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Advanced analytical determination of volatile organic compounds (VOC) and other major contaminants in water samples using GC-ion trap MS.

The GC-Ion Trap MS is recently one of the most efficient instrumental analysis recommended for understanding the chemistry of volatile organic compounds, not only in water but even in the food chain and other environmental media (air and soil). Results of the experiment conducted on water samples from Kuguri and Yatsutani sampling stations showed considerably higher levels of organic enrichment (COD = 10 mg/L and 11 mg/L respectively). Total concentrations of Pb (0.072 mg/L and 0.093 mg/L) and Cd (0.004 mg/L and 0.011 mg/L) on the other hand, invariably exceeded the maximum allowable concentrations for human health and the living environment (Pb = 0.005 mg/L; Cd = 0.001 mg/L respectively). And the toxicity levels for these contaminants at LC50 showed critical impact on rainbow trout (hypersensitive species) at 0.14 mg/L for Pb and 0.007 mg/L for Cd in 96 hours respectively. Although these major contaminants including phenol and 3-, 4-cresol, showed relatively higher toxicity impact in the experimental media, it would remain contentious to justify any associated potential dangers without regular routine water monitoring, at least for a period of one year. Nevertheless, the data could serve as a benchmark through which other phenomena can easily be investigated.

Animals↗

Indoor chemistry: ozone and volatile organic compounds found in tobacco smoke.

The deliberate generation of ozone in indoor settings has been promoted as a method to reduce the concentration of indoor pollutants. The present study examines the effect of ozone on a subset of volatile organic compounds (VOCs) found in tobacco smoke. The decays of these compounds were measured in a static room-sized chamber: (1) in the absence of ozone, (2) in the presence of moderate ozone concentrations (< 0.115 ppm), and (3) in the presence of high ozone concentrations (< 1.4 ppm). At moderate ozone concentrations there was little effect on the monitored VOCs. At high ozone concentrations there was a small, unanticipated reduction in the concentration of some of the saturated VOCs, apparently caused by OH radicals produced as a consequence of the ozone/alkene reactions. There was also a much larger reduction in the concentrations of those compounds with unsaturated carbon bonds. However, this reduction was largely matched by an increase in the concentration of a number of aldehydes. Some of these aldehydes are more potent irritants than their precursors. Furthermore, even a relatively small ventilation rate (approximately 0.1 h-1) would produce a greater reduction in the monitored VOCs than that produced by a moderate amount of ozone.

Environmental Monitoring↗

Microorganisms and volatile organic compounds in airborne dust from damp residences.

Airborne dust samples from damp (n = 9) and control (n = 9) residences were analyzed for microorganisms (molds and bacteria), bacterial markers (3-hydroxy fatty acids and muramic acid), and adsorbed volatile organic compounds (VOCs). The number of mold species was greater in the damp residences than in the controls (23 vs.18) and nine mold species were found only in damp residences. The levels of 3-hydroxy fatty acids and muramic acid correlated better in damp residences than in controls, indicating that damp conditions affect the bacterial flora of airborne dust. Identifications made by culture and microscopy of the major molds found, i.e. Aspergillus, Cladosporium, and Penicillum, coincided with the identification of VOCs known to be produced by these species. A number of additional VOCs irritating to the skin, eyes, or respiratory tract were also found. The results from this pilot study illustrate the diversity of microorganisms and VOCs present in the indoor environment and suggest that analysis of airborne dust may help to assess human exposure to microorganisms and chemical compounds.

Air Pollution, Indoor↗

Biodegradation of volatile organic compounds by five fungal species.

Five fungal species, Cladosporium resinae (ATCC 34066), Cladosporium sphaerospermum (ATCC 200384), Exophiala lecanii-corni (CBS 102400), Mucor rouxii (ATCC 44260), and Phanerochaete chrysosporium (ATCC 24725), were tested for their ability to degrade nine compounds commonly found in industrial off-gas emissions. Fungal cultures inoculated on ceramic support media were provided with volatile organic compounds (VOCs) via the vapor phase as their sole carbon and energy sources. Compounds tested included aromatic hydrocarbons (benzene, ethylbenzene, toluene, and styrene), ketones (methyl ethyl ketone, methyl isobutyl ketone, and methyl propyl ketone), and organic acids ( n-butyl acetate, ethyl 3-ethoxypropionate). Experiments were conducted using three pH values ranging from 3.5 to 6.5. Fungal ability to degrade each VOC was determined by observing the presence or absence of visible growth on the ceramic support medium during a 30-day test period. Results indicate that E. lecanii-corni and C. sphaerospermum can readily utilize each of the nine VOCs as a sole carbon and energy source. P. chrysosporium was able to degrade all VOCs tested except for styrene under the conditions imposed. C. resinae was able to degrade both organic acids, all of the ketones, and some of the aromatic compounds (ethylbenzene and toluene); however, it was not able to grow utilizing benzene or styrene under the conditions tested. With the VOCs tested, M. rouxiiproduced visible growth only when supplied with n-butyl acetate or ethyl 3-ethoxypropionate. Maximum growth for most fungi was observed at a pH of approximately 5.0. The experimental protocol utilized in these studies is a useful tool for assessing the ability of different fungal species to degrade gas-phase VOCs under conditions expected in a biofilter application.

Air Pollutants↗

A laboratory technique for investigation of diffusion and transformation of volatile organic compounds in low permeability media.

A laboratory diffusion cell technique that permits spatial and temporal estimates of porewater concentrations over short intervals suitable for estimation of effective diffusion coefficients (De) and degradation rate constants (k) of volatile organic compounds (VOCs) in saturated low permeability media is presented. The diffusion cell is a sealed cylinder containing vapour reservoirs for sampling, including a vapour reservoir source and an array of vapour-filled "mini-boreholes", which are maintained water- and sediment-free by slightly negative porewater pressures. The vapour reservoirs were sampled by Solid Phase Micro-Extraction (SPME), resulting in minimal disturbance to the experimental system. Porewater concentrations are estimated from the measured vapour concentrations. Experiments were conducted using a non-reactive medium and five VOCs with a range in partitioning properties. Calibration experiments showed that equilibrium partition coefficients could be used for calculating concentrations in the vapour reservoir source from concentrations in the SPME coating after a 1-min microextraction and that the reservoir concentration was insignificantly affected by sampling. However, equilibrium was not reached during the one-min extraction of the boreholes; the microextraction reduced the borehole vapour concentrations, leading to diffusion of VOCs from porewater into the vapour-filled borehole. Thus, empirical partitioning coefficients were required for the determination of porewater VOC concentrations. The experimental data and numerical modelling indicate masses extracted by SPME extraction are relatively small, with minimal perturbation on processes studied in diffusion experiments. This technique shows promise for laboratory investigation of diffusion and transformation processes in low permeability media.

Carbon Disulfide↗

Use of partition models in setting health guidelines for volatile organic compounds.

Partition models based on the octanol-air partition coefficients and associated quantitative structure-activity relationships (QSARs) have been developed to describe the triggering of odor detection, nasal irritation, and narcosis by common volatile organic compounds (VOCs). This study made use of the QSARs developed by Hau and Connell (1998), Indoor Air 8, 23-33) and Hau et al. (1999a, Toxicol. Sci. 47, 93-98; 1999b, Environ. Toxicol. Pharmacol. 7, 159-167) to predict the odor thresholds, nasal pungency thresholds, and anesthetic potency in humans for four groups of VOCs, namely, alkanes, alcohols, ketones, and acetates. The predicted outcomes with their estimated variability were used to evaluate the relevant guidelines on the airborne concentrations of these test groups. Threshold limit values (TLVs) for the test compounds were found to be generally capable of offering adequate protection against nasal pungency and narcosis, except for the higher alcohols (C6-C8) and sec-amyl acetate. The QSARs can also be used to set tentative guidelines for those compounds not having a TLV; values of 5 and 75 ppm were proposed for heptan-1-ol and dibutyl ketone respectively as examples.

Air Pollutants↗

Determination of very volatile organic compounds in environmental water by injection of a large amount of headspace gas into a gas chromatograph.

An injection method for a large amount of headspace gas which enables determination of trace amounts of very volatile organic compounds (VVOCs), dichlorodifluoromethane, chloromethane, vinyl chloride, bromomethane, chloroethane and trichlorofluoromethane in all kinds of environmental water was developed. A gas phase equilibrated with the water phase in a vial was purged with helium for a short time. The VVOCs were then introduced into a trapping tube packed with Tenax TA, which had been cooled using carbon dioxide. After trapping, the VVOCs were thermally desorbed and put into a GC-MS system for subsequent analysis. This method is applicable to various types of samples.

Chromatography, Gas↗

Treatment of volatile organic compounds from polyurethane and epoxy manufacture by a trickle-bed air biofilter.

The objective of this study was to evaluate the performance of a trickle-bed air biofilter (TBAB) for the removal of volatile organic compound (VOC) produced during polyurethane (PU) and epoxy manufacture. The major VOCs emitted are ethyl acetate (EA) for PU and EA and xylene for epoxy production. For the treatment of VOCs emitted during PU production, the employed coal carbon appears to be efficient as a VOC concentration buffer in the biofiltration of waste gases. Based on the results of EA and total hydrocarbon (THC) removal, it was concluded that the TBAB is suitable for controlling VOC emission during PU manufacture. For the treatment of VOCs emitted during epoxy production, it was found that the performance of the TBAB is relatively poor due to the lack of VOC sources. However, this problem could be easily solved by mixing the VOCs emitted during PU and epoxy manufacture.

Journal Article↗

Human exposure to volatile organic compounds: a comparison of organic vapor monitoring badge levels with blood levels.

We undertook a study in Albany, New York, to investigate whether volatile organic compounds (VOCs) were measurable in the blood and in the breathing-zone air of people exposed to gasoline fumes and automotive exhaust. We sampled blood of 40 subjects, placed organic vapor badges on 40 subjects, and obtained personal breathing-zone samples from 24 subjects. We limited this analysis to 19 subjects who wore the organic vapor badges for at least 5 h. VOC levels, as determined by the organic vapor badges, were highly correlated with blood levels of these same compounds. Using detection in blood as the gold standard, we found the badges to be more sensitive than conventional charcoal tube samples in detecting low levels of methyl tert-butyl ether (0.60 vs 0.08), toluene (0.95 vs 0.64), and o-xylene (0.85 vs 0.64). In this study, organic vapor badges provided data on VOC exposure that correlated with blood assay results. These organic vapor badges might provide a convenient means of determining human exposure to VOCs in epidemiologic studies.

Adult↗

Exhaled human breath measurement method for assessing exposure to halogenated volatile organic compounds.

The organic constituents of exhaled human breath are representative of blood-borne concentrations through gas exchange in the blood/breath interface in the lungs. The presence of specific compounds can be an indicator of recent exposure or represent a biological response of the subject. For volatile organic compounds (VOCs), sampling and analysis of breath is preferred to direct measurement from blood samples because breath collection is noninvasive, potentially infectious waste is avoided, and the measurement of gas-phase analytes is much simpler in a gas matrix rather than in a complex biological tissue such as blood. To exploit these advantages, we have developed the "single breath canister" (SBC) technique, a simple direct collection method for individual alveolar breath samples, and adapted conventional gas chromatography-mass spectrometry analytical methods for trace-concentration VOC analysis. The focus of this paper is to describe briefly the techniques for making VOC measurements in breath, to present some specific applications for which these methods are relevant, and to demonstrate how to estimate exposure to example VOCs on the basis of breath elimination. We present data from three different exposure scenarios: (a) vinyl chloride and cis-1,2-dichloroethene from showering with contaminated water from a private well, (b) chloroform and bromodichloromethane from high-intensity swimming in chlorinated pool water, and (c) trichloroethene from a controlled exposure chamber experiment. In all cases, for all subjects, the experiment is the same: preexposure breath measurement, exposure to halogenated VOC, and a postexposure time-dependent series of breath measurements. Data are presented only to demonstrate the use of the method and how to interpret the analytical results.

Breath Tests↗

Worker exposure and health risks from volatile organic compounds utilized in the paint manufacturing industry of Kenya.

This study provides a means for the evaluation of cleaner manufacturing and the provision of cost-effective worker health improvements in developing nations. Individual worker exposure to volatile organic compounds was measured in the paint manufacturing plants of Nairobi, Kenya. A variety of different paint production jobs were monitored, including laboratory researchers, mixers, tinters, fillers, cleaners, raw materials deliverers, and resins producers. Exposure levels were calculated based on a time-weighted average over an entire 8-10 hour workday. The paint solvents used can cause both acute and chronic health problems for the workers exposed. For example, over half of the organics monitored, i.e. benzene, styrene, and xylene, exhibit carcinogenic properties. The lifetime cancer risk from exposure to these paint solvents was estimated utilizing published cancer potencies, and the risks range from 1.90 x 10(-4) for raw materials deliverers to 2.60 x 10-2 for cleaners. The highest exposure tasks included cleaning the mixing vats and mixing the paint product, ranging from risks of 8.5 x 10(-4) to 2.6 x 10(-2), providing evidence that solvent exposure occurs due to point sources. Because of this, simple and inexpensive technologies should significantly reduce the excess exposure of workers in these manufacturing facilities. The cost of minor-innovations in the plants themselves, such as fans, drum and mixing vat covers, and respirators, could amount to as much as five times less than the estimated cost of treating workers who develop cancer due to paint solvent exposure.

Cost-Benefit Analysis↗

Optimized determination of trace jet fuel volatile organic compounds in human blood using in-field liquid-liquid extraction with subsequent laboratory gas chromatographic-mass spectrometric analysis and on-column large-volume injection.

A practical and sensitive method to assess volatile organic compounds (VOCs) from JP-8 jet fuel in human whole blood was developed by modifying previously established liquid-liquid extraction procedures, optimizing extraction times, solvent volume, specific sample processing techniques, and a new on-column large-volume injection method for GC-MS analysis. With the optimized methods, the extraction efficiency was improved by 4.3 to 20.1 times and the detection sensitivity increased up to 660 times over the standard method. Typical detection limits in the parts-per-trillion (ppt) level range were achieved for all monitored JP-8 constituents; this is sufficient for assessing human fuels exposures at trace environmental levels as well as occupational exposure levels. The sample extractions are performed in the field and only solvent extracts need to be shipped to the laboratory. The method is implemented with standard biological laboratory equipment and a modest bench-top GC-MS system.

Gas Chromatography-Mass Spectrometry↗

Development of an analytical technique and stability evaluation of 143 C3-C12 volatile organic compounds in Summa canisters by gas chromatography-mass spectrometry.

A technique using Summa canisters with cryogenic preconcentration and gas chromatographic-mass spectrometric (GC-MS) detection was developed to determine 143 C3-C12 volatile organic compounds (VOCs) including alkanes, alkenes, aromatics and halohydrocarbons in ambient and indoor air. The method detection limits and practical quantification limits were sensitive at 0.02 and 0.10 ppbv, respectively, and the method precision and accuracy were also satisfactory. The stability of C3-C12 VOC standards at ppbv levels under elevated pressure in canisters was assessed over various time intervals (from 1 week to 4 months after preparation) and most of the compounds were found to be acceptably stable with a mean recovery of 85.6 +/- 9.9% during the course of a 4-month study. However, a small fraction (approximately 6%) of the compounds, including two halohydrocarbons (bromotrichloromethane and benzyl chloride) and six alkenes (2-methylbuta-1,3-diene (isoprene), cis-4-methylpent-2-ene, cis-3-methylpent-2-ene, hept-1-ene, oct-1-ene and styrene) displayed relatively low recoveries in the range 34.6-67.9%. The loss of these compounds is most probably caused by their physical adherence to the active sites of the canister surface, chemical decomposition and/or reactions with other species. The results indicated that one must be cautious in attempting to measure these compounds owing to their instability in canisters. Overall, this analytical technique, which has been used for the determination of the VOCs under study in the toxic air pollutant monitoring network administered by the HKSAR Government, was amenable to the measurement of airborne VOCs collected both outside and inside a semi-confined car park in the present study.

Air Pollutants↗

Microwave process for volatile organic compound abatement.

The CHA Corporation has completed the U.S. Air Force Phase II Small Business Innovation Research program to investigate the feasibility of using a novel microwave-based process for the removal and destruction of volatile organic compounds (VOCs) in effluents from noncombustion sources, such as paint booth ventilation streams. Removal of solvents by adsorption, followed by the regeneration of saturated granular activated carbon (GAC) by microwave energy, was achieved in a single fixed-bed reactor. Microwave regeneration of the fixed-bed-saturated carbon restored the original GAC adsorption capacity. After 20 adsorption/regeneration cycles, the adsorption capacity dropped from 13.5 g methyl ethyl ketone (MEK)/100 g GAC to 12.5 g MEK/100 g GAC. During microwave regeneration of the GAC fixed bed, the concentrated desorbed paint solvent was oxidized by passing the solvent mixture through a fixed bed of an oxidation catalyst mixed with silicon carbide in a microwave reactor. A 98% oxidation efficiency was consistently achieved from the oxidation of VOCs in the microwave catalytic reactor.

Adsorption↗

Biogenic volatile organic compound emissions (BVOCs). I. Identifications from three continental sites in the U.S.

Vegetation composition and biomass were surveyed for three specific sites in Atlanta, GA; near Rhinelander, WI; and near Hayden, CO. At each research site emissions of biogenic volatile organic compounds (BVOCs) from the dominant vegetation species were sampled by enclosing branches in bag enclosure systems and sampling the equilibrium head space onto multi-stage solid adsorbent cartridges. Analysis was performed using a thermal desorption technique with gas chromatography (GC) separation and mass spectrometry (MS) detection. Identification of BVOCs covering the GC retention index range (stationary phase DB-1) from approximately 400 to 1400 was achieved (volatilities C4-C14).

Air Pollution↗

Volatile organic compounds in dwelling houses and stables of dairy and cattle farms in Northern Germany.

Farmers are exposed to a complex mixture of airborne substances which can represent a health hazard. Especially animal production on a farm can be a risk factor for respiratory diseases. Most studies in this context focused on bioaerosols, compounds attached to bioaerosols or on gases such as ammonia or hydrogen sulfide. Less attention was paid to volatile organic compounds (VOCs) which may also cause respiratory diseases. This pilot study presents results of measuring VOCs in the air of the dwellings and stables, as well as in the outdoor environment, of cattle farms in Northern Germany in spring and autumn. Farmers on all selected farms complained of symptoms such as asthma, rhinitis and conjunctivitis which occurred especially during work in the stable but also in the dwellings. The mean concentration of total VOC (TVOC) for the outdoor environment, the dwellings, and the stables were 100 microg m(-3), 763 microg m(-3), 322 microg m(-3) in spring and 143 microg m(-3), 544 microg m(-3), 595 microg m(-3) in autumn, respectively. There was no significant difference in season. TVOC concentrations in dwellings on farms were elevated when compared to dwellings in other environments, probably because of an additional exposure to fuels and chemicals used in agriculture. Aliphatic and alicyclic hydrocarbons, aromatic compounds, and terpenes were main compounds of the dwellings and ketones, alcohols, and esters of the stables. Terpene concentrations in the stables were low probably because straw, which was not a strong terpene emitter, was used instead of sawdust as floor covering. Large amounts of methylethylketone were encountered in the air of one stable, probably from animal exhalation caused by increased animal activity. However, it was unlikely that this caused respiratory symptoms. Generally it was likely that the concentrations of VOCs were too low to have health effects on their own. On the other hand, the VOC concentrations were in a multifactor concentration range in which health effects could occur depending on the interaction with other exposure factors. Fungal spores and bacteria were observed in addition to VOCs at the examined locations. Therefore it is possible that the observed VOCs played a role in exacerbating respiratory symptoms in this multifactor exposure.

Aerosols↗

Ambient, indoor and personal exposure relationships of volatile organic compounds in Mexico City Metropolitan Area.

Air pollution standards and control strategies are based on ambient measurements. For many outdoor air pollutants, individuals are closer to their sources (especially traffic) and there are important indoor sources influencing the relationship between ambient and personal exposures. This paper examines the relationship between volatile organic compounds (VOCs) measured at central site monitoring stations and personal exposures in the Mexico City Metropolitan Area. Over a 1-year period, personal exposures to 34 VOCs were measured for 90 volunteers from 30 families living close to one of five central monitoring stations. Simultaneous 24-h indoor, outdoor and central site measurements were also taken. Dual packed thermal desorption tubes and C(18) DNPH-coated cartridges were used for sampling VOCs and these were analyzed by GC/MS and HPLC, respectively. A factor analysis of the personal exposure data aided in grouping compounds by the most likely source type: vehicular (BTEX, styrene and 1,3-butadiene), secondary formed or photochemical (most aldehydes), building materials and consumer products (formaldehyde and benzaldehyde), cleaning solvents (tetrachloroethene and 1,1,1-trichloroethane), volatilization from water (chloroform and trichloroethene) and deodorizers (1,4-dichlorobenzene). Mean ambient, indoor and personal concentrations were 7/7/14 microg/m(3) for benzene, 1/3/3 for 1,3-butadiene, 6/20/20 for formaldehyde and 3/9/50 for 1,4-dichlorobenzene. Geometric mean (GM) ambient concentrations of trichloroethene and carbon tetrachloride were similar to GM personal exposures. While outdoor and indoor home GM concentrations for most vehicular related compounds (benzene, MTBE, xylenes and styrene) were comparable, the GM personal exposures were twice as high. Indoor concentrations of 1,3-butadiene, 1,1,1-trichloroethane, tetrachloroethane, chloroform, formaldehyde, valeraldehyde, propionaldehyde and n-butyraldehyde were comparable to personal exposures. For certain compounds, such as chloroform, aldehydes, toluene, 1,3-butadiene and 1,4-dichlorobenzene, GM personal exposures were more than two times greater than GM ambient measurements.

Adolescent↗

Volatile organic compounds as signals in a plant-herbivore system: electrophysiological responses in olfactory sensilla of the moth Cactoblastis cactorum.

The morphological sensillum types on the antennae of male and female Cactoblastis cactorum were visualized by scanning electron microscopy. Electrophysiological recordings were performed for the first time on single olfactory sensilla of C. cactorum. The male sensilla trichodea house a receptor cell responding to the putative pheromone component (9Z,12E)-tetradecadienyl acetate. The sensilla trichodea of the females were much shorter than those of the males and contained specialized receptor cells responding to certain terpenoids, the most frequent being the nerolidol-sensitive cell. The sensilla auricillica and sensilla basiconica of both sexes contained cells responding less specifically to terpenoid compounds as well as to green leaf volatiles. Cells of the sensilla coeloconica responded to aliphatic aldehydes and acids. Eight volatile organic compounds emitted by Opuntia stricta, a host plant of C. cactorum, were identified using gas chromatography-mass spectrometry, beta-caryophyllene being the major compound. Five compounds identified by gas chromatography in the headspace of O. stricta elicited responses in olfactory receptor cells of C. cactorum, nonanal being the most active compound and therefore a candidate attractant of C. cactorum.

Age Factors↗