多溴联苯醚光化学降解

多溴联苯醚(PBDEs)是一类全球性的有机污染物,近年来由于其持久性、毒性和潜在的生物蓄积性而备受关注.光化学降解是环境中多溴联苯醚的重要归趋之一.本文综述了有机溶剂、水相和固相等不同介质中人工紫外光源和太阳光下PBDEs的光降解研究成果,不仅介绍了光源、反应介质、溴取代数目和取代型式对PBDEs光解速率和光解产物的影响,也包括了基于PBDEs光解的定量结构-性质关系,并展望了环境中PBDEs光化学行为的研究前景.     

应用零价铁基材料还原和催化氧化降解多溴联苯醚

多溴联苯醚（PBDEs）是一类新型的持久性有机污染物（POPs）,由于不合理的使用和处置,在多种环境介质中均存在不同程度的污染。环境中PBDEs的降解技术已成为近年来的研究热点。大量的研究表明,零价铁（ZVI）还原脱溴降解PBDEs是一种高效快速且经济可行的治理技术。本文在总结国内外关于ZVI基材料降解PBDEs研究的基础上,分析了ZVI还原降解PBDEs的机理、动力学、影响因素及降解路径。从总体上看,ZVI作为高活性电子供体虽然能将高溴代PBDEs迅速降解为低溴代产物,但产生的低溴代PBDEs往往具有更大的环境风险,需进一步降解处理。近年来的研究表明,利用ZVI作为间接电子供体,通过催化活化H₂O₂或过硫酸盐产生高活性自由基,能够实现开环降解低溴代PBDEs。基于以上分析,通过构建一套先还原-后氧化的降解体系,有望实现高溴代PBDEs的彻底降解。最后,本文对ZVI降解PBDEs技术的后续研究进行了讨论和展望。     

环境中多溴联苯醚(PBDEs)预处理技术研究进展

多溴联苯醚(PBDEs)是一类具有生态风险的新型环境有机污染物。PBDEs作为阻燃剂已愈来愈广泛地被添加到工业产品中,并对大气、水体、沉积物、土壤等环境介质产生污染,最终危害生物和人类健康。本文概述了环境样品中PBDEs分析方法研究进展,对样品前处理技术作了评述和比较,并从不同离子源和质谱类型的角度分析比较了气相色谱-质谱联用在PBDEs检测中的应用。     

环境样品中多溴联苯醚分析方法的研究进展

多溴联苯醚(PBDEs)作为一类应用广泛的溴代阻燃剂,具有持久污染性、易于从被应用产品中脱离出来进入环境介质等特性,目前已对全球环境造成了严重危害.近年来针对PBDEs分析检测技术的报道愈来愈多,然而PBDEs不仅含量极低,而且所处基体复杂,因此样品前处理技术成为分析PBDEs类化合物的一个重要步骤,受到科学工作者的广泛重视.本文作者综述了近年来分析环境样品中PBDEs的样品前处理技术和分析检测方法的研究进展,为更好的发展准确、灵敏、快速的分析方法提供重要的参考.     

多溴二苯醚的生物代谢机制研究进展

作为一种广泛使用的阻燃剂,多溴二苯醚(PBDEs)及其衍生物羟基化多溴二苯醚(OH-PBDEs)和甲氧基化多溴二苯醚(MeO-PBDEs)等已从环境介质、各种生物体甚至人体内检测出来.但是对于生物体内低溴代PBDEs及其羟基化和甲氧基化衍生物的来源及其是否由PBDEs在生物体内代谢形成等问题,目前仍存在较多争论.由于PBDEs进入生物体后的生物转化、代谢途径与其对生物体的毒性有密切关系,因此是研究者们关注的焦点.本文在对生物体内PBDEs及其代谢物的来源和分布进行分析的基础上,综述了PBDEs在生物体内发生脱溴还原代谢和氧化代谢的研究进展,从体内原位代谢和体外模拟代谢研究两方面探讨了PBDEs的生物代谢机制、代谢途径及还原和氧化代谢中可能涉及的代谢酶,指出进一步深入开展PBDEs的生物积累和代谢研究的方向.     

多溴联苯醚及其环境问题

多溴联苯醚(PBDEs)是全球性的环境污染物,对其环境问题的研究已成为当前环境科学的一大热点,而我国PBDEs的研究刚刚起步.本文介绍了多溴联苯醚的性质、应用、污染来源、环境行为、污染水平、趋势、控制措施以及分析方法等,综述了国内外对PBDEs的研究情况,讨论了目前存在的问题,为我国开展PBDEs的研究提供参考.     

多溴联苯醚的光催化还原脱溴

多溴联苯醚(PBDEs)在生态环境中是普遍存在的并已证实具有潜在的毒性,因此PBDEs引起了环境化学领域的广泛关注。光催化技术具有可利用太阳能、反应选择性高且反应条件温和等优点,其在降解PBDEs这类污染物方面具有独特的优势。近年来光催化在降解含卤有机污染物的研究中取得长足进展。本文就多卤代芳烃类化合物中最为典型的PBDEs的光催化还原研究现状进行介绍,并着重阐述TiO_2催化剂对PBDEs的光催化还原脱溴反应的基本过程、提高光催化还原效率的途径以及光催化还原脱溴机理等。除此之外,本文也对PBDEs未来光催化还原脱溴的前景进行了简单的展望。     

溴系阻燃剂在环境及人体中的存在和代谢转化

溴系阻燃剂的广泛使用及其对环境和人体的危害,受到人们的广泛关注。本文简要介绍了在环境与生态系统及人体中存在的三种主要溴系阻燃剂：多溴联苯醚、六溴环十二烷和四溴双酚A,重点评述了它们在环境介质（污水、淤泥及沉积物）、生物体（微生物及动物）、人体中及光热作用下的代谢与转化,并详细介绍了其代谢途径及代谢产物。     

超声辅助碱解萃取-气相色谱-电子捕获检测器测定海洋沉积物中8种多溴联苯醚

将超声辅助碱液分解杂质与溶剂萃取相结合,采用气相色谱-电子捕获检测(GC-ECD)建立了一种快速高效净化、萃取海洋沉积物中8种常见多溴联苯醚(PBDEs)的分析方法。样品在2.00 mol/L NaOH甲醇溶液中超声30 min,经正己烷萃取、单层硅胶净化、正己烷洗脱、旋蒸浓缩后定容至100 μL,采用GC-ECD分析。结果表明,PBDEs各单体的加标回收率为63.6%~110.3%,相对标准偏差(RSD)为1.7%~15.5%(n=5);十溴联苯醚(BDE-209)的检出限为0.097 ng/g,其他7种单体的检出限为0.002~0.011 ng/g(信噪比为3)。该方法的准确度和精密度较高,稳定性和回收率良好,可满足沉积物中PBDEs的分析要求。利用建立的方法测定了渤海表层沉积物中PBDEs的含量,8种PBDEs总含量在1.566~6.760 ng/g之间,其中BDE-209的含量为1.461~6.438 ng/g,总体呈现出由近岸向远岸递减的趋势,表明人为活动、表层冲刷和陆地河流的输入对渤海地区PBDEs的含量有重要影响。     

高分辨气相色谱-高分辨质谱测定活性污泥中的多溴联苯醚

建立了利用高分辨气相色谱-高分辨质谱定量测定多溴联苯醚(PBDEs)的方法,参与了测定PBDEs的国际比对实验,实验结果表明该法是可行的。对不同地区（北京、山东临沂、上海）的3个污水处理厂的活性污泥进行了索氏提取、多层复合硅胶柱分离,然后用所建立的方法测定了19种多溴联苯醚单体的含量。结果表明,北京某污水处理厂的活性污泥中PBDEs的总量高于其他两者。     

Human exposure to polybrominated diphenyl ethers through the diet

Polybrominated diphenyl ethers (PBDEs), a class of brominated flame retardants, are used in a variety of consumer products being produced in notable quantities. PBDEs have been detected in environmental samples. In recent years, a marked increase in the levels of PBDEs in human biological tissues and fluids, especially breast milk, has been observed in some countries. As for other persistent organic pollutants (POPs), dietary intake is very probably the main route of exposure to PBDEs for the general population. This paper reviews the state of the science regarding human exposure to PBDEs through the diet. Because of the scarce information about it, it is concluded that studies focused on determining PBDE exposure for the population of a number of countries are clearly required. The correlation of PBDE body burdens and dietary intake of PBDEs are also necessary.     

Advances in the study of current-use non-PBDE brominated flame retardants and dechlorane plus in the environment and humans

The fate of the high production volume,currently in use,and not regulated non-polybrominated diphenyl ether(PBDE) flame retardants,such as tetrabromobisphenol A(TBBPA) ,hexabromocyclododecane(HBCD) and dechlorane plus(DP),and the alternative flame retardants of PBDE,such as BTBPE and DBDPE,in the environment has attracted increasing attention and aroused concern due to the increasing regulation and phasing-out of PBDEs.This paper reviews the distribution,bioaccumulation,human exposure and environmental beha...     

人体血清中的多溴联苯醚、邻苯二甲酸酯和双酚A的连续在线分离及气相色谱-质谱测定

建立了人体血清中多种环境雌激素:多溴联苯醚、邻苯二甲酸酯和双酚A的快速可靠的连续在线分离及在气相色谱-质谱上的分析方法.血清样品经过浓盐酸使蛋白质变性,用乙醚萃取,经硅胶柱分离出多个族组分:多溴联苯醚(Polybrominated diphenyl ethers,PBDEs)、邻苯二甲酸酯(Phthalate estcrs,PAEs)和双酚A(Bisphenol A,BPA),最后由气相色谱-质谱的选择离子检测测定.PBDEs,PAEs和BPA标准曲线回归方程拟合度R2均大于0.99,表明在测试的浓度范围内线性关系良好.PBDEs目标化合物的检出限为0.005～0.048μg/L,PAEs目标化合物的检出限为0.103～0.833μg/L,BPA的检出限是0.035 μg/L.标准样品重复样中,PBDEs的RSD(relative standard deviation)值分别为2.8％～10.9％;PAEs的RSD值为5.6％～9.9％;BPA的RSD值为3.0％.实际血清样品中,PBDEs的加标回收物PCB209(Polychloride diphenyl ether 209)的回收率范围是74.8％～88.5％;PAEs中的加标回收物DBP-D4(Dibutyl phthalateDeutorium 4)的回收率范围为78.7％～97.0％;BPA中的加标回收物BPA-D16( Bisphenol A-Deutorium 16)的回收率范围是76.3％～93.1％.本方法检测血液中多种环境雌激素灵敏度高、重现性和回收率均良好.     

“One-shot” analysis of polybrominated diphenyl ethers and their hydroxylated and methoxylated analogs in human breast milk and serum using gas chromatography-tandem mass spectrometry

The presence of polybrominated diphenyl ethers (PBDEs) and their hydroxylated (OH-BDE) and methoxylated (MeO-BDE) analogs in humans is an area of high interest to scientists and the public due to their neurotoxic and endocrine disrupting effects. Consequently, there is a rise in the investigation of the occurrence of these three classes of compounds together in environmental matrices and in humans in order to understand their bioaccumulation patterns. Analysis of PBDEs, OH-BDEs, and MeO-BDEs using liquid chromatography-mass spectrometry (LC-MS) can be accomplished simultaneously, but detection limits for PBDEs and MeO-BDEs in LC-MS is insufficient for trace level quantification. Therefore, fractionation steps of the phenolic (OH-BDEs) and neutral (PBDEs and MeO-BDEs) compounds during sample preparation are typically performed so that different analytical techniques can be used to achieve the needed sensitivities. However, this approach involves multiple injections, ultimately increasing analysis time. In this study, an analytical method was developed for a “one-shot” analysis of 12 PBDEs, 12 OH-BDEs, and 13 MeO-BDEs using gas chromatography with tandem mass spectrometry (GC-MS/MS). This overall method includes simultaneous extraction of all analytes via pressurized liquid extraction followed by lipid removal steps to reduce matrix interferences. The OH-BDEs were derivatized using N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide (TBDMS-MTFA), producing OH-TBDMS derivatives that can be analyzed together with PBDEs and MeO-BDEs by GC-MS/MS in “one shot” within a 25-min run time. The overall recoveries were generally higher than 65%, and the limits of detection ranged from 2 to 14 pg in both breast milk and serum matrices. The applicability of the method was successfully validated on four paired human breast milk and serum samples. The mean concentrations of total PBDEs, OH-BDEs, and MeO-BDEs in breast milk were 59, 2.2, and 0.57 ng g⁻¹ lipid, respectively. In serum, the mean total concentrations were 79, 38, and 0.96 ng g⁻¹ lipid, respectively, exhibiting different distribution profiles from the levels detected in breast milk. This “one-shot” GC-MS/MS method will prove useful and cost-effective in large-scale studies needed to further understand the partitioning behavior, and ultimately the adverse health effects, of these important classes of brominated flame retardants in humans.     

A simple and fast method for the simultaneous determination of polychlorinated biphenyls and polybrominated diphenyl ethers in small volumes of human serum

A fast extraction and clean-up method for the simultaneous determination of PCBs and PBDEs has been developed. The procedure consisted of a solid-phase extraction (SPE) of the analytes on an Oasis HLB cartridge and the subsequent on-line fat elimination by directly dropping the eluate from the SPE cartridge onto a second cartridge containing layers of activated neutral silica gel and sulphuric acid modified silica gel. Detection limits using a gas chromatography coupled with an ion trap detector in the tandem mass spectrometry mode were from 0.03 to 0.3 pg/microL for PCBs and from 0.07 to 1.3 pg/microL for PBDEs. Repeatability (lower than 11%) and reproducibility (lower than 17%), expressed as relative standard deviation (RSD, n=4), were satisfactory. The feasibility of the method developed for the determination of the target compounds was evaluated by participation in several rounds of interlaboratory exercises involving human serum with a wide range of PBDE and PCB concentrations. The method has been applied to the evaluation of PBDEs and PCBs in human serum samples of up to 1 mL.     

母乳中多种含卤持久性有机污染物的联合检测方法

建立了母乳中多种含卤持久性有机污染物(POPs)的联合检测方法,目标化合物主要包括六溴环十二烷(HBCDs)、多溴联苯醚(PBDEs)、多氯联苯(PCBs)和有机氯农药(OCPs)等.样品的前处理采用液液萃取、凝胶渗透色谱(GPC)净化和固相萃取(SPE)等技术,目标化合物经气相色谱-质谱联用仪(GC-MS)、液相色谱-三重四极杆串联质谱联用仪(LC-MS/MS)和气相色谱-三重四极杆串联质谱联用仪(GC-MS/MS)等进行检测.样品通过GPC除去脂肪,然后经SPE柱进一步净化并进行多组分分离,极大程度地减小了生物样品中复杂基质的干扰,适合样品量相对较小的人体样本中多种超痕量POPs的分析.应用灵敏度高、选择性更好的GC-MS/MS对样品中的PCBs和OCPs等进行分析,进一步降低基质的干扰.方法经过小牛血清加标实验验证,稳定可靠.POPs的加标回收率分别为88.7％～98.8％(PBDEs), 88.5％～92.5％(HBCDs), 67.9％～82.3％(PCBs)和81.7％～116.1％(OCPs),方法检出限分别为0.13～1.8 pg/mL(PBDEs), 0.31～1.2 pg/mL(HBCDs), 0.22～1.4 pg/mL(PCBs)和0.20～1.5 pg/mL(OCPs).采用本方法对潍坊地区20例母乳样品进行分析,结果显示,潍坊市母乳中HBCDs, PBDEs, PCBs、HCHs和DDTs的中值浓度分别为2.86, 7.76, 8.84、140和503 ng/g 脂重,此浓度水平与国内其它地区人群相当.     

气相色谱-负化学源质谱快速测定母乳中的多溴联苯醚

建立了母乳中8种多溴联苯醚(PBDEs：BDE28,BDE47,BDE99,BDE100,BDE153,BDE154,BDE183,BDE209)的气相色谱-负化学源质谱测定方法(GC-NCI/MS)。样品经索氏提取、酸化硅胶除脂、硅胶氧化铝色谱柱净化后,在7 m长的毛细管气相色谱柱上快速分离,NCI/MS以选择离子监测模式测定目标化合物。其中,三溴～七溴联苯醚采用内标法定量,十溴联苯醚(BDE209)采用同位素稀释法定量。8种PBDEs的检出限为1.74～6.35 pg/g(以脂肪计)。加标回收试验的回收率为61.5%～108%,相对标准偏差为2.06%～10.1%(n=6)。并采用母乳参考物质进一步证实了该方法的准确可靠。该方法提高了BDE209的分析灵敏度,而且分析成本相对较低,分析时间短,适于推广。     

固相萃取结合超高效液相色谱-串联质谱法及气相色谱-负化学源质谱法测定人血清中的四溴双酚A、六溴环十二烷和多溴联苯醚

建立了固相萃取同时提取、净化血清中四溴双酚A(TBBPA)、α, β, γ-六溴环十二烷(HBCD)和8种多溴联苯醚(PBDEs)同系物的样本前处理方法,并结合色谱-质谱分离分析技术检测人血清样本中该类化合物的含量。试样在加入各自的同位素内标物后以甲基叔丁基醚/正己烷(1:1, v/v)混合溶剂进行萃取,再经浓硫酸去除脂肪后,以LC-Si固相萃取柱分离HBCD/TBBPA和PBDEs。采用分步检测的方式,在50 mm长BEH C18反相色谱柱上以超高效液相色谱-串联质谱(UPLC-MS/MS)的多反应监测模式(MRM)检测HBCD和TBBPA,在15 m长的毛细管柱上以气相色谱-负化学源质谱(GC-NCI/MS)的选择离子监测模式(SIM)检测PBDEs。以胎牛血清为空白基质,当HBCD、TBBPA和BDE-209的加标水平为0.5 ng/g和5 ng/g、三溴至七溴联苯醚的加标水平为0.05 ng/g和0.5 ng/g时,它们的平均加标回收率为80.3%～108.8%,相对标准偏差为1.02%～11.42%(n=5);以信噪比(S/N)为3计算,方法的检出限(LOD)为1.81～42.16 pg/g。采用该方法对实际样品进行测定,结果表明,本方法快速、准确、灵敏度高,能够满足血清中HBCD、TBBPA和PBDEs残留的同时提取及测定的要求。