Determination of organoarsenic warfare agents in sediment samples from Skagerrak by gas chromatography-mass spectrometry

In 1945 the Norwegian authorities gave permission to scuttle ships loaded with captured chemical ammunition on board in an area approximately 14x4 km in size, 25 nautical miles south-east of Arendal. An investigation was carried out in 2002 to inspect four wrecks by using a remote-operated vehicle with video cameras. The Norwegian Defence Research Establishment (Forsvarets forskningsinstitutt, FFI) carried out the project on behalf of the Norwegian Pollution Control Authority (SFT). Sediment samples were collected at eight positions around each wreck. One of the wrecks was broken up into several smaller parts. Here sediments were collected at one additional position close to one of the parts. From each position, at least two sediment cores were taken up to the surface. One of the cores from each position was sliced into three parts that were immediately frozen. The other whole cores were frozen on board the ship and transported back to the laboratory in a freezer. In total, sediment samples from 33 different locations were collected and analysed for organoarsenic warfare agents and some of their decomposition products by gas chromatography-mass spectrometry (GC-MS) after derivatisation with 1-propanethiol. Most of the identified organoarsenic compounds found in the sediment samples are parts of the arsine oil mixture produced by Germany during World War II. The compounds were found both close to the wreck and at a somewhat longer distance from the wrecks. The highest concentrations were found in a sediment sample collected close to a bomb seen on the seabed. The organoarsenic warfare agents adamsite or lewisite were not found in any of the samples. Lewisite is not reported to have been produced during World War II, but was nevertheless looked for in the samples.     

An investigation of organic compounds in night soil and the treated water by gas chromatography-mass spectrometry

Although the rates of removal of BOD and other indicators have been studied for the evaluation of night soil^* treatment plant, there is no report about organic compounds. In order to identify trace amounts of organic compounds in night soil treatment plant at each process stage, the organic compounds in the night soil and in the treated water were subjected to anaerobic methods and analyzed by gas chromatography—mass spectrometry. Cholesterol and coprostanol as fecal sterols, indoles as odor substances and dichlorobenzene, cresol and phenol as disinfectants used in toilets were identified in the sample of night soil. As a result of anaerobic treatment the fecal sterols were degraded, oxindole remained, and phenylacetic acid was identified as a metabolite from tryptophan. These organic compounds were completely degraded by the aerobic treatment when phthalates and adipate were identified in the effluent.     

Determination of microbial colonisation in water-damaged buildings using chemical marker analysis by gas chromatography-mass spectrometry

Gas chromatography-mass spectrometry was used to determine the microbial contents of building materials subjected to water damage in a laboratory experiment and of materials collected from houses affected by water during the flood in Klodzko in south-western Poland, July 1997. The samples were examined for 3-hydroxy fatty acids, markers of bacterial endotoxin, and ergosterol, marker of fungal biomass. The amounts of both 3-hydroxy fatty acids and ergosterol were higher in materials that had been exposed to water than in unexposed ones. All markers were stable in the building materials for at least 6 weeks at room temperature and could thus be used to reveal microbial contamination even when cultivation results for bacteria and fungi were negative. Direct measurement of 3-hydroxy fatty acids and ergosterol in human environments could be a useful method, e.g. in monitoring indoor air as regards presence of potentially harmful microorganisms and microbial constituents.     

Chemical characterization of industrial wastewaters by gas chromatography-mass spectrometry

Organic pollutants in seven industrial wastewaters being discharged into the Calcasieu River in Louisiana were identified by gas chromatography-mass spectrometry. Discharge of compounds not indicated from the manufacturer's lists of products and raw materials were revealed. Chemical characterization provided information beyond that obtainable from traditional pollution measurements and information especially suitable for pollution legislation enforcement.     

Identification and determination of trace organic substances in tap water by computerized gas chromatography-mass spectrometry and mass fragmentography

Tap water was examined for the presence of trace organic substances by using the Amberlite XAD-2 resin adsorption method, computerized gas chromatography-mass spectrometry, high resolution mass spectrometry, and mass fragmentography. Chemical ionization and field desorption mass spectrometry were used for the analysis of high polar compounds. By these methods, a large number of alkylbenzenes, odorous components (menthol, acetophenone and its derivatives, and benzaldehyde), and several plasticizers (dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di(2-ethylhexyl) phthalate, di(2-ethylhexyl) adiptate, and tributyl phosphate) were found in a concentration of 1–240 parts per thousand million.     

Characterization of naphthenic acids in oil sands wastewaters by gas chromatography-mass spectrometry

The water produced during the extraction of bitumen from oil sands is toxic to aquatic organisms due largely to a group of naturally occurring organic acids, naphthenic acids (NAs), that are solubilized from the bitumen during processing. NAs are a complex mixture of alkyl-substituted acyclic and cycloaliphatic carboxylic acids, with the general chemical formula CnH(2n + Z)O2, where n is the carbon number and Z specifies a homologous family. Gas chromatography-electron impact mass spectrometry was used to characterize NAs in nine water samples derived from oil sands extraction processes. For each sample, the analysis provided the relative abundances for up to 156 base peaks, with each representing at least one NA structure. Plotting the relative abundances of NAs as three-dimensional bar graphs showed differences among samples. The relative abundance of NAs with carbon numbers < or = 21 to those in the "C22 + cluster" (sum of all NAs with carbon numbers > or = 22 in Z families 0 to -12) proved useful for comparing the water samples that had a range of toxicities. A decrease in toxicity of process-affected waters accompanied an increase in the proportion of NAs in the "C22 + cluster", likely caused by biodegradation of NAs with carbon numbers of < or = 21. In addition, an increase in the proportion of NAs in the "C22 + cluster" accompanied a decrease in the total NAs in the process-affected waters, again suggesting the selective removal of NAs with carbon numbers of < or = 21. This is the first investigation in which changes in the fingerprint of the NA fraction of process-affected waters from the oil sands operations has corresponded with measured toxicity in these waters.     

Identification of chlorinated styrenes in cormorant tissues by a computerized gas chromatography-mass spectrometry system

The results of a study concerning the identification of three unknown compounds which were detected in extracts of cormorant tissue are reported. From these results it has been concluded that one of the compounds is octachlorostyrene. It is highly probable that the other two compounds are heptachlorostyrenes. Octachlorostyrene was also detected in fish, seals and various other aquatic bird species.     

Multi-walled carbon nanotubes as solid-phase extraction adsorbents for determination of atrazine and its principal metabolites in water and soil samples by gas chromatography-mass spectrometry

A novel, simple, cost-effective, and sensitive method was developed for the determination of atrazine and its principal metabolites namely deisopropyl-atrazine (DIA) and deethyl-atrazine (DEA) in water and soil samples using multi-walled carbon nanotubes as solid-phase extraction (SPE) adsorbents coupled with gas chromatography-mass spectrometry (GC-MS). Several condition parameters, such as sample loading flow-rate, eluent and elution volume, extractant and ratio of extraction solvent to sample, were optimized to achieve good sensitivity and precision for the extraction and elution of analytes. A methanol/water solution (50%, v/v) was used to extract atrazine, DIA and DEA from soil. After the extracts went through SPE cartridges (packed with multi-walled carbon nanotubes) at a flow-rate of 4 mL min(-1), the analytes were eluted by 4 mL ethyl acetate at the rate of 1 mL min(-1) under a vacuum pump. The limit of detection (S/N=3) of the proposed method was 0.02 microg kg(-1) for atrazine in water and 0.3 microg kg(-1) in soil; 0.04 microg kg(-1) for DIA in water and 1.0 microg kg(-1) in soil; 0.05 microg kg(-1) for DEA in water and 0.8 microg kg(-1) in soil. Mean recoveries were in the range of 72.27-109.68%, and the reproducibility was accepted (RSD <13%) under the optimum conditions. This developed method was applied to determine the analytes in real environmental samples, and the concentrations of atrazine were 0.77-10.83 microg kg(-1), while DEA and DIA were not detected.     

顶空气相色谱法测定水中氯丁二烯

应用顶空气相色谱法测定饮用水及地表水中微量的氯丁二烯,色谱柱为HP-1,检测器为ECD。结果表明,所建立的方法对氯丁二烯的检出限为0.23μg/L,加标回收率为89.7%～97.7%,相对标准偏差为7.02%(n=10),适用于水中氯丁二烯的测定。     

原子荧光法测定饮用水中痕量铅

采用原子荧光法测定生活饮用水中铅的含量。试验结果表明，该方法的回归方程为y=37．00x＋28．25，r=0．999，在0．001～0．025mg／L范围内有良好的线性关系。采用该方法测定水中痕量铅能获得理想的结果，可在生活饮用水检测中推广运用。     

Stir bar sorptive extraction and trace analysis of selected endocrine disruptors in water, biosolids and sludge samples by thermal desorption with gas chromatography-mass spectrometry

Stir bar sorptive extraction (SBSE) in combination with thermal desorption coupled to gas chromatography-mass spectrometry (GC-MS) was successfully applied to analyze a range of endocrine disrupting compounds (EDCs) in wastewater, solids and sludge. The targeted EDCs include sex steroid hormones, phthalates, alkylphenols and tamoxifen. Recovery for the EDCs using this analytical technique ranged from 44% to 128%. Limit of detection (LOD) of the compounds was 2.0 ng/L for water samples and 0.02 ng/g for solid samples, whereas the limit of quantitation (LOQ) was 5.0 ng/L for water samples and 0.06 ng/g for solid samples. When this analytical technique was applied to measure EDC concentration in a biological nutrient removal (BNR) wastewater treatment plant located in South East Queensland, Australia, the results showed that there were high amounts of phthalates, alkylphenols and female hormones present in the raw influent wastewater and solids. These concentrations were dramatically reduced after passing through the various treatment zones of the bioreactor (anaerobic, aerobic and anoxic).     

吹扫捕集/GC-MS联用测定水中26种挥发性有机物

建立了吹扫-捕集与气相色谱-质谱(GC-MS)联用测定水中卤代烃、氯苯类化合物和苯系物等挥发性有机物(VOCs)的方法。采用吹扫-捕集法对水中的VOCs进行富集,热解吸后导入GC-MS分离各组分并用选择离子检测(SIM)进行测定,一次进样可同时对水中26种VOCs进行准确定性和定量。分析结果表明,VOCs的线性相关系数为0.9974～0.9999,平均加标回收率为92.3%～96.5%,相对标准偏差为1.35%～5.18%(n=6),各种挥发性有机物的检出限在0.001～0.05μg/L之间。     

生活饮用水中氯苯类化合物和溴氰菊酯的气相色谱法测定

建立了生活饮用水中氯苯类化合物和溴氰菊酯的气相色谱检测方法。该方法对1,3-二氯苯、1,4-二氯苯、1,2-二氯苯、1,3,5-三氯苯、1,2,4-三氯苯、1,2,3-三氯苯、1,2,3,5-四氯苯、1,2,4,5-四氯苯、1,2,3,4-四氯苯、五氯苯、六氯苯和溴氰菊酯的检出限分别为0.116,0.186,0.120,0.016,0.022,0.014,0.009,0.011,0.005,0.002,0.001和0.024μg/L,相对标准偏差为0.7%～3.2%,加标回收率为95%～105%。该方法可同时检测12种化合物,水样预处理简单,溶剂用量小,回收率高,精密度好且相互之间没有干扰。     

固相微萃取-色/质法鉴定易燃液体放火物

建立了固相微萃取-气相色谱/质谱鉴定常见易燃液体放火物的方法.筛选固相微萃取的条件包括萃取纤维、吸附温度、加热温度、吸附时间和解析时间.文中列出了93#汽油、航空煤油、0#柴油和通用油漆稀释刺诸样品的SPME-GC/MS总离子谱图.该方法简便、灵敏、快捷、准确、抗干扰能力强.     

Determination of phenolic endocrine disrupting chemicals and acidic pharmaceuticals in surface water of the Pearl Rivers in South China by gas chromatography-negative chemical ionization-mass spectrometry

An analytical method for phenolic endocrine disrupting chemicals and acidic pharmaceuticals in river water was developed using gas chromatography mass spectrometry (GC-MS) coupled with negative chemical ionization (NCI) technique, and used for the determination of these compounds in the Pearl Rivers (Liuxi, Zhujiang and Shijing Rivers). Derivatization using pentafluorobenzoyl chloride (PFBOCl) and pentafluorobenzyl bromide (PFBBr) before GC-MS analysis were applied and optimized for phenolic compounds and acidic compounds, respectively. The target compounds were analyzed for river waters from the upstream to downstream of the Pearl Rivers. Phenolic compounds 4-tert-octylphenol (4-t-OP), 4-nonylphenol (4-NP), bisphenol-A (BPA), estrone (E1), estradiol (E2) and triclosan (TCS) were detected at trace or low levels in the water samples from Liuxi River and Zhujiang River. Diethylstilbestrol (DES) was not detected in the Pearl Rivers. The highest concentrations of the phenolic compounds were found in Shijing River, and they were 3150 ng/L for 4-t-OP, 11,300 ng/L for 4-NP, 1040 ng/L for BPA, 79 ng/L for E1, 7.7 ng/L for E2 and 355 ng/L for TCS, respectively. Only a few acidic pharmaceuticals were detected at low concentrations in water from Liuxi River and Zhujiang River, but the highest concentrations for the acidic pharmaceuticals were also found in Shijing River. The highest concentrations detected for clofibric acid, ibuprofen, gemfibrozil, naproxen, mefenamic acid and diclofenac were 17 ng/L, 685 ng/L, 19.8 ng/L, 125 ng/L, 24.6 ng/l and 150 ng/L, respectively. The results suggest Liuxi and Zhujiang Rivers are only slightly contaminated and can be used as drinking water sources, but Shijing River is heavily polluted by the wastewater from nearby towns.     

Characterisation of riverine particulate organic matter by pyrolysis-gas chromatography-mass spectrometry

Particulate matter samples were collected in the mountainous section and river mouth at the Tech River basin, south France, during flood (December 1996) and summer (September 1997) periods. Suspended material was analysed by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) and 23 identified pyrolysis products were divided into five main fractions: aminosugars, aromatic hydrocarbons, polysaccharides, phenols and nitrogenous compounds. Analysis of relative amounts of these fractions revealed neither significant spatial nor temporal changes in the particulate organic matter composition. Nevertheless, their specific composition showed that during flooding there is a certain homogeneity in the composition of the riverine particulate organic matter, with more degraded material of pedogenic (allochthonous) character, and during the summer the results suggest the presence of two components, allochthonous and autochthonous.     

New standards for the determination of geosmin and methylisoborneol in water by gas chromatography/mass spectrometry

Deuterium labelled geosmin and methylisoborneol (MIB) have been synthesized and evaluated as internal standards in the determination of geosmin and MIB in water by closed loop stripping followed by gas chromatography/mass spectrometry (GC/MS). The labelled standards were compared with chloroalkanes added as internal standards either at the time of sampling or immediately before closed loop stripping. When added at sampling time, the new standards enabled accurate determination of the geosmin and MIB present initially, even when the samples were analysed as much as 3 weeks later. The new standards gave better precision and accuracy than the chloroalkanes and overcame the underestimation of initial analyte concentration which usually results from losses of analyte through adsorption, volatilisation, biodegradation etc. during sample storage. Geosmin had a limit of detection of<0.1ng/l and 1 ng/lwas determined with a coefficient of variation (CV) of 1.2% (n = 5). MIB was determined at 1 ng/l with a CV of 3.5% (n = 5).     

Automatic on-line monitoring of atmospheric volatile organic compounds: gas chromatography-mass spectrometry and gas chromatography-flame ionization detection as complementary systems

Traditionally air quality networks have been carrying out the continuous, on-line measurement of volatile organic compounds (VOC) in ambient air with GC-FID. In this paper some identification and coelution problems observed while using this technique in long-term measurement campaigns are described. In order to solve these problems a GC-MS was set up and operated simultaneously with a GC-FID for C₂-C₁₁ VOCs measurement.There are few on-line, unattended, long term measurements of atmospheric VOCs performed with GC-MS. In this work such a system has been optimized for that purpose, achieving good repeatability, linearity, and detection limits of the order of the GC-FID ones, even smaller in some cases. VOC quantification has been made by using response factors, which is not frequent in on-line GC-MS. That way, the identification and coelution problems detected in the GC-FID, which may led to reporting erroneous data, could be corrected.The combination of GC-FID and GC-MS as complementary techniques for the measurement of speciated VOCs in ambient air at sub-ppbv levels is proposed. Some results of the measurements are presented, including concentration values for some compounds not found until now on public ambient air VOC databases, which were identified and quantified combining both techniques. Results may also help to correct previously published VOC data with wrongly identified compounds by reprocessing raw chromatographic data.     

气相色谱/多级离子阱技术分析汽油烟尘成分

实验探讨气相色谱/质谱联用技术(GC/MS)、气相色谱/选择离子存储技术(GC/μSIS)和气相色谱/质谱/质谱技术(GC/MS/MS)在93#汽油及其烟尘成分分析中的应用.结果显示,GC/MS获得的谱图信息较全,但谱图复杂、干扰较多,对于含量较低的成分信噪比不够好,容易造成误判;GC/μSIS灵敏度较高,适合于鉴定分子量小、分子结构简单的未燃烧汽油成分;GC/MS/MS即使对于复杂样品也可以达到很高的灵敏度,但要求目标成分具有一定的结构稳定性,更适合汽油燃烧后产物的分析.     

合成锰氧化物氧化水中苯酚的研究

在实验室条件下制备出了合成锰氧化物(结构类似于δ-MnO2),研究了锰氧化物对水中微量苯酚的氧化效果,并对影响因素进行了分析.实验结果表明:合成锰氧化物对水中微量苯酚具有很好的氧化能力.在pH=3,合成锰氧化物投加量为10mg,反应720min时,合成锰氧化物对200mL质量浓度为5mg/L的苯酚去除率达到86.8%,随着pH值的升高,合成锰氧化物对苯酚的氧化能力逐渐降低,在pH=3时最大;一定范围内,随着合成锰氧化物投加量的增加以及苯酚初始浓度的增加,苯酚的氧化去除率也随之增加;合成锰氧化物对苯酚的氧化受环境中金属离子的抑制作用,其中,Na+、Ca2+、Mg2+离子的抑制效果较弱,而Pb2+、Mn2+等离子抑制作用较强,具体抑制效果为:Na+Ca2+≈Mg2+Zn2+Cu2+Ba2+Mn2+Pb2+.