Field sampling method for quantifying odorants in humid environments

Most air quality studies in agricultural environments use thermal desorption analysis for quantifying semivolatile organic compounds (SVOCs) associated with odor. The objective of this study was to develop a robust sampling technique for measuring SVOCs in humid environments. Test atmospheres were generated at ambient temperatures (23 +/- 1.5 degrees C) and 25, 50, and 80% relative humidity (RH). Sorbent material used included Tenax, graphitized carbon, and carbon molecular sieve (CMS). Sorbent tubes were challenged with 2, 4, 8, 12, and 24 L of air at various RHs. Sorbent tubes with CMS material performed poorly at both 50 and 80% RH dueto excessive sorption of water. Heating of CMS tubes during sampling or dry-purging of CMS tubes post sampling effectively reduced water sorption with heating of tubes being preferred due to the higher recovery and reproducibility. Tenaxtubes had breakthrough of the more volatile compounds and tended to form artifacts with increasing volumes of air sampled. Graphitized carbon sorbent tubes containing Carbopack X and Carbopack C performed best with quantitative recovery of all compounds at all RHs and sampling volumes tested. The graphitized carbon tubes were taken to the field for further testing. Field samples taken from inside swine feeding operations showed that butanoic acid, 4-methylphenol, 4-ethylphenol, indole, and 3-methylindole were the compounds detected most often above their odor threshold values. Field samples taken from a poultry facility demonstrated that butanoic acid, 3-methylbutanoic acid, and 4-methylphenol were the compounds above their odor threshold values detected most often, relative humidity, CAFO, VOC, SVOC, thermal desorption, swine, poultry, air quality, odor.     

Full-scale chamber investigation and simulation of air freshener emissions in the presence of ozone

Volatile organic compound (VOC) emissions from one electrical plug-in type of pine-scented air freshener and their reactions with O3 were investigated in the U.S. Environmental Protection Agency indoor air research large chamber facility. Ozone was generated from a device marketed as an ozone generator air cleaner. Ozone and oxides of nitrogen concentrations and chamber conditions such as temperature, relative humidity, pressure, and air exchange rate were controlled and/or monitored. VOC emissions and some of the reaction products were identified and quantified. Source emission models were developed to predict the time/concentration profiles of the major VOCs (limonene, alpha-pinene, beta-pinene, 3-carene, camphene, benzyl propionate, benzyl alcohol, bornyl acetate, isobornyl acetate, and benzaldehyde) emitted bythe air freshener. Gas-phase reactions of VOCs from the air freshener with O3 were simulated by a photochemical kinetics simulation system using VOC reaction mechanisms and rate constants adopted from the literature. The concentration-time predictions were in good agreement with the data for O3 and VOCs emitted from the air freshener and with some of the primary reaction products. Systematic differences between the predictions and the experimental results were found for some species. Poor understanding of secondary reactions and heterogeneous chemistry in the chamber is the likely cause of these differences. The method has the potential to provide data to predict the impact of O3/VOC interactions on indoor air quality.     

Kinetic analysis of competition between aerosol particle removal and generation by ionization air purifiers

Ionization air purifiers are increasingly used to remove aerosol particles from indoor air. However, certain ionization air purifiers also emit ozone. Reactions between the emitted ozone and unsaturated volatile organic compounds (VOC) commonly found in indoor air produce additional respirable aerosol particles in the ultrafine (<0.1 microm) and fine (<2.5 microm) size domains. A simple kinetic model is used to analyze the competition between the removal and generation of particulate matter by ionization air purifiers under conditions of a typical residential building. This model predicts that certain widely used ionization air purifiers may actually increase the mass concentration of fine and ultrafine particulates in the presence of common unsaturated VOC, such as limonene contained in many household cleaning products. This prediction is supported by an explicit observation of ultrafine particle nucleation events caused by the addition of D-limonene to a ventilated office room equipped with a common ionization air purifier.     

Novel method for enhancing the destruction of environmental pollutants by the combination of multiple plasma discharges

A novel, multistage, dielectric, packed-bed, plasma reactor has been developed and is used to efficiently destroy environmental pollutants, such as volatile organic compounds (VOCs). A three cell plasma reactor, operated at ambient pressure and low temperatures, is found to be an effective technology for complete VOC remediation in air. The combination of plasma cells in series can significantly improve the efficiency of VOC decomposition, but the combined destruction rate is not simply an additive effect, there is a synergistic enhancement related to the effect on the plasma chemistry of sequential processing in the three cells. At the same time, the formation of byproduct such as NOx is strongly suppressed, and it is possible to remediate toluene and ethylene in air, with no detectable formation of NOx or nitric acid.     

Applications of pore-expanded mesoporous silica. 7. Adsorption of volatile organic compounds

Three different varieties of mesoporous silicas were synthesized by varying the postsynthesis treatment of an as-synthesized ordered mesoporous material type MCM-41. The resulting materials consisted of a purely siliceous MCM-41, a pore-expanded MCM-41 (PE-MCM-41C), and a surfactant-laden pore-expanded MCM-41 (PE-MCM-41E) and were evaluated as adsorbents for two types of volatile organic compounds, i.e., chlorinated and aromatic hydrocarbons. Values of heat of adsorption and Henry's law constant were determined by pulse chromatography. Additionally, adsorption capacities were calculated with a dynamic method using breakthrough curves for single components in dry and humid environments. The surfactant-containing material exhibited good compatibility with chlorinated compounds in terms of heat of adsorption and efficiency in gaseous streams containing moisture. Purely siliceous mesoporous materials, i.e., MCM-41 and PE-MCM-41C, were more selective toward aromatic hydrocarbons but also gave rise to exceptionally strong adsorption.     

Distribution of volatile organic compounds over a semiconductor Industrial Park in Taiwan

This study examined volatile organic compounds (VOC) concentration in ambient air collected during the years 2000--2003 at several different locations of Hsinchu Science-based Industrial Park (HSIP) in Taiwan. A canister automated GC-MS system analyzed the volatile organics in ambient air grasp samples according to T0-15 method. Oxygenated volatiles were the most abundant VOC detected in HSIP followed by aromatics that are commonly used as solvents in the semiconductor industries. The major components measured in the ambient air are 2-propanol (29-135 ppbv), acetone (12-164 ppbv), benzene (0.7-1.7 ppbv), and toluene (13-20 ppbv). At some of the sampling locations, odorous compounds such as carbon disulfide and dimethyl sulfide levels exceed threshold values. The estimated toluene/benzene ratio is very high at most of the sites. However, the total amount of VOC is reduced over the years from 2000 to 2003 due to strict implementation on use and discharge of solvents in industries. There exists no definite seasonal pattern for sporadic occurrence of high levels of some of the volatile organics. Stagnant weather conditions with low wind speeds aid accumulation of toxic species at ground level. The results entail that hi-tech semiconductor industries are still a potential source for harmful organic substances to surrounding microenvironment.     

Halogenated volatile organic compounds from the use of chlorine-bleach-containing household products

Sodium hypochlorite (NaOCl) and many organic chemicals contained in household cleaning products may react to generate halogenated volatile organic compounds (VOCs). Halogenated VOC emissions from eight different chlorine bleach containing household products (pure and diluted) were investigated by headspace experiments. Chloroform and carbon tetrachloride were the leading compounds along with several halogenated compounds in the headspace of chlorine bleach products. One of the most surprising results was the presence of carbon tetrachloride (a probable human carcinogen and a powerful greenhouse gas that was banned for household use by the U.S. Food and Drug Administration) in very high concentrations (up to 101 mg m(-3)). By mixing surfactants or soap with NaOCl, it was shown that the formation of carbon tetrachloride and several other halogenated VOCs is possible. In addition to quantitatively determined halogenated VOCs (n = 15), several nitrogen-containing (n = 4), chlorinated (n = 10), oxygenated compounds (n = 22), and hydrocarbons (n = 14) were identified in the headspace of bleach products. Among these, 1,1-dichlorobutane and 2-chloro-2-nitropropane were the most abundant chlorinated VOCs, whereas trichloronitromethane and hexachloroethane were the most frequently detected ones. Indoor air halogenated VOC concentrations resulting from the use of four selected household products were also measured before, during, and 30 min after bathroom, kitchen, and floor cleaning applications. Chloroform (2.9-24.6 microg m(-3)) and carbon tetrachloride (0.25-459 microg m(-3)) concentrations significantly increased during the use of bleach containing products. During/ before concentration ratios ranged between 8 and 52 (25 +/- 14, average +/- SD) for chloroform and 1-1170 (146 +/- 367, average +/- SD) for carbon tetrachloride, respectively. These results indicated that the bleach use can be important in terms of inhalation exposure to carbon tetrachloride, chloroform and several other halogenated VOCs.     

VOC sorption and diffusion behavior of building materials

In this study 25 different building materials often used in timber constructions (wood based panels, gypsum boards, vapor barriers, adhesive tapes, insulation materials and sealants) were investigated with regard to their adsorption, desorption and diffusion behaviour towards volatile organic compounds (VOC). The materials were exposed to four, respectively five selected VOCs typically found in indoor air: hexanal, butyl acetate, p-xylene, nonane and α-pinene. Adsorption and desorption properties were investigated under static conditions, whereas the diffusion behavior was examined in a 0.225 m³ emission chamber with an air exchange rate of 1 h^?1. The results of the experiments indicate that some building products have a high potential to reduce VOCs in indoor air. Apart from the vapor barriers, two insulating materials and one plasterboard, all tested materials represented an adsorption efficiency of about 50 % or higher related to the injected VOC standards. Materials with high adsorption capacity bound substances strongly and desorbed them less, whereas less adsorbing materials acted inversely. The obtained results indicate that material properties and processing play a considerable role in diffusion behavior of building materials.     

Ozone modulation of volatile hydrocarbons using membrane introduction mass spectrometry

A new method that we describe as chemical modulation of volatile hydrocarbons is investigated using ozonolysis pretreatment and membrane introduction mass spectrometry (MIMS). This extension to the MIMS technique is intended to enhance the selectivity of MIMS for measuring hydrocarbons in the complex mixtures often encountered in polluted air samples. The test samples for this study were dilute (parts per billion by volume, ppbv) two-component hydrocarbon mixtures in synthetic air. Ozone reacted to completely suppress the MIMS signal from beta-pinene in a mixture of toluene and beta-pinene and the MIMS signal from cyclohexene in a mixture of cyclohexene and cyclohexane. As expected, the ozone reaction produced little attenuation of the MIMS signal from toluene and cyclohexane in the test mixtures. The basis of the method is that the products of the ozonolysis, which is rapid for alkenes, are polar compounds that are excluded by the membrane used here, as confirmed in this study. Since the modulation only affects unsaturated hydrocarbons (and other similar organic compounds), the method can be used to aid in quantitative analysis of volatile hydrocarbon compounds in air samples for air pollution monitoring.     

Changes in landfill gas quality as a result of controlled air injection

Air addition has been proposed as a technique for rapid stabilization of municipal solid waste (MSW) in landfills. The objective of this study was to observe the change in concentration of trace constituents of landfill gas in response to air addition. Air injection tests were conducted at a MSW landfill in Florida, and the concentrations of several gaseous constituents at adjacent wells within the waste were measured. The concentrations of methane, carbon dioxide, and oxygen, as well as several trace constituents, were measured both prior to and during air addition. The trace components investigated included a suite of volatile organic compounds (VOCs), nitrous oxide (N20), carbon monoxide (CO), and hydrogen sulfide (H2S). A significant increase in CO was observed in 9 of 14 monitoring points; overall, CO concentrations were found to increase as the ratio of CH4 to CO2 decreased. A significant decrease in H2S was observed at 6 of 14 monitoring points. Air injection did not have a noticeable affect on VOC or N2O concentrations compared to initial levels.     

不同气调包装对醉虾贮藏品质的影响

研究了40%CO2+60%N2和100%CO2的气调包装以及真空和空气包装4种包装方式对贮藏醉虾菌落总数、理化指标和感官指标的影响。结果表明:相对于真空和空气包装组,100%CO2或40%CO2+60%N2的气体包装,对醉虾的保鲜效果较好,其样品的菌落总数和挥发性盐基氮含量较低,质地和色泽变化较小,感官评分较高。但由于100%CO2包装随着贮藏时间的延长,气体收缩较明显导致产品包装外观不理想,40%CO2+60%N2的混合气体包装更适合于醉虾的贮藏。     

Source proximity and outdoor-residential VOC concentrations: results from the RIOPA study

Ambient volatile organic compound concentrations outside residences were measured in Elizabeth, New Jersey as part of the Relationship of Indoor, Outdoor, and Personal A:r (RIOPA) study to assess the influence of proximity of the residences to known ambient emissions sources. The closest distances between the outdoor samplers and emission sources were determined using Geographic Information Systems (GIS)techniques. Multiple regression models were developed for residential ambient concentrations of aromatic hydrocarbons (BTEX), methyl tert butyl ether (MTBE), and tetrachloroethylene (PCE). The natural log transformed ambient concentrations of BTEX were inversely associated with distances to major roadways with high traffic densities and gasoline stations, atmospheric stability, temperature, and wind speed. Ambient MTBE levels were associated with inverse distance to gas stations and interstate highways. Residential ambient PCE concentration was inversely associated with distance to dry cleaning facilities, atmospheric stability, temperature, wind speed, and relative humidity. The linear regression models that include proximity to emission sources and meteorological variables explained 16-45% of the overall variation of ambient residential VOC concentrations. Meteorological conditions, especially atmospheric stability and temperature, explained 60-90% of the total variation in the regression models. The residential ambient air concentrations were 1.5-4 times higher than the urban background levels outside homes very close (<50 m) to ambient emission sources where approximately 7% of the population live. However, the relative increase of risk for disease is small and variations in air concentration in the background urban atmosphere are greater than those from the proximity to roadways.     

Characterization of hydrophobic hypercrosslinked polymer as an adsorbent for removal of chlorinated volatile organic compounds

A hydrophobic hypercrosslinked polymer with poly (4-tert-butylstyrene-styrene-divinylbenzene) matrix (LC-1) was prepared as adsorbent for the removal of volatile organic compounds from gas streams. The content of oxygen-containing functional groups of LC-1 was about one-fourth that of commercial hypercrosslinked polymeric adsorbent (NDA-201). The results of the water vapor adsorption experiment indicated that LC-1 had a more hydrophobic surface than NDA-201. Three chlorinated volatile organic compounds (trichloroethylene, trichloromethane, and 1, 2-dichloroethane) were used to investigate the adsorption characteristics of LC-1 under dry and humid conditions. Equilibrium adsorption data in dry streams showed that LC-1 had good adsorption abilities for three chlorinated VOCs due to its abundant micropore structure. Moreover, the presence of water vapor in the gas stream had negligible effect on breakthrough time of three chlorinated VOCs adsorption onto LC-1 when values of relative humidity were equal to or below 50%; the breakthrough time of three chlorinated VOCs decreased less than 11% even if the relative humidity was 90%. Taken together, it is expected that LC-1 would be a promising adsorbent for the removal of VOCs vapor from the humid gas streams.     

不同烟熏烘烤方式对湘西腊肉挥发性成分的比较

以湖南湘西腊肉为研究对象,比较工厂快速烘烤烟熏和农家传统风干烟熏过程对湘西腊肉挥发性成分的影响。采用固相微萃取-气相色谱-质谱联用技术(SPME-GC-MS),分别对工厂快速烘烤方式的腌制结束、烘烤烟熏2 d、6 d三个阶段进行取样分析和农家传统风干烟熏的腌制结束、烟熏5 d、15 d、30 d后四个阶段的腊肉进行取样分析,比较两种加工方式成品挥发性成分的差别。在工厂和农家加工过程中分别鉴定出73种和76种挥发性成分,分析得出湘西腊肉大致挥发性成分为酯类、酸类、醛类、酮类、酚类和烃类。工厂加工腊肉成品中主体挥发性成分是酚类、醛类和烃类,其相对含量分别为62.50%、8.95%和5.08%;农家加工腊肉成品中主要挥发性成分有酚类、酯类和烃类,其相对含量分别为14.80%、0.91%和0.68%。工厂加工成品的挥发性成分在种类和相对含量上均高于农家加工成品。     

On quantitative determination of volatile organic compound concentrations using proton transfer reaction time-of-flight mass spectrometry

Proton transfer reaction - mass spectrometry (PTR-MS) has become a reference technique in environmental science allowing for VOC monitoring with low detection limits. The recent introduction of time-of-flight mass analyzer (PTR-ToF-MS) opens new horizons in terms of mass resolution, acquisition time, and mass range. A standard procedure to perform quantitative VOC measurements with PTR-ToF-MS is to calibrate the instrument using a standard gas. However, given the number of compounds that can be simultaneously monitored by PTR-ToF-MS, such a procedure could become impractical, especially when standards are not readily available. In the present work we show that, under particular conditions, VOC concentration determinations based only on theoretical predictions yield good accuracy. We investigate a range of humidity and operating conditions and show that theoretical VOC concentration estimations are accurate when the effect of water cluster ions is negligible. We also show that PTR-ToF-MS can successfully be used to estimate reaction rate coefficients between H(3)O(+) and VOC at PTR-MS working conditions and find good agreement with the corresponding nonthermal theoretical predictions. We provide a tabulation of theoretical rate coefficients for a number of relevant volatile organic compounds at various energetic conditions and test the approach in a laboratory study investigating the oxidation of alpha-pinene.     

Volatile organic compound emissions from dairy cows and their waste as measured by proton-transfer-reaction mass spectrometry

California dairies house approximately 1.8 million lactating and 1.5 million dry cows and heifers. State air regulatory agencies view these dairies as a major air pollutant source, but emissions data are sparse, particularly for volatile organic compounds (VOCs). The objective of this work was to determine VOC emissions from lactating and dry dairy cows and their waste using an environmental chamber. Carbon dioxide and methane were measured to provide context for the VOCs. VOCs were measured by proton-transfer-reaction mass spectrometry (PTR-MS). The compounds with highest fluxes when cows plus waste were present were methanol, acetone + propanal, dimethylsulfide, and m/z 109 (likely 4-methyl-phenol). The compounds with highest fluxes from fresh waste (urine and feces) were methanol, m/z 109, and m/z 60 (likely trimethylamine). Ethanol fluxes are reported qualitatively, and several VOCs that were likely emitted (formaldehyde, methylamine, dimethylamine) were not detectable by PTR-MS. The sum of reactive VOC fluxes measured when cows were present was a factor of 6-10 less than estimates historically used for regulatory purposes. In addition, ozone formation potentials of the dominant VOCs were -10% those of typical combustion or biogenic VOCs. Thus dairy cattle have a comparatively small impact on ozone formation per VOC mass emitted.     

Spectral and chemical analyses of mould development on Scots pine heartwood

Scots pine heartwood specimens were exposed to mould in controlled humid atmosphere (RH 95%, T?=20 °C) and the responses of electrical impedance and Fourier transform infrared spectroscopy (EIS and FTIR) methods were studied. The concentration of methanol soluble heartwood extractives and the emission of volatile organic compounds (VOC) were determined from the parallel samples. Results show that the spectral responses and VOC emissions were related to the mould development. According to this study, VOC emissions might be used for discriminating mould susceptible and resistant samples. FTIR spectra showed that the relation of amide (1655 cm^-1) and carbonyl peaks (1736 cm^-1) was significantly affected by mould. In the EIS analyses, there also were electrical parameters, which were significantly affected by mould. In conclusion, both spectral methods hold potential for non-destructive mould detection and monitoring of mould development.     

Volatile organic compounds in human milk: methods and measurements

The present study was conducted to optimize methods for measurement of volatile organic compounds (VOCs) by use of headspace solid-phase microextraction (HS-SPME) and to provide a preliminary assessment of levels in human milk. MTBE (methyl tert-butyl ether), chloroform, benzene, and toluene were measured from two sources of milk: a North Carolina milk bank (n = 5) and multiple samples from three women within nonsmoking households in inner-city Baltimore, MD (n = 8). In Baltimore, indoor air VOC concentrations in the respective households were also measured by active sampling and thermal desorption gas chromatography/mass spectrometry in selective ion monitoring (GC/MS/SIM) over each of the 3 days of milk collection. By application of these optimized methods, we observed median VOC concentrations in Baltimore human milk of 0.09, 0.55, 0.12, and 0.46 ng/mL for MTBE, chloroform, benzene, and toluene, respectively. For benzene, toluene, and MTBE, milk levels trended with observed indoor air concentrations. On the basis of measured concentrations in air and milk, infant average daily dose by inhalation exceeded ingestion rates by 25-135-fold. Thus, VOC exposure from breast milk is vastly exceeded by that from indoor air in nonsmoking households. Accordingly, strategies to mitigate infant VOC exposure should focus on the indoor air inhalation pathway of exposure.     

Ozone-initiated reactions with mixtures of volatile organic compounds under simulated indoor conditions

This study examines the primary and secondary products resulting from reactions initiated by adding ozone to complex mixtures of volatile organic compounds (VOC). The mixtures were representative of organic species typically found indoors, but the concentrations tended to be higher than normal indoor levels. Each 4-h experiment was conducted in a controlled environmental facility (CEF, 25 m3) ventilated at approximately 1.8 h(-1). The mixture investigated included 23 VOC (no O3), O3/23 VOC, O3/21 VOC (no d-limonene or alpha-pinene), and O3/terpene only (d-limonene and alpha-pinene). The net O3 concentration was approximately 40 ppb in each experiment, and the total organic concentration was 26 mg/m3 for the 23 VOC mixture, 25 mg/m3 for the 21 VOC mixture, and 1.7 mg/m3 for the d-limonene and alpha-pinene mixture. When the 23 VOC were added to the CEF containing no O3, no compounds other than those deliberately introduced were observed. When O3 was added to the CEF containing the 23 VOC mixture, both gas and condensed phase products were found, including aldehydes, organic acids, and submicron particles (140 microg/m3). When O3 was added to the CEF containing the 21 VOC without the two terpenes (O3/21 VOC condition), most of the products that were observed in the O3/23 VOC experiments were no longer present or present at much lower concentrations. Furthermore, the particle mass concentration was 2-7 microg/m3, indistinguishable from the background particle concentration level. When O3 was added to the CEF containing only two terpenes, the results were similar to those in the O3/23 VOC experiments, but the particle mass concentration (190 microg/m3) was higher. The results indicate that (i) O3 reacts with unsaturated alkenes under indoor conditions to generate submicron particles and other potentially irritating species, such as aldehydes and organic acids; (ii) the major chemical transformations that occurred under our experimental conditions were driven by O3/d-limonene and O3/alpha-pinene reactions; and (iii) the hydroxyl radicals (OH) that were generated from the O3/terpene reactions played an important role in the chemical transformations and were responsible for approximately 56-70% of the formaldehyde, almost all of the p-tolualdehyde, and 19-29% of the particle mass generated in these experiments.     

Measurement of emissions from air pollution sources. 3. C1-C29 organic compounds from fireplace combustion of wood

Organic compound emission rates for volatile organic compounds (VOC), gas-phase semivolatile organic compounds, and particle-phase organic compounds are measured from residential fireplace combustion of wood. Firewood from a conifer tree (pine) and from two deciduous trees (oak and eucalyptus) is burned to determine organic compound emissions profiles for each wood type including the distribution of the alkanes, alkenes, aromatics, polycyclic aromatic hydrocarbons (PAH), phenol and substituted phenols, guaiacol and substituted guaiacol, syringol and substituted syringols, carbonyls, alkanoic acids, resin acids, and levoglucosan. Levoglucosan is the major constituent in the fine particulate emissions from all three wood types, contributing 18-30% of the fine particulate organic compound emissions. Guaiacol (2-methoxyphenol), and guaiacols with additional substituents at position 4 on the molecule, and resin acids are emitted in significant quantities from pine wood combustion. Syringol (2,6-dimethoxyphenol) and syringols with additional substituents at position 4 on the molecule are emitted in large amounts from oak and eucalyptus firewood combustion, but these compounds are not detected in the emissions from pine wood combustion. Syringol and most of the substituted syringols are found to be semivolatile compounds that are present in both the gas and particle phases, but two substituted syringols that have not been previously quantified in wood smoke emissions, propionylsyringol and butyrylsyringol, are found exclusively in the particle phase and can be used to help trace hardwood smoke particles in the atmosphere. Benzene, ethene, and acetylene are often used as tracers for motor vehicle exhaust in the urban atmosphere. The contribution of wood smoke to the ambient concentrations of benzene, ethene, and acetylene could lead to an overestimate of the contribution of motor vehicle tailpipe exhaust to atmospheric VOC concentrations.