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[Research advances in the effects of elevated atmospheric carbon dioxide and ozone on biogenic VOCs emission].

The increasing concentrations of CO2 and O3 in the troposphere have become a focus of both the domestic and foreign researchers, and the emissions of biogenic volatile organic compounds (BVOCs) can be affected by the change of concentrations. The BVOCs with high chemical reactivity may affect the chemical compositions of lower atmosphere, and promote photochemistry air pollution. At one time, the greenhouse effect and global environment changes will be influenced by the BVOCs. The effects of single and joint action of CO2 and 03 on the emitting characteristics of biogenic volatile organic compounds (BVOCs) were summarized and further researches on this field, especially that of trees in urban areas under the condition of multiple environmental stresses were perspected in this paper.

Acclimatization↗

[Automated recognition of VOCs using artificial neural networks].

Quantitative analysis of FTIR spectra, which are seriously overlapped in the spectral bands, was studied by artificial neural networks. The optimum network was chosen by a new criterion, i. e. the degree of approximation. After the network was established, two kinds of spectra were resolved. It was demonstrated that accurate results could be obtained when two components were both included. In addition, the unknown spectrum could be identified and quantified. It was showed that the artificial neural network has excellent non-linear ability of solution. Meanwhile, the method provides an efficient approach to the identification and quantification of the unknown samples.

English Abstract↗

Volatile emissions from an odorous plant in response to herbivory and methyl jasmonate exposure.

Induced volatile terpenes have been commonly reported among diverse agricultural plant species, but less commonly investigated in odorous plant species. Odorous plants synthesize and constitutively store relatively large amounts of volatiles, and these may play a role in defense against herbivores. We examined the effect of herbivory and methyl jasmonate (MeJA) exposure on the release of volatile organic compounds (VOCs) in the marsh elder, Iva frutescens, which contains numerous constitutive VOCs, mainly mono- and sesquiterpenes. Our specific goal was to test for the presence of inducible VOCs in a naturally occurring plant already armed with VOCs. The abundant, native specialist leaf beetle Paria aterrima was used in herbivore induction trials. VOCs were sampled from herbivore wounded and unwounded, and from MeJA treated and untreated I. frutescens. Total VOC emissions were significantly greater in response to herbivory and MeJA treatment compared to unwounded controls. Herbivore wounding caused a substantial shift in the emission profile (42 VOCs from wounded, compared to 8 VOCs from unwounded I. frutescens), and MeJA had a similar yet less substantial influence on the emission pattern (28 VOCs from MeJA treated compared to 8 VOCs from untreated I. frutescens). Constitutive VOC emissions predominated, but some VOCs were detected only in response to herbivory and MeJA treatment, suggesting de novo synthesis. Several VOCs exhibited a delayed emission profile in contrast to the rapid release of constitutive VOCs, and principal components analysis revealed they were not associated with constitutive emissions. While I. frutescens contains many constitutive VOCs that are released immediately in response to herbivory, it also produces novel VOCs in response to feeding by the specialist P. aterrima and MeJA treatment.

Acetates↗

Respiratory symptoms and peak expiratory flow in children with asthma in relation to volatile organic compounds in exhaled breath and ambient air.

Indoor volatile organic compounds (VOCs) have been associated with asthma, but there is little epidemiologic work on ambient exposures, and no data on relationships between respiratory health and exhaled breath VOCs, which is a biomarker of VOC exposure. We recruited 26 Hispanic children with mild asthma in a Los Angeles community with high VOC levels near major freeways and trucking routes. Two dropped out, three had invalid peak expiratory flow (PEF) or breath VOC data, leaving 21. Children filled out symptom diaries and performed PEF maneuvers daily, November 1999-January 2000. We aimed to collect breath VOC samples on asthma episode and baseline symptom-free days, but six subjects only gave samples on symptom-free days. We analyzed 106 breath samples by GC-MS. Eight VOCs were quantifiable in >75% of breath samples (benzene, methylene chloride, styrene, tetrachloroethylene, toluene, m,p-xylene, o-xylene, and p-dichlorobenzene). Generalized estimating equation and mixed linear regression models for VOC exposure-response relationships controlled for temperature and respiratory infections. We found marginally positive associations between bothersome or more severe asthma symptoms and same day breath concentrations of benzene [odds ratio (OR) 2.03, 95% confidence interval (CI) 0.80, 5.11] but not other breath VOCs. Ambient petroleum-related VOCs measured on the same person-days as breath VOCs showed notably stronger associations with symptoms, including toluene, m,p-xylene, o-xylene, and benzene (OR 5.93, 95% CI 1.64, 21.4). On breath sample days, symptoms were also associated with 1-h ambient NO(2), OR 8.13 (1.52, 43.4), and SO(2), OR 2.36 (1.16, 4.81). Consistent inverse relationships were found between evening PEF and the same ambient VOCs, NO(2), and SO(2). There were no associations with O(3). Given the high traffic density of the region, stronger associations for ambient than for breath VOCs suggest that ambient VOC measurements were better markers for daily exposure to combustion-related compounds thought to be causally related to acute asthma. Alternatively, the low sample size of symptom responses (15-21 responses per 108 breath samples) may have led to the nonsignificant results for breath VOCs.

Adolescent↗

Catalytic combustion of volatile organic compounds.

Despite the success of adsorption and thermal incineration of (C)VOC emissions, there is still a need for research on techniques which are both economically more favorable and actually destroy the pollutants rather than merely remove them for recycling elsewhere in the biosphere. The catalytic destruction of (C)VOC to CO2, H2O and HCl/Cl2 appears very promising in this context and is the subject of the present paper. The experiments mainly investigate the catalytic combustion of eight target compounds, all of which are commonly encountered in (C)VOC emissions and/or act as precursors for the formation of PCDD/F. Available literature on the different catalysts active in the oxidation of (C)VOC is reviewed and the transition metal oxide complex V2O5-WO3/TiO2 appears most suitable for the current application. Different reactor geometries (e.g. fixed pellet beds, honeycombs, etc.) are also described. In this research a novel catalyst type is introduced, consisting of a V2O5-WO3/TiO2 coated metal fiber fleece. The conversion of (C)VOC by thermo-catalytic reactions is governed by both reaction kinetics and reaction equilibrium. Full conversion of all investigated VOC to CO2, Cl2, HCl and H2O is thermodynamically feasible within the range of experimental conditions used in this work (260-340 degrees C, feed concentrations 30-60 ppm). A first-order rate equation is proposed for the (C)VOC oxidation reactions. The apparent rate constant is a combination of reaction kinetics and mass transfer effects. The oxidation efficiencies were measured with various (C)VOC in the temperature range of 260-340 degrees C. Literature data for oxidation reactions in fixed beds and honeycomb reactors are included in the assessment. Mass transfer resistances are calculated and are generally negligible for fleece reactors and fixed pellet beds, but can be of importance for honeycomb monoliths. The experimental investigations demonstrate: (i) that the conversion of the hydrocarbons is independent of the oxygen concentration, corresponding to a zero-order dependency of the reaction rate; (ii) that the conversion of the hydrocarbons is a first-order reaction in the (C)VOC; (iii) that the oxidation of the (C)VOC proceeds to a higher extent with increasing temperature, with multiple chlorine substitution enhancing the reactivity; (iv) that the reaction rate constant follows an Arrhenius dependency. The reaction rate constant kr (s(-1)) and the activation energy E (kJ/mol) are determined from the experimental results. The activation energy is related to the characteristics of the (C)VOC under scrutiny and correlated in terms of the molecular weight. The kr-values are system-dependent and hence limited in design application to the specific VOC-catalyst combination being studied. To achieve system-independency, kr-values are transformed into an alternative kinetic constant K (m3/(m2u)) expressed per unit of catalyst surface and thus independent of the amount of catalyst present in the reactor. Largely different experimental data can be fitted in terms of this approach. Results are thereafter used to define the Arrhenius pre-exponential factor A*, itself expressed in terms of the activation entropy. Destruction efficiencies for any given reactor set-up can be predicted from E- and A*-correlations. The excellent comparison of predicted and measured destruction efficiencies for a group of chlorinated aromatics stresses the validity of the design approach. Since laboratory-scale experiments using PCDD/F are impossible, pilot and full-scale tests of PCDD/F oxidation undertaken in Flemish MSWIs and obtained from literature are reported. From the data it is clear that: (i) destruction efficiencies are normally excellent; (ii) the efficiencies increase with increasing operating temperature; (iii) the higher degree of chlorination does not markedly affect the destruction efficiency. Finally, all experimental findings are used in design recommendations for the catalytic oxidation of (C)VOC and PCDD/F. Predicted values of the a)VOC and PCDD/F. Predicted values of the acceptable space velocity correspond with the cited industrial values, thus stressing the validity of the design strategy and equations developed in the present paper.

Catalysis↗

Historical trends in occurrence and atmospheric inputs of halogenated volatile organic compounds in untreated ground water used as a source of drinking water.

Analyses of samples of untreated ground water from 413 community-, non-community- (such as restaurants), and domestic-supply wells throughout the US were used to determine the frequency of detection of halogenated volatile organic compounds (VOCs) in drinking-water sources. The VOC data were compiled from archived chromatograms of samples analyzed originally for chlorofluorocarbons (CFCs) by purge-and-trap gas chromatography with an electron-capture detector (GC-ECD). Concentrations of the VOCs could not be ascertained because standards were not routinely analyzed for VOCs other than trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113). Nevertheless, the peak areas associated with the elution times of other VOCs on the chromatograms can be classified qualitatively to assess concentrations at a detection limit on the order of parts per quadrillion. Three or more VOCs were detected in 100% (percent) of the chromatograms, and 77.2% of the samples contained 10 or more VOCs. The maximum number of VOCs detected in any sample was 24. Modeled ground-water residence times, determined from concentrations of CFC-12, were used to assess historical trends in the cumulative occurrence of all VOCs detected in this analysis, as well as the occurrence of individual VOCs, such as CFC-11, carbon tetrachloride (CCl(4)), chloroform and tetrachloroethene (PCE). The detection frequency for all of the VOCs detected has remained relatively constant from approximately 1940 to 2000; however, the magnitude of the peak areas on the chromatograms for the VOCs in the water samples has increased from 1940 to 2000. For CFC-11, CCl(4), chloroform and PCE, small peaks decrease from 1940 to 2000, and large peaks increase from 1940 to 2000. The increase in peak areas on the chromatograms from analyses of more recently recharged water is consistent with reported increases in atmospheric concentrations of the VOCs. Approximately 44% and 6.7% of the CCl(4) and PCE detections, respectively, in pre-1940 water, and 68% and 62% of the CCl(4) and PCE detections, respectively, in water recharged in 2000 exceed solubility equilibrium with average atmospheric concentrations. These exceedences can be attributed to local atmospheric enrichment or direct contaminant input to ground-water flow systems. The detection of VOCs at concentrations indicative of atmospheric sources in 100% of the samples indicates that untreated drinking water from ground-water sources in the US recharged within the past 60 years has been affected by anthropogenic activity. Additional inputs from a variety of sources such as spills, underground injections and leaking landfills or storage tanks increasingly are providing additional sources of contamination to ground water used as drinking-water sources.

Atmosphere↗

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.

Air Pollution, Indoor↗

Stabilities of 58 volatile organic compounds in fused-silica-lined and SUMMA polished canisters under various humidified conditions.

Fused-silica-lined (FSL) canisters and SUMMA polished (SUMMA) canisters were compared for the recoveries and the stabilities of 58 volatile organic compounds (VOCs) at low ppbv (volume/volume) levels under various humidified conditions using a three-stage preconcentration method followed by GC-MS analysis. The target VOCs included non-polar VOCs (e.g. halogenated hydrocarbons and aromatic hydrocarbons) and polar VOCs (e.g. alcohols, ketones, esters, ethers, nitriles and thiols). The three-stage preconcentration method was initially optimized for simultaneous analysis of non-polar and polar VOCs because determination of canister stability is dependent on the accuracy of analytical measurements. The method showed good linearity over the concentration range from 1 to 25 ppbv for all target analytes, and the correlation coefficients were higher than 0.9974. The method detection limits ranged from 0.023 to 0.39 ppbv. The test mixtures loaded in both type of canisters (n = 3) had concentrations of 1.7-2.5 ppbv per compound at ambient pressure under various humidified conditions (%RH = 1.6, 8.0, 27, 39, 53 and >99% with excess water present). All canister samples were initially analyzed on day 0 (after 6-12 h). The effect of competitive adsorption of water vapor and polar VOCs on active sites of interior surface was remarkably observed for SUMMA canisters. Polar VOCs had a greater requirement for water vapor to be present. The RH percentages that ensured good recovery on day 0 were RH > 8% for non-polar VOCs and RH > 27% for polar VOCs (except alcohols under the condition of RH > 99%). All thiols were not recovered from SUMMA canisters under all conditions. FSL canisters showed good recoveries of more than 86% for all VOCs under all conditions on day 0 (except alcohols under the condition of RH > 99%). The recoveries of alcohols in both canisters under the condition of RH > 99% displayed relatively low recoveries in the range 25-76% because of the partitioning effect into condensed water. The canister samples under the conditions of RH 8.0, 27, 53 and > 99% were analyzed for the stability test on days 3, 7, 14 and 28 after loading. All non-polar VOCs were reasonably stable in the FSL canisters under all examined conditions over 28 days. However, several polar VOCs that have relatively lower vapor pressure, e.g. MIBK, butyl acetate and alcohols except ethanol, showed unstable characteristics under relatively dry conditions (RH 8 and 27%) during 28 days. RH > 53% was needed to ensure good stabilities of all analytes except thiols with the recoveries of > 80% over 28 days for both canisters. Although the FSL canister showed good recoveries of more than 86% for thiols on day 0, drastic degradations were observed after day 3 and they were not detected after day 14.

Air Pollutants↗

Student's exposure to volatile organic compounds while commuting by motorcycle and bus in Taipei City.

This study examined student's exposure to volatile organic compounds (VOCs) while commuting by bus and motorcycle in Taipei, Taiwan in the winter of 1992. A total of 19 target C5-C10 VOCs on three most frequently used commuting routes were collected on Tenax-GC adsorbent tubes. The VOCs were desorbed by thermal desorption method and analyzed by GC-MS. The most abundant VOC exposure experienced by commuters was to toluene. Several alkylated benzenes, such as propyl benzenes, ethyl-methyl-benzenes and trimethyl-benzenes, were relatively abundant on the roads in Taipei. The mean benzene concentration measured in buses was 173 micrograms/m3 and motorcycles. On the average, the commuters in Taipei experienced about three to eight times higher VOC concentrations than the commuters in Los Angeles, California. Higher VOC concentrations were measured on motorcycles than in buses. The VOC concentrations were not significantly different between morning and afternoon commutes, nor among the three commuting routes. VOC concentrations measured in classroom at three schools in downtown Taipei did not vary significantly on each sampling day. However, at each school the in-classroom VOC concentrations varied significantly over the six consecutive sampling days. The VOC concentrations measured on the roads were about five times higher than those measured in the school classrooms in the city. Moderate to high correlations were found among most of the measurements of the 19 VOCs. The survey questionnaire indicated that daily commuting time ranged from 45 minutes for elementary school students to 95 minutes for vocational school students.(ABSTRACT TRUNCATED AT 250 WORDS)

Adolescent↗

Dermal absorption of neat and aqueous volatile organic chemicals in the Fischer 344 rat.

Quantification of dermal absorption of volatile organic chemicals (VOCs) from aqueous solutions is required to understand the potential health hazards resulting from skin exposure to these chemicals in contaminated water. Male Fischer 344 rats were dermally exposed (3.1-cm2 dorsal skin) to neat, one-third saturated, two-thirds saturated, or saturated aqueous solutions of 14 VOCs for 24 hr. Blood samples were obtained via indwelling jugular catheters during exposure (0, 0.5, 1, 2, 4, 8, 12, and 24 hr), and analyzed for the VOCs by gas chromatography using headspace analysis. Absorption of the neat VOCs in this series of chemicals decreased as water solubility decreased. Peak blood levels of VOCs attained during exposure for 24 hr to neat chemicals were: 1,2-dichloroethane (135.1 micrograms/ml), bromochloromethane (113.3 micrograms/ml), chloroform (51.0 micrograms/ml), benzene (24.2 micrograms/ml), tetrachloroethylene (21.1 micrograms/ml), dibromomethane (18.2 micrograms/ml), trichloroethylene (11.6 micrograms/ml), toluene (9.5 micrograms/ml), xylene (8.8 micrograms/ml), hexane (8.0 micrograms/ml), ethylbenzene (5.6 micrograms/ml), styrene (5.3 micrograms/ml), carbon tetrachloride (5.0 micrograms/ml), and 1,1,1-trichloroethane (3.4 micrograms/ml). Blood levels of 1,2-dichloroethane and benzene continued to increase during the 24-hr exposure to neat chemical, while blood levels of the other neat VOCs peaked within 4 hr and then either decreased or remained about the same for the duration of the exposure. Absorption of VOCs from one-third, two-thirds, or saturated aqueous solutions was rapid, and resulted in depletion of the chemical from the solution although only a small amount of water was absorbed. Blood levels of each VOC were directly related to the exposure concentrations. The rapid appearance of VOCs in the blood from aqueous solutions demonstrates that detectable amounts of VOCs were absorbed during exposure of only about 1% of the skin surface area of the rat.

Animals↗

Variability of environmental exposures to volatile organic compounds.

Although studies of occupational exposure to volatile organic compounds (VOCs) often partition variability across groups, and between and within persons, those of environmental exposure to VOCs have not involved such partitioning. Using data from the Environmental Protection Agency's total exposure assessment methodology (TEAM) studies, we partitioned exposure variability across cities, and between and within persons for nine VOCs. The estimated variance components decreased in the order: within-person > between-person > across city. Despite their smaller magnitudes, estimates of between-person and across-city variance components were sufficiently large to provide reasonable contrast for informative epidemiology studies of most VOCs. Estimates of between-person variance components for environmental VOCs were similar to those published for occupational VOCs (groups defined by job and factory). However, estimates of within-person variance components were much greater for environmental VOCs, probably due to the greater diversity of locations (including the workplace) visited by the general public over time. For benzene and perchloroethylene, we used a simple model to calculate numbers of personal measurements required to relate the exposure level to health outcome statistically. About 10 times more personal measurements would be required to investigate perchloroethylene exposure as compared to benzene exposure; this disparity reflects the greater within-subject variability of perchloroethylene data compared to benzene data. We conclude that variability should be partitioned for environmental VOC exposures in much the same manner as for occupational exposures. There should be sufficient variability in the levels of most VOCs across cities and between subjects to provide reasonable contrast for informative epidemiology studies, as we illustrate for exposures to benzene. Yet, epidemiologists should be wary of investigating environmental VOCs without preliminary data with which to estimate the variance structure of exposure variables.

Air Pollutants↗

Evaluation of total volatile organic compound emissions from adhesives based on chamber tests.

In 1997, Homeswest in western Australia and Murdoch University developed a project to construct low-allergen houses (LAHs) in a newly developed suburb. Before the construction of LAHs, all potential volatile organic compound (VOC) emission materials used in LAHs are required to be measured to ensure that they are low total VOC (TVOC) emission materials. This program was developed based on this purpose. In recent times, the number of complaints about indoor air pollution caused by VOCs has increased. A number of surveys of indoor VOCs have indicated that many indoor materials contribute to indoor air pollution. Although some studies have been conducted on the characteristics of VOC emissions from adhesives, most of them were focused on VOC emissions from floor adhesives. Few measurements of VOC emissions from adhesives used for wood, fabrics, and leather are available. Furthermore, most research on VOC emissions from adhesives has been done in countries with cool climates, where ventilation rates in the indoor environment are lower than those in Mediterranean climates, due to energy conservation. VOCs emitted from adhesives have not been sufficiently researched to prepare an emission inventory to predict indoor air quality and to determine both exposure levels for the Australian population and the most appropriate strategies to reduce exposure. An environmental test chamber with controlled temperature, relative humidity, and airflow rate was used to evaluate emissions of TVOCs from three adhesives used frequently in Australia. The quantity of TVOC emissions was measured by a gas chromatography/flame ionization detector. The primary VOCs emitted from each adhesive were detected by gas chromatography/mass spectrometry. The temporal change of TVOC concentrations emitted from each adhesive was tested. A double-exponential equation was then developed to evaluate the characteristics of TVOC emissions from these three adhesives. With this double-exponential model, the physical processes of TVOC emissions can be explained, and a variety of emission parameters can be calculated. These emission parameters could be used to estimate real indoor TVOC concentrations in Mediterranean climates.

Adhesives↗

Characterization of volatile organic compounds and odorants associated with swine barn particulate matter using solid-phase microextraction and gas chromatography-mass spectrometry-olfactometry.

Swine operations can affect air quality by emissions of odor, volatile organic compounds (VOCs) and other gases, and particulate matter (PM). Particulate matter has been proposed to be an important pathway for carrying odor. However, little is known about the odor-VOCs-PM interactions. In this research, continuous PM sampling was conducted simultaneously with three collocated TEOM 1400a analyzers inside a 1000-head swine finish barn located in central Iowa. Each TEOM was fitted with total suspended particulate (TSP), PM-10, PM-2.5 and PM-1 preseparators. Used filters were stored in 40 mL vials and transported to the laboratory. VOCs adsorbed/absorbed to dust were allowed to equilibrate with vial headspace. Solid-phase microextraction (SPME) Carboxen/polydimethylsiloxane (PDMS) 85 microm fibers were used to extract VOCs. Simultaneous chemical and olfactometry analyses of VOCs and odor associated with swine PM were completed using a gas chromatography-mass spectrometry-olfactometry (GC-MS-O) system. Fifty VOCs categorized into nine chemical function groups were identified and confirmed with standards. Five of them are classified as hazardous air pollutants. VOCs were characterized with a wide range of molecular weight, boiling points, vapor pressures, water solubilities, odor detection thresholds, and atmospheric reactivities. All characteristic swine VOCs and odorants were present in PM and their abundance was proportional to PM size. However, the majority of VOCs and characteristic swine odorants were preferentially bound to smaller-size PM. The findings indicate that a significant fraction of swine odor can be carried by PM. Research of the effects of PM control on swine odor mitigation is warranted.

Animals↗

Volatile biomarkers of pulmonary tuberculosis in the breath.

Pulmonary tuberculosis may alter volatile organic compounds (VOCs) in breath because Mycobacteria and oxidative stress resulting from Mycobacterial infection both generate distinctive VOCs. The objective of this study was to determine if breath VOCs contain biomarkers of active pulmonary tuberculosis. Head space VOCs from cultured Mycobacterium tuberculosis were captured on sorbent traps and assayed by gas chromatography/mass spectroscopy (GC/MS). One hundred and thirty different VOCs were consistently detected. The most abundant were naphthalene, 1-methyl-, 3-heptanone, methylcyclododecane, heptane, 2,2,4,6,6-pentamethyl-, benzene, 1-methyl-4-(1-methylethyl)-, and cyclohexane, 1,4-dimethyl-. Breath VOCs were assayed by GC/MS in 42 patients hospitalized for suspicion of pulmonary tuberculosis and in 59 healthy controls. Sputum cultures were positive for Mycobacteria in 23/42 and negative in19/42 patients. Breath markers of oxidative stress were increased in all hospitalized patients (p<0.04). Pattern recognition analysis and fuzzy logic analysis of breath VOCs independently distinguished healthy controls from hospitalized patients with 100% sensitivity and 100% specificity. Fuzzy logic analysis identified patients with positive sputum cultures with 100% sensitivity and 100% specificity (95.7% sensitivity and 78.9% specificity on leave-one-out cross-validation); breath VOC markers were similar to those observed in vitro, including naphthalene, 1-methyl- and cyclohexane, 1,4-dimethyl-. Pattern recognition analysis identified patients with positive sputum cultures with 82.6% sensitivity (19/23) and 100% specificity (18/18), employing 12 principal components from 134 breath VOCs. We conclude that volatile biomarkers in breath were sensitive and specific for pulmonary tuberculosis: the breath test distinguished between "sick versus well" i.e. between normal controls and patients hospitalized for suspicion of pulmonary tuberculosis, and between infected versus non-infected patients i.e. between those whose sputum cultures were positive or negative for Mycobacteria.

Adult↗

Risk in cleaning: chemical and physical exposure.

Cleaning is a large enterprise involving a large fraction of the workforce worldwide. A broad spectrum of cleaning agents has been developed to facilitate dust and dirt removal, for disinfection and surface maintenance. The cleaning agents are used in large quantities throughout the world. Although a complex pattern of exposure to cleaning agents and resulting health problems, such as allergies and asthma, are reported among cleaners, only a few surveys of this type of product have been performed. This paper gives a broad introduction to cleaning agents and the impact of cleaning on cleaners, occupants of indoor environments, and the quality of cleaning. Cleaning agents are usually grouped into different product categories according to their technical functions and the purpose of their use (e.g. disinfectants and surface care products). The paper also indicates the adverse health and comfort effects associated with the use of these agents in connection with the cleaning process. The paper identifies disinfectants as the most hazardous group of cleaning agents. Cleaning agents contain evaporative and non-evaporative substances. The major toxicologically significant constituents of the former are volatile organic compounds (VOCs), defined as substances with boiling points in the range of 0 degree C to about 400 degrees C. Although laboratory emission testing has shown many VOCs with quite different time-concentration profiles, few field studies have been carried out measuring the exposure of cleaners. However, both field studies and emission testing indicate that the use of cleaning agents results in a temporal increase in the overall VOC level. This increase may occur during the cleaning process and thus it can enhance the probability of increased short-term exposure of the cleaners. However, the increased levels can also be present after the cleaning and result in an overall increased VOC level that can possibly affect the indoor air quality (IAQ) perceived by occupants. The variety and duration of the emissions depend inter alia on the use of fragrances and high boiling VOCs. Some building materials appear to increase their VOC emission through wet cleaning and thus may affect the IAQ. Particles and dirt contain a great variety of both volatile and non-volatile substances, including allergens. While the volatile fraction can consist of more than 200 different VOCs including formaldehyde, the non-volatile fraction can contain considerable amounts (> 0.5%) of fatty acid salts and tensides (e.g. linear alkyl benzene sulphonates). The level of these substances can be high immediately after the cleaning process, but few studies have been conducted concerning this problem. The substances partly originate from the use of cleaning agents. Both types are suspected to be airway irritants. Cleaning activities generate dust, mostly by resuspension, but other occupant activities may also resuspend dust over longer periods of time. Personal sampling of VOCs and airborne dust gives higher results than stationary sampling. International bodies have proposed air sampling strategies. A variety of field sampling techniques for VOC and surface particle sampling is listed.

Air Pollution, Indoor↗

Transport and fate of volatile organic chemicals in unsaturated, nonisothermal, salty porous media: 1. Theoretical development.

A wide variety of volatile organic chemicals (VOC) have been applied to agricultural land or buried in chemical waste sites. The fate of these chemicals depends upon several mechanisms such as sorption, degradation, and transport in liquid and gaseous phases. Understanding the transport mechanisms affecting the volatile chemicals can lead to better management strategies. A theory describing inorganic solute transport, water and heat transfer, and the fate and transport of VOC in porous media has been developed. This theory includes matric water pressure head, solution osmotic pressure head, gravity pressure head, temperature, inorganic solute concentration, and VOC concentration gradients as driving forces for heat and mass transfer. The effect of surface tension, as a function of VOC concentration and temperature, on the matric water pressure head is included. The VOC can be associated with gas, liquid, and solid phases of the porous media. The gas and liquid phases are mobile, but the solid phase is immobile. The transfer of VOC across the gas/liquid, liquid/solid, and gas/solid interfaces is included using sorption-equilibrium assumptions at the interfaces. The VOC can degrade. This degradation is described by a first-order decay rate. The theory can be used to predict spatial and temporal variations of water content, temperature, inorganic concentration and the total concentration of VOC within a porous medium. The concentration of VOC in each phase can be predicted also.

Hot Temperature↗

Comparative risk analysis of six volatile organic compounds in California drinking water.

The widespread use and storage of volatile organic compounds (VOCs) in the United States has led to releases of these chemicals into the environment, including groundwater sources of drinking water. Many of these VOCs are commonly found in public drinking water supplies across the nation and are considered by state or federal agencies to be potentially carcinogenic to humans. In this paper, we evaluate the detection frequencies, detected concentrations, and relative cancer risks of six VOCs in drinking water sources in California from 1995 to 2001. We find that during this 7-year period, the most frequently detected VOCs in sampled drinking water sources were chloroform (12-14%), PCE (11-13%), and TCE (10-12%). Detection frequencies in water were lower for 1,1-DCE (3-6%), MTBE (1-3%), and benzene (<1%). Mean detected concentrations were also consistently above California's primary maximum contaminant level for some VOCs, including benzene, PCE, and TCE. Although none of the six VOCs necessarily poses a significant public health threat from drinking water exposures, 1,1-DCE and benzene werefound to pose the greatest cancer risk relative to the other VOCs. However, after adjusting for the occurrence of each VOC in drinking water, chloroform and PCE were found to pose the greatest relative cancer risk. Despite media reports about significant MTBE contamination of drinking watersupplies in California, MTBE detections were infrequent and this chemical was found to pose the least cancer risk relative to the other VOCs.

California↗