Analysis of BTEX and other substituted benzenes in water using headspace SPME-GC-FID: method validation

The analysis of BTEX and other substituted benzenes in water samples using solid phase microextraction (SPME) and quantification by gas chromatography with flame ionization detection (GC-FID) was validated. The best analytical conditions were obtained using PDMS/DVB/CAR fibre using headspace extraction (HS-SPME) at 50 [degree]C for 20 min without stirring. The linear range for each compound by HS-SPME with GC/FID was defined. The detection limits for these compounds obtained with PDMS/DVB/CAR fibre and GC/FID were: benzene (15 ng L(-1)), toluene (160 ng L(-1)), monochlorobenzene (54 ng L(-1)), ethylbenzene (32 ng L(-1)), m-xylene (56 ng L(-1)), p-xylene (69 ng L(-1)), styrene (35 ng L(-1)), o-xylene (42 ng L(-1)), m-dichlorobenzene (180 ng L(-1)), p-dichlorobenzene (230 ng L(-1)), o-dichlorobenzene (250 ng L(-1)) and trichlorobenzene (260 ng L(-1)). This headspace SPME-GC-FID method was compared with a previously validated method of analysis using closed-loop-stripping analysis (CLSA). The headspace SPME-GC-FID method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from the water supply system of a large area (Lisbon and neighbouring municipalities).     

Qualitative Study of Organic Compounds in Wastewaters of a Swine Slaughterhouse

The main purpose of this work was the preliminary qualitative study of organic compounds in wastewaters of swine slaughterhouses. The samples were collected in a local abattoir and submitted to Liquid-Liquid Extraction (LLE) and Solid-phase Extraction (SPE) with XAD-4^TM resin as stationary phase. The instrumental analysis was performed by Gas Chromatography with Mass Spectrometer Detector (GC/MSD). The compounds present in the LLE and SPE extracts were identified by the GC/MSD library (Wiley). The results pointed out that SPE and LLE can extract practically the same classes of compounds at the same amounts. LLE works well for the extraction of polar organic compounds, with acidified samples, while SPE presents a better performance for the extraction of less polar organic compounds. Aldehydes were main class of the compounds extracted by SPE and LLE and decenal was the major aldehyde identified. Fatty alcohols and carboxylic acids were also identified but in minor proportions.     

Characterization of an urban landfill soil by using physicochemical analysis and solid phase microextraction (SPME)—GC/MS

We have aimed at characterizing top soil samples taken in-situ from five different locations of the unregulated dumping site in Eskişehir/Turkey for a period of six months. The study is the first attempt in the city and in Turkey, regarding particularly the SPME (Solid Phase Microextraction Technique) analysis method utilized. A comprehensive research has been conducted to produce critical soil data to be used for indicating current risks as well as the urgency of rehabilitating the site and establishing a sanitary landfill in the site. Conventional physicochemical analytical methods and SPME technique were used to analyze the samples. Physicochemical analyses were performed for determining the pH, total dried matter, volatile matter, total nitrogen, phosphorus, macro elements and heavy metals. Meteorological data were also recorded for the same period. SPSS.10.0 statistical program was used to determine the correlation between meteorological data and physicochemical analysis results. Mean values were used in the correlation analyses. These data indicated that the air temperature and precipitation have significant effects on soil characteristics. SPME, coupled with GC/MS, was used to identify eighty six volatile and semi-volatile organic compounds contained in soil samples. The samples were extracted by headspace SPME with heating (δHS-SPME). SPME analyses were conducted using a commercially available polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber having a film thickness of 65 μm (Supelco) as a capture medium. The experimentally optimized headspace sampling conditions were arranged (15 min. at 50^˚C) before a 30 min. sampling period.     

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。     

原煤二氯甲烷浸取液中多环芳烃分布特征

本文用色谱／质谱／红外联用系统研究了原煤二氯甲烷浸取液中多环芳烃的种类、数量、含量及其分布特征。为进一步研究煤燃烧排放飞灰、烟气、炉渣中多环芳烃分布打下良好基础。     

Feasibility of detection and quantification of gas-phase carbonyls in indoor environments using PFBHA derivatization and solid-phase microextraction (SPME)

Solid-phase microextraction (SPME) was evaluated for the detection and quantification of the gas-phase carbonyls: citronellal, glyoxal, methylglyoxal, and beta-ionone. Prepared air samples containing the carbonyl compounds were collected at a flow rate of 2.8 L min(-1) in an impinger containing a 25% reagent water/75% methanol collection liquid. The aqueous samples were then derivatized with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA), extracted with a PDMS/DVB coated SPME fiber, and analyzed by GC-MS. Detection limits with a sample air volume of 76 L were calculated to be 0.03 ppbv, 0.34 ppbv, 0.12 ppbv, and 0.28 ppbv for citronellal, glyoxal, methylglyoxal, and beta-ionone, respectively.     

GC/MS联用仪对几种自来水中有机污染物的分析

采用美国惠普公司色谱—质谱联用仪，研究了武汉市几种自来水中所含有机污染物的种类、组成及相对含量，得出了这几种水中有机物的分布特征，分析了污染物的来源，并从不同角度比较了这几种水的污染情况。     

Identification of surfactant degradation products as toxic organic compounds present in sewage sludge

A cost-effective strategy combining chemical analysis and bioassays for the identification of polar toxic compounds in sewage sludge is reported. ToxAlert 100 bioluminescence inhibition assay was used in combination with chemical analysis involving extraction, clean-up, chromatographic separation and mass spectrometry detection. This methodology was applied to real samples of sludge from three wastewater treatment plants (WWTP) located in Catalonia (Spain) during a 3 month period. In the first step, sewage sludge was lyophilized, treated by sonication with a mixture of methanol and chloroform and finally cleaned up using a sequential solid phase extraction (SSPE) with an octadecylsilica cartridge (C18) in series with a polymeric Lichrolut EN cartridge (Lic EN). In the second step, the toxicity of each fraction of the sludge sample was investigated using the ToxAlert 100. The unequivocal identification and quantification of polar organic cytotoxic substances present in the fractionated extracts were determined by liquid chromatography-mass spectrometry (LC-MS). Major toxic compounds identified were: non-ionic polyethoxylated surfactants (nonylphenol polyethoxylates, alcohol polyethoxylates), their intermediates (polyethylene glycol polyethoxylated, nonylphenol carboxylates and polyethoxylated alcohol carboxylates), linear alkylbenzenesulfonates and heavy metals. The toxic response (in terms of bioluminescence inhibition using ToxAlert 100), defined by the 50% effective concentration (EC50), and the toxicity units (TU) for every standard non-ionic surfactant were calculated. The results provided the identification of polar cytotoxic compounds as well as the evaluation of their contribution to the total toxicity observed in sewage sludge.     

Multi-component analysis of polar water pollutants using sequential solid-phase extraction followed by LC-ESI-MS

A multi-component screening analysis method for polar to medium-polar water pollutants was developed. Sample clean-up and group separation are performed by sequential solid-phase extraction (SSPE) using automated SPE with C18 and polymeric sorbent materials. Analyses are performed by liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS) using a single-quadrupole instrument. More than 90 priority compounds of environmental interest--comprising the most important chemical and substance classes: phenols, carboxylic acids, aromatic sulfonates, aromatic amines, pharmaceuticals, surfactants, dyes, and pesticides--have been chosen for the experiments. The compounds are divided by the SSPE procedure into 3 different polarity classes. The extraction recoveries were determined in the 3 fractions for every single substance, and were for most of the analytes in the range of 50-100%. A mixture of hexane-dichloromethane was used for the elution of nonpolar compounds like alkylphenols from C18. Methanol and acetone are well suited for the elution of more polar substances. The limits of detection (LODs) were determined for all compounds. Effluents from municipal and industrial wastewater treatment plants (WWTPs) treating waste water from textile industries; and the corresponding receiving waters (rivers and lakes) have been analysed with the developed method. Urban and industrial pollution was observed in rivers and streams in the area north of Milan, Italy. In the water samples different phenols (nitrophenols, bisphenol A, nonylphenol), alkylphenol ethoxylate surfactants, their metabolites with endocrine disrupting potential, aromatic sulfonates, linear alkylbenzenesulfonate surfactants, dyes, pesticides, pharmaceuticals, and a dichlorobenzidine compound were identified.     

Development of a solid phase microextraction (SPME) method for the sampling of VOC traces in indoor air

Solid-phase microextraction (SPME) was studied for the measurement of volatile organic compounds (VOCs) in indoor air. An adsorptive PDMS/Carboxen fibre was used and an analytical methodology was developed in order to overcome competitive adsorption. Kinetics and adsorption isotherms were investigated for different sample volumes and model compounds. In order to evaluate competitive adsorption on the fibre, these compounds were studied alone and in mixture. From the results obtained, the operating conditions allowing co-adsorption of the target compounds were determined: the air sample is enclosed in a 250 mL glass bulb where the SPME fibre is exposed until adsorption equilibrium. This procedure was combined with GC/MS analysis for the identification and quantification of VOCs in indoor air. The performances were determined by using a standard gas containing 10 VOCs representative of indoor environments (acetaldehyde, acetone, BTX, alpha-pinene, trichloroethylene, alkanes). The detection limits were determined in single ion monitoring mode and for a signal to noise ratio of 3. Except acetaldehyde (6 microg m(-3)), they are all below 0.5 microg m(-3). Calibration curves are linear up to 10 micromol m(-3) for all the compounds with good correlation coefficients (above 0.99). The reproducibility ranges from 6 to 12% according to the compound. The methodology was then applied to the comparison of the VOCs content in classrooms of two different schools.     

Comparison of pressurized fluid extraction, Soxhlet extraction and sonication for the determination of polycyclic aromatic hydrocarbons in urban air and diesel exhaust particulate matter

In order to characterize and compare the chemical composition of diesel particulate matter and ambient air samples collected on filters, different extraction procedures were tested and their extraction efficiencies and recoveries determined. This study is an evaluation of extraction methods using the standard 16 EPA PAHs with HPLC fluorescence analysis. Including LC analysis also GC and MS methods for the determination of PAHs can be used. Soxhlet extraction was compared with ultrasonic agitation and pressurized fluid extraction (PFE) using three solvents to extract PAHs from diesel exhaust and urban air particulates. The selected PAH compounds of soluble organic fractions were analyzed by HPLC with a multiple wavelength shift fluorescence detector. The EPA standard mixture of 16 PAH compounds was used as a standard to identify and quantify diesel exhaust-derived PAHs. The most effective extraction method of those tested was pressurized fluid extraction using dichloromethane as a solvent.     

Characterization of the Leachate in an Urban Landfill by Physicochemical Analysis and Solid Phase Microextraction-GC/MS

The aim of this study is to evaluate extensively the characterization and identification of major pollutant parameters by paying attention to the organic chemical pollution for unregulated dumping site leachate in Eskişehir/Turkey. The study that is first and only one research has been very important data related with before new sanitary landfill site in Eskişehir city. For this purpose, in this study leachate samples were collected in-situ at monthly interval for a period of 8 months. Firstly, thirty three physicochemical parameters were monitored. Secondly, SPME technique was used for identification of organic pollutants. Meteorological data were also recorded for the same sampling period to correlate meteorological data and physicochemical parameters. Mean values are used in the correlation analysis. Correlation is shown only for the relationship between air temperature and NO₃ ⁻. No correlation has been found between rain and leachate quality parameters since the amount of rain was very low during the sampling period. However, analysis results were generally decreased in winter season when each parameter and each sampling point are examined separately. According to correlation between every parameter, especially solid content and dissolved oxygen concentration of leachate is affecting to other parameters. Also, sodium and potassium are changing proportionally with same parameters (suspended solids, fixed solids, dissolved oxygen) and high correlation between chloride and heavy metal concentration is showing. The results were statistically evaluated by use of SPSS 10.0 program. Second part of the study, the leachate was extracted by Solid Phase Microextraction (SPME) technique and then analyzed. Of the methodologies tested in this study, the best one selected was based on 100 μ m polydimethylsiloxane coated fiber (PDMS), headspace with heating (Δ HS) sampling mode and an extraction time of 15 min. at a temperature of 50 ^o C. Thirty three organic compounds in leachate were identified by GC/MS.     

固相萃取-高效液相色谱法测定水中氯酚类化合物

采用固相萃取-高效液相色谱法测定水中7种氯酚类化合物,Waters OASIS WAX柱萃取效率最高,最佳萃取时间和洗脱时间分别为60和5 min。该法的线性范围为1.0~40 mg/L,检出限为0.015~0.5μg/L,精密度为0.558%~2.22%,回收率为83.2%~105%。该法适用于地表水及饮用水中氯酚类化合物的检测。     

固相萃取-超高效液相色谱-串联质谱法快速测定环境水样中30种极性农药

建立了固相萃取-超高效液相色谱-串联质谱快速测定环境水样中30种极性农药的方法。30种极性农药经过固相萃取(SPE)富集净化,以超高效液相色谱-串联质谱(UPLC-MS-MS)多级监测模式(MRM)外标法进行定性定量分析。结果表明:环境水样中30种极性农药的检出限为0.2～5 ng/L。对同一环境样品进行了低、中、高3个不同浓度水平的加标回收实验,平均回收率为63.7%～105.1%,相对标准偏差为4.4%～21.2%。该方法快速、灵敏、准确,可有效应用于环境水样中30种极性农药的快速监测。     

固相微萃取-气相色谱法测定水源地水中SVOC

采用固相微萃取-毛细管柱电子捕获气相色谱法测定水源地水中18种半挥发性有机物,优化了萃取纤维、时间、温度、pH值、转子转速、离子强度等萃取条件。方法线性良好,18种化合物的检出限为0.000 2μg/L~0.1μg/L,实际水样加标回收率为84.3%~109%。     

Comprehensive two-dimensional gas chromatography, a valuable technique for screening and semiquantitation of different chemical compounds in ultrafine 30 nm and 50 nm aerosol particles

Comprehensive two dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-TOF-MS) was used for screening and semiquantitation of semivolatile organic compounds in aerosol particles. As the volatility was a prerequisite parameter for the analysis, some compounds were transformed via derivatization such as silylation into more volatile ones. The identification of the analytes was made by comparing the GC retention indices and the TOF mass spectra with the NIST and the Golm metabolome database reference libraries. The data treatment was simplified by exploiting an additional classification of the identified compounds, namely the main functional group or specific element present in the molecule leading to different groups of compounds. This methodology was applied to identify compounds in 30 ± 4 nm, 50 ± 5 nm and total suspended particles (TSP) collected during spring and autumn of 2009 and summer of 2010 at the Station for Measuring Forest Ecosystem Atmosphere Relations (SMEAR II) at Hyyti?l? (Finland). The number of identified compounds was higher than 400, which were the most relevant compounds present in the samples, in terms of concentrations. The analysis of aerosol particles of different sizes, collected simultaneously, revealed that the number of compounds increased with the particle size whereas the normalized response factor decreased in most of the cases, aldehydes being an exception. This decrease could be associated with the formation or aggregation of new compounds onto the particles when they grow in the atmosphere.     

快速溶剂萃取—气相色谱法分析土壤中的20种有机氯

采用加速溶剂萃取—气相色谱法对土壤中20种有机氯农药进行了提取测定.通过改变加速溶剂萃取条件,选取了最佳条件参数,减少了组份的损失;通过改变气相色谱条件,使得20种有机氯农药快速分离.该方法具有操作简便、灵敏度高、检出限低、快速、溶剂消耗少等优点,方法检出限为1.23～ 3.11 μg/kg,实际样品的加标回收率为62.3％～119.7％.     

Simultaneous analysis of endosulfan, chlorpyrifos, and their metabolites in natural soil and water samples using gas chromatography-tandem mass spectrometry

Analysis of endosulfan, chlorpyrifos, and their nonpolar metabolites in extracts from environmental aqueous and soil samples was performed using a gas chromatography-tandem mass spectrometry (GC–MS/MS) technique. Full-scan GC–MS analysis showed poor sensitivity for some of the metabolites (endodiol and endosulfan ether). A multisegment MS/MS method was developed and MS/MS parameter isolation time, excitation time, excitation voltage, and maximum excitation energy were optimized for chosen precursor ions to enhance selectivity and sensitivity of the analysis. The use of MS/MS with optimized parameters quantified analytes with significantly higher accuracy, and detection limits were lowered to ~1/6th compared with the full-scan method. Co-eluting compounds, chlorpyrifos and chlorpyrifos oxon, were also analyzed successfully in the MS/MS mode by choosing exclusive precursor ions. Analysis of soil and water phase samples from contaminated soil slurry bioreactors showed that the MS/MS method could provide more reliable estimates of these pesticide and metabolites (especially those present in low concentrations) by annulling interferences from soil organic matter.     

Injectors for capillary gas chromatography and their application to environmental analysis

The application of different injectors in capillary gas chromatography (GC) analysis of semi-volatile organic contaminants in environmental samples prepared in organic solvents is reviewed. The injectors examined include a split/splitless injector in splitless mode (SS), cold on-column (COC), and programmable temperature vaporizer (PTV) and adaptations of these injector designs. Key issues when selecting an injector include properties of the analyte, such as potential for thermal degradation or discrimination of high boiling point compounds within the injector, and the ability of the GC systems to handle large volume injections (LVI) primarily to lower detection limits and allow direct coupling with sample preparation techniques such as at-line or on-line solid phase extraction (SPE). LVI also require consideration of matrix interference issues. This review examines only injector chamber modifications that are feasible with a standard GC configuration, however some modifications to the chromatographic system to extend the range of applicability of gas chromatography analysis for environmental samples are also noted.     

超声波提取-GC/MS法测定生物体内硝基苯类化合物

以洪泽湖中6种代表性生物为研究对象，采用超声波法提取样品中硝基苯类化合物，用凝胶色谱净化、浓缩，气相色谱／质谱联用法测定。该法与索氏提取法在同等试验条件下进行加标回收试验，前者回收率高且稳定，简便可行。方法检出限为0．008μg／g～0．030μg／g，平均加标回收率为76．5％～109％，重复测定3次的RSD为1．5％～13．0％。