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Evidence for selectivity of absorption of volatile organic compounds by a polydimethylsiloxane solid-phase microextraction fibre.

Solid-phase microextraction using a 30 microns polydimethylsiloxane fibre has been used to sample the volatile organic compounds from standard mixtures and from mixtures produced by the decomposition of organic compounds. This method of sampling has been compared with the direct injection of an aliquot of headspace gas and shows an enrichment factor of approximately 100 over a 1 ml gas injection for organosulphur gases such as dimethyldisulphide. The performance of the fibre has been evaluated with respect to accuracy and precision at several concentrations in representing the composition of multicomponent mixtures. It was found that the presence of a second component in a gas sample reduced the capacity of the fibre to absorb the primary component. The selectivity of the fibre for various volatile compounds with differing functionality was also studied. It was found that the non-polar polydimethylsiloxane fibre preferentially absorbed the non-polar components of a mixture, e.g. nonane and, correspondingly, under reported the more polar components, e.g. ethanol. Hence, the fibre discriminates in favour of non-polar and against polar components in a mixture in comparison with direct analysis of a headspace sample. Thus, quantitation of a component in a multi-component mixture is liable to error from competitive interference from other components. A major advantage of the technique, however, is that it does not absorb, and therefore introduce, water into the analytical system.

Absorption↗

Fullerenes-extracted soot: a new adsorbent for collecting volatile organic compounds in ambient air.

Fullerenes-extracted soot (FES) is the by-product of fullerenes production. Retention characteristics at different temperatures for 17 volatile organic compounds (VOCs) on FES are measured. The adsorption and desorption efficiencies for VOCs on FES adsorbent tubes range from 40.8 to 117%, most of them being 100+/-20%. The values are compared with Tenax GR, an adsorbent commonly used in environmental analysis. FES can be used as an adsorbent of low cost to collect VOCs in environmental samples.

Air↗

[Seasonal trends of some volatile organic compounds inside and outside private apartments located in areas characterized by different vehicular traffic intensity of Rome].

This study was aimed at determining volatile organic compounds concentrations in indoor and outdoor sites located in Rome characterized by different traffic intensity. Indoor and outdoor air passive samplings were effected in private locations during four seasonal periods. In all sites about 50 pollutants were determined qualitatively and benzene, toluene, ethylbenzene and xylenes were determined quantitatively. The analytical results generally showed a dependence of indoor and outdoor pollutant concentrations on traffic density and a seasonal variability. Moreover, many sites were characterized by the presence of toluene and xylenes indoor concentrations higher than outdoors indicating indoor sources.

Air Pollutants, Occupational↗

Investigations into the effect on rats of volatile organic compounds released from the set of building and finishing materials.

White, male Wistar rats were exposed continuously in chamber during 3 months on volatile organic compounds emitted from set of building and finishing materials used in living areas on ship. The air contamination was checked. The following tests for determination of combined toxic effects were performed: functional activity, the body and organ weights, basic hematological determinations, serum enzyme activity (GOT, GPT, AP, LAP, LDH), serum concentrations of protein, urea, creatinine, bilirubin, lipids, cholesterol, triglycerides, and in the liver mitochondria Mg+2(-)-ATPase, concentration of cholesterol, phospholipids, and liver function after loading with benzoate. After 3 months of the exposure we observed changes in AP and LDH activities, and decrease of the concentration of serum triglycerides.

Acetates↗

Exposure to volatile organic compounds in the passenger compartment of automobiles during periods of normal and malfunctioning operation.

In-vehicle exposures to selected gasoline-derived volatile organic compounds (VOCs) and formaldehyde were examined on 113 commutes through suburban New Jersey and on 33 New Jersey/New York commutes using measurements taken in two vehicles driven in tandem during 1991-1992. Overall median exposures to VOCs were lowest on the suburban commute, slightly higher on the New Jersey Turnpike, and highest in transit through the Lincoln Tunnel. Median in-vehicle concentrations of benzene, ethylbenzene, m- and p-xylene, and o-xylene were 14 microg/m3, 6.8 microg/m3, 36 microg/m3, and 15 microg/m3, respectively. For a motorist who commutes 93.2 min daily (6.5% of the day), this corresponds to 12.1%, 10.8%, 14.9%, and 14.7% of the total daily exposures to these compounds. One vehicle, with a carbureted engine, developed malfunctions which caused gasoline emissions within the engine compartment during driving. Resultant gasoline-derived VOC concentrations in this vehicle measured much higher than in the properly maintained, fuel-injected vehicle, particularly for the low ventilation extreme. The highest in-vehicle benzene concentration measured during these malfunctions was 45.2 microg/m3. The air concentration in the vehicle driven in tandem was a factor of 25 less (1.8 microg/m3). A motorist who drives for the average daily period of 93.2 min/day in this malfunctioning automobile will have a benzene exposure of 2.8 (microg/m3)day, compared to 0.1 (microg/m3)day in the properly functioning vehicle.

Adult↗

Spatial analysis of volatile organic compounds from a community-based air toxics monitoring network in Deer Park, Texas, USA.

In the summer of 2003, ambient air concentrations of volatile organic compounds (VOCs) were measured at 12 sites within a 3-km radius in Deer Park, Texas near Houston. The purpose of the study was to assess local spatial influence of traffic and other urban sources and was part of a larger investigation of VOC spatial and temporal heterogeneity influences in selected areas of Houston. Seventy 2-h samples were collected using passive organic vapor monitors. Most measurements of 13 VOC species were greater than the method detection limits. Samplers were located at 10 residential sites, a regulatory air monitoring station, and a site located at the centroid of the census tract in which the regulatory station was located. For residential sites, sampler placement locations (e. g., covered porch vs. house eaves) had no effect on concentration with the exception of methyl tertiary-butyl ether (MTBE). Relatively high correlations (Pearson r > 0.8) were found between toluene, ethylbenzene, and o,m,p-xylenes suggesting petroleum-related influence. Chloroform was not correlated with these species or benzene (Pearson r < 0.35) suggesting a different source influence, possibly from process-related activities. As shown in other spatial studies, wind direction relative to source location had an effect on VOC concentrations.

Organic Chemicals↗

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↗

Estimation of biogenic volatile organic compounds emissions in subtropical island--Taiwan.

Elevated tropospheric ozone is harmful to human health and plants. It is formed through the photochemical reactions involving volatile organic compounds (VOCs) and nitrogen oxides (NO(x)). The elevated ozone episodes occur mainly in summer months in the United States, while the high-ozone episodes frequently occur during the fall in Taiwan. The unique landscape of Taiwan produces tremendous amounts of biogenic VOCs in the mountain regions that are adjacent to concentrated urban areas. The urban areas, in turn, generate prodigious amounts of anthropogenic emissions. Biogenic VOC emissions have direct influence on tropospheric ozone formation. To explore the air quality problems in Taiwan, this study attempts to develop a biogenic VOC emission model suitable for air quality applications in Taiwan. The emission model is based on the Biogenic Emissions Inventory System Version 2 and coupled with a detailed Taiwan land use database. The 1999 total Taiwan biogenic VOC emissions were estimated at 214,000 metric tons. The emissions of isoprene, monoterpenes, and other VOCs were about 37.2%, 30.4%, and 32.4% of total biogenic VOC emissions, respectively. The annual total biogenic VOC emission per unit area was more than two times the value of that in any European country, implying that detailed emissions estimates in any size of region will benefit the global biogenic emission inventories.

Air Pollutants↗

Diagnostic potential of breath analysis--focus on volatile organic compounds.

Breath analysis has attracted a considerable amount of scientific and clinical interest during the last decade. In contrast to NO, which is predominantly generated in the bronchial system, volatile organic compounds (VOCs) are mainly blood borne and therefore enable monitoring of different processes in the body. Exhaled ethane and pentane concentrations were elevated in inflammatory diseases. Acetone was linked to dextrose metabolism and lipolysis. Exhaled isoprene concentrations showed correlations with cholesterol biosynthesis. Exhaled levels of sulphur-containing compounds were elevated in liver failure and allograft rejection. Looking at a set of volatile markers may enable recognition and diagnosis of complex diseases such as lung or breast cancer. Due to technical problems of sampling and analysis and a lack of normalization and standardization, huge variations exist between results of different studies. This is among the main reasons why breath analysis could not yet been introduced into clinical practice. This review addresses the basic principles of breath analysis and the diagnostic potential of different volatile breath markers. Analytical procedures, issues concerning biochemistry and exhalation mechanisms of volatile substances, and future developments will be discussed.

Air↗

Organic liquids storage tanks volatile organic compounds (VOCS) emissions dispersion and risk assessment in developing countries: the case of Dar-es-Salaam City, Tanzania.

The emission estimation of nine volatile organic compounds (VOCs) from eight organic liquids storage tanks companies in Dar-es-Salaam City Tanzania has been done by using US EPA standard regulatory storage tanks emission model (TANKS 4.9b). Total VOCs atmospheric emission has been established to be 853.20 metric tones/yr. It has been established further that petrol storage tanks contribute about 87% of total VOCs emitted, while tanks for other refined products and crude oil were emitting 10% and 3% of VOCs respectively. Of the eight sources (companies), the highest emission value from a single source was 233,222.94 kg/yr and the lowest single source emission value was 6881.87 kg/yr. The total VOCs emissions estimated for each of the eight sources were found to be higher than the standard level of 40,000 kg/yr per source for minor source according to US EPA except for two sources, which were emitting VOCs below the standard level. The annual emissions per single source for each of the VOCs were found to be below the US EPA emissions standard which is 2,000 kg/yr in all companies except the emission of hexane from company F1 which was slightly higher than the standard. The type of tanks used seems to significantly influence the emission rate. Vertical fixed roof tanks (VFRT) emit a lot more than externally floating roof tanks (EFRT) and internally floating roof tanks (IFRT). The use of IFRT and EFRT should be encouraged especially for storage of petrol which had highest atmospheric emission contribution. Model predicted atmospheric emissions are less than annual losses measured by companies in all the eight sources. It is possible that there are other routes for losses beside atmospheric emissions. It is therefore important that waste reduction efforts in these companies are directed not only to reducing atmospheric emissions, but also prevention of the spillage and leakage of stored liquid and curbing of the frequently reported illegal siphoning of stored products. Emission rates for benzene, toluene, and xylene were used as input to CALPUFF air dispersion model for the calculation of spatial downwind concentrations from area sources. By using global positioning system (GPS) and geographical information system (GIS) the spatial benzene concentration contributed by organic liquid storage tanks has been mapped for Dar-es-Salaam City. Highest concentrations for all the three toxic pollutants were observed at Kigamboni area, possibly because the area is located at the wind prevailing direction from the locations of the storage tanks. The model predicted concentrations downwind from the sources were below tolerable concentrations by WHO and US-OSHA. The highest 24 hrs averaging time benzene concentration was used for risk assessment in order to determine maximum carcinogenic risk amongst the population exposed at downwind. Established risk for adult and children at 2.9x10(-3) and 1.9x10(-3) respectively, are higher than the acceptable US-EPA risk of 1x10(-6). It is very likely that the actual VOCs concentrations in some urban areas in Tanzania including Dar-es-Salaam City are much higher than the levels reported in this study when other sources such as petrol stations and motor vehicles on the roads are considered. Tanzania Government therefore need to put in place: an air quality policy and legislation, establish air quality guidelines and acquire facilities which will enable the implementation of air quality monitoring and management programmes.

Adolescent↗

The application of proton transfer reaction-mass spectrometry (PTR-MS) to the monitoring and analysis of volatile organic compounds in the atmosphere.

Proton transfer reaction-mass spectrometry (PTR-MS) is a new and emerging technique for the measurement and monitoring of volatile organic compounds (VOCs) at low concentrations in gaseous samples in more-or-less real time. Utilising chemical ionisation, it combines the desirable attributes of high sensitivity and short integration times with good precision and accuracy. Recently it has been exploited in applications related to atmospheric science. Here, the principles of operation of the PTR-MS are described, its advantages and disadvantages discussed, its inherent uncertainties highlighted, some of its uses in atmospheric sciences reviewed, and some suggestions made on its future application to atmospheric chemistry.

Air Pollutants↗

Breakthrough characteristics of volatile organic compounds in the -10 to + 170 degrees C temperature range on Tenax TA determined by microtrap technology.

In this work the breakthrough volumes (BTVs) of volatile organic compounds (VOCs) on Tenax TA were determined in the -10 to 170 degrees C temperature range by using microtrap (MT) technology. The MT technology allowed experimental investigation of the temperature dependence of BTVs. Along with the BTV data, we also discuss the thermodynamics of the temperature dependence of the BTV through a two-parameter equation In (BTV) = A1/T + C1 where T is temperature (K), A1 = -deltaH/R where deltaH is enthalpy of sorption and C1 is constant. This equation fitted well the experimental results with R2 values between 0.9737 (acetone) and 0.9995 (dimethyl disulfide), with n between 6 and 11. However, for n-pentane, n-hexane and 1-hexene it proved that a three parameter equation In (BTV) = A2/ T + BTB + C2 fitted better to the experimental results, with A2 = -deltaHT0/R, B = deltaCp/R, TB = 1n(T/T0) + (T0 - T)/T, C2 a constant, deltaHT0 the adsorption enthalpy at reference temperature T0 and deltaCp the difference in the molar heat capacity of compound under investigation between the sorbed and the free gas phase state. The statistical analysis showed for example for n-pentane now R2 = 0.9969 instead of R2 = 0.9746, and Fisher statistics F = 487 instead of F = 153, with a significance level P = 0.018 for the third parameter. The results show that microtrap technology well serves as a technology to get information on temperature dependence of BTVs in an extended range. Simultaneously, it turns out that MT technology, extending the operational temperature range, is well served by a careful investigation of the temperature dependence models of BTVs.

Organic Chemicals↗

Swine manure cleanup criteria calculation for odor causing volatile organic compounds based on manure-to-ventilation air exposure pathway.

A mathematical model was derived to calculate swine manure cleanup criteria for odor causing volatile organic compounds (VOCs) so that acceptable total dose would not exceeded through the inhalation of ventilation air in swine housing for workers and pigs. A hypothetical scenario was used which assumed that subsurface contaminant in swine manure diffuses through a layer of manure-air interface then is swept into the ventilated airspace via advection, where long-term inhalation of contaminant was assumed to occur. The philosophy of the transport model is to incorporate the age distribution of contaminated air and a first-order decay of contaminant sources into the diffusion model for simulation of air concentrations of VOCs and total exposure dose. A closed-form solution is presented to allow a series of numerical experiments for investigating the effects of adsorption characteristics between manure gas and manure, the mean age of contaminated air, effective diffusivity, and degradation coefficient on total dose. Swine manure cleanup criteria based on non-exceedence of the total hazardous dose corresponding to an acceptable risk from indoor inhalation of four selected VOCs of p-cresol, hexane, toluene, and xylene were calculated in a typical pig unit. The model can be used in the future to compute the relative effectiveness of VOCs filtration systems and/or altered ventilation rates on the VOC exposure problem in animal housing.

Air Pollutants↗

Treatment of vacutainers for use in the analysis of volatile organic compounds in human blood at the low parts-per-trillion level.

Vacutainers that are routinely used for blood collection contain significant amounts of volatile organic compounds (VOCs). These VOCs interfere with the low parts-per-trillion analysis of VOCs in whole blood either by causing false positives or by masking the presence of VOCs because of high background levels. Benzene, bromoform, ethylbenzene, m/p-xylene, o-xylene, styrene, and various hydrocarbons are the most significant sources of VOC contamination present in the vacutainers. A method of removing VOCs from 10-mL gray-top vacutainers is presented. This method uses a combination of heat and vacuum to reduce the VOCs to levels compatible with low parts-per-trillion analysis of VOCs in whole blood.

Blood Specimen Collection↗

Air to fat and blood to fat distribution of volatile organic compounds and drugs: linear free energy analyses.

Partition coefficients, K(fat), from air to human fat and to rat fat have been collected for 129 volatile organic compounds, VOCs. A linear free energy relationship, LFER, correlates the 129 values of log K(fat) with R(2)=0.958 and a standard deviation, S.D., of 0.194 log units. Use of training and test sets gives a predictive assessment of around 0.20 log units. Combination of log K(fat) with our previously listed values of log K(blood) enables blood/plasma to fat partition coefficients, as log P(fat), to be obtained for 126 VOCs. These values can be correlated with R(2)=0.847, S.D.=0.304 log units; the latter is also our assessment of the predictive capability of the LFER. Values of log P(fat) have been collected for 46 drugs, and can be fitted to an LFER with R(2)=0.811 and S.D.=0.355 log units. Unlike partition into brain or muscle, the data for VOCs and drugs cannot be combined. There are marked discrepancies for PCBs for which partition from blood/plasma into fat is very much less than that calculated from the data on VOCs or from the data on drugs.

Adipose Tissue↗

A simple calibration procedure for volatile organic compounds sampling in air with adsorptive solid-phase microextraction fibres.

Adsorptive solid-phase microextraction (SPME) fibres have proven to be a reliable means of sampling volatile organic compounds (VOCs) in air. In this work, polydimethylsiloxane/carboxen (PDMS/CAR) fibres were used to test a new approach of air sampling strategy with SPME in the lab which could lighten calibration procedure and enhance the use of this already rapid, simple, convenient and cost effective sampling technique. Indeed, only one curve can be used whatever the extraction time chosen by the analyst under constant conditions of air velocity and temperature. Ficks' law of diffusion was used to model SPME grab sampling when the fibre was totally exposed to the air sample. Experimental sampling rates were then determined by GC-FID for different sampling conditions, i.e. in a flowing air stream of known velocity ("dynamic mode") and in a stagnant air ("static mode"). These sampling rates were found to be 3.50 and 17.80 mL min(-1) for acetone, 4.06 and 21.20 mL min(-1) for 1,2-dichloroethane, 5.10 and 27.80 mL min(-1) for toluene and 5.36 and 30.80 mL min(-1) for butyl acetate, for static and dynamic sampling modes respectively. Deviation from linearity of the calibration curves, indicating that a significant fraction of the adsorption sites are occupied, were determined. They were found to be approximately equal to 0.9, 1.57, 3.82 and 4.37 nmol for acetone, dichloroethane, toluene and butyl acetate, respectively. Experimentally determined sampling rates of these isolated compounds were also valid when a complex equimolar gaseous mixture was investigated, but deviation from linearity appears earlier. Then, for a given application, sampling times should be chosen very carefully to avoid competitive adsorption and hence, bad quantitative analysis results.

Air Pollutants↗

Comparison of outdoor and indoor mobile source-related volatile organic compounds between low- and high-floor apartments.

The current study examined the hypothesis that there may be vertical variation in mobile source-related volatile organic compound (VOC) concentrations in high-rise apartment buildings. One hundred twelve homes in 56 high-rise apartment buildings with 10 or more stories participated in the study. Both the outdoor and the indoor air concentrations of three VOCs [methyl-tertiary butyl ether (MTBE), benzene, and toluene] were significantly higher for the low-floor apartments than for the high-floor apartments (P < 0.05). The median outdoor concentrations were 5.4, 6.8, and 29.1 microgram/m3, respectively, for the low-floor apartments, yet 4.4, 4.3, and 21.9 microgram/m3, respectively, for the high-floor apartments. Meanwhile, the median indoor concentrations were 6.3, 9.4, and 44.8 microgram/m3, respectively, for the low-floor apartments, yet 5.1, 7.6, and 38.8 microgram/m3, respectively, for the high-floor apartments. These findings indicate that residents of low-floor apartments are exposed to elevated residential levels of mobile source-related VOCs compared to high-floor apartment residents. The indoor concentrations of the target VOCs, except for MTBE, were significantly higher than the outdoor air concentrations for both the low and high floors (P < 0.05). Plus, the outdoor and indoor VOC concentrations were significantly different between the daytime and nighttime data sets for both low- and high-floor apartments, with a P value of less than or close to 0.05.

Air Pollutants↗

Characterization of volatile organic compounds and odors by in-vivo sampling of beef cattle rumen gas, by solid-phase microextraction, and gas chromatography-mass spectrometry-olfactometry.

Volatile organic compounds (VOCs) and odors in cattle rumen gas have been characterized by in-vivo headspace sampling by solid-phase microextraction (SPME) and analysis by gas chromatography-mass spectrometry-olfactometry (GC-MS-O). A novel device enabling headspace SPME (HS-SPME) sampling through a cannula was designed, refined, and used to collect rumen gas samples from steers. A Carboxen-polydimethylsiloxane (PDMS) fiber (85 microm) was used for SPME sampling. Fifty VOCs from ten chemical groups were identified in the rumen headspace. The VOCs identified had a wide range of molecular weight (MW) (34 to 184), boiling point (-63.3 to 292 degrees C), vapor pressure (1.05x10(-5) to 1.17x10(2) Pa), and water solubility (0.66 to 1x10(6) mg L-1). Twenty-two of the compounds have a published odor detection thresholds (ODT) of less than 1 ppm. More than half of the compounds identified are reactive and have an estimated atmospheric lifetime of <24 h. The amounts of VFAs, sulfide compounds, phenolic compounds, and skatole, and the odor intensity of VFAs and sulfide compounds in the rumen gas were all higher after feeding than before feeding. These results indicate that rumen gases can be an important potential source of aerial emissions of reactive VOCs and odor. In-vivo sampling by SPME then GC-MS-O analysis can be a useful tool for qualitative characterization of rumen gases, digestion, and its relationship to odor and VOC formation.

Animal Feed↗