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.     

Measuring partition and diffusion coefficients for volatile organic compounds in vinyl flooring

Interactions between volatile organic compounds (VOCs) and vinyl flooring (VF), a relatively homogenous, diffusion-controlled building material, were characterized. The sorption/desorption behavior of VF was investigated using single-component and binary systems of seven common VOCs ranging in molecular weight from n-butanol to n-pentadecane. The simultaneous sorption of VOCs and water vapor by VF was also investigated. Rapid determination of the material/air partition coefficient (K) and the material-phase diffusion coefficient (D) for each VOC was achieved by placing thin VF slabs in a dynamic microbalance and subjecting them to controlled sorption/desorption cycles. K and D are shown to be independent of concentration for all of the VOCs and water vapor. For the four alkane VOCs studied, K correlates well with vapor pressure and D correlates well with molecular weight, providing a means to estimate these parameters for other alkane VOCs. While the simultaneous sorption of a binary mixture of VOCs is non-competitive, the presence of water vapor increases the uptake of VOCs by VF. This approach can be applied to other diffusion-controlled materials and should facilitate the prediction of their source/sink behavior using physically-based models.     

An experimental investigation of incremental reactivities of volatile organic compounds

California has adopted a set of VOC reactivity factors for regulatory purposes that is based on a model of the ozone formation process. These incremental reactivity factors (derived by Carter) describe the amount of ozone each exhaust VOC will form under a certain set of conditions in an urban atmosphere. The main objective of this study is to measure reactivity factors using smog chamber experiments, and to compare the measurements to the Carter factors. A new facility was constructed explicitly for this study. The facility has four identical smog chambers and a temperature-controlled enclosure for the chambers. The chambers are irradiated using a set of filtered xenon arc lamps to approximate “sunlight”. The reactivities of 14 individual VOCs representative of those found in automobile exhaust and several mixtures of VOCs have been measured. The measured and Carter-reactivity factors were highly correlated, suggesting that the chemical model used by Carter accounts for the reactivities of a wide range of compounds with dramatically different uncertainties in their mechanisms. The measured results, in general, are consistent with the Carter-reactivity factors for comparing the relative reactivities of VOCs in the atmosphere. However, additional kinetic and mechanistic studies of many VOC species including aromatic isomers are needed to improve reactivity scales.     

The diffusion and sorption of volatile organic compounds through kaolinitic clayey soils

Laboratory experiments to estimate the effective molecular diffusion coefficient (D(e)) and sorption coefficient (K(d)) for volatile organic compounds through natural clayey soils were conducted using diffusion testing apparatus. The compounds tested were methyl ethyl ketone (MEK), toluene and trichloroethylene (TCE). The D(e) and K(d) values were determined by a curve fitting procedure. The compound losses, and the effects of porous disks used in the apparatus were significant. The transport of MEK was faster than that of TCE and toluene because of the lower sorption to the soils. The D(e) values of all the compounds were of the order of 10(-10) m(2)/s and smaller than the diffusion coefficient in pure aqueous solution at infinite dilution (D(0)), due to the tortuosity of the samples. The effects of the sample thickness on the parameter determination were not significant. Comparison to the K(d) values estimated from batch sorption tests and from organic carbon content (f(oc))-based predictions showed that the diffusion test results were intermediate between those from the other two methods. The diffusion tests use compacted soil samples and should be more relevant to in situ conditions, but the reliability of the tests is affected by large compound losses that cause uncertainties in their interpretation. It is recommended that more than one method be used to assess K(d) values.     

吸附浓缩-催化燃烧工艺处理低浓度大风量有机废气

对已运行的有机废气治理工程运行情况的进行分析研究,并对采用吸附浓缩-催化燃烧工艺处理低浓度大风量的有机废气工程中的各项数据进行监测,得出其最佳条件为:吸附时间18 h,空床气速0.8 m/s,吸附容量1.9%;解吸温度100~120℃,解吸时间4 h。该工程实例的监测结果表明,催化燃烧的TVOC去除效率保持在99%以上,同时,该工艺对废气中甲苯、二甲苯和TVOC的总去除率分别能达到98.3%、99.6%和97.7%。     

Cyclodextrin-based supramolecular low melting mixtures: efficient absorbents for volatile organic compounds abatement

Environmental Science and Pollution Research - Cyclodextrins (CDs) and deep eutectic solvents (DESs) are emerging absorbent materials for the removal of volatile organic compounds (VOCs). In this...     

我国挥发性有机污染地块调查评估中存在的问题及对策建议

基于多年研究和实践经验,总结了我国挥发性有机污染地块调查评估方面存在的6个问题。从科学机制角度,通过分析实际地块案例,阐述了产生这些问题的原因。最后,针对这6方面的问题分别提出了改进建议,以期为我国VOCs类污染地块调查评估和修复治理提供参考。     

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.     

Lysis of cyanobacteria with volatile organic compounds

One of bacteria collected from Lake Sagami, Japan, Brevibacillus sp., was found to have a lytic activity of cyanobacteria, but did not produce active compounds. Instead, the co-culturing of Microcystis with the Brevibacillus sp. enhanced the production of two volatile compounds, beta-cyclocitral and 3-methyl-1-butanol, and the former had a characteristic lytic activity. It was confirmed that these volatile compounds were derived from the cyanobacteria themselves. beta-Ionone, geosmin and 2-methylisoborneol derived from cyanobacteria and similar volatile compounds, terpenoids, produced by plants also had a lytic activity. The minimum inhibitory concentration values of the cyanobacterial metabolites were estimated to be higher than those of compounds from plants except for a few compounds. Among them, beta-cyclocitral only produced a characteristic color change of culture broth from green to blue. This color change is similar to the phenomenon observed when a sudden decline in growth of cyanobacteria begins in a natural environment.     

Microwave plasma conversion of volatile organic compounds

A microwave-induced, steam/Ar/O2, plasma "torch" was operated at atmospheric pressure to determine the feasibility of destroying volatile organic compounds (VOCs) of concern. The plasma process can be coupled with adsorbent technology by providing steam as the fluid carrier for desorbing the VOCs from an adsorbent. Hence, N2 can be excluded by using a relatively inexpensive carrier gas, and thermal formation of oxides of nitrogen (NOx) is avoided in the plasma. The objectives of the study were to evaluate the technical feasibility of destroying VOCs from gas streams by using a commercially available microwave plasma torch and to examine whether significant byproducts were produced. Trichloroethene (TCE) and toluene (TOL) were added as representative VOCs of interest to a flow that contained Ar as a carrier gas in addition to O2 and steam. The O2 was necessary to ensure that undesirable byproducts were not formed in the process. Microwave power applied at 500-600 W was found to be sufficient to achieve the destruction of the test compounds, down to the detection limits of the gas chromatograph that was used in the analysis. Samples of the postmicrowave gases were collected on sorbent tubes for the analysis of dioxins and other byproducts. No hazardous byproducts were detected when sufficient O2 was added to the flow. The destruction efficiency at a fixed microwave power improved with the addition of steam to the flow that passed through the torch.     

Simultaneous passive sampling of volatile organic compounds

In this paper, the results obtained in the simultaneous passive sampling of toluene, hexane, methyl ethyl ketone and ethyl acetate on activated charcoal are presented and compared with results obtained when the compounds were tested individually. Any observed deviations in the sampling rate are possibly due to the variations in the adsorption efficiency or in the coefficients of desorption caused by the presence of more than one adsorbate, though in all cases the values obtained are within the accepted margins recommended by NIOSH     

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.     

Partition of volatile organic compounds in activated sludge and wastewater

The Henry's law constant is important in the gas-liquid mass transfer process. Apparent dimensionless Henry's law constant, or the gas-liquid partition coefficient (K'H), for both hydrophilic (methanol, isopropyl alcohol, and acetone) and hydrophobic (toluene and p-xylene) organic compounds in deionized (DI) water, a wastewater with a maximum total dissolved organic carbon (DOC) content of 700 mg/L, and DI water mixed with a maximum activated sludge suspended solid (SS) concentration of 40,000 mg/L were measured using the single equilibrium technique at 293 K. Experimental results demonstrate that the K'H of any of the test volatile organic compounds varied among three situations. First, the K'H of the hydrophilic compounds in mixed liquor with the maximum SS concentration was 9-21% higher than those in DI water. Second, those for toluene and p-xylene were 77% and 93% lower, respectively, in the mixed liquor with the maximum SS concentration. Third, the K'H values of all of the test compounds in the wastewater were only 10% lower than those in DI water. A model was developed to relate K'H with wastewater DOC and the SS concentration in the activated sludge using an organic carbon-water partition coefficient and activated sludge-water partition coefficient as model parameters. The model was verified and model parameters for test compounds estimated.     

Solubility of volatile organic compounds in aqueous ammonia solution

The Ostwald solubility coefficient, L of 17 volatile organic compounds (VOCs) from the gas phase into water and dilute aqueous ammonia solutions was determined by the equilibrium partitioning in closed system-solid phase micro extraction (EPICS-SPME) method at 303 K and at 0-2.5 mol dm(-3) ammonia concentrations. Ammonia increased the solubility of all VOCs nearly linearly, but to a different extent. The difference in the solubility values in aqueous ammonia solutions (Lmix) compared to pure water (L) is explained on the basis of a Linear Solvation Energy Relationship (LSER) equation made applicable for solvent mixtures, logLmix - logL = x((sNH3 - sH2O)pi2H + (aNH3 - aH2O)Sigma2H + (bNH3 - bH2O)Sigmabeta2H + (vNH3 - VH2O)Vx). sNH3 - sH2O, aNH3 - aH2O, bNH3 - bH2O, vNH3 - vH2O are the differences of solvent parameters, x is the mole fraction, pi2H is the solute dipolarity-polarizability, Sigmaalpha2H is the effective hydrogen bond acidity of the solute, Sigmabeta2H is the effective hydrogen bond basicity of the solute and Vx, the McGowan characteristic volume. The most significant term was v, the phase hydrophobicity. The solubility behavior was explained by the change in structure of the aqueous solution: the presence of ammonia reduces the cavity effect. These findings show that the presence of compounds such as ammonia, frequently observed in environmental waters, especially wastewaters, affect the fugacity of VOCs, having consequences for the environmental partitioning of VOCs and having technical consequences towards wastewater treatment technologies.     

Measuring concentrations of volatile organic compounds in vinyl flooring

The initial solid-phase concentration of volatile organic compounds (VOCs) is a key parameter influencing the emission characteristics of many indoor materials. Solid-phase measurements are typically made using solvent extraction or thermal headspace analysis. The high temperatures and chemical solvents associated with these methods can modify the physical structure of polymeric materials and, consequently, affect mass transfer characteristics. To measure solid-phase concentrations under conditions resembling those in which the material would be installed in an indoor environment, a new technique was developed for measuring VOC concentrations in vinyl flooring (VF) and similar materials. A 0.09-m2 section of new VF was punched randomly to produce -200 0.78-cm2 disks. The disks were milled to a powder at -140 degrees C to simultaneously homogenize the material and reduce the diffusion path length without loss of VOCs. VOCs were extracted from the VF particles at room temperature by fluidized-bed desorption (FBD) and by direct thermal desorption (DTD) at elevated temperatures. The VOCs in the extraction gas from FBD and DTD were collected on sorbent tubes and analyzed by gas chromatography/mass spectrometry (GC/MS). Seven VOCs emitted by VF were quantified. Concentration measurements by FBD ranged from 5.1 microg/g VF for n-hexadecane to 130 microg/g VF for phenol. Concentrations measured by DTD were higher than concentrations measured by FBD. Differences between FBD and DTD results may be explained using free-volume and dual-mobility sorption theory, but further research is necessary to more completely characterize the complex nature of a diffusant in a polymer matrix.     

Comparison of methods for determination of volatile organic compounds in drinking water

Comparison of four methods including liquid-liquid extraction (LLE), direct aqueous injection (DAI), purge and trap (PAT) and head space (HS) were carried out in this work for determination of volatile organic compounds (VOCs) including trihalomethanes (THMs) in drinking water. This comparison is made especially to show the advantages and disadvantages and specifically the different detection limits (DL) that can be obtained for a given type of analysis. LLE is applicable only for determination of the THMs concentrations, while DAI, PAT, HS methods with different DL each of them are applicable for all VOCs, with PAT to be the most sensitive. Sampling apparatus and procedure for all these methods except of PAT are very simple and easy, but possible disadvantages for LLE and DAI are the low sensitivity and especially the detection only of THMs with LLE.     

Qualitative analysis of volatile organic compounds on biochar

Qualitative identification of sorbed volatile organic compounds (VOCs) on biochar was conducted by headspace thermal desorption coupled to capillary gas chromatographic-mass spectrometry. VOCs may have a mechanistic role influencing plant and microbial responses to biochar amendments, since VOCs can directly inhibit/stimulate microbial and plant processes. Over 70 biochars encompassing a variety of parent feedstocks and manufacturing processes were evaluated and were observed to possess diverse sorbed VOC composition. There were over 140 individual chemical compounds thermally desorbed from some biochars, with hydrothermal carbonization (HTC) and fast pyrolysis biochars typically possessing the greatest number of sorbed volatiles. In contrast, gasification, thermal or chemical processed biochars, soil kiln mound, and open pit biochars possessed low to non-detectable levels of VOCs. Slow pyrolysis biochars were highly variable in terms of their sorbed VOC content. There were no clear feedstock dependencies to the sorbed VOC composition, suggesting a stronger linkage with biochar production conditions coupled to post-production handling and processing. Lower pyrolytic temperatures (?350 °C) produced biochars with sorbed VOCs consisting of short carbon chain aldehydes, furans and ketones; elevated temperature biochars (>350 °C) typically were dominated by sorbed aromatic compounds and longer carbon chain hydrocarbons. The presence of oxygen during pyrolysis also reduced sorbed VOCs. These compositional results suggest that sorbed VOCs are highly variable and that their chemical dissimilarity could play a role in the wide variety of plant and soil microbial responses to biochar soil amendment noted in the literature. This variability in VOC composition may argue for VOC characterization before land application to predict possible agroecosystem effects.     

Speciation of volatile organic compounds from poultry production

Volatile organic compounds (VOCs) emitted from poultry production are leading source of air quality problems. However, little is known about the speciation and levels of VOCs from poultry production. The objective of this study was the speciation of VOCs from a poultry facility using evacuated canisters and sorbent tubes. Samples were taken during active poultry production cycle and between production cycles. Levels of VOCs were highest in areas with birds and the compounds in those areas had a higher percentage of polar compounds (89%) compared to aliphatic hydrocarbons (2.2%). In areas without birds, levels of VOCs were 1/3 those with birds present and compounds had a higher total percentage of aliphatic hydrocarbons (25%). Of the VOCs quantified in this study, no single sampling method was capable of quantifying more than 55% of compounds and in several sections of the building each sampling method quantified less than 50% of the quantifiable VOCs. Key classes of chemicals quantified using evacuated canisters included both alcohols and ketones, while sorbent tube samples included volatile fatty acids and ketones. The top five compounds made up close to 70% of VOCs and included: 1) acetic acid (830.1 μg m^?3); 2) 2,3-butanedione (680.6 μg m^?3); 3) methanol (195.8 μg m^?3); 4) acetone (104.6 μg m^?3); and 5) ethanol (101.9 μg m^?3). Location variations for top five compounds averaged 49.5% in each section of the building and averaged 87% for the entire building.     

Multiple microbial activities for volatile organic compounds reduction by biofiltration

In the northeast of Italy, high volatile organic carbon (VOC) emissions originate from small-medium companies producing furniture. In these conditions it is difficult to propose a single, efficient, and economic system to reduce pollution. Among the various choices, the biofiltration method could be a good solution, because microbial populations possess multiple VOC degradation potentials used to oxidize these compounds to CO2. Starting from the air emissions of a typical industrial wood-painting plant, a series of experiments studied in vitro microbial degradation of each individual VOC. Isolated strains were then added to a laboratory-scale biofiltration apparatus filled with an organic matrix, and the different VOC behavior demonstrated the potential of single and/or synergic microbial removal actions. When a single substrate was fed, the removal efficiency of a Pseudomonas aeruginosa inoculated reactor was 1.1, 1.17, and 0.33 g m(-3) hr(-1), respectively, for xylene, toluene, and ethoxy propyl acetate. A VOC mixture composed of butyl acetate, ethyl acetate, diacetin alcohol, ethoxy propanol acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, and xylene was then fed into a 2-m(3) reactor treating 100 m3 hr(-1) of contaminated air. The reactor was filled with the same mixture of organic matrix, enriched with all of the isolated strains together. During reactor study, different VOC loading rates were used, and the behavior was evaluated continuously. After a short acclimation period, the removal efficiency was > 65% at VOC load of 150-200 g m(-3) hr(-1). Quantification of removal efficiencies and VOC speciation confirmed the relationship among removal efficiencies, compound biodegradability, and the dynamic transport of each mixture component within the organic matrix. Samples of the fixed bed were withdrawn at different intervals and the heterogeneous microbial community evaluated for both total and differential compound counts.