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Volatile metabolites from some gram-negative bacteria.

A survey of volatile organic compounds (VOCs) excreted from various Gram-negative bacteria (Pseudomonas spp., Serratia spp. and Enterobacter spp.) was carried out. Compounds were identified by gas chromatography-mass spectrometry. VOCs identified included dimethyl disulphide, dimethyl trisulphide and isoprene.

Butadienes↗

Contribution of biogenic emissions to the formation of ozone and particulate matter in the eastern United States.

As anthropogenic emissions of ozone (O3) precursors, fine particulate matter (PM2.5), and PM2.5 precursors continue to decrease in the United States, the fraction of O3 and PM2.5 attributable to natural sources may become significant in some locations, reducing the efficacy that can be expected from future controls of anthropogenic sources. Modeling studies were conducted to estimate the contribution of biogenic emissions to the formation of O3 and PM2.5 in Nashville/TN and the northeastern United States. Two approaches were used to bound the estimates. In an anthropogenic simulation, biogenic emissions and their influence at the domain boundaries were eliminated. Contributions of biogenic compounds to the simulated concentrations of O3 and PM2.5 were determined by the deviation of the concentrations in the anthropogenic case from those in the base case. A biogenic simulation was used to assess the amounts of O3 and PM2.5 produced in an environment free from anthropogenic influences in emissions and boundary conditions. In both locations, the contribution of biogenic emissions to O3 was small (<23%) on a domain-wide basis, despite significant biogenic volatile organic compounds (VOC) emissions (65-89% of total VOC emissions). However, the production of O3 was much more sensitive to biogenic emissions in urban areas (22-34%). Therefore, the effects of biogenic emissions on O3 manifested mostly via their interaction with anthropogenic emissions of NOx. In the anthropogenic simulations, the average contribution of biogenic and natural sources to PM2.5 was estimated at 9% in Nashville/TN and 12% in the northeast domain. Because of the long atmospheric lifetimes of PM2.5, the contribution of biogenic/natural PM2.5 from the boundary conditions was higher than the contribution of biogenic aerosols produced within the domain. The elimination of biogenic emissions also affected the chemistry of other secondary PM2.5 components. Very little PM2.5 was formed in the biogenic simulations.

Air Pollutants↗

Development of a solid phase microextraction (SPME) method for the sampling of VOC traces in indoor air.

Solid-phase microextraction (SPME) was studied for the measurement of volatile organic compounds (VOCs) in indoor air. An adsorptive PDMS/Carboxen fibre was used and an analytical methodology was developed in order to overcome competitive adsorption. Kinetics and adsorption isotherms were investigated for different sample volumes and model compounds. In order to evaluate competitive adsorption on the fibre, these compounds were studied alone and in mixture. From the results obtained, the operating conditions allowing co-adsorption of the target compounds were determined: the air sample is enclosed in a 250 mL glass bulb where the SPME fibre is exposed until adsorption equilibrium. This procedure was combined with GC/MS analysis for the identification and quantification of VOCs in indoor air. The performances were determined by using a standard gas containing 10 VOCs representative of indoor environments (acetaldehyde, acetone, BTX, alpha-pinene, trichloroethylene, alkanes). The detection limits were determined in single ion monitoring mode and for a signal to noise ratio of 3. Except acetaldehyde (6 microg m(-3)), they are all below 0.5 microg m(-3). Calibration curves are linear up to 10 micromol m(-3) for all the compounds with good correlation coefficients (above 0.99). The reproducibility ranges from 6 to 12% according to the compound. The methodology was then applied to the comparison of the VOCs content in classrooms of two different schools.

Adsorption↗

The role of organic matter lost in kraft pulping material balances .

Efficiency improvement in a pulp mill includes minimisation of environmental discharges simultaneously with the development of pulp quality and production economy. Material balances in production processes, including fate of sidestreams, are key in proceeding these matters. Different approaches of determining the material balances increase understanding of process behaviour. We have focused on measuring sidestream (carryovers, washing water, filtrate) dissolved organic matter (DOM) in fibreline unit process blocks of softwood ECF bleached kraft production. The DOM was analysed by traditional wastewater methods (volatile solids, organic carbon, chemical oxygen demand). The measured data was combined with primarily simulated water balances and routine operational mill data in a simulation model. From this balance, yield estimate included, lost organic matter through complete degradation (CD) and volatile organic compounds (VOC) can be calculated throughout the fibreline. The sensitivity of this considerable amount (23-35 kgDVS/adt in total) to various factors is discussed in this paper.

Environmental Monitoring↗

Plant VOC emissions: making use of the unavoidable.

All plants emit substantial amounts of phytogenic volatile organic compounds (PVOCs), which include alkanes, alkenes, alcohols, aldehydes, eters, esters and carboxylic acids. Defence, communication and/or protection against extreme conditions have been proposed as reasons for these emissions. However, Rosenstiel and colleagues have recently proposed that emission of PVOCs represents a metabolic 'safety valve' by preventing the unnecessary sequestration of phosphates. Additionally, Niinemets and colleagues suggest that the emission rates of some PVOCs are determined by the principal physicochemical characteristics of the emitted compounds, such as their solubility, volatility and diffusivity, rather than by physiological mechanisms, such as their synthesis rates. These two new studies lead to the hypothesis that there is not necessarily a specific role for every PVOC emitted, given that their emission is unavoidable as result of their volatility. However, in some cases, natural selection has worked to take advantage of this volatility.

Journal Article↗

Measurement of trihalomethanes and methyl tert-butyl ether in whole blood using gas chromatography with high-resolution mass spectrometry.

The prevalence of disinfection by-products in drinking water supplies has raised concerns about possible adverse health effects from chronic exposure to these compounds. To support studies exploring the relation between exposure to trihalomethanes (THMs) and adverse health effects, an automated analytical method was developed using capillary gas chromatography (GC) and high-resolution mass spectrometry (MS) with selected ion mass detection and isotope-dilution techniques. This method quantified trace levels of THMs (including chloroform, bromodichloromethane, dibromochloromethane, and bromoform) and methyl tert-butyl ether (MTBE) in human blood. Analyte responses were adequate for measuring background levels after extraction of these volatile organic compounds with either purge-and-trap extraction or headspace solid-phase microextraction (SPME). The SPME method was chosen because of its ease of use and higher throughput. Detection limits for the SPME GC-MS method ranged from 0.3 to 2.4 ng/L, with linear ranges of three orders of magnitude. This method proved adequate for measuring the THMs and MTBE in most blood samples tested from a diverse U.S. reference population.

Environmental Monitoring↗

Processing gas chromatographic data and confidence interval calculation for partition coefficients determined by the phase ratio variation method.

The phase ratio variation (PRV) method is widely used for the determination of partition coefficient values (dimensionless Henry's law constants) by headspace gas chromatography. Traditional data processing by linear regression has several drawbacks: potential bias introduced by linearization, absence of quality indicator of the resulting value and, in case of replicate determinations, poor utilisation of the existing measurements leading to unnecessarily large confidence intervals. The paper compares existing PRV data processing methods (linear and nonlinear regression, parametric) and derives confidence intervals for the resulting partition coefficient values. The possibility of using several series of measurements to derive a single partition coefficient value with tighter and more reliable confidence intervals is presented for all three processing methods. The methods are tested on published literature data and new experimental data for 12 volatile organic compounds in water at 25 degrees C. The nonlinear regression based on several series of measurements appears to be the method of choice.

Chromatography, Gas↗

Airborne fungi and their secondary metabolites in working places in a compost facility.

The present study investigates in detail the exposure to airborne fungal spores in working places in compost facilities. The fungal species composition in the air is compared with the spectrum of microbial metabolites with regard to the physiological properties of different fungal species. The results indicate that the spectrum of microbial volatile organic compounds (MVOCs) and the production of mycotoxins can be specific for certain species. In addition to the pathogenic and allergological relevance, the fungi may have different toxicological health impacts.

Air Microbiology↗

Biomonitoring study of a group of workers potentially exposed to traffic fumes.

Risk assessment of environmental pollutants is concerned with the identification of compounds in the environment that might be hazardous to human health: measuring exposure levels, measuring cellular damage and then estimating the probability of harm occurring. The feasibility of such a comprehensive approach has been explored in this study of two groups of workers, one of which may be occupationally exposed to exhaust fumes. No statistically significant difference in cellular damage, as measured by the lymphocyte micronucleus assay, was found between these two groups of workers, although clear differences in exposure levels to volatile organic compounds were detected. A number of other factors identified in the study did show clear effects on micronucleus frequency.

Adult↗

Organic reactions without organic solvents and oils and fats as renewable raw materials for the chemical industry.

The use of organic solvents should be minimized as far as possible to reduce atmospheric volatile organic compounds (VOCs). Examples of solvent-free organic syntheses are described. The increasing usage of renewable feedstocks taking advantage of the synthetic potential of nature is another way to avoid organic solvents. Most important is the development of chemical products, i.e., coatings that can be processed without organic solvents.

Air Pollution↗

Landfarming operation of oily sludge in arid region--human health risk assessment.

Landfarming is becoming one of the most preferred treatment technologies for oily sludge disposal in the Arabian Gulf region in general, and in the Kingdom of Saudi Arabia in particular. This technology is considered to be, economical, energy efficient, and environmentally friendly with minimal residue disposal problems. Application of this technology in the region is simply based on the studies conducted in the United States of America and Europe. There have hardly been any scientific studies conducted to evaluate performance of landfarming technology under arid conditions. Recently, detailed field experimental study has been conducted to evaluate the degradation process and health risk issues in landfarming under arid conditions. The study observed volatilization as the main process of hydrocarbon degradation, which can cause significantly high concentration of airborne volatile organic compounds (VOCs) in the atmosphere leading to serious human health risk to the onsite workers. It is particularly true in the early phase of the landfarming process (first 2 months from initial loading). This paper elaborates these findings in detail.

Biodegradation, Environmental↗

Gas production and migration in landfills and geological materials.

Landfill gas, originating from the anaerobic biodegradation of the organic content of waste, consists mainly of methane and carbon dioxide, with traces of volatile organic compounds. Pressure, concentration and temperature gradients that develop within the landfill result in gas emissions to the atmosphere and in lateral migration through the surrounding soils. Environmental and safety issues associated with the landfill gas require control of off-site gas migration. The numerical model TOUGH2-LGM (Transport of Unsaturated Groundwater and Heat-Landfill Gas Migration) has been developed to simulate landfill gas production and migration processes within and beyond landfill boundaries. The model is derived from the general non-isothermal multiphase flow simulator TOUGH2, to which a new equation of state module is added. It simulates the migration of five components in partially saturated media: four fluid components (water, atmospheric air, methane and carbon dioxide) and one energy component (heat). The four fluid components are present in both the gas and liquid phases. The model incorporates gas-liquid partitioning of all fluid components by means of dissolution and volatilization. In addition to advection in the gas and liquid phase, multi-component diffusion is simulated in the gas phase. The landfill gas production rate is proportional to the organic substrate and is modeled as an exponentially decreasing function of time. The model is applied to the Montreal's CESM landfill site, which is located in a former limestone rock quarry. Existing data were used to characterize hydraulic properties of the waste and the limestone. Gas recovery data at the site were used to define the gas production model. Simulations in one and two dimensions are presented to investigate gas production and migration in the landfill, and in the surrounding limestone. The effects of a gas recovery well and landfill cover on gas migration are also discussed.

Biodegradation, Environmental↗

Materials emission of chemicals--PVC flooring materials.

Data of chemical emissions from flooring materials have been collected and investigated in a database known as METS. The emission tests are performed using the Field and Laboratory Emission Cell (FLEC). The emission rates of total volatile organic compounds (TVOC) in the boiling point range of hexane to octadecane varies from around 4,000 micrograms/(m2.h) to less than 10 micrograms/(m2.h). Results obtained 1994/95 are presented and compared with the results obtained in 1992 for similar materials. The tests are performed 4 weeks and 26 weeks after the manufacturing of the material. The emission rates of TVOC decrease on the average approximately 60% from 4 to 26 weeks. The differences and trends in emission rates of individual chemicals and their use are discussed. For many VOCs emission rates decrease rapidly and become near to or below 2 micrograms/(m2.h) (the detection limit) after 26 weeks. For a small number of individual compounds the emission rate decrease little over 26 weeks. A small number of chemicals are singled out for particular interest in a health and comfort evaluation based on the emission results.

Air Pollution, Indoor↗

NO removal by reducing agents and additives in the selective non-catalytic reduction (SNCR) process.

The effect of the additives on the selective non-catalytic reduction (SNCR) reaction has been determined in a three-stage laboratory scale reactor. The optimum reaction temperature is lowered and the reaction temperature window is widened with increasing concentrations of the gas additives (CO, CH4). The optimum reaction temperature is lowered and the maximum NO removal efficiency decreases with increasing the concentration of alcohol additives (CH3OH, C2H5OH). The addition of phenol lowers the optimum reaction temperature about 100-150 degrees C similar to that of the toluene addition. The volatile organic compounds (VOCs: C6H5OH, C7H8) can be utilized in the SNCR process to enhance NO reduction and removed at the same time. A previously proposed simple kinetic model can successfully apply the NO reduction by NH3 and the present additives.

Air Pollutants↗

Gas chromatography-mass spectrometry as a tool for estimating odour concentrations of biofilter effluents at aerobic composting and rendering plants.

The relationship between chemical concentrations (gas chromatography-mass spectrometry analysis) and odour concentrations (olfactometry) was studied for biofilter emissions from four aerobic vegetable, fruit and garden waste (VFG) composting plants and one animal rendering plant. For the VFG composting plants, the study revealed a good linear relationship of the odour concentration with the total volatile organic compounds (VOC) concentration (R2=0.97, n=16) as well as with the concentration of esters and ketones (R2=0.9, n=19). For biofilter emissions of the animal rendering plant, the total VOC concentration was a poor estimator for odour concentration. However, for this type of odour, concentrations of organic sulphur containing compounds correlated well with odour concentrations (R2=0.94, n=8). The results of the study also showed that the relationship between chemical and odour concentrations is specific for each type of odour and cannot be generalized.

Aerobiosis↗

Emissions of toxic pollutants from compressed natural gas and low sulfur diesel-fueled heavy-duty transit buses tested over multiple driving cycles.

The number of heavy-duty vehicles using alternative fuels such as compressed natural gas (CNG) and new low-sulfur diesel fuel formulations and equipped with after-treatment devices are projected to increase. However, few peer-reviewed studies have characterized the emissions of particulate matter (PM) and other toxic compounds from these vehicles. In this study, chemical and biological analyses were used to characterize the identifiable toxic air pollutants emitted from both CNG and low-sulfur-diesel-fueled heavy-duty transit buses tested on a chassis dynamometer over three transient driving cycles and a steady-state cruise condition. The CNG bus had no after-treatment, and the diesel bus was tested first equipped with an oxidation catalyst (OC) and then with a catalyzed diesel particulate filter (DPF). Emissions were analyzed for PM, volatile organic compounds (VOCs; determined on-site), polycyclic aromatic hydrocarbons (PAHs), and mutagenic activity. The 2000 model year CNG-fueled vehicle had the highest emissions of 1,3-butadiene, benzene, and carbonyls (e.g., formaldehyde) of the three vehicle configurations tested in this study. The 1998 model year diesel bus equipped with an OC and fueled with low-sulfur diesel had the highest emission rates of PM and PAHs. The highest specific mutagenic activities (revertants/microg PM, or potency) and the highest mutagen emission rates (revertants/mi) were from the CNG bus in strain TA98 tested over the New York Bus (NYB) driving cycle. The 1998 model year diesel bus with DPF had the lowest VOCs, PAH, and mutagenic activity emission. In general, the NYB driving cycle had the highest emission rates (g/mi), and the Urban Dynamometer Driving Schedule (UDDS) had the lowest emission rates for all toxics tested over the three transient test cycles investigated. Also, transient emissions were, in general, higher than steady-state emissions. The emissions of toxic compounds from an in-use CNG transit bus (without an oxidation catalyst) and from a vehicle fueled with low-sulfur diesel fuel (equipped with DPF) were lower than from the low-sulfur diesel fueled vehicle equipped with OC. All vehicle configurations had generally lower emissions of toxics than an uncontrolled diesel engine. Tunnel backgrounds (measurements without the vehicle running) were measured throughout this study and were helpful in determining the incremental increase in pollutant emissions. Also, the on-site determination of VOCs, especially 1,3-butadiene, helped minimize measurement losses due to sample degradation after collection.

Air Pollutants↗

Dermal absorption of dilute aqueous chloroform, trichloroethylene, and tetrachloroethylene in hairless guinea pigs.

Percutaneous absorption was measured in female hairless guinea pigs dermally exposed for 70 min to very dilute (approximately 10 to 100 ppb) aqueous solutions of 14C-labeled chloroform (CF), trichloroethylene (TCE), or tetrachloroethylene (PCE) in an airtight glass chamber containing no headspace. Similar experiments were conducted using aqueous solutions of TCE at 100,000 ppb. Dermal uptake was estimated by comparing the rate of radiolabel loss from chamber water in systems with and without experimental animals. After each low-concentration dermal-uptake experiment, radiolabel in total urine and feces excreted postexposure was measured and expressed as a fraction of corresponding estimated dermal uptake. For each of the compounds studied, the mean value of these fractions did not differ significantly from that obtained using animals injected with a known dose of that compound, indicating that our experimental system yielded accurate dermal-uptake estimates. The mean permeability coefficients obtained range from 0.13 cm/hr (CF) to 0.37 cm/hr (PCE); those obtained using low- vs high-concentration TCE are not significantly different. The value for CF is very close to one we calculate here from recently published data on CF uptake in human volunteers dermally exposed to aqueous CF while showering with normal tap water. Our results suggest that dermal absorption may be an important route of human exposure to chlorinated volatile organic compounds in domestic water supplies.

Animals↗

Seasonal variation of monoterpene emission from Malus domestica and Prunus avium.

Emission rates of monoterpenes released by apple (Malus domestica Borkh) and cherry (Prunus avium L.) were estimated at different phenological stages. These measurements employed a dynamic flow-through Teflon chamber, sample collection onto cartridges filled with graphitized carbon and thermal desorption gas chromatography-mass spectrometry (GC-MS) for identification and quantification of the emitted volatiles. At full bloom the release of monoterpene hydrocarbons from cherry flowers was 1213 ng g(-1) dry weight (DW) h(-1), exceeding by approximately three-fold the emission rate of apple flowers (366 ng g(-1) DW h(-1)). Observed seasonal variations in biogenic volatile organic compound (VOC) emissions ranged over several order of magnitudes. At fruit-set and ripening stages, in fact, the hydrocarbon emission dramatically decreased reaching the lowest values at harvest time when leaves were fully mature (3-9 ng g(-1) DW h(-1)). Wide diversity in the composition of compounds from the species studied was also recorded. At blooming, linalool contributed significantly to the monoterpene emission from apple (94% of the emitted carbon) while alpha-pinene and camphene represented on average more than 60% of the total emitted volatiles from cherry flowers. Among the monoterpenes identified in flowers, alpha-pinene, camphene and limonene were also found in the foliage emission of both species. Fruit trees are relevant monoterpene emitters only at blooming and thus for a short period of the vegetative cycle. When leaves are fully developed, the carbon loss due to monoterpene emissions related to the photosynthetically carbon gain is negligible.

Gas Chromatography-Mass Spectrometry↗