室内空气中挥发性有机物采样方法进展

介绍了近年来室内空气中挥发性有机物的各种采样方法及适用范围，其中重点介绍了美国环保署最新版的TO－17方法和J.Pawliszyn发明的固相微萃取法（SPME），并对一系列的采样方法进行了比较，阐述了这些方法在国内外的应用及研究进展，同时讨论了这些方法的局限性。     

室内空气中挥发性有机物的释放特征分析

房屋装修后1周、1个月、3个月、6个月、12个月采集其室内空气样品进行甲醛、苯系物浓度的测定,分析释放规律;另选某处新居于装修后24 h、1周、1个月且密闭状态下采集室内空气中总挥发性有机化合物(TVOC)样品分析研究.结果表明,房屋装修后12个月内甲醛浓度随时间呈非线性递减,多项式回归方程为:y=0.277 13-0.199 72x+0.079 74x2-0.011 67x3+0.000 525 61x4,其中y为甲醛质量浓度,mg/m3;x为时间,月;各苯系物浓度也随时间呈逐渐下降趋势,且通过SPSS13.0软件进行Spearman相关性分析,发现各苯系物间显著相关;装修后不同时间段室内空气中TVOC组分发生变化,随着房屋封闭时间延长,TVOC浓度超标严重;TVOC组分的增多或减少是由于室内装修材料TVOC释放的增强或减弱,以及门窗缝隙所带来的微弱通风造成,无二次污染物的生成.     

活性炭吸附室内空气中挥发性有机化合物

活性炭吸附室内空气中挥发性有机化合物的１０％穿透时间与气相浓度及挥发性有机化合物的种类有关,通过对苯、甲苯和丙酮的实验研究,得出了由高浓度估算室内低浓度时炭床１０％穿透时间的经验公式ｔｂ,１＝ｔｂ,ｈ（Ｃ０,１／Ｃ０,ｈ）＾ａ,其中ａ值是与炭床性能及挥发性有机化合物种类有关的参数,可通过实验确定。     

二次热解吸-气相色谱-质谱分析室内挥发性有机化合物

采用二次热解吸-气相色谱.质谱法对室内空气进行了定量和定性分析,共检出挥发性有机物245种,包括烷烃、烯烃、芳香类化合物、卤代烃、醇、醛、酮、酯、醚等化合物,住宅类室内空气中挥发性有机化合物浓度平均值明显高于办公类室内这些物质的浓度平均值,对室内空气样品分析中的特例进行了可能的污染源解析,推测室内过量使用液体胶粘剂有可能是引起污染物严重超标的原因之一.     

室内环境中挥发性有机物释放过程的数学模型

根据组成结构,将室内环境中释放挥发性有机物(VOCs)的建筑装饰材料划分为单层干材料、单层湿材料、多层组合材料等类型,总结了这三种材料的VOCs释放特征、传输过程和数学模型研究现状,分析了模型的特点和适用范围,指出了模型研究发展的趋势,对应用中模型的选择提出了指导性建议.     

Photocatalytic oxidation of volatile organic compounds using fluorescent visible light

Photocatalytic oxidation (PCO) of volatile organic compounds (VOCs) is a highly attractive alternative technology for purification and deodorization of indoor air. The main objectives of this study were to demonstrate that a common fluorescent visible light (FVL) lamp can be used to effectively remove by PCO low concentrations of VOCs from slightly contaminated air and to provide some fundamental and technical details on the process. The target VOC was n-butanol, which is a standard reference odorant. Its PCO was studied under a long residence time in a 3.7-L cylindrical reactor with commercial titanium dioxide (TiO2) as the reference photocatalyst and using mostly FVL for illumination. For comparison only, a UV (black) light lamp was used. The gas-phase products were detected and quantified online by gas chromatography (GC). The effects of reactor residence time, of inlet concentration, and of the relative light intensity on the efficiency of the process were also evaluated. At a high n-butanol concentration (0.1 vol %), butanal and propanal were identified as the intermediate products of the process; ethanal appeared when the initial concentration was < or = 850 ppm(v). This indicates that PCO leading to CO2 and H2O is relatively slow and proceeds in a stepwise manner. Although the efficiency of the process with an FVL lamp was significantly lower than when using a UV black light, complete PCO of low concentrations was achieved for 100 ppm(v). In a search for a material with photoactivation extended to higher wavelengths or increased photoactivity, several samples of transition metal- or silver ion-doped (2 atomic %) TiO2 as well as SrTi(1-x-)Fe(x)O3 (x = 0.1 and 0.15) perovskites were included in the study. None of these materials was more active than pure TiO2. The results of this study open new horizons in the area of in door air quality (IAQ) control.     

Heterogeneous photocatalysis of aromatic and chlorinated volatile organic compounds (VOCs) for non-occupational indoor air application

The current study evaluated the technical feasibility of applying TiO2 photocatalysis to the removal of low-ppb concentrations of volatile organic compounds (VOCs) commonly associated with non-occupational indoor air quality issues. A series of experiments was conducted to evaluate five parameters (relative humidity (RH), hydraulic diameter (HD), feeding type (FT) for VOCs, photocatalytic oxidation (PCO) reactor material (RM), and inlet port size (IPS) of PCO reactor) in relation to the PCO destruction efficiencies of the selected target VOCs. None of the target VOCs exhibited any significant dependence on the RH, which is inconsistent with a previous study where, under conditions of low humidity and a ppm toluene inlet level, a drop in the PCO efficiency was reported with a decreasing humidity. However, the other four parameters (HD, RM, FT, and IPS) were found to be important for better VOC removal efficiencies as regards the application of TiO2 photocatalytic technology for cleansing non-occupational indoor air. The PCO destruction of VOCs at concentrations associated with non-occupational indoor air quality issues was up to nearly 100%, and the CO generated during PCO was a negligible addition to indoor CO levels. Accordingly, a PCO reactor would appear to be an important tool in the effort to improve non-occupational indoor air quality.     

Determination of organic compounds in indoor air with potential reference to air quality

Concentrations of 15 volatile organic compounds have been investigated in the air of two schoolrooms. The chemical analysis included enrichment on porous polymer beads, heat desorption and gas Chromatographic separation on a capillary column connected to either a flame ionization detector or a mass spectrometer. Samples were collected from the indoor air both in the presence and in the absence of the pupils (boys and girls, age 16–19) as well as from the ambient outdoor air. The qualitative composition of indoor and outdoor air was found to be about the same : aliphatic and aromatic hydrocarbons predominate, though indoors the number of compounds detected is larger and the concentrations are higher. Both the number and the concentration increase in the presence of humans. The mean concentrations of acetone and the sum of the concentrations of C₂-alkylbenzenes were 7.7 and 8.2 μg m⁻³ respectively in an unoccupied room and increased to 19.8 and 12.1 μg m⁻³ respectively in an occupied room.     

Joint representation of physical locations and volatile organic compounds in indoor air from a healthy and a sick building

Many modern, energy-efficient buildings have been labeled “sick”, in view of the fact that their occupants display an unusually large number of sensory symptoms (e.g. eye irritation, dry skin and perception of persistent odors). Air samples were taken from locations (17) in two Stockholm preschools, one considered healthy, the other, sick. The samples (170) were analyzed by gas chromatography/mass spectrometry (GC/MS) and 33 volatile organic compounds were identified and quantified by GC peak heights. The relationship between chemicals and locations in the two preschools was represented spatially by correspondence analysis and other statistical techniques. The analyses clearly distinguish among the buildings and among locations within each building, including whether the sample was collected outdoors or indoors. Within the sick preschool, concentrations of light aromatic hydrocarbons increased with distance from the air supply, but there was no similar gradient in the healthy preschool. The chief results obtained by the comparatively new method of correspondence analysis are supported further by a discriminant analysis and a principal components analysis.     

A sensitive diffusion sampler for the determination of volatile organic compounds in ambient air

We developed a diffusive sampling device (DSD-voc) for volatile organic compounds (VOCs) which is suitable for collection of low level VOCs and analysis with thermal desorption. This sampling device is composed of two parts, an exposure part made of a porous polytetrafluoroethylene (PTFE) filter, and an analysis part made of stainless-steel tubing. The DSD-voc collects VOCs through the mechanism of molecular diffusion. Collection is controlled by moving the adsorbent from the exposure part to the analysis part by changing the posture of the DSD-voc. Adsorbates in the DSD-voc were analyzed by GC/MS with a thermal desorption cold trap injector (TCT). The TCT has the advantage of being able to accept the entire quantity of VOCs. We connected a condenser between the DSD-voc and the trap tube to prevent moisture from freezing in the trap tube when the sampler was packed with strong adsorbent. We also examined the desorption efficiency for VOCs from several types of adsorbents (Carboxen^TM 1000, Carbosieve^TM G, Carbosieve S III, Carbotrap^TM B, and activated carbon) over a wide range of temperatures. Carboxen 1000 was suitable for the determination of VOCs with a low boiling point range, from CFC12 to hexane, while Carbotrap B was suitable for VOCs from hexane to 1,4-dichlorobenzene. The limits of detection with Carboxen 1000 and Carbotrap B were 0.036–0.046 and 0.0035–0.014 ppb, respectively, for a sampling duration of 24 h. Coefficients of variation for concentrations of major VOCs ranged from 3.8 to 14%. It is possible to estimate atmospheric VOCs at sub-parts per billion (sub-ppb), with high sensitivity, by using both adsorbents in combination.     

室内空气净化技术

概述了室内空气污染的类型 ,全面介绍了目前各种室内空气净化技术及其进展 ,并且分析了各技术的优缺点。此外 ,提出将膜分离与光催化技术相结合 ,能克服当前各种技术的局限性的构想。这一组合技术可能成为今后该领域研究的一个重要方向     

室内空气总挥发性有机物检测的热解吸参数优化

总挥发性有机物(TVOC)是评价室内空气质量最重要的指标。为了提高TVOC检测的准确度,选取解吸气流量、热解吸温度、进样时间和热解吸时间四项因素设计正交实验,以热解吸率作为指标,对TVOC的热解吸过程进行了优化。并讨论在优化后参数的控制下,TVOC各组分的检测准确度。实验结果表明,优化的热解吸条件下各参数指标分别为解吸气流量40 mL/min、热解吸温度280℃、进样时间120 s、热解吸时间30 s。检测准确度的结果表明,在优化热解吸参数的控制下,各组分的回收率在90.3%～97.3%之间,满足TVOC的实际检测需求。     

Measurements of air–surface exchange rates of volatile organic compounds

Vertical gradients of volatile organic compounds (VOCs) were measured over a maize field and a soybean field in 1995 and 1996, respectively, in the Lower Coastal Plains of North Carolina. The measurements over the maize field were conducted in its early growth period, during May 1995, and the measurements over the soybean field were conducted in its middle and later growth periods during July through August 1996 at the same location. These measurements were combined with micrometeorological flux measurements to determine emission flux measurements for various VOCs. This measurement programme was part of project NOVA (Natural emissions of Oxidant precursors: Validation of techniques and Assessment) to estimate the flux of VOCs. Methanol was identified as the major biogenic compound for both years with the average flux of 3450 ± 1456 µg/m²/hr over maize and 3079 ± 2766 µg/m²/hr over soybean. Acetone is another compound that was identified as a biogenic compound for both years with the average flux of 425 ± 223 µg/m²/hr over maize and 2701 ± 1710 µg/m²/hr over soybean. In addition to biogenic compounds, a large number of aromatic compounds, including styrene and 1,2,4-trimethylbenzene, were also identified as emissions from the ground over the soybean field.     

Dynamic air sampling of volatile organic compounds using solid phase microextraction

A new dynamic air sampling system was devised and evaluated in conjunction with solid phase microextraction (SPME) fiber materials for extracting odor-causing volatile organic compounds (VOCs) present in swine building environments. Utilizing a standard solution consisting of 11 compounds (i.e., volatile fatty acids, indoles, and phenol), sampling times, volumes, and flow rates were adjusted to establish optimal extraction conditions. Results indicated that the sampling system was effective with the Carboxen/Polydimethylsiloxane (CAR/PDMS) fiber in extracting all 11 standard compounds. The best sampling conditions for the extraction were a 100-mL sampling vial subjected to a continuous flow of 100 mL/min for 60 min. The gas chromatographic analysis showed that the reproducibility was within acceptable ranges for all compounds (RSD=4.24-17.26% by peak areas). In addition, field tests revealed that the sampling system was capable of detecting over 60 VOCs in a swine house whose major components were identified by gas chromatography-mass spectrometry (GC-MS) and by their retention times as volatile fatty acids, phenols, indole, and skatole. The field tests also showed that considerably different levels of VOCs were present in various parts of the swine building.     

Assessment of indoor levels of volatile organic compounds and carbon dioxide in schools in Kuwait

Indoor air quality (IAQ) in schools is a matter of concern because children are most vulnerable and sensitive to pollutant exposure. Conservation of energy at the expense of ventilation in heating, ventilation, and air conditioning (HVAC) systems adversely affects IAQ. Extensive use of new materials in building, fitting, and refurbishing emit various pollutants such that the indoor environment creates its own discomfort and health risks. Various schools in Kuwait were selected to assess their IAQ. Comprehensive measurements of volatile organic compounds (VOCs) consisting of 72 organic compounds consisting of aliphatic (C₃–C₆), aromatic (C₆–C₉), halogenated (C₁–C₇), and oxygenated (C₂–C₉) functional groups in indoor air were made for the first time in schools in Kuwait. The concentrations of indoor air pollutants revealed hot spots (science preparation rooms, science laboratories, arts and crafts classes/paint rooms, and woodworking shops/decoration rooms where local sources contributed to the buildup of pollutants in each school. The most abundant VOC pollutant was chlorodifluoromethane (R22; ClF₂CH), which leaked from air conditioning (AC) systems due to improper operation and maintenance. The other copious VOCs were alcohols and acetone at different locations due to improper handling of the chemicals and their excessive uses as solvents. Indoor carbon dioxide (CO₂) levels were measured, and these levels reflected the performance of HVAC systems; a specific rate or lack of ventilation affected the IAQ. Recommendations are proposed to mitigate the buildup of indoor air pollutants at school sites.

Implications: Indoor air quality in elementary schools has been a subject of extreme importance due to susceptibility and sensibility of children to air pollutants. The schools were selected based on their surrounding environment especially downwind direction from the highly industrialized zone in Kuwait. Extensive sampling from different sites in four schools for comprehensive VOCs and CO₂ were completed for an extended period of over a year. Different hot spots were identified where leaked refrigerant and inadequate handling of laboratory solvents contributed to the high VOCs in the respective locations. CO₂ levels reflected HVAC performance and poor ventilation. A list of recommendations has been proposed to eradicate these high levels of air pollution.     

Vertical and diurnal characterization of volatile organic compounds in ambient air in urban areas

More than half of the world's population lives in cities, and their populations are rapidly increasing. Information on vertical and diurnal characterizations of volatile organic compounds (VOCs) in urban areas with heavy ambient air pollution can help further understand the impact of ambient VOCs on the local urban environment. This study characterized vertical and diurnal variations in VOCs at 2, 13, 32, 58, and 111 m during four daily time periods (7:00 to 9:00 a.m., 12:00 to 2:00 p.m., 5:00 to 7:00 p.m., and 11:00 p.m. to 1:00 a.m.) at the upwind of a high-rise building in downtown, Kaohsiung City, Taiwan. The study used gas chromatography-mass spectrometry to analyze air samples collected by silica-coated canisters. The vertical distributions of ambient VOC profiles showed that VOCs tended to decrease at greater heights. However, VOC levels were found to be higher at 13 m than at ground level at midnight from 11:00 p.m. to 1:00 a.m. and higher at 32 than 13 m between 7:00 and 9:00 a.m. These observations suggest that vertical dispersion and dilution of airborne pollutants could be jointly affected by local meteorological conditions and the proximity of pollution sources. The maximum concentration of VOCs was recorded during the morning rush hours from 7:00 to 9:00 a.m., followed by rush hours from 5:00 to 7:00 p.m., hours from 12:00 to 2:00 p.m., and hours from 11:00 p.m. to 1:00 a.m., indicating that the most VOC compounds in urban air originate from traffic and transportation emissions. The benzene-toluene-ethyl benzene-xylene (BTEX) source analysis shows that BTEX at all heights were mostly associated with vehicle transportation activities on the ground.     

The validation of a passive sampler for indoor and outdoor concentrations of volatile organic compounds

Volatile organics compounds (VOCs) are ubiquitous in the air we breathe. The use of passive samplers to measure these concentrations can be an effective technique. When exposed for long durations, a passive sampler may be a good tool for investigating chronic exposures to chemicals in the environment. A passive sampler that was designed for occupational exposures can be used as such a tool. Laboratory validation under as many conditions as possible needs to be accomplished so as to characterize the sampler with known parameters. This paper describes the methods and results of an investigation into the validity of using a passive monitor to sample VOCs for a three-week period. Two concentration levels, two relative humidities, and five VOCs were studied. Results indicate that the samplers work best under conditions of high concentration with low relative humidity and low concentration with high relative humidity. For the passive sampler, excluding chloroform, percent deviations from the predicted values varied between -41 and +22 percent; while the values between the passive and the active samplers varied between -27 and +24 percent. Benzene, heptane, and perchloroethylene were sampled with equal precision and accuracy.     

Photocatalytic degradation of volatile organic compounds at the gas-solid interface of a TiO2 photocatalyst

In the present work, photocatalytic degradation of volatile organic compounds including gas-phase trichloroethylene (TCE), acetone, methanol and toluene over illuminated TiO2 was closely examined in a batch photoreactor as a function of water vapor, molecular oxygen and reaction temperature. Water vapor enhanced the photocatalytic degradation rate of toluene, but was inhibitive for acetone, and, there was an optimum water vapor concentration in the TCE and methanol removal. In a nitrogen atmosphere, it showed lower photocatalytic degradation rate than in air and pure oxygen. Thus, it could be concluded that oxygen is an essential component in photocatalytic reactions by trapping photogenerated electrons on the semiconductor surface and by decreasing the recombination of electrons and holes. As for the influence of reaction temperature, it was found that photocatalytic degradation was more effective at a moderate temperature than at an elevated temperature for each compound.     

Nonvolatile,semivolatile, or volatile: Redefining volatile for volatile organic compounds

Although widely used in air quality regulatory frameworks, the term “volatile organic compound” (VOC) is poorly defined. Numerous standardized tests are currently used in regulations to determine VOC content (and thus volatility), but in many cases the tests do not agree with each other, nor do they always accurately represent actual evaporation rates under ambient conditions. The parameters (time, temperature, reference material, column polarity, etc.) used in the definitions and the associated test methods were created without a significant evaluation of volatilization characteristics in real world settings. Not only do these differences lead to varying VOC content results, but occasionally they conflict with one another. An ambient evaporation study of selected compounds and a few formulated products was conducted and the results were compared to several current VOC test methodologies: SCAQMD Method 313 (M313), ASTM Standard Test Method E 1868-10 (E1868), and U.S. EPA Reference Method 24 (M24). The ambient evaporation study showed a definite distinction between nonvolatile, semivolatile, and volatile compounds. Some low vapor pressure (LVP) solvents, currently considered exempt as VOCs by some methods, volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents they are meant to replace. Conversely, bio-based and heavy hydrocarbons did not readily volatilize, though they often are calculated as VOCs in some traditional test methods. The study suggests that regulatory standards should be reevaluated to more accurately reflect real-world emission from the use of VOC containing products.

Implications:The definition of VOC in current test methods may lead to regulations that exclude otherwise viable alternatives or allow substitutions of chemicals that may limit the environmental benefits sought in the regulation. A study was conducted to examine volatility of several compounds and a few formulated products under several current VOC test methodologies and ambient evaporation. This paper provides ample evidence to warrant a reevaluation of regulatory standards and provides a framework for progressive developments based on reasonable and scientifically justifiable definitions of VOCs.     

Nonpoint sources of volatile organic compounds in urban areas-relative importance of land surfaces and air

Volatile organic compounds (VOCs) commonly detected in urban waters across the United States include gasoline-related compounds (e.g. toluene, xylene) and chlorinated compounds (e.g. chloroform, tetrachloroethane [PCE], trichloroethene [TCE]). Statistical analysis of observational data and results of modeling the partitioning of VOCs between air and water suggest that urban land surfaces are the primary nonpoint source of most VOCs. Urban air is a secondary nonpoint source, but could be an important source of the gasoline oxygenate methyl-tert butyl ether (MTBE). Surface waters in urban areas would most effectively be protected by controlling land-surface sources.