Determination of volatile organic compounds in recycled polyethylene terephthalate and high-density polyethylene by headspace solid phase microextraction gas chromatography mass spectrometry to evaluate the efficiency of recycling processes

A method for the determination of volatile organic compounds (VOCs) in recycled polyethylene terephthalate and high-density polyethylene using headspace sampling by solid-phase microextraction and gas chromatography coupled to mass spectrometry detection is presented. This method was used to evaluate the efficiency of cleaning processes for VOC removal from recycled PET. In addition, the method was also employed to evaluate the level of VOC contamination in multilayer packaging material containing recycled HDPE material. The optimisation of the extraction procedure for volatile compounds was performed and the best extraction conditions were found using a 75 μm carboxen-polydimethylsiloxane (CAR-PDMS) fibre for 20 min at 60 °C. The validation parameters for the established method were linear range, linearity, sensitivity, precision (repeatability), accuracy (recovery) and detection and quantification limits. The results indicated that the method could easily be used in quality control for the production of recycled PET and HDPE.     

Volatile organic compounds in urban atmospheres: Long-term measurements of ambient air concentrations in differently loaded regions of Leipzig

For the comprehensive characterization of ambient air concentrations of a broad spectrum of volatile organic compounds (VOCs) an analytical method is described, consisting of adsorptive enrichment, thermal desorption without cryofocusing, and capillary gas chromatographic separation. The method was applied during two-week measuring campaigns in winter and summer 1995, and in the winter of 1996. Long-term sampling was carried out at sampling points in residential areas in the suburbs and near the city center of Leipzig. About 70 VOCs – mainly hydrocarbons from propene to hexadecane – were identified both by GC-MS and chromatographic retention data and quantified after external calibration. Mean values of VOC concentrations obtained during the sampling periods are reported and discussed with regard to the topographical location of the sampling points in the Leipzig area, seasonal variations, and possible emission sources.     

Development and validation of a method for air-quality and nuisance odors monitoring of volatile organic compounds using multi-sorbent adsorption and gas chromatography/mass spectrometry thermal desorption system

An analytical method based on thermal desorption (TD) coupled to gas chromatography (GC) and mass spectrometry detection (MS) has been developed and validated for the determination of a wide range of odor nuisance and air-quality volatile organic compounds (VOC) in air. New generation isocyanates, isocyanato- and isothiocyanatocyclohexane, have been included for the first time as target compounds due to their high occurrence in air samples. A dynamic air sampling method to trap gas and vapor on multi-sorbent tubes using portable pump equipment has been also developed. Sorbent tubes were filled with Carbotrap (70mg), Carbopack X (100mg) and Carboxen-569 (90mg). Validation of the TD-GC-MS method showed good selectivity, sensibility and precision according to Compendium Method TO-17 (US Environment Protection Agency) criteria. Limits of detection (signal-to-noise=3, ng in tube) ranges were 0.004-0.03ng (alcanes), 0.001-0.1ng (aromatics), 0.03-14ng (aldehydes), 0.003-7ng (alcohols), 0.003-0.04ng (chlorides), 0.02-0.5ng (esters), 0.002-0.1ng (ketones), 0.01-0.53ng (terpenes), 14-97ng (amides), 0.2-10ng (isocyanates) and 0.001ng (carbon disulfide). The linear dynamic range was over 3-5 orders of magnitude, depending of the VOC. TD-GC-MS analysis was reproducible, with relative standard deviation (n=5) within 20%. VOCs breakthrough examination showed no significant losses when about 2000ng standard was prepared. In order to evaluate the performance of the developed method on real samples, several industrial and urban air samples were analysed. VOCs were found to be stable on the sorbent tubes for at least 1 week when stored at 4 degrees C.     

Development of a Method for Determination of Volatile Organic Compounds (C6-C9) by Thermal Desorption-Gas Chromatography. Application to Urban and Rural Atmospheres.

ABSTRACT

An analytical method for the determination of 15 Volatile Organic Compounds (VOC): benzene, n-heptane, toluene, n-octane, chlorobenzene, ethylbenzene, m-xylene, o-xylene, p-xylene, isopropylbenzene, n-propylbenzene, n-decane, 1,4-dichlorobenzene, 1,3-dichlorobenzene and 1,2-dichlorobenzene, by thermal desorption coupled with gas chromatography (GC) was proposed. The flame ionisation detector (FID) and mass spectrometry (MS) detector were used. The variables that have an influence on the desorption process (time, inert gas flow and temperature) were studied, obtaining detection limit ranges from 15 to 120 pg (GC-FID), 3.8 to 32 pg (GC-MS, SIM mode) and 15 to 300 pg (GC-MS, SCAN mode). In order to detect possible VOC urban sources, samples were taken from 6 points in A Coruña (N.W. Spain) to analyse. Sampling time and flow rate were 30 minutes and 50 mL/min respectively. VOC profile and their total concentrations can be considered as typical of an urban area. Other samples were also obtained from a nearly rural zone to determine the influence of these VOC sources.     

一次热解吸直接进样浓缩方法的研究--室内大气中挥发性有机化合物的分析

研制了新型的一次热解吸直接进样热解析仪．考察了新型热解吸仪热解吸定量的重复性、准确性、热解析率、线性等性能．通过实际采样分析证明,该方法提高了浓缩倍数,操作简单,易于掌握,定量重复性好、准确度高,分析结果可靠．适合大批量样品的分析测试．     

Measurement of toxic volatile organic compounds in indoor air of semiconductor foundries using multisorbent adsorption/thermal desorption coupled with gas chromatography-mass spectrometry

A method for the qualitative and quantitative analysis of volatile organic compounds (VOCs) in the air of class-100 clean rooms at semiconductor fabrication facilities was developed. Air samples from two semiconductor factories were collected each hour on multisorbent tubes (including Carbopack B, Carbopack C, and Carbosieve SIII) with a 24-h automatic active sampling system and analyzed using adsorption/thermal desorption coupled with gas chromatography-mass spectrometry. Experimental parameters, including thermal desorption temperature, desorption time, and cryofocusing temperature, were optimized. The average recoveries and the method detection limits for the target compounds were in the range 94-101% and 0.31-0.89 ppb, respectively, under the conditions of a 1 L sampling volume and 80% relative humidity. VOCs such as acetone, isopropyl alcohol, 2-heptanone, and toluene, which are commonly used in the semiconductor and electronics industries, were detected and accurately quantified with the established method. Temporal variations of the analyte concentrations observed were attributed to the improper use of organic solvents during operation.     

Construction of an automated gas chromatography/mass spectrometry system for the analysis of ambient volatile organic compounds with on-line internal standard calibration

An automated sampling and enrichment apparatus coupled with a gas chromatography/mass spectrometry (GC/MS) technique was constructed for the analysis of ambient volatile organic compounds (VOCs). A sorbent trap was built within the system to perform on-line enrichment and thermal desorption of VOCs onto GC/MS. In order to improve analytical precision, calibration accuracy, and to safe-guard the long-term stability of this system, a mechanism to allow on-line internal standard (I.S.) addition to the air sample stream was configured within the sampling and enrichment apparatus. A sub-ppm (v/v) level standard gas mixture containing 1,4-fluorobenzene, chloropentafluorobenzene, 1-bromo-4-fluorobenzene was prepared from their pure forms. A minute amount of this I.S. gas was volumetrically mixed into the sample stream at the time of on-line enrichment of the air sample to compensate for measurement uncertainties. To assess the performance of this VOC GC/MS system, a gas mixture containing numerous VOCs at sub-ppb (v/v) level served as the ambient air sample. Various internal standard methods based on total ion count (TIC) and selective ion monitoring (SIM) modes were attempted to assess the improvement in analytical precision and accuracy. Precision was improved from 7-8% RSD without I.S. to 2-3% with I.S. for the 14 target VOCs. Uncertainties in the calibration curves were also improved with the adoption of I.S. by reducing the relative standard deviation of the slope (Sm%) by an average a factor of 4, and intercept (Sb%) by a factor of 2 for the 14 target VOCs.     

Comparative study of solvent extraction and thermal desorption methods for determining a wide range of volatile organic compounds in ambient air

This paper compares two analytical methods for determining levels of 90 volatile organic compounds (VOCs) commonly found in industrial and urban atmospheres. Both methods are based on two official methods for determining benzene levels and involve collecting samples by active adsorptive enrichment on solid sorbents. The first method involves solvent extraction and uses activated charcoal as a sorbent. After sampling, the sorbent is extracted with 1 mL of carbon disulfide and then 1 μL of the extract is analysed in a GC-MS. The second method involves thermal desorption (TD) and uses Tenax TA and Carbograph 1TD as sorbents, which allows the whole sample to be analysed. In general, the thermal desorption method showed the best repetitivity and recovery and the lowest limit of detection and quantification for all target compounds. Because of its lower sensitivity, the solvent extraction method needs the preconcentration of large sample volumes of air (720 L vs. 2.64 L for the thermal desorption method) to yield similar limits of detection.The performance of both methods in real samples was tested in a location near to a petrochemical complex. The results of the 24-h samples for the solvent extraction method were compared with the average of 12 2-h samples for the TD method. In some cases, both methods found differences in the VOC concentrations, especially in those compounds whose concentrations fluctuate significantly during the day.     

Determination of volatile organic compounds in contaminated air using semipermeable membrane devices

Semipermeable membrane devices (SPMDs) were evaluated as passive samplers for the determination of 26 volatile organic compounds (VOCs) in contaminated air of occupational environments. A direct methodology based on the use of head-space-gas chromatography-mass spectrometry (HS-GC-MS) was developed for VOCs determinations in SPMDs, without any sample pre-treatment and avoiding the use of solvents. A desorption temperature of 150 °C for 10 min was sufficient for a sensitive VOCs determination providing limits of detection in the range of 15 ng SPMD⁻¹ for 21 of 26 studied compounds. Linear and equilibrium uptake models were established for each VOC from compound isotherms. Highly volatile compounds were slightly absorbed and moderately volatile compounds were strongly absorbed by SPMDs. This study is the first precedent of the use of SPMDs for the simultaneous sampling of a wide number of VOCs. The use of SPMDs is a simple and low cost alternative to ordinary sampling devices such as Radiello^® diffusive samplers or badge-type solid-phase supports.     

顶空-气相色谱-质谱联用法同时测定紫外光固化胶印油墨中27种溶剂残留

建立了同时测定紫外光固化（UV）胶印油墨中27种溶剂残留（挥发性有机化合物,VOCs）的顶空-气相色谱-质谱联用（HS-GC-MS）法。将UV胶印油墨样品模拟印刷制成一定面积、厚度的试样,在紫外灯下烘烤1 min,经80℃、45 min静态顶空后,通过VOC专用毛细管柱分离和质谱检测,外标法定量。27种VOCs均呈现良好的线性关系,相关系数（R²）均≥0.9950;方法的检出限（LODs,S/N=3）为0.001~0.310 mg/m²,定量限（LOQs,S/N=10）为0.003~0.920 mg/m²;样品的平均加标回收率为80%~108%,相对标准偏差（RSD）<6%（n=6）。该方法制样便捷,灵敏度高,精密度好,准确度高,将其应用于实际UV胶印油墨样品的检测,取得了良好效果。     

System for the generation of standard gas mixtures of volatile and semi-volatile organic compounds for calibrations of solid-phase microextraction and other sampling devices

Standard gases are used for quality control and quality assurance, development of analysis methods and novel air sampling devices. The use of solid-phase microextraction (SPME) and other novel technologies for research in the area of air sampling and analysis requires systems/devices for reliable standard gas generation and sampling. In this paper we describe a new gas standard generating system for volatile organic compounds (VOCs) and semi-VOCs that was designed, built, and tested to facilitate fundamental and applications research with SPME. The system provided for the generation of a wide range of VOC/semi-VOC concentrations and mixing various standard gases, estimation of detection limits, testing the effects of sampling time, air temperature and relative humidity, testing the effects of air velocity and ozone on sampling/extractions. The system can be also used for calibrations of analytical instrumentation, quality control and quality assurance checks, and cross-validations of SPME with/and other sampling techniques.     

A review of advances and new developments in the analysis of biological volatile organic compounds

Biological volatile organic compounds (VOCs) are interlinked to biological metabolism and bacterial populations localized on the surfaces of biological samples. The characteristics of biological VOCs at different physiological status or metabolism phases are various, which contain crucial bio-information. In this review, the significance of the study of biological VOCs was introduced, and crucial techniques greatly influencing the investigation were summarized and reviewed including efficient sampling, suitable analytical and bio-information distillation techniques. From the preliminary identification of biological VOC components to the interpretation of biological VOC characteristics is a great improvement in this field, which would provide more abundant bio-information during biological metabolism. Owing to complicated biological VOC compositions, any single sampling or bio-information distillation method could not obtain complete biological VOCs and interpret the biological VOC characteristics, and would result in the loss of effective bio-information. The combination of some suitable sampling and bio-information distillation techniques for the study of biological VOCs and the related bio-information will be a novel trend in the future.     

Relaxed eddy accumulation,a new technique for measuring emission and deposition fluxes of volatile organic compounds by capillary gas chromatography and mass spectrometry

The possibility afforded by a new relaxed eddy accumulation system in the determination of emission and deposition fluxes of volatile organic compounds (VOCs) by chromatographic techniques will be presented. The system, especially designed to limit sampling artifacts, uses adsorption traps filled with solid sorbents as reservoirs for VOC collection. Enriched compounds were analyzed by capillary GC and positive identification and quantification of eluted compounds was Achieved by mass-spectrometric detection. The method has been used to quantify the emission and deposition of both biogenic and anthropogenic VOCs over a Mediterranean forest ecosystem located in Central Italy. For the first time, both daily and seasonal trends of anthropogenic and biogenic VOCs will be reported. The consistency of monoterpene fluxes with predictions based on the knowledge of VOC emission from the dominant vegetation species will be tested. Data have been used to develop a novel algorithm to predict the seasonality of biogenic emission from the forest ecosystem.     

热脱附-气相色谱-质谱法应用于工业源废气中挥发性有机物的目标和非目标筛查

建立了固相吸附热脱附-气相色谱-质谱(TD-GC-MS)综合筛查工业源废气中挥发性有机物(VOCs)的方法。对两种型号的固相吸附管进行了比较,最终选择使用Tenax SS TD Tubes吸附管。气体样品以恒定流速通过吸附管,富集分析物,经热脱附后,用GC-MS进行检测,目标化合物以内标法定量,非目标化合物的含量以甲苯的响应系数计算。方法检出限为1.06~5.44 ng,以采样体积300 mL计算,目标化合物的检出限为0.004~0.018 mg/m~3。吸附管平均加标回收率为78.4%~89.4%,相对标准偏差为3.9%~14.4%(n=7)。应用该方法对大连市某垃圾焚烧发电厂排放的废气进行VOCs目标及非目标化合物综合筛查,共检出29种VOCs,其中仅5种VOCs为预先设定的目标化合物,另外24种为非目标化合物,5种目标化合物含量仅占所有检出物总量的26.7%。证明了工业源废气VOCs分析中非目标化合物筛查的重要性,该研究思路对完整测定工业源挥发性有机污染物分布具有一定的借鉴意义。     

室内空气中挥发性有机化合物污染及检测方法

室内空气中挥发性有机污染物的释放严重影响了室内空气质量,本文较详细的叙述了这些有机污染物的来源、种类及处理方法等,并对空气中VOCs的采集和检测方法作以介绍,阐述了不同机制的热解吸仪与气相色谱联用时的优缺点及其应用．     

热脱附-气相色谱-三重四极杆串联质谱法测定环境空气中的挥发性有机物

采用热脱附(TD)结合气相色谱-三重四极杆串联质谱(GC-MS/MS)建立了环境空气中23种挥发性有机物(VOCs)同时检测的分析方法。空气样品通过主动采样的方式富集到装有Tenax-TA填料的热脱附管中,热解吸后在选择反应监测(SRM)模式下用GC-MS/MS进行检测,内标法定量。结果表明,23种VOCs在0.01~1 ng和1~100 ng低、高两个范围内线性关系良好,相关系数(r²)均大于0.99,方法定量限为0.00008~1 μ g/m³。加标水平为2、10和50 ng时,23种VOCs的平均回收率为77%~124%。除了最低加标水平的氯苯,相对标准偏差(RSD, n=6)均小于20%。对市内3个采样点的环境空气进行测定,其中苯、甲苯、乙苯、二甲苯、苯乙烯、1,2,4-三甲基苯和六氯丁二烯均有检出。实验证明,该TD和GC-MS/MS相结合的检测方法具有准确、可靠、灵敏度高等优点,适用于环境空气中VOCs的同时测定。     

A passive sampling-based analytical strategy for the determination of volatile organic compounds in the air of working areas

An analytical methodology based on the use of a polyethylene layflat tube filled with activated carbon and Florisil (ACFL-VERAM) was employed for the passive sampling of volatile organic compounds (VOCs) in the air of working areas of packing industries. VOCs amount in the ACFL-VERAM sampler was directly determined through head-space-gas chromatography-mass spectrometry (HS-GC-MS) allowing a direct determination in only 20 min without the need of any previous treatment. Uptake parameters, like sampling rate (R_S) and sampler-air partition coefficient (K_SA), were determined for every studied VOC from adsorption isotherm data. Additionally, experimental equations have been proposed to predict R_S and K_SA from the octanol-air partition coefficients reported in the literature. The proposed methodology reaches method detection levels from 0.007 to 0.2 mg m⁻³ for the studied VOCs.     

An automated monitoring system for VOC ozone precursors in ambient air: development,implementation and data analysis

An automated system for the monitoring of volatile organic compound (VOC) ozone precursors in ambient air is described. The measuring technique consists of subambient preconcentration on a cooled trap followed by thermal desorption and GC/FID analysis. First, the technical development, which permits detection limits below 0.05 ppbv to be reached, proceeded in two steps: (1) the determination of optimum sampling parameters (trap composition and conditioning, outlet split, desorption temperature); (2) the development of a reliable calibration method based on a highly accurate standard. Then, a 4-year field application of the hourly measuring chain was carried out at two urban sites. On the one hand, quality control procedures provided the best VOC identification (peak assignment) and quantification (reproducibility, blank system control). On the other hand, the success and performances of the routine experience (88% of the measurements covered more than 40 target compounds) indicated the high quality and suitability of the instrumentation which is actually applied in several French air quality monitoring networks. Finally, an example of data analysis is presented. Data handling identified important organic compound sources other than vehicle exhaust.     

Validation and modelling of a novel diffusive sampler for determining concentrations of volatile organic compounds in air

A novel diffusive sampler that combines radial and axial diffusion has been developed that improves upon existing commercially available designs. The POcket Diffusive (POD) sampler has been validated under laboratory and field conditions for the measurements of VOCs in ambient air. Laboratory tests varied sampling conditions of temperature (−30–40 C), humidity (10–80%), wind velocity (0.1–4 m s⁻¹), and concentration (0.5–50 μg m⁻³) for a number of specific VOCs. An overall uncertainty of circa 9% for the measurement of benzene is calculated for the validation tests, in compliance with the data quality objectives of the EU air quality directive 2008/50/EC. A semi-empirical diffusion model has been developed to estimate sampling rates for compounds that were not tested, and for conditions outside of tested ranges during validation. The diffusion model (and validation tests) shows a low influence of environmental conditions on the sampling rate for the POD sampler. Average reproducibility values of circa 3% are reported with overall sampling uncertainties ranging from 9% to 15%, for the whole range of tested conditions, depending on the compound. The adsorbent cartridge is compatible with existing thermal desorption systems in the market. The diffusive sampler can modify the sampling rate by changing the diffusive body within a range of different porosities. Field tests, conducted in parallel with independent quality controlled canister sampling, confirmed the ease of use and quality of VOC measurements with the POD sampler, for compounds that were, and were not, evaluated during laboratory tests.