Comparison of isopentane and isobutane as chemical ionization reagent gases.
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Anthropogenic activities contribute to the release of a wide variety of volatile organic compounds (VOC) into microenvironments. Developing and implementing new air sampling technologies that allow for the characterization of exposures to VOC can be useful for evaluating environmental and health concerns arising from such occurrences. A novel air sampler based on the use of a capillary flow controller connected to evacuated canisters (300 mL, 1 and 6 L) was designed and tested. The capillary tube, used to control the flow of air, is a variation on a sharp-edge orifice flow controller. It essentially controls the velocity of the fluid (air) as a function of the properties of the fluid, tube diameter and length. A model to predict flow rate in this dynamic system was developed. The mathematical model presented here was developed using the Hagen-Poiseuille equation and the ideal gas law to predict flow into the canisters used to sample for long periods of time. The Hagen-Poiseuille equation shows the relationship between flow rate, pressure gradient, capillary resistance, fluid viscosity, capillary length and diameter. The flow rates evaluated were extremely low, ranging from 0.05 to 1 mL min(-1). The model was compared with experimental results and was shown to overestimate the flow rate. Empirical equations were developed to more accurately predict flow for the 300 mL, 1 and 6 L canisters used for sampling periods ranging from several hours to one month. The theoretical and observed flow rates for different capillary geometries were evaluated. Each capillary flow controller geometry that was tested was found to generate very reproducible results, RSD < 2%. Also, the empirical formulas developed to predict flow rate given a specified diameter and capillary length were found to predict flow rate within 6% of the experimental data. The samplers were exposed to a variety of airborne vapors that allowed for comparison of the effectiveness of capillary flow controllers to sorbent samplers and to an online gas chromatograph. The capillary flow controller was found to exceed the performance of the sorbent samplers in this comparison.
Control of low-concentration pollutants from a semiconductor process vent stream using a wet-scrubbing technique is a challenging task to meet Taiwan environmental emission standards. An efficient wet-scrubber is designed on a pilot scale and tested to control low concentration acid and base waste-gas emission. The scrubber system consisted of two columns, i.e., a fine spray column [cutoff diameter (based on volume), Dv(50) = 15.63 microm; Sauter mean diameter (SMD) = 7.62 microm], which is especially efficient for NH3 removal as the pH of the spraying liquid is approximately 7 followed by a packed column with a scrubbing liquid pH approximately 9.0 mainly for acids removal. It is observed that use of the surfactants in low concentration about 10(-4) M and 10(-7) M in the spray liquid and in the scrubbing liquid, respectively, remarkably enhances the removal efficiency of the system. A traditional packed column (without the spray column and the surfactant) showed that the removal efficiencies of NH3, HF, and HCl for the inlet concentration range 0.2 to 3 ppm were (n = 5) 22.6+/-3.4%, 43.4+/-5.5%, and 40.4+/-7.4%, respectively. The overall efficiencies of the proposed system (the spray column and the packed column) in the presence of the surfactant in the spray liquid and in the scrubbing liquid forthese three species were found to increase significantly (n = 5) from 60.3+/-3.6 to 82.8+/-6.8%, 59.1+/-2.7 to 83.4+/-4.2%, and 56.2+/-7.3 to 81.0+/-6.7%, respectively. In this work, development of charge on the gas-liquid interface due to the surfactants has been measured and discussed. It is concluded that the presence of charge on the gas-liquid interface is the responsible factor for enhancement of the removal efficiency (mass-transfer in liquid phase). The effects of the type of surfactants, their chain length, concentration in liquid, etc. on the removal efficiency are discussed. Since the pilot tests were performed under the operating conditions similar to most of the wet-scrubbers operated in semiconductors manufacturing facilities for inorganic pollutants, this study can be applied to modify the existing wet-scrubbers to enhance the removal efficiencies, especially for low-concentration pollutants.
The adsorption isotherms of a series of aromatic hydrocarbons on n-hexane soot were measured as a function of temperature and partial pressure in a coated-wall flow tube coupled to an electron-impact mass spectrometer. The specific surface area was determined for each of the samples by measuring the BET isotherm of Kr at 77 K. The gas-to-surface uptakes were fully reversible with the extent of adsorption increasing with decreasing temperature and increasing partial pressures. At low partial pressures, the isotherms were well modeled by the Langmuir isotherm for all experimental conditions, and the adsorption was found to saturate at one monolayer of coverage at approximately 2 x 10(14) molecule cm(-2). For the less volatile species, evidence for multilayer adsorption was observed and the BET isotherm was used instead. The experimental enthalpies of adsorption were consistently higher than the enthalpies of vaporization for all compounds. A linear free-energy relationship was developed between the Langmuir equilibrium constant for adsorption and the compound's (sub-cooled) liquid vapor pressure, providing validation for the use of such relationships in assessing gas-particle partitioning of aromatic hydrocarbons to soot aerosols in the environment. The experimental results were compared to the Junge-Pankow gas-to-aerosol partitioning model.
The contamination of groundwater by geogenic arsenic is the cause of major health problems in south and southeast Asia. Various hypotheses proposing that As is mobilized by the reduction of iron (oxy)hydroxides are now under discussion. One important and controversial question concerns the possibility that As contamination might be related to the extraction of groundwater for irrigation purposes. If As were mobilized by the inflow of re-infiltrating irrigation water rich in labile organic carbon, As-contaminated groundwater would have been recharged after the introduction of groundwater irrigation 20-40 years ago. We used environmental tracer data and conceptual groundwater flow and transport modeling to study the effects of groundwater pumping and to assess the role of reinfiltrated irrigation water in the mobilization of As. Both the tracer data and the model results suggest that pumping induces convergent groundwater flow to the depth of extraction and causes shallow, young groundwater to mix with deep, old groundwater. The As concentrations are greatest at a depth of 30 m where these two groundwater bodies come into contact and mix. There, within the mixing zone, groundwater age significantly exceeds 30 years, indicating that recharge of most of the contaminated water occurred before groundwater irrigation became established in Bangladesh. Hence, at least at our study site, the results call into question the validity of the hypothesis that re-infiltrated irrigation water is the direct cause of As mobilization; however, the tracer data suggest that, at our site, hydraulic changes due to groundwater extraction for irrigation might be related to the mobilization of As.
Protein film voltammetry is a powerful method for probing the chemistry of redox-active sites in metalloproteins. The technique affords precise potential control over a tiny quantity of material that is manipulated on an electrode surface, providing information on ligand- or metal-exchange reactions coupled to electron transfer. This is illustrated by examples of transformations of the iron-sulfur clusters in ferredoxins. Protein film voltammetry is particularly advantageous in studies of metalloenzymes for which the current response is proportional to catalytic activity: kinetic data of extremely high signal/noise ratio are obtained for highly active enzymes. We present a series of interesting examples in which catalytic activity varies in unusual ways with applied potential, surveying information that can be obtained from cyclic voltammetry and then looking beyond this method to controlled potential-step experiments that yield kinetic and mechanistic details. Recent results on the voltammetry of the highly active [NiFe]-hydrogenase from Allochromatium vinosum illustrate how it is possible to use the precise kinetic information from potential-step experiments to diagnose subtle details of transformations between catalytically active and inactive states of an enzyme. Protein film voltammetry thus complements spectroscopic techniques and other physical methods, revealing the chemistry of systems that might appear intractable or convoluted by other means.
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In aqueous solution, a deep-cavity cavitand was shown to self-assemble into dimeric nano-capsules via the sequestration of gaseous-phase hydrocarbons. The sequestration, assembly, and entrapment process was shown to be dependent on the hydrocarbon. Thus, by way of example, butane could be selectively sequestered from a propane-butane mixture.
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