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Personal exposure to volatile organic compounds. I. Direct measurements in breathing-zone air, drinking water, food, and exhaled breath.

A pilot study to test methods of estimating personal exposures to toxic substances and corresponding body burdens was carried out between July and December 1980. Individual exposures to about a dozen volatile organic compounds in air and drinking water were measured for nine volunteers in Bayonne and Elizabeth, New Jersey, and for three volunteers in Research Triangle Park, North Carolina during three 3-day visits over the 6-month period. Breath samples were also collected from all subjects on each visit. Composite food samples were collected in each locality. Sampling and analytical methods for air, water, food, and breath were evaluated and found generally capable of detecting concentrations as low as 1 microgram/m3 in air and breath, and 1 ng/g in water and food. About 230 personal air samples, 170 drinking water samples, 66 breath samples, and 4 food samples (16 composites) were analyzed for the target chemicals. Ten compounds were present in air and eight were transmitted mainly through that medium. The two target trihalomethanes (chloroform and bromodichloromethane) were predominantly transmitted through water and beverages. Food appeared to be a minor route of exposure, except possibly for trichloroethylene in margarine. Seven compounds were present in more than half of the breath samples. Diurnal and seasonal variations were noted in air and water concentrations of some compounds, with summer levels generally higher. For some chemicals, weekday air exposures were significantly higher than weekend exposures. Some, but not all, of the potentially occupationally exposed individuals had significantly higher workplace exposures to several chemicals. Distributions of air exposures were closer to log normal than normal for most chemicals. Several chemicals were highly correlated with each other in personal air samples, indicating possible common sources of exposure.

Air Pollutants↗

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↗

Sorption kinetics of selected volatile organic compounds in humin.

Each component of the chemically heterogeneous soil exhibits a unique sorption behavior toward organic sorbates. The sorption kinetics of some volatile organic compounds (VOCs) in pressed humin disks was investigated by tracking the weight change of the disks with a microbalance. Higher sorbing capacity for more polar VOCs as well as C13 nuclear magnetic resonance data indicates that humin was more hydrophilic than Aldrich humic acid (Milwaukee, WI, USA). The apparent diffusivity of acetone, toluene, and hexane in the disks ranged from 10(-8) to 10(-10) cm2/s. The sorbed toluene in humin does not seem persistent to desorption; however, acetone and hexane, either as polar or linear compounds in humin, show persistence against desorption. On completion of the desorption experiments, there were approximately 35 and 20% sorbate residue for acetone and hexane, respectively.

Acetone↗

Identification of volatile organic compounds emitted in the field by oilseed rape (Brassica napus ssp. oleifera) over the growing season.

BACKGROUND: Oilseed rape has been associated by rural dwellers with seasonal symptoms, such as sneezing, coughing, headache and eye irritation, during its flowering season, for a number of years. This study was performed to identify the volatile chemicals emitted from oilseed rape in the field. OBJECTIVE: The objective of this study was to establish which volatile chemicals may be causative factors of oilseed rape allergy/toxicity. METHODS: The volatile organic compounds were sampled over the flowering period using a modified entrainment technique for headspace analysis under field conditions. These volatiles were then identified using thermal desorption-gas chromatography-mass spectrometry. RESULTS: The major constituents identified were the monoterpenes limonene, sabinene, beta-myrcene, and cis-3-hexen-l-ol acetate, a 'green leaf' volatile. The minor constituents included monoterpenes, sesquiterpenes, short chain aldehydes and ketones, other 'green leaf' volatiles and organic sulphides including the respiratory irritant, dimethyl disulphide. CONCLUSIONS: This report highlights the diversity of volatile chemicals emitted by oilseed rape and confirms field emissions to be broadly similar to those found previously in laboratory studies. A review is carried out on the scientific literature already published on oilseed rape flower headspace analysis.

Aldehydes↗

Variations in the emissions of volatile organic compounds from the toner for a specific photocopier.

A laboratory thermal desorption apparatus was used to measure emissions from a number of nominally identical photocopier toners--manufactured to meet the specifications of one specific model copier--when these toners were heated to fuser temperature (180-200 degrees C). The objective was to assess how potential volatile organic compound (VOC) emissions from the toner for a given copier can vary, depending upon the production run and the supplier. Tests were performed on a series of toner (and associated raw polymer feedstock) samples obtained directly from a toner manufacturer, representing two production runs using a nonvented extrusion process, and on toner cartridges purchased from two local retailers, representing three different production lots (histories unknown). The results showed that the retailer toners consistently had up to 350% higher emissions of some major compounds (expressed as microgram of compound emitted/g of toner), and up to 100% lower emissions of others, relative to the manufacturer toners (p < or = 0.01). The manufacturer toners from one production run had emissions of certain compounds, and of total VOCs, that were modestly higher (13-18%) than those from the other run (p < or = 0.01). The emission differences between the retailer and manufacturer toners are probably due to differences in the manufacturing processes and/or feedstocks used to produce the toners from these different sources.

Air Pollution, Indoor↗

Development and validation of a method for air-quality and nuisance odors monitoring of volatile organic compounds using multi-sorbent adsorption and gas chromatography/mass spectrometry thermal desorption system.

An analytical method based on thermal desorption (TD) coupled to gas chromatography (GC) and mass spectrometry detection (MS) has been developed and validated for the determination of a wide range of odor nuisance and air-quality volatile organic compounds (VOC) in air. New generation isocyanates, isocyanato- and isothiocyanatocyclohexane, have been included for the first time as target compounds due to their high occurrence in air samples. A dynamic air sampling method to trap gas and vapor on multi-sorbent tubes using portable pump equipment has been also developed. Sorbent tubes were filled with Carbotrap (70mg), Carbopack X (100mg) and Carboxen-569 (90mg). Validation of the TD-GC-MS method showed good selectivity, sensibility and precision according to Compendium Method TO-17 (US Environment Protection Agency) criteria. Limits of detection (signal-to-noise=3, ng in tube) ranges were 0.004-0.03ng (alcanes), 0.001-0.1ng (aromatics), 0.03-14ng (aldehydes), 0.003-7ng (alcohols), 0.003-0.04ng (chlorides), 0.02-0.5ng (esters), 0.002-0.1ng (ketones), 0.01-0.53ng (terpenes), 14-97ng (amides), 0.2-10ng (isocyanates) and 0.001ng (carbon disulfide). The linear dynamic range was over 3-5 orders of magnitude, depending of the VOC. TD-GC-MS analysis was reproducible, with relative standard deviation (n=5) within 20%. VOCs breakthrough examination showed no significant losses when about 2000ng standard was prepared. In order to evaluate the performance of the developed method on real samples, several industrial and urban air samples were analysed. VOCs were found to be stable on the sorbent tubes for at least 1 week when stored at 4 degrees C.

Adsorption↗

Measurement of volatile organic compounds in exhaled breath as collected in evacuated electropolished canisters.

A set of three complementary analytical methods were developed specifically for exhaled breath as collected in evacuated stainless steel canisters using gas chromatographic-mass spectrometric detection. The first is a screening method to quantify the carbon dioxide component (generally at 4-5% concentration), the second method measures the very volatile high-level endogenous compounds [e.g. acetone and isoprene at 500-1000 parts per billion by volume (ppbv), methanol, ethanol, dimethylsulfide at 2-10 ppbv], and the third method is designed to measure trace-level environmental contaminants and other endogenous volatile organic compounds (VOCs) (sub-ppbv) in breath. The canister-based sample format allows all three methods to be applied to each individual sample for complete constituent characterization. Application of these methods is shown to be useful in the following ways: analysis of CO2 levels indicates the approximate quantity of alveolar breath collected (as opposed to whole breath) in a sample; levels of major endogenous compounds are shown to be influenced by physical activities and subsequent recovery periods; and environmental exposures to xenobiotic VOCs can be characterized by assessment of post-exposure breath elimination curves. The instrumentation and methodology are described and example chromatograms and quantitative data plots demonstrating the utility of the methods are presented.

Acetone↗

Biofiltration of a mixture of volatile organic compounds on granular activated carbon.

The performance of a biofilter packed with Active Carbon (AC) was evaluated. The effluent (alcohol, ketones, esters, aromatic and chlorinated compounds) treated was a representative mixture of most common industrial emissions. To achieve a better knowledge of multicomponent adsorption mechanisms, and to underline the interest of inoculating AC, a control abiotic humidified filter had been operated in the same conditions as the biofilter. For a load of 110 g VOC m(-3) AC h(-1), after 55 days of operation, the removal efficiency was higher in the biotic than in the abiotic filter (85% vs 55%, respectively). Moreover, in the biofilter, at steady state, the elimination of all compounds was almost complete except for chlorinated compounds and p-xylene (removal efficiency of 25% and 64%, respectively). The microbial colonization of AC involved a decrease of the adsorption sites accessibility and enhanced the treatment of VOCs (volatile organic compounds) having a lower affinity for activated carbon. Moreover, while aromatic compounds and MIBK were eliminated along the overall height of the biofilter, pollutants with reduced affinity for AC, such as methanol, acetone, and halogenated compounds were only treated on the second half of the reactor. Thus, the affinity for activated carbon was an important parameter controlling the biodegradation process. Nevertheless, the use of AC as packing material in biofilters treating complex mixtures of VOCs is limited. Actually, similar removal efficiency could be reached, in the same conditions, for a biofilter packed with granular peat. Furthermore, for the biofilter packed with AC, the column height necessary to remove biodegradable compounds, with reduced affinity for the support, was important.

Adsorption↗

Determination of low nanogram/millilitre levels of volatile organic compounds in on-purpose and by-product hydrochloric acids.

Hydrochloric acid (HCl) is used in the food industry as a processing aid in the manufacture of certain foods. HCl is manufactured, either directly from inorganic sources, i.e. "on-purpose' or indirectly as a by-product from the production of organic compounds generally intended for non-food applications. By-product HCl potentially may contain traces of the manufactured product, its precursors, and other reaction by-products. Many of the potential contaminants are volatile organic compounds (VOCs) such as vinyl chloride and benzene. A study was conducted to determine whether there were differences between the levels of VOCs found in HCl samples collected from two on-purpose HCl manufacturers and two by-product HCl manufacturers. Process water used to manufacture the HCl also was analysed. Twenty-nine VOCs were determined by purge- and-trap concentration and capillary gas chromatography/mass spectrometry. Of these, nine were found in the process water and in both the by-product and on-purpose HCl samples at total VOC levels of less than 116 ng/ml. The levels of total VOCs identified in the two on-purpose HCl samples were 58 and 80 ng/ml; the levels of total VOCs identified in the two by-product samples were 41 and 115 ng/ml. The process water appeared to be the source of most of the contaminants. These results show that the levels of VOCs found in the two types of acid are comparable.

Food Handling↗

A catalogue of urban hydrocarbons for the city of Leeds: atmospheric monitoring of volatile organic compounds by thermal desorption-gas chromatography.

A method has been developed for the speciation and quantitative determination of hydrocarbons in urban air in the city of Leeds. Hydrocarbons were pre-concentrated by adsorbent tube air sampling and analyzed using thermal desorption and gas chromatography with flame ionization detection and structural confirmation by mass spectrometric detection. While automated volatile organic compound (VOC) analyzers produced data for a maximum of about 30 compounds simultaneously, with the method described here, a total of 68 C6-C12 hydrocarbons were measured simultaneously in one analysis at parts per billion (ppb) levels. Several monitoring surveys were performed, one during the winter of 1993 and the other in the summer of 1994, at a number of sites to investigate the levels of VOCs identified in the urban air of Leeds.

Absorption↗

Determinants of exposure to volatile organic compounds in four Oklahoma cities.

To begin to develop generalized models for estimating personal exposure to ambient air pollutants within diverse populations, the design of the Oklahoma Urban Air Toxics Study incorporated eight dichotomous macroenvironmental and household factors that were hypothesized to be potential determinants of exposure. Personal, indoor, and outdoor samples of volatile organic compounds (VOCs) were collected over 24-h monitoring periods in 42 households, together with activity diaries and data on the participants' residences. The distributions of the VOC concentrations were moderately to highly left-censored, and were mostly bimodal. The ATSDR minimal risk level (MRL) was exceeded in a small number of the samples. Personal and indoor concentrations tended to be higher than outdoor concentrations, indicating that indoor exposures were dominated by indoor sources. However, indoor concentrations were not correlated with the permeability of the residence, suggesting that the observed indoor concentrations reflected mostly localized, short-term emissions. The influence of the eight dichotomous factors and of the presence of an attached garage was evaluated using the Wilcoxon rank-sum test and by comparison of "excursion fractions", that is, the fractions of each distributions exceeding 10% of the MRL. Dry weather and absence of children in the household were found to be associated with higher exposures in personal or indoor exposures. Given the small sample size, it is possible that these factors were confounded with unidentified household characteristics or activities that were the true determinants of exposure.

Adult↗

Detection of aromatic catabolic gene expression in heterogeneous organic matter used for reduction of volatile organic compounds (VOC) by biofiltration.

A qualitative procedure of purified DNA/RNA co-extraction from complex organic matter, used as biofilter support for removing volatile organic compounds, was set up and applied to detect xylene monooxygenase gene expression by RT-PCR. A DNA/RNA extraction protocol based on a combination of sample lyophilization pre-treatment and CTAB--phenol/chloroform extraction procedure was optimized for the recovery of purified nucleic acids [100-500 ng DNA (10 kb) and 0.5-2 microg of rRNA 16S from 100 mg matrix]. PCR and RT-PCR protocols were established to detect xylene monooxygenase gene expression starting from differentially induced organic matrices obtained by biofiltration technology. This work allowed the microbial degradation activities in heterogeneous organic solid media to be studied and suggests a rapid method to follow specific biological activities during solid and/or semisolid organic substrates biotransformation.

Air Microbiology↗

A study of volatile organic compounds evolved from the decaying human body.

Two men were found dead near the island of Samos, Greece, in the Mediterranean sea. The estimated time of death for both victims was 3-4 weeks. Autopsy revealed no remarkable external injuries or acute poisoning. The exact cause of death remained unclear because the bodies had advanced decomposition. Volatile organic compounds (VOCs) evolved from these two corpses were determined by thermal desorption/gas chromatography/mass spectrometry analysis (TD/GC/MS). Over 80 substances have been identified and quantified. The most prominent among them were dimethyl disulfide (13.39 nmol/L), toluene (10.11 nmol/L), hexane (5.58 nmol/L), benzene 1,2,4-trimethyl (4.04 nmol/L), 2-propanone (3.84 nmol/L), 3-pentanone (3.59 nmol/L). Qualitative and quantitative differences among the evolved VOCs and CO2 mean concentration values might indicate different rates of decomposition between the two bodies. The study of the evolved VOCs appears to be a promising adjunct to the forensic pathologist as they may offer important information which can be used in his final evaluation.

Adult↗

Source apportionment of exposure to toxic volatile organic compounds using positive matrix factorization.

Data from the Total Exposure Assessment Methodology studies, conducted from 1980 to 1987 in New Jersey (NJ) and California (CA), and the 1990 California Indoor Exposure study were analyzed using positive matrix factorization, a receptor-oriented source apportionment model. Personal exposure and outdoor concentrations of 14 and 17 toxic volatile organic compounds (VOCs) were studied from the NJ and CA data, respectively. Analyzing both the personal exposure and outdoor concentrations made it possible to compare toxic VOCs in outdoor air and exposure resulting from personal activities. Regression analyses of the measured concentrations versus the factor scores were performed to determine the relative contribution of each factor to total exposure concentrations. Activity patterns of the NJ and CA participants were examined to determine whether reported exposures to specific sources correspond to higher estimated contributions from the factor identified with that source. For a subset of VOCs, a preliminary analysis to determine irritancy-based contributions of factors to exposures was carried out. Major source types of toxic VOCs in both NJ and CA appear to be aromatic sources resembling automobile exhaust, gasoline vapor, or environmental tobacco smoke for personal exposures, and automobile exhaust or gasoline vapors for outdoor concentrations.

Activities of Daily Living↗

Effectiveness of photocatalytic filter for removing volatile organic compounds in the heating, ventilation, and air conditioning system.

Nowadays, the heating, ventilation, and air conditioning (HVAC) system has been an important facility for maintaining indoor air quality. However, the primary function of typical HVAC systems is to control the temperature and humidity of the supply air. Most indoor air pollutants, such as volatile organic compounds (VOCs), cannot be removed by typical HVAC systems. Thus, some air handling units for removing VOCs should be added in typical HVAC systems. Among all of the air cleaning techniques used to remove indoor VOCs, photocatalytic oxidation is an attractive alternative technique for indoor air purification and deodorization. The objective of this research is to investigate the VOC removal efficiency of the photocatalytic filter in a HVAC system. Toluene and formaldehyde were chosen as the target pollutants. The experiments were conducted in a stainless steel chamber equipped with a simplified HVAC system. A mechanical filter coated with Degussa P25 titania photocatalyst and two commercial photocatalytic filters were used as the photocatalytic filters in this simplified HVAC system. The total air change rates were controlled at 0.5, 0.75, 1, 1.25, and 1.5 hr(-1), and the relative humidity (RH) was controlled at 30%, 50%, and 70%. The ultraviolet lamp used was a 4-W, ultraviolet-C (central wavelength at 254 nm) strip light bulb. The first-order decay constant of toluene and formaldehyde found in this study ranged from 0.381 to 1.01 hr(-1) under different total air change rates, from 0.34 to 0.433 hr(-1) under different RH, and from 0.381 to 0.433 hr(-1) for different photocatalytic filters.

Air Conditioning↗

Volatile organic compound testing of a population living near a hazardous waste site.

Accurate measures of individual exposure are critical in reducing misclassification and establishing scientifically valid associations between health outcomes and exposures to environmental contaminants. As part of a community health study, the Agency for Toxic Substances and Disease Registry conducted exposure testing for volatile organic compounds (VOCs) in the blood of people residing near an industrial complex. The purposes of the study were to assess recent exposures to VOCs in this community and to assess the utility of conducting blood VOC testing on populations near hazardous waste sites. One hundred blood specimens from the target area and 106 blood specimens from the control area were collected for analysis. The blood VOC levels in the target-area participants were compared to those in the control area and to a national reference population. Of the 31 separate VOCs for which testing was done, only acetone was statistically significantly (p < 0.05) higher in target-area participants (1,636 parts per billion [ppb]) than in control-area participants (1,353 ppb). 1,1,1-Trichloroethane was found at higher geometric mean levels in the control group (0.169 ppb) than in the target group (0.115 ppb) (p = 0.01). Median blood levels of 2-butanone and 1,4-dichlorobenzene were slightly higher in both target- and control-area groups than in the national reference population, but neither area was statistically significantly higher than the national reference population for any contaminant measured. Overall, there appeared to be no association between residing in the target area and elevated blood VOC levels. Based on the results of this study, blood VOC testing should be limited to populations living near sites where environmental testing has shown recent, elevated VOC exposure, or where unusual circumstances of illness may be attributed to VOC exposure.

Acetone↗

Exhaled volatile organic compounds in patients with non-small cell lung cancer: cross sectional and nested short-term follow-up study.

BACKGROUND: Non-invasive diagnostic strategies aimed at identifying biomarkers of lung cancer are of great interest for early cancer detection. The aim of this study was to set up a new method for identifying and quantifying volatile organic compounds (VOCs) in exhaled air of patients with non-small cells lung cancer (NSCLC), by comparing the levels with those obtained from healthy smokers and non-smokers, and patients with chronic obstructive pulmonary disease. The VOC collection and analyses were repeated three weeks after the NSCLC patients underwent lung surgery. METHODS: The subjects' breath was collected in a Teflon bulb that traps the last portion of single slow vital capacity. The 13 VOCs selected for this study were concentrated using a solid phase microextraction technique and subsequently analysed by means of gas cromatography/mass spectrometry. RESULTS: The levels of the selected VOCs ranged from 10(-12) M for styrene to 10(-9) M for isoprene. None of VOCs alone discriminated the study groups, and so it was not possible to identify one single chemical compound as a specific lung cancer biomarker. However, multinomial logistic regression analysis showed that VOC profile can correctly classify about 80% of cases. Only isoprene and decane levels significantly decreased after surgery. CONCLUSION: As the combination of the 13 VOCs allowed the correct classification of the cases into groups, together with conventional diagnostic approaches, VOC analysis could be used as a complementary test for the early diagnosis of lung cancer. Its possible use in the follow-up of operated patients cannot be recommended on the basis of the results of our short-term nested study.

Aged↗

Designing reverse-flow packed bed reactors for stable treatment of volatile organic compounds.

Reverse-flow packed bed reactors can be used to treat gaseous pollutants from chemical plants. This article describes the design and operation of a modified reverse-flow reactor (MRFR) which has a recuperator on each end of the reactor and a reaction zone in the middle. The recuperators have low thermal dispersion and the reaction zone has a high thermal dispersion, obtained by placing metal inserts into the bed, parallel with the gas flow. Performance of the MRFR during extended lean and rich conditions is determined with analytical analysis and compares well with numerical simulations of CO oxidation; however, the theory is expected to be useful for any reaction kinetics. A major advantage of this MRFR design is an extended time for the reactor to extinguish during lean conditions. This work also describes MRFR performance with internal reactor cooling, which can be used as a control mechanism to maintain reactor temperature for proper removal of volatile organic compounds.

Air Pollutants↗