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Chemical and mutagenic analysis of volatile organic compounds in Raleigh air samples at three different elevations before, during, and after Hurricane Gordon.

Volatile organic compounds (VOCs) were collected and measured at a television tower 10 km southeast of downtown Raleigh, North Carolina at three different levels (Surface, < 1 m; Mid, 240 m; and Top, 433 m) during the summer and fall of 1994. The combined presence of ozone, arenes, and nitrogen oxides (NOx) suggested possible nitration of arenes during atmospheric mixing. Air samples, therefore, were collected using XAD-filled canisters at each level on the tower prior to, during, and after Hurricane Gordon. Collected air samples were Soxhlet extracted and analyzed with the Salmonella typhimurium microsuspension mutagenicity assay using strains YG1021 and YG1026 which are sensitive to nitrarenes. Significant mutagenicity was observed only in the Top and Mid level samples for the post-hurricane, normal weather air samples. Surface samples were not mutagenic, which suggests the long-range transport of these mutagenic nitrarenes.

Air Pollutants↗

Volatile organic compounds in breath as markers of lung cancer: a cross-sectional study.

BACKGROUND: Many volatile organic compounds (VOCs), principally alkanes and benzene derivatives, have been identified in breath from patients with lung cancer. We investigated whether a combination of VOCs could identify such patients. METHODS: We collected breath samples from 108 patients with an abnormal chest radiograph who were scheduled for bronchoscopy. The samples were collected with a portable apparatus, then assayed by gas chromatography and mass spectroscopy. The alveolar gradient of each breath VOC, the difference between the amount in breath and in air, was calculated. Forward stepwise discriminant analysis was used to identify VOCs that discriminated between patients with and without lung cancer. FINDINGS: Lung cancer was confirmed histologically in 60 patients. A combination of 22 breath VOCs, predominantly alkanes, alkane derivatives, and benzene derivatives, discriminated between patients with and without lung cancer, regardless of stage (all p<0.0003). For stage 1 lung cancer, the 22 VOCs had 100% sensitivity and 81.3% specificity. Cross-validation of the combination correctly predicted the diagnosis in 71.7% patients with lung cancer and 66.7% of those without lung cancer. INTERPRETATION: In patients with an abnormal chest radiograph, a combination of 22 VOCs in breath samples distinguished between patients with and without lung cancer. Prospective studies are needed to confirm the usefulness of breath VOCs for detecting lung cancer in the general population.

Aged↗

The use of solid-phase microextraction in conjunction with a benchtop quadrupole mass spectrometer for the analysis of volatile organic compounds in human blood at the low parts-per-trillion level.

The analysis of volatile organic compounds (VOCs) in whole human blood at the low parts-per-trillion level has until recently required the use of a high-resolution mass spectrometer to obtain the specificity and detection limits required for epidemiological studies of VOC exposure in the general public. Because of the expense and expertise required to operate and maintain a high-resolution instrument, the applicability of this method has been limited. These limitations are overcome in a new method using automated headspace solid-phase microextraction (SPME) in conjunction with a gas chromatograph and a benchtop quadrupole mass spectrometer. A combination of SPME and multiple single-ion monitoring minimizes the interferences and chemical noise associated with whole blood samples. This method permits the analysis of 10 VOCs in human blood while simplifying the sample preparation and reducing the possible exposure of the analyst to blood aerosols. Twelve samples can be run successively in a fully automated mode, thus eliminating the need for operator attention. Detection limits are below 50 ppt (pg/mL) for a majority of the VOCs tested with a 5-mL sample.

Calibration↗

Association of domestic exposure to volatile organic compounds with asthma in young children.

AIM: To investigate the association between domestic exposure to volatile organic compounds (VOCs) and asthma in young children. METHODS: A population based case-control study was conducted in Perth, Western Australia in children aged between 6 months and 3 years. Cases (n = 88) were children recruited at Princess Margaret Hospital accident and emergency department and discharged with asthma as the primary diagnosis; 104 controls consisted of children from the same age group without an asthma diagnosis identified through the Health Department of Western Australia. Information regarding the health status of the study children and characteristics of the home was collected using a standardised questionnaire. Exposure to VOCs, average temperature and relative humidity were measured in winter and summer in the living room of each participating household. RESULTS: Cases were exposed to significantly higher VOC levels (microg/m3) than controls (p<0.01). Most of the individual VOCs appeared to be significant risk factors for asthma with the highest odds ratios for benzene followed by ethylbenzene and toluene. For every 10 unit increase in the concentration of toluene and benzene (microg/m3) the risk of having asthma increased by almost two and three times, respectively. CONCLUSIONS: Domestic exposure to VOCs at levels below currently accepted recommendations may increase the risk of childhood asthma. Measurement of total VOCs may underestimate the risks associated with individual compounds.

Adolescent↗

Environmental exposure of commuters in Mexico City to volatile organic compounds as assessed by blood concentrations, 1998.

OBJECTIVE: To assess the extent of exposure for Volatile Organic Compounds (VOCs) among nonoccupationally exposed commuters in Mexico City. MATERIAL AND METHODS: Blood concentrations of benzene, toluene, ethylbenzene, m-/p-xylene, o-xylene and methyl tert-butyl ether were determined on samples collected from participants after the morning commute. RESULTS: Median blood concentrations of benzene (0.11 microg/l), ethylbenzene (0.081 microg/l), m-/p-xylene (0.32 microg/l) and toluene (0.56 microg/l) in the Mexico City participants were all approximately two times higher than in a nonsmoking subset of the Third National Health and Nutrition Examination Survey population of the United States. On the other hand, median VOC blood levels were similar to medians observed in other studies involving commuters in specific U.S. cities, despite the fact that only half the Mexico City study participants commuted by personal vehicles compared with all U.S. commuters. CONCLUSIONS: These results reflect the extent of the air pollution problem in Mexico City. The surrounding topography exacerbates the problems caused by heavy vehicular traffic, poor emission-control devices on older vehicles, and poor maintenance practices. Elevated levels of gasoline components in the blood of nonoccupationally exposed commuters emphasize the need for regulatory initiatives and mass-transit options to reduce hydrocarbon emissions and thus reduce the risk for nonoccupational exposure for the residents of Mexico City.

Adult↗

Solid-phase microextraction gas chromatography/mass spectrometric analysis of volatile organic compounds in water

In this work, a solid-phase microextraction (SPME) method for the extraction of volatile organic compounds (VOCs) from water samples has been developed. Fifty-five volatile compounds (from the sixty listed in EPA method no. 524.2) were extracted from aqueous solutions using an SPME fiber coated with Carboxen-polydimethylsiloxane (Carboxen-PDMS), 75 &mgr;m film thickness. Time of sampling and chromatographic separation conditions were optimised. Standard solutions of VOC mixtures with concentrations as low as 0.05 ppb were analysed and their signal/noise ratios measured. Linearity of response for each component of the mixture was tested and mass spectral quality evaluated. A comparison with purge and trap analysis of VOCs was made. The method was applied to real-world samples of drinking, surface and leaching waters. Copyright 1999 John Wiley & Sons, Ltd.

Journal Article↗

Determination of specific volatile organic compounds synthesised during Tuber borchii fruit body development by solid-phase microextraction and gas chromatography/mass spectrometry.

Fruit body development is a particular phase of the Tuber life cycle, characterised by the aggregation of different types of hyphae, i.e., vegetative hyphal cells and highly specialised reproductive hyphae (asci). In order to identify the volatile organic compounds (VOCs) produced in different stages of the Tuber borchii ripening fruit body, solid-phase microextraction with gas chromatography and mass spectrometry was used. The volatile organic compounds were extracted using a DVB/CAR/PDMS 50/30 microm fiber placed for 10 min at room temperature in the truffle headspace. The results obtained reveal 49 compounds each of which was present only in a particular stage of maturation. 1-octen-3-ol, aromadendrene, alpha-farnesene and other terpenoid compounds were of particular interest, and their possible biological roles are discussed. The production of aromadendrene in the completely unripe fruit body suggests the existence of communication events in the early stage of ascomata formation between the fungus and the host plant. alpha-Farnesene could represent a chemotactic attractant to saprophytic organisms in order to disperse the fungal spores in the environment. The identification of the VOCs produced by truffles during their maturation could give information about the processes underlying this phase of Tuber life cycle.

Ascomycota↗

The automated sample preparation system MixMaster for investigation of volatile organic compounds with mid-infrared evanescent wave spectroscopy.

For efficient development assessment, and calibration of new chemical analyzers a large number of independently prepared samples of target analytes is necessary. Whereas mixing units for gas analysis are readily available, there is a lack of instrumentation for accurate preparation of liquid samples containing volatile organic compounds (VOCs). Manual preparation of liquid samples containing VOCs at trace concentration levels is a particularly challenging and time consuming task. Furthermore, regularly scheduled calibration of sensors and analyzer systems demands for computer controlled automated sample preparation systems. In this paper we present a novel liquid mixing device enabling extensive measurement series with focus on volatile organic compounds, facilitating analysis of water polluted by traces of volatile hydrocarbons. After discussing the mixing system and control software, first results obtained by coupling with an FT-IR spectrometer are reported. Properties of the mixing system are assessed by mid-infrared attenuated total reflection (ATR) spectroscopy of methanol-acetone mixtures and by investigation of multicomponent samples containing volatile hydrocarbons such as 1,2,4-trichlorobenzene and tetrachloroethylene. Obtained ATR spectra are evaluated by principal component regression (PCR) algorithms. It is demonstrated that the presented sample mixing device provides reliable multicomponent mixtures with sufficient accuracy and reproducibility at trace concentration levels.

Electronic Data Processing↗

Adsorbent materials commonly used in air analysis for adsorptive enrichment and thermal desorption of volatile organic compounds.

A review is given dealing with commonly used adsorbent materials in ambient air analysis of volatile organic compounds (VOCs). The adsorbents covered in the paper are selected in consideration of their compatibility with thermal desorption. Initially, we discuss the requirements that an adsorbent should fulfill, and useful parameters for the selection and evaluation of an appropriate material. Then, the most important materials are presented considering their properties, advantages, and drawbacks. A few applications are given, but a complete review of sampling techniques and applications dealing with adsorptive enrichment and thermal desorption is beyond the scope of this paper.

Adsorption↗

Volatile organic compounds concentrations in residential indoor and outdoor and its personal exposure in Korea.

To date, personal volatile organic compounds (VOCs) exposure and residential indoor and outdoor VOCs levels have not been characterized in Korea. In this study, residential indoor and outdoor VOCs concentrations were measured and compared simultaneously with the personal exposure for each of 30 participants in a medium city, Asan, and in a metropolitan city, Seoul. Factors that influence personal VOCs exposures were assessed in relation to house characteristics and time activity information. All VOC concentrations were measured using passive samplers during a 24-h period and analyzed using GC-MS. Ten target VOCs were benzene, trichloroethylene, toluene, o-xylene, p-xylene, ethylbenzene, MIBK, n-octane, styrene, and 1,2-dichlorobenzene. Residential indoor and outdoor VOCs concentrations measured in Seoul were significantly higher than those in Asan. Indoor/outdoor (I/O) ratios for all target compounds ranged from 0.94 to 1.51 and I/O ratios of Asan were a little higher than those of Seoul. Results indicate that time activity information can be used to predict personal exposures, although such predictions will result in an over estimation compared to measured exposures. Factors which influence the indoor VOCs level and its personal exposure in relation to house characteristics included house age, indoor smoking, and house type.

Air Pollutants↗

Analysis of biogenic volatile organic compounds in zucchini flowers: identification of scent sources.

An analytical method has been applied to determine volatile organic compounds in zucchini flowers. In a first step, the analytical method was applied to characterize the main scents emitted by whole male and female living flowers of three main commercial cultivars of zucchini (Tosca, Chapin, and Consul). In a second step, the compounds were quantified in different parts of the living flowers to identify the contribution of nectar, petals, anther, and stigma to the aroma profile of the flower. The analytical method is based on headspace solid-phase microextraction coupled on-line with GC and tandem MS detection (HS-SPME-GC-MS/MS). A reference compound is added to samples as part of the field quality control procedure to check for likely analyte losses or sample decomposition. The reference compound also acts as an internal standard for quantification purposes. Results have been statistically studied applying principal component analysis (PCA), which shows that three components explain more than 91% of the variance. PCA emphasizes the great importance of nectar as being the main source of 1,4-dimethoxybenzene and 1,2,4-trimethoxybenzene, which influence the aroma profile of flowers. The remaining components can be accounted for by emissions from petals and sexual organs (adroecium and gynoecium anthers or stigmas).

Anisoles↗

Blood concentrations of volatile organic compounds in a nonoccupationally exposed US population and in groups with suspected exposure.

Exposure to certain volatile organic compounds (VOCs) commonly occurs in industrialized countries. We developed a method for measuring 32 VOCs in 10 mL of whole blood at low concentration. We used this method to determine the internal dose of these compounds in 600 or more people in the US who participated in the Third National Health and Nutrition Examination Survey. From our study results, we established a reference range for these VOCs in the general population of the US. We found detectable concentrations of 1,1,1-trichloroethane, 1,4-dichlorobenzene, 2-butanone, acetone, benzene, chloroform, ethylbenzene, m,p-xylene, styrene, tetrachloroethane, and toluene in most of the blood samples of nonoccupationally exposed persons. The accuracy of VOC evaluations depends on the ability of investigators to make sensitive and reproducible measurements of low concentrations of VOCs and to eliminate all sources of interference and contamination.

Environmental Exposure↗

Determination of complex mixtures of volatile organic compounds in ambient air: an overview.

This article reviews developments in the sampling and analysis of volatile organic compounds (VOCs) in ambient air since the 1970s, particularly in the field of environmental monitoring. Global monitoring of biogenic and anthropogenic VOC emissions is briefly described. Approaches used for environmental monitoring of VOCs and industrial hygiene VOC exposure assessments are compared. The historical development of the sampling and analytical methods used is discussed, and the relative advantages and disadvantages of sorbent and canister methods are identified. Overall, there is considerable variability in the reliability of VOC estimates and inventories. In general, canister methods provide superior precision and accuracy and are particulary useful for the analysis of complex mixtures of VOCs. Details of canister methods are reviewed in a companion paper.

Adsorption↗

Workplace monitoring for volatile organic compounds using thermal desorption-gas chromatography-mass spectrometry.

The interest in the identification of volatile organic compounds in the workplace has been a major focus of many National Institute for Occupational Safety and Health (NIOSH) field studies. A primary technique for sampling and analysis of these compounds is summarized by NIOSH Manual of Analytical Methods (NMAM) 2549. This is a screening method that uses a multi-bed sorbent to trap a wide variety of compounds and compound classes. Thermal desorption techniques are used as a first attempt to characterize potential contaminants in a workplace and to determine what future sampling and analyses must be performed. Field examples are provided to show the versatility of thermal desorption methods and techniques. Due to their sensitivity, thermal desorption tube methods are sometimes required in order to measure the workplace concentrations of unusual compounds. In other situations, the exposures are too high or varied to make thermal desorption tubes practical. In these cases, the identification of contaminants with thermal desorption tubes leads to new method developments for the quantification of specific compounds using more conventional solid sorbent-solvent desorption based methods.

Air Pollution, Indoor↗

Determination of selected microbial volatile organic compounds by diffusive sampling and dual-column capillary GC-FID--a new feasible approach for the detection of an exposure to indoor mould fungi?

A new, analytically valid procedure is described to assess the exposure of human beings to the so-called microbial volatile organic compounds (MVOCs) in air. The method can be used routinely for large sample numbers and is especially valuable as a basis for further research on the correlation between single MVOCs and indoor mould growth. The procedure is based on the fact that fungi produce a variety of volatile organic compounds, such as 3-methylbutan-1-ol, 3-methylbutan-2-ol, fenchone, heptan-2-one, hexan-2-one, octan-3-one, octan-3-ol, pentan-2-ol, alpha-terpineol, and thujopsene, which they emit into the indoor environment. Using diffusive samplers, these MVOCs are adsorbed onto charcoal during a sampling interval of four weeks. The described method is thus superior to existing methods which use short-term active sampling. After desorption with carbon disulfide, the MVOCs were determined by dual-column gas chromatography with flame ionization detection using the large-volume injection technique for sample introduction. The detection limits ranged between 0.15 and 0.53 microgram m-3, within-series precision was found to range between 6.5 and 19.0%, and recovery was between 77 and 118%. The procedure has been successfully applied in the context of a large field study to measure the indoor MVOC exposure in children's rooms of 132 dwellings. The objective of the study was to examine the relation between indoor mould growth, the indoor MVOC exposure and the prevalence of adverse health effects. Information about mould formation has been obtained by a questionnaire and by the determination of colony forming units of mould fungi in mattress dust. With the exception of 3-methylbutan-2-ol, fenchone, nonan-2-one, octan-2-one, and thujopsene, indoor air concentrations of all MVOCs under investigation were significantly higher inside damp and mouldy dwellings. From the primary MVOCs under investigation, 3-methylbutan-1-ol, hexan-2-one, heptan-2-one, and octan-3-ol were found to be most reliable indicators for mould formation. A correlation was also found between selected MVOCs and the occurrence of mould species in mattress dust. Aspergillus sp. correlated with heptan-2-one, hexan-2-one, octan-3-ol, octan-3-one, and alpha-terpineol, while the occurrence of Eurotium sp. was correlated with higher indoor air concentrations of 3-methylbutan-1-ol, 3-methylbutan-2-ol, heptan-2-one, hexan-2-one, octan-3-ol, and thujopsene. Children living in dwellings with elevated MVOC levels had a higher prevalence of asthma, hay fever, wheezing, and irritations of the eyes. These positive associations persisted after controlling for confounding factors such as age, sex, body-mass index, number of siblings, social status, passive smoking, type of heating, and ventilation habits. However, they were not statistically significant. This lack of significance may be a result of the small number of investigated samples.

Air Pollution, Indoor↗

Use of chloroflurocarbons as internal standards for the measurement of atmospheric non-methane volatile organic compounds sampled onto solid adsorbent cartridges.

Solid adsorbents have proven useful for determining the vertical profiles of volatile organic compounds (VOCs) using sampling platforms such as balloons, kites, and light aircraft, and those profiles provide valuable information about the sources, sinks, transformations, and transport of atmospheric VOCs. One of the largest contributions to error in VOC concentrations is the estimation of the volume of air sampled on the adsorbent cartridge. These errors arise from different sources, such as variations in pumping flow rates from changes in ambient temperature and pressure with altitude, and decrease in the sampling pump battery power. Another significant source for sampling rate variations are differences in the flow resistance of individual sampling cartridges. To improve the accuracy and precision of VOC measurements, the use of ambient chlorofluorocarbons (CFCs) as internal standards was investigated. A multibed solid adsorbent, AirToxic (Supelco), was chosen for its wide sampling range (C3-C12). Analysis was accomplished by thermal desorption and dual detection GC/FID/ECD, resulting in sensitive and selective detection of both VOCs and CFCs in the same sample. Long-lived chlorinated compounds (CFC-11, CFC-12, CFC-113, CCl4 and CH3CCl3) banned by the Montreal Protocol and subsequent amendments were studied for their ability to predict sample volumes using both ground-based and vertical profiling platforms through the boundary layer and free troposphere. Of these compounds, CFC-113 and CCl4 were found to yield the greatest accuracy and precision for sampling volume determination. Use of ambient CFC-113 and CCl4 as internal standards resulted in accuracy and precision of generally better than 10% for the prediction of sample volumes in ground-, balloon-, and aircraft-based measurements. Consequently, use of CFCs as reference compounds can yield a significant improvement of accuracy and precision for ambient VOC measurements in situations where accurate flow control is troublesome.

Adsorption↗

Emission of volatile organic compounds by apple trees under spider mite attack and attraction of predatory mites.

Emission rates of volatile organic compounds (VOCs) from Pirus malus L. subsp. mitis (Wallr.) var. Golden Delicious and var. Starking attacked by the phytophagous mite Panonychus ulmi Koch, and their attractiveness to the predatory mites Amblyseius andersoni Chant and Amblyseius californicus McGregor, were studied during three years. A large variability was found in the emission of individual VOCs depending on the infestation, the apple tree variety and the date. There were larger total VOC emission rates and larger total VOC leaf concentrations in apple trees attacked by phytophagous mites, especially in the var. Starking. In infested trees of this variety, there were also more predatory mites. An olfactometer assay showed that predatory mites preferentially chose branches infested by Panonychus ulmi (85% went to infested branches vs 15% to uninfested control branches) indicating that volatiles may be used as cues to find their prey.

Animals↗

On the induction of volatile organic compound emissions by plants as consequence of wounding or fluctuations of light and temperature.

Among the volatile organic compounds (VOCs) emitted by plants, some are characteristic of stress conditions, but their biosynthesis and the metabolic and environmental control over the emission are still unclear. We performed experiments to clarify whether (1) the emission following wounding can occur at distance from the wounding site, from VOC pools subjected to metabolic signals; and (2) the emission of biogenic VOCs generated by membrane damage (e.g. consequent to wounding or ozone exposure) can also be induced by exposure to high light and high temperature, recurrent in nature. In Phragmites australis, leaf cutting caused large and rapid bursts of acetaldehyde both at the cutting site and on parts of the cut leaf distant from the cutting site. This emission was preceded by a transient stomatal opening and did not occur in conditions preventing stomatal opening. This suggests the presence of a large pool of leaf acetaldehyde whose release is under stomatal control. VOCs other than isoprene, particularly acetaldehyde and (E)-2-hexenal, one of the C-6 compounds formed by the denaturation of membrane lipids, were released by leaves exposed to high temperature and high light. The high-temperature treatment (45 degrees C) also caused a rapid stimulation and then a decay of isoprene emission in Phragmites leaves. Isoprene recovered to the original emission level after suspending the high-temperature treatment, suggesting a temporary deficit of photosynthetically formed substrate under high temperature. Emission of C-6 compounds was slowly induced by high temperature, and remained high, indicating that membrane denaturation occurs also after suspending the high-temperature treatment. Conversely, the emission of C-6 compounds was limited to the high-light episode in Phragmites. This suggests that a membrane denaturation may also occur in conditions that do not damage other important plant processes such as the photochemistry of photosynthesis of photoinhibition-insensitive plants. In the photoinhibition-sensitive Arabidopsis thaliana mutant NPQ1, a large but transient emission of (E)-2-hexenal was also observed a few minutes after the high-light treatment, indicating extensive damage to the membranes. However, (E)-2-hexenal emission was not observed in Arabidopsis plants fumigated with isoprene during the high-light treatment. This confirms that isoprene can effectively protect cellular membranes from denaturation. Our study indicates that large, though often transient, VOC emissions by plants occur in nature. In particular, we demonstrate that VOCs can be released by much larger tissues than those wounded and that even fluctuations of light and temperature regularly observed in nature can induce their emissions. This knowledge adds information that is useful for the parameterization of the emissions and for the estimate of biogenic VOC load in the atmosphere.

Aldehydes↗