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).     

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.     

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。     

On-site Comparison of Canister and Solid-Sorbent Trap Collection of Highly Volatile Hydrocarbons in Ambient Atmospheres

A field experiment for the comparison of the efficiency of canisters and adsorption multibed tubes for sampling atmospheric highly volatile hydrocarbons at ppbv levels is described. The canister was passivated by the Summa process and the adsorption tubes were filled with Carbotrap C, Carbotrap B and Carbosieve S-III. The sampling with the adsorption tubes was performed at ambient temperature and at -10°C. The highest concentrations were generally obtained with canisters but these results are very similar to those obtained with refrigerated multibed adsorption tubes. Both methods appear to be equivalent for most of the highly volatile hydrocarbons encountered in moderately polluted urban areas. In contrast, sampling with ambient temperature tubes provides lower concentrations. This study has also shown that K2CO3 drying efficiently removes humidity from air samples allowing the obtention of reliable concentration data on highly volatile hydrocarbons at ppbv levels. These drying tubes can easily be re-conditioned and tested for blanks and memory effects, which greatly facilitates the control of external contamination and sample cross-contamination.     

苏玛罐采样-GC-FID/MS同时测定环境空气中多种VOCs

采用苏玛罐采样-大气预浓缩仪结合气相冷柱箱与Deans Switch中心切割技术,将C2～C3组分切割至HP-PLOT/Q+PT柱,用FID检测器分析,其余组分通过DB-1柱子分离后进入质谱分析,实现1次进样同时测定环境空气中57种PAMS和65种TO-15.结果表明:108种VOCs在0.15 nmol/mol～8....     

环境空气中挥发性有机物监测技术细化研究

真空罐/气相色谱-质谱法是我国目前用于环境空气中挥发性有机物（VOCs）监测的主要方法。对该方法的采样前及采样环节的技术细节（包括流量控制器和过滤器的校准检查,采样罐的性能检查,样品的采集、运输及保存）,以及实验室分析环节的技术细节（包括色谱柱的选择,内标物的选择,湿度及气体稀释仪对分析结果的影响,标准曲线绘制方式和系统性能优劣的判断）进行讨论和分析。并针对以上技术细节提出解决方案和注意事项,以期为分析人员提供技术参考。     

Influence of Relative Humidity and Ozone on the Sampling of Volatile Organic Compounds on Carbotrap/Carbosieve Adsorbents

By using a dynamic dilution system, the atmospheric measurement of 11 selected toxics VOCs (ethylene, acetylene, propene, 1-butene, 1,3-butadiene, 1-pentene, 1-hexene, benzene, toluene, ethylbenzene, m+p-xylene) from the list WHO of 1996 and TO-14 method of US EPA by preconcentration by thermal desorption (TD), analysis by gas chromatography (GC), identification and quantification with a flame ionisation detector (FID) was developed and validated in term of metrology, especially the techniques of sampling of these VOCs with adsorbents cartridges "Air Toxics" when used with an "UMEG sampler" equipped in the inlet with a nafion membrane. In particular the influence of climatic conditions (temperature and relative humidity) and the influence of chemical factors like ozone, on the representativity of sampling were studied. Experiments made with various humidities showed that the addition of a nafion membrane in the inlet of the sampling system was required. Without this membrane, losses of compounds were observed for RH >50%. With this membrane, storage for 2 weeks in a refrigerator, as for canisters, did not induce a loss of compounds. No significative decrease of concentrations of the studied VOCs after 14 days storage, which are known to react with ozone, were observed with an ozone concentrations of 55 ppb. One explanation is that nafion membrane, placed in the inlet of the sampler, will neutralize ozone before entering the sampling tubes. This observation is in accordance with literature which states that the sampling of VOCs on Carbotrap cartridges without ozone scrubber induce a loss of compounds.     

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)).     

废气样品中甲烷的保存条件研究

气相色谱法检测废气中甲烷,样品保存容器可选择玻璃注射器、惰性气袋、真空瓶、苏码罐等,实验室对此做了比较研究。结果表明:玻璃注射器气密性较差,样品须在8 h内完成分析;真空瓶携带不方便,苏码罐价格昂贵,两者使用较少;使用玻璃注射器采集,然后注入惰性气袋保存的方法最佳,样品至少可稳定保存7d。     

气质联用法测定环境空气中有机硫化物

采用 SUMMA罐采集空气样品,在预浓缩系统中经3级冷阱捕集后,用气相色谱-质谱联用技术测定环境空气中7种痕量有机硫化物。对试验条件进行优化,使得甲硫醇、乙硫醇、甲硫醚、二硫化碳、噻吩、乙硫醚和二甲二硫醚等7种有机硫化物在21．47μg/m3～336．43μg/m3范围内线性良好。试验表明,7种有机硫化物的方法检出限为0．004μg/m3～0．036μg/m3;标准气体平行测定6次结果的 RSD为2．7％～6．2％,加标回收率为92．2％～97．5％。用该方法测定实际空气样品,并与傅立叶红外光谱法测定的结果进行比对,结果令人满意。     

Performance evaluation of a sorbent tube sampling method using short path thermal desorption for volatile organic compounds

Air sampling, using sorbents, thermal desorption and gas chromatography, is a versatile method for identifying and quantifying trace levels of volatile organic compounds (VOCs). Thermal desorption can provide high sensitivity, appropropriate choices of sorbents and method parameters can accommodate a wide range of compounds and high humidity, and automated short-path systems can minimize artifacts, losses and carry-over effects. This study evaluates the performance of a short-path thermal desorption method for 77 VOCs using laboratory and field tests and a dual sorbent system (Tenax GR, Carbosieve SIII). Laboratory tests showed that the method requirements for ambient air sampling were easily achieved for most compounds, e.g., using the average and standard deviation across target compounds, blank emissions were < or = 0.3 ng per sorbent tube for all target compounds except benzene, toluene and phenol; the method detection limit was 0.05 +/- 0.08 ppb, reproducibility was 12 +/- 6%, linearity, as the relative standard deviation of relative response factors, was 16 +/- 9%, desorption efficiency was 99 +/- 28%, samples stored for 1-6 weeks had recoveries of 87 +/- 9%, and high humidity samples had recoveries of 102 +/- 12%. Due to sorbent, column and detector characteristics, performance was somewhat poorer for phenol groups, ketones, and nitrogen containing compounds. The laboratory results were confirmed in an analysis of replicate samples collected in two field studies that sampled ambient air along roadways and indoor air in a large office building. Replicates collected under field conditions demonstrated good agreement except for very low concentrations or large (> 41 volume) samples of high humidity air. Overall, the method provides excellent performance and satisfactory throughput for many applications.     

生活垃圾填埋场空气中VOCs组成及年际变化

采用SUMMA罐采样-气相色谱-质谱法采集并分析了2006—2010年4、10月上海某生活垃圾填埋场及周边环境空气中挥发性有机物(VOCs)的种类和含量变化情况。结果表明,共检测出34种VOCs化合物,以单环芳烃、甲基乙基酮、卤代脂肪烃为主,其中19种化合物属于美国环保局重点控制的空气中有害污染物;填埋区作业面是填埋堆体内部VOCs释放的重要途径之一,其中甲基乙基酮、甲苯、乙苯、间/对-二甲苯对TVOCs质量浓度贡献率超过60%;生活垃圾填埋场及周边环境空气中TVOCs质量浓度年季变化较稳定,但同年度内秋季浓度高于春季。     

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.     

Assessing the risk to firefighters from chemical vapors and gases during vehicle fire suppression

Despite the frequent occurrence of vehicle fires, very few studies investigating firefighters' potential inhalation exposures during vehicle fire suppression have been conducted. In this paper, we present an assessment of firefighters' health risk from vehicle fire suppression that accounts for the mixture of gases and vapors likely to be found in these fires. Summa canisters were used to collect emissions from the engine and cabin fires of a single vehicle and were analyzed for 75 volatile organic compounds (VOCs). Firefighters' breathing zone concentrations (BZCs) of aromatic hydrocarbons, aldehydes, isocyanates, and carbon monoxide were measured during the suppression of three vehicle fires. The Summa canister and BZC data were used to develop a simple model for predicting BZCs for the compounds that were not measured in the firefighters' breathing zones. Hazard quotients (HQs) were calculated by dividing the predicted and measured BZCs by the most conservative short-term exposure limits (STELs) or ceiling limits. Hazard indices (HIs) were determined by adding HQs for compounds grouped by the target organ for acute health effects. Any HIs above unity represented unacceptable risks. According to this mixture analysis, the estimated 95(th) percentile of the exposure distribution for the study population represents ≥ 9.2 times the acceptable level of risk to the respiratory tract and eyes. Furthermore, chemicals known or reasonably anticipated to be human carcinogens contributed to > 45% of these HIs. While STELs are not usually based on carcinogenicity, maintaining exposures below STELs may protect individuals from the biological stress that could result from short-term exposures to carcinogens over time. Although vehicle fires are suppressed quickly (<10 min), this assessment suggests that firefighters have the potential to be overexposed to acute toxins during vehicle fire suppression and should therefore wear self-contained breathing apparatus at all times during vehicle fire response.     

Measurement and Interpretation of Concentrations of Urban Atmospheric Organic Compounds

The presence of volatile organic compounds (VOCs) from traffic and other sources in urban areas is a cause for concern about public health. Canister, chemical derivatisation, particulate sampling and adsorption sampling techniques were used to measure VOC concentrations of a wide range of compounds (C6-C40) during a four day campaign in south London with subsequent laboratory analysis of the samples. Compounds quantified included alkanes, mono- and poly-nuclear aromatic hydrocarbons. Also the first sequential measurements of carbonyl compounds (C1-C8) in a UK urban area are presented. Results from canister and adsorption sampling methods are compared. A comparison of the results with other urban data is presented and the temporal variations in VOC concentrations were interpreted with reference to the prevalent wind speeds and directions. The CALINE4 line source dispersion model was generally successful in reproducing the daytime 12 hour average concentrations of selected VOCs.     

Validation of a passive atmospheric deposition sampler for polybrominated diphenyl ethers

An atmospheric deposition sampler was validated with respect to polybrominated diphenyl ethers (PBDEs), a compound group that is widely used as flame retardants in many types of consumer products. The deposition sampler consists of an adsorption cartridge that is connected to a glass funnel. Extraction tests with spiked cartridges using soxhlet extraction with acetone revealed recoveries of >80% for all of the investigated PBDEs. Once adsorbed, PBDEs are stable, as proven by extractions of spiked cartridges that were stored outdoors and collected after different periods of time, up to 84 days. High recoveries indicate that degradation of adsorbed PBDEs does not play a role under realistic field conditions. Bulk deposition rates of PBDEs were determined in a field test with 3 replicates, and a possible breakthrough of target compounds was assessed in the field using a second adsorption cartridge in series. No breakthrough of target compounds could be observed within a sampling period of 61 days, and a bulk deposition rate of approximately 1 ng m(-2) day(-1) for the sum of all analysed PBDEs was measured. The highest deposition rates were measured for octa-brominated congeners, followed by BDEs 99, 183, 153, and 47. Overall, the sampler was successfully validated regarding the atmospheric deposition of PBDEs.     

基于SOA和O3生成潜势的上海市VOCs优控物种研究

为评估上海市挥发性有机物(VOCs)对二次有机气溶胶(SOA)和臭氧生成潜势的贡献,采用SUMMA罐采样实验室GC-FID/MS分析方法开展了环境空气104种臭氧前体物和TO-15组分分析,采用DNPH吸附管采样实验室HPLC高效液相色谱法开展了环境空气13种醛酮类组分分析。结果表明:2018年8-11月上海市代表点位VOCs摩尔分数均值范围为20. 61~50. 38 nmol/mol,臭氧生成潜势(OFP)均值范围为60. 55~184. 12μg/m^3,二次有机气溶胶生成潜势(AFP)为21. 63~61. 72μg/m^3。醛酮类和芳香烃类是OFP的主要贡献因子,贡献占比分别为31. 5%~55. 2%和21. 6%~37. 8%。芳香烃类对AFP贡献超过90%。从主要组分构成来看,城区人口密集区点位乙烷、丙烷浓度最高,其他点位甲醛浓度最高;甲醛对OFP贡献最大;间/对二甲苯在浦东书院点位AFP贡献最大,其他点位为甲苯。OFP和AFP双控物种各点位均有4~5个主要物种,以芳香烃类为主。     

Comparison of 24 h averaged VOC monitoring results for residential indoor and outdoor air using Carbopack X-filled diffusive samplers and active sampling--a pilot study

Analytical results obtained by thermal desorption GC/MS for 24 h diffusive sampling of 11 volatile organic compounds (VOCs) are compared with results of time-averaged active sampling at a known constant flow rate. Air samples were collected with co-located duplicate diffusive sampling tubes and one passivated canister. A total of eight multiple-component sampling events took place at fixed positions inside and outside three private homes. Subsequently, a known amount of sample air was transferred from the canister to an adsorbent tube for analysis by thermal desorption GC/MS. Results for the 11 most prevalent compounds--Freon 11, 1,3-butadiene, benzene, toluene, tetrachloroethene, ethylbenzene, m,p-xylene, o-xylene, 4-ethyltoluene, 1,3,5-trimethylbenzene, and p-dichlorobenzene--show that the ratio of average study values (diffusive sampling to active sampling) is 0.92 with 0.70 and 1.14 extreme ratios. Absolute percent difference for duplicate samples using diffusive sampling was <10% for the four most prevalent compounds. Agreement between the two sampling approaches indicates that the prediction of approximately constant diffusive sampling rates based on previous laboratory studies is valid under the field conditions.     

Atmospheric BTEX concentrations in the vicinity of the crude oil refinery of the Baltic region

Among chemical industries, petroleum refineries have been identified as large emitters of a wide variety of pollutants. Benzene, toluene, ethylbenzene, and xylene (BTEX) form an important group of aromatic volatile organic compounds (VOCs) because of their role in the troposphere chemistry and the risk posed to human health. A very large crude oil refinery of the Baltic States (200,000 bbl/day) is situated in the northern, rural part of Lithuania, 10 km from the town of Ma?eikiai (Lithuania). The objectives of this study were: (1) to determine of atmospheric levels of BTEX in the region rural and urban parts at the vicinity of the crude oil refinery; and (2) to investigate the effect of meteorological parameters (wind speed, wind direction, temperature, pressure, humidity) on the concentrations measured. The averaged concentration of benzene varied from 2.12 ppbv in the rural areas to 2.75 ppbv in the urban areas where the traffic was determined to be a dominant source of BTEX emissions. Our study showed that concentration of benzene, as strictly regulated air pollutant by EU Directive 2008/50/EC, did not exceed the limit of 5 ppbv in the region in the vicinity of the crude oil refinery during the investigated period. No significant change in air quality in the vicinity of the oil refinery was discovered, however, an impact of the industry on the background air quality was detected. The T/B ratio (0.50-0.81) that was much lower than 2.0, identified other sources of pollution than traffic.     

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.