地表水中24种有机氯农药和19种多氯联苯的自动SPE-GC-MS/MS分析

有机氯农药和多氯联苯均属于半挥发性的持久性有机污染物,绝大部分都被列入美国EPA优先控制污染物黑名单中.目前国内外测定地表水中有机氯农药和多氯联苯的分析方法有:气相色谱法、气相色谱-质谱法、高效液相色谱法、核     

热脱附结合GC-MS测定大气总悬浮颗粒物中的半挥发性有机物

本文建立了热脱附结合气相色谱质谱联用仪测定大气总悬浮颗粒物中半挥发性有机污染物(SVOCs)的分析方法.利用Tenax采样管采集环境空气样品,加入一定量的氘代内标物进行分析,减少了常规半挥发性样品前处理过程及溶剂的消耗,提高了SVOCs的检测效率.在5—200 ng的浓度范围内,各SVOCs的线性相关系数均在0.995以上,对10 ng的标准溶液连续加标、热解析分析6次,多数化合物峰面积比的RSD%在5%以下,各SVOCs的最低检出限均小于0.34 ng,可达到对大气中SVOCs的分析要求,为环境空气SVOCs快速检测提供新的分析方法做借鉴.     

气相色谱-质谱/嗅辨法同步分析地表水中特征异味物质初探

建立了大体积固相萃取-气相色谱-质谱/嗅辨同步分析方法,实现了实验室定性分析与人体嗅觉相结合的检测体系,用于地表水中半挥发性主要致味有机物质的鉴别.该方法能较为准确地判别地表水中0.312μg·L~(-1)的硝基苯类、氯苯类、多环芳烃类物质的气味.采集有代表性的2个废水样品和6个地表水样品,结果表明,同步检测方法定性检出半挥发性主要致味有机物质气味与原始水样气味有显著相关性,但致味物质与污染物在水体的含量没有相关性.该方法为水体异味污染事故的鉴定提供方法借鉴,对水中异味物质的溯源具有指导作用.     

ASE 快速溶剂萃取仪提取持久性有机污染物（POPs）的应用（一）

持久性有机污染物（POPs）是指具有高毒性、生物蓄积型和半挥发性、在环境中持久存在且能在大气中长距离迁移并沉积回地球的极地地区,对人类监控和环境造成严重危害的有机化学污染物,1997年,联合国环境规划署决定对12种POPs物质立即采取行动减少或消除它们的产生.这12种有机污染物包括9种有机氯杀虫剂：滴滴涕、六氯苯、氯丹、     

Waters高效GPC分级净化系统：复杂环境样品分级的有效工具

近二十年来,凝胶渗透色谱(GPC)净化一直是环境分析工作中样品制备的重要手段.在用气相色谱(GC)或气-质联用(GC/MS)分析之前,用GPC方法进行净化,可以从土壤、淤泥、动物和植物细胞的有机溶剂提取物中去除低挥发性组分.对于许多危险废弃物的净化过程而言,GPC净化更是必不可少的步骤.     

有机物筛查软件在环境预警中的应用

使用固相萃取法富集地表水水体中的农药类有机污染物,以气相色谱质谱和全筛查软件进行分析定性、半定量,同时以气相色谱质谱法的SIM模式对半定量结果进行验证,验证结果证明除水体中的酸、醇、酮类外其它物质的回收率符合监测指标要求.验证结果显示,该种筛查方法对于在无外界标准物质和目标物未知的前提下,能够对水体中大多数潜在农药类有机污染物进行预警监测.     

珠江表层沉积物中有机氯农药含量及分布

为研究珠江地区有机氯农药现阶段的污染水平,本研究于2009年采集珠江地区19个表层沉积物样品,利用高分辨气相色谱与高分辨质谱联用(HRGC-HRMS)检测了9种持久性有机污染物包括六六六、滴滴涕、六氯苯、灭蚁灵、七氯、异狄氏剂、九氯、氯丹和环氧七氯.其中六六六、滴滴涕和六氯苯的含量较高,分别为<0.001—1.98 ng.g-1(干重),<0.01—5.07 ng.g-1(干重)和<0.01—1.54 ng.g-1(干重).对六六六和滴滴涕组分研究发现,珠江地区的有机氯农药残留可能主要来自于历史残留.参照Long等给出的毒性评价标准对珠江采样区进行生态评价发现,滴滴涕类有机氯农药对该区生物可能仍存在生态风险.     

采用Agilent 5977B单四极杆气质联用系统测定土壤中的多氯联苯含量

本文采用Agilent 7890B气相色谱/5977B单四极杆气质联用系统测定土壤样品中的多氯联苯(PCB)含量.文中所述样品前处理及仪器分析方法完全参照国家环境保护标准《土壤和沉积物多氯联苯的测定气相色谱-质谱法》(HJ 743—2015).利用微波消解和加压快速溶剂萃取两种不同的提取方法,结合磺化净化法和弗罗里硅土净化法,对土壤样品进行提取与净化.该方法应用于土壤中18种PCB化合物的分析测定,样品加标回收率和方法检测限分别为67%—97%和0.25—0.58μg·kg~(-1),满足HJ 743—2015规定的60%—130%和0.4—0.6μg·kg~(-1)的要求.     

GC及GC／MS分析大气中气相有机污染物

采用毛细管气相色谱法及毛细管气相色谱-质谱法,结合低温吸附、冷凝浓缩等技术测定了大气中气相有机污染物。本法以液氮为致冷剂,高分子微球GDX-102为吸附剂,铜毛细管为浓缩管,可测定大气中ppb级的气相有机物,准确发能满足环境样品的分析要求。讨论了大气气相有机物的浓缩条件以及样品的定性和定量分析,并利用此法测定了长春市某交通要道的大气气相有机污染物。     

地下水中挥发性有机污染物的快速直接测定

采用液样浓缩器-气相色谱-质谱-数据系统(LSC/GC/MS/DS)联用装置快速直接测定地下水中挥发性有机污染物,分离鉴定出两个城市的地下水样中多种污染物。实验表明,该法简易快速。本文还讨论了方法的优点、局限性及改进措施。     

Determination of selected semi-volatile organic compounds in water using automated online solid-phase extraction with large-volume injection/gas chromatography/mass spectrometry

A rapid, sensitive, and cost-effective analytical method was developed for the analysis of selected semi-volatile organic compounds in water. The method used an automated online solid-phase extraction technique coupled with programmed-temperature vaporization large-volume injection gas chromatography/mass spectrometry. The water samples were extracted by using a fully automated mobile rack system based on x-y-z robotic techniques using syringes and disposable 96-well extraction plates. The method was validated for the analysis of 30 semivolatile analytes in drinking water, groundwater, and surface water. For a sample volume of 10 mL, the linear calibrations ranged from 0.01 or 0.05 to 2.5 ??g·L^?1, and the method detection limits were less than 0.1 ??g·L^?1. For the reagent water samples fortified at 1.0 ??g·L^?1 and 2.0 ??g·L^?1, the obtained mean absolute recoveries were 70%?C130% with relative standard deviations of less than 20% for most analytes. For the drinking water, groundwater, and surface water samples fortified at 1.0 ??g·L^?1, the obtained mean absolute recoveries were 50%?C130% with relative standard deviations of less than 20% for most analytes. The new method demonstrated three advantages: 1) no manipulation except the fortification of surrogate standards prior to extraction; 2) significant cost reduction associated with sample collection, shipping, storage, and preparation; and 3) reduced exposure to hazardous solvents and other chemicals. As a result, this new automated method can be used as an effective approach for screening and/or compliance monitoring of selected semi-volatile organic compounds in water.     

GC-MS测定土壤中阿特拉津、六氯苯等十种农药残留

建立了气相色谱-质谱-选择离子监测(GC-MS-SIM)同时测定土壤中10种农药(三嗪类除草剂、酰胺类除草剂和有机氯农药)的多残留分析方法.样品采用正己烷/丙酮(1:1,V/V)超声提取、氟罗里硅土柱层析净化、GC-MS-SIM测定.10种农药在0.01(0.02)-1.0(2.0)mg·l~(-1)范围内线性良好,相关系数介于0.9963-0.9998之间;在10,50和250 ng·g~(-1)添加水平下,平均回收率介于81%-117%之间,相对标准偏差均小于14.4%;方法检出限达到ppb至sub-ppb级(0.1-1.3 ng·g~(-1)).将此方法应用于辽宁省不同性质土壤中70个实际土壤样品的分析,阿特拉津、乙草胺、六氯苯、丁草胺、狄氏剂和艾氏剂有检出,该法对不同性质土壤具有广泛适用性.     

土壤中有机污染物的气相色谱-四极杆飞行时间质谱非靶标筛查

本文基于气相色谱-四极杆飞行时间质谱(GC-QTOF/MS)对宜昌某化学工业园区内的土壤进行潜在有机污染物的非靶标筛查.根据已有高分辨数据库和保留时间信息,采用精确质量数提取筛查流程识别出样品中96种污染物,主要以多环芳烃及其代谢产物、氯苯类和农药为主.进一步通过未知物分析软件解卷积功能和质谱NIST数据库的匹配,发现了如二氯苯胺、9-芴酮、3-甲基二苯并噻吩等更多的污染物.该方法能够快速筛查和识别出样品中潜在有机污染物,为当地污染物的风险管控提供借鉴意义.     

On the detoxification of benthic bivalves contaminated by POPs: insights from experimental and modelling approaches

Rearing benthic bivalves that are contaminated by persistent organic pollutants (POPs) in areas with low pollution levels permits their natural detoxification. Here, we present the results of novel detoxification experiments conducted with the Manila clam (Tapes philippinarum) in the Venice Lagoon; these experiments were conducted both in summer and winter. Measurements of dioxins (PCDD), furans (PCDF), polychlorinated biphenyl (PCB) and hexachlorobenzene (HCB) concentrations in clam flesh over time after their resettlement in cleaner areas allowed for determining the minimum time required to reach safe toxicity levels. Moreover, dioxin fingerprint dynamics demonstrated successful detoxification from industrial contaminants. A simple bioaccumulation/detoxification model applied to the collected data provided for the first time estimation of detoxification rates and half-lives for POP congeners in clam flesh. This work provides a basis for considering natural detoxification as a viable solution for safely exploiting resources otherwise restricted from human consumption due to associated health risks.     

基于风险分析的流域优先有机污染物筛查:研究与应用

应用高通量分析方法对大清河流域47个沉积物中的潜在风险有机污染物进行了分析,共筛查到104种有毒有机污染物。应用基于风险分析的筛查体系对检出率高于10%的54种污染物进行了概率风险评估,筛查出11种具有潜在风险的流域优先有机污染物,包括农药(特草克、氨磺磷、枯莠隆)、工业用品及副产物(二苯胺、9,10-蒽醌、萘、2-甲基萘)及家庭及个人护理品(咖啡因、苯乙酮、苯甲酮、联苯)等。结果表明,基于风险分析的流域污染物筛查方法体系可成功地对流域内优先污染物进行识别与筛查,为流域管理提供科学依据。     

Use of the ouput of a lead risk assessment model to establish soil lead cleanup levels

Three general methods to calculate soil contaminant cleanup levels are assessed: the truncated lognormal approach, Monte Carlo analysis, and the house-by-house approach. When these methods are used together with a lead risk assessment model, they yield estimated soil lead cleanup levels that may be required in an attempt to achieve specified target blood lead levels for a community. The truncated lognormal approach is exemplified by the Society for Environmental Geochemistry and Health (SEGH) model, Monte Carlo analysis is exemplified by the US EPA's LEAD Model, and the house-by-house approach is used with a structural equation model to calculate site-specific soil lead cleanup levels. The various cleanup methods can each be used with any type of lead risk assessment model. Although all examples given here are for lead, the cleanup methods can, in principle, be used as well with risk assessment models for other chemical contaminants to derive contaminant-specific soil cleanup levels.     

利用EIA法快速筛查垃圾焚烧飞灰和烟气中的二恶英毒性水平

基于CAPE技术公司的兔子复合克隆抗体的二恶英(PCDD/F)酶免疫分析试剂盒,建立了快速检测垃圾焚烧飞灰和烟气中PCDD/F毒性(TEQ值)的方法.试剂盒的最低检测限为3.3pg·tube-1(即3.3pgTEQ每EIA试管),线性检测范围为10～30pg·tube-1.样品经甲苯索氏抽提后过硅胶柱连接小碳柱净化处理,TCDD/F的回收率大约为50%,与原飞灰PCDD/F分布模式相比净化处理后样品中的TCDD/F含量明显降低.用净化处理后的飞灰溶液作标准溶液,绘制PCDD/F剂量-效应关系曲线,定量分析了2个飞灰样品和2个烟气样品的TEQ浓度,结果表明分析样品的TEQ实测值(HRGC/HRMS分析获得)与预测值(标准曲线计算值)的相对偏差(Rd)均小于15%,说明用该方法定量分析垃圾焚烧飞灰和烟气中PCDD/F毒性是可行的.     

巢湖生态系统中微量有机污染物的研究进展

本文综述了目前巢湖生态系统中微量有机污染物研究的主要进展。巢湖微量有机污染物研究起步较晚,但发展较快。目前已研究的微量有机污染物包括有机氯农药、多氯联苯、多环芳烃、多溴联苯醚、邻苯二甲酸酯、全氟烷基酸类物质、四溴双酚A、抗生素和有机磷农药。研究内容主要包括水、大气、降尘、沉积物、悬浮物、水生生物等多介质分布、来源解析、跨界面迁移、归趋模拟与风险评估等方面。期望本文的综述,可以为巢湖微量有机污染物风险管理和水质改善提供重要决策支撑,对于在其他湖泊开展此类研究有所裨益。     

Detection of organic contamination in sediments by double-shoot pyrolysis–GC/MS

Pyrolysis coupled with gas chromatography–mass spectrometry (Py–GC–MS) has been previously proved to be an appropriate tool for the screening of organic contaminants in sediments. In this work the double-shoot pyrolysis technique has been applied to assess the contamination degree of sediment samples from Castro Marim Natural Park (South Portugal) and the Ria of Huelva (SW Spain). Compounds released both by thermodesorption at sub-pyrolysis temperatures (250–280°C) and subsequent pyrolysis (300–500°C) revealed information on the origin of the sedimentary organic matter and the occurrence of organic contamination in the sediments. Thermal desorption was found to be effective in releasing organic contaminants from spiked samples. However, in real sediments samples, higher pyrolysis temperatures (>300°C) were necessary to detect the occurrence of organic contaminants. Particularly polycyclic aromatic hydrocarbons (PAHs) and linear alkylbenzenes (LABs) were detected in variable proportions in most sediment samples.     

气相色谱-质谱联用测定母乳中合成麝香

建立了凝胶渗透色谱(GPC)柱和硅胶柱净化,气相色谱-质谱(GC/MS)测定母乳中合成麝香的分析方法.实验结果表明:GC/MS在0.01μg.ml-1到1μg.ml-1的浓度范围内对4种常见合成麝香(佳乐麝香HHCB、吐纳麝香AHTN、二甲苯麝香MX和酮麝香MK)均有良好的线性响应,4种合成麝香的基质加标回收率为76%—115%,相对标准偏差为2.8%—7.4%.利用信噪比(5/1)确定该方法的定性检测限,HHCB,AHTN,MX为5ng.g-1脂重,MK为4ng.g-1脂重,定量检测限为定性检测限的2倍.采用上述方法分析了上海母乳样品中合成麝香的浓度和分布特征,发现母乳中普遍存在这4种合成麝香,浓度分别为HHCB92±70;AHTN16±12;MX26±22;MK16±14ng.g-1脂重,与欧美国家的污染水平相比,总体含量偏低.