenyl ethers (BDEs), dichloro-diphenyldichloroethylene (p,p’-DDE), pentachlorophenol (PCP), and hexabromocyclododecane (HBCDD). We used the mental development index (MDI) and the motor development index (PDI) of the Bayley Scales of Infant Development II (BSID-II) to assess children’s mental and motor development (mean = 100; delayed score <85). ResultsHigher prenatal PCB-153 levels were associated with a delayed MDI score at 18 months. None of the other compounds were associated with a delayed score, but several associations were found between OHC levels and BSID-II scores. The sum of all six OH-PCBs and three individual OH-PCBs, 4-OH-PCB-107, 3-OH-PCB-153, and 4′−OH-PCB-172, correlated positively with MDI at 30 months. The compound 3′−OH-PCB-138 showed a similar trend. A higher 4-OH-PCB-187 was associated with a lower MDI at 18 months. We found a similar trend for higher BDE-99. Higher BDE levels were associated with higher PDI at 18 months. The levels of p,p’-DDE-, PCP, and HBCDD were not associated with BSID-II scores at 18 months. ConclusionsHigher prenatal levels of PCB-153 were associated with a delayed MDI score at 18 months. None of the other compounds were associated with a delayed score, but several associations were found between OHC levels and BSID-II scores. Prenatal OH-PCBs were positively associated with mental development at 30 months, whereas one OH-PCB was negatively associated at 18 months. BDE levels were positively associated with psychomotor development. Prenatal p,p’-DDE, PCP, and HBCDD levels were not associated with neurodevelopment at 18 months.

Levels of polybrominated diphenyl ethers and hexabromocyclododecane in treatment plant sludge: Implications on sludge management

Past usage of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) in commercial products resulted in their continuous emission from sources. Wastewater treatment plants (WWTP) are the main sinks resulting from their industrial and domestic usage as well as atmospheric deposition. This preliminary study examined levels of PBDEs and HBCDD in urban and industrial WWTP sludge samples for the first time from Turkey. PBDE concentrations (sum of 26 congeners) of eight samples collected from four WWTPs were between 300 and 655 ng g−1 dw and 67–2.5*107 ng g−1 dw, and HBCDD concentrations (sum of α-, β-, and γ- diastereoisomers) ranged 75–616 ng g−1 dw and 13–416 ng g−1 dw, for urban and industrial WWTP samples, respectively. Although PBDEs have never been produced in Turkey, the highest PBDE concentration in sewage sludge worldwide was identified in one of the WWTPs. PBDE and HBCDD levels in other sludge samples were comparable to those reported in the literature. Application of a chemical mass balance model (CMB) suggested: (i) the main source of PBDEs as deca-BDE mixture; (ii) influence of a background air PBDE profile for one of the industrial WWTPs, having low contamination; (iii) indoor dust PBDE contamination as another source for urban WWTPs. The preliminary results for BFR levels in Turkey were discussed in terms of sludge disposal methods used worldwide, and the need for regulatory limits for BFRs in sludge management.

Human biomonitoring in Australian children: Brominated flame retardants decrease from 2006 to 2015

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) were used intensively as flame retardants, worldwide. They have been detected in human serum samples and PBDEs have been found to be elevated in young children. Commercial Penta- and Octa-PBDE mixtures were banned in Australia in 2005, while HBCDD was banned worldwide in 2013. We investigated PBDE and HBCDD concentrations in serum collected from young children. We also investigated temporal trends in PBDE concentration 10 years after their Australian ban.Surplus human blood serum samples were collected through a pathology clinic (n = 800), in 2014/15, stratified by age (0–6, 6–12, 12–18, 18–24, 24–30, 30–36, 36–42, 42–48, 48–54 and 54–60 months) and sex and pooled for analysis of PBDEs (BDEs −28, −47, −99, −100, −153, −154, −183) and HBCDD. In 2014/15, the geometric mean concentration of the sum of all PBDEs measured (ΣPBDEs) was 4.5 ng/g lipid (median: 4.6 ng/g lipid, range: 0.88–26 ng/g lipid). A positive association between BDE-47 concentration and age was observed (R = 0.41, p = 0.008), however there were no trends between other PBDE congeners or HBCDD and age. There were no significant differences between genders for PBDEs (t-test, p = 0.802) or HBCDD (t-test, p = 0.740).The highest concentrations observed were in pools from the females 30–36 month (26 ng/g lipid) and Males 6–12 month (21 ng/g lipid) categories. BDEs −47 and −99 were the predominant congeners with a combined average contribution of 75% of ΣPBDEs.PBDEs showed a significant reduction in children aged 0–4 years over an eight year period. In 2014/15, the mean (range) concentration of BDE-47 is 2.8 (0.23 to 11) ng/g lipid compared to pools in 2006/07 at 19 (3–55) ng/g lipid (p < 0.0001) and for BDE-153 is 0.73 (<0.1 = −2.9) ng/g lipid compared to pools in 2006/07 at 4.7 (2−10) ng/g lipid (p < 0.0001). HBCDD concentrations were lower than PBDEs with a mean concentration of 0.45 ng/g lipid. There were no temporal trends observed for HBCDD when compared to samples collected in 2012. The dominant stereoisomer was α-HBCDD (mean = 0.38 ng/g lipid) with an average contribution of 65% towards ΣHBCDD.Levels of PBDEs in young Australian children have significantly decreased since the bans of commercial Penta- and Octa-BDE in 2005. There has been no observed decrease in HBCDD levels in Australian children since its ban in 2012.

Occurrence of tetrabromobisphenol a (TBBPA) and hexabromocyclododecane (HBCD) in soil and road dust in Chongqing, western China, with emphasis on diastereoisomer profiles, particle size distribution, and human exposure

Currently, the HBCDs were listed in Annex A by the Stockholm Convention, and the knowledge on the contamination of TBBPA and HBCDs in soil and road dust in China is still limited, and it is unclear what role is played by dust particle size distribution. In this study, a total of 81 soil and 43 road dust samples were analyzed with TBBPA and ΣHBCDs concentrations ranging from < LOQ to 33.8 ng/g dw (dry weight) and 0.43–15.2 ng/g dw in soil, and from < LOQ to 74.1 ng/g dw and 7.25–14.0 ng/g dw in road dust, respectively. TBBPA and HBCDs exhibited different spatial distribution patterns in soil, where relatively high levels of HBCDs were found in industrial area and commercial area, while high levels of TBBPA were detceted in residential area. However, no distinct variation in spatial distribution of these two compounds was observed in road dust. Different diastereoisomer profiles of HBCDs were also found with γ-HBCD predominating in soil and α-HBCD occupying a large proportion in road dust. The α-/γ-HBCD values in road dust were significantly greater (T-test, P < 0.05) than those in soil, which suggested that γ-HBCD in road dust were likely to transform into α-HBCD compared with soil. The distribution of dust particle size showed that HBCDs levels were increasing with the decreasing in particle sizes, while the TBBPA showed some “accidental” peak values in specific diameter ranges. The estimated daily intakes (EDIs) of TBBPA and HBCDs were assessed through dust ingestion, dermal absorption and inhalation via road dust, and all the exposure estimates were well below the reference dose (RfD), but the toddlers were more vulnerable to TBBPA and HBCDs intakes, which should be paid more attention.