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Sampling and monitoring of biogenic emissions by eucalyptus leaves using membrane extraction with sorbent interface (MESI).

Membrane extraction with sorbent interface (MESI) has been applied to monitor plant fragrance volatiles emitted into indoor air. The main components of the MESI system are a membrane module and a trap, which can be connected directly to a GC or GC-MS for simultaneous multicomponent extraction and monitoring. A polydimethylsiloxane (PDMS) membrane and two different traps, PDMS and Tenax, as well as a DC current supply for trap desorption have been applied in this research. After the membrane module is placed in contact with the plant, the MESI/GC-MS provides semicontinuous characterization of volatile compounds emitted. The MESI device has been applied to monitor the biogenic volatile organic compounds released during the first 8 h after a branch was cut from a Eucalyptus dunnii tree. The study demonstrates that the MESI system is a simple and useful tool for monitoring changes in emission processes as a function of time.

Chemistry Techniques, Analytical↗

Exposure assessment model for odor causing VOCs volatilization from stored pig slurry.

A mathematical model taking into account source depletion with time and the actual thickness of manure layer was derived to evaluate indoor inhalation exposure dynamics to three selected odor causing volatile organic compounds (VOC-odors) of p-cresol, toluene, and xylene volatilization from stored pig slurry. The model assumes that pig slurry is undisturbed and the VOC-odors released in a contaminated layer and transported through a clean layer as well as a manure-air interface boundary. The model simulates time-dependent volatilization, the depletion of source contaminant via both volatilization and degradation, and could be used with a contaminated zone of finite thickness. For a given VOC-odor, the predicted total exposure and resulting manure cleanup criteria can be a large variability depending on the model whether a finite or infinite manure layer thickness was considered. Results obtained from model comparisons suggest that the model incorporating depth-varying of manure layer and contaminant source depletion is more suitable to evaluate the VOC-odor exposure dynamics in swine housing bioclimate.

Air Pollution, Indoor↗

Focus issue: plant communication.

This week's issues of Science and Science's STKE focus on plant signaling with an emphasis on volatile organic compounds. Science emphasizes the chemistry of and information encoded by plant volatiles and how plants, plant pathogens, or humans utilize this aromatic information. Articles and resources at STKE highlight the evolution of olfactory signal transduction, describe the biosynthetic and signaling pathways of the plant hormone jasmonate, and provide an animated overview of how the plant hormone auxin regulates gene expression.

Arabidopsis Proteins↗

Air quality assessments for two recent Space Shuttle flights.

Degradation of air quality in the Space Shuttle environment through chemical contamination and high solid-particulate levels may affect crew performance and health. A comprehensive study of the Shuttle atmosphere was undertaken during the STS-40 (Spacelab Space Life Sciences 1) and STS-42 (Spacelab International Microgravity Laboratory 1) missions to determine the effectiveness of contaminant control procedures by measuring concentrations of volatile organic compounds and analyzing particulate matter trapped on air filters. Analysis of volatile contaminants showed that the air was toxicologically safe to breathe during both missions with the exception of one period during STS-40 when the Orbiter Refrigerator/Freezer was releasing noxious gases into the middeck. Chemical analyses of selected particles collected on air filters facilitated their positive identification. Trace amounts of rat hair and food particles were found in the STS-40 Spacelab filters; a trace amount of soilless plant-growth media was detected in the STS-42 Spacelab filter. The low levels of particles released from these Spacelab experiments indicate that containment measures were effective.

Air Pollution, Indoor↗

Modeling nonsteady-state conditions and kinetics of mass transport for hydrophobic compounds in activated-sludge treatment.

A new model that describes the fate of hydrophobic and volatile organic compounds in activated-sludge treatment includes two novel features. First, all of the mass balances are nonsteady state, which allows the model to describe the effects of transients in loading, temperature, or operation. Second, the model describes the mass transfer of hydrophobic compounds with kinetics, not equilibrium. A series of examples demonstrate the new features of the model and how they can be important. When the kinetics of mass transfer are not fast, hydrophobic compounds remain significantly out of equilibrium, even when the system is operating at steady state. When the loading of a hydrophobic compound increases, its aqueous-phase concentration approaches (but does not quite reach) its steady-state concentration much more rapidly than does the density of the adsorbed hydrophobic compound. Finally, the importance of mass-transport kinetics between the aqueous and sorbed phases suggests that research should be focused on this poorly understood mechanism in activated sludge.

Adsorption↗

Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate.

The formation of organic compounds during the decomposition of iron oxalate dihydrate (IOD) was investigated as a possible analog for abiotic organic synthesis in geological systems. After heating at 330 degrees C for 2-4 days, IOD decomposed to a mixture of the minerals siderite and magnetite plus gas and non-volatile organic compounds. The organic products included an extremely large variety of compounds, making identification of individual reaction products difficult. However, the non-volatile products were dominated by several homologous series of alkylated cyclic compounds mostly containing a single aromatic ring, including alkylphenols, alkylbenzenes, alkyltetrahydronaphthols, and alkyltetrahydronaphthalenes. Traces of n-alkanols, n-alkanoic acids, n-alkanones, and n-alkanes were also identified. Carbon in the gas phase was predominantly CO2 (+CO?), with lesser amounts of light hydrocarbons to > C6 including all possible branched and normal isomers of the alkanes and alkenes. The organic products were apparently the result of two concurrent reaction processes: (1) condensation of the two-carbon units present in the initial oxalate moiety, and (2) Fischer-Tropsch-type synthesis from CO2 or CO generated during the experiment. Compounds produced by the former process may not be characteristic of synthesis from the single-carbon precursors which predominate in geologic systems, suggesting iron oxalate decomposition may not provide a particularly suitable analog for investigation of abiotic organic synthesis. When water was included in the reaction vessels, CO2 and traces of methane and light hydrocarbon gases were the only carbon products observed (other than siderite), suggesting that the presence of water allowed the system to proceed rapidly towards equilibrium and precluded the formation of metastable organic intermediates.

Ferrosoferric Oxide↗

Solid-phase microextraction gas chromatography/mass spectrometry: a new method for species identification of truffles.

This study describes a rapid method to identify different truffle species by analysis of their volatile compound fraction using static headspace solid-phase microextraction gas chromatography/mass spectrometry. The volatile organic compounds (VOCs) were extracted using a new 2-cm 50/30 microm DVB/CAR/PDMS fiber placed for 10 min in the headspace of the truffle sample with the vial maintained at 20 degrees C (in a thermostatically controlled analysis room). The mass spectra of the VOC chromatograms were represented as 'fingerprints' of the analysed samples. Next, stepwise factorial discriminant analysis afforded a limited number of characteristic fragment ions that allowed a classification of the truffle species studied. This new method provides an effective approach to rapid quality control and identification of truffle species by analysis of their volatile fraction. Moreover, this method offers the advantage of minimizing thermal, mechanical, and chemical modifications of the truffles, thereby reducing the risk of analytical artifacts.

Fungi↗

Nonparticulate components of diesel exhaust promote constriction in coronary arteries from ApoE-/- mice.

Air pollution is positively associated with increased daily incidence of myocardial infarction and cardiovascular mortality. We hypothesize that air pollutants, primarily vapor phase organic compounds, cause an enhancement of coronary vascular constriction. Such events may predispose susceptible individuals to anginal symptoms and/or exacerbation of infarction. To develop this hypothesis, we studied the effects of nonparticulate diesel exhaust constituents on (1) electrocardiographic traces from ApoE-/- mice exposed whole-body and (2) isolated, pressurized septal coronary arteries from ApoE-/- mice. ApoE-/- mice were implanted with radiotelemetry devices to assess electrocardiogram (ECG) waveforms continuously throughout exposures (6 h/day x 3 days) to diesel exhaust (0.5 and 3.6 mg/m3) in whole-body inhalation chambers with or without particulates filtered. Significant bradycardia and T-wave depression were observed, regardless of the presence of particulates. Pulmonary inflammation was present only in the whole exhaust-exposed animals at the highest concentration. Fresh diesel exhaust or air was bubbled through the physiologic saline tissue bath prior to experiments to enable the isolated tissue exposure; exposed saline contained elevated levels of several volatile carbonyls and alkanes, but low to absent levels of polycyclic aromatic hydrocarbons. Vessels were then assayed for constrictive and dilatory function. Diesel components enhanced the vasoconstrictive effects of endothelin-1 and reduced the dilatory response to sodium nitroprusside. These data demonstrate that nonparticulate compounds in whole diesel exhaust elicit ECG changes consistent with myocardial ischemia. Furthermore, the volatile organic compounds in the vapor phase caused enhanced constriction and reduced dilatation in isolated coronary arteries caused by nonparticulate components of diesel exhaust.

Air Pollutants↗

Use of serially coupled capillary columns with different polarity of stationary phases for the separation of the natural complex volatile mixture of the marine red alga Corallina elongata.

Separation of a complex of natural volatile compounds using serially coupled capillary columns with different polarity of stationary phases by gas chromatography-mass spectrometry from the medicinal marine red alga Corallina elongata is reported. Nearly 200 hydrocarbons, halogen compounds, fatty acids, and other metabolites were found. Using this gas chromatography procedure we demonstrate the successful separation of different volatile organic compounds.

Adsorption↗

Atmospheric carbonaceous aerosols over grasslands of central Europe and a Boreal forest.

A labour-intensive analytical technique was applied to atmospheric particulate matter samples collected in a German urban/industrial influenced grassland location (Melpitz) and in a Finnish forest area (Hyytiälä) in order to achieve a detailed chemical speciation of the organic content. The representative nature of the solvent and water-extractable fractions was determined. The organic compounds identified in the solvent extracts are represented by primary compounds with both anthropogenic and biogenic origin, which mainly derive from the vegetation waxes and from petrogenic sources. Secondary products resulting from the oxidation of volatile organic compounds were also detected. The German meadow presented the highest levels of sugars and acidic compounds in the water extracts, whilst polyols were the most abundant class in the Finnish forest. The major compounds of these classes were malic acid, mannitol, arabitol, glucose and sucrose. Levoglucosan was also found in the water extract.

Aerosols↗

The mechanism of nutrients dissolved out of a synthetic composite bead filter material in a biofilter.

In this study, an optimal process to prepare a synthetic material having nutrient (PVA/peat/KNO(3) composite bead) is developed. The equilibrium water-soluble nitrogen content in the composite bead prepared by this process is 8.25-10.06 mg N/g dry solid. The mass-transport process for the water-soluble nitrogen dissolved out of the composite bead was also investigated. The dissolved out process occurs in two stages: external mass transport occurs in the early stage and the intraparticle diffusion process occurs in the long-term stage. The rate of water-soluble nitrogen dissolved out in both stages is concentration dependent. The path of nitrogen dissolved out is that the nitrogen dispersed in the peat and PVA phases simultaneously diffused into the outer PVA phase and out of the bead surface. The moisture holding capacity of the composite bead bed is better than the compost bed. The percentage of removed volatile organic compounds (VOCs) can remain at levels higher than 99% for a longer time (about 230 d) as the composite bead immersed in a KNO(3) aqueous solution before packing with an optimal concentration of KNO(3) aqueous solution of 0.384 M. The rate of nitrogen dissolved out in the intraparticle diffusion process could be used as an index to predict the microbial growth rate in the biofilter.

Air Pollutants↗

Trichloroethene levels in human blood and exhaled breath from controlled inhalation exposure.

The organic constituents of exhaled human breath are representative of bloodborne 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, sampling and analysis of breath is preferred to direct measurement from blood samples because breath collection is noninvasive, potentially infectious waste is avoided, the sample supply is essentially limitless, and the measurement of gas-phase analytes is much simpler in a gas matrix rather than in a complex biological tissue such as blood. However, to assess the distribution of a contaminant in the body requires a reasonable estimate of the blood level. We have investigated the use of noninvasive breath measurements as a surrogate for blood measurements for (high) occupational levels of trichloroethene in a controlled exposure experiment. Subjects were placed in an exposure chamber for 24 hr; they were exposed to 100 parts per million by volume trichloroethene for the initial 4 hr and to purified air for the remaining 20 hr. Matched breath and blood samples were collected periodically during the experiment. We modeled the resulting concentration data with respect to their time course and assessed the blood/breath relationship during the exposure (uptake) period and during the postexposure (elimination) period. Estimates for peak blood levels, compartmental distribution, and time constants were calculated from breath data and compared to direct blood measurements to assess the validity of the breath measurement methodology. Blood/breath partition coefficients were studied during both uptake and elimination. At equilibrium conditions at the end of the exposure, we could predict actual blood levels using breath elimination curve calculations and a literature value partition coefficient with a mean ratio of calculated:measured of 0.98 and standard error (SE) = 0.12 across all subjects. blood/breath comparisons at equilibrium resulted in calculated in vivo partition coefficients with a mean of 10.8 and SE = 0.60 across all subjects and experiments and 9.69 with SE = 0.93 for elimination-only experiments. We found that about 78% of trichloroethene entering the body during inhalation exposure is metabolized, stored, or excreted through routes other than exhalation.

Administration, Inhalation↗

Airborne chemical compounds on dairy farms.

The chemical environment that dairy farmers are exposed to during milking was investigated. Volatile organic compounds (VOCs) were analysed and identified, and the levels of formaldehyde, ammonia and carbon dioxide were measured in eight farms in northern Sweden. Both stationary and personal samples were taken. A total of 70 VOCs were identified from the adsorbent samples, with p-cresol, 2-butanone, ethyl acetate, alpha-pinene and delta 3-carene occurring at the highest levels. All monitored levels were significantly lower for compounds having a stated highest occupational exposure level (OEL). Using multivariate techniques some differences in the composition of the workplace air between and within the farms were found. No difference was found between personal exposure and the surrounding environment in the cowshed.

Agriculture↗

The formation and function of plant volatiles: perfumes for pollinator attraction and defense.

Plants synthesize and emit a large variety of volatile organic compounds with terpenoids and fatty-acid derivatives the dominant classes. Whereas some volatiles are probably common to almost all plants, others are specific to only one or a few related taxa. The rapid progress in elucidating the biosynthetic pathways, enzymes, and genes involved in the formation of plant volatiles allows their physiology and function to be rigorously investigated at the molecular and biochemical levels. Floral volatiles serve as attractants for species-specific pollinators, whereas the volatiles emitted from vegetative parts, especially those released after herbivory, appear to protect plants by deterring herbivores and by attracting the enemies of herbivores.

Adaptation, Physiological↗

Measurements of biogenic hydrocarbons and carbonyl compounds emitted by trees from temperate warm Atlantic rainforest, Brazil.

This study is part of a three-year project on biogenic volatile organic compound (VOC) emissions from trees of the temperate warm Atlantic rainforest found in the metropolitan area of Sao Paulo City (MASP). No study of VOC emission rates from plant species has been carried out in the temperate warm Atlantic rainforest of Brazil prior to this work. Eleven species were selected (Alchornea sidifolia, Cupania oblongifolia, Cecropia pachystachia, Syagrus romanzoffiana, Casearia sylvestris, Machaerium villosum, Trema micrantha, Croton floribundus, Myrcia rostrata, Solanum erianthum and Ficus insipida) and some of them were studied in urban, sub-urban and forest areas inside the MASP in order to evaluate biogenic VOC composition at sites characterized by different emission sources. Biogenic VOC emissions were determined by placing branches of plants in a dynamic enclosure system, an all-Teflon cuvette, and by sampling the compounds in the air leaving the cuvette. Pre-concentration using adsorbents to retain the VOC, followed by GC-MS after thermal desorption of the sample, was employed to determine the amount of biogenic hydrocarbons. The collection of carbonyl compounds on a 2,4-dinitrophenylhydrazine coated silica followed by HPLC-UV was used to analyze low molecular weight carbonyl compounds. Emission rates of isoprene, alpha-pinene, camphene and limonene ranged from 0.01 to 2.16 microg C h(-1) g(-1) and emission rates of aldehydes (C(2)-C(6)), acrolein, methacrolein and 2-butanone ranged from 1.5 x 10(-2) to 2.3 micro g C h(-1) g (-1). Ambient and leaf temperatures, relative humidity, light intensity, O(3) and NO(x) levels in the local atmosphere were monitored during experiments. It was possible to identify different biogenic VOCs emitted from typical plants of temperate warm Atlantic rainforest. The emission rates were reported as a function of the type of site investigated and were only provided for compounds for which quantification was feasible. Other biogenic compounds were only identified.

Brazil↗

A dynamic dilution system-based evaluation of the procedure adopted for determining ozone precursor volatile compounds.

A dynamic dilution system was created to evaluate the performance and the reliability of ozone precursor volatile organic compound (VOC) sampling ("TO-Can" canisters) and analysis (thermal desorption/gas chromatography/flame ionisation detection) techniques used by the "Laboratoire Interregional de Chimie du Grand Est (LIC)". Different atmospheres of VOCs were generated at concentrations between 0.8 and 25 ppb, with temperatures of 0, 10, 20 and 30 degrees C, and with relative humidities of 0, 30, 50, 70 and 90%. These conditions are generally representative of those commonly observed in ambient air in the eastern France. This dynamic dilution allows the simulation of a wide range of scenarios (concentrations, temperatures and relative humidities). After assessing the capacity and performance of the system, it was applied in order to evaluate the recoveries and stabilities of VOCs from canisters used for the collection and analysis of two mixtures of VOCs. The first mixture contained six alkanes (ethane, propane, butane, pentane, hexane and heptane), and the second contained five alkenes (ethene, propene, butene, 1-pentene and 1-hexene), five aromatics (benzene, toluene, ethylbenzene, m-xylene and o-xylene), acetylene, and 1,3-butadiene. No significant losses of alkanes from the canisters were observed after 21 days of storage, and good recoveries of alkanes from the canisters (>80%) were obtained regardless of the concentration, the temperature and the relative humidity. However, losses of certain aromatics were noted at low relative humidity.

Chromatography, Gas↗

Peak tailoring concept in gas chromatographic analysis of volatile organic pollutants in the atmosphere.

An automated gas chromatographic system aiming at performing unattended analysis of volatile organic compounds (VOCs) was developed in laboratory. To encompass VOCs of a wide range of volatility, two different designs of enrichment and separation methods were adopted and compared with performance in analyzing ozone precursors of C3-C12. In the dual-trap dual-column design, lower boiling species (C3-C6) are enriched and separated by one set of trap and column (porous layer open tubular (PLOT)), whereas the enrichment and separation for the higher boiling species (C6-C12) are performed by the other set (wall-coated open tubular (WCOT)). Undesired peaks also inevitably appear on both chromatograms often causing annoyances. To reduce complexity of both the apparatus and the resulting chromatograms, the heart-cut technique was adopted as a base for developing a system, which only uses one trap and one flame ionization detector for constructing two-dimensional GC with PLOT and DB-1. Methods were developed to allow the auxiliary flow pressure in the heart-cut device to be programmed to create dual effects, which not only can perform regular heart-cut actions but can also temporally hold up species in the precolumn for prescribed time intervals. Because it is characteristic for PLOT chromatograms to have reproducible blank retention time windows, segments of a DB-1 trace are produced by the auxiliary flow program aligning perfectly in time with the gaps of the PLOT trace. Subsequently, the two column flows are merged and channeled into single flame ionization detector to produce a very condensed "tailored" chromatogram which is equivalent to overlaying a PLOT and a DB-1 chromatogram on top of each other, except that no peaks are overlapped. This innovative "peak tailoring" concept based on the heart-cut technique is simple in design, easy to build, and extremely rugged for long-term continuous operation as fewer moving parts are involved, which is beneficial for deploying in remote monitoring stations.

Air Pollutants↗

Elevated concentrations of acetone and unidentified compounds in the breath of alcohol abusers.

A highly sensitive gas chromatographic assay was used to measure volatile organic compounds in the breath. Samples of breath from three groups of subjects were studied: normal volunteers (n = 15), acutely intoxicated alcohol abusers (n = 11), and abstinent alcohol abusers (n = 13). Acetone levels were significantly higher in the acutely intoxicated subjects than in the normals (p less than 0.05) or the abstinent alcohol abusers (p less than 0.05). Chromatographic peaks arising from 13 unidentified compounds in the breath were observed; two of these unidentified compounds were observed only in the intoxicated and abstinent alcohol abusers. Statistically significance was achieved in only one unidentified peak; elevated levels of this compound were seen in both acutely intoxicated alcohol abusers (p less than 0.01) and in the abstinent alcohol abusers (p less than 0.01) when they were compared to normal subjects.

Acetone↗