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Biogenic volatile organic compound emissions (BVOCs). II. Landscape flux potentials from three continental sites in the U.S.

Landscape flux potentials for biogenic volatile organic compounds (BVOCs) were derived for three ecosystems in the continental U.S. (Fernbank Forest, Atlanta, GA; Willow Creek, Rhinelander, WI; Temple Ridge, CO). Analytical data from branch enclosure measurements were combined with ecological survey data for plant species composition and biomass. Other quantitative flux measurements at the leaf and landscape level were incorporated to scale the results from the enclosure measurements to the landscape level. Flux estimates were derived by using a one week ambient temperature and light record (30 min time resolution) and adjusting all emission rates to these conditions with temperature and light correction algorithms.

Colorado↗

Nasal effects of a mixture of volatile organic compounds and their ozone oxidation products.

OBJECTIVE: Our objective was to determine if low levels of a mixture of volatile organic compounds (VOCs) and their ozone (O3) oxidation products, similar to what might be found in "sick buildings," cause nasal irritation and inflammation under controlled exposure conditions. METHODS: Healthy, nonsmoking women (n=130) completed 2-hour controlled exposures to VOCs, VOCs and O3, and a masked air "MA" control in random order at least 1 week apart. VOCs and O3 concentrations were approximately 25 mg/m and approximately 40 ppb, respectively. Nasal symptoms were rated before, during, and after exposure. Nasal lavage fluid was analyzed for polymorphonuclear cells, total protein, interleukin-6, and interleukin-8. RESULTS: We found no significant differences in symptoms or markers of nasal inflammation between exposure conditions. CONCLUSIONS: Results suggest that VOCs and their oxidation products may not cause acute nasal effects at low concentrations.

Adult↗

Quantitative determination of volatile organic compounds (VOC) in milk by multiple dynamic headspace extraction and GC-MS.

A method for the accurate determination of volatile organic compounds (VOC) in milk samples has been developed and tested. It combines multiple dynamic headspace extraction with GC-MS. Absolute amounts of VOC in the liquid phase are obtained by determining the first order kinetic dependence of the stepwise extraction of the analytes and internal standards from the liquid matrix. Compounds released from milk were collected on a train of traps filled with different solid sorbents to cover all components having a number of carbon atoms ranging from 4 to 15. They were analysed by GC-MS after thermal desorption of VOC from the collecting traps. Quantification of VOC in milk was performed using deuterated compounds as internal standards. The method was used to follow seasonal variations of monoterpenes in goat milk and to detect the impact of air pollution on the quality of milk.

Animals↗

Measurement of volatile organic compounds in sediments of the Scheldt estuary and the Southern North Sea.

The concentrations and distribution of 13 priority volatile organic compounds (VOCs) were determined in sediments of the Scheldt estuary and the Belgian continental shelf, using a modified Tekmar LSC 2000 purge-and-trap system coupled to GC-MS. The method allows a sample intake of up to 50 g wet weight and detection limits are between 0.003 ng/g (tetrachloromethane) and 0.16 ng/g (m- and p-xylene). The repeatability (n = 5) varied between 4% (benzene) and 17% (toluene) and the recoveries ranged from 59% (1,1-dichloroethane) to 99% (tetrachloromethane). Because of the nature of the contaminants, special attention was paid to analyte losses and contamination of the samples during storage aboard the research vessel. Spiked sediment samples were prepared in the laboratory and stored aboard under the same conditions as the environmental samples. The recoveries for these samples varied between 94 and 130%, which suggests that storage had no adverse effect on the samples. No detectable VOC concentrations were found for most of the sampling stations. However, in the Antwerp harbour area, significant concentrations of VOCs were found. The sorption behaviour as predicted from laboratory equilibrium partitioning experiments gives an indication of the in situ partitioning behaviour of VOCs. Although VOCs in sediments should, in general, not be regarded as a major problem in the marine environment, high local concentrations may be a cause of concern.

Geologic Sediments↗

Volatile organic compound (VOC) analysis and sources of limonene, cyclohexanone and straight chain aldehydes in axenic cultures of Calothrix and Plectonema.

The volatile organic compounds (VOCs) in four standing cultures of axenic benthic cyanobacteria (Calothrix and Plectonema) were studied by GC/MS analysis. To verify the biogenic origin of the VOCs, 13C-labelling experiments were performed, and the differences in labelling were used to differentiate between biogenic and non-biogenic sources. Strongly labelled biogenic compounds were derived from the shikimate (cresol, skatole), isoprenoid (beta-cyclocitral, beta-ionone, geosmin) and fatty acid pathways (5Z-heptadecene, 3-octanone, 1-hexanol). New odour compounds derived from microorgansims were beta-cyclogeraniol, dihydro-beta-ionone and 2-hydroxy-2,6,6-trimethylcyclohexanone. The latter compound had already been found in lake water, but could not be assigned to a particular organism. Straight chain aldehydes (octanal, nonanal, decanal), cyclohexanone, cyclohexanol and limonene were unlabelled beyond their natural isotope ratio. Therefore, the biogenic origin of these compounds is doubtful despite their occurrence in axenic cultures. The observation that limonene was a racemate supports this view. The precursors and reactions that lead to the formation of these non-biogenic compounds are unknown and it may be that they are formed by the analytical procedures rather than then being present in the culture medium.

Aldehydes↗

Quantitative structure-activity relationships for nasal pungency thresholds of volatile organic compounds.

A model was developed for describing the triggering of nasal pungency in humans, based on the partition of volatile organic compounds (VOCs) between the air phase and the biophase. Two partition parameters are used in the model: the water-air partition coefficient and the octanol-water partition coefficient. The model was validated using data from the literature, principally on alcohols, acetates and ketones. The model suggests that all test compounds, regardless of their chemical functional groups, bind to a common receptor site within the hydrophobic interior of the bilayer membrane of the trigeminal nerve endings. There is probably only a slight, non-specific interaction between the VOC molecule and the receptor molecule, whereas this type of non-specific interaction for the detection of odor is much stronger. In practical terms, the suggestion that all VOCs share a common irritation receptor site implies that nasal-pungency thresholds of individual VOCs may be additive. Quantitative structure-activity relationships (QSARs) for nasal-pungency thresholds were also developed from the model, which can be used to predict nasal-pungency thresholds of common VOCs. Although the present model does not offer additional precision over that of M.H. Abraham et al., 1996, Fundam. Appl. Toxicol. 31, 71-76, it requires fewer descriptors and offers a physiological basis to the QSAR. Another advantage of the present model is that it also provides a basis for comparison between the olfactory process and nasal pungency.

Air Pollutants↗

Concentrations of volatile organic compounds at a building with health and comfort complaints.

For four separate periods over a 1-yr span, the concentrations of volatile organic compounds (VOCs) have been measured at a facility with a history of occupant complaints. The reported symptoms were characteristic of "sick building syndrome." This study was initiated to determine if VOC levels were higher than those measured in "complaint-free" buildings and, if so, to identify sources and other factors that might contribute to the elevated concentrations. VOCs were collected with passive samplers, using a sampling interval that lasted from 3 to 4 weeks. Following collection, the samplers were extracted, and the compounds in the extract were separated and identified using standard gas chromatographic-mass spectrometric procedures. Over 40 different organic compounds with concentrations in excess of 1 microgram/m3 were identified; several species had values greater than 100 micrograms/m3. For each of the first three sampling periods, the total concentration of VOCs detected using this methodology was in excess of 3 mg/m3. Sources of the identified compounds included cleaning products, floor wax, latex paints, and reentrained motor vehicle exhaust. However, the dominant source was the hydraulic system for the buildings' elevators. Compounds were volatilizing from the hydraulic fluid used in this system. Neither the elevator shafts nor the mechanical room housing the fluid reservoirs were vented to the outside. The problem was compounded by the relatively small amount of outside air used for ventilation at this facility (less than 6 L/sec [12 cfm]/occupant or about 1/4 air change/hr). At such low ventilation rates, compounds with strong sources can achieve high steady-state concentrations within the facility. Recommendations have been made to reduce the VOC levels at this site. Although implementing the recommendations will be costly, even a slight improvement in employee productivity will offset these costs.

Air Pollutants↗

Quantification of 31 volatile organic compounds in whole blood using solid-phase microextraction and gas chromatography-mass spectrometry.

The prevalence of exposure to volatile organic compounds (VOCs) has raised concern about possible health effects resulting from chronic human exposure. To support studies exploring the relation between VOC exposure and health effects, we developed an automated analytical method using solid-phase microextraction (SPME), capillary gas chromatography (GC), and quadrupole mass spectrometry (MS). This method quantifies trace levels (low parts per trillion) of 14 halogenated alkanes, 5 halogenated alkenes, 10 aromatic compounds, and 2 other VOCs in human blood. Detection limits for the SPME-GC-MS method range from 0.005 to 0.12 microg/L, with linear calibration curves spanning three orders of magnitude. The improved throughput of this method will enable us to expand biomonitoring efforts to assess nonoccupational VOC exposure in large epidemiological studies.

Gas Chromatography-Mass Spectrometry↗

Exposure to volatile organic compounds for individuals with occupations associated with potential exposure to motor vehicle exhaust and/or gasoline vapor emissions.

Workers who work near volatile organic compounds (VOCs) source(s), motor vehicle exhausts and/or gasoline vapor emissions, are suspected to be exposed to highly-elevated VOC levels during their work-time. This study confirmed this suspicion and evaluated the work-time exposure VOCs for traffic police officers, parking garage attendants, service station attendants, roadside storekeepers and underground storekeepers, by measuring the concentrations of six aromatic VOCs in workplace air, or personal air and breath samples. For nearly all target VOCs, the post-work breath concentrations of the workers were slightly or significantly higher than the pre-work breath concentrations, depending on the compound and occupation. Furthermore, both the pre- and post-work breath concentrations of the workers showed elevated levels compared with a control group of college students. The post-work breath concentrations were significantly correlated with the personal air concentrations, while the pre-work breath concentrations were not. Smoking workers were not always exposed to higher aromatic VOC levels than non-smoking workers. The breath and personal air concentrations for all the target compounds were both higher for underground parking garage attendants than for ground-level parking attendants. For all the target compounds except toluene, storekeepers exhibited similar levels of exposure for all store types. Print shopkeepers recorded the highest toluene exposure.

Adult↗

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

Distribution coefficients, K(mus), from the gas phase to the muscle have been collected for volatile organic compounds (VOCs). For 114 VOCs, a linear free energy relationship (LFER) yields an equation for log K(mus) with R(2) = 0.944 and SD = 0.267; construction of a training and test set shows that the LFER can predict further values to around 0.30 log units. The combination of the log K(mus) values with values for air to blood yields distribution coefficients from blood to muscle, log P(mus), for 110 VOCs; the corresponding LFER has R(2) = 0.537 and SD = 0.207 and a predictive capability of 0.22 log units. We also collected data on the distribution of drugs from blood or plasma to muscle and showed that the two sets of data can be combined. A LFER for blood/plasma to muscle for 59 drugs has R(2) = 0.745 and SD = 0.253 and a predictive capability of 0.25 log units. Finally, we show that the in vitro data on VOCs and the in vivo data on drugs can be combined; a LFER on the total data for 163 compounds has R(2) = 0.595, SD = 0.220, and a predictive capability of about 0.25 log units.

Air↗

Sub-second thermal desorption of a micro-sorbent trap for the analysis of ambient volatile organic compounds.

This study investigates a novel approach of fast thermal desorption on a micro-sorbent trap for analyzing ambient volatile organic compounds (VOCs) by gas chromatography with flame ionization detection. Unlike conventional approaches, the temperature feedback mechanism for temperature control was abandoned, which often poses a limit to the heating speed due to slow response of the sensor and the control algorithm. Instead, a series of programmed a.c. pulses was given to the Ni-Cr wire coiled around the micro-trap to perform instant heating from room temperature to 250 degrees C within a fraction of a second, maintained at 250 degrees C during injection, and subsequently to 300 degrees C for trap cleaning. Temperature fluctuation around a high temperature set point could be maintained within +/- 10 degrees C. Significant improvement in resolution and peak height was obtained compared to a trap with temperature feedback and control algorithm. While keeping resolution at a satisfactory level, the sub-second desorption approach allows faster chromatography and at the same time increases the sensitivity of VOC analysis.

Chromatography, Gas↗

Changes in immunological and hematological parameters of female residents exposed to volatile organic compounds in the city of Kaohsiung, Taiwan.

The objective of this study was to assess the effects, if any, of volatile organic compounds (VOCs) in the ambient air of Kaohsiung, Taiwan, on certain hematological and immunological parameters of 153 female study participants. The major source of VOCs was vehicle emissions. The participants were selected from three areas, each area at a different distance from a freeway. Results indicated that total concentrations of VOCs and a subgroup of 25 VOCs (VOC25) ranged from 250 to 335 ppb and 89 to 113 ppb, respectively. The distribution of VOC concentrations did not correlate with distance from the freeway. The participants living in the area with higher VOC concentrations had significantly higher abnormalities of white blood cells (WBC) and hemoglobin (Hb). In addition, IgG and IgA counts were significantly lower for the participants in the area with higher VOCs than for participants in the area with lower VOCs. This finding indicates that VOCs in ambient air may suppress immunological variables.

Adult↗

Exposure to volatile organic compounds in residences adjacent to dyeing industrial complex.

OBJECTIVES: The present study was designed to evaluate residential exposure to selected volatile organic compounds (VOCs) relative to the proximity of the Daegu dyeing industrial complex (DDIC). METHODS: A series of surveys was conducted to measure the concentrations of five aromatic VOCs (toluene, benzene, m-xylene, p-xylene, and o-xylene) and methyl tertiary-butyl ether (MTBE) in the industrial outdoor air within the DDIC and in residential outdoor and indoor air based on the relative proximity of the DDIC. RESULTS: The geometric mean (GM) toluene value for the outdoor air samples from residential area R1 located near the DDIC (255 microg/m(3)) was about seven-times higher than that from residential area R2 located further away from the DDIC (36.9 microg/m(3)), whereas no significant difference was found in the outdoor air concentrations of the other target compounds between the two residential areas. Moreover, the elevated outdoor toluene levels outweighed the indoor sources with respect to the environmental exposure of residents near the DDIC. However, for the other target VOCs there was no significant difference between the residential exposure of residents living close to and a certain distance away from the DDIC. CONCLUSIONS: The present study confirmed that residents in neighborhoods near the DDIC were exposed to elevated outdoor toluene levels compared with residents living further away from such a source. Furthermore, it appeared that the DDIC was a potential contributor to the nearby residential outdoor toluene levels.

Air Pollutants, Occupational↗

Minimization of water vapor interference in the analysis of non-methane volatile organic compounds by solid adsorbent sampling.

Water vapor can be a significant interference in the analysis of air for non-methane volatile organic compounds (NMVOCs) using solid-adsorbent sampling techniques. The adsorbent materials used in sampling cartridges have different hydrophobic characteristics, and it is therefore necessary to characterize solid-adsorbent cartridges over a wide range of humidity. Controlled humidity experiments were performed to assess the extent of water vapor interference when samples are collected onto AirToxics solid-adsorbent cartridges. It was found that elevating the temperature of the cartridge to 10 degrees C above the temperature of the air sample greatly reduced water vapor adsorption and interferences and resulted in > or = 90% recovery of NMVOCs, biogenic VOCs and chlorofluorocarbons. Similar collection efficiencies were obtained at ambient temperature by reducing the relative humidity to > or = 60% in the sample by dilution with dry, scrubbed ambient air. A procedure also was developed and optimized for dry-purging cartridges prior to analysis. However, under optimized conditions, significant losses of C3-C5 compounds still occurred under highly humid conditions. It was determined that these losses were due to reduced retention during sampling rather than loss during the dry purge procedure. The dry purge method was shown to be adequate at high humidities for sampling NMVOCs with retention indices greater than 500.

Adsorption↗

Thermal desorption/gas chromatographic/mass spectrometric analysis of volatile organic compounds in the offices of smokers and nonsmokers.

The indoor air quality of the offices of smokers and nonsmokers was surveyed for volatile organic compound identities and concentrations. These results were examined to determine whether environmental tobacco smoke contamination could be distinguished from airborne pollutants outgassing from other sources. It was not possible to positively attribute volatile organic contaminants to environmental tobacco smoke. It was possible to distinguish between smokers' and nonsmokers' offices by determining airborne nicotine levels.

Air↗

Development of a cryogen-free concentration system for measurements of volatile organic compounds.

An innovative cryogen-free concentrator system for measurement of atmospheric trace gases at the parts per trillion level has been developed with detection by routinely used gas chromatographic methods. The first-generation system was capable of reaching a trapping temperature of -186 degrees C, while the current version can reach -195 degrees C. A Kleemenko cooler is used to create liquid nitrogen equivalent trapping conditions and eliminate the use of solid absorbents, a potential source of artifacts. The method utilizes dual-stage trapping with individual cold regions. The two stages are cooled to -20 and -175 degrees C for water management and sample enrichment, respectively. Both stages house a Silonite-coated stainless steel sample loop; the second stage loop is filled with 1-mm-diameter glass beads, which provide an inert surface area for analyte concentration. In our application, the complete system employed four channels utilizing two flame ionization detectors, one electron capture detector, and a mass spectrometer. The system was automated for unattended operation and was deployed off the New England east coast on Appledore Island to measure a suite of ambient non-methane hydrocarbons, halocarbons, alkyl nitrates, and oxygenated volatile organic compounds during the International Consortium for Atmospheric Research on Transport and Transformation field campaign in summer 2004. This robust system quantified 98 ambient volatile organic compounds with precisions ranging from 0.3 to 15%.

Journal Article↗

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

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

Adsorption↗

Performance evaluation of a sorbent tube sampling method using short path thermal desorption for volatile organic compounds.

Air sampling, using sorbents, thermal desorption and gas chromatography, is a versatile method for identifying and quantifying trace levels of volatile organic compounds (VOCs). Thermal desorption can provide high sensitivity, appropropriate choices of sorbents and method parameters can accommodate a wide range of compounds and high humidity, and automated short-path systems can minimize artifacts, losses and carry-over effects. This study evaluates the performance of a short-path thermal desorption method for 77 VOCs using laboratory and field tests and a dual sorbent system (Tenax GR, Carbosieve SIII). Laboratory tests showed that the method requirements for ambient air sampling were easily achieved for most compounds, e.g., using the average and standard deviation across target compounds, blank emissions were < or = 0.3 ng per sorbent tube for all target compounds except benzene, toluene and phenol; the method detection limit was 0.05 +/- 0.08 ppb, reproducibility was 12 +/- 6%, linearity, as the relative standard deviation of relative response factors, was 16 +/- 9%, desorption efficiency was 99 +/- 28%, samples stored for 1-6 weeks had recoveries of 87 +/- 9%, and high humidity samples had recoveries of 102 +/- 12%. Due to sorbent, column and detector characteristics, performance was somewhat poorer for phenol groups, ketones, and nitrogen containing compounds. The laboratory results were confirmed in an analysis of replicate samples collected in two field studies that sampled ambient air along roadways and indoor air in a large office building. Replicates collected under field conditions demonstrated good agreement except for very low concentrations or large (> 41 volume) samples of high humidity air. Overall, the method provides excellent performance and satisfactory throughput for many applications.

Adsorption↗