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[Advanced development of remote sensing FTIR in air environment monitoring].

Remote sensing FTIR(RS-FTIR) is one of the most important technologies in atmospheric pollutant monitoring. It has several prevailing advantages: (1) high resolution and high selectivity; (2) it requiring no sampling and no sample preprocessing; (3) capability of detecting several compounds simultaneously; (4) real time, long distance, and automatic monitoring. So it is extraordinarily appropriate for the quantitative and qualitative determination, and remote, real time, dynamic monitoring of air contaminant, especially the toxic volatile organic compounds (VOCs). The present paper reviews the research progress in remote sensing FTIR for air monitoring made by the Laboratory of Advanced Spectroscopy in recent years, including chemometrics, computed tomography, FTIR spectra interpretation, spatial distribution of air pollutant concentration and passive remote monitoring, etc. These research findings show that the rapid development and application of remote sensing FTIR accelerated the temporal and spatial extension of analytical chemistry, and it will by all means have wide prospects in atmospheric environmental monitoring.

English Abstract↗

Reducing 1,3-dichloropropene emissions from soil columns amended with thiourea.

Soil fumigants are becoming an important source of volatile organic compounds (VOCs) in air, especially in some agricultural areas. In this study, we used thiourea to construct a reactive surface barrier (RSB) at the soil surface for reducing 1,3-dichloropropene (1,3-D) volatilization. The agrochemical thiourea could rapidly transform volatile 1,3-D to nonvolatile products via an SN2 nucleophilic substitution reaction. A catalytic mechanism in thiourea-amended soil facilitated the conversion process. A packed soil column system was employed to investigate the emissions and distribution of 1,3-D and optimize the original fumigant emission-reduction strategy. Volatilization of 1,3-D from the soil surface was significantly reduced in columns amended with a thiourea RSB compared with that of bare soil. Volatilization flux and cumulative emissions decreased with increasing thiourea application rate and increasing fumigation depth in packed soil columns. Surface amendment with the RSB did not affect the subsurface distribution of 1,3-D in the soil profile. Combined application of a thiourea RSB and plastic tarps had a synergetic effect in emission control and could eliminate the relatively high fumigant flux that occurs upon tarp disruption. Therefore, this reduced-risk practice was very effective in reducing atmospheric emissions of VOCs from soil treatment with halogenated fumigants.

Allyl Compounds↗

Indoor sorption of surrogates for sarin and related nerve agents.

Sorption rate parameters were determined for three organophosphorus (OP) compounds [dimethyl methylphosphonate (DMMP), diethyl ethylphosphonate (DEEP), and triethyl phosphate (TEP)] as surrogates for the G-type nerve agents sarin (GB), soman (GD), and tabun (GA). OP surrogates were injected and vaporized with additional volatile organic compounds into a 50 m3 chamber finished with painted wallboard. Experiments were conducted at two furnishing levels: (i) chamber containing only hard surfaces including a desk, a bookcase, tables, and chairs and (ii) with the addition of plush materials including carpet with cushion, draperies, and upholstered furniture. Each furnishing level was studied with aged and new painted wallboard. Gas-phase concentrations were measured during sealed chamber adsorb and desorb phases and then fit to three mathematical variations of a previously proposed sorption model having a surface sink and allowing for an embedded sink. A four-parameter model allowing unequal transport rates between surface and embedded sinks provided excellent fits for all conditions. To evaluate the potential effect of sorption, this model was incorporated into an indoor air quality simulation model to predict indoor concentrations of a G-type agent and a nonsorbing agent for hypothetical outdoor releases with shelter-in-place (SIP) response. Sorption was simulated using a range of parameters obtained experimentally. Simulations considered outdoor Gaussian plumes of 1- and 5-h duration and infiltration rates of 0.1, 0.3, and 0.9 h(-1). Indoor toxic loads (TL) for a 10-h SIP were calculated as integral C2 dt for a G-type agent. For the 5-h plume, sheltering reduced TLs for the nonsorbing agent to approximately 10-65% of outdoor levels. Analogous TLs for a G-type agent were 2-31% or 0.3-12% of outdoor levels assuming slow or moderate sorption. The relative effect of sorption was more pronounced for the longer plume and higher infiltration rates.

Adsorption↗

Biodegradation of hydrocarbons vapors: Comparison of laboratory studies and field investigations in the vadose zone at the emplaced fuel source experiment, Airbase Vaerløse, Denmark.

The natural attenuation of volatile organic compounds (VOCs) in the unsaturated zone can only be predicted when information about microbial biodegradation rates and kinetics are known. This study aimed at determining first-order rate coefficients for the aerobic biodegradation of 13 volatile petroleum hydrocarbons which were artificially emplaced as a liquid mixture during a field experiment in an unsaturated sandy soil. Apparent first-order biodegradation rate coefficients were estimated by comparing the spatial evolution of the resulting vapor plumes to an analytical reactive transport model. Two independent reactive numerical model approaches have been used to simulate the diffusive migration of VOC vapors and to estimate degradation rate coefficients. Supplementary laboratory column and microcosm experiments were performed with the sandy soil at room temperature under aerobic conditions. First-order kinetics adequately matched the lab column profiles for most of the compounds. Consistent compound-specific apparent first-order rate coefficients were obtained by the three models and the lab column experiment, except for benzene. Laboratory microcosm experiments lacked of sensitivity for slowly degrading compounds and underestimated degradation rates by up to a factor of 5. Addition of NH3 vapor was shown to increase the degradation rates for some VOCs in the laboratory microcosms. All field models suggested a significantly higher degradation rate for benzene than the rates measured in the lab, suggesting that the field microbial community was superior in developing benzene degrading activity.

Bacteria↗

Behavior of organic polymers in drinking water purification.

Synthetic organic polymers used to purify drinking water are severely limited in that their impurities and by-products harm human health. In this study, the undesired effects resulted from chlorination and the enhanced attenuation of toxic organic compounds in drinking water from using synthetic organic polymer coagulants were investigated. In the simulated drinking water purification processes, synthetic organic polymers were used as coagulant aids, reacted with a disinfectant(chlorine) and formed a large number of volatile organic compounds (VOCs). Chloroform and benzene which, are carcinogenic compounds, had the maximum formation potential. Experimental results indicated that the total formation potential of these disinfection by-products significantly increased in the presence of turbidity. On the other hand, adding organic polymers to the coagulation systems resulted in more extensive remove of toxic organic compounds and turbidity. In coagulation and flocculation processes, the formation of clay/polymer complexes can facilitate the removal of toxic organic compounds in contaminated water.

Aluminum Silicates↗

Potential for reduction of odorous compounds in swine manure through diet modification.

Recent public concern about air pollution from pork production units has prompted more research to develop methods to reduce and control odors. Masking agents, enzymes and bacterial preparations, feed additives, chemicals, oxidation processes, air scrubbers, biofilters, and new ventilation systems have been studied. Research relating the effects of the swine diet on manure odors has been scarce. Introducing feed additives to bind ammonia, change digesta pH, affect specific enzyme activity, and mask odors has been either costly or not consistently successful. Recent research emphasis has focused on manipulating the diet 1) to increase the nutrient utilization of the diet to reduce excretion products, 2) to enhance microbial metabolism in the lower digestive tract to reduce excretion of odor-causing compounds, and 3) to change the physical characteristics of urine and feces to reduce odor emissions. Primary odor-causing compounds evolve from excess degradable proteins and lack of specific fermentable carbohydrates during microbial fermentation. Reductions in ammonia emissions by 28 to 79% through diet modifications have been reported. Limited research on reduction of other odorous volatile organic compounds through diet modifications is promising. Use of synthetic amino acids with reduced intact protein levels in diets significantly reduces nitrogen excretions and odor production. Addition of nonstarch polysaccharides and specific oligosaccharides further alters the pathway of nitrogen excretion and reduces odor emission. Continued nutritional and microbial research to incorporate protein degradation products, especially sulfur-containing organics, with fermentable carbohydrates in the lower gastrointestinal tract of pigs will further control odors from manure.

Animal Feed↗

Livestock odors: implications for human health and well-being.

The purpose of this paper is to examine the potential effects of livestock odors on the health and well-being of neighbors. Complaints of odor nuisance have become more frequent in communities surrounding areas with high concentrations of livestock. This increase in complaints from livestock odors parallels increased complaints of odor in general, including ammonia, diesel exhaust, beauty products, cleaners, and paints. Persons who report symptoms from odors generally find problems with many different types of odorous compounds. A review of recent studies suggests that the main complaints of health symptoms from odors are eye, nose, and throat irritation, headache, and drowsiness. Sensory irritation (pungency) can be produced by a broad range of odorous volatile organic compounds from trees, flowers, foods (pepper and ginger) as well as emissions from livestock operations. Odors can also potentially affect mood and memory. Further research is required to assess fully the health impact of odors in order to establish recommendations for air quality guidelines based on scientific data.

Air Pollution↗

Priming of plant defense responses in nature by airborne signaling between Artemisia tridentata and Nicotiana attenuata.

Plants release volatile organic compounds (VOCs) in response to wounding and herbivore attack, some of which trigger responses in neighboring unattacked plants in the laboratory under conditions that are not likely to occur in the real world. Whether plants 'eavesdrop' on the volatile emissions of their neighbors in nature is not known. The best documented field study of between-species signaling via above-ground VOCs involves increases in fitness parameters of native tobacco (Nicotiana attenuata) transplanted adjacent to clipped sagebrush (Artemesia tridentata tridentata). Clipped sagebrush releases many biologically active VOCs, including methyl jasmonate (MeJA), methacrolein and a series of terpenoid and green leaf VOCs, of which MeJA, while active under laboratory conditions, is not released in sufficient quantities to directly elicit induced resistance in the field. Here we demonstrate, with laboratory and field-based experiments, that priming (rather than direct elicitation) of native N. attenuata's induced chemical defenses by a sagebrush-released VOC bouquet can account for earlier findings. With microarrays enriched in N. attenuata herbivore-regulated genes, we found transcriptional responses in tobacco growing adjacent to clipped sagebrush foliage, but failed to detect the direct elicitation of defensive chemicals or proteins. However, we observed an accelerated production of trypsin proteinase inhibitors when Manduca sexta caterpillars fed on plants previously exposed to clipped sagebrush. This readying of a defense response, termed priming, results in lower total herbivore damage to plants exposed to clipped sagebrush and in a higher mortality rate of young Manduca caterpillars. Our study demonstrates priming of plant defense responses as a mechanism of plant-plant signaling in nature, and provides an example for the analysis of between-plant signaling under ecologically realistic conditions. Although we describe priming as a potential mechanism for signaling between plants in nature, we critically discuss the ecological relevance of the particular interaction.

Animals↗

Ingestion, inhalation, and dermal exposures to chloroform and trichloroethene from tap water.

Individuals are exposed to volatile compounds present in tap water by ingestion, inhalation, and dermal absorption. Traditional risk assessments for water often only consider ingestion exposure to toxic chemicals, even though showering has been shown to increase the body burden of certain chemicals due to inhalation exposure and dermal absorption. We collected and analyzed time-series samples of expired alveolar breath to evaluate changes in concentrations of volatile organic compounds being expired, which reflects the rate of change in the bloodstream due to expiration, metabolism, and absorption into tissues. Analysis of chloroform and trichloethene in expired breath, compounds regulated in water, was also used to determine uptake from tap water by each route (inhalation, ingestion, or absorption). Each route of exposure contributed to the total exposure of these compounds from daily water use. Further, the ingestion dose was completely metabolized before entering the bloodstream, whereas the dose from the other routes was dispersed throughout the body. Thus, differences in potential biologically effective doses depend on route, target organ, and whether the contaminant or metabolite is the biologically active agent.

Adult↗

Comparison of micro-scale simultaneous distillation-extraction and stir bar sorptive extraction for the determination of volatile organic constituents of grape juice.

Traditional micro-scale simultaneous distillation-extraction (SDE) and stir bar sorptive extraction (SBSE) were compared for their effectiveness in the extraction of volatile organic compounds in a synthetic grape juice and a real grape juice (Huxelrebe, a variety of half Muscat ancestry) from an English vineyard. The novel immersion-mode SBSE method, using stir bars with PDMS sorbent, was optimised using the synthetic grape juice. Although mean percent relative recoveries and reproducibilities (%CV) of the SBSE method were inferior to SDE (28.4 and 8.5%, respectively, against 86.9 and 6.3%), the former method proved to be significantly more sensitive: 126 aroma compounds in Huxelrebe grape juice were identified using SBSE, against 98 using SDE. This allowed the identification of a number of volatile components that have not been reported previously in the juice or wine from the grapes of Muscat varieties.

Beverages↗

Predicting emissions of SVOCs from polymeric materials and their interaction with airborne particles.

A model that predicts the emission rate of volatile organic compounds (VOCs) from building materials is extended and used to predict the emission rate of semivolatile organic compounds (SVOCs) from polymeric materials. Reasonable agreement between model predictions and gas-phase di-2-ethylhexyl phthalate (DEHP) concentrations is achieved using data collected in a previous experimental study that measured emissions of DEHP from vinyl flooring in two very different chambers. While emissions of highly volatile VOCs are subject to "internal" control (the material-phase diffusion coefficient), emissions of the very low volatility SVOCs are subject to "external" control (partitioning into the gas phase, the convective mass-transfer coefficient, and adsorption onto interior surfaces). The effect of SVOCs partitioning onto airborne particles is also examined. The DEHP emission rate is increased when the gas-phase concentration is high, and especially when partitioning to the airborne particles is strong. Airborne particles may play an important role in inhalation exposure as well as in transporting SVOCs well beyond the source. Although more rigorous validation is needed, the model should help elucidate the mechanisms governing emissions of phthalate plasticizers, brominated flame retardants, biocides, and other SVOCs from a wide range of building materials and consumer products.

Air Pollutants↗

Levels of benzene and other volatile aromatic compounds in the blood of non-smokers and smokers.

The concentrations of benzene, toluene, ethylbenzene, and o-, m-and p-xylene were measured in venous blood samples collected from 13 non-smokers and 14 cigarette smokers. The blood samples were analysed by a purge and trap technique followed by gas chromatography/mass spectrometry/computer analysis. The above-mentioned volatile organic compounds (VOC) could be detected in measurable amounts in all blood samples. This finding seems to reflect the ubiquitous exposure of humans to these agents in the urban environment, in non-smokers as well as in smokers. Smokers were found to have significantly higher blood concentrations of benzene (median 547 ng/l) and toluene (median 2201 ng/l) than non-smokers (median 190 ng/l and 1141 ng/l, respectively). The concentrations of ethylbenzene and xylenes also tended to be higher in smokers when compared to non-smokers. The different concentrations of these compounds in the blood of non-smokers appear to reflect the common concentration pattern found in outdoor urban air as well as in indoor air and also seem to be influenced by the different blood/air partition coefficients of these compounds. The results indicate that smoking is associated with a significant additional exposure to VOC, in particular to benzene and toluene.

Benzene Derivatives↗

A case study on identification of airborne organic compounds and time courses of their concentrations in the cabin of a new car for private use.

The cabin of an automobile can be considered to be a part of the living environment because many people spend long periods of time during business, shopping, recreation or travel activities. However, little is known about the interior air contamination due to organic compounds diffusing from the interior materials used in the interior of automobiles. In the present study, the compounds in the interior air of a new car were identified, and the time courses of their concentrations were examined for over 3 years after the delivery (July, 1999). A total of 162 organic compounds, involving many aliphatic hydrocarbons and aromatic hydrocarbons, were identified. High concentrations of n-nonane (458 microg/m(3) on the day following delivery), n-decane (1301 microg/m(3)), n-undecane (1616 microg/m(3)), n-dodecane (716 microg/m(3)), n-tridecane (320 microg/m(3)), 1-hexadecene (768 microg/m(3)), ethylbenzene (361 microg/m(3)), xylene (4003 microg/m(3)) and 2,2'-azobis(isobutyronitrile) (429 microg/m(3)) were detected, and the sum of the concentrations determined for all compounds excluding formaldehyde (TVOC) was approximately 14 mg/m(3) on the day after the delivery. The concentrations of most compounds decreased with time, but increased with a rise of the interior temperature. The TVOC concentration in the next summer (July, 2000) was approximately one-tenth of the initial concentration. During the 3-year study period, the TVOC concentrations in summer exceeded the indoor guideline value (300 mug/m(3)) proposed by [Seifert B. Volatile organic compounds. In: Maroni M, Seifert B, Lindvall T, editors. Indoor air quality. A comprehensive reference book. Air quality monographs, vol. 3. Netherlands: Elsevier Science; 1995. p. 819-21]. The interior temperature and days lapsed after delivery were the main factors affecting the interior concentrations of most compounds according to multiple linear regression analysis. The results of this study offer useful fundamental data for investigations on air pollution in automotive cabins due to the organic compounds diffusing from the interior materials.

Air Pollution, Indoor↗

Short-term health effects of an industrial toxic waste landfill: a retrospective follow-up study in Montchanin, France.

A retrospective follow-up study was conducted in 1990 to assess the short-term health impacts of an industrial waste landfill. The site, located since 1979 in a French town of 6,000 inhabitants (about 100 m from the nearest houses) released volatile organic compounds (VOCs) into the air and provoked intense health concern in the community. The landfill was subsequently closed in 1988. Subjects were 694 inhabitants residing in three different parts of town. Individual exposure was estimated, using a dispersion model of volatile air pollutants and accommodated the daily activity patterns of each individual within the area under investigation. Surrogate morbidity data were derived from measurement of the consumption of drugs prescribed for specific therapeutic categories over a 3-y period (18 mo before and 18 mo after the site was closed). Although differences were not statistically significant, the most exposed subjects had been prescribed more drugs for diseases possibly linked to emissions from the site before it closed than the least exposed individuals. There was a suggestion of a slight trend in the consumption of drugs for ear, nose, and throat and pulmonary ailments with individual exposure levels. These results, and the review of toxicological data for some of the VOCs released by the dump, support the decision to close the site.

Environmental Exposure↗

Water transformation in the media of biofilters controlled by Rhodococcus fascians in treating an ethyl acetate-contaminated airstream.

Biofilters do not provide much water for bacteria to grow. To use them efficiently and properly, it is essential to understand the kinetics of water transformation and to control moisture levels. This study aims to clarify whether the metabolism of microorganisms will improve the water-holding capacity of media or will intensify drying. This experiment was conducted in duplicate, that is, both with and without bacterial inoculation. Both the constant water content mode and the declining water content mode show that microbial growth in a log phase will enhance drying. In contrast, the bacteria growing in a logarithmic decline phase will improve water-holding capacity. Basically, water evaporation can result from the latent heat obtained from microbial respiration or from the physical temperature difference between the unsaturated air and the wet media. Two ways that biofilters can gain water are from water incorporated into bacteria cells and from water obtained from the oxidation of volatile organic compounds (VOCs).

Air Pollution↗

Comprehensive two-dimensional gas chromatography/mass spectrometric analysis of pepper volatiles.

The headspace compositions of 13 pepper and peppercorn samples of different species, colloquially also referred to as pepper, were analyzed, and more than 300 compounds were tentatively characterized by means of comprehensive two-dimensional gas chromatography in tandem with flame ionization detection, quadrupole mass spectrometric detection and time-of-flight mass spectrometric detection (GC x GC-FID, GC x GC/qMS and GC x GC/TOFMS, respectively). The analysis of volatile organic compounds (VOCs) was performed after solid-phase microextraction (SPME) using a 75-microm PDMS/DVB fibre. Fingerprint comparison between the three techniques permitted peaks to be assigned in the GC x GC-FID experiment based on the analogous MS analysis, taking into account retention shifts arising from method variations. When using GC x GC/TOFMS, about five times more peaks were identified than in GC x GC/qMS. Retention indices for all peaks were calculated in the bi-dimensional column set comprising of a 5% phenyl polysilphenylene-siloxane primary column and a polyethylene glycol second column. The spectra obtained by both mass detection techniques (qMS and TOFMS) give very similar results when spectral library searching was performed. The majority of the identified compounds eluted as pure components as a result of high-resolution GC x GC separations, which significantly reduces co-elution, and therefore increases the likelihood that pure spectra can be obtained. The differences between TOFMS and qMS (in fast scanning mode) spectra were generally small. Whilst spectral quality and relative ion ratios across a narrow peak (e.g. w(b) approximately 100-150 ms) do vary more for the fast peaks obtained in GC x GC/qMS operation, than with TOFMS, in general adequate spectral matching with the library can be achieved.

Gas Chromatography-Mass Spectrometry↗

Detection of volatile organic peroxides in indoor air.

A supercritical fluid extraction cell filled with adsorbent (Carbotrap and Carbotrap C) was used directly as a sampling tube to enrich volatile organic compounds in air. After sampling, the analytes were extracted by supercritical fluid CO2 with methanol as modifier. Collected organic peroxides were then determined by a RP-HPLC method developed and validated previously using post-column derivatization and fluorescence detection. Some volatile organic peroxides were found in indoor air in a new car and a newly decorated kitchen in the lower microg m(-3) range. tert-Butyl perbenzoate, di-tert-butyl peroxide, and tert-butylcumyl peroxide could be identified.

Air Pollution, Indoor↗

Formation of stable chlorinated hydrocarbons in weathering plant material.

Though several chlorinated organic compounds produced by humans are carcinogenic and toxic, some are also produced by the biotic and abiotic processes in the environment. In situ x-ray spectroscopy data indicate that natural organic matter in soils, sediments, and natural waters contain stable, less volatile organic compounds with chlorinated phenolic and aliphatic groups as the principal Cl forms. These compounds are formed at rapid rates from the transformation of inorganic Cl during humification of plant material and, thus, play a critical role in the cycling of Cl and of several major and trace elements in the environment and may influence human health.

Benzopyrans↗