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PubMed2002

Effect of ambient temperature on losses of volatile nitrogen compounds from stored laying hen manure.

Eight one tonne lots of laying hen manure were stored in individual, environmentally controlled chambers for 18-weeks at one of four constant temperatures: 12, 15, 20 and 25 degrees C. The losses of volatile nitrogen compounds, ammonia, and changes in dry matter and pH were measured during the storage period. There was a linear (P < 0.001) loss of nitrogen from the manure over the 18-week storage period. This loss represented approximately 60% of the initial nitrogen present in the manure. The rate of nitrogen loss increased non-linearly (P < 0.05) with increasing storage temperature. Poultry housing systems that provide low temperature storage of manure are recommended to reduce the volatile nitrogen losses from egg-laying enterprises.

Animals↗
PubMed1998

A novel apparatus for the exposure of cultured cells to volatile agents.

This article presents a novel exposure apparatus that allows the exposure of cultured cells to volatile chemicals, e.g., inhalation anesthetics. The apparatus consists of an exposure chamber and a tightly linked vaporizer unit with pumps and valves allowing adjustable fluxes of mixtures of test chemicals and carrier gas under open and closed-circuit conditions. The exposure chamber uses commercially available cell culture flasks and accommodates up to 12 flasks simultaneously. Both modules fit into a standard culture incubator. The exposure chamber may be mounted onto an oscillating axis to tilt the cultures periodically forth and back, thus allowing direct contact of the cells with test atmosphere. The vaporizer unit is connected to a personal computer which lets the experimenter set the "open" and "close" intervals of individual valves thereby controlling the composition and flow rate of the test gas mixture. The vapor concentration of test chemicals can be monitored at the inlet and outlet using infrared photodetectors or mass spectrometers. Computer-aided processing of exposure protocols allows unattended runs. Exposure protocols can be scripted and stored on disk, thus ensuring interexperimental reproducibility of complex exposure profiles. As an application example, the effect of three volatile anesthetics, halothane, enflurane, and isoflurane, on the viability of three commercially available cell lines (A549--human lung carcinoma, HTC-rat hepatoma, MDCK--Madin-Darby canine kidney) was investigated. After exposure to haloalkyl vapors (3%) for 6 and 24 h, respectively, significantly increased LDH levels versus controls, indicating cellular membrane damage, were detected in A549 and hepatoma cells after exposure for 24 h. Hepatoma cells showed a significant LDH release also after 6 h exposure to isoflurane. On the other hand, LDH release from MDCK cells was not significantly different from controls even after 24 h of continuous exposure to any of the tested anesthetics.

Anesthetics, Inhalation↗
PubMed2003

Genotoxic effects of volatile organic compounds in a chemical factory as evaluated by the Tradescantia micronucleus assay and by chemical analysis.

The clastogenic effects of volatile organic compounds in the workplace air of a chemical factory were studied by means of the Tradescantia micronucleus (Trad-MCN) assay and chemical analysis. Sampling was performed at a chemical factory producing PVC film in Cheong-ju, South Korea. Inflorescences of Tradescantia BNL 4430 were placed for 2, 6, and 9 h at the height of 1.40 m at two locations in the workplace and one outdoor of the chemical industry. Air samplings were conducted in the same places and the collected tube samples were analyzed by automatic thermal desorption/gas chromatography/mass spectrometry (ATD/GC/MS). The frequencies of micronuclei in specimens exposed for 2 h in sites 1-3 were 6.13 +/- 0.47, 5.40 +/- 1.60, and 2.93 +/- 0.43 MCN per 100 tetrads, respectively. GC/MS analysis proved the presence of various volatile organic compounds such as trichloroethylene, toluene, ethyl benzene, (m, p, o)-xylene, styrene, 1,3,5-trimethyl benzene, and 1,2,4-trimethyl benzene. Mean values of toluene measured by 2 h sampling in sites 1-3 were 1946.6, 1368.3, and 340.1 microg/m3, respectively. The toluene concentrations in sites 1 and 2 were at least four to six times higher than that in site 3. The micronucleus frequencies increased with exposure time. In addition, there was a correlation between the micronucleus frequencies and toluene concentration in the air (R2 = 0.96). The results of this in situ monitoring proved the applicability of the Trad-MCN assay combined with chemical analysis for monitoring genotoxic chemicals in the work environment.

Air Pollutants, Occupational↗
PubMed2002

Volatile fraction and sensory characteristics of Manchego cheese. 2. Seasonal variation.

An automatic purge and trap apparatus, coupled to a GC-MS was used to study the seasonal variability of the volatile fraction of raw milk Manchego cheese. Both season and dairy significantly affected abundance of most volatile compounds. Most aldehydes, methyl ketones, n-alcohols, and secondary alcohols reached significantly higher concentrations in spring cheeses. Branched chain alcohols showed significantly higher concentrations in autumn and winter cheeses, while significantly higher amounts of diketones were found in summer cheeses. Most ethyl esters reached higher concentrations in spring and winter cheeses and lower in autumn cheeses. Lower concentrations of alpha-pinene were found in spring cheeses, and higher amounts of limonene were observed in winter cheeses. Heptane and octane were significantly more abundant in summer cheeses. No significant seasonal differences were found either for quality or intensity scores.

Alcohols↗
PubMed2003

Application of low-temperature glassy carbon-coated macrofibers for solid-phase microextraction analysis of simulated breath volatiles.

With increasing interest in the detection of disease-related volatile organic compounds (VOCs) found in human breath, breath analysis could prove to be a very useful diagnostic tool, especially for the early detection of lung cancer. Solid-phase microextraction (SPME) is a technique well suited for breath analysis and has been applied to studying VOCs in the nanomolar concentration range. However, many compounds of interest in human breath are excreted at picomolar concentrations and may be unsuitable for analysis using conventional SPME sorbent phases. To extend the concentration range of conventional SPME, a novel 4-cm-long, low-temperature glassy carbon (LTGC) macrofiber was developed. The LTGC SPME macrofibers were used to extract five lung cancer-related VOCs (2-methylheptane, styrene, propylbenzene, decane, undecane) at conditions simulating human breath, and they were analyzed via gas chromatography/mass spectrometry. Results show that detection limits are lower using the SPME macrofibers compared to a conventional SPME fiber, in the low- to sub-picomolar range for the compounds of interest, which should be adequate for the analysis of these compounds in human breath. Also, the LTGC SPME macrofibers demonstrate significantly greater extraction efficiencies, sensitivity, and peak identification accuracy compared to that of commercial PDMS/DVB fibers without excessive chromatographic peak broadening. The use of SPME macrofibers broadens the potential range of application of SPME where the rapid extraction of very low levels of volatile compounds is required.

Alkanes↗
PubMed2005

Silicon microfabricated column with microfabricated differential mobility spectrometer for GC analysis of volatile organic compounds.

A 3.0-m-long, 150-microm-wide, 240-microm-deep channel etched in a 3.2-cm-square silicon chip, covered with a Pyrex wafer, and coated with a dimethyl polysiloxane stationary phase is used for the GC separation of volatile organic compounds. The column, which generates approximately 5500 theoretical plates, is temperature-programmed in a conventional convection oven. The column is connected through a heated transfer line to a microfabricated differential mobility spectrometer. The spectrometer incorporates a 63Ni source for atmospheric-pressure chemical ionization of the analytes. Nitrogen or air transport gas (flow 300 cm(3)/min) drives the analyte ions through the cell. The spectrometer operates with an asymmetric radio frequency (RF) electric field between a pair of electrodes in the detector cell. During each radio frequency cycle, the ion mobility alternates between a high-field and a low-field value (differential mobility). Ions oscillate between the electrodes, and only ions with an appropriate differential mobility reach a pair of biased collectors at the downstream end of the cell. A compensation voltage applied to one of the RF electrodes is scanned to allow ions with different differential mobilities to pass through the cell without being annihilated at the RF electrodes. A unique feature of the device is that both positive and negative ions are detected from a single experiment. The combined microfabricated column and detector is evaluated for the analysis of volatile organic compounds with a variety of functionalities.

Chromatography, Gas↗
PubMedDate not supplied

Permeation of volatile compounds through starch films.

The aim of this study was to gain insight into the factors that affect the permeation of volatiles through starch films. These films were obtained by casting gelatinized starch/water/glycerol mixtures. The films were dried and conditioned under different conditions (temperature and relative humidity) resulting in films that vary in the degree of starch crystallinity and glycerol and water content. The permeation of two model volatiles (carvone and diacetyl) at 20 degrees C and at 30, 60, or 90% relative humidity (RH) was analyzed gravimetrically. Further, the solubility of the two model compounds (under conditions where the permeation experiments were carried out) was determined. From the obtained permeation and solubility data, the diffusion coefficients of these compounds in the different starch films were calculated. The crystallinity in the starch films increased with increasing water content of the films during preparation. The water content of the resulting films in turn increased with increasing glycerol and when the films were exposed to a higher RH during drying or conditioning. For films with the same composition, the flux for diacetyl was greater than for carvone. The solubilities of diacetyl and carvone were slightly dependent on the properties of the films. It was found that with increasing starch crystallinity the diffusion coefficient for both compounds decreases, which is probably due to the impermeability of starch crystallites. Interestingly, in films with about the same extent of crystallinity, the diffusion can be described with the free volume model, with water and glycerol determining the amount of free volume.

Crystallization↗
PubMed2001

Fate of selenium in coal combustion: volatilization and speciation in the flue gas.

In light of Title I of the Clean Air Act Amendments of 1990, selenium will most probably be considered for regulation in the electric power industry. This has generated interest for removing this element from fossil-fired flue gas. This study deals with coal combustion: selenium volatilization and its speciation in the cooled flue gas were investigated to better understand its chemical behavior to validate the thermodynamic approach to such complex systems and to begin developing emission control strategies. Se volatility is influenced by several factors such as temperature, residence time, fuel type, particle size, and Se speciation of the fuels, as well as the forms of the Se inthe spiked coal/coke. Spiked coke and coal samples were burned in a thermobalance, and atomic Se and its dioxide were identified in the cooled combustion flue gas by X-ray photoelectron spectroscopy (XPS). A thermodynamic calculation was applied to a complex system including 54 elements and 3,200 species that describes the coal combustion. Several theoretical predictions concerning Se behavior, such as its speciation in flue gas, agreed well with experiments, which supports using thermodynamics for predicting trace element chemistry in combustion systems.

Air Pollutants↗
PubMed2001

Thin-film solid-phase extraction to measure fugacities of organic chemicals with low volatility in biological samples.

To investigate the environmental fate, food chain bioaccumulation, and toxicity of organic chemicals, it is often preferable to measure the chemical's fugacity rather than its concentration. However, simple methods to do this are rare. This paper presents a novel yet simple method to measure fugacities of a range of poorly volatile hydrophobic organic chemicals ranging in octanol-air partition coefficients from 10(5.6) to 10(9.2). Thin films of ethylene vinyl acetate coated on glass surfaces are used as solid-phase samplers of contaminated biological tissues. The technique is applied to fish tissue samples and spiked fish diets to determine method feasibility, equilibration times, reproducibility, and property characteristics of the thin films. It is concluded that the method provides an attractive technique to measure chemical fugacities in biological tissues without requiring solvent extractions and cleanup. The method is further expected to be applicable to investigate the fugacity of semivolatile and poorly volatile organic chemicals in air, water, sediments, and soil.

Chemistry Techniques, Analytical↗
PubMed2001

Formation and emission of volatile polonium compound by microbial activity and polonium methylation with methylcobalamin.

We observed biologically mediated emission of Po from culture solution inoculated sea sediment extract and incubated under natural light/dark cycle condition or dark condition the emitted Po compound would be lipophilic because of effective collection in organic solvent. Sterilization of the culture medium with antibiotics or CuSO4 completely suppressed growth of microorganisms and resulted in no emission of Po, indicating biological activity of microorganisms is responsible for formation and emission of volatile Po compound. Po emission also occurred when seawater was used as a culture medium. Our finding indicates a possibility of biotic source for atmospheric Po in the environment, which has been believed to be originated from abiotic sources. We compared emission behavior of Po and S in the culture experiments, the elements belong to XVI group in the Periodical Table, and consider that their emission mechanisms involved would be different though the emission of both elements is supported by biological activity of microorganisms. One of the chemical forms of S emitted was confirmed to be dimethyl sulfide (DMS) but that of Po is not known. Methylation experiments of Po with methylcobalamin demonstrated a formation and emission of volatile Po compound. The methylation of Po with methylcobalamin might be related to the observed Po emission in the culture experiments.

Air Pollutants↗
PubMed2001

Atmospheric lifetimes and fates of selected fragrance materials and volatile model compounds.

Fragrance materials are semivolatile organic compounds widely used in consumer products. Despite their generally low volatility, it is expected that a fraction of these compounds will volatilize into the atmosphere, where they can photolyze, react with OH radicals, NO3 radicals and O3, and/or undergo wet and dry deposition. Using relative rate methods, rate constants have been measured at 296 +/- 2 K for the gas-phase reactions of OH radicals, NO3 radicals, and 03 with the fragrance materials 1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)ethanone (OTNE), acetyl cedrene [(3R-(3a,3ab,7b,8aa))-1-(2,3,4,7,8,8a-hexahydro-3,6,8,8-tetramethyl-1H-3a,7-methanoazulen-5-yl)ethan-1-one], and HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethycyclopenta-[gamma]-2-benzopyran) as well as with isochroman which is structurally related to HHCB. Measured rate constants (in cm3 molecule(-1) s(-1) units) are OH radical reactions [OTNE, (9.85 +/- 0.88) x 10(-11); acetyl cedrene, (7.7 +/- 1.6) x 10(-11); HHCB, (2.6 +/- 0.6) x 10(-11); and isochroman, (3.7 +/- 0.6) x 10(-11)], NO3 radical reactions [OTNE, (1.71 +/- 0.19) x 10(-11) and acetyl cedrene, (4.1 +/- 1.0) x 10(-15)], and O3 reactions [OTNE, (2.1 +/- 0.5) x 10(-18) and acetyl cedrene, <2.2 x 10(-18)] where the error limits are two least-squares standard deviations. Rate constants for the OH radical reactions predicted by a structure-reactivity estimation method agree well with the measured values. The dominant tropospheric loss processes for the compounds studied are calculated to be in a reaction with OH radicals during daytime and, for OTNE and acetyl cedrene, with NO3 radicals during nighttime. The calculated atmospheric lifetimes due to daytime reaction with the OH radical are a few hours or less for the fragrance materials studied and indicate that these specific compounds will not undergo long-range transport in the atmosphere.

Air Pollutants↗
PubMed2002

Investigation of the volatile organic substances that cause the characteristic odor of pentachlorophenol treated wood utility poles.

The nature of the volatile organic compounds that could be at the origin of the characteristic odor of treated wood utility poles was investigated by the study of compositional changes in the chromatographic profiles of fresh-pentachlorophenol (PCP) solvent samples and weathered samples collected from an in-service red pine pole. Over 99 peaks were identified in the chromatogram of the fresh solvent from which a large portion of the C3-, C4-, C5-, C6-alkylbenzene isomers and early eluting n-alkanes was missing from the analysis of weathered samples. Three domains in the chromatographic profile (volatile, semivolatile, and nonvolatile components) were confirmed by assessing the headspace of fresh-PCP solvent samples using direct syringe sampling and solid-phase microextraction. A first level of field validation was achieved using an emission cell for measuring substances emanating from sapwood specimens at different temperatures. The average latent heat of vaporization (deltaHvap) of the PCP-solvent components was estimated at 99.9 kJ/mol from these results. Finally, the analysis of airborne substances at a treating plant and a utility pole storage site confirmed that the C4-, C5-, and C6-alkylbenzene isomers could contribute to the characteristic odor perceived by humans.

Air Pollutants↗
PubMed2002

Ozone modulation of volatile hydrocarbons using membrane introduction mass spectrometry.

A new method that we describe as chemical modulation of volatile hydrocarbons is investigated using ozonolysis pretreatment and membrane introduction mass spectrometry (MIMS). This extension to the MIMS technique is intended to enhance the selectivity of MIMS for measuring hydrocarbons in the complex mixtures often encountered in polluted air samples. The test samples for this study were dilute (parts per billion by volume, ppbv) two-component hydrocarbon mixtures in synthetic air. Ozone reacted to completely suppress the MIMS signal from beta-pinene in a mixture of toluene and beta-pinene and the MIMS signal from cyclohexene in a mixture of cyclohexene and cyclohexane. As expected, the ozone reaction produced little attenuation of the MIMS signal from toluene and cyclohexane in the test mixtures. The basis of the method is that the products of the ozonolysis, which is rapid for alkenes, are polar compounds that are excluded by the membrane used here, as confirmed in this study. Since the modulation only affects unsaturated hydrocarbons (and other similar organic compounds), the method can be used to aid in quantitative analysis of volatile hydrocarbon compounds in air samples for air pollution monitoring.

Air Pollutants↗
PubMed2004

Laboratory setup for long-term monitoring of the volatilization of hazardous materials: preliminary tests of O-ethyl S-2-(N,N-diisopropylamino)ethyl methylphosphonothiolate on asphalt.

Contrary to commonly used pesticides, the rate of volatilization of extremely toxic chemicals such as the nerve agent O-ethyl S-2-(N,N-diisopropylamino)ethyl methylphosphonothiolate (VX) cannot be readily obtained under environmental conditions due to its high mammalian toxicity that would require extraordinary precautions. An alternative is a laboratory setup that would be used to obtain environmentally relevant data required for risk assessment studies. In this paper we describe a newly designed climatic hood that enables control of temperature, humidity, and air velocity within less than +/- 0.5% fluctuations during continuous operation. The performance of the evaporation system togetherwith the sampling and analytical procedures produced a meaningful concentration profile of vapors obtained from a 15 mg sample of VX dispersed as small droplets over a 10 x 16 cm piece of asphalt road. The released vapors amounted to approximately 30% of the applied mass, and its time course was best fitted to a triexponential curve with rate constants changing over time from 2.2 to 0.03 h(-1). The asphalt enhanced a specific degradation pathway of VX that is relatively minor in aqueous solutions. Results provide the first data on the volatilization of VX from samples of asphalt road, and offer an insight into VX behavior in the environment.

Chemical Warfare Agents↗
PubMed2004

Receptor model comparisons and wind direction analyses of volatile organic compounds and submicrometer particles in an arid, binational, urban air shed.

The relationship between continuous measurements of volatile organic compounds sources and particle number was evaluated at a Photochemical Assessment Monitoring Station Network (PAMS) site located near the U.S.-Mexico Border in central El Paso, TX. Sources of volatile organic compounds (VOCs) were investigated using the multivariate receptor model UNMIX and the effective variance least squares receptor model known as Chemical Mass Balance (CMB, Version 8.0). As expected from PAMS measurements, overall findings from data screening as well as both receptor models confirmed that mobile sources were the major source of VOCs. Comparison of hourly source contribution estimates (SCEs) from the two receptor models revealed significant differences in motor vehicle exhaust and evaporative gasoline contributions. However, the motor vehicle exhaust contributions were highly correlated with each other. Motor vehicle exhaust was also correlated with the ultrafine and accumulation mode particle count, which suggests that motor vehicle exhaust is a source of these particles at the measurement site. Wind sector analyses were performed using the SCE and pollutant data to assess source location of VOCs, particle count, and criteria pollutants. Results from this study have application to source apportionment studies and mobile source emission control strategies that are ongoing in this air shed.

Air Pollutants↗
PubMed2003

Volatilization of weathered chiral and achiral chlordane residues from soil.

To mitigate the impact on the environment of persistent organic pollutants (POPs), we must understand thoroughly their environmental fate. Residues of many of these pollutants are still present in soil years after their legitimate uses were banned. In this report, the volatilization of one such persistent pollutant, chlordane, from a field where it was applied approximately 40 years ago, is examined in detail overthe course of several years. Ambient air samples were collected at three heights above the treated soil throughout the investigation. Air samples were also collected at several background sites in Connecticut for comparison. Analysis of these samples shows that chlordane volatilization from soil continues to occur long after initial application, at rates dependent on both temperature and cultivation of the soil. Comparison of relative concentrations and enantiomeric profiles for components of technical chlordane in atmospheric samples from a variety of sources suggests a regional, urban input of chlordane to the ambient air over Connecticut, possibly related to the widespread termiticidal use of chlordane in home foundation soils.

Chlordan↗
PubMed2000

Volatile methoxybenzene compounds in grains with off-odors.

More than 20 volatile methoxybenzene compounds were found in a set of 745 corn, sorghum, soybean, and wheat samples obtained from official grain inspectors. Most samples containing methoxybenzenes were off-odor. By using an autosampler, volatiles were purged from whole grain at 80 degrees C, collected on Tenax, and then thermally desorbed and transferred to a gas chromatograph-mass spectrometer for separation and identification. Use of an infrared detector aided identification of some compounds, especially isomers with similar mass spectra. Samples with insect odor had 1,4-dimethoxybenzene and its 2-methyl, 2-ethyl, and 2-methoxy derivatives that appeared to be derived from 1,4-quinones, which are known (except for 2-methoxy) defensive secretions of Tribolium insects. Samples with mostly musty, sour, and/or smoke odors commonly contained methoxybenzene and 1, 2-dimethoxybenzene along with their 4-ethyl and 4-ethenyl derivatives, 4-chloro-1-methoxybenzene, and/or 2-methoxyphenol and its 4-ethyl derivative. Other methoxybenzenes were also found, including methoxy derivatives of other phenols and N-heterocyclic compounds. Co-occurrences and correlations of levels of some compounds were also reported to indicate relationships with odors and inter-relationships among compounds.

Anisoles↗
PubMed2000

Mechanism of volatile compound production during storage of sunflower Oil.

Volatile compounds formed in the course of the thermal decomposition of hydroperoxides during storage of sunflower oil were analyzed by headspace solid-phase microextraction sampling followed by gas chromatographic separation and mass spectral detection. The determining role of alkoxyl radicals in the process has been proven by electron spin resonance spectroscopic measurements. On the basis of analytical results, the reaction networks and mechanisms were constructed by computer modeling to describe the formation of volatile products of radical decomposition of hydroperoxides. We established that off-flavor aliphatic aldehydes are originated from only the alkoxyl radicals derived from trigliceride of linoleic acid. To find a specific additive, which redirects the formation of these radicals toward production of more stable species, is suggested.

Electron Spin Resonance Spectroscopy↗