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A theoretical study of properties and reactions involving arsenic and selenium compounds present in coal combustion flue gases.

Species of arsenic and selenium thought to be present in coal combustion flue gases were studied using density functional theory and a broad range of ab initio methods. At each level of theory, the calculated geometries and vibrational frequencies of each species as well as the reaction enthalpies of anticipated reactions were compared with experimental data where available. Comparisons between each calculation are given along with a discussion of the better performance of some theoretical calculations for a given species/reaction.

Air Pollutants↗

Surface-assisted transient displacement charge technique. II. Effect of gases on photoinduced charge transfer in self-assembled monolayers.

Surface-assisted photoinduced transient displacement charge (SPTDC) technique was used to study charge transfer in self-assembled monolayers of 7-diethylaminocoumarin covalently linked to an oxide surface in the atmosphere of different gases. The dipole signal was found to be opposite to that in solution and dependent on the nature of the gas and its pressure. The results were explained by collision-induced relaxation that impedes uninhibited tilting of molecules onto the surface. Collisions with paramagnetic oxygen induce intersystem crossing to long-lived triplet dipolar states of coumarin with the rate close to half of that for the collision rate.

Coumarins↗

Composition of solar flare noble gases preserved in meteorite parent body regolith.

The isotopic composition (long-term average) of solar flare (SF) Ne has been determined by three isotope correlation techniques applied to data measured on chemically etched pyroxene separates prepared from the Kapoeta meteorite, which is known to contain implanted solar gases. The SF 20Ne/22Ne ratio obtained is 11.6 +/- 0.2 and confirms previous determinations of this SF ratio in lunar and meteoritic samples. The same SF Ne composition is also obtained by applying an ordinate intercept technique to the same data set. The ordinate intercept technique was also applied to the Ar and He data, on which the three-isotope correlation technique cannot be applied. The isotopic composition of SF Ar and SF He so obtained are SF 36Ar/38Ar = 4.9 +/- 0.1 and SF 4He/3He = 3800 +/- 200, which are significantly different from the solar wind (SW) Ar and SW He values of approximately 5.35 and approximately 2500, respectively. Correlation between 20Ne/22Ne and 36Ar/38Ar for the same data set also gives a similar SF 36Ar/38Ar ratio of 4.8 +/- 0.2. The determined SF He, Ne and Ar isotopic ratios differ from those in SW by 52%, 17% and 9%, respectively, but the elemental compositions of 4He/36Ar and 20Ne/36Ar do not show obvious differences between SF and SW. The concentration of the SF component in Kapoeta pyroxenes is approximately 20% that of the SW component, which is orders of magnitude higher than expected from SW and SF proton flux measurements. Variations in elemental and isotopic composition of He, Ne and Ar in SF relative to SW are found to correlate well with a (Z/A)2 dependence, indicating a rigidity-dependent particle spectrum in solar flares.

Argon↗

Behaviour of intraocular gases.

The changes in volume of intraocular bubbles of air, sulphur hexafluoride, perfluoropropane and mixtures of these gases, were studied in human eyes, following vitrectomy for treatment of retinal detachment. The implications of these findings, for the provision of optimal internal tamponade in the treatment of retinal detachment, are discussed.

Air↗

Terrestrial nitrogen and noble gases in lunar soils.

The nitrogen in lunar soils is correlated to the surface and therefore clearly implanted from outside. The straightforward interpretation is that the nitrogen is implanted by the solar wind, but this explanation has difficulties accounting for both the abundance of nitrogen and a variation of the order of 30 per cent in the 15N/14N ratio. Here we propose that most of the nitrogen and some of the other volatile elements in lunar soils may actually have come from the Earth's atmosphere rather than the solar wind. We infer that this hypothesis is quantitatively reasonable if the escape of atmospheric gases, and implantation into lunar soil grains, occurred at a time when the Earth had essentially no geomagnetic field. Thus, evidence preserved in lunar soils might be useful in constraining when the geomagnetic field first appeared. This hypothesis could be tested by examination of lunar farside soils, which should lack the terrestrial component.

Atmosphere↗

Distinction of gases with a semiconductor sensor depending on the scanning profile of a cyclic temperature.

A gas-sensing system based on a dynamic nonlinear response is reported to improve the selectivity in the sensor response toward sample gases. A cyclic temperature composed of fundamental and second harmonics was applied to a SnO(2) semiconductor gas sensor and the resulting conductance of the sensor was analyzed by fast Fourier transformation (FFT). The dynamic nonlinear responses to the gas species were further characterized depending on the scanning profile of the temperature. These characteristic sensor responses under the application of second-harmonic perturbation were theoretically considered based on a reaction-diffusion model for the semiconductor surface.

Electrochemistry↗

Examination of (e,2e) scattering models by comparison of momentum profiles of noble gases between experiment and theory.

Momentum profiles have been measured for the two outermost atomic orbitals of noble gases, Ar, Kr and Xe, at incident electron energy of about 2 keV using a newly developed multichannel (e,2e) spectrometer. The experimental results exhibit significantly improved statistics compared with those achieved in previous studies while covering a wide range of momenta up to 3.6 a.u. The results are compared with theoretical calculations using four (e,2e) scattering models, the plane-wave impulse and Born approximations (PWIA and PWBA), and the distorted-wave impulse and Born approximations (DWIA and DWBA). The DWIA and DWBA scattering models have been found to satisfactorily reproduce the experimental momentum profiles in terms of both shape and intensity over the entire momentum range covered, indicating the importance of distorted wave effects for quantitatively describing (e,2e) reaction.

Computer Simulation↗

Determination of respiratory gases (CO2, O2, Ar and N2) with gas solid chromatography.

A method was developed for gas chromatographic separation of respiratory gases (CO2, O2, Ar and N2). Oxygen was catalystically reduced to H2O by palladium, with H2 as carrier gas. CO2 and H2O were separated on a Porapack Q column and detected separately. After absorption of CO2 and H2O, Ar and N2 were separated by a molecular sieve column and recorded by the reference cell. Comparison with the Scholander technique gave the correlation coefficient 0.997 for CO2 and 0.992 for O2 respectively. All values were close to the line of identity. We found it necessary to calibrate with a known gas mixture before each set of analyses for accurate determinations.

Argon↗

An exposure system to study the effects of water-soluble gases on PM-induced toxicity.

An aerosol generation and exposure system to evaluate the role of water-soluble gases in particulate matter (PM)-induced injury was designed, built, and validated by generating test atmospheres to study the role of hydrogen peroxide in PM-induced toxicity. In this system, particle number concentration, size distribution, hydrogen peroxide concentration, and water concentration can all be varied. An ammonium sulfate aerosol with mass median diameter 0.46 +/- 0.01 microm was used as a model atmospheric aerosol because ammonium sulfate is a major component of the fine aerosol, and the water uptake of ammonium sulfate aerosol is well characterized. The following four test atmospheres were generated: (1) ammonium sulfate aerosol, (2) an aerosol containing hydrogen peroxide and ammonium sulfate, (3) vapor-phase hydrogen peroxide, and (4) particle-free air. All test atmospheres were maintained at a relative humidity of 85%. Particle size distribution, number concentration, total hydrogen peroxide concentration, temperature, and relative humidity were measured continuously in the exposure chamber. The gas-particle partitioning of hydrogen peroxide was calculated using total hydrogen peroxide concentration, the Henry's law constant for hydrogen peroxide in water, and aerosol water content. We found that the aerosol generation system produced stable concentrations throughout the 2-hour exposures.

Aerosols↗

Removal of acetone and methylacetate mixtures from waste gases by a trickle-bed air biofilter.

The biofilter process is a relatively new technology that has been proven more cost-effective than traditional technologies for treating low-strength and some high-strength volatile organic compounds (VOCs) from waste gases. Acetone (AT) and methylacetate (MA) mixtures are commonly encountered from the manufacture of artificial rubber or polyurethane resin. This research attempts to employ a trickle-bed air biofilter (TBAB) for treating AT and MA mixtures under different influent carbon loadings. In the pseudo-steady-states, the elimination capacities of AT and MA increased but the removal efficiencies decreased with increased influent carbon loading. The removal efficiencies of MA were higher than those of AT showing that MA is a preferred substrate in the ATMA waste gas and the differences were enhanced at a high carbon loading. Greater than 95% AT removal and nearly complete MA removal were achieved with influent carbon loadings of AT and MA below 20 and 27 g m(-1) h(-1), respectively. The TBAB appears very efficient for treating ATMA emission with low to medium carbon loadings.

Acetates↗

Mapping the air in real-time to visualize the flow of gases and vapors: occupational and environmental applications.

This article describes a new method for measuring and mapping pollutants in air in real-time which can be used for visualizing the flow of gases and vapors in both indoor industrial and outdoor environmental applications. This method uses open-path Fourier Transform Infrared (OP-FTIR) spectrometry and computed tomography for real-time mapping of concentrations of chemicals in air. These maps may be used to evaluate human exposures, source emissions and air dispersion models; thus, this method can be used for both industrial and environmental sampling. It is being developed using computer simulations, and chamber and field studies. Computer simulations used simulated test concentration data to create maps; the original maps of concentrations were compared with the tomographic reconstructed maps. In the chamber studies, tracer gas was released into the chamber and measurements from a tomographic system were compared with point sample measurements taken at the same time. When sulfur hexafluoride was injected in a stable flow field position in the chamber, the concentrations reconstructed by the concentration maps were within +/- 15.9 percent of the measured point samples; overall, they were within +/- 27 percent of the measured point samples. On a 12-foot by 14-foot grid of cells used to model the chamber, the average peak location error was within one foot. The peak location error refers to the error involved in locating the point of highest concentration in the plume. For the field study, field-generated tomographic maps were compared with concentrations estimated using the Industrial Source Complex-Short Term (ISCST) model. Fairly good correlation (R2 = 0.67) was found between the five-minute overall-average cell concentrations in the tomographic and ISCST model maps. Overall, the tomographic map concentrations over-predicted the ISCST model concentrations by 24 percent. Optical remote sensing and computed tomography shows promise as a method to produce spatially and temporally resolved two-dimensional concentration maps indoors and outdoors. These maps would provide near real-time visualization of contaminant generation, movement, concentrations, and emission rates for multiple chemicals simultaneously at low limits of detection.

Air Pollution↗

Removal of BTEX vapor from waste gases by a trickle bed biofilter.

The system performance of a trickle bed biofilter for treating single and mixed benzene, toluene, ethylbenzene, and o-xylene (BTEX) vapors from waste gases was investigated under different gas flow rates and influent BTEX concentrations. When a single substrate was fed, removal efficiencies of greater than 90% could be achieved for the loads below 64 g benzene/m3/hr, 110 g toluene/m3/hr, 53 g ethylbenzene/m3/hr, and 55 g o-xylene/m3/hr. When a mixed substrate was fed, removal efficiencies of each compound could be above 90% at BTEX loads below 96 g/m3/hr. The trickle bed biofilter appears to be an effective treatment process for removing both single and mixed BTEX vapors with low to high loads. Under similar substrate loads, BTEX vapors were preferentially biodegraded in the order of toluene, benzene, o-xylene, and ethylbenzene. The volumetric removal rates (elimination capacities) of BTEX vapors for a single-substrate feed were higher than those for a mixed-substrate feed under similar substrate loads; these differences were enhanced at higher substrate loads and less significant for a preferred substrate.

Air Pollutants, Occupational↗

Biotreatment of hydrogen sulfide- and ammonia-containing waste gases by fluidized bed bioreactor.

Gas mixtures of H2S and NH3 are the focus of this study of research concerning gases generated from animal husbandry and treatments of anaerobic wastewater lagoons. A heterotrophic microflora (a mixture of Pseudomonas putida for H2S and Arthrobacter oxydans for NH3) was immobilized with Ca-alginate and packed into a fluidized bed reactor to simultaneously decompose H2S and NH3. This bioreactor was continuously supplied with H2S and NH3 separately or together at various ratios. The removal efficiency, removal rate, and metabolic product of the bioreactor were studied. The results showed that the efficiency remained above 95% when the inlet H2S concentration was below 30 ppm at 36 L/hr. Furthermore, the apparent maximum removal and the apparent half-saturation constant were 7.0 x 10(-8) g-S/cell/day and 76.2 ppm, respectively, in this study. The element sulfur as a main product prevented acidification of the biofilter, which maintained the stability of the operation. As for NH3, the greater than 90% removal rate was achieved as long as the inlet concentration was controlled below 100 ppm at a flow rate of 27 L/hr. In the NH3 inlet, the apparent maximum removal and the apparent half-saturation constant were 1.88 x 10(-6) g-N/cell/day and 30.5 ppm, respectively. Kinetic analysis showed that 60 ppm of NH3 significantly suppressed the H2S removal by Pseudomonas putida, but H2S in the range of 5-60 ppm did not affect NH3 removal by Arthrobacter oxydans. Results from bioaerosol analysis in the bioreactor suggest that the co-immobilized cell technique applied for gas removal creates less environmental impact.

Ammonia↗

Surface compositions of carbon sorbents exposed to simulated low-rank coal flue gases.

Bench-scale testing of elemental mercury (Hg0) sorption on selected activated carbon sorbents was conducted to develop a better understanding of the interaction among the sorbent, flue gas constituents, and Hg0. The results of the fixed-bed testing under simulated lignite combustion flue gas composition for activated carbons showed some initial breakthrough followed by increased mercury (Hg) capture for up to approximately 4.8 hr. After breakthrough, the Hg in the effluent stream was primarily in an oxidized form (>90%). Aliquots of selected activated carbons were exposed to simulated flue gas containing Hg0 vapor for varying time intervals to explore surface chemistry changes as the initial breakthrough, Hg capture, and oxidation occurred. The samples were analyzed by X-ray photoelectron spectroscopy to determine changes in the abundance and forms of sulfur, chlorine, oxygen, and nitrogen moieties as a result of interactions of flue gas components on the activated carbon surface during the sorption process. The data are best explained by a competition between the bound hydrogen chloride (HCl) and increasing sulfur [S(VI)] for a basic carbon binding site. Because loss of HCl is also coincident with Hg breakthrough or loss of the divalent Hg ion (Hg2+), the competition of Hg2+ with S(VI) on the basic carbon site is also implied. Thus, the role of the acid gases in Hg capture and release can be explained.

Adsorption↗

Emission of dust and gases in tubular cored wire welding of steel.

The emission of dusts and gases, which are generated during tubular cored wire welding and which are hazardous to health and the environment, were studied. Tests included various kinds of tubular electrode wires used for welding steel, that is, rutile flux cored wires, basic flux cored wires, and metal cored wires for welding unalloyed, low-alloy, and high-alloy steels as well as self-shielded flux cored wires used for welding low-alloy steels. The research results make it possible to assess the influence of the type of wire and welding conditions on the emission volume and to compare chemical hazards generated during tubular cored wire welding with those typical for other arc welding processes.

Air Pollutants, Occupational↗

Fourier transform infrared (FTIR) spectroscopy for monitoring airborne gases and vapors of industrial hygiene concern.

There are few available analytical methods with which an industrial hygienist can perform near real-time identification and quantitation of gases and vapors in the workplace. At present, the instruments that come the closest to fulfilling this need are based on either Fourier transform infrared (FTIR) spectroscopy or mass spectroscopy (MS). In order to investigate the applicability of FTIR to the qualitative and quantitative analysis of gas and vapor emissions in the workplace, an investigation was carried out to choose optimal conditions that could maximize the signal from individual target analytes and minimize the potential for interference. In all cases, the limit of detection (LOD) of individual air contaminants was below the threshold limit value (TLV).

Air Pollutants, Occupational↗

Role of leaflet asymmetry in the permeability of model biological membranes to protons, solutes, and gases.

Bilayer asymmetry in the apical membrane may be important to the barrier function exhibited by epithelia in the stomach, kidney, and bladder. Previously, we showed that reduced fluidity of a single bilayer leaflet reduced water permeability of the bilayer, and in this study we examine the effect of bilayer asymmetry on permeation of nonelectrolytes, gases, and protons. Bilayer asymmetry was induced in dipalmitoylphosphatidylcholine liposomes by rigidifying the outer leaflet with the rare earth metal, praseodymium (Pr3+). Rigidification was demonstrated by fluorescence anisotropy over a range of temperatures from 24 to 50 degrees C. Pr3+-treatment reduced membrane fluidity at temperatures above 40 degrees C (the phase-transition temperature). Increased fluidity exhibited by dipalmitoylphosphatidylcholine liposomes at 40 degrees C occurred at temperatures 1-3 degrees C higher in Pr3+-treated liposomes, and for both control and Pr3+-treated liposomes permeability coefficients were approximately two orders of magnitude higher at 48 degrees than at 24 degrees C. Reduced fluidity of one leaflet correlated with significantly reduced permeabilities to urea, glycerol, formamide, acetamide, and NH3. Proton permeability of dipalmitoylphosphatidylcholine liposomes was only fourfold higher at 48 degrees than at 24 degrees C, indicating a weak dependence on membrane fluidity, and this increase was abolished by Pr3+. CO2 permeability was unaffected by temperature. We conclude: (a) that decreasing membrane fluidity in a single leaflet is sufficient to reduce overall membrane permeability to solutes and NH3, suggesting that leaflets in a bilayer offer independent resistances to permeation, (b) bilayer asymmetry is a mechanism by which barrier epithelia can reduce permeability, and (c) CO(2) permeation through membranes occurs by a mechanism that is not dependent on fluidity.

Acetamides↗

Energy dependence of W for alpha particles in N2, CO2, CH4, Ar, H2 and Rossi-type tissue-equivalent gases.

Average energy required to form an ion pair (W) was determined in N2, CO2, CH4, Ar, H2 and Rossi-type tissue-equivalent gas. Alpha particles from a 241Am source were used. W was determined at alpha energies of 5.37, 3.12, 1.08 and 0.46 MeV. The ratio of total ionisation produced (for fixed alpha particle energy) in experimental gas to that produced in argon was measured. This ratio was then multiplied by the previously determined W value for argon gas (26.29 eV per ion pair) to yield W for various experimental gases. Energy of the 241Am alpha particles was degraded by using air as an absorbing material. Empirical relations W = alpha + betaE-1/2 and W = alpha1 + beta1E-1 were fitted to the experimental data. Both functions fit reasonably well in the range 0.4--5.37 MeV. Below about 0.4 MeV the first function provides a better fit to the data of Boring et al. (1965).

Alpha Particles↗