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Simultaneous analysis of phytohormones, phytotoxins, and volatile organic compounds in plants.

Phytohormones regulate the protective responses of plants against both biotic and abiotic stresses by means of synergistic or antagonistic actions referred to as signaling crosstalk. A bottleneck in crosstalk research is the quantification of numerous interacting phytohormones and regulators. The chemical analysis of salicylic acid, jasmonic acid, indole-3-acetic acid, and abscisic acid is typically achieved by using separate and complex methodologies. Moreover, pathogen-produced phytohormone mimics, such as the phytotoxin coronatine (COR), have not been directly quantified in plant tissues. We address these problems by using a simple preparation and a GC-MS-based metabolic profiling approach. Plant tissue is extracted in aqueous 1-propanol and mixed with dichloromethane. Carboxylic acids present in the organic layer are methylated by using trimethylsilyldiazomethane; analytes are volatilized under heat, collected on a polymeric absorbent, and eluted with solvent into a sample vial. Analytes are separated by using gas chromatography and quantified by using chemical-ionization mass spectrometry that produces predominantly [M+H]+ parent ions. We use this technique to examine levels of COR, phytohormones, and volatile organic compounds in model systems, including Arabidopsis thaliana during infection with Pseudomonas syringae pv. tomato DC3000, corn (Zea mays) under herbivory by corn earworm (Helicoverpa zea), tobacco (Nicotiana tabacum) after mechanical damage, and tomato (Lycopersicon esculentum) during drought stress. Numerous complex changes induced by pathogen infection, including the accumulation of COR, salicylic acid, jasmonic acid, indole-3-acetic acid, and abscisic acid illustrate the potential and simplicity of this approach in quantifying signaling crosstalk interactions that occur at the level of synthesis and accumulation.

Abscisic Acid↗

Ecological risks to fossorial vertebrates from volatile organic compounds in soil.

The past several years has seen an increased awareness of the need to conduct ecological risk assessments (ERAs) for hazardous waste sites. One technique used in ERAs involves estimating contaminant exposure to individual animals of selected species, which is then compared to a reference dose derived from the literature. Exposure estimates are conducted on those species which are representative of the different trophic levels found at the site. In many terrestrial systems, fossorial (burrowing) vertebrates are found in both lower and upper trophic levels. As part of the ERA conducted for Site 300, Lawrence Livermore National Laboratory's high-explosive test facility, contaminant exposures were estimated for fossorial and nonfossorial vertebrates spanning two trophic levels. The results of the evaluation revealed that a significant pathway by which fossorial vertebrates could be exposed to trichloroethylene in soil was through the inhalation of contaminated subsurface burrow air. This was the first time that the importance of this ecological exposure pathway has been recognized. The results of this analysis suggest that further research into the ecological significance of subsurface burrow air contaminated with volatile organic compounds is warranted.

Air Pollutants↗

Column performance and stability for high-speed vacuum-outlet GC of volatile organic compounds using atmospheric pressure air as carrier gas.

The development of lightweight, portable GC instrumentation is handicapped by the need for compressed carrier gas to drive the separation. The use of air as carrier gas eliminates the need for compressed gas tanks. If a vacuum pump is used to pull carrier gas and injected samples through the column, atmospheric pressure air can be used as carrier gas. Vacuum outlet operation also improves performance for high-speed separations by reducing detector dead time and by shifting optimal carrier gas velocity to higher values. Under vacuum outlet conditions using atmospheric pressure air as carrier gas, a 6-m-long, 0.25-mm-i.d. capillary column can generate approximately 12,500 theoretical plates, and a 12-m-long column can generate approximately 44,000 plates but with a 3-4-fold increase in separation time. The principal issues in column selection for high-speed GC with air as a carrier gas are efficiency and stability. Several bonded and nonbonded stationary phases were evaluated for use with air as carrier gas in the analysis of volatile organic compounds of interest in airmonitoring applications. These include dimethylpolysiloxane, 50% phenyl-50% methyl polysiloxane, 50% cycanopropylphenyl-50% methyl polysiloxane, trifluoropropyl polysiloxane, poly(ethylene glycol), and dicyanoallyl polysiloxane (nonbonded). The dimethyl polysiloxane and the trifluoropropyl polysiloxane columns showed good efficiency and no significant deterioration after 5 days of continuous operation with air as carrier gas. The 50% phenyl-50% methyl polysiloxane and the 50% cycanopropylphenyl-50% methyl polysiloxane columns showed poorer efficiency, and the poly(ethylene glycol) and dicyanoallyl polysiloxane columns showed excessive deterioration in air.

Air↗

Collection of a single alveolar exhaled breath for volatile organic compounds analysis.

Measurement of specific organic compounds in exhaled breath has been used as an indicator of recent exposure to pollutants or as an indicator of the health of an individual. A typical application involves the collection of multiple breaths onto a sorbent cartridge or into an evacuated canister with the use of a relatively complex sampling apparatus. A new method has been developed wherein a single exhaled breath is directly transferred from the mouth into an evacuated 1 l or 1.8 l stainless steel SUMMA canister. The single breath canister (SBC) method avoids the necessity for a complex sampling system requiring maintenance and cleaning and allows easy collection of samples. Additionally, it is possible to collect a rapid sequence of samples from a subject to establish the elimination curve subsequent to an exposure to specific volatile organic compounds with a theoretical resolution of adjacent breaths. The SBC method was compared to an accepted canister based sampling system to assure comparability and then used to demonstrate its utility by measuring the absorption and elimination of chloroform during and after exposure to chlorinated shower water.

Breath Tests↗

Volatile organic compound emissions from latex paint--Part 1. Chamber experiments and source model development.

Latex paints are widely used in residential and commercial indoor environments. The surface areas covered by the paints in these environments are relatively large. Thus, latex paints have the potential for having a major impact on indoor air quality (IAQ). A study was undertaken to develop methods for evaluating the impact of latex paint emission on IAQ. Small chamber experiments using stainless steel and painted and unpainted gypsum board substrates were conducted to determine the emission characteristics of latex paint. The emissions from the stainless steel were relatively short lived (3 to 4 days), whereas the emissions from gypsum board lasted for over 200 days. Because gypsum board is a common substrate for latex paint, all emission models were developed for the gypsum board substrates. The data from the small chamber tests led to the development of two empirical and two mass-transfer-based source emission models. Approximately 100 to 200 days of data were required to estimate the parameters required for the empirical models. Only 8 days of data were required to estimate the parameters for the mass-transfer-based models. The final models use paint formulation and mass transfer correlations to predict the emissions of the major individual volatile organic compounds emitted by latex paint.

Air Pollution, Indoor↗

A comparison of sampling and analysis methods for low-ppbC levels of volatile organic compounds in ambient air.

A carefully designed study was conducted during the summer of 1998 to collect samples of ambient air by canisters and compare the analysis results to direct sorbent preconcentration results taken at the time of sample collection. Thirty-two 1 h sample sets were taken, each composed of a "near-real-time" sample analyzed by an autoGC-MS XonTech 930/Varian Saturn 2000 system, and Summa and Silco canisters. Hourly total non-methane organic carbon (TNMOC), ozone, and meteorological measurements were also made. Each canister was analyzed on the autoGC-MS system for a target list of 108 volatile organic compounds (VOCs) and on a manual cryosampling GC-FID system. Comparisons were made between the collection and analysis methods. Because of the low sample loading (150-250 ppbC TNMOC), these comparisons were a stringent test of sample collection and analysis capabilities. The following specific conclusions may be drawn from this study. Reasonable precision (within 15% mean difference of duplicate analyses from the same canister) can be obtained for analyses of target VOCs at low-ppbC concentrations. Relative accuracy between the GC-MS and GC-FID analysis methods is excellent, as demonstrated by comparisons of analyses of the same canisters, if measurements are sufficiently above the detection limits. This is especially significant as the GC-MS and GC-FID were independently calibrated. While statistically significant differences may be observed between the results from canister and near-real-time samples, the differences were generally small and there were clear correlations between the canister results and the near-real-time results. Canister cleanliness limits detection below the EPA Method TO-14 acceptance standard of 0.2 ppbv (0.2-2 ppbC for target analytes).

Air Pollutants↗

[Halogenated volatile organic compounds in bottled mineral water and soft drinks].

74 mineral natural water samples and 56 samples of different commercial drinks have been analysed by head-space chromatography in order to evidence the presence of volatile halogenated organic compounds (VHO). Trihalomethanes (THM) as drinking water chlorination by-products and trichloroethane, carbon tetrachloride, trichloroethylene and tetrachloroethylene as ubiquitarious substances have been investigated. The presence of VHO has been evidenced in 20,3% of mineral natural water samples and in the 58,9% of the commercial soft drinks: this latest group has usually shown higher levels of the investigated compounds. The results of the present study has been compared with a similar study performed in 1991 in the same area: the VHO values observed in the present study appear to be lower than those obtained in the previous study.

Beverages↗

Volatile organic compounds produced during the aerobic biological processing of municipal solid waste in a pilot plant.

The volatile organic carbon (VOC) and odours emitted during the aerobic biological processing of municipal solid waste (MSW) was studied in a pilot-scale reactor. VOCs were detected by different techniques on solid waste samples and the outlet air stream, before and after a biofilter. Organic compounds (alpha-pinene, beta-myrcene, D-limonene) were also measured in condensate water and leachate from the process. Results showed uniformity in the composition of the air in the solid waste samples, air sampled during the process and condensed water, indicating a matrix-derived origin of these compounds. Leachates, however, contained substances with a quite different molecular structure from the compounds identified in the gaseous fraction. Most of the substances in the gaseous effluent had a hydrocarbon-like structure, mainly terpenoids. The odour produced and detected through olfactometry agreed with GC-MS analyses. This was true above all for terpenes.

Air Pollutants↗

Selected volatile organic compounds in residential air in the city of Ottawa, Canada.

Airborne levels of selected volatile organic chemicals (VOCs) that are priorities for exposure assessment under the Canadian Environmental Protection Act (CEPA) 1999 were measured in both indoor air and outdoor air of 75 residential houses, in the city of Ottawa, Canada, during the winter of 2002/2003. The houses were randomly selected using Ottawa 2001 population census data. VOCs were collected on adsorbent tubes and measured by thermal desorption GC/MS. Among 37 chemicals monitored, 17 were detected with a frequency greater than 80% in indoor air; 9 were between 30% and 80%; 7 were between 1% and 30%; and 4 were not detected. Concentrations of VOCs in both indoor and outdoor air are presented. Virtually all of the target VOCs were detected more frequently and were present at significantly higher levels, in indoor air than in outdoor air. As an indication of the contribution of indoor levels of these chemicals, ratios of the concentration found in indoor air to outdoor air (I/O) and the indoor source strength expressed in estimated emission rate per house are also presented. Compared with earlier published studies including a 1991/1992 Canadian national survey of VOCs in residential air, levels of target analytes in indoor air in this study were lower for a number of chemicals, indicating a possible trend toward decreased inhalation exposure to these chemicals in residential environments. This study has yielded up-to-date information on levels of a variety of priority airborne chemicals in residential air, which is being used to estimate current exposure to these substances as input to health risk assessments and risk management actions under CEPA 1999.

Air Pollutants↗

Ranking of volatile organic compounds for tropospheric degradability by oxidants: a QSPR approach.

The limited availability and variability of data related to atmospheric degradation reaction is a very relevant issue in studies related to environmental fate and behavior of chemicals. For screening purposes, the experimental data of the oxidation rate constants for the reactions with the radicals OH, NO3 and with ozone of 65 heterogeneous organic compounds were explored by Principal Component Analysis: a ranking of volatile organic chemicals (VOC) according to their relative overall atmospheric degradability and an atmospheric persistence index (ATPIN) is proposed. This index has been modeled by theoretical molecular descriptors to obtain MLR models with high predictive power, both internally and externally validated, and the definition of chemical domain applicability. This procedure allows a fast ranking of VOCs according to their tendency to be degraded by atmospheric oxidants, starting only from the knowledge of their molecular structure.

Air Pollutants↗

The influence of personal activities on exposure to volatile organic compounds.

Seven persons volunteered to perform 25 common activities thought to increase personal exposure to volatile organic chemicals (VOCs) during a 3-day monitoring period. Personal, indoor, and outdoor air samples were collected on Tenax cartridges three times per day (evening, overnight, and daytime) and analyzed by GC-MS for 17 target VOCs. Samples of exhaled breath were also collected before and after each monitoring period. About 20 activities resulted in increasing exposure to one or more of the target VOCs, often by factors of 10, sometimes by factors of 100, compared to exposures during the sleep period. These concentrations were far above the highest observed outdoor concentrations during the length of the study. Breath levels were often significantly correlated with previous personal exposures. Major exposures were associated with use of deodorizers (p-dichlorobenzene); washing clothes and dishes (chloroform); visiting a dry cleaners (1,1,1-trichloroethane, tetrachloroethylene); smoking (benzene, styrene); cleaning a car engine (xylenes, ethylbenzene, tetrachloroethylene); painting and using paint remover (n-decane, n-undecane); and working in a scientific laboratory (many VOCs). Continuously elevated indoor air levels of p-dichlorobenzene, trichloroethylene, 1,1,1-trichloroethane, carbon tetrachloride, decane, and undecane were noted in several homes and attributed to unknown indoor sources. Measurements of exhaled breath suggested biological residence times in tissue of 12-18 hr and 20-30 hr for 1,1,1-trichloroethane and p-dichlorobenzene, respectively.

Activities of Daily Living↗

Volatile organic compounds from the combustion of human and animal tissue.

The volatile by-products of the combustion of ordinary fuels such as wood, polystyrene, polyethylene, urethane foam, PVC and the like are well known to the forensic fire debris examiner. When a fire involves a human body, volatile species are produced that are not so well known, including various alkenes and aldehydes. These have sometimes been mistaken for the residues of unusual accelerants. In an attempt to document what volatiles are produced by the combustion of animal fat and human fat, the authors have used an open-tube pyrolysis probe as a microfurnace to burn small samples of unembalmed subcutaneous fat from human, avian and porcine sources, and collect volatiles by charcoal strip adsorption. The volatile products were analyzed by GC/MS. Predominant species included aldehydes in the C6-C10 range, homologous series of alkenes and alkanes, and other hydrocarbon products. These results were compared to those obtained by free-burning (open flame in air) of similar specimens and to the volatiles detected in debris from beneath a human cadaver in a test fire. Differences between the volatile profiles produced by human fat as compared to pork and chicken fat and adventitious sources of such volatiles are discussed.

Adipose Tissue↗

Volatile organic compound emissions during the composting of biosolids from a domestic wastewater treatment plant.

VOCs emitted by two composting static piles of biosolids coming from the "El Salitre" wastewater treatment plant (Bogotá, Colombia) were analysed during the composting process. Each pile in its sampling time was maintained with a different aeration system. The sampling was made using Solid Phase Microextraction (SPME); separation and identifications were made using Gas Chromatography (GC) coupled to Mass Spectrometry (MS). Aliphatic and aromatic hydrocarbons, chlorinated compounds, ketones, mercaptans, alcohols and amines were identified in concentrations greater than the norms stipulated by the EPA for inhalation in humans beings. The emission behavior varied according to the aeration system used.

Alcohols↗