分析仪器联用技术的发展动向

分析仪器联用技术已在环境样品分析中得到应用，并有广阔的发展前景。本文介绍了色谱-色谱、色谱-原子光谱、离子色谱联用技术、色谱-质谱、色谱-傅立叶变换红外光谱、色谱-核磁共振波谱（NMR）联用技术在分析环境样品方面的应用。     

HPLC-ICP/MS联用技术在环境有机汞分析中的应用

简述了近年来高效液相色谱-电感耦合等离子体质谱联用技术（HPLC-ICP/MS）在环境有机汞分析中的应用进展，介绍了水、土壤和沉积物及生物样品的前处理方法，对仪器设备的要求和分析条件，以及线性范围、检出限、精密度与准确度等方法性能参数，并对现有文献方法的适用性进行了总结。     

大气压光电离技术及其在环境污染物分析中的应用

介绍了液相色谱-质谱联用(LC-MS)技术中新型软电离技术大气压光电离法(APPI)的基本原理、鼻子源结构以及电离的影响因素,综述了LC-APPI-MS在环境污染物定性定量分析中的应用.     

GC-MS法测定多种有机磷农药残留

以HP-35MS色谱柱代替传统的HP-5MS色谱柱,试验了蔬菜、水果中多种有机磷农药残留的气-质联用快速检测方法。采用选择离子扫描(SIM)模式,根据保留时间和特征离子丰度比,可在40 m in内定性和定量检测30种有机磷农药残留。通过对蔬菜、水果等样品多次试验验证,添加量为0.01μg~1.00μg时,回收率在79.5%~106%之间,相对标准偏差<10%,检出限为6.6×10-10g~8.7×10-9g,均比使用HP-5MS色谱柱有所改善。     

柳州市大气颗粒物中多环芳烃的种类和时空分布特征及来源

采用气相色谱/质谱联用技术(GC/MS)检测了柳州市大气颗粒物样品中的PAHs,比较了柳州市各区大气颗粒物中多环芳烃含量的差异以及不同季节对多环芳烃含量的影响,讨论了其分布规律及污染源.     

使用全扫描和选择离子扫描两种方式建立土壤和沉积物中16种多环芳烃的气相色谱四级杆质谱联用仪分析方法

文章建立气相色谱四级杆质谱联用分析土壤和沉积物中16种多环芳烃的测定方法。参考《土壤和沉积物多环芳烃的测定气相色谱质谱法》(HJ805-2016)和《全国土壤污染状况详查土壤样品分析测试方法技术规定》采用全扫描和选择离子扫描两种方式优化定性、定量分析步骤。结合实际对土壤和沉积物中多环芳烃进行了加压流体萃取(ASE)的提取和GPC净化方式,建立了土壤和沉积物中16种多环芳烃的气相色谱四级杆质谱联用仪分析方法。     

DPX快速萃取程序升温大体积进样GC/MS法测定水中19种多溴联苯化合物

建立DPX快速吸附萃取、程序升温(PTV)大体积进样与气相色谱/质谱(GC/MS)联用,SIM模式同时测定水中19种多溴联苯(PBBs)单体的方法。该方法在PBBs质量浓度1~50μg/L范围内线性良好,19种PBBs单体检出限为0.147~0.230μg/L,相对标准偏差为6.61%~10.5%,加标回收率为61.5%~82.6%。     

两种凝胶色谱在农药残留分析中的应用比较

介绍了凝胶色谱法的基本原理和工作方式及其在农药残留分析中的应用,对比了传统的全自动凝胶色谱和在线凝胶色谱-质谱联用两种凝胶色谱仪的特点。通过土壤样品有机磷和有机氯农药加标回收试验,表明两种凝胶色谱在农药残留分析中的净化效果差异不大,而在线凝胶色谱-质谱联用在检测快速化、在线化和溶剂使用少量化、微量化方面更具优势。     

气相色谱/质谱(GC/MS)联用在我国环境监测中的应用

从系统分析和有机污染分析等方面出发 ,概述了气相色谱 质谱 (GC MS)联用在我国大气、水质、土壤等环境监测中所取得的重要成果 ,例如可测定多环芳烃、硝基多环芳烃、多氯二苯并二、多氯二苯并呋喃、农药、酚类、多氯联苯、恶臭、有机酸、有机硫化合物和苯系物、卤代烃、氯苯类等挥发性化合物 ,以及多组分有机污染物。     

GC-MS测定土壤中酞酸酯类化合物

采用毛细管柱气相色谱-质谱联用选择离子检测(GC-MS-SIM)技术,结合快速萃取和佛罗里硅土柱净化方法分析土壤中的六种酞酸酯类(PAEs)化合物。结果表明,六种PAEs峰形好,平均加标回收率为76.7%~110%,相对标准偏差为2.5%~4.5%。方法具有操作简便、回收率高、纯化效果好和对环境友好的特点,且具有很强的实用性。     

Techniques and methods for the determination of haloacetic acids in potable water

Haloethanoic (haloacetic) acids (HAAs) are formed as disinfection byproducts (DBPs) during the chlorination of natural water to make it fit for consumption. Sundry analytical techniques have been applied in order to determine the concentrations of the HAAs in potable water supplies: gas chromatography (GC-MS, GC-ECD); capillary electrophoresis (CE); liquid chromatography (LC), including ion chromatography (IC); and electrospray ionization mass spectrometry (ESI-MS). Detection limits required to analyze potable water samples can be regularly achieved only by GC-ECD and ESI-MS. Without improvements in preconcentration or detector sensitivity, CE and LC will not find application to potable water supplies. The predominant GC-ECD methods use either diazomethane or acidified methanol to esterify (methylate) the carboxylic acid moiety. For HAA5 analytes, regulated under the EPA's Stage 1 DBP Rule, diazomethane is satisfactory. For HAA9 data gathered under the Information Collection Rule, acidified methanol outperforms diazomethane, which suffers from photo-promoted side reactions, especially for the brominated trihaloacetic acids. Although ESI-MS can meet sensitivity and selectivity requirements, limited instrumentation availability means this technique will not be widely used for the time being. However, ESI-MS can provide valuable confirmatory information when coupled with GC-ECD in a research setting.     

DBP Levels in Chlorinated Drinking Water: Effect of Humic Substances

Chlorination is the most widely used technique for disinfection of drinking water. A consequence of chlorination is the formation of Disinfection By-Products (DBPs). The formation of DBPs in drinking water results from the reaction of chlorine with naturally occurring organic materials, principally humic and fulvic acids. This paper focuses on the effect of humic substances on the formation of twenty-four compounds belonging to different categories of DBPs. This investigation was conducted in two water treatment plants in Greece, Menidi and Galatsi, from July 1999 to April 2000. Humic substances were determined by the diethylaminoethyl (DEAE) method with subsequent UV measurement. The techniques used for the determination of DBPs were liquid-liquid extraction, gas chromatography and mass spectrometry. The concentrations of DBPs were generally low. Total trihalomethanes (TTHMs) ranged from 5.1 to 24.6 microg L(-1), and total haloacetic acids (HAAs) concentration ranged from 8.6 to 28.4 microg L(-1), while haloaketones (HKs) and chloral hydrate (CH) occurred below 1 microg L(-1). The content of humic substances was found to influence the formation of DBPs and especially TTHMs, trichloroacetic acid (TCA), dibromoacetic acid (DBA), CH, 1,1-dichloropropanone (1.1-DCP) and 1,1,1-trichloropropanone (1,1,1-TCP). Seasonal variation of TTHMs and HAAs generally followed that of humic substances content with peaks occurring in autumn and spring. The trends of 1,1-DCP, 1,1,1-TCP and CH formation seemed to be in contrast to TTHMs and HAAs. Trends of formation of individual compounds varied in some cases, probably due to influence of parameters other than humic substances content. Statistical analysis of the results showed that the concentrations of TTHMs, CH, 1,1-DCP, 1,1,1-TCP, TCA and DBA are strongly affected from humic substances content (at 0.01 confidence level). The opposite is true for dichloroacetic acid (DCA) concentration. Humic substances also vary to a statistically significant degree during different months, as well as the concentrations of TTHMs, CH, 1,1-DCP, 1,1,1-TCP, TCA and DCA. The variance of DBA was not statistically significant. Regarding the effect of sampling station, humic substances content showed no statistically significant difference between the two raw water sources studied.     

Penetration of polar brominated DBPs through the activated carbon columns during total organic bromine analysis

Total organic bromine (TOBr) is a collective parameter representing all the brominated organic disinfection byproducts (DBPs) in water samples. TOBr can be measured using the adsorption-pyrolysis method according to Standard Method 5320B. This method involves that brominated organic DBPs are separated from inorganic halides and concentrated from aqueous solution by adsorption onto the activated carbon (AC). Previous studies have reported that some commonly known brominated DBPs can partially penetrate through the AC during this adsorption step. In this work, the penetration of polar brominated DBPs through AC and ozone-modified AC was explored with two simulated drinking water samples and one chlorinated wastewater effluent sample. Polar brominated DBPs were selectively detected with a novel precursor ion scan method using electrospray ionization-triple quadrupole mass spectrometry. The results show that 3.4% and 10.4% of polar brominated DBPs (in terms of total ion intensity) in the chlorinated Suwannee River fulvic acid and humic acid samples, respectively, penetrated through the AC, and 19.6% of polar brominated DBPs in the chlorinated secondary wastewater effluent sample penetrated through the AC. The ozone-modification of AC minimized the penetration of polar brominated DBPs during the TOBr analysis.     

在线固相萃取-超高效液相色谱-三重四极杆质谱快速测定地表水中磺胺类抗生素

建立了在线固相萃取-超高效液相色谱-三重四极杆质谱联用技术测定地表水中痕量磺胺类抗生素的方法。样品经滤膜过滤,HLB在线固相萃取小柱富集纯化,以Acquity BEH 130为分析柱,三重四极杆质谱进行检测,外标法定量。通过在线固相萃取,并对色谱和质谱等条件进行优化,该方法检出限为0.2~1.1 ng/L,回收率为80.6%~113%,相对标准偏差<10.6%,浓度范围内线性良好（r＞0.9972）,满足了磺胺类抗生素痕量分析测试的要求,且分析时间仅需17min。该方法灵敏度高、分析速度快,对于保障水环境安全,及时提供污染信息,有效应对环境应急突发事件具有十分重要的意义。     

The role of GC-MS and LC-MS in the discovery of drinking water disinfection by-products

Gas chromatography-mass spectrometry (GC-MS) has played a pivotal role in the discovery of disinfection by-products (DBPs) in drinking water. DBPs are formed when disinfectants, such as chlorine, ozone, chlorine dioxide or chloramine, react with natural organic matter in the water. The first DBP known--chloroform--was identified by Rook in 1974 using GC-MS. Soon thereafter, chloroform and other trihalomethanes were found to be ubiquitous in chlorinated drinking water. In 1976, the National Cancer Institute published results linking chloroform to cancer in laboratory animals, and an important public health issue was born. Mass spectrometry and, specifically, GC-MS became the key tool used for measuring these DBPs in water and for discovering other DBPs that were formed. Over the last 25 years, hundreds of DBPs have been identified, mostly through the use of GC-MS, which has spawned additional health effects studies and regulations. Early on, GC with low resolution electron ionization (EI)-MS was used, together with confirmation with chemical standards, for identification work. Later, researchers utilized chemical ionization (CI)-MS to provide molecular weight information and high resolution El-MS to aid in the determination of empirical formulae for the molecular ions and fragments. More recently, liquid chromatography-mass spectrometry (LC-MS) with either electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) has been used to try to uncover highly polar DBPs that most experts believe have been missed by earlier GC-MS studies. Despite 25 years of research in the identification of new DBPs, new ones are being discovered every year, even for chlorine which has been the most extensively studied.     

Disinfection By-Products in Water Produced by Ozonation and Chlorination

Water produced by advanced treatment of a groundwater was evaluated to determine the amount of DBPs (Disinfection By-Products) including trihalomethanes (THMs). Both Gas Chromatography (GC) and Gas Chromatography/Mass Spectrometry (GS/MS) were adopted for detection and identification of DBPs such as trihalomethanes (THMs), halo-acetic acids (HAAs) and aldehydes. Two disinfection modes (ozonation followed by chlorination and chlorination alone) were compared to determine the DBPs generation. The mutagenitic acivity of ozonated water, chlorinated water after ozonation and potable water was assessed using the Ames test. Chloroform, dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) were the main constituents of THMs and HAAs, respectively. THMs accounted for more than 85% of all DBPs measured, whereas haloacetic acids accounted for around 14%. Ozonation followed by chlorination proved to be better in terms of THMs and HAAs control. The combined system produced 28.3% less DBPs compared to chlorination alone. Ozonation was found capable of reducing mutagenic matter in the groundwater by 54.7%. The combined system also resulted in water with no mutagenicity.     

水中异味物质分析方法研究进展

介绍了水体异味现象及异味物质组分,综述了闭环捕集、吹扫捕集、液液萃取、固相萃取、固相微萃取、搅拌棒吸附萃取等样品前处理技术。指出气相色谱/质谱联用具有很强的分离和定性定量能力,与上述前处理技术联用是目前水体异味物质分析应用最广泛的方法。     

气相色谱—串联质谱法检测水中苯霜灵、甲霜灵、噁霜灵残留量

建立水中甲霜灵、苯霜灵、噁霜灵农药残留量的气相色谱—串联质谱(GC-MS/MS)的检测分析方法。样品采用乙腈提取、固相萃取(SPE)柱净化。采用GC-MS/MS分析时,三种农药在15 mim内完全分离并流出。添加浓度加标回收率为80.6%~88.4%,相对标准偏差(RSD)小于5.0%。在0.01~0.20 mg/L质量浓度范围之间线性关系良好(r~20.999 0)。该方法的灵敏度、精密度和准确度均满足农药残留分析要求,适用于水中的农药残留的快速筛查与定性、定量分析。     

饮用水消毒副产物基因毒性与致癌性研究进展

简述了饮用水消毒副产物（DBPs）的基因毒性与致癌性的研究进展。从Ames试验、SOS/umu试验、彗星试验、微核试验及一些新颖的致突变试验结果对DBPs基因的毒性，以及从毒理学实验、流行病学研究和致癌风险评估3个方面对DBPs的致癌性进行了分析和总结，以期为今后饮用水DBPs毒性效应及其致毒机理研究提供参考，进而促进饮用水质量管理与立法的发展。     

长江南京段新兴污染物污染特征及风险评估

在长江南京段上游至下游依次布设6个采样点采集水样,使用固相萃取和LC-MS/MS相结合的方法对5种选定药物的质量浓度进行测定,并采用风险熵模型评估其生态风险。结果表明,6个采样点均检测到药物存在。其中,四环素、红霉素、罗红霉素和氯霉素的检出率为100%,最高检出值为10.29 ng/L(氯霉素)。与国内外其他地表水相比,长江南京段水中的药物质量浓度较低。生态风险评估结果表明,长江南京段水中5种药物的风险熵值均低于1,对水生生物不存在高风险。