利用保留时间锁定软件对水中挥发性有机物进行气相色谱测定

使用保留时间锁定软件 (RTL) ,在气相色谱体系中建立了水质中 5 3种挥发性有机物的保留时间数据库 ,使原始的保留时间成为化合物定性的可靠参数 ,实现了未知样品在色谱仪上的定性 ,提高了分析效率。     

Soil sampling and analysis for volatile organic compounds

Concerns over data quality have raised many questions related to sampling soils for volatile organic compounds (VOCs). This paper was prepared in response to some of these questions and concerns expressed by Remedial Project Managers (RPMs) and On-Scene Coordinators (OSCs). The following questions are frequently asked:

1. Is there a specific device suggested for sampling soils for VOCs?
2. Are there significant losses of VOCs when transferring a soil sample from a sampling device (e.g., split spoon) into the sample container?
3. What is the best method for getting the sample from the split spoon (or other device) into the sample container?
4. Are there smaller devices such as subcore samplers available for collecting aliquots from the larger core and efficiently transferring the sample into the sample container?
5. Are certain containers better than others for shipping and storing soil samples for VOC analysis?
6. Are there any reliable preservation procedures for reducing VOC losses from soil samples and for extending holding times?

Guidance is provided for selecting the most effective sampling device for collecting samples from soil matrices. The techniques for sample collection, sample handling, containerizing, shipment, and storage described in this paper reduce VOC losses and generally provide more representative samples for volatile organic analyses (VOA) than techniques in current use. For a discussion on the proper use of sampling equipment the reader should refer to other sources (Acker, 1974; U.S. EPA, 1983; U.S. EPA, 1986a). Soil, as referred to in this report, encompasses the mass (surface and subsurface) of unconsolidated mantle of weathered rock and loose material lying above solid rock. Further, a distinction must be made as to what fraction of the unconsolidated material is soil and what fraction is not. The soil component here is defined as all mineral and naturally occurring organic material that is 2 mm or less in size. This is the size normally used to differentiate between soils (consisting of sands, silts, and clays) and gravels. Although numerous sampling situations may be encountered, this paper focuses on three broad categories of sites that might be sampled for VOCs:

1. Open test pit or trench.
2. Surface soils (<5 ft in depth).
3. Subsurface soils (>5 ft in depth).

     

A two-column method for long-term monitoring of non-methane hydrocarbons (NMHCs) and oxygenated volatile organic compounds (o-VOCs)

A method has been developed for concurrent analysis of C2-C7 hydrocarbons and C2-C5 oxygenated volatile organic compounds (o-VOCs) including alcohols, aldehydes, ketones and ethers. A multi-bed, Peltier-cooled adsorbent trap, consisting of Carboxen 1000 and Carbopack B, was used to acquire one sample per hour. Upon injection the sample was split in an approximately 50:50 ratio between a 50 m aluminium oxide (Al2O3) porous layer open tubular (PLOT) column and a 10 m LOWOX column. Eluents from each column were then analysed using flame ionisation detection (FID). Regular calibration of the system was performed using a standard cylinder mixture at the parts per billion by volume (ppbV) level for non-methane hydrocarbons (NMHCs) and a permeation tube method for the oxygenated species. The system is fully automated with NMHC detection limits between 1 and 10 parts per trillion by volume (pptV) and o-VOC detection limits between 10 and 40 pptV.     

A comparison of sampling and analysis methods for low-ppbC levels of volatile organic compounds in ambient air

A carefully designed study was conducted during the summer of 1998 to collect samples of ambient air by canisters and compare the analysis results to direct sorbent preconcentration results taken at the time of sample collection. Thirty-two 1 h sample sets were taken, each composed of a "near-real-time" sample analyzed by an autoGC-MS XonTech 930/Varian Saturn 2000 system, and Summa and Silco canisters. Hourly total non-methane organic carbon (TNMOC), ozone, and meteorological measurements were also made. Each canister was analyzed on the autoGC-MS system for a target list of 108 volatile organic compounds (VOCs) and on a manual cryosampling GC-FID system. Comparisons were made between the collection and analysis methods. Because of the low sample loading (150-250 ppbC TNMOC), these comparisons were a stringent test of sample collection and analysis capabilities. The following specific conclusions may be drawn from this study. Reasonable precision (within 15% mean difference of duplicate analyses from the same canister) can be obtained for analyses of target VOCs at low-ppbC concentrations. Relative accuracy between the GC-MS and GC-FID analysis methods is excellent, as demonstrated by comparisons of analyses of the same canisters, if measurements are sufficiently above the detection limits. This is especially significant as the GC-MS and GC-FID were independently calibrated. While statistically significant differences may be observed between the results from canister and near-real-time samples, the differences were generally small and there were clear correlations between the canister results and the near-real-time results. Canister cleanliness limits detection below the EPA Method TO-14 acceptance standard of 0.2 ppbv (0.2-2 ppbC for target analytes).     

A catalogue of urban hydrocarbons for the city of Leeds: atmospheric monitoring of volatile organic compounds by thermal desorption-gas chromatography

A method has been developed for the speciation and quantitative determination of hydrocarbons in urban air in the city of Leeds. Hydrocarbons were pre-concentrated by adsorbent tube air sampling and analyzed using thermal desorption and gas chromatography with flame ionization detection and structural confirmation by mass spectrometric detection. While automated volatile organic compound (VOC) analyzers produced data for a maximum of about 30 compounds simultaneously, with the method described here, a total of 68 C6-C12 hydrocarbons were measured simultaneously in one analysis at parts per billion (ppb) levels. Several monitoring surveys were performed, one during the winter of 1993 and the other in the summer of 1994, at a number of sites to investigate the levels of VOCs identified in the urban air of Leeds.     

An improved dual channel PERCA instrument for atmospheric measurements of peroxy radicals

This paper describes a new dual-channel PEroxy RadiCal Amplification (PERCA) instrument, which has been designed to improve the time resolution and signal to noise and to reduce the interference caused by variations in ambient ozone concentrations. The instrument was run at the Weybourne Atmospheric Observatory (WAO), North Norfolk, during WAOWEX (Weybourne Atmospheric Observatory Winter Experiment) in January/February 2002 and INSPECTRO (Influence of clouds on the spectral actinic flux in the lower troposphere) in September 2002. The performance of the instrument is assessed and compared to that of a single channel instrument. In particular, it is shown how the precision is greatly improved in fluctuating background ozone conditions. In addition the improved time response of the instrument allows changes in peroxy radical concentrations to be related to rapid changes in nitric oxide concentrations and the ozone photolysis frequency, j(O(1)D).     

A novel in vitro exposure technique for toxicity testing of selected volatile organic compounds

Exposure to vapours of volatile chemicals is a major occupational and environmental health concern. Toxicity testing of volatile organic compounds (VOCs) has always faced significant technological problems due to their high volatility and/or low solubility. The aim of this study was to develop a practical and reproducible in vitro exposure technique for toxicity testing of VOCs. Standard test atmospheres of xylene and toluene were generated in glass chambers using a static method. Human cells including: A549-lung derived cell lines, HepG2-liver derived cell lines and skin fibroblasts, were grown in porous membranes and exposed to various airborne concentrations of selected VOCs directly at the air/liquid interface for 1 h at 37 degrees C. Cytotoxicity of test chemicals was investigated using the MTS (3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium) and NRU (neutral red uptake) assays following 24 h incubation. Airborne IC(50) (50% inhibitory concentration) values were determined using dose response curves for xylene (IC(50)=5350+/- 328 ppm, NRU; IC(50)=5750+/- 433 ppm, MTS in skin fibroblast) and toluene (IC(50)=0 500+/- 527 ppm, NRU; IC(50)=11,200 +/- 1,044 ppm, MTS in skin fibroblast). Our findings suggest that static direct exposure at the air/liquid interface is a practical and reproducible technique for toxicity testing of VOCs. Further, this technique can be used for inhalational and dermal toxicity studies of volatile chemicals in vitro as the exposure pattern in vivo is closely simulated by this method.     

人体接触挥发性有机化合物的生物标志物

生物标志物是阐明接触与健康损害之间关系的工具。综述了３７ 篇文献,简单论述了挥发性有机化合物的各种生物标志物,这些生物标志物包括暴露生物标志物,效应生物标志物和易感性生物标志物。还简述了各种生物标志物之间的相互关系,并介绍了各种生物标志物的研究现状和发展前景,以及应用它们来评价ＶＯＣｓ对人体健康的影响。     

Workplace monitoring for volatile organic compounds using thermal desorption-gas chromatography-mass spectrometry

The interest in the identification of volatile organic compounds in the workplace has been a major focus of many National Institute for Occupational Safety and Health (NIOSH) field studies. A primary technique for sampling and analysis of these compounds is summarized by NIOSH Manual of Analytical Methods (NMAM) 2549. This is a screening method that uses a multi-bed sorbent to trap a wide variety of compounds and compound classes. Thermal desorption techniques are used as a first attempt to characterize potential contaminants in a workplace and to determine what future sampling and analyses must be performed. Field examples are provided to show the versatility of thermal desorption methods and techniques. Due to their sensitivity, thermal desorption tube methods are sometimes required in order to measure the workplace concentrations of unusual compounds. In other situations, the exposures are too high or varied to make thermal desorption tubes practical. In these cases, the identification of contaminants with thermal desorption tubes leads to new method developments for the quantification of specific compounds using more conventional solid sorbent-solvent desorption based methods.     

Determination of volatile organic compounds pollution sources in malaysian drinking water using multivariate analysis

A field investigation was conducted at all water treatment plants throughout 11 states and Federal Territory in Peninsular Malaysia. The sampling points in this study include treatment plant operation, service reservoir outlet and auxiliary outlet point at the water pipelines. Analysis was performed by solid phase micro-extraction technique with a 100 μm polydimethylsiloxane fibre using gas chromatography with mass spectrometry detection to analyse 54 volatile organic compounds (VOCs) of different chemical families in drinking water. The concentration of VOCs ranged from undetectable to 230.2 μg/l. Among all of the VOCs species, chloroform has the highest concentration and was detected in all drinking water samples. Average concentrations of total trihalomethanes (THMs) were almost similar among all states which were in the range of 28.4--33.0 μg/l. Apart from THMs, other abundant compounds detected were cis and trans-1,2-dichloroethylene, trichloroethylene, 1,2-dibromoethane, benzene, toluene, ethylbenzene, chlorobenzene, 1,4-dichlorobenzene and 1,2-dichloro - benzene. Principal component analysis (PCA) with the aid of varimax rotation, and parallel factor analysis (PARAFAC) method were used to statistically verify the correlation between VOCs and the source of pollution. The multivariate analysis pointed out that the maintenance of auxiliary pipelines in the distribution systems is vital as it can become significant point source pollution to Malaysian drinking water.     

Validation of evacuated canisters for sampling volatile organic compounds in healthcare settings

Healthcare settings present a challenging environment for assessing low-level concentrations of specific volatile organic compounds (VOCs) in the presence of high background concentrations of alcohol from the use of hand sanitizers and surface disinfectants. The purposes of this laboratory-based project were to develop and validate a sampling and analysis methodology for quantifying low-level VOC concentrations as well as high-level alcohol concentrations found together in healthcare settings. Sampling was conducted using evacuated canisters lined with fused silica. Gas chromatography/mass spectrometry analysis was performed using preconcentration (for ppb levels) and loop injection (for ppm levels). For a select list of 14 VOCs, bias, precision, and accuracy of both the preconcentration and loop injection methods were evaluated, as was analyte stability in evacuated canisters over 30 days. Using the preconcentration (ppb-level) method, all validation criteria were met for 13 of the 14 target analytes-ethanol, acetone, methylene chloride, hexane, chloroform, benzene, methyl methacrylate, toluene, ethylbenzene, m,p-xylene, o-xylene, alpha-pinene, and limonene. Using the loop injection (ppm-level) method, all validation criteria were met for each analyte. At ppm levels, alpha-pinene and limonene remained stable over 21 days, while the rest of the analytes were stable for 30 days. All analytes remained stable over 30 days at ppb levels. This sampling and analysis approach is a viable (i.e., accurate and stable) methodology that will enable development of VOC profiles for mixed exposures experienced by healthcare workers.     

An evaluation of a fast sampling procedure for the trace analysis of volatile organic compounds in ambient air

This study deals with the evaluation of a fast method for sampling of volatile organic compounds in ambient air. Special bags made of an inert material are used together with a large handpump which allows a sampling of one liter per second. After the sampling, the pollutants are concentrated by adsorption on Tenax and transfered by heat desorption, to a small capillary precolumn cooled with liquid nitrogen, or directly trapped on the precolumn. The suitability of this technique was evaluated by sampling complex synthetic mixtures of known concentration and composition, after which the samples were submitted to a series of operations such as transport, aging, changing of the humidity, heating and cooling, irradiation, etc. Changes in the original mixtures, caused by adsorption, diffusion, chemical or photochemical reactions were investigated by GC-MS analysis. The results of the study show that under certain conditions the samples can be preserved for a rather long period of time without noticeable changes in composition. However for certain compounds, severe quantitative losses occur after one day storage. Finally a practical application of this method is described in a recent case of strong odour annoyance by a chemical plant in the north of Belgium.     

Analysis of volatile organic compounds released during food decaying processes

A number of volatile organic compounds (VOCs) including acetone, methyl ethyl ketone, toluene, ethylbenzene, m,p-xylene, styrene, and o- xylene released during food decaying processes were measured from three types of decaying food samples (Kimchi (KC), fresh fish (FF), and salted fish (SF)). To begin with, all the food samples were contained in a 100-mL throwaway syringe. These samples were then analyzed sequentially for up to a 14-day period. The patterns of VOC release contrasted sharply between two types of fish (FF and SF) and KC samples. A comparison of data in terms of total VOC showed that the mean values for the two fish types were in the similar magnitude with 280 ± 579 (FF) and 504 ± 1,089 ppmC (SF), while that for KC was much lower with 16.4 ± 7.6 ppmC. There were strong variations in VOC emission patterns during the food decaying processes between fishes and KC that are characterized most sensitively by such component as styrene. The overall results of this study indicate that concentration levels of the VOCs differed significantly between the food types and with the extent of decaying levels through time.     

Emission of volatile organic compounds from religious and ritual activities in India

Worshipping activity is a customary practice related with many religions and cultures in various Asian countries, including India. Smoke from incense burning in religious and ritual places produces a large number of health-damaging and carcinogenic air pollutants include volatile organic compounds (VOCs) such as formaldehyde, benzene, 1,3 butadiene, styrene, etc. This study evaluates real-world VOCs emission conditions in contrast to other studies that examined emissions from specific types of incense or biomass material. Sampling was conducted at four different religious places in Raipur City, District Raipur, Chhattisgarh, India: (1) Hindu temples, (2) Muslim graveyards (holy shrines), (3) Buddhist temples, and (4) marriage ceremony. Concentrations of selected VOCs, respirable particulate matter (aerodynamic diameter, <5 μm), carbon dioxide, and carbon monoxide were sampled from the smoke plumes. Benzene has shown highest emission factor (EF) among selected volatile organic compounds in all places. All the selected religious and ritual venues have shown different pattern of VOC EFs compared to laboratory-based controlled chamber studies.     

A novel approach to evaluation of adsorbents for sampling indoor volatile organic compounds associated with symptom reports

This article addresses problems that complicate attempts to compare methods when several factors may be associated with an effect, but it is not known which factors are relevant. Chemicals that may contribute to 'sick building syndrome' (SBS), and thus should be sampled in investigations of SBS, are not currently known. A study was undertaken to compare the utility of three adsorbents (Carbopack B, Chromosorb 106 and Tenax TA) for detecting differences in personal chemical exposure to volatile organic compounds in indoor air, between persons with and without SBS symptoms (cases and controls). On the basis of office workers' responses to a questionnaire, 15 cases and 15 controls were chosen. They simultaneously carried diffusive samplers with adsorbents during a week at work, and the acquired samples were analysed by gas chromatography/mass spectrometry (GC/MS). The adsorbents were then compared in terms of their ability to separate cases and controls in partial least square discriminant analysis (PLS-DA) models. This method of comparison takes into account detected differences in chemical exposure between cases and controls measured with the different adsorbents. Tenax TA gave the best PLS-DA models for separating cases and controls, but a combination of measurements with Tenax TA and Carbopack B gave better PLS-DA models than models based on measurements from either adsorbent alone. Adding measurements from Chromosorb 106 did not improve the results.     

环境空气中痕量挥发性有机硫监测分析方法研究

采用预浓缩系统与GC MS联用,建立了环境空气中痕量挥发性有机硫的分析方法,该法用苏玛罐或Tedlar袋采集空气样品在预浓缩系统中经液氮于-160℃冷冻浓缩后,进入GC MS进行分析。甲硫醇、乙硫醇、甲硫醚、乙硫醚、二甲二硫的最低检出限分别为2 0、1 0、1 0、1 0、0 5μg m3。经6次的重复测定,其相对标准偏差小于9 0%。该方法已用于环境空气的测定,取得了令人满意的结果。     

Investigation and assessment of volatile organic compounds in water sources in China

456 water samples collected from 152 water sources in 2006 were analyzed for 21 volatile organic compounds (VOCs). Concentrations of 21 VOCs ranged from below method detection limits of the laboratory to 7.65 ??g/L (toluene), but seldom exceeded the concentration limits set in the National Drinking Water Quality Standards (GB5749-2006) or the National Environmental Quality Standards for Surface Water (GB3838-2002) of China. Of the 21 individual VOCs analyzed, 11 VOCs were detected in at least one sample at or above 1.0 ??g/L; 6.6% of the water samples had a detection of at least one VOC at or above 1.0 ??g/L, and 2.6% had a detection of at least two VOCs at or above 1.0 ??g/L. Based on the statistical data of detection frequencies above the method detection limits, 75% of the samples detected at least one VOC, and 65% of the samples detected at least two VOCs. Chloroform, toluene, and 1,2-dichloroethene were the three most frequently detected VOCs, with detection frequencies of 76.97%, 68.42%, and 44.08%, respectively. Volatile halogenated hydrocarbons and gasoline components were the two most frequently detected VOC groups.     

Compact semi-automatic incident sampler for personal monitoring of volatile organic compounds in occupational air

Suddenly occurring and time limited chemical exposures caused by unintended incidents might pose a threat to many workers at various work sites. Monitoring of exposure during such occasional incidents is challenging. In this study a compact, low-weight and personal semi-automatic pumped unit for sampling of organic vapor phase compounds from occupational air during sporadic and suddenly occurring incidents has been developed, providing simple activation by the worker potentially subjected to the sudden occurring exposures when a trained occupational hygienist is not available. The sampler encompasses a tube (glass or stainless steel) containing an adsorbent material in combination with a small membrane pump, where the adsorbent is capped at both ends by gas tight solenoid valves. The sampler is operated by a conventional 9 V battery which tolerates long storage time (at least one year), and is activated by pulling a pin followed by automatic operation and subsequent closing of valves, prior to shipping to a laboratory. The adjustable sampling air flow rate and the sampling time are pre-programmed with a standard setting of 200 mL min(-1) and 30 min, respectively. The average airflow in the time interval 25-30 min compared to average airflow in the interval 2-7 min was 92-95% (n = 6), while the flow rate between-assay precisions (RSD) for six different samplers on three days each were in the range 0.5-3.7%. Incident sampler recoveries of VOCs from a generated VOC atmosphere relative to a validated standard method were between 95 and 102% (+/-4-5%). The valves that seal the sampler adsorbent during storage have been shown to prevent an external VOC atmosphere (500 mg m(-3)) to enter the adsorbent tube, in addition to that the sampler adsorbent is storable for at least one month due to absence of ingress of contaminants from internal parts. The sampler was also suitable for trapping of semi-volatile organophosphates.     

空气中挥发性有机物(VOCs) 的监测方法研究

建立了热脱附仪和气相色谱-质谱联用测定室内空气和环境空气中35种挥发性有机污染物的分析方法,方法的最低检出限为0.1～0.9μg/m3, 20μg/m3挥发性有机物标准经6次的重复测定,其相对标准偏差小于8.4%.该方法已用于室内空气和环境空气的测定,取得令人满意的结果.