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Biodegradation of aromatic compounds and TCE by a filamentous bacteria-dominated consortium.

The Michaelis-Menten biodegradation kinetics (k and Ks) of aromatic compounds and trichloroethene (TCE) by an aerobic enrichment culture grown on phenol and dominated by a unique filamentous bacterium were measured. The average k and Ks values for phenol, benzene (B), toluene (T), ethylbenzene (E), o-xylene (oX), p-xylene (pX), naphthalene and TCE in g per g VSS-d and mg L-1 were 5.72 and 0.34, 1.20 and 0.51, 2.09 and 0.47, 0.77 and 0.23, 0.61 and 0.16, 0.73 and 0.23, 0.17 and 0.18, and 0.16 and 0.18, respectively. Significant variability in these measured kinetics was noted between tests conducted over the 5-month period during which the fed-batch culture with a 5-day solids retention time was maintained; the coefficient of variation of the k and Ks values ranged from 11-43% and 4-50%, respectively. This variation was significantly greater than the method measurement error on a given date. Degradation of BTEoXpX mixtures could be described by a basic competitive inhibition model. Batch tests during which the culture was fed individual BTEX compounds showed the culture grew poorly on the xylenes and had poor subsequent xylene degradation rates. This work indicates the potential to simultaneously treat a mixture of volatile organic compounds using this consortium, and the ability to predict the mixture biodegradation rates on the basis of the individual compound biodegradation kinetics.

Algorithms↗

Air quality modeling of interpollutant trading for ozone precursors in an urban area.

Emission trading is a market-based approach designed to improve the efficiency and economic viability of emission control programs; emission trading has typically been confined to trades among single pollutants. Interpollutant trading (IPT), as described in this work, allows for trades among emissions of different compounds that affect the same air quality end point, in this work, ambient ozone (O3) concentrations. Because emissions of different compounds impact air quality end points differently, weighting factors or trading ratios (tons of emissions of nitrogen oxides (NO(x)) equivalent to a ton of emissions of volatile organic compounds [VOCs]) must be developed to allow for IPT. In this work, IPT indices based on reductions in O3 concentrations and based on reductions in population exposures to O3 were developed and evaluated using a three-dimensional gridded photochemical model for Austin, TX, a city currently on the cusp of nonattainment with the National Ambient Air Quality Standards for O3 concentrations averaged over 8 hr. Emissions of VOC and NO(x) from area and mobile sources in Austin are larger than emissions from point sources. The analysis indicated that mobile and area sources exhibited similar impacts. Trading ratios based on maximum O3 concentration or population exposure were similar. In contrast, the trading ratios did exhibit significant (more than a factor of two) day-to-day variability. Analysis of the air quality modeling indicated that the daily variability in trading ratios could be attributed to daily variations in both emissions and meteorology.

Air Pollutants↗

[Parameters of the liquid-liquid extraction of toxicologically relevant organic compounds. Part 1: Methodology of the experimental determination of partition constants and pH-dependent partition quotients; results obtained with acidic compounds].

Though liquid-liquid extraction is most widely used technique for isolating organic compounds (drugs, poisons), its fundamental parameters (partition constants and dissociation constants) are not determined explicitly in most cases; they are mostly estimated indirectly together with other factors in the form of resultants (total yield, detection sensitivities). For this reason we determined the partition quotients and their pH-dependence for more than 300 slightly volatile organic compounds (mainly drugs) in two-phase systems (aqueous buffer solution/solvent non-miscible with water). Nearly all the determinations were performed using diethyl ether and chloroform; other organic solvents were applied especially in studying slightly extractable compounds. The results obtained with 63 acidic compounds are reported.

Acids↗

[Micromethods for determining organic solvents in blood by headspace analysis].

The evaluation in industrial exposure to volatile organic compounds based on assessing concentrations of unchanged substances in blood of exposed workers seems to gain increasing interest. The main obstacle to a wide application of this method is the difficulty in collecting venous blood samples. Many authors suggest determining volatiles in capillary blood samples because they display the same concentrations as the arterial blood samples. The collection of capillary blood samples is much more convenient in occupational setting than the collection of venous blood samples. The aim of this study was to develop micromethod for determining organic solvents in small blood samples (100 mm3) by gas chromatography with headspace technique. 1.8 cm3 glass vessels (Sapelco) with screw caps, silicone rubber membranes and aluminium foil pads were used. After addition of 0.1 cm3 of blood and 2.0 cm3 of aqueous solution of internal standard, the vessels were closed tightly and shaken for 30 min. at 70 degrees C in water bath. Then about 1 cm3 of the gas phase was sampled with a gastight syringe (Hamilton) injected into the gas chromatograph. The parameters of the recently developed methods for determining organic solvents in blood samples, including linearity, precision, reproducibility, stability and sensitivity, are fully compatible with the principles of biological monitoring.

Air Pollutants, Occupational↗

Large-scale resonance amplification of optical sensing of volatile compounds with chemoresponsive visible-region diffraction gratings.

Micropatterning of the vapochromic charge-transfer salt, [Pt(CNC6H4C10H21)4][Pd(CN)4], on transparent platforms yields transmissive chemoresponsive diffraction gratings. Exposure of the gratings to volatile organic compounds (VOCs) such as chloroform and methanol leads to VOC uptake by the porous material comprising the grating lattice or framework, and a change in the material's complex refractive index, ñ. The index change is accompanied by a change in the degree of index contrast between the lattice and the surrounding medium (in this case, air), and a change in the diffraction efficiency of the grating. When a monochromatic light source that is not absorbed by the lattice material is employed as a probe beam, only changes in the real component of ñ are sensed. Under these conditions, the grating behaves as a nonselective, but moderately sensitive, sensor for those VOCs capable of permeating the porous lattice material. When a probe color is shifted to a wavelength coincident with the vapochromic charge-transfer transition of the lattice material, the sensor response is selectively amplified by up to 3.5 orders of magnitude, resulting in greatly enhanced sensitivity and some degree of chemical specificity. On the basis of studies at four probe wavelengths, the amplification effect is dominated by resonant changes in the imaginary component of the refractive index. The observed wavelength- and analyte-dependent amplification effects are quantitatively well described by a model that combines a Kramers-Kronig analysis with an effective-medium treatment of dielectric effects.

Journal Article↗

Semi-volatile species in PM2.5: comparison of integrated and continuous samplers for PM2.5 research or monitoring.

Fine particles in urban atmospheres contain substantial quantities of semi-volatile material [e.g., NH4NO3 and semi-volatile organic compounds (SVOCs)] that are lost from particles during collection on a filter. Several diffusion denuder samplers have been developed for the determination of both NO3- and organic semi-volatile fine particulate components. The combination of technology used in the BOSS diffusion denuder sampler and the Harvard particle concentrator has resulted in the Particle Concentrator-Brigham Young University Organic Sampling System (PC-BOSS) for the 24-hr (or less) integrated collection of PM2.5, including NH4NO3 and semi-volatile organic material. Modification of the BOSS sampler allows for the weekly determination of these same species. Combination of BOSS denuder and tapered element oscillating microbalance (TEOM) monitor technology has resulted in the real-time ambient mass sampler (RAMS) for the continuous measurement of PM2.5, including the semi-volatile components. Comparison of the results obtained with the BOSS and with each of the newly developed modifications of the BOSS indicates that the modified versions can be used for the continuous, daily, or weekly monitoring of PM2.5, including semi-volatile species, as appropriate to the design of each sampler.

Air Pollutants↗

[The gas chromatographic analysis of volatile compounds on the compact MKhP chromatograph].

Methods of analysis of biological specimens, alcohol beverages, and technological liquids in columns with standard adsorbents carbopaque B and C with carbowax 20M, widely used abroad, are described and examples of analyses presented. A special portable chromatographer (MCP) with flame ionization detector has been designed. It is intended for analysis of volatile organic compounds (alcohols, carbohydrates, organochlorine compounds, glycols, esters, etc.) in columns of different polarity. The system of processing of chromatographic findings permits a quantitative analysis of complex chromatograms and automated identification of substances in biological samples by using the available database.

Alcohols↗

Differentiation of isobaric compounds using chemical ionization reaction mass spectrometry.

The technique of proton transfer reaction mass spectrometry (PTR-MS) couples a proton transfer reagent, usually H3O+, with a drift tube and mass spectrometer to determine concentrations of volatile organic compounds. Here we describe a first attempt to use chemical ionization (CI) reagents other than proton transfer species inside a PTR-MS instrument. The ability to switch to other types of CI reagents provides an extra dimension to the technique. This capability is demonstrated by focusing on the ability to distinguish several isobaric aldehydes and ketones, including the atmospherically important molecules methacrolein and methyl vinyl ketone. Two CI reagents were selected, H3O+ and NO+, both being cleanly generated in a low intensity radioactive source prior to injection into the drift tube. By recording spectra with both of these reagents, the contributions from different isobaric molecules can be separated by virtue of their unique spectrometric 'fingerprints'. The work demonstrates that this form of instrumentation is not restricted to proton transfer reagents and is the basis of a more general technique, chemical ionization reaction mass spectrometry (CIRMS).

Journal Article↗

Xenobiotic organic compounds in leachates from ten Danish MSW landfills--chemical analysis and toxicity tests.

A monitoring program comprising chemical analysis and biological toxicity testing of leachate samples from 10 Danish landfills (six engineered and four uncontrolled) revealed the presence of 55 different xenobiotic organic compounds (XOCs) and 10 degradation products of XOCs. The compounds belong to the following groups: BTEX, C3-benzenes, bicyclo compounds, napthalenes, chlorinated aliphatics, phenols (chloro-, methyl-, dimethyl, nonyl-), pesticides, and phthalates. Concentrations of single XOCs ranged from <0.1 to 2220 microg/L. A pesticide screening including 101 different compounds resulted in detection of 18 pesticides and three degradation products. The findings of degradation products of toluene, phenols, phthalates, pesticides, and nonylphenol ethoxylates show that degradation occurred inside the landfills. In biotests with bacteria and algae it was found that the non-volatile organic compounds were toxic as the samples only needed to be pre-concentrated from 1.3 to 9.4 times to give 50% inhibition of the test organisms. One of the ten samples proved to be genotoxic in the umuC test after 141 times pre-concentration. A major part of the organic chemicals causing toxicity remains unknown and it is recommended to combine chemical analyses and biotests in future monitoring programs.

Bacteria↗

Enzymatic decomposition of elicitors of plant volatiles in Heliothis virescens and Helicoverpa zea.

Feeding by larvae of Heliothis virescens induces cotton, corn and tobacco plants to release blends of volatile organic compounds that differ in constituent proportions from blends released when Helicoverpa zea larvae feed on the same plant species. The same elicitors (and analogs) of plant biosynthesis and release of volatiles, originally identified in oral secretions of Spodoptera exigua larvae, were also found in oral secretions of H. virescens and H. zea. However, relative amounts of these compounds, particularly N-(17-hydroxylinolenoyl)-L-glutamine (volicitin), 17-hydroxylinolenic acid, and N-linolenoyl-L-glutamine, varied among batches of oral secretions, more so in H. virescens than in H. zea. This variation was due to cleavage of the amide bond of the fatty acid-amino acid conjugates by an enzyme, or enzymes, originating in the midgut. The enzymatic activity in guts of H. virescens was significantly greater than that found in guts of H. zea. Furthermore, H. zea frass contains N-linolenoyl-L-glutamine in more than 0.1% wet weight, while this conjugate comprises only 0.003% wet weight in H. virescens frass. These results indicated that physiological differences between these two species affect the proportions of volicitin and its analogs in the caterpillars. Whether this causes different proportions of volatiles to be released by plants damaged by each caterpillar species is yet to be determined.

Journal Article↗

Trends in Europe to reduce the indoor air pollution of VOCs.

A strong research tradition in the European countries about volatile organic compounds (VOCs) and indoor air quality has led to several consensus reports about stategies for VOC measurements including the development of methods to measure VOC emissions from building products. European and Nordic standards have been developed for emission testing including several national and international labeling schemes. Proposals for guidelines for a number of different VOCs have been developed either nationally or by consensus. A compound-by-compound approach for health evaluation of VOCs has become more common and there appears to be a growing recognition to focus on the biologic relevance of organic compounds in indoor air (OCIAs).

Air Pollution, Indoor↗

Biodegradation of petroleum hydrocarbon vapors: laboratory studies on rates and kinetics in unsaturated alluvial sand.

Predictions of natural attenuation of volatile organic compounds (VOCs) in the unsaturated zone rely critically on information about microbial biodegradation kinetics. This study aims at determining kinetic rate laws for the aerobic biodegradation of a mixture of 12 volatile petroleum hydrocarbons and methyl tert-butyl ether (MTBE) in unsaturated alluvial sand. Laboratory column and batch experiments were performed at room temperature under aerobic conditions, and a reactive transport model for VOC vapors in soil gas coupled to Monod-type degradation kinetics was used for data interpretation. In the column experiment, an acclimatization of 23 days took place before steady-state diffusive vapor transport through the horizontal column was achieved. Monod kinetic parameters Ks and vmax could be derived from the concentration profiles of toluene, m-xylene, n-octane, and n-hexane, because substrate saturation was approached with these compounds under the experimental conditions. The removal of cyclic alkanes, isooctane, and 1,2,4-trimethylbenzene followed first-order kinetics over the whole concentration range applied. MTBE, n-pentane, and chlorofluorocarbons (CFCs) were not visibly degraded. Batch experiments suggested first-order disappearance rate laws for all VOCs except n-octane, which decreased following zero-order kinetics in live batch experiments. For many compounds including MTBE, disappearance rates in abiotic batch experiments were as high as in live batches indicating sorption. It was concluded that the column approach is preferable for determining biodegradation rate parameters to be used in risk assessment models.

Biodegradation, Environmental↗

Combined physical, chemical and biological treatments of wastewater containing organics from a semiconductor plant.

Wastewater containing organics from a semiconductor plant was experimentally investigated in this study. The wastewater is characterized by strong color, high chemical oxygen demand (COD), a large amount of refractory volatile organic compounds and low biodegradability. Because of these characteristics, treatment of this wastewater by traditional activated sludge method is essentially impossible. In the present work, combined physical, chemical and biological methods were synergistically utilized to tackle the wastewater. The combined treatment consisted of air stripping, modified Fenton oxidation and sequencing batch reactor (SBR) method. Air stripping was employed to remove the majority of volatile organic components (notably isopropyl alcohol) from the wastewater, while the Fenton treatment decomposed the remaining refractory organics leading to simultaneous reductions of wastewater COD and color. After proper dilution with other low-strength, organics-containing wastewater stream, the wastewater effluent was finally treated by the SBR method. Experimental tests were conducted to determine the effectiveness and the optimum operating conditions of each treatment process. Test results clearly demonstrated the advantages of the combined treatments. The treatment train was found capable of lowering the wastewater COD concentration from as high as 80,000 mg/l to below 100mg/l and completely eliminating the wastewater color. The overall water quality of the final effluent exceeded the direct discharge standard and the effluent can even be considered for reuse.

Air↗

Diffusion studies of VOC mixtures in a building material.

Volatile organic compound (VOC) adsorption by indoor materials will reduce peak concentrations, and subsequent desorption will prolong the presence of a compound indoors. Diffusion within materials plays an important role in this context. The purpose of this paper is to present two experimental set-ups to study VOC diffusion, and to show corresponding experimental results. The Field and Laboratory Emission Cell (FLEC) is in both cases an integral part of the set-up. The mass flow of VOC mixtures across gypsum board is studied. Diffusion of less polar VOCs in gypsum board can be fast (diffusion coefficients of 0.001-0.003 m2/h). Diffusion coefficients of chlorinated compounds are correlated with boiling points and molecular areas. Different compounds show similar diffusion properties.

Adsorption↗

Removal mechanisms of VOCs in an activated sludge process.

This study investigated the factors in plant operating parameters effecting volatile organic compound (VOC) removal and elucidated each individual mechanism in an activated sludge process (ASP). The results suggest that stripping increase with an increase in Henry's law constant with the exception of toluene, which differed because of the effect of biodegradation competition. The emission rate can be controlled by increasing the active biomass concentration (X(b)) in the aeration basin, hydraulic retention time (HRT), and oxygen transfer efficiency (OTE). Increasing X(b) enhances total VOC removal and biodegradation, which reduces the fraction of the stripping removal. Longer HRT can reduce stripping removal significantly if other variables such as oxygen requirement and OTE are held constant. For the same volatile compound, a process with higher air-to-water ratio requires a higher active biomass concentration to reduce stripping removal. Increasing OTE decreases the air-to-water ratio requirement, which reduces the gas-phase transfer of VOCs into the atmosphere. The results show a reasonable agreement between measured and predicted stripping values.

Biodegradation, Environmental↗

The floral volatile, methyl benzoate, from snapdragon (Antirrhinum majus) triggers phytotoxic effects in Arabidopsis thaliana.

Previously it has been shown that the floral scent of snapdragon flowers consists of a relatively simple mixture of volatile organic compounds (VOCs). These compounds are thought to be involved in the attraction of pollinators; however, little is known about their effect on other organisms, such as neighboring plants. Here, we report that VOCs from snapdragon flowers inhibit Arabidopsis root growth. Out of the three major snapdragon floral volatiles, myrcene, (E)-beta-ocimene, and methyl benzoate (MB), MB was found to be primarily responsible for the inhibition of root growth. Ten micromoles MB reduced root length by 72.6%. We employed a microarray approach to identify the MB target genes in Arabidopsis that were responsible for the root growth inhibition phenotype in response to MB. These analyses showed that MB treatment affected 1.33% of global gene expression, including cytokinin, auxin and other plant-hormone-related genes, and genes related to seed germination processes in Arabidopsis. Accordingly, the root growth of cytokinin (cre1) and auxin (axr1) response mutants was less affected than that of the wild type by the volatile compound: roots of the treated mutants were reduced by 45.1 and 56.2%, respectively, relative to untreated control mutants.

Antirrhinum↗

Analysis of exhausts emitted by i.c. engines and stationary burners, by means of u.v. extinction and fluorescence spectroscopy.

Optical investigations of the exhausts emitted by internal combustion (i.c.) engines and a stationary burner were performed, in order to assess their relative role as sources of organic matter to the atmosphere. Extinction spectra of air-diluted exhausts in the 200-400 nm u.v. band reveal the expected existence of gaseous trace-species (NO, NO2 and SO2) and carbonaceous particulate matter (soot). In addition, after subtracting the absorption contribution from known species, a strong residual absorption band remains below 250 nm, which is attributed to organic aromatic matter, involving no more than two aromatic rings. A set of ex situ extinction and laser induced fluorescence (LIF) experiments were carried out on condensed combustion-water samples. Extinction measurements from the water samples show absorption spectra similar to those observed from air-diluted samples, which are attributed to low volatility organic compounds, as they are trapped in the condensed phase. Combining the indications of extinction data for both air-diluted and condensed samples, it is suggested that the absorbing species might be molecular clusters of one/two aromatic rings. LIF spectra from condensed samples evidence two fluorescence bands, centered above 300 and 400 nm, respectively, whose intensities correlate with the combustion regimes. Analogous optical analysis on rain samples, collected in an urban area, showed that rain absorption and fluorescence spectra are similar to those found in condensed exhaust samples, which is consistent with the prevailing contribution of i.c. engines to the urban air pollution. The combined experimental data suggest that the absorbing and fluorescent species trapped in the condensed samples are organic (aromatic) compounds, involving mostly one two aromatic rings structural units, since they do not absorb above 250 nm. The overall molecular weight of the trapped material is likely heavy as they show low volatility.

Journal Article↗

Screening procedure for 21 amphetamine-related compounds in urine using solid-phase microextraction and gas chromatography-mass spectrometry.

A specific, sensitive, and rapid procedure for the screening of 21 amphetamine-related compounds in urine is developed using solid-phase microextraction (SPME) and gas chromatography-mass spectrometry. Very clean extracts are obtained in one step with SPME using silica fibers coated with a 100-micron polydimethylsiloxane stationary phase. Temperature, time, pH, and salt saturation are optimized to obtain consistent extraction. An excellent chromatographic separation of the underivatized analytes is obtained with a specially treated nonpolar capillary column (Supelco PTA-5, 30 m x 0.32-mm i.d., 0.5-micron film thickness) dedicated to amino compounds. Selected ion monitoring of three fragments per analyte and one for each of the three deuterated internal standards elicits a high selectivity and detection limits between 1 and 50 ng/mL (i.e., low enough to verify positive results obtained with immunochemical assays). The method is linear in a narrow range (from the detection limit up to 500 ng/mL) when all the amphetamines are assayed together but shows a good linearity up to 2000 ng/mL when the molecules are determined individually. Repeatability is not satisfactory for all compounds but could probably be improved by strictly controlling the extraction time (e.g., by automating the whole procedure using an autosampler). The use of SPME reduces the interference due to urinary low-volatility organic compounds and avoids the risks related to the use of organic solvents. To our knowledge, this technique is the first one allowing the sensitive determination of such a number of amphetamine analogs.

Amphetamine↗