Long-term measurement of volatile organic compounds in ambient air by canister-based one-week sampling method

A canister-based 1 week sampling method using a mechanical flow controller and a 6 L fused-silica-lined canister was evaluated for the long-term measurement of 47 VOCs in ambient air at pptv (volume/volume) to ppbv levels by use of a three-stage preconcentation method followed by GC-MS analysis. The GC conditions were initially optimized for complete separations of several pptv-level VOCs (e.g. vinyl chloride, 1,3-butadiene, acrylonitrile, 1,2-dichloroethane and chloroform) in ambient air because the selected ions are easily interfered with by coexisting C4-, C5-hydrocarbons and analytes presented at ppbv levels. Thirty-four VOCs determined by the 1 week and 24 h sampling method in December 16-22 (2002) had concentrations of 6.0-15000 pptv per compound. Concentrations of 28 VOCs (including polar VOCs (e.g. methyl isobutyl ketone and butyl acetate)) obtained by the method were approximately equal to the mean values calculated from 24 h sampling (< +/- 10% deviation). Six VOCs that had low concentrations of 6.0-43 pptv showed more than +/- 10% deviation. Thirteen VOCs were not detected during the entire sampling period. The effect of relative humidity or ozone for the specific VOCs (e.g. MIBK, butyl acetate, vinyl chloride, 1,3-butadiene and styrene) was negligible.     

Development and comparison of methods using MS scan and selective ion monitoring modes for a wide range of airborne VOCs

Adsorbent sampling with analysis by thermal desorption, gas chromatography and mass spectrometry (TD/GC/MS) offers many advantages for volatile organic compounds (VOCs) and thus is increasingly used in many applications. For environmental samples and other complex mixtures, the MS detector typically is operated in the scan mode to aid identification of co-eluting compounds. However, scan mode does not achieve the optimal sensitivity, thus compounds occurring at low concentrations may not be detected. This paper develops and evaluates the application of a more sensitive TD/GC/MS method using selective ion monitoring (SIM) that is applicable to VOC mixtures found in ambient and indoor air. Based on toxicity and prevalence, 94 VOCs (including terpenes, aromatic, halogenated and aliphatic compounds) were selected as target compounds. Two analytical methods were developed: a conventional full scan method for ions from 29 to 270 m/z; and a SIM method using 16 time windows and different ions selected for the compounds in each window. Both methods used the same Tenax GR adsorbent sampling tubes, TD and GC parameters, and target and qualifier ions. Laboratory tests determined calibrations, method detection limits (MDLs), precisions, recoveries and storage stability. Field tests compared scan and SIM mode analyses for duplicate samples of indoor air in 51 houses and outdoor air at 41 sites. Statistical analyses included the development of error/precision models. The laboratory tests showed that most compounds demonstrated excellent precision (<10% for concentrations exceeding approximately 0.5 microg m(-3)), good linearity, near identical calibrations for scan and SIM modes, a wide dynamic range (up to 1500 microg m(-3)), and negligible storage losses after 1 month (7 compounds showed moderate losses). SIM mode MDLs ranged from 0.004 to 0.27 microg m(-3), representing a modest (1.1 to 22-fold) improvement compared to scan mode. However, in field tests the SIM method detected significantly more compounds (e.g., styrene and chloroform). Error models fit most compounds and allow quantification of errors at selected percentiles. Overall, while the new SIM method is somewhat time-consuming to develop, it offers greater sensitivity and maintains the high selectivity of traditional scan methods.     

Evaluation of a fluorometric method for measuring low concentrations of ammonia in ambient air

A fluorometric method developed for measuring low concentrations of ammonium in marine and freshwater ecosystems was adapted for the analysis of ammonia in ambient air. The modified method entails collection of samples on an acid-treated solid adsorbent followed by analysis using a fluorometer. Optimal results were obtained using a commercially available sorbent tube containing 100 mg of acid-treated silica gel for sample collection, and an analytical protocol consisting of sample desorption in DI water, addition of orthopthaldialdehyde (OPA) working reagent, and room temperature incubation. Method accuracy and precision were evaluated by comparing experimentally determined quantities of ammonia to expected levels for sample loadings ranging from 0.16 [micro sign]g to 550 [micro sign]g-accuracy was generally within +/-20%. The estimated LOQ for the method is 0.08 [micro sign]g ammonia per sample which represents a 25-375-fold improvement in sensitivity compared to current NIOSH and OSHA methods for the measurement of ammonia in ambient air. The new method should be useful for applications requiring measurement of low concentrations of ammonia using personal sampling equipment or in the characterization of short-term fluctuations of ammonia concentrations in air.     

超低沸点挥发性有机物测定中的要点分析

采用大气浓缩仪-气相色谱法测定超低沸点挥发性有机物乙烷、乙烯、丙烷、丙烯、乙炔,选用PLOT-Q柱分析,控制真空罐内相对湿度约50%,通过优化测定条件使方法线性良好,5种低沸点化合物的检出限为0.08 nmol/mol～0.2 nmol/mol,样品保存时间不超过10 d。用该方法测定某地区环境空气中VOCs,结果检出率均为100%。     

Ambient level volatile organic compound (VOC) monitoring using solid adsorbents--recent US EPA studies

Ambient air spiked with 1-10 ppbv concentrations of 41 toxic volatile organic compounds (VOCs) listed in US Environmental Protection Agency (EPA) Compendium Method TO-14A was monitored using solid sorbents for sample collection and a Varian Saturn 2000 ion trap mass spectrometer for analysis. The adsorbent was a combination of graphitic carbon and a Carboxen-type carbon molecular sieve. The method detection limits (MDLs) for 11 samples were typically 0.5 parts per billion by volume (ppbv) and lower except for bromomethane and chloromethane, both of which exhibited breakthrough. Thirty-day sample storage on the sorbents resulted in less than a 20% change for most compounds, and water management was required for humid samples to avoid major anomalous decreases in response during analyses. The adsorbent-based system, a system using canister-based monitoring, and a semi-continuous automated GC/MS (autoGC) monitoring system with a Tenax GR/Carbotrap B/Carbosieve S-III adsorbent preconcentrator were compared using spiked ozone concentrations as a variable. In this comparison, the target compounds included a number of n-aldehydes as well as those listed in TO-14A. The effects of ozone on the TO-14A compounds were relatively minor with the exception of negative artifacts noted for styrene and 1,1,2,2-tetrachloroethane. However, a small, systematic decrease in response was evident for a number of aromatic VOCs and 1,1,2,2-tetrachloroethane when ozone was increased from 50 to 300 ppbv. Method averages for multiple runs under the same conditions were typically within +0.25 ppbv of their mean for most compounds. For n-aldehydes, strong positive artifacts using the autoGC preconcentrator and strong negative artifacts for the canister-based and carbon sorbent approaches caused major disagreement among methods. These artifacts were mostly eliminated by using MnO2 ozone scrubbers, although loss of the n-aldehydes for all methods occurred after a single sample collection of 1 h duration, apparently due to the interaction of the n-aldehydes and products of the O3, MnO2 reaction on the scrubber.     

油田周边环境典型敏感区大气挥发性有机物特征

采用苏玛罐采样-超低温预浓缩气相色谱质谱联用方法,开展油田特征VOCs成分的分析工作.通过对某油田生产开发区及周边环境敏感区环境空气的持续监测,发现油田特征VOCs的整体扩散规律,低温、温度骤降以及高湿度环境极不利于VOCs扩散,对特征VOCs成分解析并核算其光化学反应特征,明确了臭氧生成潜势,研究表明烷烃及苯系物对臭...     

24 h diffusive sampling of toxic VOCs in air onto Carbopack X solid adsorbent followed by thermal desorption/GC/MS analysis-laboratory studies

Diffusive sampling of a mixture of 42 volatile organic compounds (VOCs) in humidified, purified air onto the solid adsorbent Carbopack X was evaluated under controlled laboratory conditions. The evaluation included variations in sample air temperature, relative humidity and ozone concentration. Linearity of samples with loading was examined both for a constant concentration with time varied up to 24 h and for different concentrations over 24 h. Reverse diffusion and its increase with accumulation of sample were determined for all compounds. Tubes were examined for blank levels, change of blanks with storage time, and variability of blanks. Method detection limits were determined based on seven replicate samples. Based on this evaluation, 27 VOCs were selected for quantitative monitoring in the concentration range from approximately 0.1 to 4 ppbv. Comparison results of active and diffusive samples taken over 24 h and under the same simulated ambient conditions at a constant 2 ppbv were interpreted to estimate the effective diffusive sampling rates (ml min(-1)) and their uncertainties and to calculate the corresponding diffusive uptake rates (ng ppmv(-1) min(-1)).     

Volatile Organic Compounds: Sampling Methods and Their Worldwide Profile in Ambient Air

The atmosphere is a particularly difficult analytical system because of the very low levels of substances to be analysed, sharp variations in pollutant levels with time and location, differences in wind, temperature and humidity. This makes the selection of an efficient sampling technique for air analysis a key step to reliable results. Generally, methods for volatile organic compounds sampling include collection of the whole air or preconcentration of samples on adsorbents. All the methods vary from each other according to the sampling technique, type of sorbent, method of extraction and identification technique. In this review paper we discuss various important aspects for sampling of volatile organic compounds by the widely used and advanced sampling methods. Characteristics of various adsorbents used for VOCs sampling are also described. Furthermore, this paper makes an effort to comprehensively review the concentration levels of volatile organic compounds along with the methodology used for analysis, in major cities of the world.     

Stabilities of 58 volatile organic compounds in fused-silica-lined and SUMMA polished canisters under various humidified conditions

Fused-silica-lined (FSL) canisters and SUMMA polished (SUMMA) canisters were compared for the recoveries and the stabilities of 58 volatile organic compounds (VOCs) at low ppbv (volume/volume) levels under various humidified conditions using a three-stage preconcentration method followed by GC-MS analysis. The target VOCs included non-polar VOCs (e.g. halogenated hydrocarbons and aromatic hydrocarbons) and polar VOCs (e.g. alcohols, ketones, esters, ethers, nitriles and thiols). The three-stage preconcentration method was initially optimized for simultaneous analysis of non-polar and polar VOCs because determination of canister stability is dependent on the accuracy of analytical measurements. The method showed good linearity over the concentration range from 1 to 25 ppbv for all target analytes, and the correlation coefficients were higher than 0.9974. The method detection limits ranged from 0.023 to 0.39 ppbv. The test mixtures loaded in both type of canisters (n = 3) had concentrations of 1.7-2.5 ppbv per compound at ambient pressure under various humidified conditions (%RH = 1.6, 8.0, 27, 39, 53 and >99% with excess water present). All canister samples were initially analyzed on day 0 (after 6-12 h). The effect of competitive adsorption of water vapor and polar VOCs on active sites of interior surface was remarkably observed for SUMMA canisters. Polar VOCs had a greater requirement for water vapor to be present. The RH percentages that ensured good recovery on day 0 were RH > 8% for non-polar VOCs and RH > 27% for polar VOCs (except alcohols under the condition of RH > 99%). All thiols were not recovered from SUMMA canisters under all conditions. FSL canisters showed good recoveries of more than 86% for all VOCs under all conditions on day 0 (except alcohols under the condition of RH > 99%). The recoveries of alcohols in both canisters under the condition of RH > 99% displayed relatively low recoveries in the range 25-76% because of the partitioning effect into condensed water. The canister samples under the conditions of RH 8.0, 27, 53 and > 99% were analyzed for the stability test on days 3, 7, 14 and 28 after loading. All non-polar VOCs were reasonably stable in the FSL canisters under all examined conditions over 28 days. However, several polar VOCs that have relatively lower vapor pressure, e.g. MIBK, butyl acetate and alcohols except ethanol, showed unstable characteristics under relatively dry conditions (RH 8 and 27%) during 28 days. RH > 53% was needed to ensure good stabilities of all analytes except thiols with the recoveries of > 80% over 28 days for both canisters. Although the FSL canister showed good recoveries of more than 86% for thiols on day 0, drastic degradations were observed after day 3 and they were not detected after day 14.     

Indoor/ambient residential air toxics results in rural western Montana

Indoor and ambient concentrations of 21 volatile organic compounds (including 14 hazardous air pollutants) were measured in the homes of nearly 80 western Montana (Missoula) high school students as part of the 'Air Toxics Under the Big Sky' program during the 2004/2005 and 2005/2006 school years. Target analytes were measured using low flow air sampling pumps and sorbent tubes, with analysis of the exposed samples by thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS). The results reported here present the findings of the first indoor/ambient air toxics monitoring program conducted in a semi-rural valley location located in the Northern Rocky Mountain/Western Montana region. Of all of the air toxics quantified in this study, toluene was found to be the most abundant compound in both the indoor and ambient environments during each of the two school years. Indoor log-transformed mean concentrations were found to be higher when compared with ambient log-transformed mean concentrations at P < 0.001 for the majority of the compounds, supporting the results of previous studies conducted in urban areas. For the air toxics consistently measured throughout this program, concentrations were approximately six times higher inside the student's homes compared to those simultaneously measured directly outside their homes. For the majority of the compounds, there were no significant correlations between indoor and ambient concentrations.     

环境空气VOCs在线监测中标准气体的比对研究

环境空气中挥发性有机物(VOCs)的在线监测技术近年来受到普遍关注.相对于传统的离线手工监测,在线监测能够解决监测数据时空代表性不足的问题,同时更好地满足环境质量连续监测和研究的需要.现有环境空气常规气体在线监测技术规范对量值溯源有较高的要求,其中标准气体的溯源和比对是质量控制和质量保证的根本.通过构建上海市环境空气V...     

SUMMA罐采样-GC/MS法测定吸烟室内空气中挥发性有机物

采用空气预浓缩与气相色谱/质谱联用技术对空气中59种痕量挥发性有机化合物进行定性与定量分析,应用研究的技术对吸烟室烟草空气中的挥发性有机物成分定性解析,对59种常见挥发性有机污染物定量检测.室内环境烟草空气中检出多种挥发性有机污染物,主要有烯烃、烷烃、苯系物等有害成分,不仅对被动吸烟人群造成危害,同时也影响大气环境质量...     

“罐采样-实验室分析”测定环境空气中117种挥发性有机物要点分析

“罐采样-实验室分析”是当前测定环境空气中挥发性有机物的主流方法。结合已有资料,针对方法涉及的采样、样品运输与保存、分析测试等环节,考察了环境空气中挥发性有机物监测的主要影响因素。罐选择、清洁度、气密性、惰性化是样品保存的先决条件;采样流量控制器的气密性、流量校准等是保证监测准确的基本要素;温度变化对样品保存产生影响;标准气体的湿度、配置平衡时间、保存时间、配制准确性和内标气体的保存时间等会导致校准和溯源产生偏差。样品中的水分及二氧化碳是分析过程中影响监测结果准确性的干扰因素,实验室有机溶剂也会干扰分析的准确性。     

VOCs在线监测系统与SUMMA罐采样-气质联用法的比对分析

将挥发性有机污染物在线监测系统与实验室内SUMMA罐采样气质联用法(GC-MS)的挥发性有机物分析进行了标准气体和实际空气样品的分析比对,并对偏差原因作分析,提出在线监测系统的维护建议。结果表明,挥发性有机物在线监测系统的监测结果与实验室方法有一定的可比性,可用于大气中挥发性有机污染物的在线监测。     

Background concentrations of individual and total volatile organic compounds in residential indoor air of Schleswig-Holstein, Germany

During a monitoring campaign concentrations of volatile organic compounds (VOCs) were measured in indoor air of 79 dwellings where occupants had not complained about health problems or unpleasant odour. Parameters monitored were the individual concentration of 68 VOCs and the total concentration of all VOCs inside the room. VOCs adsorbed by Tenax TA were then analysed by means of thermal desorption, gas chromatography and mass spectrometry. The analytical procedure and quantification was done according to the recommendation of the ECA-IAQ Working Group 13 which gave a definition of the total volatile organic compound (TVOC) concentration. Using this recommendation TVOC-concentrations ranged between 33 and 1600 microg m(-3) with a median of 289 microg m(-3). Compounds found in every sample and with the highest concentrations were 2-propanol, alpha-pinene and toluene. Save for a few samples, all concentrations measured have been a factor 2 to 10 lower, compared to data from similar studies. Only a few terpenes and aldehydes were found exceeding published reference data or odour threshold concentrations. However, it has been found that sampling and analysing methods do have a considerable impact on the results, making direct comparisons of studies somewhat questionable. 47% of all samples revealed concentrations exceeding the threshold value of 300 microg TVOC m(-3) set by the German Federal Environmental Agency as a target for indoor air quality. Using the TVOC concentration as defined in the ECA-IAQ methodology is instrumental in assessing exposure to VOCs and identifying sources of VOCs. The background concentrations determined in this study can be used to discuss and interpret target values for individual and total volatile organic compounds in indoor air.     

Evaluation of the effect of different sampling time periods and ambient air pollutant concentrations on the performance of the Radiello diffusive sampler for the analysis of VOCs by TD-GC/MS

The effect of different sampling exposure times and ambient air pollutant concentrations on the performance of Radiello? samplers for analysis of volatile organic compounds (VOCs) is evaluated. Quadruplicate samples of Radiello? passive tubes were taken for 3, 4, 7 and 14 days. Samples were taken indoors during February and March 2010 and outdoors during July 2010 in La Canonja (Tarragona, Spain). The analysis was performed by automatic thermal desorption (ATD) coupled with capillary gas chromatography (GC)/mass spectrometry detection (MS). The results show significant differences (t-test, p < 0.05) between the amounts of VOCs obtained from the sum of two short sampling periods and a single equivalent longer sampling period for 65% of all the data. 17% of the results show significantly larger amounts of pollutant in the sum of two short sampling periods. Back diffusion due to changes in concentrations together with saturation and competitive effects between the compounds during longer sampling periods could be responsible for these differences. The other 48% of the results that are different show significantly larger amounts in the single equivalent longer sampling period. The remaining 35% of the results do not show significant differences. Although significant differences are observed in the amount of several VOCs collected over two shorter sampling intervals compared to the amount collected during a single equivalent longer sampling period, the ratios obtained are very close to unity (between 0.7 and 1.2 in 75% of cases). We conclude that Radiello? passive samplers are useful tools if their limitations are taken into account and the manufacturer's recommendations are followed.     

列车车厢内装材料VOCs释放特性研究

列车车厢内的空气质量对乘客的健康和乘坐舒适度有明显影响.密闭车厢的内装材料所释放的挥发性有机物(VOCs)是影响车厢内环境空气质量的主要污染物.为研究25G型客车车厢内空气VOCs浓度的分布机理及扩散规律,采用环境测试舱法和扫描电镜(SEM)表征,对车厢主要内装材料(座椅坐垫、PVC地板、墙板等)的VOCs释放速率进行...     

Development and validation of methods for environmental monitoring of cyclophosphamide in workplaces

Methods to monitor contamination of workplaces with antineoplastic drugs have been developed and validated. Cyclophosphamide (CP) was used as a model compound as it is one of the most commonly used antineoplastic drugs. A wipe sampling method to detect contamination with CP at surfaces was developed. A personal air sampling method to sample gas and vapour on solid sorbent tubes and particles with filters was also developed. Wipe and filter samples were extracted and sorbent samples were eluted, all with ethyl acetate. The samples were analysed with liquid chromatography tandem mass spectrometry. (2)H(6)-labelled cyclophosphamide was used as an internal standard. The between-day precision was 2-5% for wipe samples, 4-6% for sorbent samples and 3-8% for filter samples. The limit of detection was 0.02 ng CP per sample for the wipe and filter methods and 0.03 ng CP per sample for the solid sorbent method. Wipe sampling on surfaces made of different materials resulted in mean recoveries between 78-106%. The desorption recovery was between 97-102% for the wipe samples, 97% for the sorbent samples and 101% for the filter samples. Samples were stable for up to 2 months at 5 degrees C and -20 degrees C and for about 2 d at room temperature. The developed methods were applied to the measurement of contamination with CP in a hospital pharmacy. Trace amounts of CP, 1.3 and 1.4 ng, were detected on surfaces in the pharmacy.     

Characterizations of volatile organic compounds during high ozone episodes in Beijing,China

Air samples were collected in Beijing from June through August 2008, and concentrations of volatile organic compounds (VOCs) in those samples are here discussed. This sampling was performed to increase understanding of the distributions of their compositions, illustrate the overall characteristics of different classes of VOCs, assess the ages of air masses, and apportion sources of VOCs using principal compound analysis/absolute principal component scores (PCA/APCS). During the sampling periods, the relative abundance of the four classes of VOCs as determined by the concentration-based method was different from that determined by the reactivity approach. Alkanes were found to be most abundant (44.3–50.1%) by the concentration-based method, but aromatic compounds were most abundant (38.2–44.5%) by the reactivity approach. Aromatics and alkenes contributed most (73–84%) to the ozone formation potential. Toluene was the most abundant compound (11.8–12.7%) during every sampling period. When the maximum incremental reactivity approach was used, propene, toluene, m,p-xylene, 1-butene, and 1,2,4-trimethylbenzene were the five most abundant compounds during two sampling periods. X/B, T/B, and E/B ratios in this study were lower than those found in other cities, possibly due to the aging of the air mass at this site. Four components were extracted from application of PCA to the data. It was found that the contribution of vehicle exhaust to total VOCs accounted for 53% of VOCs, while emissions due to the solvent use contributed 33% of the total VOCs. Industrial sources contributed 3% and biogenic sources contributed 11%. The results showed that vehicle exhausts (i.e., unburned vehicle emissions + vehicle internal engine combustion) were dominant in VOC emissions during the experimental period. The solvent use made the second most significant contribution to ambient VOCs.     

吹扫捕集-气相色谱质谱法分析土壤和沉积物中挥发性有机物

采用吹扫捕集-气相色谱质谱法对土壤和沉积物中挥发性有机物进行分析,优化了实验条件,所有物质的相对标准偏差小于5.0％,土壤样回收率在78.2％ ～99.8％之间,沉积物样的回收率在55.2％～95.2％之间.