多溴联苯醚、六溴环十二烷和四溴双酚A在环境中污染现状的研究进展

作为最主要的三大传统溴系阻燃剂(BFRs),多溴联苯醚(PBDEs)、六溴环十二烷(HBCD)、四溴双酚A(TBBPA)具有半挥发性、环境持久性和远距离传输性,目前在全球各种环境介质、生物体内广泛存在.毒理学研究表明,PBDEs、HBCD、TBBPA均具有明显的生物毒性和致癌性,对生态环境和人体健康存在潜在危害.本文简要概述了PBDEs、HBCD、TBBPA的使用现状,综述了全球范围内非生物体(灰尘、水体、土壤、沉积物、污泥)和生命体内(植物、动物、人体)等3种传统BFRs的污染水平、特征、暴露途径和毒性,并讨论了当前存在问题,最后对PBDEs、HBCD、TBBPA的未来研究进行了初步展望.     

多溴联苯醚胁迫下鲫鱼肝脏微粒体CYP3A1和GST的响应

以鲫鱼Carassius auratus Linn.为试验鱼类,研究了其暴露于不同质量浓度的2,2',4,4'-四溴联苯醚(PBDE-47)和十溴联苯醚(PBDE-209)后鱼肝微粒体中CYP3A1和GST酶活性的动态变化.结果表明,鲫鱼在0.10～5.00 mg·L-1的PBDE-47和5.00～50.0 mg·L-1的PBDE-209中暴露15 d后,除0.10 mg·L-1PBDE-47、5.00 mg·L-1和10.0 mg·L-1PBDE-209试验组外,其余各试验组的鱼肝微粒体中CYP3A1被诱导,呈显著的剂量.效应关系.CYP3A1的活性随着作用时间的延续而上升,到试验第15天时达到最高,但上升速率最快的阶段为试验的第0-5天.而GST酶则表现出不同的特点,呈先升高后降低的趋势.经过15 d试验,除0.10 mg·L-1PBDE.47和5.00 mg·L-1PBDE-209以外的各试验组鲫鱼肝脏微粒体中的GST活性仅为对照组的12.74%～85.35%,表明PBDEs已对鱼体肝脏GST产生了较为严重的影响.研究表明,鱼类肝脏微粒体中CYP3A1和GST酶可作为污染生物标志物来评价PBDEs的早期污染毒理效应.     

溴系阻燃剂的毒理学研究进展

溴系阻燃剂(brominated flame retardants,BFRs)广泛应用于塑料、电子、建筑、纺织等材料和产品中,在多种环境介质中都可以检测到BFRs的存在。目前市场上的溴系阻燃剂主要有3种:四溴双酚A(tetrabromobisphenol A,TBBPA)、多溴联苯醚(polybrominated diphenyl ethers,PBDEs)和六溴环十二烷(hexa bromocyclododecanes,HBCDs)。近年来,进入环境中的BFRs在数量和种类上迅速增加,由此引发的环境效应日益受到国际社会广泛关注,有关BFRs的毒理学研究也成为相关领域的焦点内容。在总结近年来国内外相关研究的基础上,就BFRs在内分泌干扰效应、肝脏毒性、生殖毒性和神经毒性等方面的研究现状及需要进一步研究的内容进行了综述。     

加速溶剂萃取-超高效液相色谱/大气压化学电离/串联三重四极杆质谱法同时检测土壤中7种溴代阻燃剂

正溴代阻燃剂(BFRs)是一种广泛应用于纺织、塑料以及电子电器产品中的卤素有机阻燃剂,主要包括多溴联苯醚(PBDEs)、六溴环十二烷(HBCD)和四溴双酚A(TBBPA).这些化合物具有高亲脂性、难降解性和生物积累性的毒性特征.BFRs广泛存在于水体、土壤、大气及生物体内,并可对生物体的神经系统和内分泌系统造成难以逆转的损害.采用气相色谱(GC)分析BFRs时,HBCD易发生异构体间的相互转化,无法区分HBCD的3种异构体.且HBCD和     

室内环境中多溴联苯醚的污染特征和暴露风险研究进展

多溴联苯醚(polybrominated diphenyl ethers,PBDEs)是一类常见的溴代阻燃剂,具有生育毒性、生殖毒性以及致癌性等慢性毒性.作为典型的溴代阻燃剂,多溴联苯醚常被加入到各种产品中以提高产品的安全性,但在各种商业产品的使用过程中,多溴联苯醚会不可避免地逸出至室内环境中,存在于空气或者灰尘中被人体摄入.研究表明,人类一生有80%—90%的时间处于室内环境中,因此,通过了解目前室内环境中多溴联苯醚的污染现状,进而评估通过室内环境暴露多溴联苯醚对人体的潜在危害极为重要.本文总结了室内环境中多溴联苯醚的浓度水平、组成特征以及人体暴露风险,并对未来的研究提出建议.     

多溴联苯醚对芳香烃受体的激活作用及其介导毒性的研究进展

多溴联苯醚(polybrominated diphenyl ethers,PBDEs)是一类全球广泛存在的有机污染物,由于具有环境持久性,远距离传输,生物可累积性及对生物和人体有毒害效应等特性,是当前环境科学的热点研究对象之一.PBDEs的毒性包括生殖毒性、神经毒性、内分泌干扰、DNA损伤、免疫影响等,对人类以及环境具有潜在的威胁.芳香烃受体(aryl hydrocarbon receptor,AhR)是一种配体激活转录因子,诱导许多编码药物代谢酶的基因,可以被二噁英强效激活并引发一系列毒性.PBDEs具有与二噁英相似的结构,而被认为是一种潜在的AhR配体,但是PBDEs通过AhR介导的毒性机理仍然不明确.本文介绍和讨论了近10多年来PBDEs对AhR激活作用的研究,以及诱导的基因表达和毒性效应.虽然各文献的研究手段以及结论不尽相同,大多数研究表明大部分PBDEs对AhR的激活效果较为微弱,但仍有些PBDE需要引起重视.例如,BDE-126在大鼠肝细胞中的激活作用比其同系物更为突出,BDE-99可以激活斑马鱼胚胎中的AhR.此外,大多数羟基化或甲氧基化多溴联苯醚在家禽胚胎肝细胞、大鼠肝癌细胞中可以激活AhR,且可能比PBDEs具有更高的毒性和生物积累性.     

BDE-28及BDE-99对斑马鱼早期生命阶段HPT、HPG和HPA轴功能基因表达水平的影响

2,4,4'-三溴联苯醚(2,4,4'-tribromodiphenyl,BDE-28)和2,2',4,4',5-五溴联苯醚(2,2',4,4',5-pentabromodiphenyl ether,BDE-99)在水环境中广泛存在,并且发现在我国长江下游鱼体内和底泥中检出含量较高。目前针对2,2’,4,4’-四溴联苯醚(2,2',4,4'-tetrabromodiphenyl ether,BDE-47)的水生生物内分泌干扰效应和机制报道较多,而对于检出水平较高的BDE-28和BDE-99的相关方面研究还比较缺乏。本文将斑马鱼鱼卵分别暴露于2、20和200μg·L~(-1)的BDE-28和BDE-99溶液中,借助q-RT-PCR的方法研究它们对斑马鱼幼鱼的下丘脑-垂体-甲状腺(hypothalamus-pituitary-thyroidal,HPT)、下丘脑-垂体-性腺(hypothalamuspituitary-gonadal,HPG)和下丘脑-垂体-肾上腺(hypothalamus-pituitary-adrenal,HPA)轴上50个基因的影响。结果发现,在受精后120 h(hours post fertilization,hpf)时,暴露于2、20和200μg·L~(-1)的BDE-28和BDE-99的实验组中斑马鱼HPT、HPG和HPA轴上相关基因的表达均受到影响,其中BDE-28主要导致三轴相关基因显著上调,而BDE-99导致三轴相关基因显著下调。BDE-28和BDE-99对斑马鱼早期阶段3个主要内分泌分子通路的影响将导致内分泌功能的改变,从而可能会对斑马鱼的后期生长发育产生影响。另外,主成分分析发现2种不同溴取代个数的PBDE类物质(BDE-28和BDE-99)通过不同的毒性机制对斑马鱼产生不良影响。     

典型羟基化多溴联苯醚(OH-PBDEs)小鼠肝微粒体的体外代谢及关键代谢CYP450酶系的研究

羟基化多溴联苯醚(OH-PBDEs)是一类具有内分泌干扰效应的酚类化合物,本研究以小鼠肝脏微粒体作为研究对象,考察了4种典型OH-PBDEs(3-OH-BDE-47、5-OH-BDE-47、6-OH-BDE-47和2′-OH-BDE-68)的体外代谢.研究结果表明,4种OH-PBDEs在小鼠肝脏微粒体中均能被代谢;OH-PBDE结构上的醚键(O)、羟基(OH)和溴原子(Br)的相对位置会影响其代谢效率,OH位于苯环上醚键邻位更有利于其代谢,即6-OH-BDE-47表现出相对较高的代谢率;抑制剂实验发现CYP1A2和CYP3A4是4种典型OH-PBDEs主要的CYP450代谢亚型.     

内质网应激介导的凋亡在PBDE-47致大鼠海马损伤中的作用

为了明确内质网应激(endoplasmic reticulum stress,ERS)介导的凋亡在2,2’,4,4’-四溴联苯醚(2,2’,4,4’-tetrabromodiphenylether,PBDE-47)致大鼠神经毒性中的作用,在脑发育的突增期(出生第10天),分别用0 mg·kg~(-1)、1 mg·kg~(-1)、5 mg·kg~(-1)和10mg·kg~(-1)PBDE-47进行单次灌胃染毒,并从出生第8天开始每天给予150 mg·kg~(-1)ERS抑制剂4-苯基丁酸(phenylbutyric acid,PBA),持续3周。仔鼠出生第8周末,从对照组、10 mg·kg~(-1)PBDE-47处理组、150 mg·kg~(-1)PBA处理组和150 mg·kg~(-1)PBA+10mg·kg~(-1)PBDE处理组中随机选取8只大鼠进行水迷宫实验。然后将所有动物断头处死,分离大鼠海马组织,观察其海马组织形态学改变、测定ERS标志分子(GRP78、IRE1和CHOP)和凋亡相关蛋白Cyt c的表达水平。结果显示,10 mg·kg~(-1)PBDE-47处理可导致雌性大鼠海马CA4区细胞排列紊乱、锥形神经细胞数量减少甚至消失,尼氏小体数量减少,大鼠逃避潜伏期延长(P0.05)。5和10 mg·kg~(-1)PBDE-47处理可显著上调ERS相关蛋白IRE1和CHOP的表达水平(P0.05),并明显增强海马组织凋亡相关蛋白Cyt c的表达。PBA干预可明显降低PBDE-47诱导的IRE1和CHOP以及Cyt c蛋白的表达水平,提示PBDE-47可通过ERS介导凋亡,导致大鼠海马组织损伤,从而影响大鼠学习记忆功能。     

电子废弃物拆解地水体多溴联苯醚分布特征

为了解和比较广东贵屿电子废弃物拆解地和珠三角城市地区水体中多溴联苯醚的种类、含量及分布特征,于2011年9月在广东贵屿周边地区和广州采集了20个地下水、7个地表水和4个珠江水,用反相C18萃取小柱提取净化后,利用气相色谱-质谱法测定了样品中的8种多溴联苯醚（PBDEs）。研究结果表明：贵屿地区地下水中PBDEs浓度总体上较高,总质量浓度范围为2.54~71.74 ng·L-1,平均为22.97 ng·L-1,各类PBDEs的检出率为25%~95%。三溴联苯醚（BDE28）、四溴联苯醚（BDE47）、五溴联苯醚（BDE99和BDE100之和）、六溴联苯醚（BDE153和BDE154之和）、七溴联苯醚（BDE183）和十溴联苯醚（BDE209）的质量浓度分布分别为nd~0.64、nd~18.43、nd~25.26、nd~13.92、nd~9.06和nd~15.60 ng·L-1。从物种上来看,分别源于四溴、五溴和十溴联苯醚产品的BDE47、BDE99和BDE209是贵屿地区地下水样中的优势同系物。通过比率P=（BDE47＋BDE99）/BDE209研究发现：低溴代联苯醚比高溴代联苯醚更易被地表径流迁移转换进入到地下水中。贵屿地区地表水中PBDEs的质量浓度范围为3.41~63.83 ng·L-1,平均总质量浓度为19.38 ng·L-1,稍低于当地地下水中PBDEs的平均总质量浓度,PBDEs的组成以高溴代的BDE209为特征,与世界其他水体研究结果相比,可以发现贵屿地区的地表水中PBDEs的平均总质量浓度明显偏高,说明该地区的地表水受到较严重的PBDEs污染,必须引起足够的重视。珠江水中PBDEs的总质量浓度范围为3.48~20.84 ng·L-1,平均为10.39 ng·L-1,表明近年来珠江水体中PBDEs污染有逐渐恶化的趋势。     

Solvent effects on quantitative analysis of brominated flame retardants with Soxhlet extraction

Reliable quantifications of brominated flame retardants (BFRs) not only ensure compliance with laws and regulations on the use of BFRs in commercial products, but also is key for accurate risk assessments of BFRs. Acetone is a common solvent widely used in the analytical procedure of BFRs, but our recent study found that acetone can react with some BFRs. It is highly likely that such reactions can negatively affect the quantifications of BFRs in environmental samples. In this study, the effects of acetone on the extraction yields of three representative BFRs [i.e., decabrominated diphenyl ether (decaBDE), hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA)] were evaluated in the Soxhlet extraction (SE) system. The results showed that acetone-based SE procedure had no measureable effect for the recovery efficiencies of decaBDE but could substantially lower the extraction yields for both TBBPA and HBCD. After 24 h of extraction, the recovery efficiencies of TBBPA and HBCD by SE were 93 and 78% with acetone, 47 and 70% with 3:1 acetone:n-hexane, and 82 and 94% with 1:1 acetone:n-hexane, respectively. After 72 h of extraction, the extraction efficiencies of TBBPA and HBCD decreased to 68 and 55% with acetone, 0 and 5% with 3:1 acetone/n-hexane mixtures, and 0 and 13% with 1:1 acetone/n-hexane mixtures, respectively. The study suggested that the use of acetone alone or acetone-based mixtures should be restricted in the quantitative analysis of HBCD and TBBPA. We further evaluated nine alternative solvents for the extraction of the three BFRs. The result showed that diethyl ether might be reactive with HBCD and may not be considered as the alternative to acetone used solvents for the extraction of HBCD.     

磷酸三苯酯(TPP)和磷酸三(2-氯异丙基)酯(TCPP)诱导人胚肾细胞HEK293凋亡的机制研究

磷系阻燃剂对人体的潜在毒性作用引起了国内外研究者的广泛关注。肾脏是机体重要的排毒器官,若肾脏细胞受损,可能影响肾脏功能的正常发挥。本研究以人胚肾细胞HEK293为研究对象,结合传统毒理学实验,筛选出磷酸三苯酯(TPP)及磷酸三(2-氯异丙基)酯(TCPP)诱导人胚肾细胞HEK293凋亡的关键靶标基因p53。在此基础上采用分子对接模拟和光谱法分析发现,TPP和TCPP分别以嵌插方式和沟槽方式结合p53-DNA,改变基因片段的框架结构,启动分子起始事件,通过影响相关基因(Bax、Hrk、Bcl-2和Bad)的表达量,导致线粒体途径释放cyt c,最终激活Caspase 7实现细胞凋亡。研究结果阐明了此类污染物诱导凋亡的作用机制,为毒害化学品的污染防控提供理论依据。     

六溴环十二烷(HBCD)对H4细胞和SK-N-AS细胞脱碘酶2和3表达的影响

六溴环十二烷(hexabromocyclododecane,HBCD)与多溴联苯醚(polybrominated diethyl ethers,PBDEs)复合污染体系,对人类健康尤其神经系统所造成的潜在危害及其机制一直是笔者课题组的研究方向。HBCD是广泛使用的溴化阻燃剂,与PBDEs一样,会通过干扰内分泌系统、影响甲状腺激素分泌及损伤神经系统,对生物体产生发育神经毒性。作为系列研究之一,本研究以H4人脑神经胶质瘤细胞和SK-N-AS人神经母细胞瘤细胞为体外生物模型,通过观察HBCD对H4细胞Ⅱ型脱碘酶(Dio2)和SK-N-AS细胞Ⅲ型脱碘酶(Dio3)表达的调控,初步探讨了HBCD对神经系统局部甲状腺激素水平的潜在影响。H4细胞和SK-N-AS细胞分别暴露于0、1、3和9μmol·L-1HBCD 24 h后,采用MTT法检测细胞活力,Western Blot和RT-PCR法分别分析Dio2和Dio3蛋白和基因的表达,酶联免疫吸附测定(ELISA)法检测H4细胞脑源性神经细胞营养因子(BDNF)的分泌。结果表明,HBCD以剂量依赖方式降低H4细胞和SK-N-AS细胞生存率,引起H4细胞Dio2蛋白和基因表达下调,而致SK-N-AS细胞Dio3蛋白和基因表达上调。此外,HBCD还降低H4细胞BDNF的分泌。这表明,HBCD很可能通过影响神经和胶质细胞脱碘酶的表达,影响脑局部甲状腺激素水平,从而引起神经系统损伤及发育神经毒性。     

BDE-47对4种海洋微藻抗氧化酶活性的影响

运用实验生态学和生物化学的方法,研究了不同质量浓度的2,2',4,4'-四溴联苯醚(BDE-47)对海水小球藻Chlorellaautotropica,牟氏角毛藻Chaetoceros muelleri,中肋骨条藻Skeletonema costatum和赤潮异弯藻Heterosigam akashiwo的抗氧化酶活性的影响.结果表明:在实验设定质量浓度范围内(0.1～2.5 μg·L~(-1)),4种微藻的超氧化物歧化酶(SOD)和过氧化氢酶(CAT)均能出现一定的应激活性,以减少BDE-47胁迫对藻细胞自身的危害,但是酶活增加的幅度却有很大不同.与赤潮异弯藻和中肋骨条藻相比,海水小球藻和牟氏角毛藻的SOD和CAT对BDE-47具有较高的敏感性.4种海洋微藻的SOD和CAT对BDE-47的敏感性顺序依次为:海水小球藻>牟氏角毛藻>中肋骨条藻>赤潮异弯藻.因此,海水小球藻的SOD和CAT可以作为指示海洋环境中BDE-47污染水平的生物标志物.     

(Persistent) Organic pollutants in Germany: results from a pilot study within the 2015 moss survey

Background

Since 1990, every 5 years, moss sampling is conducted within the European moss monitoring programme to assess the atmospheric deposition of airborne pollutants. Besides many other countries, Germany takes regularly part at these evaluations. Within the European moss monitoring 2015, more than 400 moss samples across Germany were taken according to a harmonized methodology for the assessment heavy metal and nitrogen input. In a pilot programme, eight of these sites were chosen for additional investigations on a broad range of organic contaminants to evaluate their accumulation in moss and thereby their presence in atmospheric deposition in Germany. Target compound classes comprised polycyclic aromatic hydrocarbons (PAH), polychlorinated dibenzodioxins and –furans (PCDD/F), dioxin-like and non-dioxin-like polychlorinated biphenyls (dl-PCB, ndl-PCB), polyfluorinated alkyl substances, classical flame retardants as well as emerging chlorinated and brominated flame retardants. In total, 120 target compounds were analysed. For some analytes, comparisons of accumulation in moss and tree leave samples were possible.

Results

Except for certain flame retardants, PFAS, and ndl-PCB, substances of all other compound classes could be quantified in moss samples of all sites. Concentrations were highest for PAH (40–268 ng g^?1) followed by emerging flame retardants (0.5–7.7 ng g^?1), polybrominated diphenyl ethers (PBDE; 0.3–3.7 ng g^?1), hexabromocyclododecane (HBCD; 0.3–1.2 ng g^?1), dl-PCB (0.04–0.4 ng g^?1) and PCDD/F (0.008–0.06 ng g^?1).

Conclusions

Results show the widespread atmospheric distribution and deposition of organic contaminants across Germany as well as the suitability of moss as bioaccumulation monitor for most of these compound classes. Compared to nearby tree leaf samples, accumulation potential of moss appeared to be higher for pollutants of high octanol–air partition coefficient (K_OA) and octanol–water partition coefficient (K_OW).

     

Polybrominated diphenyl ether (PBDE) levels in the blood of pure vegetarians (vegans)

Intake of many persistent organic pollutants (POPs) including dioxins, dibenzofurans and PCBs is almost exclusively from gastrointestinal ingestion of animal fats in the diet. With polybrominated diphenyl ether (PBDE) brominated flame retardants (BFRs), no consensus exists at present as to the extent of intake from food, from indoor dust or other routes of intake. Vegans, or pure vegetarians, were previously found to have low body burden of dioxins and dibenzofurans in blood. Data reported here for the first time show a trend towards lower PBDE levels with longer time periods without ingestion of food of animal origin in 8 adult residents of the United States. A stronger relationship between lower PBDE levels and time without meat, specifically, is consistent with substantial PBDE intake from meat relative to fish or dairy products in Americans. These vegans had somewhat lower PBDE levels with a range 12.4–127 and a median 23.9?ppb than published reports of US general population samples which had a range of 4–366 and median of 26?ppb. Our findings suggest that food of animal origin may be a major but not the sole contributor to human body burden of PBDEs.     

Formation of 2,3,7,8‐tetrabromodibenzodioxin and ‐furan by thermolysis of polymers containing brominated flame retardants

Several plastic products which are used in areas exposed to fire hazards contain flame retardants. A group of important flame retardants are brominated aromatic compounds, and it is believed that they thermally generate polybrominated dibenzodioxins (PBrDD) and dibenzofurans (PBrDF).

The formation of 2,3,7,8‐Tetrabromodibenzodioxin (TBrDD) and ‐Tetrabromodibenzofuran (TBrDF) from various plastics with brominated flame retardants under different thermolysis conditions is presented. At 600 °C, 2,3,7,8‐TBrDD and ‐TBrDF in concentrations of 0.01–7 and 0.01–6 ppm, respectively, are formed from plastics containing decabromodiphenylether or polybromodiphenylether as flame retardant. With increasing temperature the concentration of these isomers decreases until they are no longer detectable above 800 °C (detection limit: 0.01 ppm).

The hypothetical reaction pathways for the formation of 2,3,7,8‐TBrDD and ‐TBrDF by thermolysis of decabromodiphenylether are proposed.

The solubility and photochemical properties of 2,3,7,8‐TBrDD in different solvents are given.     

十溴联苯醚在单次暴露的孕和非孕SD大鼠血液内的吸收分布

五溴联苯醚、八溴联苯醚被禁以后,十溴联苯醚（BDE-209〉97%）是现在唯一仍在全球范围内广泛使用的多溴联苯醚阻燃剂。BDE-209在环境介质和生物体,甚至人体的血液、母乳中普遍存在,而且BDE-209的环境含量呈上升趋势。在实验室条件下,BDE-209可以通过生物代谢,或光降解、热降解转换形成毒性更强的低溴代PBDEs、羟基甲氧基PBDEs、致癌物多溴二苯并二噁英/呋喃（PBDD/DFs）。所以BDE-209的环境行为及生物效应成为环境污染物领域研究的热点之一。目前,关于BDE-209对妊娠期生物体的暴露研究还是很少。研究了十溴联苯醚在单次暴露的孕和非孕SD大鼠血液内的吸收代谢。结果表明,BDE-209可以被孕和非孕SD大鼠吸收,孕和非孕SD大鼠血液中吸收的BDE-209都可以快速的排出。BDE209在孕和非孕SD大鼠体内存在脱溴代谢,主要的脱溴代谢物是3种nona-BDE（sBDE-206,-207,-208）和五种octa-BDEs（BDE-196,-197/204,-198/203）,其中3种nona-BDEs是主要的代谢物,而BDE-207是nona-BDEs中含量最大的单体。BDE-209及其脱溴代谢物nona-BDEs的清除速率,在SD孕鼠的体内快于SD非孕鼠,而且在暴露实验的后期还存在统计意义的显著差异性。     

Brominated flame retardants and dechlorane plus on a remote high mountain of the eastern Tibetan Plateau: implications for regional sources and environmental behaviors

We investigated the occurrence of halogenated flame retardants (HFRs) including polybrominated diphenyl ethers (PBDEs), six novel brominated flame retardants (NBFRs) and dechlorane plus in air and soils on the eastern slope of Mt. Gongga on the eastern Tibetan Plateau. We detected all of the NBFR except bis(2-ethylhexyl)-tetrabromophthalate and pentabromoethyl benzene. NBFRs constituted the most prevalent group. BDE-28 and BDE-47 dominated among the PBDE congeners. Decabromodiphenyl ethane was detected at relatively high levels up to 171 pg/m³ and 1450 pg/g dry weight in air and soils, respectively; however, it appeared to be easily degraded in the environment. A general decreasing trend was observed among the HFR concentrations with increasing altitude, and this was due to the prominent contribution of source emissions over possible influence of environmental conditions. This study also suggests that HFRs are supplied to forest soils mainly in the form of precipitation and retained in the O horizon layers.