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Characterisation of odorants emissions from landfills by SPME and GC/MS.

Odorous compounds from a landfill have been characterised by gas-chromatography-mass-spectrometry, identifying about 100 volatile organic compounds. Air samples from different landfill sites and from the environment have been analysed after a solid-phase microextraction on a three-phase fiber, DVB/Carboxen/PDMS, which allowed a preconcentration and the chromatographic data obtained from the most significant emission sources have been submitted to chemometric analysis in order to better establish specific markers of olfactory pollution. For example limonene was a typical tracer of fresh wastes, while p-cymene was characteristic of leachate and biogas. By the developed analytical procedure it has been evaluated the efficiency of a scrubber plant utilised in the landfill in order to remove malodour compounds. The average removal efficiency was not very high (about 23.5%) due to scarce ability in removing low polarity compounds. Furthermore, it has been demonstrated the suitability of a microgas chromatograph for the continuous on-site monitoring of air pollution in order to rapidly individuate emission sources of olfactive nuisances.

Air Pollutants↗

Modulation techniques and applications in comprehensive two-dimensional gas chromatography (GC x GC).

More than a decade after Phillips' first published work this article reviews recent developments in comprehensive two-dimensional gas chromatography (GC x GC). Special attention is devoted to the further development and diversity of modulation devices. These include heated sweepers, cryofocused modulators, and a variety of diaphragm valve-switching strategies. It is demonstrated that all modulation approaches can be very well suited to GC x GC, depending on the particular application. Diaphragm-valve modulation is very powerful for volatile organic compounds. Slotted heater and cryofocused modulation are preferred for samples that contain non-volatile components. Applications ranging from petroleum to environmental and biological samples are illustrated. Extension of the technique to GC x GC-mass spectrometry (MS) is also discussed and trends for future research activity are pointed out.

Chromatography, Gas↗

Structures, photoluminescence, and reversible vapoluminescence properties of neutral platinum(II) complexes containing extended pi-conjugated cyclometalated ligands.

Reacting K2PtCl4 with the tridentate R-C(wedge)N(wedge)C-H2 ligands 2,6-di-(2'-naphthyl)-4-R-pyridine (R = H, 1a; Ph, 1b; 4-BrC6H4, 1c; 3,5-F2C6H3, 1d) in glacial acetic acid, followed by heating in dimethyl sulfoxide (DMSO), gave complexes [(R-C(wedge)N(wedge)C)Pt(DMSO)] (2a-d). In the crystal structures of 2a-c, the molecules are paired in a head-to-tail orientation with Pt...Pt separations >6.3 A, and there are extensive close C-H...pi (d = 2.656-2.891 A), pi...pi (d = 3.322-3.399 A), and C-H...O=S (d = 2.265-2.643 A) contacts. [(Ph-C(wedge)N(wedge)C)Pt(PPh3)] (3) was prepared by reacting 2b with PPh3. Reactions of 2a-d with bis(diphenylphosphino)methane (dppm) gave [(R-C(wedge)N(wedge)C)2Pt2(mu-dppm)] (4a-d). Both head-to-head (syn) and head-to-tail (anti) conformations were found for 4a.6CHCl3.C5H12, whereas only one conformation was observed for 4b.2CHCl3 (syn), 4c.3CH2Cl2 (syn), and 4d.2CHCl3 (anti). In the crystal structures of 4a-d, there are close intramolecular Pt...Pt contacts of 3.272-3.441 A in the syn conformers, and long intramolecular Pt...Pt separations of 5.681-5.714 A in the anti conformers. There are weak C-H...X (d = 2.497-3.134 A) and X...X (X = Cl or Br; d = 2.973-3.655 A) interactions between molecules 4a-d and occluded CHCl3/CH2Cl2 molecules, and their solvent channels are of varying diameters (approximately 9-28 A). Complexes 2a-d, 3, and 4a-d are photoluminescent in the solid state, with emission maxima at 602-643 nm. Upon exposure to volatile organic compounds, 4a shows a fast and reversible vapoluminescent response, which is most intense with volatile halogenated solvents (except CCl4). Powder X-ray diffraction analysis of desolvated 4a revealed a more condensed molecular packing of syn and anti complexes than crystal 4a.6CHCl3.C5H12.

Cyclization↗

Bacterial volatiles induce systemic resistance in Arabidopsis.

Plant growth-promoting rhizobacteria, in association with plant roots, can trigger induced systemic resistance (ISR). Considering that low-molecular weight volatile hormone analogues such as methyl jasmonate and methyl salicylate can trigger defense responses in plants, we examined whether volatile organic compounds (VOCs) associated with rhizobacteria can initiate ISR. In Arabidopsis seedlings exposed to bacterial volatile blends from Bacillus subtilis GB03 and Bacillus amyloliquefaciens IN937a, disease severity by the bacterial pathogen Erwinia carotovora subsp. carotovora was significantly reduced compared with seedlings not exposed to bacterial volatiles before pathogen inoculation. Exposure to VOCs from rhizobacteria for as little as 4 d was sufficient to activate ISR in Arabidopsis seedlings. Chemical analysis of the bacterial volatile emissions revealed the release of a series of low-molecular weight hydrocarbons including the growth promoting VOC (2R,3R)-(-)-butanediol. Exogenous application of racemic mixture of (RR) and (SS) isomers of 2,3-butanediol was found to trigger ISR and transgenic lines of B. subtilis that emitted reduced levels of 2,3-butanediol and acetoin conferred reduced Arabidopsis protection to pathogen infection compared with seedlings exposed to VOCs from wild-type bacterial lines. Using transgenic and mutant lines of Arabidopsis, we provide evidence that the signaling pathway activated by volatiles from GB03 is dependent on ethylene, albeit independent of the salicylic acid or jasmonic acid signaling pathways. This study provides new insight into the role of bacteria VOCs as initiators of defense responses in plants.

Arabidopsis↗

Analysis of volatile compounds in some typical Brazilian fruits and juices by SPME-GC method.

This paper describes the analysis of volatile organic compounds (VOC) in typical Brazilian fruit and fruit juices by a solid-phase microextraction (SPME) method using a capillary gas chromatography system with flame ionization detection and mass spectrometry (GC-MS). A SPME holder with a 100-microm polydimethilsiloxane fibre coating was utilized. The optimal conditions were desorption at 220 degrees C for 1 min, absorption at 50 degrees C for 20 min and 4.00 ml of sample in the headspace vial. The method gave good precision and showed a linear response. More than 100 VOC were identified in the fruit and juices studied by GC-MS. The method was employed to quantify ethanol, naphthalene and benzoic acid in four different species of Brazilian fruit and their juices.

Anacardium↗

Collection of domestic waste. Review of occupational health problems and their possible causes.

During the last decade, a growing interest in recycling of domestic waste has emerged, and action plans to increase the recycling of domestic waste have been agreed by many governments. A common feature of these plans is the implementation of new systems and equipment for the collection of domestic waste which has been separated at source. However, only limited information exists on possible occupational health problems related to such new systems. Occupational accidents are very frequent among waste collectors. Based on current knowledge, it appears that the risk factors should be considered as an integrated entity, i.e. technical factors (poor accessibility to the waste, design of equipment) may act in concert with high working rate, visual fatigue due to poor illumination and perhaps muscle fatigue due to high work load. Musculoskeletal problems are also common among waste collectors. A good deal of knowledge has accumulated on mechanical load on the spine and energetic load on the cardio-pulmonary system in relation to the handling of waste bags, bins, domestic containers and large containers. However, epidemiologic studies with exposure classification based on field measurement are needed, both to further identify high risk work conditions and to provide a detailed basis for the establishment of occupational exposure limits for mechanical and energetic load particularly in relation to pulling, pushing and tilting of containers. In 1975, an excess risk for chronic bronchitis was reported for waste collectors in Geneva (Rufèner-Press et al., 1975) and data from the Danish Registry of Occupational Accidents and Diseases also indicate an excess risk for pulmonary problems among waste collectors compared with the total work force. Surprisingly few measurements of potentially hazardous airborne exposures have been performed, and the causality of work-related pulmonary problems among waste collectors is unknown. Recent studies have indicated that implementation of some new waste collection systems may result in an increased risk of occupational health problems. High incidence rates of gastrointestinal problems, irritation of the eye and skin, and perhaps symptoms of organic dust toxic syndrome (influenza-like symptoms, cough, muscle pains, fever, fatigue, headache) have been reported among workers collecting the biodegradable fraction of domestic waste. The few data available on exposure to bio-aerosols and volatile compounds have indicated that these waste collectors may be simultaneously exposed to multiple agents such as dust containing bacteria, endotoxin, mould spores, glucans, volatile organic compounds, and diesel exhaust. Several studies have reported similar health problems as well as high incidence rates of pulmonary disease among workers at plants recycling domestic waste.(ABSTRACT TRUNCATED AT 400 WORDS)

Accidents, Occupational↗

Detection and quantitation of multiple volatile compounds in tissues by GC and GC/MS.

Qualitative and quantitative analysis of tissues and body fluids for multiple volatile organic compounds were performed by a combination of packed and open tubular capillary GC and GC/MS. This paper describes methods for such analyses in a case involving the exposure of two persons to methyl ethyl ketone, methyl isobutyl ketone, toluene and the three isomeric xylenes. Tissue and body fluid concentrations of these substances in the two decedents are presented and discussed briefly.

Butanones↗

Modeling the formation of secondary organic aerosol (SOA). 2. The predicted effects of relative humidity on aerosol formation in the alpha-pinene-, beta-pinene-, sabinene-, delta 3-carene-, and cyclohexene-ozone systems.

Atmospheric oxidation of volatile organic compounds can lead to the formation of secondary organic aerosol (SOA) through the gas/particle (G/P) partitioning of the oxidation products. Since water is ubiquitous in the atmosphere, the extent of the partitioning for any individual organic product depends not only on the amounts and properties of the partitioning organic compounds, but also on the amount of water present. Predicting the effects of water on the atmospheric G/P distributions of organic compounds is, therefore, central to understanding SOA formation. The goals of the current work are to gain understanding of how increases in RH affect (1) overall SOA yields, (2) water uptake by SOA, (3) the behaviors of individual oxidation products, and (4) the fundamental physical properties of the SOA phase that govern the G/P distribution of each of the oxidation products. Part 1 of this series considered SOA formation from five parent hydrocarbons in the absence of water. This paper predicts how adding RH to those systems uniformly increases both the amount of condensed organic mass and the amount of liquid water in the SOA phase. The presence of inorganic components is not considered. The effect of increasing RH is predicted to be stronger for SOA produced from cyclohexene as compared to SOA produced from four monoterpenes. This is likely a result of the greater general degree of oxidation (and hydrophilicity) of the cyclohexene products. Good agreement was obtained between predicted SOA yields and laboratory SOA yield data actually obtained in the presence of water. As RH increases, the compounds that play the largest roles in changing both the organic and water masses in the SOA phase are those with vapor pressures that are intermediate between those of essentially nonvolatile and highly volatile species. RH-driven changes in the compound-dependent G/P partitioning coefficient Kp result from changes in both the average molecular weight MWom of the absorbing organic/water phase, and the compound-dependent activity coefficient zeta values. Adding water to the SOA phase by increasing the RH drives down MWom and thereby uniformly favors SOA condensation. The effect of RH on zeta values is compound specific and depends on the hydrophilicity of the specific compound of interest; the more hydrophilic a compound, the more increasing RH will favor its condensation into the SOA phase. The results also indicate that it may be a useful first approximation to assume that zeta = 1 for many compounds making up SOA mixtures.

Aerosols↗

Kinetics and mechanisms of UV-photodegradation of chlorinated organics in the gas phase.

Over the last two decades, the application of photodegradation for the destruction of a wide spectrum of organic compounds in air has gained considerable interest in abating environmental pollution. This paper presents the results of a fundamental study conducted to evaluate the gas phase oxidation kinetics of volatile organic compounds (VOCs) with respect to different parameters pertinent to the operating conditions of air stripping and soil vapor extraction processes. Photodegradations of three chlorinated VOCs: chloroform, carbon tetrachloride (CTC) and trichloroethylene (TCE), were investigated in a semi-batch reactor using a low-pressure mercury UV lamp. The effects of different experimental parameters, such as the initial concentrations of the VOCs, the reaction medium, relative humidity, light intensity, temperature and the effect of mixture that may influence the kinetics of the gas phase photodegradation were evaluated. Mechanisms of photodegradation as supported by the experimental data are also proposed.

Air Pollutants↗

A stepwise procedure for assessment of the microbial respiratory activity of soil samples contaminated with organic compounds.

Soil respiration measurements are used frequently for the characterization of soil samples. Identical methods are used for the ecotoxicological characterization of contaminated soil samples as well as for quantification of the active microbial biomass in agriculturally used soils. In this study four soil samples contaminated with large amounts of volatile organic compounds, polyaromatic hydrocarbons, or nitroaromatic compounds are characterized after stepwise addition of carbon, nitrogen, and phosphorus. The respiration kinetics are assessed over a period of 5 days. By means of qualitative evaluation of the results, it is demonstrated that this stepwise addition allows one to distinguish between growth-promoting effects of biodegradable organic compounds on the one hand and the toxic influence of these compounds on the other hand. Finally it is stated that a comprehensive ecotoxicological characterization cannot be performed routinely using only one or several parameters of respiration curves. There is need for further research and validation if soil respiration measurements are to be performed quantitatively in the future.

Environmental Monitoring↗

Characterization and source identification of hydrocarbons in water samples using multiple analytical techniques.

This paper describes a case study in which multiple analytical techniques were used to identify and characterize trace petroleum-related hydrocarbons and other volatile organic compounds in groundwater samples collected in a bedrock aquifer exploited for drinking water purposes. The objective of the study was to confirm the presence of gasoline and other petroleum products or other volatile organic pollutants in those samples in order to assess the respective implication of each of the potentially responsible parties to the contamination of the aquifer. In addition, the degree of contamination at different depths in the aquifer was also of interest. The analytical techniques used for analyses of water samples included gas chromatography-mass spectrometry (GC-MS) and capillary GC with flame-ionization detection, solid-phase microextraction and headspace GC-MS techniques. Chemical characterization results revealed the following: (1) The hydrocarbons in sample A (near-surface groundwater, 0-5 m) were clearly of two types, one being gasoline and the other a heavy petroleum product. The significant distribution of five target petroleum-characteristic alkylkated polycyclic aromatic hydrocarbon homologues and biomarkers confirmed the presence of another heavy petroleum product. The concentrations of the TPHs (total petroleum hydrocarbons) and BTEX (collective name of benzene, toluene, ethylbenzene, and p-, m-, and o-xylenes) were determined to be 1070 and 155 microg/kg of water for sample A, respectively. (2) The deepest groundwater (sample B, collected at a depth ranging between 15 and 60 m) was also contaminated, but to a much lesser degree. The concentrations of the TPH and BTEX were determined to be only 130 and 2.6 microg/kg of water for sample B, respectively. (3) The presence of a variety of volatile chlorinated compounds to the groundwater was also clearly identified.

Chromatography, Gas↗

Mechanism of transport and distribution of organic solvents in blood.

Little is known about the mechanism of transport and distribution of volatile organic compounds in blood. Studies were conducted on five typical organic solvents to investigate how these compounds are transported and distributed in blood. Groups of four to five rats were exposed for 2 hr to 500 ppm of n-hexane, toluene, chloroform, methyl isobutyl ketone (MIBK), or diethyl ether vapor; 94, 66, 90, 51, or 49%, respectively, of these solvents in the blood were found in the red blood cells (RBCs). Very similar results were obtained in vitro when aqueous solutions of these solvents were added to rat blood. In vitro studies were also conducted on human blood with these solvents; 66, 43, 65, 49, or 46%, respectively, of the added solvent was taken up by the RBCs. These results indicate that RBCs from humans and rats exhibited substantial differences in affinity for the three more hydrophobic solvents studied. When solutions of these solvents were added to human plasma and RBC samples, large fractions (51-96%) of the solvents were recovered from ammonium sulfate-precipitated plasma proteins and hemoglobin. Smaller fractions were recovered from plasma water and red cell water. Less than 10% of each of the added solvents in RBC samples was found in the red cell membrane ghosts. These results indicate that RBCs play an important role in the uptake and transport of these solvents. Proteins, chiefly hemoglobin, are the major carriers of these compounds in blood. It can be inferred from the results of the present study that volatile lipophilic organic solvents are probably taken up by the hydrophobic sites of blood proteins.

Administration, Inhalation↗

Gaseous and particulate emissions from prescribed burning in Georgia.

Prescribed burning is a significant source of fine particulate matter (PM2.5) in the southeastern United States. However, limited data exist on the emission characteristics from this source. Various organic and inorganic compounds both in the gas and particle phase were measured in the emissions of prescribed burnings conducted at two pine-dominated forest areas in Georgia. The measurements of volatile organic compounds (VOCs) and PM2.5 allowed the determination of emission factors for the flaming and smoldering stages of prescribed burnings. The VOC emission factors from smoldering were distinctly higher than those from flaming except for ethene, ethyne, and organic nitrate compounds. VOC emission factors show that emissions of certain aromatic compounds and terpenes such as alpha and beta-pinenes, which are important precursors for secondary organic aerosol (SOA), are much higher from active prescribed burnings than from fireplace wood and laboratory open burning studies. Levoglucosan is the major particulate organic compound (POC) emitted for all these studies, though its emission relative to total organic carbon (mg/g OC) differs significantly. Furthermore, cholesterol, an important fingerprint for meat cooking, was observed only in our in situ study indicating a significant release from the soil and soil organisms during open burning. Source apportionment of ambient primary fine particulate OC measured at two urban receptor locations 20-25 km downwind yields 74 +/- 11% during and immediately after the burns using our new in situ profile. In comparison with the previous source profile from laboratory simulations, however, this OC contribution is on average 27 +/- 5% lower.

Air Pollutants↗

Analysis of odour and taste problems in high-density polyethene.

The compounds that cause off-flavours in plastics, have been recognized mainly as carbonyl compounds (aldehydes, ketones and esters). They occur in low concentrations, and due to their low-threshold odour concentrations, their typical odours were identified. Most of these off-flavour compounds are volatile. Chemical analysis of smelling compounds requires a very sensitive method with a high-resolution capability. The analysis of volatile organic compounds (VOCs) in high density polyethene (HD-PE) granules and waters in which the granules have been shaken for 4 h, were carried out by gas chromatography-mass spectrometry-sniffing system (GC-MS-SNIFF) and by gas chromatography-fourier transform infrared spectroscopy-sniffing system (GC-FTIR-SNIFF). A purge-and-trap technique was used to introduce the VOCs from samples into the gas chromatograph. Leaching waters of HD-PE granules were also evaluated by panel. This panel agreed upon six descriptive attributes for odour: sweet, chemical, stale, dusty, foul and floor-cloth. The attributes for taste were: sweet, metallic, stony, pungent, dusty, plastic, foul, stink bug and candle grease.

Chromatography, Gas↗

Closed-chamber inhalation pharmacokinetic studies with hexamethyldisiloxane in the rat.

Gas uptake methods together with physiologically based pharmacokinetic (PBPK) modeling have been used to assess metabolic parameters and oral absorption rates for a wide variety of volatile organic compounds. We applied these techniques to study the in vivo metabolism of hexamethyldisiloxane (HMDS), a volatile siloxane with low blood/air (partition coefficient PB approximately 1.00) and high fat/blood partitioning (partition coefficient PF approximately 300). In contrast to other classes of metabolized volatiles, metabolic parameters could only be estimated from closed-chamber results with confidence by evaluating both closed-chamber disappearance curves and constant concentration inhalation studies. The constant-concentration inhalation results refine the estimate of the blood/air partition coefficient and constrain model structure for storage of the lipophilic compound in blood and tissues. The gas uptake results, from Fischer 344 rats (male, 8-9 wk old) exposed to initial HMDS air concentrations from 500 to 5000 ppm, were modeled with a 5-tissue PBPK model. Excellent fits were obtained with diffusion-limited uptake of HMDS in fat and a lipid storage pool in the blood. Metabolism, restricted to the liver, was described as a single saturable process (V(max) = 113.6 micro mol/h/kg; K(m) = 42.6 micro mol/L) and was affected by inhibitors (diethyldithiocarbamate) or inducers (phenobarbital) of cytochrome P-450s. Exhalation kinetics of HMDS after oral/intraperitoneal administration showed low bioavailability and significant lag times, also quite different from results of other classes of volatile hydrocarbons. In general, estimates of metabolic clearance by gas uptake studies were improved by simultaneous examination of time-course results from constant concentration inhalation studies. This conclusion is likely to hold for any volatile lipophilic compound with low blood/air partitioning.

Adipose Tissue↗

Effects of ionic strength on the production of short chain volatile hydrocarbons by Dunaliella salina (Teodoresco).

The effect of ionic strength on the production of short chain volatile hydrocarbons was studied in cultures of Dunaliella salina. Axenic cultures of D. salina were grown at three different ionic strengths 0.5, 2 and 3 M of NaCl in Johnson (J/1) culture medium [Journal of Bacteriology 95 (1968) 1461] under the following laboratory growth conditions: a 12:12 h photoperiod, 300 micromolm(-2)s(-1) of photosynthetic active radiation (PAR) provided by a fluorescent lamp of 40 W combined with a 100 W incandescent lamp at 20 +/- 1 degrees C at pH 7.5. C1 to C5 hydrocarbons were detected using a head space technique and GC-FID. Cell numbers and growth rate was greatest at 2 M NaCl 4.3 x 10(6) cellml(-1) after a 15 days period of culture. Maximum hydrocarbon production was measured in the concentration of 0.5 NaCl with lower production rates in the more concentrated solutions. The principal hydrocarbon was pentane at 0.5 M but was ethane in 2 and 3 M solutions. Production rates for individual compounds ranged between 0.13 and 22 x 10(-15) microgCcell(-1)h(-1). It is suggested that the ability to produce and release volatile organic compounds of D. salina is related to osmotic conditions established by the ionic strength of growth solution.

Alkanes↗

Quantification of volatile organics in soil aging experiments using fourier transform infrared spectroscopy.

On-line Fourier transform infrared (FT-IR) spectroscopy was applied to monitor the concentration of halogenated volatile organic compounds in a sample-preparation process that simulates long-term, slow accumulation of contaminants in soils (i.e., aging). Artificial aging is conducted by circulating a supercritical fluid solution containing the contaminant(s) of interest through a packed soil column. Mid-infrared spectra of several volatile halocarbons were measured in supercritical Xe and CO(2) to evaluate possible interferences from the strong absorption of CO(2). Although some of the C-X bands were partially masked in supercritical CO(2), all of the compounds studied had distinct spectral features in the region 1400-700 cm(-1) and could be monitored in either solvent. Quantitative measurements of halogenated volatile organics in supercritical CO(2) were demonstrated with CCl(4). Excellent results were obtained over the range 7-280 mM. Representative artificial aging experiments were conducted on two test soils using CCl(4) as the contaminant. On-line (FT-IR) estimates of the aged soil concentrations were 1.3-4.4 times higher than off-line concentrations obtained by gas chromatography/mass spectrometry. The discrepancies were primarily ascribed to post-aging losses that occurred during depressurization and subsequent sample handling. FT-IR spectroscopy is shown to be a powerful tool for monitoring soil loading behavior and for developing artificial aging protocols.

Carbon↗

The kinetic of the catalytic decomposition of methyl isobutyl ketone over a Pt/gamma-Al2O3 catalyst.

Environmental catalysis also can refer to catalytic technologies for reducing emission of environmentally unacceptable compounds. Catalytic decomposition also is one of the cost-effective technologies to solve the troublesome volatile organic compounds. This study treated methyl isobutyl ketone (MIBK) by a commercial catalyst, Pt/gamma-Al(2)O(3), in an isothermal fixed bed differential reactor. The effects of O(2) and MIBK content in carrier gas on the catalysis's reaction rate are also observed. Three kinetic models, i.e. the Mars and van Krevelen model, Langmuir-Hinshelwood model and power-rate law were applied to best fit the experimental results. The results indicate that the kinetic behavior of MIBK oxidation with catalysis can be accounted for by using the rate expression of the Mars and van Krevelen model and Langmuir-Hinshelwood model. Kinetic parameters are also determined on the basis of the differential reactor data. The experimental results are compared with those of the model predicted.

Air Pollutants↗