Levels and distribution of brominated flame retardants in the soil of Harbin in China

This study reports the presence of brominated flame retardants in the topsoil in and around Harbin, a city in northeastern China. Samples of soil were collected from 17 locations in 2006, and the levels of 9 polybrominated diphenylethers （PBDEs 17, 28, 47, 66, 99, 100, 153, 154, and 183） ranged from 2.45 to 55.9 pg/g dry weight （dw） with a mean of 26.3 pg/g dw. These levels are very low comparing with those for some cities in Europe and USA. BDE 209 and hexabromocyclododecane were the two dominant congeners, with mean concentrations of 520 pg/g dw and 1750 pg/g dw, respectively. The concentrations of the total nine PBDE congeners clearly decreased from urban areas to background, but the compositions of individual congeners differed. Proportions of heavier congeners decreased while those of lighter congeners increased, along urban-rural-background transect, providing evidence for an urban fractionation effect. Correlation analysis indicated similar sources for PBDEs, hexabromocyclododecane, and 1,2-bis（2,4,6-tribromophenoxy）-ethane from urban areas but pentabromoethylbenzene was probably present due to long-range atmospheric transport. Principal component analysis was used to determine the characteristics of the relationships among these brominated flame retardants in the field.

A Simplified Analytical Procedure for Simultaneous Determination of Alkylphenol Ethoxylates and Brominated Flame Retardants in Fish Tissue Samples from Vaal River,South Africa

In this study, the concentration of alkylphenol ethoxylates (APEs) and brominated flame retardants (BFRs) were determined in fish samples, Labeo umbratus and Carp, collected from the Vaal River in South Africa. Ultrasonic-assisted extraction technique was used to extract the organic contaminants from fish samples, and the resulting extract was purified by sulphuric acid lipid removal followed by Strata X-cartridge SPE clean-up. The APEs and BFRs were derivatized using heptafluorobutyric anhydride before analysis with GC-MS. In both types of fish samples, lower oligomers of APEs were more abundant than the higher oligomers, while HBCD, BDE99 and PBB101 were the dominant BFRs. The concentrations of these pollutants ranged from 1.061 ng/g lipids (t-BP) in Labeo umbratus to 11.860 ng/g lipids (HBCD) in Carp.

Research Progress on a Novel Brominated Flame Retardant :Tris(2,3- dibromopropyl) Isocyanurate(TBC)

This review summarizes the environmental levels,toxicity effects and analytical development of Tris(2,3-dibromopropyl)Isocyanurate(TBC).Further study is required on the environmental behavior of TBC,mechanism of toxicity and alternative development.

Detection of novel brominated flame retardants (NBFRs) in the urban soils of Melbourne, Australia

A range of brominated flame retardants(BFRs)have been incorporated into polymeric materials like plastics,electronic equipment,foams and textiles to prevent fires.The most common of these,polybrominated diphenyl ethers(PBDEs),have been subject to legislated bans and voluntary withdrawal by manufacturers in North America,Europe and Australia over the past decade due to long-range atmospheric transport,persistence in the environment,and toxicity.Evidence has shown that replacement novel brominated flame retardants(NBFRs)are released to the environment by the same mechanisms as PBDEs and share similar hazardous properties.The objective of the current research was to characterize soil contamination by NBFRs in the urban soils of Melbourne,Australia.A variety of industrial and nonindustrial land-uses were investigated with the secondary objective of determining likely point sources of pollution.Six NBFRs;pentabromotoluene(PBT),pentabromoethylbenzene(PBEB),hexabromobenzene(HBB),2-ethylhexyl-2,3,4,5-tetrabromobenzoate(EH-TBB),1,2-bis(2,4,6-tribromophenoxy)ethane(BTBPE)and decabromodiphenyl ethane(DBDPE)were measured in 30 soil samples using selective pressurized liquid extraction(S-PLE)and gas chromatography coupled to triple quadrupole mass spectrometry(GC-MS/MS).NBFRs were detected in 24/30 soil samples with S5NBFR concentrations ranging from nd-385 ng/g dw.HBB was the most frequently detected compound(14/30),while the highest concentrations were observed for DBDPE,followed by BTBPE.Electronic waste recycling and polymer manufacturing appear to be key contributors to NBFR soil contamination in the city of Melbourne.A significant positive correlation between S8PBDEs and S5NBFR soil concentrations was observed at waste disposal sites to suggest that both BFR classes are present in Melbourne's waste streams,while no association was determined among manufacturing sites.This research provides the first account of NBFRs in Australian soils and indicates that these emerging contaminants possess a similar potential to contaminate Melbourne soils as PBDEs.

溴系阻燃剂(BFRs)的动物内分泌干扰(ED)研究

近年来,防火溴系阻燃剂(Brominated flame retardants,BFRs)是在聚合物和织物中应用最为广泛的阻燃剂之一,广泛应用于各种家用和工业产品。BFRs属持久性有机污染物,目前在环境中已普遍存在,已在国际上引起了广泛的关注。由于BFRs的使用量在逐年增大,在土壤、沉积物、大气和生物体中普遍检测出BFRs。BFRs对水生动物、鸟类、哺乳动物都存在不同程度的毒害作用,其分布的广泛性、难降解性和对人体健康的不确定性已引起人们的普遍关注。基于国外动物毒理学研究成果,文章综合论述了BFRs及其代谢化合物对不同动物的内分泌干扰活性,主要介绍了对甲状腺激素水平、雌激素水平、雄激素水平及对动物神经系统发育的影响,为评价BFRs对动物和人类的健康影响提供理论基础。

凝胶渗透色谱-硅胶柱-气相色谱-负化学离子源质谱测定生物介质中49种BFRs类化合物

建立了生物介质内22种多溴联苯（ PBBs）和27种多溴联苯醚（ PBDEs）的净化和分析方法。通过分析不同时间段凝胶渗透色谱（ GPC）洗脱液中49种化合物含量，得出不同化合物凝胶色谱洗脱曲线。样品经过凝胶渗透色谱-混合硅胶柱净化后，再使用GC-（ NCI）/MS对样品进行检测。实验结果表明，PBBs和PBDEs检出限分别为0.02～0.88 pg/g和0.01～74.00 pg/g。对实验过程进行验证发现，样品不同浓度加标回收率为80％～120％，相对标准偏差小于20％。该方法具有良好的净化效果、准确度和精密度，拥有良好的线性范围及检出限，满足生物介质中溴代阻燃剂的检测分析实际要求。

城市和电子垃圾拆解区室内灰尘中溴代阻燃剂(BFRs)的浓度和生物有效性

本文以广州市区和电子垃圾拆解区室内灰尘为研究对象,分析不同粒径(50—2000μm)灰尘中溴代阻燃剂(brominated flame retardants,BFRs)的浓度、组成和生物有效性.广州市区灰尘中BFRs以十溴二苯乙烷(decabromodiphenyl ethane,DBDPE)(4930—7280 ng·g^-1)为主,电子垃圾拆解区以十溴联苯醚(polybrominated diphenyl ether 209,BDE209)(5570—602600 ng·g^-1)为主.对比研究结果发现,城市灰尘中BFRs的分布无粒径差异,而电子垃圾拆解区最细粒径灰尘中BFRs含量最高.广州市区灰尘中BFRs生物有效性随化合物的lg Kow增加而降低.电子垃圾拆解区灰尘生物有效性显著低于市区灰尘,表明在电子垃圾拆解区灰尘中电子垃圾碎片的存在很大程度上降低了BFRs的生物有效性.人体暴露评估结果显示,广州市区人体暴露风险低于电子垃圾拆解区暴露风险.

新型溴代阻燃剂(NBFRs)的生态毒性效应研究进展

由于传统的溴代阻燃剂(brominated flame retardants,BFRs),如多溴二苯醚(PBDEs)和六溴环十二烷(HBCD)等具有较高的生态风险,作为替代物的新型溴代阻燃剂(novel BFRs,NBFRs)被越来越多地生产和使用,如六溴苯(HBB)、五溴甲苯(PBT)、十溴二苯乙烷(DBDPE)、1,2-双(2,4,6-三溴苯氧基)乙烷(BTBPE)、四溴邻苯二甲酸双(2-乙基己基)酯(TBPH)和2,3,4,5,6,-五溴乙苯(PBEB)等。大量的NBFRs的生产、使用和废弃,导致其不可避免地释放到环境中,对生态环境和人类健康造成潜在的威胁。已有研究发现很多NBFRs不仅具有急性毒性、肝脏毒性、内分泌干扰毒性和发育毒性等毒性效应,也具有生物富集、积累和放大效应,存在生态风险。但目前缺乏系统和总结性的研究概述,故基于现有的研究结果,本文综述了有代表性的NBFRs的毒性效应研究内容和问题,并提出今后主要的研究方向。

Thermal Decomposition of Printed Circuit Board in the Presence of Zinc Oxide under Inert and Oxidative Atmosphere: Emission Behavior of Inorganic Brominated Compounds

Thermal degradation of a FR-4 type printed circuit board, PCB, containing brominated flame retardant has been studied both in inert and oxidative atmosphere for the emission control of harmful brominated compounds. The presence of oxygen in atmosphere resulted in the reduction of the yield of hydrogen bromide, one of the major brominated compounds in thermal treatment, and in the enhancement of the formation of bromine and hypobromous acid. The intentional addition of zinc oxide to the PCB powder sample gave rise to the fixation of Br as zinc bromide. It also resulted in the promotion of the release of brominated compounds in comparison to the case of pure PCB. Thus, the addition of the oxide can be a benefit with respect to the bromine fixation and the kinetics of thermal treatment of PCB as well as metal recovery.

A review of polybrominated diphenyl ethers and alternative brominated flame retardants in wildlife from China:Levels,trends,and bioaccumulation characteristics

Accelerated industrialization and urbanization,and unregulated disposal of waste of electric and electronic equipment（e-waste） in China have caused environmental pollution of brominated flame retardants（BFRs）.This review summarized the levels,trends,and bioaccumulation characteristics of polybrominated diphenyl ethers（PBDEs） and other potential alternative BFRs including hexabromocyclododecanes（HBCDs）,1,2-bis（2,4,6-dibromophenoxy） ethane（BTBPE） and decabromodiphenylethane（DBDPE） in wildlife from China.PBDE levels in wildlife from China were generally higher than those from other parts in Asia,and were comparable to those from Europe but were lower than those from North America.However,wildlife from the e-waste recycling sites in South China and East China contained much higher PBDEs compared to other reports around the world,suggesting the heavy contamination of PBDEs in these regions.The alternative BFRs were also detected in wildlife,revealing that the animals are exposed to these chemicals,in addition to PBDEs.Temporal trends indicated by levels in marine mammals from South China suggested that PBDE levels increased from the beginning of 1990s to 2000s,but decreased from the middle of 2000s,followed by relatively steady levels.In contrast,HBCDs were found to be continuously increasing from 1997 to 2007,indicating the increasing usage of HBCDs in China in recent years.Compared to PBDE profiles found in other parts,aquatic species and birds from China contained relatively higher contributions of BDE28 and 209,respectively,suggesting the possible different usage pattern of PBDEs.Future works including keeping monitoring at a reasonable scale and frequency to make sure levels near urban centers indicative of population do not increase are needed.Additionally,focus effort on e-waste recycling regions to look for impacts and to determine if regulation/controls are resulting in lower environmental contamination,and incorporation of sentinel species in monitoring efforts are recommended.

Concentrations and distribution of novel brominated flame retardants in the atmosphere and soil of Ny-Alesund and London Island,Svalbard,Arctic

Novel brominated flame retardants(NBFRs)were investigated in Arctic air and soil samples collected from Ny-?lesund and London Island,Svalbard,during Chinese scientific research expeditions to the Arctic during 2014–2015.The concentrations of 9 NBFRs in the Arctic air and soil were 4.9–8.7 pg/m3(average 6.8 pg/m3)and 101–201 pg/g dw(average 150 pg/g dw),respectively.The atmospheric concentration of hexabromobenzene(HBB)was significantly correlated with that of pentabromotoluene(PBT)and pentabromobenzene(PBBz),suggesting similar source and environmental fate in the Arctic air.No significant spatial difference was observed among the different sampling sites,both for air and soil samples,indicating that the effects of the scientific research stations on the occurrence of NBFRs in the Arctic were minor.The fugacities from soil to air of pentabromoethylbenzene(PBEB),2,3-dibromopropyl 2,4,6-tribromophenyl ether(DPTE),and decabromodiphenylethane 1,2-bis(pentabromophenyl)ethane(DBDPE)were lower than the equilibrium value,indicating a nonequilibrium state of these compounds between air and soil,the dominant impact of deposition and the net transport from air to soil.The correlation analysis between the measured and predicted soil-atmosphere coefficients based on the absorption model showed that the impact of the soil organic matter on the distribution of NBFRs in the Arctic region was minor.To the best of our knowledge,this work is one of the limited reports on atmospheric NBFRs in the Arctic and the first study to investigate the occurrence and fate of NBFRs in the Arctic soil.

Temporal trends in concentrations of legacy and novel brominated flame retardants in house dust from Birmingham in the United Kingdom

Concentrations of polybrominated diphenyl ethers(PBDEs),hexabromocyclododecane(HBCDD),tetrabromobisphenol-A(TBBPA)and two potential replacements decabromodiphenylethane(DBDPE)and 1,2-bis(2,4,6-tribromophenoxy)ethane(BTBPE)were measured in dust samples collected from 14 homes across Birmingham(UK).Concentrations were compared with those from the same city in previous studies to ascertain any temporal changes and to assess the effects of legislative restrictions.The average PHBCDDs concentration(46,000 ng/g;median=280 ng/g)included the highest dust concentration recorded globally(570,000 ng/g).This is despite the listing of HBCDD under the Stockholm Convention in 2013,demonstrating that decreases in indoor contamination will likely be slow as existing sources are gradually discarded.In contrast,concentrations of BDE-47(mean=5.7 ng/g;median=0.93 ng/g)and BDE-99(mean=11 ng/g;median=2.9 ng/g)were significantly lower than in all previous(p<0.01)studies in the same city since 2006,suggesting restrictions on the Penta-BDE formulation have been effective.The average BDE-209 concentration(4800 ng/g;median=1600 ng/g)is lower than the peak average concentration,which was observed in 2007(280,000 ng/g),however this is not a significant decline,probably due to the later imposition of Deca-BDE restrictions compared to those on Penta-BDE.Decreases in PBDE concentrations have coincided with a significant(p<0.01)increase in DBDPE concentrations(average=1500 ng/g;median=660 ng/g)since 2014,suggesting its use as a replacement flame retardant for Deca-BDE.While no significant change was detected for BTBPE(average 11 ng/g;median=0.84 ng/g in this study);concentrations of TBBPA(average=34 ng/g;median=35 ng/g)were significantly lower(p<0.05)than in 2007(average 62 ng/g).The decreases observed in PBDE concentrations,demonstrates that legislation has been effective in reducing the commercial use of PBDEs,however this has coincided with increases of alternative flame retardants such as DBDPE.

A hybrid monolithic column based on flower-shaped zeolitic imidazolate framework for efficient capillary microextraction of brominated flame retardants

A novel flower-shaped zeolitic imidazolate framework(ZIF) doped organic-inorganic hybrid monolithic column(ZIF-HMC) was prepared by a simple sol-gel "one-step" method and utilized for efficient capillary microextraction(CME) of four brominated flame retardants.The prepared monolithic was characterized by Fourier transform infrared,scanning electron microscopy,X-ray photoelectron spectroscopy,energy disperse spectroscopy,and N_(2) adsorption-desorption.The parameters of CME were optimized by orthogonal array design.Under the optimal conditions,the ZIF-HMC showed excellent extraction efficiency,the limit of detection(LODs) and the limit of quantification(LOQs) were in the range of0.52$3.1 mg/L and 1.7$10 mg/L,respectively,and the proposed method demonstrated good recovery(88.8%–116.6%) with the RSD less than 13.6% and a reusability of at least 30 times.The ZIF-HMC possessed great potential for separating organic pollutants and the strategy used here could be extended to prepare other derivatized HMC functionalized monoliths.

Particle size distribution of brominated flame retardants in house dust from Japan

The present study was conducted to examine the concentrations,profiles,and mass distributions of polybrominated diphenyl ethers(PBDEs),hexabromocyclododecanes(HBCDs),and polybrominated dibenzo-p-dioxins/furans(PBDD/Fs)based on the particle sizes of house dust samples from five homes in Japan.After removal of impurities from house dust from vacuum cleaner bags,selected indoor dust samples were size fractionated(>2 mm,1-2 mm,0.5-1 mm,250-500 mm,106-250 mm,53-106 mm,and<53 mm).Fluffy dust was collected separately for particle size analysis.PBDEs,HBCDs,and PBDFs were detected in all the samples analyzed.In general,PBDE levels of particulate and fluffy dust were comparable and the highest concentrations were found in 106-250 mm or 53-106 mm fractions.HBCD concentrations in fluffy dust were higher than those in particulate dust,and their levels were the highest in 106-250 mm and 250e500 mm factions,respectively.The highest concentrations of all three compound groups were not found in particles<53 mm in size,suggesting that the distribution of brominated flame retardants does not depend solely on the surface area-to-volume ratios of dust particles.The concentrations of PBDEs and PBDD/Fs depended principally on the concentrations in particles<53 mm in size because the predominant mass of particulate dust were found in this fraction.The mesh size used for sample preparation will thus have little effect on the concentrations as long as particles<53 mm are included.In contrast,HBCD concentrations increased by as much as 80%when particles>250 mm in size and fluffy dust were included.The conclusion is that particulate dust<250 mm in size without fluffy dust should be used to analyze dust for brominated flame retardants.

Toxicity of the brominated flame retardant tris-(2,3-dibromopropyl) isocyanurate in zebrafish (Danio rerio)

Tris-(2,3-dibromopropyl) isocyanurate (TBC) is a heterocyclic brominated flame retardant that was recently detected in the environment in China.TBC is semi-volatile and can accumulate in the lipid of some species,but little is known about its effect on aquatic organisms.We exposed adult zebrafish to 0,0.25,1 and 4mg/L TBC for 28 d and measured the effect on survival,growth,histopathology,hormone levels,enzyme activity,and gene expression.TBC exposure had no effect on survival or growth.We observed significant damage to the liver and gill,including hepatocellular swelling and fatty degeneration in the liver as well as proliferation and edema of epithelial cells in the gills.In addition,exposure to 4mg/L TBC induced proliferation of goblet cells in the intestine of both sexes,acellular areas in the testis,and thinly scattered vitellogenic granules in vitellogenic oocytes.TBC exposure had no effect on the levels of thyroid hormones,testosterone,estradiol,liver superoxide dismutase activity,malondialdehyde content,and brain cholinesterase activity.By contrast,hepatic vitellogenin and cytochrome P4501A gene expression was significantly down-regulated in both male and female zebrafish in response to TBC exposure.Our results suggest that exposure to TBC causes a variety of potential reproductive and endocrine toxic effects.

溴代阻燃剂与杀虫剂对斜生栅藻的毒性效应

为了明确溴代阻燃剂和杀虫剂对微藻的毒性效应,以斜生栅藻为模型生物,研究了3种溴代阻燃剂(BFRs)、3种新烟碱杀虫剂(NNIs)、3种有机磷杀虫剂(OIs)对其单一及联合毒性.结果表明,BFRs、NNIs、QIs单一及二元混合体系均诱导斜生栅藻产生了低浓度促进、高浓度抑制的Hormesis效应.Hormesis效应的产生与藻细胞内活性氧(ROS)水平密切相关,ROS水平的适度升高促进了微藻生长,甚至可能导致藻华的产生,而ROS显著升高则抑制微藻生长.9种污染物的预测无效应浓度(PNEC)均落在Hormesis刺激作用区间内,说明采用剂量-效应曲线预测的PNEC值会高估上述污染物对水生生态的风险.基于独立作用模型(IA)发现18种二元混合体系对斜生栅藻的联合毒性作用具有浓度依赖特征.

婴儿配方奶粉中3种新型溴代阻燃剂参考物质候选物的研制

目的研制婴儿配方奶粉中五溴甲苯、六溴苯和1,2-双(2,4,6-三溴苯氧基)乙烷3种新型溴代阻燃剂的参考物质候选物。方法以市售婴儿配方奶粉为研究基质,经加水溶解、标准添加、均质、干燥、粉碎、筛分和分装等工序制备后,用同位素稀释-大气压气相色谱-串联质谱法进行目标物的均匀性检验和稳定性考察。分别采用F检验和一元线性模拟方程评价参考物质候选物的均匀性和稳定性数据。结果均匀性检验的分析结果显示3种新型溴代阻燃剂的F均小于临界值F(1.964)。稳定性考察的分析结果显示,在40℃放置10 d或–20℃避光放置6个月的条件下,候选物的特性量值未观测到明显变化。结论本研究研制的婴儿配方奶粉中3种新型溴代阻燃剂参考物质候选物的均匀性、稳定性良好,符合参考物质的预期要求,能够为进一步形成参考物质提供物质基础。

大气压气相色谱-串联质谱法同时测定血清中多溴二苯醚和新型溴代阻燃剂

建立了大气压气相色谱-串联质谱(APGC-MS/MS)同时测定人体血清8种多溴二苯醚(PBDEs)和9种新型溴代阻燃剂(NBFRs)的方法。0.3 g血清样品经HLB柱固相萃取和30%酸性硅胶柱净化处理后,用DB-5HT毛细管柱(15 m×0.25 mm×0.10μm)分离,APGC-MS/MS检测分析。PBDEs和NBFRs的检测分别采用同位素稀释法和内标法。采用血清标准参考物质SRM 1958和基质加标进行方法验证,与SRM 1958给出的参考质量分数值范围对比,多溴二苯醚各化合物浓度的测定值均在参考质量分数值的范围内,相对标准偏差(RSD,n=6)为6.1%~18%。NBFRs的基质加标回收率为81.7%~126%,RSD为6.2%~18%。该方法灵敏度和准确度高、方法性能稳定,满足人体血清中溴代阻燃剂检测的要求。

青藏高原新型溴代阻燃剂的污染现状与研究展望

阻燃剂作为在工业上被广泛用作电子产品、汽车、聚氨酯泡沫、纺织品等消费品的添加剂,用于降低易燃材料着火的可能性。传统的阻燃剂如多溴联苯醚已在多项研究中证明存在环境污染和毒性问题,为了解决这些问题,以十溴二苯基乙烷(DBDPE)为代表的一系列新型阻燃剂(NBFRs)应运而生。作为新污染物的一种,NBFRs在环渤海地区、京津冀地区等工业发达区域和两极地区等偏远区域均有报道。青藏高原作为世界的第三极,工业化程度低,人迹罕至,与两极地区一样,是研究NBFRs大气长距离迁移与对环境影响的重要区域。文章综述了近年来青藏高原地区进行的NBFRs研究,包括土壤、苔藓、大气以及水体等介质,研究区域涵盖青藏高原的多个典型地区。在青藏高原已有报道中,DBDPE的浓度和检出率在各项基质中均为最高值。但当前在青藏高原进行的研究仍然较少,需要进一步研究,以弥补新污染物在青藏高原地区研究的空白。

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.