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Coal tar pitch volatiles and polycyclic aromatic hydrocarbons exposures in expansion joint-making operations on a construction site: a case study.

This case study describes occupational exposures to coal tar pitch volatiles (CTPV) as benzene soluble fraction (BSF), polycyclic aromatic hydrocarbons (PAHs) and total particulates at a unique operation involving the use of coal tar in the making of expansion joints in construction of a multi-level airport parking garage. A task-based exposure assessment approach was used. A set of 32 samples was collected and analyzed for total particulate and CTPV-BSF. Twenty samples of this set were analyzed for PAHs. Current American Conference of Governmental Industrial Hygienists (ACGIH(R)) respective threshold limit value-time weighted average (TLV-TWA) for insoluble particulates not otherwise specified (PNOS) is 10 mg/m(3) as inhalable dust, which roughly corresponds to 4 mg/m(3) total particulate; for CTPV as BSF the TLV is 0.2 mg/m(3), and for specific PAHs such as benzo(a)-pyrene (B[a]P), ACGIH suggests keeping exposure as low as practicable. The recommended Swedish exposure limit for B(a)P is 2 microg/m(3). The highest exposure levels measured were 12.8 mg/m(3) for total particulate, 1.9 mg/m(3) for coal tar pitch volatiles as BSF, and 12.8 microg/m(3) for B(a)P. Several of the CTPV-BSF results were over the TLV of 0.2 mg/m(3). The data set is limited; therefore, caution should be used in its interpretation.

Coal Tar↗

Air sampling and analysis of volatile organic compounds with solid phase microextraction.

Solid phase microextraction (SPME) presents many advantages over conventional analytical methods by combining sampling, preconcentration, and direct transfer of the analytes into a standard gas chromatograph (GC). Since its commercial introduction in the early 1990s, SPME has been successfully applied to the sampling and analysis of environmental samples. This paper presents an overview of the current methods for air sampling and analysis with SPME using both grab and time-weighted average (TWA) modes. Methods include total volatile organic compounds (TVOCs), formaldehyde, and several target volatile organic compounds (VOCs). Field sampling data obtained with these methods in indoor air were validated with conventional methods based on sorbent tubes. The advantages and challenges associated with SPME for air sampling are also discussed. SPME is accurate, fast, sensitive, versatile, and cost-efficient, and could serve as a powerful alternative to conventional methods used by the research, industrial, regulatory, and academic communities.

Air Pollutants↗

Contribution of the gasoline distribution cycle to volatile organic compound emissions in the metropolitan area of Mexico City.

Gasoline distribution in the metropolitan area of Mexico City (MAMC) represents an area of opportunity for the abatement of volatile organic compound (VOC) emissions. The gasoline distribution in this huge urban center encompasses several operations: (1) storage in bulk and distribution plants, (2) transportation to gasoline service stations, (3) unloading at service stations' underground tanks, and (4) gasoline dispensing. In this study, hydrocarbon (HC) emissions resulting from breathing losses in closed reservoirs, leakage, and spillage from the operations just listed were calculated using both field measurements and reported emission factors. The results show that the contribution of volatile HC emissions due to storage, distribution, and sales of gasoline is 6651 t/year, approximately 13 times higher than previously reported values. Tank truck transportation results in 53.9% of the gasoline emissions, and 31.5% of emissions are generated when loading the tank trucks. The high concentration of emissions in the gasoline transportation and loading operations by tank trucks has been ascribed to (1) highly frequent trips from distribution plant to gasoline stations, and vice versa, to cope with excessive gasoline sales per gasoline station; (2) low leakproofness of tank trucks; and (3) poor training of employees. In addition, the contribution to HC evaporative and exhaust emissions from the vehicles of the MAMC was also evaluated.

Air Pollutants↗

Volatile hydrocarbon emissions from a diesel fuel-contaminated soil bioremediation facility.

Concerns have been expressed that emissions of volatile hydrocarbons (HCs) from bioremediation facilities containing soils contaminated with petroleum HCs may negatively impact regional air quality or human health. Little information is available regarding the emission of HCs from bioremediation sites, and few field studies have been performed during which the flux of HCs has been directly measured during bioremediation. To aid in answering questions about the impact of bioremediation facilities on the atmospheric environment, a two-part field study was conducted over summer 1996 at a remote landfarm in northern Ontario where diesel fuel-contaminated soil was undergoing bioremediation. Volatile total hydrocarbon (THC) atmospheric flux measurements were successfully taken over 18 days using a flux gradient micrometeorological technique incorporating a THC detector constructed in-house. Peak THC emissions reached 131 microg C/m2/sec shortly after implementation and tilling of the landfarm soil. The influence of soil temperature and tillage on THC emissions was examined. Off-site inhalation exposure was considered with the aid of an areal source model and results from speciated air samples collected on sorbent tubes and analyzed via gas chromatography/mass spectrometry (GCMS) techniques.

Biodegradation, Environmental↗

Occurrence and abatement of volatile sulfur compounds during biogas production.

Volatile sulfur compounds (VSCs) in biogas originating from a biogas production plant and from a municipal sewage water treatment plant were identified. Samples were taken at various stages of the biogas-producing process, including upgrading the gas to vehicle-fuel quality. Solid-phase microextraction was used for preconcentration of the VSCs, which were subsequently analyzed using gas chromatography in combination with mass spectrometry. Other volatile organic compounds present also were identified. The most commonly occurring VSCs in the biogas were hydrogen sulfide, carbonyl sulfide, methanethiol, dimethyl sulfide, and dimethyl disulfide, and hydrogen sulfide was not always the most abundant sulfur (S) compound. Besides VSCs, oxygenated organic compounds were commonly present (e.g., ketones, alcohols, and esters). The effect of adding iron chloride to the biogas reactor on the occurrence of VSCs also was investigated. It was found that additions of 500-g/m3 substrate gave an optimal removal of VSCs. Also, the use of a prefermentation step could reduce the amount of VSCs formed in the biogas process. Moreover, in the carbon dioxide scrubber used for upgrading the gas, VSCs were removed efficiently, leaving traces (ppbv levels). The scrubber also removed other organic compounds.

Air Pollutants↗

A simple model for estimating emissions of volatile organic compounds from grass and cut grass in urban airsheds and its application to two Australian cities.

Grass, and particularly cut grass, recently has been shown to emit significant amounts of volatile organic compounds (VOCs) into the atmosphere. Some components of these emissions are highly reactive and may contribute to photochemical smog in urban areas. A simple model for estimating the VOC emissions from grass and for grass cutting that allows these processes to be included in urban/regional emissions inventories is presented here. Using previous work and recent literature values, estimates are made of these biogenic volatile organic compound (BVOC) emissions for two typical urban airsheds, those including the cities of Sydney and Melbourne in Australia. Grass and cut grass could contribute approximately 2% for Sydney and 3% for Melbourne of the total VOCs emitted into these urban atmospheres annually. These contributions could rise to 4 and 5%, respectively, during the weekends of the summer growing season and, thus, could contribute to weekday/weekend ozone differences. It is recommended that the emissions of BVOCs from grass and cut grass be included in urban and global emissions inventories so that more accurate predictions of smog chemistry can be determined.

Australia↗

Characterization of volatile organic compounds in smoke at municipal structural fires.

The objective of this study was to characterize volatile organic compounds (VOCs) found at municipal structural fires in order to identify sources of long-term health risks to firefighters, which may be contributing factors in heart disease and cancer. Firefighters collected air into evacuated Summa canisters inside burning buildings at nine municipal structural fires under conditions where they judged that at least some firefighters might remove their self-contained breathing apparatus masks. Volatile organic compounds were identified and quantified for 144 target compounds using cryogenic preconcentration and gas chromatography/mass spectral detection (GC/MSD) methodology operating in selected ion monitoring mode. Samples were also analyzed in SCAN mode and examined for the appearance of substances that were not present in the instrument standard calibration mixture. The spectra of municipal structural fires were surprisingly similar and remarkable for their simplicity, which was largely due to the dominating presence of benzene along with toluene and naphthalene. Propene and 1,3-butadiene were found in all of the fires, and styrene and other alkyl-substituted benzene compounds were frequently identified. Similar "fingerprints" of the same 14 substances (propene, benzene, xylenes, 1-butene/2-methylpropene, toluene, propane, 1,2-butadiene, 2-methylbutane, ethylbenzene, naphthalene, styrene, cyclopentene, 1-methylcyclopentene, isopropylbenzene) previously identified at experimental fires burning various solid combustible materials were also found at municipal structural fires, accounting for 76.8% of the total VOCs measured. Statistically significant positive correlations were found between increasing levels of benzene and levels of propene, the xylenes, toluene, 1-butene/2-methylpropene, 1,3-butadiene, and naphthalene. Given the toxicity/carcinogenicity of those VOCs that were found in the highest concentrations, particularly benzene, 1,3-butadiene, and styrene, further investigation of VOC exposures of firefighters is warranted. Benzene, or its metabolic product s-phenylmercapturic acid in urine, was identified as a suitable chemical marker for firefighter exposure to combustion products.

Alkenes↗

An apparatus for generation of vapors from liquids of low volatility for use in inhalation toxicity studies.

While it is usually a simple matter to perform inhalation exposures to vapors from low-boiling liquids, inhalation exposures to vapors of high-boiling liquids present problems, especially the risk of decomposing the test substance by use of excessive heat. This work describes a device for the volatilization of high-boiling liquids, in a manner suitable for conducting inhalation exposures, without requiring heat input, which avoids this difficulty. The device is based on counter-current volatilization employing a multi-plate high efficiency distillation column. The column is thermostated below ambient temperature, which increases stability of operation and flexibility of application.

Occupational Exposure↗

Rubber manufacture: sampling and identification of volatile pollutants.

Volatile pollutants produced from several rubber goods manufacturing processes were sampled and analyzed. Samples were collected in the vulcanization areas of a shoe-sole factory, a tire retreading operation, and also in the extrusion areas of the retreading operation and an insulated cable manufacturer. Volatile organics from the vulcanization and extrusion operations were collected on activated charcoal, desorbed with trichlorofluoromethane and analyzed by GC/MS. Approximately 100 different compounds were identified and quantitated; their cumulative concentrations ranged from 25 to 27000 micrograms/cubic meter.

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↗

Volatile organic compounds produced during irradiation of mail.

In 2001, Bacillus anthracis spores were delivered through the United States postal system in a series of bioterrorist acts. Controls proposed for this threat included sanitization with high-energy electrons. Solid phase microextraction was used with gas chromatography/mass spectrometry for field sampling and analysis of volatile compounds apparently produced from polymeric materials such as cellulose and plastics, immediately following processing of mail at a commercial irradiation facility. Solid phase microextraction and direct sampling of air into a cryogenically cooled temperature programmable inlet were used in the laboratory for gas chromatography/mass spectrometry analysis of air in contact with irradiated mail, envelopes only (packaged identically to mail), and air inside irradiated plastic mail packaging bags (with neither mail nor envelopes). Irradiated mail or envelope systems produced hydrocarbons such as propane, butane, pentane, hexane, heptane, methylpentanes, and benzene; and oxygen-containing compounds such as acetaldehyde, acrolein, propionaldehyde, furan, 2-methylfuran, methanol, acetone, 2-butanone, and ethanol. In addition to hydrocarbons, methyl and ethyl nitrate were detected in irradiated bags that contained only air, suggesting reactive nitrogen species formed from air irradiation reacted with hydroxy-containing compounds to give nitro esters. The similarities of volatile compounds in irradiated systems containing paper to those observed by researchers studying cellulose pyrolysis suggests common depolymerization and degradation mechanisms in each case. These similarities should guide additional work to examine irradiated mail for chemical compounds not detectable by methods used here.

Air Pollution, Indoor↗

A novel personal air sampling device for collecting volatile organic compounds: a comparison to charcoal tubes and diffusive badges.

Evacuated canisters have been used for many years to collect ambient air samples for gases and vapors. Recently, significant interest has arisen in using evacuated canisters for personal breathing zone sampling as an alternative to sorbent sampling. A novel flow control device was designed and built at McGill University. The flow control device was designed to provide a very low flow rate, <0.5 mL/min, to allow a sample to be collected over an extended period of time. Previous experiments run at McGill have shown agreement between the mathematical and empirical models to predict flow rate. The flow control device combined with an evacuated canister (capillary flow control-canister) was used in a series of experiments to evaluate its performance against charcoal tubes and diffusive badges. Air samples of six volatile organic compounds were simultaneously collected in a chamber using the capillary flow control-canister, charcoal tubes, and diffusive badges. Five different concentrations of the six volatile organic compounds were evaluated. The results from the three sampling devices were compared to each other and to concentration values obtained using an online gas chromatograph (GC). Eighty-four samples of each method were collected for each of the six chemicals. Results indicate that the capillary flow control-canister device compares quite favorably to the online GC and to the charcoal tubes, p > 0.05 for most of the tests. The capillary flow control-canister was found to be more accurate for the compounds evaluated, easier to use, and easier to analyze than charcoal tubes and passive dosimeter badges.

Air Movements↗

[Variations in the pattern of ruminal volatile free fatty acids, acetoacetate and glucose in the blood plasma of lactating cows after a period of fasting and renewed feeding].

3 lactating cows were fasted for 4 days and then again received food. The trial was performed to investigate the effect of fasting on the concentration and molar proportion of volatile fatty acids in the rumen, on the concentration of free fatty acids and glucose in blood plasma and on the acetoacetate concentration in the blood. Fasting produced a considerable decrease in the total concentration of volatile fatty acids. Processes of ruminal fermentation were characterized, during the fasting period, by a continuous increase in the molar proportions of acetic acid, isobutyric acid and isovaleric acid whereas a significant decline observed to occur in the molar proportions of propionic acid and butyric acid. The reciprocal behaviour of acetate and propionate under conditions of fasting lead to a linear increase in the C2 to C3 ratio from 4.4 : 1 to 9,6 : 1. With renewed food supply all fermentation data returned to normal levels. The concentrations of blood glucose declined after 24 hrs of fasting, remained at the same level for the following 2 days and rose again to normal values on the 4th day of fasting. The concentration of acetoacetate decreased significantly on the first day of fasting to values that were 4 times as high as the initial value. The concentration of free fatty acids in blood plasma increased tremendously to a value 40 times as high as that observed at the beginning of the fasting period. It proved to be a good indicator for the energy requirements of the organism.

Acetoacetates↗

[Estimation of the net energy using volatile acids produced in the process of in-vitro digestion with ruminal fluid].

47 types of green feeds and roughages were subjected to an in-vitro fermentation with dilute ruminal fluid. The volatile fatty acids produced in this process were determined quantitatively in accordance with the method of digestibility estimation proposed by Tilley and Terry (1963). An average of 5 Mol FFS (FFS=volatile fatty acids) was found per kg of dried feed, a value is also reported in the literature. The ratios of acetate to propionate to n-butyrate to iso-butyrate to n-valerianate were 64.2 : 25.4 : 6.6 : 0.8 : 1.5 : 1.5. In this ratio, propionic acid predominated so that acetic acid and n-butyric acid were misrepresented compared with the data of in-vivo measurements made for the corresponding foodstuffs. Consequently, it is only within certain limits that values of FFS concentrations obtained in vitro may be used for estimating net energy data, disregardful of the fact that the FFS are the main source of metabolizable energy in ruminants. The reliability index for an estimation of Starch Equivalents and NEFr based on the above-mentioned method was found to be considerable lower (0.71 and 0.80) than that based on in-vitro digestibility measurements (0.86).

Animal Feed↗

[The dynamics of the content of ammonia and volatile fatty acids in the rumen fluid during the use of dry feed rations in the cow].

The development of the pH-value, the molar quota of volatile fatty acids and of the NH3 content in the change from silage rations to dried rations on the basis of pelleted feed and in dependence on the time after the beginning of feeding was tested in studies of the rumen fluid of four cows in order to explain the causes of the very low NH3 content of the rumen fluid in feeding experiments with rations based on pelleted straw-concentrate mixtures. An influence of the ration type and the time after the beginning of feeding on the molar quota of the individual volatile fatty acids and the NH3 content was ascertained. The ration type tested can cause an NH3 content in the rumen fluid below 1 mmol/l.

Ammonia↗

Solid phase microextraction: measurement of volatile organic compounds (VOCs) in Dhaka City air pollution.

A solid phase microextraction (SPME) technique was applied for the sampling of volatile organic compounds (VOCs) in ambient air polluted by two stroke autorickshaw engines and automobile exhausts in Dhaka city, Bangladesh. Analysis was carried out by capillary gas chromatography (GC) and GC-mass spectrometry (MS). The methodology was tested by insitu sampling of an aromatic hydrocarbon mixture gas standard with a precision of +/-5% and an average accuracy of 1-20%. The accuracy for total VOCs concentration measurement was about 7%. VOC's in ambient air were collected by exposing the SPME fiber at four locations in Dhaka city. The chromatograms showed signature similar to that of unburned gasoline (petrol) and weathered diesel containing more than 200 organic compounds; some of these compounds were positively identified. These are normal hydrocarbons pentane (n-C5H2) through nonacosane (n-C29H60), aromatic hydrocarbons: benzene, toluene, ethylbenzene, n-propylbenzene, n-butylbenzene, 1,3,5-trimethylbenzene, xylenes, and 1-isocyanato-3-methoxybenzene. Two samples collected near an autorickshaw station contained 783000 and 1479000 microg/m3 of VOCs. In particular, the concentration of toluene was 50-100 times higher than the threshold limiting value of 2000 microg/m3. Two other samples collected on street median showed 135000 microg/m3 and 180000 microg/m3 of total VOCs. The method detection limit of the technique for most semi-volatile organic compounds was 1 microg/m3.

Air Pollutants↗

Effect of conditioning on discrimination of oilseed rape volatiles by the honeybee: use of a combined gas chromatography-proboscis extension behavioural assay.

The coupled gas chromatography-proboscis extension assay technique was used on restrained worker bees to study responses to components of an extract of oilseed rape floral volatiles. Bees were stimulated with the effluent from the gas chromatograph after either paired or unpaired conditioning to the extract, or after a control treatment. Proboscis extension activity was elicited in six areas of the chromatogram. However, the number of bees responding in two of these areas were too low to be considered in the present study. One significant area of activity was associated with the major component, (E,E)-alpha-farnesene, whilst the others were associated with several minor components. Although all three groups of bees, irrespective of the treatments applied, showed some responses to the components eluting from the GC column, only bees subjected to paired conditioning consistently responded when re-tested to the mixture. In addition, paired conditioning increased the responsiveness of individuals in terms of the number of bees responding at least once to the effluent from the gas chromatograph. This work confirmed the occurrence of key compounds in floral volatile mixtures. Possible synergistic/inhibitory effects between components, relating to olfactory experience, are discussed.

Animals↗

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↗