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A full evaporation headspace technique with capillary GC and ITD: a means for quantitating volatile organic compounds in biological samples.

The full evaporation technique (FET), which is a variant of headspace analysis used to overcome matrix effects, was combined with capillary gas chromatography (GC) and ion-trap detection (ITD). The aim was to enable quantitative tests of volatile organic compounds (VOCs) in blood and postmortem tissue samples. FET was applied to sample sized less than 35 mg whose VOCs were released from the matrix at an equilibration temperature of 130 degrees C. A capillary column with a nonpolar stationary phase was used for GC, and ITD was performed with the mass spectrometer run in full-scan mode. The potential of FET-GC-ITD was studied for the analysis of blood samples spiked with low concentrations of ethanol, acetone, 2-propanol, and 2-butanone and on brain tissue that contained methyl tert-butyl ether (MTBE), Benzene, toluene, ethylbenzene, o-, m-, and p-xylene, and propylbenzene. Samples were obtained from the bodies of victims who had inhaled smoke during an arson or accidental fire. There was a linear relationship between peak area and sample size, which indicates that the conditions of full evaporation were met and that the matrix effect was negated. The total analyte amount in the test sample at the limit of quantitation was in the range of 0.4-1 nmol for polar VOCs in blood and 0.03-0.1 nmol for nonpolar VOCs in brain tissue. Data on precision and accuracy of the method are reported.

Alcohols↗

Two-dimensional on-line detection of brominated and iodinated volatile organic compounds by ECD and ICP-MS after GC separation.

Inductively coupled plasma-mass spectrometry (ICP-MS) was coupled to a gas chromatographic (GC) system with electron capture detector (ECD), which enables relatively easy characterization and quantification of brominated and iodinated (halogenated) volatile organic compounds (HVOCs) in aquatic and air samples. The GC-ECD system is connected in series with an ICP-MS by a directly heated transfer line and an outlet port-hole for elimination of the ECD make-up gas during ignition of the plasma. The hyphenated GC-ECD/ICP-MS system provides high selectivity and sensitivity for monitoring individual HVOCs under fast chromatographic conditions. The ECD is most sensitive for the detection of chlorinated and brominated but the ICP-MS for iodinated compounds. The greatest advantage of the use of an ICP-MS is its element-specific detection, which allows clear identification of compounds in most cases. The absolute detection limits for ICP-MS are 0.5 pg for iodinated, 10 pg for brominated, and 50 pg for chlorinated HVOCs with the additional advantage that calibration is almost independent on different compounds of the same halogen. In contrast to that detection limits for ECD vary for the different halogenated compounds and lie in the range of 0.03-11 pg. The two-dimensional GC-ECD/ICP-MS instrumentation is compared with electron impact mass spectrometry (EI-MS) and microwave induced plasma atomic emission detection (MIP-AED). Even if EI-MS has additional power in identifying unknown peaks by its scan mode, the detection limits are much higher compared with GC-ECD/ICP-MS, whereas the selective ion monitoring mode (SIM) reaches similar detection limits. The MIP-AED detection limits are at the same level as EI-MS in the scan mode.

Air Pollutants↗

Delivery levels and behavior of 1,3-butadiene, acrylonitrile, benzene, and other toxic volatile organic compounds in mainstream tobacco smoke from two brands of commercial cigarettes.

Mainstream tobacco smoke (MTS) was collected from Camel and Marlboro cigarettes for the determination of the delivery levels and equilibrium gas/particle partitioning constants K(p) (m(3) microg(-)(1)) of 26 volatile organic compounds (VOCs) of toxicological interest. K(p) values are important for understanding the fractional distribution of each compound of interest between the gas and the particle phases of MTS. The experimental method involved (i) drawing a smoke sample into a Teflon sampling bag at 20 degrees C, (ii) allowing the smoke particulate matter (PM) to collect on the walls of the bag, (iii) sampling the bag to determine the initial gas phase concentration of each VOC, (iv) removing the gas phase from the bag, (v) refilling the bag with humidified nitrogen gas, (vi) reestablishing the gas/PM equilibrium, and (vii) redetermining the gas phase concentrations. For each smoke sample, a comparison of the initial and redetermined gas phase concentrations allowed calculation of the total (i.e., gas + particle) delivery level (= m(tot), ng cig(-)(1)) and K(p) value (= c(p)/c(g)) at 20 degrees C for each compound, where c(p) (ng microg(-)(1)) = concentration in the PM phase and c(g) (ng m(-)(3)) = concentration in the gas phase. Significant deliveries were observed for a number of carcinogenic VOCs. For the Camel cigarettes tested, the average m(tot) values for 1,3-butadiene, acrylonitrile, and benzene were 10(4.6), 10(4.4), and 10(4.8) ng cig(-)(1), respectively; for Marlboro, the m(tot) values were 10(5.0), 10(4.6), and 10(4.7) ng cig(-)(1), respectively. For each of the 26 VOCs, the smoke PM from the two brands yielded very similar K(p) values at 20 degrees C. In addition, the vapor pressure-dependent K(p) values of the 26 VOCs were in close agreement with predictions made by the Pankow theory of absorptive gas/particle partitioning [Pankow, J. F. (1994) Atmos. Environ. 28, 185-188]. These results can be used in general predictions of chemical behavior in tobacco smoke, including deposition mechanisms and rates in the respiratory tract from inhaled MTS. Example calculations are provided to illustrate how the gas phase fraction at equilibrium (f(g,e)) increases strongly with increasing compound vapor pressure and temperature and with dilution of the inhaled tobacco smoke total PM concentration (microg m(-)(3)).

Acrylonitrile↗

Volatile organic compounds from leaves litter.

Qualitative composition of volatile emissions of litter of five species of deciduous trees was investigated by GC-MS. The list of identified substances contains more than 70 organic compounds of various classes. It was established that the composition of components emitted by the litter into the gas phase greatly differs from that of essential oils extracted by hydrodistillation from turned leaves collected from trees during fall. It is suggested that most compounds found in litter emissions are products of vital activity of microorganisms decomposing it. The reported data indicate that after the vegetative period is over the decomposition processes of litter are important seasonal sources of reactive organic compounds under the forest canopy.

Environmental Monitoring↗

Sampling and analysis of volatile organic compounds in bovine breath by solid-phase microextraction and gas chromatography-mass spectrometry.

A relatively noninvasive method consisting of a face mask sampling device, solid-phase microextraction (SPME) fibers, and a gas chromatography-mass spectrometry (GC-MS) for the identification of volatile organic compounds (VOCs) in bovine breath was developed. Breath of three morbid steers with respiratory tract infections and three healthy steers were sampled seven times in 19 days for 15 min at each sampling. The breath VOCs adsorbed on the divinylbenzene (DVB)-Carboxen-polydimethyl siloxane (PDMS) 50/30 microm SPME fibers were transported to a laboratory GC-MS system for separation and identification with an in-house spectral library of standard chemicals. A total of 21 VOCs were detected, many of them for the first time in cattle breath. Statistical analyses using Chi-square test on the frequency of detection of each VOC in each group was performed. The presence of acetaldehyde (P < or = 0.05) and decanal (P < or = 0.10) were associated more with clinically morbid steers while methyl acetate, heptane, octanal, 2,3-butadione, hexanoic acid, and phenol were associated with healthy steers at P < or = 0.10. The results suggest that noninvasive heath screening using breath analyses could become a useful diagnostic tool for animals and humans.

Animals↗

Contaminated site remedial investigation and feasibility removal of chlorinated volatile organic compounds from groundwater by activated carbon fiber adsorption.

Groundwater contaminated by dense, non-aqueous phase liquids (DNAPLs) such as chlorinated solvents has become a serious problem in some regions of Taiwan. The sources of these contaminants are due to industrial discharges. These chlorinated volatile organic compounds (VOCs) have been proven to be carcinogenic to humans. The groundwater is used for domestic drinking water supply in some cities of Taiwan and the severely contaminated groundwater has to be treated in order to meet the requirement of drinking water standards. This study covers two areas of work. In the first part, polluted groundwater samples were collected from the contaminated site and analytical results indicated measurable concentrations of 12 representative chlorinated VOCs in water samples. The primary VOCs detected included trichloroethene (TCE), tetrachloroethene (PCE), 1,1,2-trichloroethane (1,1,2-TCA), and 1,1-dichloroethene (1,1-DCE). Second, to remove VOCs groundwater was treated using adsorption on activated carbon fiber (ACF). This involved pumping groundwater through vessels containing ACF. Most VOCs, including TCE, PCE, 1,1,2-TCA, and DCE, were readily adsorbed onto ACF and are removed from the water stream. Our study showed that the technology was able to significantly reduce chlorinated VOCs concentrations in groundwater.

Adsorption↗

Volatile organic compounds cytotoxicity and expression of HSP72, HSP90 and GRP78 stress proteins in cultured human cells.

The aim of this study was to determine whether overexpression of stress proteins (SPs) could be a sensitive biomarker for cell injury due to exposure to low doses of volatile organic compounds (VOCs) such as benzene, ethylbenzene, toluene, xylene, and chlorinated derivatives (ClB). Sublethal and cytotoxic threshold concentrations of the VOCs were determined by studying the growth rate of normal (fibroblasts) or tumor-derived human cell lines (A549, HepG2) exposed for 4 days to VOCs. Changes in SP expression as a function of concentrations were investigated by Western blotting.VOC toxicity was found to be correlated with their degree of chlorination and their hydrophobicity. Cytotoxic threshold concentrations (no-observed effect concentration, NOEC) were found to be similar for the three cell lines. It was observed that using a mixture of VOCs, each of them at concentration below the NOEC, resulted in an actual toxicity to the cells. This finding reveals a synergistic effect and should be taken into account when assessing threshold risk and exposure limit values in the worker's environment when several pollutants may be present. HSP72 and HSP90 expression levels were not affected whereas GRP78 expression was increased by all the VOCs. Taking into account the specific molecular function of GRP78, it suggests that VOC exposure results in misfolded or underglycosylated protein accumulation in the endoplasmic reticulum. GRP78 overexpression was closely related to the magnitude of growth inhibition due to increasing concentrations of each VOC. The overexpression was found to be significant for concentrations 5 to 30 times higher than NOEC, indicating that, under our experimental conditions, GRP78 expression cannot be considered as a sensitive biomarker of exposure to environmental VOCs.

Benzene↗

Determination of physiological levels of volatile organic compounds in blood using static headspace capillary gas chromatography with serial triple detection.

A static capillary gas chromatographic method using three different detectors [photoionization detector (PID), electron capture detector (ECD) and flame ionization detector (FID)] switched in series is presented for the determination of volatile organic compounds (VOCs) in sub microgram l-1 levels. The method was applied for the analysis of selected environmentally and occupationally relevant non-halogenated and chlorinated aromatic hydrocarbons (e.g., benzene, toluene, xylenes, dichlorobenzenes) as well as chlorinated aliphatic hydrocarbons (e.g., trichloroethene, tetrachloroethene) in blood samples. Detailed investigations, in respect to the figures of merit were carried out. For most of the selected VOCs detection limits (calculated as the three-fold standard deviation of low level calibration standards) in the range from 26 (benzene) to 67 ng l-1 (m/p-xylene) were achieved which are comparable with those reported for dynamic headspace techniques in combination with mass spectrometric detection. For the individual VOCs the within-series precision varied from 4 to 19% and the day-to-day precision from 11 to 28%. Regarding PID as well as FID the calibration graphs for all substances were linear up to at least 10 micrograms l-1 while the ECD response was linear up to concentrations of about 0.6 microgram l-1 for the halogenated compounds. Our method is applicable for the quantitative determination of VOCs in blood in the occupationally as well as in the physiologically relevant (normal) concentration range.

Air Pollutants↗

[A method for determination of volatile organic compounds in drinking water by purge and trap in combination with gas chromatograph/mass spectrometry].

OBJECTIVE: To establish a method of purge and trap in combination with gas chromatograph/mass spectrometry(P and T-GC/MS) for the rapid determination of minimum multi-mixture of volatile organic compounds (VOCs) in drinking water simultaneously. METHODS: The experimental conditions of P and T, such as desorption temperature, desorption time, the type of the trap and the analytical conditions of GC were optimized. 54 VOCs in drinking water were determined by P and T-GC/MS. RESULTS: The method enjoyed a wide linear range and good precision, the method detection limit(MDL) was 0.01 - 0.5 microg/L, the average recoveries of the method was 90% - 110% and the relative standard deviation (RSD) was 1.24%-7.79%. CONCLUSION: The results showed that the method was accurate and high sensitivity and might be good for application and suitable for trace analysis of VOCs in drinking water.

Gas Chromatography-Mass Spectrometry↗

Effect of exposure to volatile organic compounds on plasma levels of neuropeptides, nerve growth factor and histamine in patients with self-reported multiple chemical sensitivity.

Plasma levels of substance P, vasoactive intestinal peptide and nerve growth factor, but not histamine, were elevated in patients with self-reported multiple chemical sensitivity (sMCS). Exposure to volatile organic compounds (VOC) increased plasma levels of all parameters in these patients, while it had no effect in normal subjects or patients with atopic eczema/dermatitis syndrome (AEDS). Exposure to VOC also enhanced skin wheal responses induced by histamine in patients with sMCS, while it failed to do so in normal or AEDS subjects. These results indicate that exposure to VOC may enhance neurogenic inflammation with concomitant enhancement of histamine-induced responses.

Adult↗

The German Environmental Survey 1990/92 (GerES II): sources of personal exposure to volatile organic compounds.

In the framework of the second German Environmental Survey carried out in the Western part of Germany in 1990/91 (GerES IIa) 113 adults aged 25-69 years were selected at random from the total study population of about 2500 to investigate personal exposure to about 70 volatile organic compounds (VOCs). Each subject wore a diffusive badge-type sampler for 1 week. The VOCs determined included alkanes, aromatics, aliphatic halocarbons, terpenes, and oxygen-containing compounds. Multivariate regression analysis was carried out to determine and quantify the major sources of personal exposure to various VOCs. In this paper, results are given for benzene, and C8- and C9-aromatics. Being subject to environmental tobacco smoke was found to be the most important determinant of benzene exposure, but automobile-related activities such as driving a car or refuelling, were also associated with significantly increased levels of benzene. The major determinant of C8- and C9-aromatics concentrations was occupational exposure. Emissions from paints, lacquers, newspapers, magazines and print-works were also important contributors to C8-aromatics exposure. Renovation, painting and smoking were associated with a significant increase of the exposure to C9-aromatics.

Adult↗

A universal temperature controlled membrane interface for the analysis of volatile and semi-volatile organic compounds.

A universal temperature controlled membrane interface (TCMI) has been constructed for hollow-fibre membranes. The membrane temperature is controllable in the range -70 to 250 degrees C using an electric heater and a flow of cooled nitrogen or helium gas. Volatile and semi-volatile organic compounds may be detected either by continuous diffusion across the membrane or by in-membrane pre-concentration followed by thermal desorption into the detector. The TCMI interface is demonstrated in combination with mass spectrometry and GC-MS, for the determination of VOCs and SVOCs in aqueous and air samples and for the on-line monitoring of a bioreactor.

Flow Injection Analysis↗

Elevated internal exposure of children in simulated acute inhalation of volatile organic compounds: effects of concentration and duration.

When deriving health-based exposure limits in recent years, increasing attention has been drawn to susceptible subpopulations, in particular to children. We investigated the differences in kinetics between children and adults during inhalation of styrene as a typical category-3 volatile organic compound (VOC), i.e., a gas with a low reactivity and low water solubility allowing a high rate of alveolar absorption. Internal exposure was simulated using a physiologically based kinetic model over a broad range of airborne concentrations (1-1000 ppm) and for an exposure time of up to 8 h according to the scenario in the acute exposure guideline level (AEGL) program. Age-specific anatomical and physiological parameters and compound-specific data was derived from the literature. The calculated concentrations in arterial blood are higher in children than in adults, and are highest in the newborn. For an 8-h exposure to low concentrations, the calculated arterial concentration in the newborn is higher by a factor of 2.3 than in the adult. This is due mainly to the relatively high ventilation rate and the immature metabolism. With increasing airborne concentration, the ratio of arterial concentrations (newborn/adult) increases to a maximum of 3.8 at 130 ppm in ambient air, and declines with further increments of concentration to a value of 1.7. This is because the metabolism of the newborn becomes non-linear at lower concentrations than in adults. At high concentrations, metabolism is saturated in both age groups. For shorter exposures, the dose dependency of the concentration ratios (newborn/adult) is less pronounced. This is the first article to show that the intraspecies assessment factor may vary with concentration and duration of exposure.

Administration, Inhalation↗

Volatile organic compounds detected in the atmosphere of NASA's Biomass Production Chamber.

Atmospheres of enclosed environments in which 20 m2 stands of wheat, potato, and lettuce were grown were characterized and quantified by gas chromatography-mass spectrometry. A large number (in excess of 90) of volatile organic compounds (VOCs) were identified in the chambers. Twenty eight VOC's were assumed to be of biogenic origin for these were not found in the chamber atmosphere when air samples were analyzed in the absence of plants. Some of the compounds found were unique to a single crop. For example, only 35% of the biogenic compounds detected in the wheat atmosphere were unique to wheat, while 36% were unique to potato and 26% were unique to lettuce. The number of compounds detected in the wheat (20 compounds) atmosphere was greater than that of potato (11) and lettuce (15) and concentration levels of biogenic and non-biogenic VOC's were similar.

Air↗

[Preparation of a solid-phase microextraction fiber coated with gamma-Al2O3 and determination of volatile organic compounds in aqueous and gaseous samples].

A method for the preparation of a novel gamma-Al2O3 coated layer on fibers for solid-phase microextraction (SPME) was developed. The adsorption and desorption properties of the coated fibers were studied by the extraction of some volatile organic compounds such as benzene, toluene, ethylbenzene and xylene isomers (BTEXs) from aqueous samples. The calibration graphs were linear in the range 0.01 mg/L to 3 mg/L and the detection limits for BTEX compounds were between 1 microg/L and 10 microg/L. Also the gamma-Al2O3 coated fibers exhibited a good thermal stability (to 350 degrees C ) and reproducibility with relative standard deviation of 8.3%. It can be used to determine organic compounds in the real gaseous samples.

Aluminum Oxide↗

Analysis of semi-volatile organic compounds in aqueous samples by microwave-assisted headspace solid-phase microextraction coupled with gas chromatography-electron capture detection.

The pretreatment technique of microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) has been developed and studied for the extraction of semi-volatile organic compounds (SVOCs) in aqueous samples prior to chromatographic analysis. The optimum conditions for obtaining extraction efficiency, such as the extraction time, extraction temperature, addition of salts, and the ratio of sample to headspace volume parameters were investigated. Experimental results indicated that the proposed MA-HS-SPME technique attained the best extraction efficiency under the optimized conditions, i.e., irradiation of extraction solution (20mL aqueous sample in 40mL headspace vial with no addition of salt) under 30W microwave power for 30min at 70 degrees C. The detection was linear at 1-250ng/L with correlation coefficient exceeding 0.997. The detection limits obtained were between 0.2-10.7ng/L, repeatability range from 2 to 15%. Real water samples collected from known sites in southern Taiwan were analyzed using the optimized conditions.

Chlorobenzenes↗

Were volatile organic compounds the inducing factors for subjective symptoms of employees working in newly constructed hospitals?

This study demonstrated possible relationships between environmental, personal, and occupational factors and changes in the subjective health symptoms of 214 employees after the relocation of a hospital in a region of Japan. Eight indoor volatile organic compounds (VOCs) were detected in at least one of the 19 rooms investigated, and total VOC (TVOC) concentrations in 8 rooms exceeded the advisable value (400 microg/m(3)) established by the Ministry of Health, Labour and Welfare of Japan. Formaldehyde was detected in all the investigated rooms, but none of the results exceeded the guideline value (100 microg/m(3)). Multiple logistic regression analysis was applied to select variables significantly associated with the subjective symptoms that can be induced by sick building syndrome. The results showed that subjective symptoms of deterioration in the skin, eye, ear, throat, chest, central nervous system, autonomic system, musculoskeletal system, and digestive system among employees were associated mainly with gender difference and high TVOC concentrations (>1200 microg/m(3)). Long work hours (>50 h per week) in females and smoking in males were to be blamed for the deterioration of their symptoms. The present findings suggest that to protect employees from indoor environment-related adverse health effects, it is necessary to reduce the concentration of indoor chemicals in new buildings, to decrease work hours, and to forbid smoking.

Adult↗

Volatile organic compounds in the blood of persons in Kuwait during the oil fires.

Between March and November of 1991, approximately 9000 workers from 43 different countries battled the burning oil wells in Kuwait. To document the exposure of persons in Kuwait during the oil well fires to volatile organic compounds (VOCs), we obtained samples of blood from 14 U.S. personnel in Kuwait City in May of 1991 (group I) and 40 American firefighters working in the oil fields in October of 1991 (group II). Concentrations of VOCs in group I and group II were compared with those of a random sample of 114 persons in the United States (reference group). The median concentrations of VOCs in group I were equal to or lower than those in the reference group. We found significant differences between the median concentrations of several VOCs in group II and the reference group. Median levels of ethylbenzene were about 10 times higher among group II than among the reference group (0.53 microgram/l vs 0.052 microgram/l). Median levels of benzene, m-/p-xylene, o-xylene, styrene, and toluene among group II were more than double those of the reference group. Although firefighters had higher median concentrations of VOCs than the reference group, those American personnel in Kuwait not involved in fighting the oil fires had concentrations of VOCs comparable to those in the reference group. Blood VOC measurements indicate a significant increase in exposure to VOCs in firefighters, but do not demonstrate this in personnel in Kuwait City.

Adult↗