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Sample records for acid vapor hno3

  1. Reactions between Criegee Intermediates and the Inorganic Acids HCl and HNO3 : Kinetics and Atmospheric Implications.

    PubMed

    Foreman, Elizabeth S; Kapnas, Kara M; Murray, Craig

    2016-08-22

    Criegee intermediates (CIs) are a class of reactive radicals that are thought to play a key role in atmospheric chemistry through reactions with trace species that can lead to aerosol particle formation. Recent work has suggested that water vapor is likely to be the dominant sink for some CIs, although reactions with trace species that are sufficiently rapid can be locally competitive. Herein, we use broadband transient absorption spectroscopy to measure rate constants for the reactions of the simplest CI, CH2 OO, with two inorganic acids, HCl and HNO3 , both of which are present in polluted urban atmospheres. Both reactions are fast; at 295 K, the reactions of CH2 OO with HCl and HNO3 have rate constants of 4.6×10(-11)  cm(3)  s(-1) and 5.4×10(-10)  cm(3)  s(-1) , respectively. Complementary quantum-chemical calculations show that these reactions form substituted hydroperoxides with no energy barrier. The results suggest that reactions of CIs with HNO3 in particular are likely to be competitive with those with water vapor in polluted urban areas under conditions of modest relative humidity. PMID:27440012

  2. Optical detection of concentrations for mixed acid: HF and HNO3

    NASA Astrophysics Data System (ADS)

    Kang, Gumin; Kim, Kyoungsik

    2009-02-01

    Mixed acid, which consist of HF and HNO3, is used as a good etchant for silicon dioxide in the wet etching and pickling process of stainless steel. The optical detection of concentration for such mixed acids is crucial to optimize and cut costs in the manufacturing process. Optical detection in the IR regime has been utilized to measure the concentration of the mixed acid for HF and HNO3, because that has several strong absorption peaks, which is contributed by vibrational mode of each acid molecular in this spectrum. In this research, we observed the concentrations of mixed acid to consist of HF and HNO3, as we measured the absorption intensity of OH- stretch and NO3 - stretch band by optical spectroscopy. The concentration range of HF over 1.5-3 wt% and that of HNO3 over 2-10 wt% were studied in room temperature.

  3. Water vapor effect on the HNO3 yield in the HO2 + NO reaction: experimental and theoretical evidence.

    PubMed

    Butkovskaya, Nadezhda; Rayez, Marie-Thérèse; Rayez, Jean-Claude; Kukui, Alexandre; Le Bras, Georges

    2009-10-22

    The influence of water vapor on the production of nitric acid in the gas-phase HO(2) + NO reaction was determined at 298 K and 200 Torr using a high-pressure turbulent flow reactor coupled with a chemical ionization mass spectrometer. The yield of HNO(3) was found to increase linearly with the increase of water concentration reaching an enhancement factor of about 8 at [H(2)O] = 4 x 10(17) molecules cm(-3) ( approximately 50% relative humidity). A rate constant value k(1bw) = 6 x 10(-13) cm(3) molecule(-1) s(-1) was derived for the reaction involving the HO(2)xH(2)O complex: HO(2)xH(2)O + NO --> HNO(3) (1bw), assuming that the water enhancement is due to this reaction. k(1bw) is approximately 40 times higher than the rate constant of the reaction HO(2) + NO --> HNO(3) (1b), at the same temperature and pressure. The experimental findings are corroborated by density functional theory (DFT) calculations performed on the H(2)O/HO(2)/NO system. The significance of this result for atmospheric chemistry and chemical amplifier instruments is briefly discussed. An appendix containing a detailed consideration of the possible contribution from the surface reactions in our previous studies of the title reaction and in the present one is included. PMID:19780600

  4. Nucleation of Mixed Nitric Acid-Water Ice Nanoparticles in Molecular Beams that Starts with a HNO3 Molecule.

    PubMed

    Lengyel, Jozef; Pysanenko, Andriy; Kočišek, Jaroslav; Poterya, Viktoriya; Pradzynski, Christoph C; Zeuch, Thomas; Slavíček, Petr; Fárník, Michal

    2012-11-01

    Mixed (HNO3)m(H2O)n clusters generated in supersonic expansion of nitric acid vapor are investigated in two different experiments, (1) time-of-flight mass spectrometry after electron ionization and (2) Na doping and photoionization. This combination of complementary methods reveals that only clusters containing at least one acid molecule are generated, that is, the acid molecule serves as the nucleation center in the expansion. The experiments also suggest that at least four water molecules are needed for HNO3 acidic dissociation. The clusters are undoubtedly generated, as proved by electron ionization; however, they are not detected by the Na doping due to a fast charge-transfer reaction between the Na atom and HNO3. This points to limitations of the Na doping recently advocated as a general method for atmospheric aerosol detection. On the other hand, the combination of the two methods introduces a tool for detecting molecules with sizable electron affinity in clusters. PMID:26296012

  5. Vapor pressures of solid hydrates of nitric acid - Implications for polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Worsnop, Douglas R.; Fox, Lewis E.; Zahniser, Mark S.; Wofsy, Steven C.

    1993-01-01

    Thermodynamic data are presented for hydrates of nitric acid: HNO3.H2O, HNO3.2H2O, HNO3.3H2O, and a higher hydrate. Laboratory data indicate that nucleation and persistence of metastable HNO3.2H2O may be favored in polar stratospheric clouds over the slightly more stable HNO3.3H2O. Atmospheric observations indicate that some polar stratospheric clouds may be composed of HNO3.2H2O and HNO3.3H2O. Vapor transfer from HNO3.2H2O to HNO3.3H2O could be a key step in the sedimentation of HNO3, which plays an important role in the depletion of polar ozone.

  6. Vapor pressures of solid hydrates of nitric Acid: implications for polar stratospheric clouds.

    PubMed

    Worsnop, D R; Zahniser, M S; Fox, L E; Wofsy, S C

    1993-01-01

    Thermodynamic data are presented for hydrates of nitric acid: HNO(3).H(2)O, HNO(3).2H(2)O, HNO(3).3H(2)O, and a higher hydrate. Laboratory data indicate that nucleation and persistence of metastable HNO(3).2H(2)O may be favored in polar stratospheric clouds over the slightly more stable HNO(3).3H(2)O. Atmospheric observations indicate that some polar stratospheric clouds may be composed of HNO(3).2H(2)O and HNO(3).3H(2)O. Vapor transfer from HNO(3).2H(2)O to HNO(3).3H(2)O could be a key step in the sedimentation of HNO(3), which plays an important role in the depletion of polar ozone. PMID:17757475

  7. Composition and freezing of aqueous H2SO4/HNO3 solutions under polar stratospheric conditions

    NASA Technical Reports Server (NTRS)

    Beyer, K. D.; Seago, S. W.; Chang, H. Y.; Molina, M. J.

    1994-01-01

    The results of laboratory investigations of the freezing behavior of aqueous acid solutions indicate that in the stratosphere H2SO/H2O aerosol droplets would not freeze at temperatures above the ice frost point in the absence of HNO3; however, in the presence of typical levels of HNO3 liquid sulfuric acid aerosols take up significant amounts of HNO3 and H2O vapors and freeze much more readily. This is a consequence of the very rapid change in composition of the liquid droplets as the temperature drops to within two to three degrees of the equilibrium temperature at which HNO3 and H2O vapors would co-condense to form a liquid solution. In the high latitude stratosphere this HNO3/H2O 'dew point' is typically around 192-194 K at 100 mbar.

  8. Redox reactions of Pu(IV) and Pu(III) in the presence of acetohydroxamic acid in HNO(3) solutions.

    PubMed

    Tkac, Peter; Precek, Martin; Paulenova, Alena

    2009-12-21

    The reduction of Pu(IV) in the presence of acetohydroxamic acid (HAHA) was monitored by vis-NIR spectroscopy. All experiments were performed under low HAHA/Pu(IV) ratios, where only the Pu(IV)-monoacetohydroxamate complex and Pu uncomplexed with HAHA were present in relevant concentrations. Time dependent concentrations of all absorbing species were resolved using molar extinction coefficients for Pu(IV), Pu(III), and the Pu(AHA)(3+) complex by deconvolution of spectra. From fitting of the experimental data by rate equations integrated by a numeric method three reactions were proposed to describe a mechanism responsible for the reduction and oxidation of plutonium in the presence of HAHA and HNO(3). Decomposition of Pu(AHA)(3+) follows a second order reaction mechanism with respect to its own concentration and leads to the formation of Pu(III). At low HAHA concentrations, a two-electron reduction of uncomplexed Pu(IV) with HAHA also occurs. Formed Pu(III) is unstable and slowly reoxidizes back to Pu(IV), which, at the point when all HAHA is decomposed, can be catalyzed by the presence of nitrous acid. PMID:19904974

  9. Chemical Corrosion of Liquid-Phase Sintered SiC in Acidic/Alkaline Solutions Part 1. Corrosion in HNO3 Solution

    NASA Astrophysics Data System (ADS)

    Zhang, Lei; Zhang, Ming; He, Xinnong; Tang, Wenming

    2016-03-01

    The corrosion behavior of the liquid-phase sintered SiC (LPS-SiC) was studied by dipping in 3.53 mol/L HNO3 aqueous solution at room temperature and 70 °C, respectively. The weight loss, strength reduction and morphology evolution of the SiC specimens during corroding were revealed and also the chemical corrosion process and mechanism of the SiC specimens in the acidic solution were clarified. The results show that the corrosion of the LPS-SiC specimens in the HNO3 solution is selective. The SiC particles are almost free from corrosion, but the secondary phases of BaAl2Si2O8 (BAS) and Y2Si2O7 are corroded via an acid-alkali neutralization reaction. BAS has a higher corrosion rate than Y2Si2O7, resulting in the formation of the bamboo-leaf-like corrosion pits. As the SiC specimens etched in the HNO3 solution at room temperature for 75 days, about 80 μm thickness corrosion layer forms. The weight loss and bending strength reduction of the etched SiC specimens are 2.6 mg/cm2 and 52%, respectively. The corrosion of the SiC specimens is accelerated in the 70 °C HNO3 solution with a rate about five times bigger than that in the same corrosion medium at room temperature.

  10. Anomalous HNO3/NO(x) ratio of remote tropospheric air: Conversion of nitric acid to formic acid and NO(x)?

    NASA Technical Reports Server (NTRS)

    Chatfield, Robert B.

    1994-01-01

    The N oxidation ratio, (HNO3)/(NO(x)), in the free troposphere is measured at approx. 1 to 9 (averaging approx. 5), consistently lower than the values of 15-100 which known theory suggests to be reached rapidly. This discrepancy casts doubt on current models' abilities to predict effects of NO sources on remote (NO), and so also (O3) and (OH). HNO3-to-NO(x) recycling processes involving HCHO in solution are appealing explanations for the ratio. Known chemical theory are illustrated using a Lagrangian box model of the mid-troposphere which simulates characteristic episodes form NO(x) input to HNO3 washout. Ratio and budget constraint equations for No(y) can usefully restrict conceivable explanations of missing chemistry of fast nitrogen cycling; most explanations could be called 'fast-cycles' or 're-NO(x)-ification.' These equations also show how current global models may suggest spuriously good N oxidation ratios and errors in OH. Aerosol or cloud droplets reactions with HCHO may produce (a) formic acid (which needs an appropriate source) and NO(x), or alternatively, (b) hydroxymethyl nitrate (or methyl dinitrate), which might supply a large, variable amount of 'missing NO(y) not currently measurable except by NO(y) instruments.

  11. Demonstration of HNO3 Eddy Flux Measurements at the Boulder Atmospheric Observatory Using Active Passivation

    NASA Astrophysics Data System (ADS)

    Roscioli, J. R.; Herndon, S. C.; Zahniser, M. S.; Nelson, D. D.; Zaragoza, J.; Pollack, I. B.; Fischer, E. V.

    2015-12-01

    Eddy flux measurements of "sticky" molecules have historically proven difficult due to strong interactions with instrument surfaces. A novel approach has been developed to improve these response times, enabling flux measurements of nitric acid (HNO3) and and ammonia (NH3). Deliberate addition of the vapor of perfluorinated acids and bases into a sample stream serves to eject existing surface-bound sample molecules and passivate instrument surfaces. HNO3 response times for an Aerodyne quantum cascade laser absorption spectrometer (QCLAS) improve by a factor of 60-fold when actively passivating. This approach was used during field measurements of HNO3 fluxes at the Boulder Atmospheric Observatory, where an actively passivated inertial inlet at 8 m height yielded HNO3 deposition fluxes of 0.5 - 2 nmol/m2/sec. The dependence of the deposition flux upon urban vs rural outflow is discussed.

  12. Heterogeneous interaction of carboxylic acids with pure ice and HNO3-doped ice surfaces at upper tropospheric/lower stratospheric temperatures

    NASA Astrophysics Data System (ADS)

    Papagiannakopoulos, P.; Pettersson, J. B. C.; Papadimitriou, V. C.; Romanias, M. N.

    2012-04-01

    The heterogeneous interaction of atmospheric trace gases with ice surfaces plays an important role in the chemistry of the upper troposphere and lower stratosphere (UT/LS) region. In particular, the uptakes of carboxylic acids, such as formic (HC(O)OH), acetic (CH3C(O)OH), propionic (CH3CH2C(O)OH), and butyric (CH3CH2CH2C(O)OH) acids, on pure ice or HNO3-doped ice particles in dense cirrus clouds or polar stratospheric clouds may be significant in removing these acids from the UT/LS. The aim of the present study was to investigate the adsorption of gaseous carboxylic acids on thin ice and HNO3-doped ice films over the temperature range 195-208 K and at low gaseous pressures, using a Knudsen flow reactor combined with a quadrupole mass spectrometer. The initial uptake coefficients, γo, were measured as a function of temperature and at low surface coverage; the inverse temperature dependence of γo indicates that the uptake proceeds via the formation of an intermediate precursor state. The uptakes of formic and acetic acids were well represented by Langmuir adsorption model, and the temperature independent saturation surface coverage, Nmax, on pure ice films were (2.94 ± 0.67)×1014 molecule cm-2, and (2.11 ± 0.16)×1014 molecule cm-2, respectively; in excellent agreement with coated-wall laminar flow tube (CWLFT) technique values. Light nitration (1.96 and 7.69 wt%) of ice films resulted in more efficient uptakes and larger Nmax values that may be attributed to in-bulk diffusion or change in nature of gas-ice surface interaction. The uptake profiles of propionic and butyric acids on pure ice and HNO3-doped ice films over the temperature range 195-206 K were unsaturated, which indicated high solubility and rapid diffusion of these acids into the ice bulk. The kinetics of these uptakes γ(t) were very well represented by the diffusion non-dissociating resistor model, and H*d(D)1/2 values were independent of concentration and in the range 1 to 20 m s-1/2; H*d is the

  13. Mass accommodation coefficient measurements for HNO3, HCl and N2O5 on water, ice and aqueous sulfuric acid droplet surfaces

    NASA Technical Reports Server (NTRS)

    Worsnop, Douglas; Zahniser, Mark; Kolb, Charles; Watson, Lyn; Vandoren, Jane; Jayne, John; Davidovits, Paul

    1988-01-01

    Preliminary results are reported of the direct measurement of accommodation coefficients for HNO3, N2O5 and HCl on water drops, aqueous sulfuric acid drops and ice particles. The heterogeneous chemistry of these species together with ClONO2 has been implicated in the ozone depletion observed in the Antarctic stratosphere during the spring in the last eight years. The most plausible chemical mechanism involves the removal of nitrogen oxide species via condensation on ice particles in polar stratospheric clouds resulting in a increase in the active chlorine species responsible for the ozone depletion. The observation of low NO2 and high ClO densities in the Antarctic stratosphere last summer appear to be consistent with such a mechanism.

  14. Fast-response airborne in situ measurements of HNO3 during the Texas 2000 Air Quality Study

    NASA Astrophysics Data System (ADS)

    Neuman, J. A.; Huey, L. G.; Dissly, R. W.; Fehsenfeld, F. C.; Flocke, F.; Holecek, J. C.; Holloway, J. S.; Hübler, G.; Jakoubek, R.; Nicks, D. K.; Parrish, D. D.; Ryerson, T. B.; Sueper, D. T.; Weinheimer, A. J.

    2002-10-01

    Nitric acid (HNO3) was measured from an aircraft in the planetary boundary layer and free troposphere up to 7 km on 14 flights during the Texas Air Quality Study in August and September 2000. HNO3 mixing ratios were measured at 1 Hz using a fast-response chemical ionization mass spectrometer with SiF5- reagent ions. HNO3 measurement using this highly selective ion chemistry is insensitive to water vapor and is not degraded by interferences from other species. Rapid time response (1 s) was achieved using a heated Teflon inlet. In-flight standard addition calibrations from a HNO3 permeation source were used to determine the instrument sensitivity of 1.1 ± 0.1 ion counts pptv-1 s-1 over the duration of the study. Contributions to the HNO3 signal from instrument artifacts were accounted for by regularly performing in-flight instrument background checks, where HNO3 was removed from the ambient air sample by diverting the sampled air though a nylon wool scrubber. Measurement inaccuracy, which is determined from uncertainties in the standard addition calibrations, was ±10%. Measurement precision at low HNO3 levels was ±25 pptv (1σ) for the 1 Hz data and ±9 pptv for 10 s averages of the 1 s measurements. Coincident in situ measurements of other reactive nitrogen species are used to examine NOy partitioning and HNO3 formation during this month long measurement campaign. The sum of the individually measured reactive nitrogen species is shown to be in agreement with the measured NOy. HNO3 formation in plumes from electric utility power plants, urban areas, and petrochemical facilities was studied. The observed differences in the fractional contribution of HNO3 to NOy in plumes from different anthropogenic source types are discussed.

  15. Spectroscopic study of HNO3 dissociation on ice.

    PubMed

    Marchand, Patrick; Marcotte, Guillaume; Ayotte, Patrick

    2012-12-13

    A detailed spectroscopic study of HNO(3):H(2)O binary amorphous mixtures, and of the adsorption of HNO(3) onto ice, is reported. Using a classical optics model, the extent of intermixing and of ionic dissociation of adsorbed HNO(3), which forms a strong acid with liquid water, is determined as a function of HNO(3) coverage and temperature. Even at temperatures as low as 45 K, where intermixing is limited to at most a few molecular layers at the interface, ionic dissociation of adsorbed HNO(3) is observed to be extensive. While some amount of molecularly adsorbed HNO(3) is observed at the surface of ice at 45 K, its ionic dissociation occurs irreversibly upon heating the ice substrate to 120 K. The molecularly adsorbed state of HNO(3) is not restored upon cooling, suggesting HNO(3) is a metastable entity at the surface of ice. Therefore, despite ionic dissociation of HNO(3) being thermodynamically favored, it appears to be kinetically inhibited at the surface of amorphous solid water at temperatures below 120 K. PMID:23130955

  16. Accurate Fourier transform infrared (FT-IR) spectroscopy measurements of nitrogen dioxide (NO2) and nitric acid (HNO3) calibrated with synthetic spectra.

    PubMed

    Flores, Edgar; Viallon, Joële; Moussay, Philippe; Wielgosz, Robert Ian

    2013-10-01

    A novel method for determining the accuracy of laboratory-based measurements of nitrogen dioxide (NO2) and nitric acid (HNO3) mole fractions using Fourier transform infrared (FT-IR) spectroscopy 1 cm(-1) resolution instruments calibrated with synthetic spectra has been developed. The traceability of these measurement results is to the reference line strength data contained within the high-resolution transmission molecular absorption (HITRAN) database. Incorporating a proper estimate of the uncertainty of this data into the measurement results will ensure that the SI traceable values are encompassed within the uncertainty of the measurement results. The major contributors to the uncertainties of the results are, in descending order of importance, the uncertainty in the line strength values (HITRAN 2004), the uncertainty attributed to the generation of reference spectra (including knowledge of the optical path length of the FT-IR gas cell), and temperature measurements of the gas. The stability of the FT-IR instrument itself is only a minor contributor to the overall uncertainty of the measurements. FT-IR measurements of NO2 mole fractions at nominal values of 10 μmol mol(-1) calibrated with synthetic spectra lead to standard uncertainties of 0.34 μmol mol(-1) (3.4% relative). In contrast, calibration of the FT-IR instrument with SI traceable gas standards generated by a dynamic weighing system resulted in measurements results with standard uncertainties of 0.04 μmol mol(-1) (0.4% relative). When comparing the consistency of measurement results based on the synthetic calibration method against those obtained by calibrations with SI traceable gas standards, the existence of a potential bias of ~5% was observed, although this was within the stated uncertainties of the results. The FT-IR measurements of HNO3 mole fractions at nominal values of 200 nmol mol(-1) calibrated with synthetic spectra resulted in values with standard uncertainties of 23 nmol mol(-1) (11

  17. Condensation of HNO3 and HCl in the winter polar stratospheres

    NASA Technical Reports Server (NTRS)

    Toon, Owen B.; Pinto, Joseph; Hamill, Patrick; Turco, Richard P.

    1986-01-01

    Nitric acid and hydrochloric acid vapors may condense in the winter polar stratospheres. Nitric acid clouds, unlike water ice clouds, would form at the temperatures at which polar stratospheric clouds (PSCs) are observed and would have optical depths of the magnitude observed suggesting that HNO3 is a dominant component of PSCs. ClO, N2O5 and ClNO3 may react on cloud particle surfaces yielding additional HNO3, HCl, and HOCL. In the vicinity of PSCs these reactions could deplete the stratosphere of photochemically active NO(x) species. The sedimentation of PSCs may remove these materials from the stratosphere. The loss of vapor phase NO(x) might allow halogen-based chemistry to create the ozone hole.

  18. Interactions of Gaseous HNO3 with Self-Assembled Monolayers at Various Relative Humidities at Room Temperature

    NASA Astrophysics Data System (ADS)

    Nishino, N.; Finlayson-Pitts, B. J.

    2012-12-01

    Deposition of gaseous nitric acid (HNO3) to surfaces is an important loss process in the tropospheric boundary layer, and is generally considered as a sink for oxides of nitrogen (NOx). It is known that adsorbed HNO3 reacts on inorganic surfaces such as silica and aluminum oxide, forming surface nitrate ions and releasing gaseous species that include NO, NO2, and HONO. However, surfaces found in the boundary layer (e.g., airborne particles, building materials, vegetation etc. ) often hold organic compounds as well but there are few studies of the interaction of gas phase HNO3 with such surface-adsorbed organics. We report here the results of studies of the interaction of gaseous HNO3 with self-assembled monolayers (SAMs) used as a model for the surface of hydrophobic organic films in the boundary layer. SAMs were prepared on a germanium attenuated total reflectance (ATR) crystal that had been previously coated with a 20 nm silicon oxide (SiOx) layer. Individual SAMs of various lengths and structures, as well as mixtures of SAMS, were selected to study effects of the surface structure and order/disorder on the interaction with HNO3. SAMs were exposed to a flow of gaseous HNO3 in N2 in the absence and presence of water vapor (20-90% relative humidity), and surface species monitored in real time using Fourier Transform Infrared (FTIR) spectroscopy. The nature of the interaction of HNO3 with these surfaces will be presented and the implications for heterogeneous chemistry and photochemistry in the boundary layer discussed.

  19. Effect of Acids on Water Vapor Uptake by Pyrogenic Silica

    PubMed

    Bogdan; Kulmala

    1997-07-01

    Effect of gaseous HCl and HNO3 on the water vapor uptake by pyrogenic silica was studied at different relative humidities (RH) for pure water and different compositions of binary and ternary vapor mixtures. Experiments showed that the ability of silica to uptake water strongly depends on RH and on the type of acids and their concentration in the vapor mixtures. At low acid concentration in the binary mixtures the influence of acids is probably small. Water uptake by silica does not change monotonically with acid concentration: at first it decreases and then starts to grow. However, the presence of acids promotes water uptake, and the effect is very significant at low RH. HCl seems to be more effective acid to enhance water uptake than HNO3 . In the case of ternary mixtures the adsorbed weight of water is a bit larger than that adsorbed from the binary mixtures. Acids are accumulated by silica surface, and the accumulation is larger for nitric acid. PMID:9241208

  20. Vertical distribution of ozone and nitric acid vapor on the Mammoth Mountain, eastern Sierra Nevada, California.

    PubMed

    Bytnerowicz, Andrzej; Parker, David R; Padgett, Pamela E

    2002-01-01

    In August and September 1999 and 2000, concentrations of ozone (O3) and nitric acid vapor (HNO3) were monitored at an elevation gradient (2184-3325 m) on the Mammoth Mountain, eastern Sierra Nevada, California. Passive samplers were used for monitoring exposure to tropospheric O3 and HNO3 vapor. The 2-week average O3 concentrations ranged between 45 and 72 ppb, while HNO3 concentrations ranged between 0.06 and 0.52 microg/m3. Similar ranges of O3 and HNO3 were determined for 2 years of the study. No clear effects of elevation on concentrations of the two pollutants were detected. Concentrations of HNO3 were low and at the background levels expected for the eastern Sierra Nevada, while the measured concentrations of O3 were elevated. High concentrations of ozone in the study area were confirmed with an active UV absorption O3 monitor placed at the Mammoth Mountain Peak (September 5-14, 2000, average 24-h concentration of 56 ppb). PMID:12806035

  1. Measuring tropospheric HNO3 - Problems and prospects for Nylon filter and mist chamber techniques

    NASA Astrophysics Data System (ADS)

    Talbot, R. W.; Vijgen, A. S.; Harriss, R. C.

    1990-05-01

    A series of laboratory and field measurements was performed to evaluate the mist chamber technique for determining tropospheric HNO3 concentrations. Both the mist chamber and standard Nylon filter techniques exhibit high collection efficiency and excellent agreement measuring HNO3 vapors from a permeation source. When simultaneously sampling ambient air in eastern Virginia, the Nylon filter measured an average of 70 percent higher HNO3 concentration than the mist chamber technique. The results indicate that O3 causes a low-level positive artifact interference in HNO3 measurements performed with the filter technique. This O3-induced error is small, however, compared to the large difference between atmospheric HNO3 concentrations determined with the two techniques. It is hypothesized that unidentified (organic?) nitrogen species in the atmosphere react for form NO3(-) on the filter and this phenomenon may interfere with Nylon filter measurements of HNO3 vapor. These potential interferences did not appear to affect measurements of HNO3 with the mist chamber method.

  2. Measuring tropospheric HNO3 - Problems and prospects for Nylon filter and mist chamber techniques

    NASA Technical Reports Server (NTRS)

    Talbot, R. W.; Vijgen, A. S.; Harriss, R. C.

    1990-01-01

    A series of laboratory and field measurements was performed to evaluate the mist chamber technique for determining tropospheric HNO3 concentrations. Both the mist chamber and standard Nylon filter techniques exhibit high collection efficiency and excellent agreement measuring HNO3 vapors from a permeation source. When simultaneously sampling ambient air in eastern Virginia, the Nylon filter measured an average of 70 percent higher HNO3 concentration than the mist chamber technique. The results indicate that O3 causes a low-level positive artifact interference in HNO3 measurements performed with the filter technique. This O3-induced error is small, however, compared to the large difference between atmospheric HNO3 concentrations determined with the two techniques. It is hypothesized that unidentified (organic?) nitrogen species in the atmosphere react for form NO3(-) on the filter and this phenomenon may interfere with Nylon filter measurements of HNO3 vapor. These potential interferences did not appear to affect measurements of HNO3 with the mist chamber method.

  3. Absorption of Near UV Light by HNO3/NO3(-) on Sapphire Surfaces.

    PubMed

    Sangwan, Manuvesh; Stockwell, William R; Stewart, Devoun; Zhu, Lei

    2016-05-12

    We have determined absorption of the near UV light (290-345 nm) by nitric acid (HNO3) deposition on sapphire window surfaces as a function of the HNO3 pressure, by using Brewster angle cavity ring-down spectroscopy. Apparent monolayer HNO3 surface absorption cross sections have been obtained; they range between (1.7 ± 1.1) × 10(-19) and (0.29 ± 0.03) × 10(-19) cm(2)/molecule. When nitric acid cross section values on sapphire surfaces were divided by those on fused silica surfaces for which only molecular HNO3 adsorption was reported, a new absorption band appeared in the 320-345 nm region. The shape of this absorption band is similar to that reported for surface nitrate (NO3(-)) at quartz/water interfaces, but is red-shifted by about 10 nm. Our study suggests that a small percentage (<7%) of adsorbed HNO3 formed by HNO3 deposition on sapphire surfaces is dissociated into surface nitrate on the time scale of about 5-7 min. Background transmission changes in the 320-350 nm region after exposing clean sapphire surfaces with many repeated HNO3 deposition/evacuation cycles are consistent with surface nitrate formation. We obtained nitrate surface absorption cross section data over 320-350 nm range. We also modeled photolysis rates of HNO3/NO3(-) on urban grimes. Atmospheric implications of the results are discussed. PMID:27111736

  4. Exceedingly Low Freezing Rates of Aqueous Hno3 and Hno3/h2so4 Droplets Under Polar Stratospheric Conditions

    NASA Astrophysics Data System (ADS)

    Knopf, D. A.; Koop, T.; Luo, B.; Weers, U. G.; Peter, T.

    In the Arctic winter 1999/2000 large particles containing nitric acid were observed during in situ field measurements. These large particles are important for the deni- trification of the Arctic stratosphere. It has been proposed that such particles form by homogeneous nucleation of nitric acid hydrates from liquid stratospheric aerosol droplets. Homogeneous nucleation rates of NAT (Nitric Acid Trihydrate) and NAD (Nitric Acid Dihydrate) have been determined in laboratory experiments for binary HNO3/H2O solutions only at supersaturations much larger than observed in the stratosphere. Therefore, an extrapolation of such laboratory data is required for the modelling of stratospheric particle formation and subsequent denitrification. We will present new laboratory data of homogeneous nucleation rates of NAT and NAD from droplets consisting of both binary HNO3/H2O as well as ternary HNO3/H2O/H2SO4 solutions. Optical microscopy has been used to deduce the droplet freezing tempera- tures. The nature of the crystallized solids was identified by Raman spectroscopy. The freezing data have been analyzed within the framework of classical nucleation theory. Our results are consistent with previously published laboratory aerosol data. However, for stratospheric conditions, we infer homogeneous nucleation rates to be lower by orders of magnitude than the extrapolation currently in use. We conclude that homo- geneous nucleation of NAT and NAD is not sufficient to explain the observed number concentrations of large nitric acid containing particles in the stratosphere.

  5. Miniaturizing and automation of free acidity measurements for uranium (VI)-HNO3 solutions: Development of a new sequential injection analysis for a sustainable radio-analytical chemistry.

    PubMed

    Néri-Quiroz, José; Canto, Fabrice; Guillerme, Laurent; Couston, Laurent; Magnaldo, Alastair; Dugas, Vincent

    2016-10-01

    A miniaturized and automated approach for the determination of free acidity in solutions containing uranium (VI) is presented. The measurement technique is based on the concept of sequential injection analysis with on-line spectroscopic detection. The proposed methodology relies on the complexation and alkalimetric titration of nitric acid using a pH 5.6 sodium oxalate solution. The titration process is followed by UV/VIS detection at 650nm thanks to addition of Congo red as universal pH indicator. Mixing sequence as well as method validity was investigated by numerical simulation. This new analytical design allows fast (2.3min), reliable and accurate free acidity determination of low volume samples (10µL) containing uranium/[H(+)] moles ratio of 1:3 with relative standard deviation of <7.0% (n=11). The linearity range of the free nitric acid measurement is excellent up to 2.77molL(-1) with a correlation coefficient (R(2)) of 0.995. The method is specific, presence of actinide ions up to 0.54molL(-1) does not interfere on the determination of free nitric acid. In addition to automation, the developed sequential injection analysis method greatly improves the standard off-line oxalate complexation and alkalimetric titration method by reducing thousand fold the required sample volume, forty times the nuclear waste per analysis as well as the analysis time by eight fold. These analytical parameters are important especially in nuclear-related applications to improve laboratory safety, personnel exposure to radioactive samples and to drastically reduce environmental impacts or analytical radioactive waste. PMID:27474315

  6. Physical Chemistry of the H2SO4/HNO3/H2O System: Implications for Polar Stratospheric Clouds.

    PubMed

    Molina, M J; Zhang, R; Wooldridge, P J; McMahon, J R; Kim, J E; Chang, H Y; Beyer, K D

    1993-09-10

    Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO(3) hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H(2)SO(4)/H(2)O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO(3) vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO(3) and H(2)O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H(2)SO(4) solutions and on solid H(2)SO(4) hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles. PMID:17745351

  7. Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Molina, M. J.; Zhang, R.; Wooldridge, P. J.; Mcmahon, J. R.; Kim, J. E.; Chang, H. Y.; Beyer, K. D.

    1993-01-01

    Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

  8. The Reduction of HNO3 to HONO by Volatile Organic Compounds Associated with Rush Hour Traffic

    NASA Astrophysics Data System (ADS)

    Rutter, A. P.; Malloy, Q.; Scheuer, E.; Gutierrez, C.; Calzada, M.; Dibb, J. E.; Griffin, R. J.

    2012-12-01

    Nitrous acid (HONO) is an important source of OH radicals in urban environments. However, the sources of HONO are not completely understood, which makes modeling urban atmospheric chemistry difficult. During a previous field study in Houston, TX a correlation was observed between increases in HONO and organic aerosol freshly emitted by motor vehicle traffic during morning rush hours (Ziemba et al., 2010). This source of HONO could not be explained by primary HONO emissions, and the hypothesis was drawn that the HONO was being formed from the reduction of HNO3 by the organic aerosols emitted by motor vehicles. To test this hypothesis, nitric acid (HNO3) was combined in a flow tube with aerosols made from automobile engine oil, which were used as a model for the organic aerosols emitted by rush hour traffic. Reduction of the HNO3 to HONO was observed, although the reaction was found to occur with the volatile organic carbon compounds (VOCs) found in the aerosol vapor, and not the particle surfaces. To explore this further Teflon raschig rings were added to the flow tube to increase surface area but the reaction was not enhanced, confirming the reaction to be homogeneous. The HONO formation observed ranged between 0.1 and 0.5 ppb hr-1 with a mean of 0.3±0.1 ppb hr-1, for typical nitric acid concentrations of 4-5 ppb and estimated concentrations of the reactive components in the engine oil vapor of between 200 and 300 ppt. The observations in this study compared well to the cited field study which observed formation rates between 0.05 and 0.5 ppb hr-1 with an average of 0.3±0.15 ppb hr-1. Water vapor was found to decrease the HONO formation rate by 0.1 ppb hr-1 for every1% of increase in the water mixing ratio. Reference Ziemba L.D., Dibb J.E., Griffin R.J., Anderson C.H., Whitlow S.I., Lefer B.L., Rappenglueck B., and Flynn J. (2010) Heterogeneous conversion of nitric acid to nitrous acid on the surface of primary organic aerosol in an urban atmosphere. Atmospheric

  9. Impact of future land cover changes on HNO3 and O3 surface dry deposition

    NASA Astrophysics Data System (ADS)

    Verbeke, T.; Lathière, J.; Szopa, S.; de Noblet-Ducoudré, N.

    2015-07-01

    Dry deposition is a key component of surface-atmosphere exchange of compounds, acting as a sink for several chemical species. Meteorological factors, chemical properties of the trace gas considered and land surface properties are strong drivers of dry deposition efficiency and variability. Under both climatic and anthropogenic pressure, the vegetation distribution over the Earth has been changing a lot over the past centuries, and could be significantly altered in the future. In this study, we perform a modeling investigation of the potential impact of land-cover changes between present-day (2006) and the future (2050) on dry deposition rates, with special interest for ozone (O3) and nitric acid vapor (HNO3), two compounds which are characterized by very different physico-chemical properties. The 3-D chemistry transport model LMDz-INCA is used, considering changes in vegetation distribution based on the three future projections RCPs 2.6, 4.5 and 8.5. The 2050 RCP 8.5 vegetation distribution leads to a rise up to 7 % (+0.02 cm s-1) in VdO3 and a decrease of -0.06 cm s-1 in VdHNO3 relative to the present day values in tropical Africa, and up to +18 and -15 % respectively in Australia. When taking into account the RCP 4.5 scenario, which shows dramatic land cover change in Eurasia, VdHNO3 increases by up to 20 % (annual-mean value) and reduces VdO3 by the same magnitude in this region. When analyzing the impact of dry deposition change on atmospheric chemical composition, our model calculates that the effect is lower than 1 ppb on annual mean surface ozone concentration, for both for the RCP8.5 and RCP2.6 scenarios. The impact on HNO3 surface concentrations is more disparate between the two scenarios, regarding the spatial repartition of effects. In the case of the RCP 4.5 scenario, a significant increase of the surface O3 concentration reaching locally up to 5 ppb (+5 %) is calculated on average during the June-August period. This scenario induces also an increase of

  10. Strongly reduced Si surface recombination by charge injection during etching in diluted HF/HNO3.

    PubMed

    Greil, Stefanie M; Schöpke, Andreas; Rappich, Jörg

    2012-08-27

    Herein, we investigate the behaviour of the surface recombination of light-induced charge carriers during the etching of Si in alkaline (KOH) and acidic etching solutions of HF/HNO(3)/CH(3)COOH (HNA) or HF/HNO(3)/H(3)PO(4) (HNP) at different concentration ratios of HF and HNO(3) by means of photoluminescence (PL) measurements. The surface recombination velocity is strongly reduced during the first stages of etching in HF/HNO(3)-containing solutions pointing to a interface well passivated by the etching process, where a positive surface charge is induced by hole injection from NO-related surface species into the Si near-surface region (back surface field effect). This injected charge leads to a change in band bending by about 150 mV that repulses the light-induced charge carriers from the surface and therefore enhances the photoluminescence intensity, since non-radiative surface recombination is reduced. PMID:22761060

  11. SIMPLE DESIGN FOR AUTOMATION OF TUNGSTEN(VI) OXIDE TECHNIQUE FOR MEASUREMENT OF NH3, AND HNO3

    EPA Science Inventory

    The tungstic acid technique for collection and analysis of NH3 and HNO3 concentrations in the ambient air has been automated in a simple and cost-effective design. The design allows complete separation of HNO3 and NH3 during detection. Unattended operation in field trials has bee...

  12. Acidification of rain in the presence of SO2, H2O2, O3, and HNO3

    SciTech Connect

    Overton, J.H. Jr; Durham, J.L.

    1982-01-01

    The production of acid sulfate and the accumulation of acid nitrate are calculated for falling raindrops using a physico-chemical model that accounts for the mass transfer of SO2, H2O2, O3, HNO3, and CO2. The acidification is postulated to occur through the absorption of free gaseous HNO3 and the absorption and reaction of SO2, H2O2, and O3 to yield H2SO4. Investigated are the relative effectivness of H2O2(aq) and O3(aq) for oxidizing SO2(aq) to yield H(+1) and SO-2(-2), and the role of HNO3(aq) in acidifying raindrops and influencing SO4(-2) formation. Results indicate: that H2O2 is more effective than O3, HNO3 inhibits SO4(-2) formation due to O3 oxidation, and in all cases, HNO3 is important in acidifying rain.

  13. Atmospheric corrosion effects of HNO 3—Comparison of laboratory-exposed copper, zinc and carbon steel

    NASA Astrophysics Data System (ADS)

    Samie, Farid; Tidblad, Johan; Kucera, Vladimir; Leygraf, Christofer

    The influence of nitric acid (HNO 3) on the atmospheric corrosion of copper, zinc and carbon steel was investigated in laboratory exposures at 65% relative humidity (RH), 25 °C and 0.03 cm s -1 air velocity. The deposition velocity ( Vd) of HNO 3 on the specimens, the corrosion rates and corrosion products were determined by gravimetry, ion chromatography, X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) microspectroscopy. Comparisons were also made with literature data on the corrosion effects of sulfur dioxide (SO 2), nitrogen dioxide (NO 2) and ozone (O 3). At 65% RH, the Vd of HNO 3 on all metals was at least 70% of that of an ideal absorbent, i.e., an impregnated filter with perfect absorption for HNO 3. The Vd of HNO 3 was much higher than that of SO 2, NO 2 or O 3, which is mainly attributed to the relatively high sticking coefficient, high solubility and high reactivity of HNO 3 compared to the other gases. During identical exposures to HNO 3, the corrosion rate of carbon steel was nearly three times higher than that of copper or zinc. However, when comparing the corrosion effects induced by HNO 3 with those induced by SO 2 alone or in combination with either NO 2 or O 3, HNO 3 turned out to be far more aggressive than SO 2. Relative to SO 2, zinc is the metal most sensitive to HNO 3, followed by copper and with carbon steel least sensitive to HNO 3.

  14. NARSTO EPA SS HOUSTON NH3 HNO3 DATA

    Atmospheric Science Data Center

    2014-04-25

    NARSTO EPA SS HOUSTON NH3 HNO3 DATA Project Title:  NARSTO ... Ion Chromatograph Location:  Houston, Texas Spatial Resolution:  Point Measurements ...   Order Data Guide Documents:  Houston HN3 HNO3 Guide Houston Project Plan  (PDF) ...

  15. Interhemispheric differences in polar stratospheric HNO3, H2O, ClO, and O3

    NASA Technical Reports Server (NTRS)

    Santee, M. L.; Read, W. G.; Waters, J. W.; Froidevaux, L.; Manney, G. L.; Flower, D. A.; Jarnot, R. F.; Harwood, R. S.; Peckham, G. E.

    1995-01-01

    Simultaneous global measurements of nitric acid (HNO3), water (H2O), chlorine monoxide (ClO), and ozone (O3) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO3 was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H2O after mid-July. By mid-August, near the time of peak ClO, abundances of gas-phase HNO3 and H2O were extremely low. The concentrations of HNO3 and H2O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO3 or H2O were observed in the 1992-1993 Arctic winter vortex. Although ClO was enhanced over the Arctic as it was over the Antarctic, Arctic O3 depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone 'hole' is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.

  16. Interhemispheric differences in polar stratospheric HNO3, H2O, ClO, and O3

    SciTech Connect

    Santee, M.L.; Read, W.G.; Waters, J.W.; Froidevaux, L.; Manney, G.L.; Flower, D.A.; Jarnot, R.F.; Harwood, R.S.; Peckham, G.E.

    1995-02-01

    Simultaneous global measurements of nitric acid (HNO3), water (H2O), chlorine monoxide (ClO), and ozone (O3) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO3 was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H2O after mid-July. By mid-August, near the time of peak ClO, abundances of gas-phase HNO3 and H2O were extremely low. The concentrations of HNO3 and H2O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO3 or H2O were observed in the 1992-1993 Arctic winter vortex. Although ClO was enhanced over the Arctic as it was over the Antarctic, Arctic O3 depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone `hole` is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.

  17. Interhemispheric Differences in Polar Stratospheric HNO3, H2O, CIO, and O3.

    PubMed

    Santee, M L; Read, W G; Waters, J W; Froidevaux, L; Manney, G L; Flower, D A; Jarnot, R F; Harwood, R S; Peckham, G E

    1995-02-10

    Simultaneous global measurements of nitric acid (HNO(3)), water (H(2)O), chlorine monoxide (CIO), and ozone (O(3)) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO(3) was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H(2)O after mid-July. By mid-August, near the time of peak CIO, abundances of gas-phase HNO(3) and H(2)O were extremely low. The concentrations of HNO(3) and H(2)O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO(3) or H(2)O were observed in the 1992-1993 Arctic winter vortex. Although CIO was enhanced over the Arctic as it was over the Antarctic, Arctic O(3) depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone "hole" is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone. PMID:17813911

  18. Adsorption of butanol vapor on active carbons with nitric acid hydrothermal modification.

    PubMed

    Cao, Yuhe; Wang, Keliang; Wang, Xiaomin; Gu, Zhengrong; Gibbons, William; Vu, Han

    2015-11-01

    Butanol can be produced from biomass via fermentation and used in vehicles. Unfortunately, butanol is toxic to the microbes, and this can slow fermentation rates and reduce butanol yields. Butanol can be efficiently removed from fermentation broth by gas stripping, thereby preventing its inhibitory effects. Original active carbon (AC) and AC samples modified by nitric acid hydrothermal modification were assessed for their ability to adsorb butanol vapor. The specific surface area and oxygen-containing functional groups of AC were tested before and after modification. The adsorption capacity of unmodified AC samples was the highest. Hydrothermal oxidation of AC with HNO3 increased the surface oxygen content, Brunauer-Emmett-Teller (BET) surface area, micropore, mesopore and total pore volume of AC. Although the pore structure and specific surface area were greatly improved after hydrothermal oxidization with 4M HNO3, the increased oxygen on the surface of AC decreased the dynamic adsorption capacity. PMID:26291412

  19. Persistent Water-Nitric Acid Condensate with Saturation Water Vapor Pressure Greater than That of Hexagonal Ice.

    PubMed

    Gao, Ru-Shan; Gierczak, Tomasz; Thornberry, Troy D; Rollins, Andrew W; Burkholder, James B; Telg, Hagen; Voigt, Christiane; Peter, Thomas; Fahey, David W

    2016-03-10

    A laboratory chilled mirror hygrometer (CMH), exposed to an airstream containing water vapor (H2O) and nitric acid (HNO3), has been used to demonstrate the existence of a persistent water-nitric acid condensate that has a saturation H2O vapor pressure greater than that of hexagonal ice (Ih). The condensate was routinely formed on the mirror by removing HNO3 from the airstream following the formation of an initial condensate on the mirror that resembled nitric acid trihydrate (NAT). Typical conditions for the formation of the persistent condensate were a H2O mixing ratio greater than 18 ppm, pressure of 128 hPa, and mirror temperature between 202 and 216 K. In steady-state operation, a CMH maintains a condensate of constant optical diffusivity on a mirror through control of only the mirror temperature. Maintaining the persistent condensate on the mirror required that the mirror temperature be below the H2O saturation temperature with respect to Ih by as much as 3 K, corresponding to up to 63% H2O supersaturation with respect to Ih. The condensate was observed to persist in steady state for up to 16 h. Compositional analysis of the condensate confirmed the co-condensation of H2O and HNO3 and thereby strongly supports the conclusion that the Ih supersaturation is due to residual HNO3 in the condensate. Although the exact structure or stoichiometry of the condensate could not be determined, other known stable phases of HNO3 and H2O are excluded as possible condensates. This persistent condensate, if it also forms in the upper tropical troposphere, might explain some of the high Ih supersaturations in cirrus and contrails that have been reported in the tropical tropopause region. PMID:26447682

  20. Condensation of HNO3 on falling ice particles - Mechanism for denitrification of the polar stratosphere

    NASA Technical Reports Server (NTRS)

    Wofsy, S. C.; Salawitch, R. J.; Yatteau, J. H.; Mcelroy, M. B.; Gandrud, B. W.

    1990-01-01

    Ice particles created in polar stratospheric cooling events are predicted to descend into Type I PSCs and accrete a coating of nitric acid trihydrate (NAT) that inhibits evaporation. Coated particles efficiently strip HNO3 from the atmosphere, providing a mechanism for denitrification without significant dehydration. Coatings that disintegrate may release large particles of NAT that influence subsequent particle growth.

  1. Rate of reaction of OH with HNO3

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Ravishankara, A. R.; Kreutter, N. M.; Shah, R. C.; Nicovich, J. M.; Thompson, R. L.; Wuebbles, D. J.

    1981-01-01

    Measurements of the kinetics of the reaction of OH with HNO3, and mechanisms of HNO3 removal from the stratosphere, are reported. Bimolecular rate constants were determined at temperatures between 224 and 366 K by monitoring the concentrations of OH radicals produced by HNO3 photolysis and HNO3 according to their resonance fluorescence and 184.9-nm absorption, respectively. The rate constant measured at 298 K is found to be somewhat faster than previously accepted values, with a negative temperature dependence. Calculations of a one-dimensional transport-kinetic atmospheric model on the basis of the new rate constant indicate reductions in O3 depletion due to chlorofluoromethane release and NOx injection, of magnitudes dependent on the nature of the reaction products.

  2. Atmospheric corrosion effects of HNO 3—method development and results on laboratory-exposed copper

    NASA Astrophysics Data System (ADS)

    Samie, Farid; Tidblad, Johan; Kucera, Vladimir; Leygraf, Christofer

    The effects of the atmospheric pollutant nitric acid (HNO 3) on materials compared to other corrosive gases, e.g. sulphur dioxide (SO 2), nitrogen dioxide (NO 2) or ozone (O 3), have so far received little or no attention. The high sticking coefficient of HNO 3 makes this gas one of the most difficult gases to work with. A new apparatus has now successfully been developed for studying the atmospheric corrosion effects of HNO 3 on materials. HNO 3 concentration measurements up to 1080 μg m -3 (420 ppb) were performed by dissolving the gas in water and analysing the nitrate concentration with ion chromatography (IC). Small changes in relative humidity (RH) largely affect the concentration of this pollutant in the exposure chamber and the high sticking coefficient of this gas on copper and quartz glass has been shown. The quartz glass surface, however, became saturated after a certain time of exposure and at 82% RH, the number of monolayers on the surface was estimated to be 10-13. Initial results of copper samples exposed to HNO 3 show that at 63% RH and 25 °C, the deposition of HNO 3 on copper is slightly lower than on a perfect absorber. The loss of HNO 3 during exposure of the samples showed good agreement with the amount of nitrates dissolved from surfaces of the samples after exposure. FT-IR, XRD and IC analyses of copper exposed to HNO 3 and mass loss and mass gain analyses confirmed cuprite (Cu 2O) and the basic copper nitrate, gerhardtite, as the main corrosion products. Deposition, as well as the corrosion effect, of HNO 3 on copper appeared to be greater than that of any of the other above-mentioned pollutants.

  3. The vapor pressures of supercooled NHO3/H2O solutions. [in polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Hanson, David R.

    1990-01-01

    A procedure utilizing the Gibbs-Duhem relation is used to extrapolate vapor pressures of supercooled HNO3 mixtures to 190 K. Values of A and B from the equation logP = A - B/T are presented for solutions between 0.20 and 0.25 mole fraction HNO3. In the stratosphere, if sufficient HNO3 vapor is present because it has not come into equilibrium with the nitric acid trihydrate, supercooled nitric acid solutions could condense at temperatures up to 1.5 + or - 0.8 K above the ice point.

  4. The uptake of HNO3 on meteoric smoke analogues

    NASA Astrophysics Data System (ADS)

    Frankland, Victoria L.; James, Alexander D.; Feng, Wuhu; Plane, John M. C.

    2015-05-01

    The uptake of HNO3, H2O, NO2 and NO was studied on meteoric smoke particle analogues using a low-pressure Knudsen cell operating at 295 K. The analogues used were olivine (MgFeSiO4) and a haematite/goethite (Fe2O3/FeO(OH)) mixture synthesised by the sol-gel process. For uptake on MgFeSiO4, the following uptake coefficients were obtained: γ(HNO3)=(1.8±0.3)×10-3, γ(H2O)=(4.0±1.3)×10-3, γ(NO2)=(5.7±0.2)×10-4 and γ(NO)<3×10-4. γ(HNO3) did not show a dependence on the mass of MgFeSiO4 in the Knudsen cell (when varied by a factor of 6) implying that, because of relatively efficient uptake, HNO3 is removed only by near-surface particles. This was corroborated by application of a surface uptake model. Saturating the MgFeSiO4 particles with water vapour before exposing them to NO2 increased γ(NO2) to (2.1±0.7)×10-3, but had a very small effect on γ(HNO3). For uptake on Fe2O3/FeO(OH), γ(HNO3)=(1.5±0.2)×10-3. These results were then included in a whole atmosphere chemistry-climate model, which shows that the heterogeneous removal on meteoric smoke particles in the winter polar vortex between 30 and 60 km appears to provide an important sink for HNO3.

  5. Temperature dependence of the HNO3 UV absorption cross sections

    NASA Technical Reports Server (NTRS)

    Burkholder, James B.; Talukdar, Ranajit K.; Ravishankara, A. R.; Solomon, Susan

    1993-01-01

    The temperature dependence of the HNO3 absorption cross sections between 240 and 360 K over the wavelength range 195 to 350 nm has been measured using a diode array spectrometer. Absorption cross sections were determined using both (1) absolute pressure measurements at 298 K and (2) a dual absorption cell arrangement in which the absorption spectrum at various temperatures is measured relative to the room temperature absorption spectrum. The HNO3 absorption spectrum showed a temperature dependence which is weak at short wavelengths but stronger at longer wavelengths which are important for photolysis in the lower stratosphere. The 298 K absorption cross sections were found to be larger than the values currently recommended for atmospheric modeling (DeMore et al., 1992). Our absorption cross section data are critically compared with the previous measurements of both room temperature and temperature-dependent absorption cross sections. Temperature-dependent absorption cross sections of HNO3 are recommended for use in atmospheric modeling. These temperature dependent HNO3 absorption cross sections were used in a two-dimensional dynamical-photochemical model to demonstrate the effects of the revised absorption cross sections on loss rate of HNO3 and the abundance of NO2 in the stratosphere.

  6. Infrared spectra of solid films formed from vapors containing water and nitric acid

    NASA Technical Reports Server (NTRS)

    Smith, Roland H.; Leu, Ming-Taun; Keyser, Leon F.

    1991-01-01

    The paper presents infrared spectra recorded at 188 K for crystalline mono- and trihydrates of nitric acid formed by vapor deposition, along with spectra of fully deuterated forms of these compounds. The spectra are interpreted in terms of the known ionic structures of the hydrates and the known spectra of oxonium and nitrate ions. Two additional species were identified: a molecular hydrogen-bonded HNO3-H2O complex, stable only at temperatures below 120 or 150 K, and a substance considered to be a crystalline mixtgure of trihydrate and ice. The relevance of these findings to the stratospheric ozone hole problem is discussed.

  7. HNO3 profiles obtained during the EASOE campaign

    NASA Technical Reports Server (NTRS)

    Murcray, F. J.; Starkey, J. R.; Williams, W. J.; Matthews, W. A.; Schmidt, U.; Aimedieu, P.; Camy-Peyret, C.

    1994-01-01

    A small cryogenically cooled spectrometer system designed to obtain atmospheric emission spectra in the 7.5 micrometer to 13.0 micrometer region was flown piggyback on 9 balloon flights from ESRANGE (67.9 deg N, 21.2 deg E) during the European Arctic Stratospheric Ozone Experiment (EASOE) campaign. Initial analysis of the spectra obtained has been concentrated on obtaining HNO3 profiles for the various flights. HNO3 profiles for 17 December 1991, 9 January 1992, 22 January 1992, 5 February 1992 and 14 March 1992 are presented.

  8. Comparison of the CIBA HNO_3 model with UARS observations

    NASA Astrophysics Data System (ADS)

    Gille, J.; Bailey, P.; Massie, S.; Roche, A.; Kumer, J.; Lyjak, L.

    The CIRA HNO_3 model is based on the 7 months of data from the LIMS experiment on Nimbus 7. Now CLAES and ISAMS, two instruments on UARS, are providing further observations. Preliminary CLAES results are here compared with the CIRA model. There is agreement on the broad features of the HNO_3 distribution. CLAES data provide the first direct observations of the Northern Hemisphere summer, and of the atmosphere poleward of 64 S. Because the data are still being evaluated and improved, it is premature to draw any quantitative conclusions at this time.

  9. Interactions of gaseous HNO3 and water with individual and mixed alkyl self-assembled monolayers at room temperature.

    PubMed

    Nishino, Noriko; Hollingsworth, Scott A; Stern, Abraham C; Roeselová, Martina; Tobias, Douglas J; Finlayson-Pitts, Barbara J

    2014-02-14

    The major removal processes for gaseous nitric acid (HNO3) in the atmosphere are dry and wet deposition onto various surfaces. The surface in the boundary layer is often covered with organic films, but the interaction of gaseous HNO3 with them is not well understood. To better understand the factors controlling the uptake of gaseous nitric acid and its dissociation in organic films, studies were carried out using single component and mixtures of C8 and C18 alkyl self-assembled monolayers (SAMs) attached to a germanium (Ge) attenuated total reflectance (ATR) crystal upon which a thin layer of SiOx had been deposited. For comparison, diffuse reflectance infrared Fourier transform spectrometry (DRIFTS) studies were also carried out using a C18 SAM attached to the native oxide layer on the surface of silicon powder. These studies show that the alkyl chain length and order/disorder of the SAMs does not significantly affect the uptake or dissociation/recombination of molecular HNO3. Thus, independent of the nature of the SAM, molecular HNO3 is observed up to 70-90% relative humidity. After dissociation, molecular HNO3 is regenerated on all SAM surfaces when water is removed. Results of molecular dynamics simulations are consistent with experiments and show that defects and pores on the surfaces control the uptake, dissociation and recombination of molecular HNO3. Organic films on surfaces in the boundary layer will certainly be more irregular and less ordered than SAMs studied here, therefore undissociated HNO3 may be present on surfaces in the boundary layer to a greater extent than previously thought. The combination of this observation with the results of recent studies showing enhanced photolysis of nitric acid on surfaces suggests that renoxification of deposited nitric acid may need to be taken into account in atmospheric models. PMID:24352159

  10. HO2NO2 and HNO3 in the coastal Antarctic winter night: a "lab-in-the-field" experiment

    NASA Astrophysics Data System (ADS)

    Jones, A. E.; Brough, N.; Anderson, P. S.; Wolff, E. W.

    2014-11-01

    Observations of peroxynitric acid (HO2NO2) and nitric acid (HNO3) were made during a 4 month period of Antarctic winter darkness at the coastal Antarctic research station, Halley. Mixing ratios of HNO3 ranged from instrumental detection limits to ~8 parts per trillion by volume (pptv), and of HO2NO2 from detection limits to ~5 pptv; the average ratio of HNO3 : HO2NO2 was 2.0(± 0.6) : 1, with HNO3 always present at greater mixing ratios than HO2NO2 during the winter darkness. An extremely strong association existed for the entire measurement period between mixing ratios of the respective trace gases and temperature: for HO2NO2, R2 = 0.72, and for HNO3, R2 = 0.70. We focus on three cases with considerable variation in temperature, where wind speeds were low and constant, such that, with the lack of photochemistry, changes in mixing ratio were likely to be driven by physical mechanisms alone. We derived enthalpies of adsorption (ΔHads) for these three cases. The average ΔHads for HNO3 was -42 ± 2 kJ mol-1 and for HO2NO2 was -56 ± 1 kJ mol-1; these values are extremely close to those derived in laboratory studies. This exercise demonstrates (i) that adsorption to/desorption from the snow pack should be taken into account when addressing budgets of boundary layer HO2NO2 and HNO3 at any snow-covered site, and (ii) that Antarctic winter can be used as a natural "laboratory in the field" for testing data on physical exchange mechanisms.

  11. HO2NO2 and HNO3 in the coastal Antarctic winter night: a "lab-in-the-field" experiment

    NASA Astrophysics Data System (ADS)

    Jones, A. E.; Brough, N.; Anderson, P. S.; Wolff, E. W.

    2014-05-01

    Observations of peroxynitric acid (HO2NO2) and nitric acid (HNO3) were made during a 4 month period of Antarctic winter darkness at the coastal Antarctic research station, Halley. Mixing ratios of HNO3 ranged from instrumental detection limits to ∼8 parts per trillion by volume (pptv), and of HO2NO2 from detection limits to ∼5 pptv; the average ratio of HNO3 : HO2NO2 was 2.0(± 0.6):1, with HNO3 always present at greater mixing ratios than HO2NO2 during the winter darkness. An extremely strong association existed for the entire measurement period between mixing ratios of the respective trace gases and temperature: for HO2NO2, R2 = 0.72, and for HNO3, R2 = 0.70. We focus on three cases with considerable variation in temperature, where wind speeds were low and constant, such that, with the lack of photochemistry, changes in mixing ratio were likely to be driven by adsorption/desorption mechanisms alone. We derived enthalpies of adsorption (ΔHads) for these three cases. The average ΔHads for HNO3 was -42 ± 7 kJ mol-1 and for HO2NO2 was -56 ± 3 kJ mol-1; these values are extremely close to laboratory-derived values. This exercise demonstrates (i) that adsorption to/desorption from the snow pack should be taken into account when addressing budgets of boundary layer HO2NO2 and HNO3 at any snow-covered site, and (ii) that Antarctic winter can be used as a~natural "laboratory in the field" for testing data on physical exchange mechanisms.

  12. HO2NO2 and HNO3 in the coastal Antarctic winter night: A "lab-in-the-field" experiment

    NASA Astrophysics Data System (ADS)

    Jones, Anna; Brough, Neil; Anderson, Philip; Wolff, Eric

    2015-04-01

    Observations of peroxynitric acid (HO2NO2) and nitric acid (HNO3) were made during a 4 month period of Antarctic winter darkness at the coastal Antarctic research station, Halley. Mixing ratios of HNO3 ranged from instrumental detection limits to 8 parts per trillion by volume (pptv), and of HO2NO2 from detection limits to 5 pptv; the average ratio of HNO3:HO2NO2 was 2.0(±0.6):1, with HNO3 always present at greater mixing ratios than HO2NO2 during the winter darkness. An extremely strong association existed for the entire measurement period between mixing ratios of the respective trace gases and temperature: for HO2NO2, R2 = 0.72, and for HNO3, R2 = 0.70. We focus on three cases with considerable variation in temperature, where wind speeds were low and constant, such that, with the lack of photochemistry, changes in mixing ratio were likely to be driven by physical mechanisms alone. We derived enthalpies of adsorption (ΔHads) for these three cases. The average ΔHads for HNO3 was -42±2 kJ.mol-1 and for HO2NO2 was -56±1kJ.mol-1; these values are extremely close to those derived in laboratory studies. This exercise demonstrates i) that adsorption to/desorption from the snow pack should be taken into account when addressing budgets of boundary layer HO2NO2 and HNO3 at any snow-covered site, and ii) that Antarctic winter can be used as a natural 'laboratory in the field' for testing data on physical exchange mechanisms.

  13. Heterogeneous conversion of N2O5 to HNO3 in the post-Mount Pinatubo eruption stratosphere

    NASA Technical Reports Server (NTRS)

    Rinsland, C. P.; Gunson, M. R.; Abrams, M. C.; Lowes, L. L.; Zander, R.; Mahieu, E.; Goldman, A.; Ko, M. K. W.; Rodriguez, J. M.; Sze, N. D.

    1994-01-01

    Simultaneous stratospheric volume mixing ration (VMR) profiles of dinitrogen pentoxide (N2O5) and nitric acid (HNO3) at sunrise between 25 deg N and 15 deg S latitude and profiles of HNO3 at sunset between 42 deg S and 53 deg S latitude have been derived from 0.01/cm resolution infrared solar occultation spectra recorded 9.5 months after the massive eruption of the Mount Pinatubo volcano in the Philippine Islands. The measurements were obtained by the atmospheric trace molecule spectroscopy (ATMOS) Fourier transform spectrometer during the ATLAS 1 shuttle mission (March 24 to April 2, 1992). The measured HNO3 VMRs are higher at all altitudes and latitudes than corresponding values measured by the limb infrared monitor of the stratosphere (LIMS) instrument during the same season in 1979, when the aerosol loading was near background levels. The largest relative increase in the HNO3 VMR occurred near the equator at 30-km altitude, where the ATMOS/ATLAS 1 values are about a factor of 2 higher than the LIMS measurements. Two-dimensional model calculations show that the increase in HNO3 and the ATMOS/ATLAS 1 measurement of a steep decrease in the N2O5 VMR below 30 km can be explained by the enhanced conversion of N2O5 to HNO3 on the surfaces of the Mount Pinatubo sulfate aerosols. Our profile results demonstrate the global impact of the N2O5 + H2O yields 2HNO3 heterogeneous reaction in altering the partitioning of stratospheric odd nitrogen after a major volcanic eruption.

  14. Isotopes of HNO3 in Air and Snow at Summit, Greenland

    NASA Astrophysics Data System (ADS)

    Jarvis, J. C.; Hastings, M. G.; Steig, E. J.

    2007-12-01

    The ice core record of nitric acid (HNO3, or nitrate, NO3-), a final sink for atmospheric NO and NO2, potentially contains valuable information about past changes in our atmosphere. Through reactions with OH and ozone, NOx (NO and NO2) is closely linked to the oxidizing capacity of the atmosphere. However, the interpretation of nitrate ice core records is complicated by post-depositional processing of nitrate, whereby photolysis and volatilization can result in nitrate losses from the snow surface. Quantitatively understanding the air-to-snow transfer of nitric acid is a necessary step in unraveling ice core records of nitrate. We present isotopic measurements (15N/14N and 18O/16O) of HNO3 in air and snow from Summit, Greenland. Preliminary results show that the δ15N of HNO3 is similar in surface snow and in air sampled 1.5 meters above the snow surface. The δ18O of HNO3 is significantly higher in the surface snow versus the air samples. Previous studies of nitrate in precipitation have suggested that the δ15N of nitrate is influenced by sources of precursor NOx while the δ18O of nitrate is influenced by the chemical pathways of nitrate production. We discuss the possibility that the difference in δ18O between the air and snow samples may be an indication that the air samples contain nitrate that was photolyzed and recycled from the snow surface. The similarity between δ15N in air and snow samples suggests that, despite the possibility of nitrate recycling, there is no net loss of nitrate from the snow surface. The utility of comparisons between variations in the δ15N of nitrate and changes in the source regions of air masses reaching Summit will also be discussed.

  15. ACIDIFICATION OF RAIN IN THE PRESENCE OF SO2, H2O2, O3, AND HNO3

    EPA Science Inventory

    The production of acid sulfate and the accumulation of acid nitrate are calculated for falling raindrops using a physico-chemical model that accounts for the mass transfer of SO2, H2O2, O3, HNO3, and CO2. The acidification is postulated to occur through the absorption of free gas...

  16. Satellite observations of upper atmosphere O3 and HNO3 from the Limb Infrared Monitor of the Stratosphere /LIMS/ experiment on Nimbus 7

    NASA Technical Reports Server (NTRS)

    Russell, J. M., III; Remsberg, E. E.; Gille, J. C.; Gordley, L. L.

    1981-01-01

    The Limb Infrared Monitor of the Stratosphere (LIMS) experiment, launched on-board the Nimbus satellite, was designed to measure both day and night limb radiance which is used to infer upper atmosphere temperature profiles and chemical compound concentrations important in the study of ozone chemistry. The LIMS instrument is a six channel, limb scanning, thermal radiometer which uses HgCdTe detectors, cooled to approximately 64 K. Measurements include ozone, water vapor, nitrogen dioxide, and nitric acid. The ozone and nitric acid channels are centered at approximately 9.6 microns and 11.3 microns, respectively. Results from the channels are described with an emphasis on data validation. The O3 and HNO3 channels have demonstrated high measurement precision.

  17. Model/Data Comparisons of NO2 and HNO3

    NASA Astrophysics Data System (ADS)

    Remsberg, E. E.; Natarajan, M.; Thompson, R. E.; Gordley, L. L.

    2001-05-01

    NASA Reference Publication 1292 [Prather and Remsberg, 1993] contains reports of the stratospheric model simulations of NOy for 1980, when the effects of volcanic aerosols on the partitioning of NOy should have been minimal. Those model runs included heterogeneous chemistry on background aerosols. Model values of NO2 and HNO3 were compared with those from the archived Nimbus 7 LIMS dataset, and the models exhibited the seasonal asymmetry that was observed for the LIMS HNO3. Still there were model/data differences that did not seem to be related solely to the variations among the model transport fields. Since then, we have updated the LIMS emissivity tables (spectroscopic parameters) and developed new algorithms for retrieving the profiles of the LIMS species, and we will show that there is improved agreement between these new data and the early results from most of the models. However, because there have also been improvements since 1992 in model transport of N2O and in the relevant chemical mechanisms for the generation and partitioning of NOy, it is recommended that the various models be rerun for the 1980 case and recompared with this latest version of the LIMS dataset.

  18. Participation of HNO3 CIMS Instrument in the Sage III Ozone Loss and Validation Experiment (SOLVE)

    NASA Technical Reports Server (NTRS)

    Eisele, F. L.

    2001-01-01

    This project was part of a larger SOLVE project led by Paul Wennberg at California Institute of Technology. The work completed on this project included participating in the installation and preflight testing of a new chemical ionization mass spectrometer for measuring gas and particle phase nitric acid on the ER-2. The investigators subsequently participated in SOLVE where additional instrument improvements were made and a substantial data set was generated. The two Georgia Tech investigators that participated in this work (Fred Eisele and Dave Tanner) had previously been responsible for much of the design and construction of the ion source and mass spectrometer which would be used to measure HNO3 in SOLVE, with Caltech focusing on inlets, calibration, gas supplies/pumping computer control, and overall integration. Thus, a similar focus remained during the SOLVE measurements though all investigators worked on most if not all aspects of the instrument at some point in the mission. Some of the more interesting results from the study included measurements of nitric acid on what are thought to be 5-20 microns diameter individual particles which could supply a local mechanism for HNO3 removal, Nitric acid measurements on SOLVE were completed as a collaborative effort with a great deal of overlap between this project and the larger parent project led by Paul Wennberg. As such, the instrumentation used, its operation, and the resulting measurements are far more fully discussed in the attached report (appendix A) which describes the joint SOLVE nitric acid measurement effort.

  19. Impact of future land-cover changes on HNO3 and O3 surface dry deposition

    NASA Astrophysics Data System (ADS)

    Verbeke, T.; Lathière, J.; Szopa, S.; de Noblet-Ducoudré, N.

    2015-12-01

    Dry deposition is a key component of surface-atmosphere exchange of compounds, acting as a sink for several chemical species. Meteorological factors, chemical properties of the trace gas considered and land surface properties are strong drivers of dry deposition efficiency and variability. Under both climatic and anthropogenic pressure, the vegetation distribution over the Earth has been changing a lot over the past centuries and could be significantly altered in the future. In this study, we perform a modeling investigation of the potential impact of land-cover changes between the present day (2006) and the future (2050) on dry deposition velocities at the surface, with special interest for ozone (O3) and nitric acid (HNO3), two compounds which are characterized by very different physicochemical properties. The 3-D chemistry-transport model LMDz-INCA is used, considering changes in vegetation distribution based on the three future projections, RCPs 2.6, 4.5 and 8.5, and present-day (2007) meteorology. The 2050 RCP 8.5 vegetation distribution leads to a rise of up to 7 % (+0.02 cm s-1) in the surface deposition velocity calculated for ozone (Vd,O3) and a decrease of -0.06 cm s-1 in the surface deposition velocity calculated for nitric acid (Vd,HNO3) relative to the present-day values in tropical Africa and up to +18 and -15 %, respectively, in Australia. When taking into account the RCP 4.5 scenario, which shows dramatic land-cover change in Eurasia, Vd,HNO3 increases by up to 20 % (annual-mean value) and reduces Vd,O3 by the same magnitude in this region. When analyzing the impact of surface dry deposition change on atmospheric chemical composition, our model calculates that the effect is lower than 1 ppb on annual-mean surface ozone concentration for both the RCP 8.5 and RCP 2.6 scenarios. The impact on HNO3 surface concentrations is more disparate between the two scenarios regarding the spatial repartition of effects. In the case of the RCP 4.5 scenario, a

  20. Atmospheric corrosion effects of HNO 3—Influence of concentration and air velocity on laboratory-exposed copper

    NASA Astrophysics Data System (ADS)

    Samie, Farid; Tidblad, Johan; Kucera, Vladimir; Leygraf, Christofer

    A recently developed experimental set-up has been used to explore the atmospheric corrosion effects of nitric acid (HNO 3) on copper, in particular the influence of concentration and air velocity. Characterization and quantification of the corrosion products on exposed samples were performed with Fourier transform infrared (FT-IR) microspectrocscopy, ion chromatography, X-ray diffraction (XRD), micro-balance and microscopy. At low air velocity (0.03 cm s -1) HNO 3 deposition and weight gain of copper increased linearly with concentration up to 400 μg m -3 or 156 ppb. The influence of air velocity on corrosion of copper was tested within the range of 0.03-35.4 cm s -1. Although the air velocity in this study was significantly lower than typical outdoor wind values, a high HNO 3 concentration of the air velocity of 35.4 cm s -1 resulted in a relatively high deposition velocity ( Vd) of 0.9 cm s -1 on the metal surface and 1.2 cm s -1 on an ideal absorbent, which would imply a limiting deposition velocity on the copper surface ( Vd,surf) of 3.6 cm s -1. Results obtained in this study emphasize the importance for future research on the corrosion effects of HNO 3 on materials as very little has so far been done in this field.

  1. Water-soluble nitrogen at the New Hampshire sea coast: HNO3, aerosols, precipitation, and fog

    NASA Astrophysics Data System (ADS)

    Jordan, C. E.; Talbot, R. W.; Keim, B. D.

    2000-11-01

    An intensive sampling program was carried out from May 1994 through November 1997 on the shore of the Gulf of Maine in New Castle, New Hampshire. Daily (24 hour averages) samples of bulk aerosol and gas phase HNO3, precipitation, and 20 aerosol size distributions were obtained. Particulate NH4+ and gas phase HNO3 were the dominant water-soluble nitrogen species in the atmosphere. There was a summer peak in the mixing ratios of both of these species. Daily mixing ratios of HNO3 and all aerosol species were highly variable, yet the annual averages tended to be similar from one year to the next. The concentrations of all the inorganic species we measured in precipitation were generally higher than those of two National Acid Deposition Program (NADP) coastal sites. In particular, the annual volume-weighted means for NO3- (22-27μmol/L) and NH4+ (11-17μmol/L) were found to be 20%-60% and 40%-90% higher, respectively, than those reported from Cape Cod, Massachusetts. Nitrate was the dominant inorganic nitrogen ion in precipitation at New Castle. In autumn, concentrations of continentally derived species in precipitation decreased substantially while sea salts increased. There was insufficient NH3 to fully neutralize HNO3 and H2SO4 in aerosols and precipitation. The overall atmospheric chemistry in this region was heavily dominated by anthropogenic pollution products. The samples collected were used in conjunction with 1000 hPa streamlines to classify sampled air masses according to their surface level transport and chemistry. Eight characteristic groups were defined; of these the three primary groups were polluted continental, ``clean'' continental, and marine. Highly variable mixing ratios of HNO3 and aerosol species were observed within each group from day to day, yet each group had a unique average chemical signature. On average, the HNO3 and aerosol mixing ratios observed in 1995 were roughly a factor of 2 lower than seen for the groups in other years. Overall

  2. Measurements of HCl and HNO3 with the new research aircraft HALO - Quantification of the stratospheric contribution to the O3 and HNO3 budget in the UT/LS

    NASA Astrophysics Data System (ADS)

    Jurkat, Tina; Kaufmann, Stefan; Voigt, Christiane; Zahn, Andreas; Schlager, Hans; Engel, Andreas; Bönisch, Harald; Dörnbrack, Andreas

    2013-04-01

    Dynamic and chemical processes modify the ozone (O3) budget of the upper troposphere/lower stratosphere, leading to locally variable O3 trends. In this region, O3 acts as a strong greenhouse gas with a net positive radiative forcing. It has been suggested, that the correlation of the stratospheric tracer hydrochloric acid (HCl) with O3 can be used to quantify stratospheric O3 in the UT/LS region (Marcy et al., 2004). The question is, whether the stratospheric contribution to the nitric acid (HNO3) budget in the UT/LS can be determined by a similar approach in order to differentiate between tropospheric and stratospheric sources of HNO3. To this end, we performed in situ measurements of HCl and HNO3 with a newly developed Atmospheric chemical Ionization Mass Spectrometer (AIMS) during the TACTS (Transport and Composition in the UTLS) / ESMVal (Earth System Model Validation) mission in August/September 2012. The linear quadrupole mass spectrometer deployed aboard the new German research aircraft HALO was equipped with a new discharge source generating SF5- reagent ions and an in-flight calibration allowing for accurate, spatially highly resolved trace gas measurements. In addition, sulfur dioxide (SO2), nitrous acid (HONO) and chlorine nitrate (ClONO2) have been simultaneously detected with the AIMS instrument. Here, we show trace gas distributions of HCl and HNO3 measured during a North-South transect from Northern Europe to Antarctica (68° N to 65° S) at 8 to 15 km altitude and discuss their latitude dependence. In particular, we investigate the stratospheric ozone contribution to the ozone budget in the mid-latitude UT/LS using correlations of HCl with O3. Differences in these correlations in the subtropical and Polar regions are discussed. A similar approach is used to quantify the HNO3 budget of the UT/LS. We identify unpolluted atmospheric background distributions and various tropospheric HNO3 sources in specific regions. Our observations can be compared to

  3. Microphysical properties of synoptic scale polar stratospheric clouds: in situ measurements of unexpectedly large HNO3 containing particles in the Arctic vortex

    NASA Astrophysics Data System (ADS)

    Molleker, S.; Borrmann, S.; Schlager, H.; Luo, B.; Frey, W.; Klingebiel, M.; Weigel, R.; Ebert, M.; Mitev, V.; Matthey, R.; Woiwode, W.; Oelhaf, H.; Dörnbrack, A.; Stratmann, G.; Grooß, J.-U.; Günther, G.; Vogel, B.; Müller, R.; Krämer, M.; Meyer, J.; Cairo, F.

    2014-05-01

    In January 2010 and December 2011 synoptic scale PSC fields were probed during seven flights of the high altitude research aircraft M-55 Geophysica within the RECONCILE (Reconciliation of essential process parameters for an enhanced predictability of Arctic stratospheric ozone loss and its climate interaction.) and the ESSenCe (ESSenCe: ESA Sounder Campaign) projects. Particle size distributions in a diameter range between 0.46 μm and 40 μm were recorded simultaneously by up to four different optical in situ instruments. Three of these particle instruments are based on the detection of forward scattered light by single particles. The fourth instrument is a grey scale optical array imaging probe. Optical particle diameters of up to 35 μm were detected with particle number densities and total particle volumes exceeding previous Arctic measurements. Also, gas phase and particle bound NOy were measured, as well as water vapor concentrations, and other variables. Two remote sensing particle instruments, the Miniature Aerosol Lidar (MAL) and the backscatter sonde (MAS, Multiwavelenght Aerosol Scatterometer) showed the synoptic scale of the encountered PSCs. The particle mode below 2 μm in size diameter has been identified as supercooled ternary solution droplets (STS). The PSC particles in the size range above 2 μm in diameter are considered to consist of nitric acid hydrates or ice, and the particles' high HNO3 content was confirmed by the NOy instrument. Assuming a particle composition of nitric acid trihydrate (NAT), the optically measured size distributions result in particle-phase HNO3 mixing ratios exceeding available stratospheric values. In particular, with respect to the denitrification by sedimentation of large HNO3-contaning particles, generally considered as NAT, our new measurements raise questions concerning composition, shape and nucleation pathways. Measurement uncertainties are discussed concerning probable overestimations of measured particle sizes

  4. Microphysical properties of synoptic-scale polar stratospheric clouds: in situ measurements of unexpectedly large HNO3-containing particles in the Arctic vortex

    NASA Astrophysics Data System (ADS)

    Molleker, S.; Borrmann, S.; Schlager, H.; Luo, B.; Frey, W.; Klingebiel, M.; Weigel, R.; Ebert, M.; Mitev, V.; Matthey, R.; Woiwode, W.; Oelhaf, H.; Dörnbrack, A.; Stratmann, G.; Grooß, J.-U.; Günther, G.; Vogel, B.; Müller, R.; Krämer, M.; Meyer, J.; Cairo, F.

    2014-10-01

    In January 2010 and December 2011, synoptic-scale polar stratospheric cloud (PSC) fields were probed during seven flights of the high-altitude research aircraft M-55 Geophysica within the RECONCILE (Reconciliation of essential process parameters for an enhanced predictability of Arctic stratospheric ozone loss and its climate interaction) and the ESSenCe (ESSenCe: ESA Sounder Campaign) projects. Particle size distributions in a diameter range between 0.46 and 40μm were recorded by four different optical in situ instruments. Three of these particle instruments are based on the detection of forward-scattered light by single particles. The fourth instrument is a grayscale optical array imaging probe. Optical particle diameters of up to 35μm were detected with particle number densities and total particle volumes exceeding previous Arctic measurements. Also, gas-phase and particle-bound NOy was measured, as well as water vapor concentrations. The optical characteristics of the clouds were measured by the remote sensing lidar MAL (Miniature Aerosol Lidar) and by the in situ backscatter sonde MAS (Multiwavelength Aerosol Scatterometer), showing the synoptic scale of the encountered PSCs. The particle mode below 2μm in size diameter has been identified as supercooled ternary solution (STS) droplets. The PSC particles in the size range above 2μm in diameter are considered to consist of nitric acid hydrates, and the particles' high HNO3 content was confirmed by the NOy instrument. Assuming a particle composition of nitric acid trihydrate (NAT), the optically measured size distributions result in particle-phase HNO3 mixing ratios exceeding available stratospheric values. Therefore the measurement uncertainties concerning probable overestimations of measured particle sizes and volumes are discussed in detail. We hypothesize that either a strong asphericity or an alternate particle composition (e.g., water ice coated with NAT) could explain our observations. In particular

  5. Measurement of OH, H2SO4, MSA, and HNO3 Aboard the P-3B Aircraft

    NASA Technical Reports Server (NTRS)

    Eisele, F. L.

    2003-01-01

    This paper addresses the measurement of OH, H2SO4, MSA, and HNO3 aboard the P-3B aircraft under the following headings: 1) Performance Report; 2) Highlights of OH, H2SO4, and MSA Measurements Made Aboard the NASA P-3B During TRACE-P; 3) Development and characteristics of an airborne-based instrument used to measure nitric acid during the NASA TRACE-P field experiment.

  6. The NO(x)-HNO3 System in the Lower Stratosphere: Insights from In Situ Measurements and Implications of the J(HNO3)-[OH] Relationship

    NASA Technical Reports Server (NTRS)

    Perkins, K. K.; Hanisco, T. F.; Cohen, R. C.; Koch, L. C.; Stimpfle, R. M.; Voss, P. B.; Bonne, G. P.; Lanzendorf, E. J.; Anderson, J. G.; Wennberg, P. O.

    2001-01-01

    During the 1997 Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission, simultaneous in situ observations of NOx and HOx radicals, their precursors, and the radiation field were obtained in the lower stratosphere. We use these observations to evaluate the primary mechanisms that control NOx-HNO3 exchange and to understand their control over the partitioning between NO2 and HNO3 in regions of continuous sunlight. We calculate NOx production (PNOx) and loss (LNOx) in a manner directly constrained by the in situ measurements and current rate constant recommendations, using approaches for representing albedo, overhead O3 and [OH] that reduce model uncertainty. We find a consistent discrepancy of 18% between modeled rates of NOx production and loss (LNOx = 1.18P(sub NOx)), which is within the measurement uncertainty of +/- 27%. The partitioning between NOx production processes is [HNO3 + OH (41 +/- 2)%; HNO3 + hv (59 +/- 2)%] and between NOx loss processes is [NO2 + OH, 90% to >97%; BrONO2 + H2O, 10% to <3%]. The steady-state description of NOx-HNO3 exchange reveals the significant influence of the tight correlation between the photolysis rate of HNO3 and [OH] established by in situ measurements throughout the lower stratosphere. Parametrizing this relationship, we find: (1) the steady-state value of [NO2](sub 24h-avg)/[HNO3] in the continuously sunlit, lower stratosphere is a function only of temperature and number density; and (2) the partitioning of NOx production between HNO3 + OH and HNO3 + hv is nearly constant throughout most of the lower stratosphere. We describe a methodology (functions of latitude, day, temperature, and pressure) for accurately predicting the steady-state value of [NO2](sub 24h-avg)/[HNO3] and the partitioning of NOx production within these regions. The results establish a metric to compare observations of [NO2](sub 24h-avg)/[HNO3] within the continuously sunlit region and provide a simple diagnostic for evaluating the

  7. HNO3 From MLS: Building on the UARS Legacy With Aura Measurements

    NASA Astrophysics Data System (ADS)

    Santee, M. L.; Manney, G. L.; Read, W. G.; Livesey, N. J.; Filipiak, M. J.; Waters, J. W.

    2003-12-01

    The Microwave Limb Sounder (MLS) onboard the Upper Atmosphere Research Satellite (UARS) measured the global distribution of stratospheric HNO3 over annual cycles for much of the 1990s, albeit with reduced sampling frequency in the latter half of the decade. The UARS MLS HNO3 dataset, unique in its scope, has previously been studied to explore the seasonal, interhemispheric, and interannual variations in the distribution of HNO3. This work, however, suffered from a number of limitations: It was confined to a single level in the lower stratosphere (465 K potential temperature), it was based on version~4 MLS data, and it relied heavily on zonal-mean comparisons of the evolution of HNO3 in the northern and southern hemispheres. Here we update and significantly expand the previous work by examining the distribution of HNO3 throughout the lower and middle stratosphere from 420 to 960 K. We use version~6 MLS HNO3 data, which, in addition to having much better precision, a larger vertical range, and better definition of the HNO3 profile, have also been corrected to account for the neglect of some excited vibrational state lines that caused the version~4 (and version~5) retrievals to substantially overestimate HNO3 peak values. In addition, we calculate averages over equivalent latitude, which are more representative of vortex behavior than zonal means, especially in the Arctic. This work provides a comprehensive picture of the behavior of stratospheric HNO3 during the UARS timeframe and establishes an important baseline for upcoming measurements from the EOS Aura mission, which will include a second-generation MLS experiment. The capability of EOS MLS is greatly enhanced over that of UARS MLS. We review the anticipated improvements in the EOS MLS HNO3 measurements (e.g., better spatial and temporal coverage, better horizontal and vertical resolution, larger vertical range), show some results from retrieval simulations, and discuss a few specific polar process studies that

  8. Kinetics of Heterogeneous Reaction of CaCO3 Particles with Gaseous HNO3 Over a Wide Range of Humidity

    SciTech Connect

    Liu, Yong; Gibson, Elizabeth R.; Cain, Jeremy P.; Wang, Hai; Grassian, Vicki H.; Laskin, Alexander

    2008-02-21

    Heterogeneous reaction kinetics of gaseous nitric acid (HNO3) with calcium carbonate (CaCO3) particles was investigated using the Particle-on-Substrate Stagnation Flow Reactor (PS-SFR). The technique utilizes the exposure of substrate deposited, isolated, and narrowly dispersed particles to a gas mixture of HNO3/H2O/N2 followed by microanalysis of individual reacted particles using computer-controlled scanning electron microscopy with energy-dispersive X-ray analysis (CCSEM/EDX). The first series of experiment was conducted at atmospheric pressure, room temperature and constant relative humidity (40%) with a median dry particle diameter pD = 0.85 μm, particle loading densities 2×104 ≤ Ns ≤ 6×106 cm–2 and free stream HNO3 concentrations of 7, 14 and 25 ppb. The apparent, pseudo first-order rate constant for the reaction was determined from oxygen enrichment in individual particles as a function of particle loading. Quantitative treatment of the data using a diffusion-kinetic model yields lower limit to the net reaction probability γnet ≥ 0.06 (×3/÷2). In the second series of experiments, HNO3 uptake on CaCO3 of the same particle size was examined over a wide range of relative humidity, from 10 to 80%. The lower limit for the net reaction probability was found to increase with an increase in the relative humidity, from γnet ≥ 0.003 at RH = 10% to 0.21 at 80%.

  9. FTIR Spectroscopy of HNO3 and NO2 Relevant to Stratospheric Wake Analysis

    NASA Technical Reports Server (NTRS)

    Abina, Rafiu A.; Misra, Prabhakar; Okabe, Hideo; Chu, P. M.; Sams, Robert L.

    1997-01-01

    The Fourier Transform Infrared (FTIR) technique has been employed to measure absolute concentrations of nitric acid (HNO3) and nitrogen dioxide (NO2) with 1/cm resolution and an absorption pathlength of 4 m under quasi-static and flow conditions at atmospheric pressure and room temperature. Water features seen under quasi-static conditions diminished in intensity under flowing conditions. Nitric acid was observed in the 1660-1760/cm range, while nitrogen dioxide was detected both in the 1536-1660 and 1213-1400/cm ranges. Concentrations of nitrogen dioxide and nitric acid were determined to be 11.9 and 4.35 parts per million (ppm), respectively, with an uncertainty of 0.2 ppm. Experiments are underway with a 10 m cell to measure the absorption of nitric acid, water, sulfur dioxide, hydrochloric acid and ammonia on various materials such as glass, teflon, stainless steel and aluminum used for implementation of the flow system. Such materials will be used for the measurements of stratospheric trace gases by the Quartz Crystal Microbalance (QCM) and Surface Acoustic Wave (SAW) devices.

  10. Retrieval of HCl and HNO3 Profiles from Ground-Based FTIR Data Using SFIT2

    NASA Technical Reports Server (NTRS)

    Connor, Brian; Wood, Stephen W.; Keys, J. Gordon; Rinsland, Curtis P.; Murcray, Frank J.

    1998-01-01

    A recently developed algorithm, SFIT2, is used to assess profile information available in ground-based FTIR measurements of HCl and HNO3 and to analyze spectra recorded at Lauder, New Zealand, and Arrival Heights, Antarctica. It is shown that the altitude range of HCI retrievals may be extended by using multiple spectral lines. A preliminary analysis of a five year record of HNO3 at Lauder shows that the Pinatubo aerosol caused a large increase of HNO3 in a layer at about 20-30 km while having little effect at lower altitude.

  11. Temperature dependent absorption cross-sections of HNO3 and N2O5

    NASA Technical Reports Server (NTRS)

    Rattigan, Oliver V.; Harwood, Matthew H.; Jones, Rod L.; Cox, Richard A.

    1994-01-01

    Absorption cross-sections for HNO3 and N2O5 have been measured in the wavelength region 220-450 nm, using a dual beam diode array spectrometer with a spectral resolution of 0.3 nm. The results for both compounds are in good agreement with recommended values at room temperature. However, the cross-sections of both HNO3 and N2O5 show a marked reduction with decreasing temperature in the range 295-233 K. The calculated photolysis rate of HNO3 at the low temperatures and high solar zenith angles characteristic of the polar winter and spring is significantly lower than previously estimated.

  12. H2SO4/HNO3/H2O Phase Diagram in Regions of Stratospheric Importance

    NASA Astrophysics Data System (ADS)

    Beyer, K. D.; Hansen, A. R.; Raddatz, N.

    2003-12-01

    We have investigated the region of the H2SO4/HNO3/H2O ternary liquid/solid phase diagram bounded by ice, nitric acid trihydrate (NAT), and sulfuric acid tetrahydrate (SAT) using differential scanning calorimetry (DSC) and infrared spectroscopy of thin films. We report measurements and analysis of the eutectic melting curves in the ternary system of the hydrates mentioned as well as the temperature of the eutectics: ice/SAT/NAT, ice/sulfuric acid hemihexahydrate (SAH)/NAT, and SAT/NAT. We report for the first time an analysis of the content of the solid phase of completely frozen samples and find that sulfuric acid octahydrate (SAO) is often present in frozen ternary samples and can be a significant portion of the solid phase. We provide a description of how the melting path of a frozen ternary sample can be predicted using the ternary phase diagram. We have parameterized our melting point data and provide equations to generate the ternary melting surface. Finally, we compare our results to the historic work of Carpenter & Lehrmann (Carpenter, C. D.; Lehrman, A. Trans. AIChE 1925, 17, 35) and to other more recent work.

  13. Enhanced Haze Ratio on Glass by Novel Vapor Texturing Method.

    PubMed

    Lee, Seunghwan; Balaji, Nagarajan; Ju, Minkyu; Park, Cheolmin; Kim, Jungmo; Chung, Sungyoun; Lee, Youn-Jung

    2016-05-01

    State-of-the-art optical trapping designs are required to enhance the light trapping capabilities of tandem thin film silicon solar cells. The wet etch process is used to texture the glass surface by dipping in diluted acidic solutions such as HNO3 (nitric acid) and HF (hydrofluoric acid). For vapor texturing, the vapor was generated by adding silicon to HF:HNO3 acidic solution. The anisotropic etching of vapor textured wafers resulted in an etching depth of about 2.78 μm with reduced reflectance of 5%. We achieved a high haze value of 74.6% at a 540 nm wavelength by increasing the etching time and HF concentration. PMID:27483862

  14. Observations of lower-stratospheric ClONO2, HNO3, and aerosol by the UARS CLAES experiment between January 1992 and April 1993

    NASA Technical Reports Server (NTRS)

    Roche, A. E.; Kumer, J. B.; Mergenthaler, J. L.; Nightingale, R. W.; Uplinger, W. G.; Ely, G. A.; Potter, J. F.; Wuebbles, D. J.; Connell, P. S.; Kinnison, D. E.

    1994-01-01

    This paper discusses simultaneous measurements of stratospheric ClONO2, HNO3, temperature, and aerosol extinction coefficient by the Cryogenic Limb Array Etalon Spectrometer (CLAES) on the NASA Upper Atmosphere Research Satellite (UARS), obtained over the period 9 January 1992 through 23 April 1993. The discussion concentrates on the stratosphere region near 21 km of particular interest to heterogeneously driven ozone depletion. For periods between 12 June and 1 September 1992 at latitudes poleward of about 60 deg S, when temperatures were below type I polar stratospheric cloud (PSC) formation thresholds throughout the lower stratosphere, CLAES observed high levels of PSCs coincident with highly depleted fields of both HNO3 and ClONO2. By 17 September, the incidence of PSCs had greatly diminished in the lower stratosphere, but both CLONO2 and HNO3 remained highly depleted. These observations are consistent with the removal of gaseous HNO3 through the formation of nitric acid trihydrate (NAT) particles and the removal of ClONO2 through heterogeneous reactions on the particle surfaces. They also suggest substantial denitrification of the lower Antarctic vortex through sedimentation of PSC particles. In the Northern Hemisphere winter of 1992/93 far fewer PSCs were observed in the Arctic lower-stratosphere vortex, which had shorter periods and more localized regions of cold temperatures. Both HNO3 and ClONO2 maintained much higher levels inside the Arctic vortex than seen in the Antarctic throughout the winter/spring period. Following 28 February 1993 when Arctic vortex temperatures rose above 195 K, ClONO2 was observed in large quantities (greater than 2.1 ppbv near 21 km) inside the vortex. The persistence of relatively high levels of HNO3 inside the Arctic spring vortex compared with the low levels seen in the Antarctic spring vortex suggest a much lower level of denitrification in the Arctic.

  15. LIMS HNO3 data above 5 mbar - Corrections based on simultaneous observations of other species

    NASA Technical Reports Server (NTRS)

    Jackman, C. H.; Kaye, J. A.; Guthrie, P. D.

    1985-01-01

    The Limb Infrared Monitor of the Stratosphere (LIMS) instrument monitored four trace gases (O3, H2O, HNO3, and NO2) and the temperature in the stratosphere and mesosphere. Recently, the seven months LIMS data, including the time from Oct. 25, 1978 to May 29, 1979, have become available to the scientific community. It is pointed out that the measurements are of great use in studying the dynamics and chemistry of the stratosphere. The LIMS HNO3 data appear to show a realistic behavior below 5 mbar, but above 5 mbar, the data appear to be too high. In the present paper, the LIMS HNO3 behavior is discussed, taking into account the reason for the unrealistic appearance of the data. Other LIMS data are used to derive HNO3 above 5 mbar through the intermediate species OH.

  16. HNO 3 analyzer by scrubber difference and the NO-ozone chemiluminescence method

    NASA Astrophysics Data System (ADS)

    Yamamoto, Masatoshi; Tamaki, Motonori; Bandow, Hiroshi; Maeda, Yasuaki

    A fast response analyzer for HNO 3 in highly polluted air is described. The time resolution attainable was 12 s. The method is based on the difference in a technique for HNO 3-scrubbed and non-scrubbed air and the reduction of HNO 3 to NO with the use of a line of catalytic converters and a method for the subsequent NO-ozone chemiluminescence. A sample air stream, in which particulates are removed with a Teflon filter, is divided into two channels. CH-1 is directly connected to the converter line, and CH-2 contains a HNO 3 scrubber packed with a nylon fiber that goes to another converter line. Each converter line is composed of a hot quartz-bead converter (QBC) and a molybdenum converter (MC) in a series. A QBC reduces HNO 3 to (NO+NO 2), which is called NO x. The MC reduces the NO x to NO. For CH-1, the analyzer detects most compounds that typically comprise NO y (J. Geophys. Res. 91 (1986) 9781). These CH-1 compounds are called NO y' hereafter (NO y-particulate nitrate) because the particulates are removed by the filter. A difference in the detector signal for the two channels indicates HNO 3. For a blank test, atmospheric air in which HNO 3 was pre-scrubbed by an extra nylon fiber was introduced to the analyzer. Variations in the blank value were 0.38±0.42 and 0.34±0.55 ppb during the high readings (NO y'-HNO 3 ) (called NO y* hereafter) (111±12 ppb, N=180), and low NO y* readings (62±8 ppb, N=180), respectively, indicating that the lowest detection limit of the analyzer is 1.1 ppb (2 σ). When the data obtained with the analyzer is compared to the data using the denuder method, a linear correlation with the regression of Y=0.973 X+0.077 ( r2=0.916 ( N=20)) in the range of 0-6.5 ppb HNO 3 is obtained, which is an excellent agreement. Atmospheric monitoring was carried out at Kobe. Although the average concentration of HNO 3 was 2.6±1.3 ppb, ca.10 ppb for a HNO 3 concentration was occasionally observed when the NO y* concentration was high, i.e., more than

  17. Measurements of HNO3 and N2O5 using ion drift-chemical ionization mass spectrometry during the MILAGRO/MCMA-2006 campaign

    NASA Astrophysics Data System (ADS)

    Zheng, J.; Zhang, R.; Fortner, E. C.; Volkamer, R. M.; Molina, L.; Aiken, A. C.; Jimenez, J. L.; Gaeggeler, K.; Dommen, J.; Dusanter, S.; Stevens, P. S.; Tie, X.

    2008-11-01

    An ion drift-chemical ionization mass spectrometer (ID-CIMS) was deployed in Mexico City between 7 and 31 March to measure gas-phase nitric acid (HNO3) and dinitrogen pentoxide (N2O5 during the Mexico City Metropolitan Area (MCMA)-2006 field campaign. The observation site was located at the Instituto Mexicano del Petróleo in the northern part of Mexico City urban area with major emissions of pollutants from residential, vehicular and industrial sources. Diurnally, HNO3 was less than 200 parts per trillion (ppt) during the night and early morning. The concentration of HNO3 increased steadily from around 09:00 a.m. central standard time (CST), reached a peak value of 0.5 to 3 parts per billion (ppb) in the early afternoon, and then declined sharply to less than half of the peak value near 05:00 p.m. CST. An inter-comparison between the ID-CIMS and an ion chromatograph/mass spectrometer (ICMS) showed a good agreement between the two HNO3 measurements (R2=0.75). The HNO3 mixing ratio was found to anti-correlate with submicron-sized aerosol nitrate, suggesting that the gas-particle partitioning process was a major factor in determining the gaseous HNO3 concentration. Losses by irreversible reactions with mineral dust and via dry deposition also could be important at this site. Most of the times during the MCMA 2006 field campaign, N2O5 was found to be below the detection limit (about 30 ppt for a 10 s integration time) of the ID-CIMS, because of high NO mixing ratio at the surface (>100 ppb) during the night. An exception occurred on 26 March 2006, when about 40 ppt N2O5 was observed during the late afternoon and early evening hours under cloudy conditions before the build-up of NO at the surface site. The results revealed that during the MCMA-2006 field campaign HNO3 was primarily produced from the reaction of OH with NO2 and regulated by gas/particle transfer and dry deposition. The production of HNO3 from N2O5 hydrolysis during the nighttime was small because of

  18. Theoretical study of atmospheric clusters: HNO3:HCl:H2O

    NASA Astrophysics Data System (ADS)

    Gomez, P. C.; Escribano, R. M.; Galvez, O.

    2009-04-01

    Water, nitric acid and hydrogen chloride play an important role in several atmospheric processes, as individual species, and also interacting in the complex reactions related to ozone depletion in polar stratospheric clouds (PSC). The atmospheric importance of the ternary system HCl:HNO3:H2O was recognized long ago [1]. It is also known that HCl attaches to the surface of PSC particles formed by nitric acid hydrates in what can be considered the first step of the heterogeneous reactions leading to the release of the active chlorine molecule [2]. Recently, HCl was detected dissolved in liquid particles with HNO3/H2O by in situ measurements in the Artic stratosphere [3]. The study of simple models including these three species at a high level of theory can be the first step towards the understanding of all possible kinds of bonding and structures that can arise among these molecules, and can constitute the embryo of more complex mixtures with higher amounts of water or variable proportions of their constituents. This kind of calculations have been successfully performed in the past [4,5]. We present in this contribution our results on the structure and spectroscopical properties of the many different ways that these molecules can be bonded in what are predicted to be thermodynamically stable species. The calculations are performed by density functional methods (B3LYP) using Dunning's quadruple-zeta augmented correlated consisted basis sets (aug-cc-pVQZ). This work has been supported by the Spanish Ministry of Education, Projects FIS2007-61686 and CTQ2008-02578/BQU. We wish to thank also CESGA (Centro de Supercomputacion de Galicia), where some of these calculations were carried out. References: [1] O. B. Toon, P. Hamill, R. P. Turco, J. Pinto. Geophys. Res. Lett. 1986, 13, 1284. [2] Molina, M. J.; Zhang, R.; Wooldridge, P. J.; McMahon, J. R.; Kim, J. E.; Chang, H. Y.; Beyer, K. D. Science 1993, 261,1418. [3] C. Weiser, K. Mauersberger, J. Schreiner, N. Larsen, F

  19. Investigation of Interfacial and Bulk Dissociation of HBr, HCl, and HNO3 Using Density Functional Theory-Based Molecular Dynamics Simulations

    SciTech Connect

    Baer, Marcel; Tobias, Douglas J.; Mundy, Christopher J.

    2014-12-18

    In this study we investigate the free energy barrier associated with the dissociation of strong acids, XH (HBr, HCl and HNO3) deprotonation, and subsequent formation of ionpairs, X–___H3O+ in the vicinity of the air-water interface. We will show that the free energy for acid dissociation for HCl and HNO3 show significant differences at the air-water than under bulk solvation conditions producing a picture where at the interface associated molecular species can be stable. For the strongest acid we consider, HBr the more traditional picture of acids is preserved in the vicinity of the air-water interface. Our results have implications for our understanding of acids, and their surface tensions at the air-water interface.

  20. MIPAS database: new HNO3 line parameters at 7.6  µm validated with MIPAS satellite measurements

    NASA Astrophysics Data System (ADS)

    Perrin, Agnès; Flaud, Jean-Marie; Ridolfi, Marco; Vander Auwera, Jean; Carlotti, Massimo

    2016-05-01

    Improved line positions and intensities have been generated for the 7.6 µm spectral region of nitric acid. They were obtained relying on a recent reinvestigation of the nitric acid band system at 7.6 µm and comparisons of HNO3 volume mixing ratio profiles retrieved from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) limb emission radiances in the 11 and 7.6 µm domains. This has led to an improved database called MIPAS-2015. Comparisons with available laboratory information (individual line intensities, integrated absorption cross sections, and absorption cross sections) show that MIPAS-2015 provides an improved description of the 7.6 µm region of nitric acid. This study should help to improve HNO3 satellite retrievals by allowing measurements to be performed simultaneously in the 11 and 7.6 µm micro-windows. In particular, it should be useful to analyze existing MIPAS and IASI spectra as well as spectra to be recorded by the forthcoming Infrared Atmospheric Sounding Interferometer - New Generation (IASI-NG) instrument.

  1. Dissolution behavior of 304 stainless steel in HNO3/HF mixtures

    NASA Astrophysics Data System (ADS)

    Covino, B. S.; Scalera, J. V.; Driscoll, T. J.; Carter, J. P.

    1986-01-01

    The dissolution behavior of type 304 stainless steel was studied in typical pickling environments in an effort to reduce the unnecessary loss of the critical metals nickel and chromium during the pickling process. Dissolution rates were determined for a 90-minute exposure to HNO3/HF solutions ranging from 0.8 M to 3.5 M HNO3 and 0.5 M to 2.6 M HF at 30°, 50°, 70°, and 90 °C and containing 0 to 0.21 M dissolved Fe, Cr, or Ni. Dissolution rates increased as a function of increasing HNO3 concentration from 0.4 M to 1.5 M HNO3, decreased at higher HNO3 concentrations, and increased with increasing HF concentration. Experiments to determine the effect of temperature on the dissolution reaction gave a lower activation energy for solutions with higher HNO3 concentrations. The dissolved Fe and Cr decreased the dissolution rate of 304 stainless steel, while dissolved Ni had essentially no effect. The Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) studies of films resulting from exposure to several HNO3/HF solutions indicated that the fluoride did not penetrate the thin nonprotective films but remained on the outer surface of the film. The scanning Auger microscopy (SAM) studies indicated that the fluoride was uniformly distributed over the surface. Both the dissolution and surface studies are consistent with a dissolution process which is controlled by reactions occurring either in solution or at the film-solution interface.

  2. Unveiling the shape-diversified silicon nanowires made by HF/HNO3 isotropic etching with the assistance of silver

    NASA Astrophysics Data System (ADS)

    Chen, Chia-Yun; Wong, Ching-Ping

    2014-12-01

    Hydrofluoric (HF)/nitric (HNO3)/acetic (CH3COOH) acid, normally referred to as the HNA method, is a widely utilized technique for performing isotropic etching on silicon (Si) in industrial Si-based processing and device construction. Here, we reported a novel etching strategy based on a HF/HNO3 process with the assistance of silver (Ag) nano-seeds, offering good controllability in preparing diversified Si nanostructure arrays with particularly smooth top surfaces. The involved mechanism was visualized by systematically investigating both the time and temperature dependencies on the etching kinetics with various ratios of HF to HNO3. Moreover, by testing different Ag+-ion containing oxidants on Si etching, we have re-examined the state-of-the-art metal-assisted chemical etching (MaCE) using HF/AgNO3 etchants. In contrast with previous reports, we found that the interplay of hole injections from Ag+ and NO3- ions to the valence band of Si collectively contributes to the unidirectional dissolution of Si. Finally, we explored the engineering of the Ag nano-seeds to regularize the orientation of the etched nanowires formed on non-Si (100) wafers, which further provides a reliable pathway for constructing the desired morphologies of one-dimensional Si nanostructures regardless of wafer orientation.Hydrofluoric (HF)/nitric (HNO3)/acetic (CH3COOH) acid, normally referred to as the HNA method, is a widely utilized technique for performing isotropic etching on silicon (Si) in industrial Si-based processing and device construction. Here, we reported a novel etching strategy based on a HF/HNO3 process with the assistance of silver (Ag) nano-seeds, offering good controllability in preparing diversified Si nanostructure arrays with particularly smooth top surfaces. The involved mechanism was visualized by systematically investigating both the time and temperature dependencies on the etching kinetics with various ratios of HF to HNO3. Moreover, by testing different Ag

  3. Quantum chemical study of ternary mixtures of: HNO3:H2SO4:H2O

    NASA Astrophysics Data System (ADS)

    Verdes, M. A.; Gómez, P. C.; Gálvez, O.

    2009-04-01

    Water, nitric acid and sulfuric acid are important atmospheric species as individual species and as hydrogen-bonded aggregates involved in many physical-chemical processes both superficial and bulk. The importance of heterogeneous chemical reactions taking place on ice surfaces, either solid water or solid water plus nitric or sulfuric acid, is well established now in relation to the ozone-depleting mechanisms. Also the importance of liquid droplets formed by HNO3.H2SO4.H2O as components of PSC was soon recognized [1-3]. Finally the physical properties of finely divided aqueous systems is an interesting and active field of research in which theoretical information on the microphysical domain systems may help to understand and rationalize the wealth of experimental information. This can also be the initial step in the study of more complex mixtures with higher amounts of water or variable proportions of their constituents. This kind of calculations have been successfully performed in the past[4]. We present here our results on the structure and spectroscopic and thermodynamic properties of the energy-lowest lying structures among those thermodynamically stable formed by linking the acids plus water. The calculations have been carried out by means of DFT methods (in particular the successful B3LYP) using different basis sets that contain appropriate sets of polarization and diffuse functions up to quadruple-Z quality (Dunninǵs aug-cc-pVQZ). Careful assessment of the dependability of the methodology used has been carried out. This work has been supported by the Spanish Ministry of Education, Projects FIS2007-61686 and CTQ2008-02578/BQU References: [1] Carslaw, K. S. et al.: Geophys. Res. Lett. 21, 2479-2482, 1994 [2] Drdla, K. Et al. :Geophys. Res. Lett. 21, 2473-2478, 1994 [3] Tabazadeh, A. et al.: Geophys. Res. Lett 21, 1619-1622, 1994 [4] Escribano, R et al.: J. J. Chem. Phys A 2003, 107, 652.

  4. Influence of monolayer amounts of HNO3 on the evaporation rate of H2O over ice in the range 179 to 208 K: a quartz crystal microbalance study.

    PubMed

    Delval, Christophe; Rossi, Michel J

    2005-08-18

    The evaporation flux J(ev) of H2O from thin H2O ice films containing between 0.5 and 7 monolayers of HNO3 has been measured in the range 179 to 208 K under both molecular and stirred flow conditions in isothermal experiments. FTIR absorption of the HNO3/H2O condensate revealed the formation of metastable alpha-NAT (HNO(3).3H2O) converting to stable beta-NAT at 205 K. After deposition of HNO3 for 16-80 s on a 1 mum thick pure ice film at a deposition rate in the range (6-60) x 10(12) molecules s(-1) the initial evaporative flux J(ev)(H2O) was always that of pure ice. J(ev)(H2O) gradually decreased with the evaporation of H2O and the concomitant increase of the average mole fraction of HNO3, chi(HNO3), indicating the presence of an amorphous mixture of H2O/HNO3 that is called complexed or (c)-ice whose vapor pressure is that of pure ice. The final value of J(ev) was smaller by factors varying from 2.7 to 65 relative to pure ice. Depending on the doping conditions and temperature of the ice film the pure ice thickness d(D) of the ice film for which J(ev) < 0.85J(ev)(pure ice) varied between 130 and 700 nm compared to the 1000 nm thick original ice film at 208 and 191 K, respectively, in what seems to be an inverse temperature dependence. There exist three different types of H2O molecules under the present experimental conditions, namely (a) free H2O corresponding to pure ice, (b) complexed H2O or c-ice, and (c) H2O molecules originating from the breakup of NAT or amorphous H2O/HNO3 mixtures. The significant decrease of J(ev)(H2O) with increasing chi(HNO3) leads to an increase of the evaporative lifetime of atmospheric ice particles in the presence of HNO3 and may help explain the occurrence of persistent and/or large contaminated ice particles at certain atmospheric conditions. PMID:16834079

  5. Kinetics of Acid-Catalyzed Dehydration of Cyclic Hemiacetals in Organic Aerosol Particles in Equilibrium with Nitric Acid Vapor.

    PubMed

    Ranney, April P; Ziemann, Paul J

    2016-04-28

    Previous studies have shown that 1,4-hydroxycarbonyls, which are often major products of the atmospheric oxidation of hydrocarbons, can undergo acid-catalyzed cyclization and dehydration in aerosol particles to form highly reactive unsaturated dihydrofurans. In this study the kinetics of dehydration of cyclic hemiacetals, the rate-limiting step in this process, was investigated in a series of environmental chamber experiments in which secondary organic aerosol (SOA) containing cyclic hemiacetals was formed from the reaction of n-pentadecane with OH radicals in dry air in the presence of HNO3. A particle beam mass spectrometer was used to monitor the formation and dehydration of cyclic hemiacetals in real time, and SOA and HNO3 were quantified in filter samples by gravimetric analysis and ion chromatography. Measured dehydration rate constants increased linearly with increasing concentration of HNO3 in the gas phase and in SOA, corresponding to catalytic rate constants of 0.27 h(-1) ppmv(-1) and 7.0 h(-1) M(-1), respectively. The measured Henry's law constant for partitioning of HNO3 into SOA was 3.7 × 10(4) M atm(-1), ∼25% of the value for dissolution into water, and the acid dissociation constant was estimated to be <8 × 10(-4), at least a factor of 10(4) less than that for HNO3 in water. The results indicate that HNO3 was only weakly dissociated in the SOA and that dehydration of cyclic hemiacetals was catalyzed by molecular HNO3 rather than by H(+). The Henry's law constant and kinetics relationships measured here can be used to improve mechanisms and models of SOA formation from the oxidation of hydrocarbons in dry air in the presence of NOx, which are conditions commonly used in laboratory studies. The fate of cyclic hemiacetals in the atmosphere, where the effects of higher relative humidity, organic/aqueous phase separation, and acid catalysis by molecular H2SO4 and/or H(+) are likely to be important, is discussed. PMID:27043733

  6. Study of the laser-induced decomposition of HNO3/ 2-Nitropropane mixture at static high pressures

    NASA Astrophysics Data System (ADS)

    Bouyer, Viviane; Hébert, Philippe; Doucet, Michel

    2007-06-01

    HNO3 / 2-Nitropropane is a well known energetic material on which Raman spectroscopy measurements at static high pressure in a diamond anvil cell (DAC) have already been conducted at CEA/LE RIPAULT in order to examine the evolution of the mixture as a function of composition and pressure [1]. The purpose of the work presented here was to study the laser-induced decomposition of these energetic materials at static high pressures by measuring the combustion front propagation rate in the DAC. First of all, the feasibility of the experimental device was checked with a well known homogeneous explosive, nitromethane. Our results were consistent with those of Rice and Foltz [2]. Then, we investigated the initiation of NA / 2NP mixture as a function of nitric acid proportion, for a given pressure. We chose the mixture for which both the combustion propagation rate and detonation velocity are maximum and we examined the evolution of the front propagation velocity as a function of pressure and energy deposit. [1] Hebert, P., Regache, I., and Lalanne, P., ``High-Pressure Raman Spectroscopy study of HNO3 / 2-Nitropropane Mixtures. Influence of the Composition.'' Proceedings of the 42nd European High-Pressure Research Group Meeting, Lausanne, Suisse, 2004 [2] Rice, S.F., et al., Combustion and Flame 87 (1991) 109-122.

  7. Removal of uranium and gross radioactivity from coal bottom ash by CaCl2 roasting followed by HNO3 leaching.

    PubMed

    Lei, Xuefei; Qi, Guangxia; Sun, Yinglong; Xu, Hui; Wang, Yi

    2014-07-15

    A roast-leach method using CaCl2 and HNO3 to remove uranium and gross radioactivity in coal bottom ash was investigated. Heat treatment of the ash with 100% CaCl2 (900°C, 2h) significantly enhanced uranium leachability (>95%) compared with direct acid-leaching (22.6-25.5%). The removal efficiency of uranium and gross radioactivity increased steeply with increasing CaCl2 content, from 10% to 50%, and a HNO3 leaching time from 5 min to 1h, but remained nearly constant or decreased slightly with increasing CaCl2 dosage >50% or acid-leaching time >1h. The majority of the uranium (87.3%), gross α (92.9%) and gross β (84.9%) were removed under the optimized roast-leach conditions (50% CaCl2, 1M HNO3 leaching for 1h). The mineralogical characteristics of roasted clinker indicated that molten CaCl2 promoted the incorporation of Ca into silica and silicates and resulted in its progressive susceptibility to acid attack. Uranium and other radionuclides, most likely present in the form of silicates or in association with miscellaneous silicates in the highest density fraction (>2.5g mL(-1)), were probably leached out as the result of the acid decomposition of newly formed "gelatinizing silicates". PMID:24922094

  8. Simultaneous Observations fo Polar Stratospheric Clouds and HNO3 over Scandinavia in January, 1992

    NASA Technical Reports Server (NTRS)

    Massie, S. T.; Santee, M. L.; Read, W. G.; Grainger, R. G.; Lambert, A.; Mergenthaler, J. L.; Dye, J. E.; Baumbardner, D.; Randel, W. J.; Tabazadeh, A.; Tie, X.; Pan, L.; Figarol, F.; Wu, F.; Brasseur, G. P.

    1996-01-01

    Simultaneous observations of Polar Stratospheric Cloud aerosol extinction and HNO3 mixing ratios over Scandinavia are examined for January 9-10, 1992. Data measured by the Microwave Limb Sounder (MLS), Cryogenic Limb Array Etalon, Spectrometer (CLAES), and Improved Stratospheric and Mesospheric Sounder (ISAMA) experiments on the Upper Atmosphere Research Satellite (UARS) are examined at locations adjacent to parcel trajectory positions.

  9. Observations of total RONO2 over the boreal forest: NOx sinks and HNO3 sources

    NASA Astrophysics Data System (ADS)

    Browne, E. C.; Min, K.-E.; Wooldridge, P. J.; Apel, E.; Blake, D. R.; Brune, W. H.; Cantrell, C. A.; Cubison, M. J.; Diskin, G. S.; Jimenez, J. L.; Weinheimer, A. J.; Wennberg, P. O.; Wisthaler, A.; Cohen, R. C.

    2013-05-01

    In contrast with the textbook view of remote chemistry where HNO3 formation is the primary sink of nitrogen oxides, recent theoretical analyses show that formation of RONO2 (ΣANs) from isoprene and other terpene precursors is the primary net chemical loss of nitrogen oxides over the remote continents where the concentration of nitrogen oxides is low. This then increases the prominence of questions concerning the chemical lifetime and ultimate fate of ΣANs. We present observations of nitrogen oxides and organic molecules collected over the Canadian boreal forest during the summer which show that ΣANs account for ~20% of total oxidized nitrogen and that their instantaneous production rate is larger than that of HNO3. This confirms the primary role of reactions producing ΣANs as a control over the lifetime of NOx (NOx = NO + NO2) in remote, continental environments. However, HNO3 is generally present in larger concentrations than ΣANs indicating that the atmospheric lifetime of ΣANs is shorter than the HNO3 lifetime. We investigate a range of proposed loss mechanisms that would explain the inferred lifetime of ΣANs finding that in combination with deposition, two processes are consistent with the observations: (1) rapid ozonolysis of isoprene nitrates where at least ~40% of the ozonolysis products release NOx from the carbon backbone and/or (2) hydrolysis of particulate organic nitrates with HNO3 as a product. Implications of these ideas for our understanding of NOx and NOy budget in remote and rural locations are discussed.

  10. Observations of total RONO2 over the boreal forest: NOx sinks and HNO3 sources

    NASA Astrophysics Data System (ADS)

    Browne, E. C.; Min, K.-E.; Wooldridge, P. J.; Apel, E.; Blake, D. R.; Brune, W. H.; Cantrell, C. A.; Cubison, M. J.; Diskin, G. S.; Jimenez, J. L.; Weinheimer, A. J.; Wennberg, P. O.; Wisthaler, A.; Cohen, R. C.

    2013-01-01

    In contrast with the textbook view of remote chemistry where HNO3 formation is the primary sink of nitrogen oxides, recent theoretical analyses show that formation of RONO2 (ΣANs) from isoprene and other terpene precursors is the primary net chemical loss of nitrogen oxides over the remote continents where the concentration of nitrogen oxides is low. This then increases the prominence of questions concerning the chemical lifetime and ultimate fate of ΣANs. We present observations of nitrogen oxides and organic molecules collected over the Canadian boreal forest during the summer that show that ΣANs account for ~ 20% of total oxidized nitrogen and that their instantaneous production rate is larger than that of HNO3. This confirms the primary role of reactions producing ΣANs as a control over the lifetime of NOx (NOx = NO + NO2) in remote, continental environments. However, HNO3 is generally present in larger concentrations than ΣANs indicating that the atmospheric lifetime of ΣANs is shorter than the HNO3 lifetime. We investigate a range of proposed loss mechanisms that would explain the inferred lifetime of ΣANs finding that in combination with deposition, two processes are consistent with the observations: (1) rapid ozonolysis of isoprene nitrates where at least ~ 40% of the ozonolysis products release NOx from the carbon backbone and/or (2) hydrolysis of particulate organic nitrates with HNO3 as a product. Implications of these ideas for our understanding of NOx and NOy budget in remote and rural locations are discussed.

  11. Aerodynamic gradient measurements of the NH3-HNO3-NH4NO3 triad using a wet chemical instrument: an analysis of precision requirements and flux errors

    NASA Astrophysics Data System (ADS)

    Wolff, V.; Trebs, I.; Ammann, C.; Meixner, F. X.

    2010-02-01

    The aerodynamic gradient method is widely used for flux measurements of ammonia, nitric acid, particulate ammonium nitrate (the NH3-HNO3-NH4NO3 triad) and other water-soluble reactive trace compounds. The surface exchange flux is derived from a measured concentration difference and micrometeorological quantities (turbulent exchange coefficient). The significance of the measured concentration difference is crucial for the significant determination of surface exchange fluxes. Additionally, measurements of surface exchange fluxes of ammonia, nitric acid and ammonium nitrate are often strongly affected by phase changes between gaseous and particulate compounds of the triad, which make measurements of the four individual species (NH3, HNO3, NH4+, NO3- necessary for a correct interpretation of the measured concentration differences. We present here a rigorous analysis of results obtained with a multi-component, wet-chemical instrument, able to simultaneously measure gradients of both gaseous and particulate trace substances. Basis for our analysis are two field experiments, conducted above contrasting ecosystems (grassland, forest). Precision requirements of the instrument as well as errors of concentration differences and micrometeorological exchange parameters have been estimated, which, in turn, allows the establishment of thorough error estimates of the derived fluxes of NH3, HNO3, NH4+, and NO3-. Derived median flux errors for the grassland and forest field experiments were: 39% and 50% (NH3), 31% and 38% (HNO3), 62% and 57% (NH4+), and 47% and 68% (NO3-), respectively. Additionally, we provide the basis for using field data to characterize the instrument performance, as well as subsequent quantification of surface exchange fluxes and underlying mechanistic processes under realistic ambient measurement conditions.

  12. Aerodynamic gradient measurements of the NH3-HNO3-NH4NO3 triad using a wet chemical instrument: an analysis of precision requirements and flux errors

    NASA Astrophysics Data System (ADS)

    Wolff, V.; Trebs, I.; Ammann, C.; Meixner, F. X.

    2009-10-01

    The aerodynamic gradient method is widely used for flux measurements of ammonia, nitric acid, particulate ammonium nitrate (the NH3-HNO3-NH4NO3 triad) and other water-soluble reactive trace compounds. The surface exchange flux is derived from a measured concentration difference and micrometeorological quantities (turbulent exchange coefficient). The significance of the measured concentration difference is crucial for the significant determination of surface exchange fluxes. Additionally, measurements of surface exchange fluxes of ammonia, nitric acid and ammonium nitrate are often strongly affected by phase changes between gaseous and particulate compounds of the triad, which make measurements of the four individual species (NH3, HNO3, NH4+, NO3-) necessary for a correct interpretation of the measured concentration differences. We present here a rigorous analysis of results obtained with a multi-component, wet-chemical instrument, able to simultaneously measure gradients of both gaseous and particulate trace substances. Basis for our analysis are two field experiments, conducted above contrasting ecosystems (grassland, forest). Precision requirements of the instrument as well as errors of concentration differences and micrometeorological exchange parameters have been estimated, which, in turn, allows the establishment of thorough error estimates of the derived fluxes of NH3, HNO3, NH4+, and NO3-. Derived median flux errors for the grassland and forest field experiments were: 39 and 50% (NH3), 31 and 38% (HNO3), 62 and 57% (NH4+), and 47 and 68% (NO3-), respectively. Additionally, we provide the basis for using field data to characterize the instrument performance, as well as subsequent quantification of surface exchange fluxes and underlying mechanistic processes under realistic ambient measurement conditions.

  13. Quantum chemical study of atmospheric aggregates: HCl•HNO3•H2SO4.

    PubMed

    Verdes, Marian; Paniagua, Miguel

    2014-06-01

    HCl, HNO3 and H2SO4 are implicated in atmospheric processes in areas such as polar stratospheric clouds in the stratosphere. Ternary complexes of HCl, HNO3 and H2SO4 were investigated by ab initio calculations at B3LYP level of theory with aug-cc-pVTZ and aug-cc-pVQZ basis sets, taking into account basis set superposition error (BSSE). The results were assessed in terms of structures (five hexagonal cyclic structures and two quasi-pentagonal cyclic structures), inter-monomeric parameters (all ternary complexes built three hydrogen bonds), energetics (seven minima obtained), infrared harmonic vibrational frequencies (red shifting of complexes from monomers), and relative stability of complexes, which were favorable when the temperature decreases under stratospheric conditions, from 298 K to 188 K, and in concrete, at 210 K, 195 K and 188 K. PMID:24844391

  14. The transport of atmospheric NOx and HNO3 over Cape Town

    NASA Astrophysics Data System (ADS)

    Abiodun, B. J.; Ojumu, A. M.; Jenner, S.; Ojumu, T. V.

    2014-01-01

    Cape Town, the most popular tourist city in Africa, usually experiences air pollution with unpleasant odour in winter. Previous studies have associated the pollution with local emission of pollutants within the city. The present study examines the transport of atmospheric pollutants (NOx and HNO3) over South Africa and shows how the transport of pollutants from the Mpumalanga Highveld, a major South African industrial area, may contribute to the pollution in Cape Town. The study analysed observation data (2001-2008) from the Cape Town air-quality network and simulation data (2001-2004) from a regional climate model (RegCM) over southern Africa. The simulation accounts for the influence of complex topography, atmospheric conditions, and atmospheric chemistry on emission and transport of pollutants over southern Africa. Flux budget analysis was used to examine whether Cape Town is a source or sink for NOx and HNO3 during the extreme pollution events. The results show that extreme pollution events in Cape Town are associated with the lower level (surface - 850 hPa) transport of NOx from the Mpumalanga Highveld to Cape Town, and with a tongue of high concentration of HNO3 that extends from the Mpumalanga Highveld to Cape Town along the south coast of South Africa. The prevailing atmospheric conditions during the extreme pollution events feature an upper-level (700 hPa) anticyclone over South Africa and a lower-level col over Cape Town. The anticyclone induces a strong subsidence motion, which prevents vertical mixing of the pollutants and caps high concentration of pollutants close to the surface as they are transported from the Mpumalanga Highveld toward Cape Town. The col accumulates the pollutants over the city. This study shows that Cape Town can be a sink for the NOx and HNO3 during extreme pollution events and suggests that the accumulation of pollutants transported from other areas (e.g. the Mpumalanga Highveld) may contribute to the air pollution in Cape Town.

  15. Arsenic bioaccessibility in contaminated soils: Coupling in vitro assays with sequential and HNO3 extraction.

    PubMed

    Li, Shi-Wei; Li, Jie; Li, Hong-Bo; Naidu, Ravi; Ma, L Q

    2015-09-15

    Arsenic bioaccessibility varies with in vitro methods and soils. Four assays including unified BARGE method (UBM), Solubility Bioaccessibility Research Consortium method (SBRC), in vitro gastrointestinal method (IVG), and physiologically based extraction test (PBET), were used to determine As bioaccessibility in 11 contaminated soils (22-4,172 mg kg(-1)). The objective was to understand how bioaccessible As by different methods was related to different As pools based on sequential extraction and 0.43 M HNO3 extraction. Arsenic bioaccessibility was 7.6-25, 2.3-49, 7.3-44, and 1.3-38% in gastric phase (GP), and 5.7-53, 0.46-33, 2.3-42, and 0.86-43% in intestinal phase (IP) for UBM, SBRC, IVG, and PBET, respectively, with HNO3-extractable As being 0.90-60%. Based on sequential extraction, As was primarily associated with amorphous (AF3; 17-79%) and crystallized Fe/Al oxides (CF4; 6.4-73%) while non-specifically sorbed (NS1), specifically sorbed (SS2), and residual fractions (RS5) were 0-10%, 3.4-20% and 3.2-25%. Significant correlation was found between As bioaccessibility by PBET and NS1+SS2 (R(2) = 0.55-0.69), and UBM-GP and NS1 + SS2 + AF3 (R(2) = 0.58), indicating PBET mostly targeted As in NS1+SS2 whereas UBM in NS1 + SS2 + AF3. HNO3-extractable As was correlated to bioaccessible As by four methods (R(2) = 0.42-0.72) with SBRC-GP having the best correlation. The fact that different methods targeted different As fractions in soils suggested the importance of validation by animal test. Our data suggested that HNO3 may have potential to determine bioaccessible As in soils. PMID:25897696

  16. Simulations of the Vertical Redistribution of HNO3 by NAT or NAD PSCs: The Sensitivity to the Number of Cloud Particles Formed and the Cloud Lifetime

    NASA Technical Reports Server (NTRS)

    Jensen, Eric J.; Tabazadeh, Azadeh; Drdla, Katja; Toon, Owen B.; Gore, Warren J. (Technical Monitor)

    2000-01-01

    Recent satellite and in situ measurements have indicated that limited denitrification can occur in the Arctic stratosphere. In situ measurements from the SOLVE campaign indicate polar stratospheric clouds (PSCs) composed of small numbers (about 3 x 10^ -4 cm^-3) of 10-20 micron particles (probably NAT or NAD). These observations raise the issue of whether low number density NAT PSCs can substantially denitrify the air with reasonable cloud lifetimes. In this study, we use a one dimensional cloud model to investigate the verticle redistribution of HNO3 by NAT/NAD PSCs. The cloud formation is driven by a temperature oscillation which drops the temperature below the NAT/NAD formation threshold (about 195 K) for a few days. We assume that a small fraction of the available aerosols act as NAT nuclei when the saturation ratio of HNO3 over NAT(NAD) exceeds 10(l.5). The result is a cloud between about 16 and 20 km in the model, with NAT/NAD particle effective radii as large as about 10 microns (in agreement with the SOLVE data). We find that for typical cloud lifetimes of 2-3 days or less, the net depletion of HNO3 is no more than 1-2 ppbv, regardless of the NAT or NAD particle number density. Repeated passes of the air column through the cold pool build up the denitrification to 3-4 ppbv, and the cloud altitude steadily decreases due to the downward transport of nitric acid. Increasing the cloud lifetime results in considerably more effective denitrification, even with very low cloud particle number densities. As expected, the degree of denitrification by NAT clouds is much larger than that by NAD Clouds. Significant denitrification by NAD Clouds is only possible if the cloud lifetime is several days or more. The clouds also cause a local maximum HNO3 mixing ratio at cloud base where the cloud particles sublimate.

  17. Observed levels and trends of gaseous SO2 and HNO3 at Mt. Waliguan, China: results from 1997 to 2009.

    PubMed

    Lin, Weili; Xu, Xiaobin; Yu, Xiaolan; Zhang, Xiaochun; Huang, Jianqing

    2013-04-01

    Long-term measurements of SO2 and HNO3, particularly those from the background sites, are rarely reported. We present for the first time the long-term measurements of SO2 and HNO3 at Waliguan (WLG), the only global baseline station in the back-land of the Eurasian Continent. The concentrations of SO2 and HNO3 were observed at WLG from 1997 to 2009. The observed annual mean concentrations of SO2 and HNO3 at WLG were 1.28 +/- 0.41 and 0.22 +/- 0.19 microg/m3, respectively. The HNO3 concentrations were much higher in warmer seasons than in colder seasons, while the SO2 concentrations showed a nearly reversed seasonal pattern. In most months, the concentration of HNO3 was significantly correlated with that of SO2, suggesting that some common factors influence the variations of both gases and the precursors of HNO3 may partially be from the SO2-emitting sources. The SO2 concentration had a very significant (P < 0.0001) decreasing trend (-0.2 microg/(m3 x yr)) in 1997-2002, but a significant (P < 0.05) increasing trend (+0.06 microg/(m3 x yr)) in 2003-2009. The HNO3 concentration showed no statistically significant trend during 1997-2009. While the decrease of SO2 in 1997-2002 agrees with the trend of global SO2 emissions, the increase in 2003-2009 is not consistent with the decreasing trends in many other regions over the world. Trajectory analysis suggests that the airmasses from the northern Qinghai-Tibetan Plateau and the Takla Makan Desert regions contributed significantly to the increasing trends of SO2 and HNO3 at WLG in 2003-2009, with a rate of +0.13 microg/(m3 x yr) and +0.007 microg/(m3 x yr), respectively. PMID:23923781

  18. Evidence that nitric acid increases relative humidity in low-temperature cirrus clouds.

    PubMed

    Gao, R S; Popp, P J; Fahey, D W; Marcy, T P; Herman, R L; Weinstock, E M; Baumgardner, D G; Garrett, T J; Rosenlof, K H; Thompson, T L; Bui, P T; Ridley, B A; Wofsy, S C; Toon, O B; Tolbert, M A; Kärcher, B; Peter, Th; Hudson, P K; Weinheimer, A J; Heymsfield, A J

    2004-01-23

    In situ measurements of the relative humidity with respect to ice (RHi) and of nitric acid (HNO3) were made in both natural and contrail cirrus clouds in the upper troposphere. At temperatures lower than 202 kelvin, RHi values show a sharp increase to average values of over 130% in both cloud types. These enhanced RHi values are attributed to the presence of a new class of HNO3-containing ice particles (Delta-ice). We propose that surface HNO3 molecules prevent the ice/vapor system from reaching equilibrium by a mechanism similar to that of freezing point depression by antifreeze proteins. Delta-ice represents a new link between global climate and natural and anthropogenic nitrogen oxide emissions. Including Delta-ice in climate models will alter simulated cirrus properties and the distribution of upper tropospheric water vapor. PMID:14739457

  19. Can laboratory data explain field observations: The fluxes of HNO3 and HNO4 from snow in the lab and in Antarctica

    NASA Astrophysics Data System (ADS)

    Bartels-Rausch, Thorsten

    2015-04-01

    equilibrium partitioning of HNO3 and HNO4 that one would expect based on selected laboratory data. Both, adsorption to the surface of the snow and uptake to the bulk forming a solid solution are discussed (HNO3 only). Further, I address the question, if the snow holds enough HNO3 and HNO4 at its surface or in its bulk (HNO3 only) to fuel the observed emissions. Thus both equilibrium conditions and molecular flux budgets are discussed. These calculations show that adsorption/desorption can indeed explain the observed mixing ratio in the Antarctic boundary layer. Release from a solid solution seems to be too slow. Jones, A. E., Brough, N., Anderson, P. S., & Wolff, E. W. (2014). HO2NO2 and HNO3 in the coastal Antarctic winter night: a "lab-in-the-field" experiment. Acpd, 14(9), 12771-12796. Interactive comment on "HO2NO2 and HNO3 in the coastal Antarctic winter night: a "lab-in-the-field" experiment" by A. E. Jones et al. , T. Bartels-Rausch thorsten.bartels-rausch@psi.ch Received and published: 11 July 2014 Legrand, M., Preunkert, S., Frey, M., Bartels-Rausch, T., Kukui, A., King, M. D., et al. (2014). Large mixing ratios of atmospheric nitrous acid (HONO) at Concordia (East Antarctic plateau) in summer: a strong source from surface snow? Atmospheric Chemistry and Physics Discussions, 14(8), 11749-11785. doi:10.5194/acpd-14-11749-2014 Ulrich, T., Ammann, M., Leutwyler, S., & Bartels-Rausch, T. (2012). The adsorption of peroxynitric acid on ice between 230 K and 253 K. Atmospheric Chemistry and Physics, 12(4), 1833-1845. doi:10.5194/acp-12-1833-2012

  20. Growth of nitric acid hydrates on thin sulfuric acid films

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Middlebrook, Ann M.; Wilson, Margaret A.; Tolbert, Margaret A.

    1994-01-01

    Type I polar stratospheric clouds (PSCs) are thought to nucleate and grow on stratospheric sulfate aerosols (SSAs). To model this system, thin sulfuric acid films were exposed to water and nitric acid vapors (1-3 x 10(exp -4) Torr H2O and 1-2.5 x 10(exp -6) Torr HNO3) and subjected to cooling and heating cycles. Fourier Transform Infrared (FTIR) spectroscopy was used to probe the phase of the sulfuric acid and to identify the HNO3/H2O films that condensed. Nitric acid trihydrate (NAT) was observed to grow on crystalline sulfuric acid tetrahydrate (SAT) films. NAT also condensed in/on supercooled H2SO4 films without causing crystallization of the sulfuric acid. This growth is consistent with NAT nucleation from ternary solutions as the first step in PSC formation.

  1. Growth of nitric acid hydrates on thin sulfuric acid films

    NASA Astrophysics Data System (ADS)

    Iraci, Laura T.; Middlebrook, Ann M.; Wilson, Margaret A.; Tolbert, Margaret A.

    1994-05-01

    Type I polar stratospheric clouds (PSCs) are thought to nucleate and grow on stratospheric sulfate aerosols (SSAs). To model this system, thin sulfuric acid films were exposed to water and nitric acid vapors (1 - 3 × 10-4 Torr H2O and 1 - 2.5 × 10-6 Torr HNO3) and subjected to cooling and heating cycles. FTIR spectroscopy was used to probe the phase of the sulfuric acid and to identify the HNO3/H2O films that condensed. Nitric acid trihydrate (NAT) was observed to grow on crystalline sulfuric acid tetrahydrate (SAT) films. NAT also condensed in/on supercooled H2SO4 films without causing crystallization of the sulfuric acid. This growth is consistent with NAT nucleation from ternary solutions as the first step in PSC formation.

  2. Temperature dependence of HNO3 absorption in the 11.3-micron region

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Bonomo, F. S.; Valero, F. P. J.; Goorvitch, D.; Boese, R. W.

    1981-01-01

    Laboratory spectra have been obtained for HNO3 with a Michelson-type Fourier transform interferometer using absorption cells with path lengths of 10.3, 25.5, and 49.8 cm at temperatures of 240, 248, 283, and 294 K. The measurements lead to a total band intensity value of 642 plus or minus 5% per sq cm amagat, which is a temperature independent value after the gas density correction has been made. However, the temperature dependence of the spectral absorption coefficients is apparent in the 885 kayser region.

  3. Materials compatibility for 238Pu-HNO3/HF solution containment: 238Pu aqueous processing

    NASA Astrophysics Data System (ADS)

    Reimus, M. A.; Pansoy-Hjelvik, M. E.; Silver, G.; Brock, J.; Nixon, J.; Ramsey, K. B.; Moniz, P.

    2000-07-01

    The Power Source Technologies Group at Los Alamos National Laboratory is building a 238Pu Aqueous Scrap Recovery Line at the Plutonium Facility. The process line incorporates several unit operations including dissolution, filtration, ion exchange, and precipitation. During 1997-1999, studies were carried out to determine the chemistry used in the full-scale process. Other studies focussed on the engineering design of the operation. Part of the engineering design was to determine, in compatibility studies, the materials for reaction and storage vessels which will contain corrosive 238Pu-HNO3/HF solutions. The full-scale line is to be operational by the end of year 2000.

  4. A Chamber Investigation of Nitric Acid-Soot Aerosol Chemistry at 298 K

    SciTech Connect

    Disselkamp, Robert S.; Carpenter, Michael A.; Cowin, James P.

    2000-10-02

    Long-pathlength infrared absorption spectroscopy was used to investigate nitric acid-soot aerosol chemistry at 298 K and 0.5 % relative humidity. Experiments were performed by introducing nitric acid vapor (PHNO3~3 Pa, Ptotal~40 kPa) into a teflon-coated chamber and initiating acquisition of infrared spectra at 3 minute time intervals. After 36 minutes of data collection, soot powder was rapidly expanded into nitric acid contained in the chamber to generate a soot-HNO3 aerosol. Infrared spectra collected before, and after, soot introduction to the chamber were used to characterize chamber wall reaction processes and soot aerosol chemistry, respectively. Three soot types were investigated (Degussa FW2, Cabot Monarch 1000, and crystalline graphite), each yielding similar chemistry. Upon soot introduction to the chamber both HNO3 uptake and NO2 production occurred, with the molar ratio of HNO3 uptake to NO2 production varying from 1.2 to 2.9 for the three soot types studied. Unreacted HNO3 was present at the conclusion of each of the aerosol experiments, indicating incomplete conversion of HNO3 into NO2. This observation suggested that "active" sites at the soot surface responsible for the reduction of HNO3 are not regenerated (i.e., formed) in the reaction process. In essence, a titration occurred between these active sites and HNO3. The NO2 concentrations produced, the soot mass concentrations used, and the BET measured specific surface area of the powders allowed computation of the surface density of active sites of ~4.0x10-18 m2/active site (describing all three powders studied). This is the first reported measurement of surface density of active sites for nitric acid chemistry on soot. Since atmospheric heterogeneous reactions that exhibit surface deactivation may, in principle, affect trace gas concentration, we perform an assessment in this regard.

  5. Condensation of acetol and acetic acid vapor with sprayed liquid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A cellulose-derived fraction of biomass pyrolysis vapor was simulated by evaporating acetol and acetic acid (AA) from flasks on a hot plate. The liquid in the flasks was infused with heated nitrogen. The vapor/nitrogen stream was superheated in a tube oven and condensed by contact with a cloud of ...

  6. Heat-Exchange Fluids for Sulfuric Acid Vaporizers

    NASA Technical Reports Server (NTRS)

    Lawson, D. D.; Petersen, G. R.

    1982-01-01

    Some fluorine-substituted organic materials meet criteria for heat-exchange fluids in contact with sulfuric acid. Most promising of these are perfluoropropylene oxide polymers with degree of polymerization (DP) between 10 and 50. It is desirable to have DP in high range because vapor pressure of material decreases as DP increases, and high-DP liquids have lower loss due to vaporization.

  7. Investigation of catalytic reduction and filter techniques for simultaneous measurements of NO, NO2, and HNO3 in the stratosphere

    NASA Technical Reports Server (NTRS)

    Wendt, J.; Fabian, Peter; Flentje, G.; Kourtidis, K.

    1994-01-01

    A concept for measuring stratospheric NOy-species is presented which utilizes the catalytic reduction of NO2 and HNO3 over heated metal catalysts and the chemisorption of HNO3 on Nylon. Using the Max Planck Institute for Aeronomy (MPAE) chemiluminescent balloon-borne sonde, stratospheric NO and NO2 profiles have been measured since 1983. NO is detected by chemiluminescence produced in reaction with O3 while NO2 needs first to be converted to NO over a heated stainless steel catalyst. To improve this technique for simultaneously measuring HNO3, the catalytic reduction of NO2 and HNO3 over several metal catalysts and the chemisorption of NO2 and HNO3 on Nylon have been investigated in laboratory tests. The results of these tests under simulated stratospheric conditions are presented in detail in this paper. They demonstrate that the simultaneous measurement of NO, NO2 and HNO3 is indeed possible with the combination of stainless steel or Au as a catalyst and a nylon filter.

  8. Is NO3/N2O5 chemistry a source of aerosol HNO3 in the San Joaquin Valley?

    NASA Astrophysics Data System (ADS)

    Minejima, C.; Wooldridge, P. J.; Cohen, R. C.

    2009-12-01

    Sensitive and continuous measurements of NO3 + N2O5 concentrations were made at Arvin from March 1 to March 30, 2007 using Thermal Dissociation-Laser Induced Fluorescence (TD-LIF) to investigate the role of NO3 and N2O5 as a cause of high ammonium nitrate (NH4NO3) aerosol concentrations in California’s San Joaquin Valley (SJV). NH4NO3 is produced via a reaction of HNO3 and NH3. And HNO3 is the limiting reagent for NH3 is emitted in large amount from agricultural sources and motor vehicles in the SJV. NO3 and N2O5 play an important part in producing HNO3. Nighttime production of HNO3 through a heterogeneous N2O5 reaction with H2O on aerosol surfaces was investigated by measuring the NO3 + N2O5 concentrations. Peak values of N2O5 mixing ratio often exceeded 100 pptv and ranged between 25-320 pptv. Size resolved particle number was measured to estimate aerosol surface load and it was found that heterogeneous N2O5 reaction with the estimated surface load could explain only up to a few % of HNO3 production. Here the necessary HNO3 production is calculated by assuming the aerosol lifetime with respect to deposition and/or transport out of PBL is 1 day. Other possible passes to produce HNO3 are the day time NO2 + OH reaction, nighttime NO3 + anthropogenic HC reactions, and NO3 + biogenic HC reactions. Contribution of each pass was estimated by auxiliary measurements and knowledge from literature. Daytime HNO3 production was calculated from the measured NO2 concentration at the nearest CARB site and OH concentration from literature to show that it may account for ~25 % of HNO3 required. Total non methane hydrocarbons (NMHCs), which is mostly anthropogenic, is measured at the CARB site. Assuming the similar compositions of NMHCs in Sacramento, NO3 + anthropogenic HCs are calculated to be as fast to explain 40 - 70 % of NO3 + N2O5 loss. HNO3 yield from these reactions are not well known. The upper limit of HNO3 production, however, can be estimated by assuming unity yield

  9. Method for the separation of acid from acid-laden vapors

    SciTech Connect

    Hansen, L.J.

    1992-02-11

    This patent describes a method for the removal of hydrochloric or sulfuric acid from vapor laden with the acid. It comprises: contacting the acid-laden vapors with packing materials in a zone containing the packing materials wherein the packing materials are formed of polyester resin containing from about 5 to 40 weight percent aluminum sulfate crystals.

  10. Study of the Laser-Induced Decomposition of HNO3/2-NITROPROPANE Mixture at Static High Pressure

    NASA Astrophysics Data System (ADS)

    Bouyer, V.; Hébert, P.; Doucet, M.

    2007-12-01

    The objective of the work presented here is to study the laser-induced decomposition of a condensed HNO3/2-nitropropane mixture containing 58% nitric acid. On the macroscopic scale, this energetic material detonates. Under static high pressure, the formation of an H-bonded complex with that particular composition was demonstrated in a previous study. The high pressure behavior of the complex showed the presence of a solid-solid phase transition around 18 GPa. The combustion front propagation velocity was recorded between 6 and 31 GPa. The analysis of the optical properties of the reaction products as well as the recording of their Raman spectra showed two different combustion regimes. Below 18 GPa, total combustion takes place in the sample and a black residue only composed of soot remains in the cell. Above 18 GPa, the combustion leads to a clear residue with little carbon present. However, the Raman spectra of the remaining sample show new features indicating the presence of species which are not yet clearly identified. The pressure limit between these two behaviors corresponds to the phase transition pressure measured for the complex.

  11. The determination of HNO3 column amounts from tunable diode laser heterodyne spectrometer spectra taken at Jungfruajoch, Switzerland

    NASA Technical Reports Server (NTRS)

    Fogal, P. F.; Murcray, D. G.; Martin, N. A.; Swann, N. R.; Woods, P. T.; Mcelroy, C. T.

    1994-01-01

    In May of 1991 a tunable diode laser heterodyne spectrometer built by the National Physical Laboratory was operated at the International Scientific Station of the Jungfraujoch (46.5 deg N, 8.0 deg E, altitude 3.56 km). Nitric acid spectra in the region of 868 wavenumbers were recorded at sunset and sunrise on two separate days at a resolution of 0.0013 wavenumbers with a signal-to-noise ratio of approximately 130:1. A vertical column amount of HNO3 of 1.61 x 10(exp 16) molecules/sq cm was determined using an atmospheric transmission model developed at the University of Denver. The mean of a number of mid-latitude, northern hemisphere profiles was used as the initial profile for the inversion. A comparison of different initial profiles provides information on the sensitivity of the retrieved column amount of 1.61 x 10(exp 16) molecules/sq cm lies within the range of values published in the World Meteorological Organization Report no. 16 (1986), but is considerably larger than the value of (0.99 - 1.29) x 10(exp 16) reported by Rinsland et al. (1991) for June during the period 1986 to 1990.

  12. Phase equilibria of H2SO4, HNO3, and HCl hydrates and the composition of polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  13. Phase Equilibria of H2SO4, HNO3, and HCl Hydrates and the Composition of Polar Stratospheric Clouds

    NASA Technical Reports Server (NTRS)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  14. Potential heat exchange fluids for use in sulfuric acid vaporizers

    NASA Technical Reports Server (NTRS)

    Lawson, D. D.; Petersen, G. R.

    1979-01-01

    A series of perhalocarbons are proposed as candidate heat exchange fluids for service in thermochemical cycles for hydrogen production that involve direct contact of the fluid with sulfuric acid and vaporization of the acid. The required chemical and physical criteria of the liquids are described and the results of some preliminary high temperature test data are presented.

  15. Atmospheric corrosion effects of HNO 3—Influence of temperature and relative humidity on laboratory-exposed copper

    NASA Astrophysics Data System (ADS)

    Samie, Farid; Tidblad, Johan; Kucera, Vladimir; Leygraf, Christofer

    The effect of HNO 3 on the atmospheric corrosion of copper has been investigated at varied temperature (15-35 °C) and relative humidity (0-85% RH). Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction (XRD) confirmed the existence of cuprite and gerhardtite as the two main corrosion products on the exposed copper surface. For determination of the corrosion rate and for estimation of the deposition velocity ( Vd) of HNO 3 on copper, gravimetry and ion chromatography has been employed. Temperature had a low effect on the corrosion of copper. A minor decrease in the mass gain was observed as the temperature was increased to 35 °C, possibly as an effect of lower amount of cuprite due to a thinner adlayer on the metal surface at 35 °C. The Vd of HNO 3 on copper, however, was unaffected by temperature. The corrosion rate and Vd of HNO 3 on copper was the lowest at 0% RH, i. e. dry condition, and increased considerably when changing to 40% RH. A maximum was reached at 65% RH and the mass gain remained constant when the RH was increased to 85% RH. The Vd of HNO 3 on copper at ⩾65% RH, 25 °C and 0.03 cm s -1 air velocity was as high as 0.15±0.03 cm s -1 to be compared with the value obtained for an ideal absorbent, 0.19±0.02 cm s -1. At sub-ppm levels of HNO 3, the corrosion rate of copper decreased after 14 d and the growth of the oxide levelled off after 7 d of exposure.

  16. Spectrometric analysis of process etching solutions of the photovoltaic industry--determination of HNO3, HF, and H2SiF6 using high-resolution continuum source absorption spectrometry of diatomic molecules and atoms.

    PubMed

    Bücker, Stefan; Acker, Jörg

    2012-05-30

    The surface of raw multicrystalline silicon wafers is treated with HF-HNO(3) mixtures in order to remove the saw damage and to obtain a well-like structured surface of low reflectivity, the so-called texture. The industrial production of solar cells requires a consistent level of texturization for tens of thousands of wafers. Therefore, knowing the actual composition of the etch bath is a key element in process control in order to maintain a certain etch rate through replenishment of the consumed acids. The present paper describes a novel approach to quantify nitric acid (HNO(3)), hydrofluoric acid (HF), and hexafluosilicic acid (H(2)SiF(6)) using a high-resolution continuum source graphite furnace absorption spectrometer. The concentrations of Si (via Si atom absorption at the wavelength 251.611 nm, m(0),(Si)=130 pg), of nitrate (via molecular absorption of NO at the wavelength 214.803 nm, [Formula: see text] ), and of total fluoride (via molecular absorption of AlF at the wavelength 227.46 nm, m(0,F)=13 pg) were measured against aqueous standard solutions. The concentrations of H(2)SiF(6) and HNO(3) are directly obtained from the measurements. The HF concentration is calculated from the difference between the total fluoride content, and the amount of fluoride bound as H(2)SiF(6). H(2)SiF(6) and HNO(3) can be determined with a relative uncertainty of less than 5% and recoveries of 97-103% and 96-105%, respectively. With regards to HF, acceptable results in terms of recovery and uncertainty are obtained for HF concentrations that are typical for the photovoltaic industry. The presented procedure has the unique advantage that the concentration of both, acids and metal impurities in etch solutions, can be routinely determined by a single analytical instrument. PMID:22608457

  17. Infrared studies of sulfuric acid and its impact on polar and global ozone

    NASA Astrophysics Data System (ADS)

    Iraci, Laura Tracy

    Sulfuric acid aerosols are present throughout the lower stratosphere and play an important role in both polar and global ozone depletion. In the polar regions, stratospheric sulfate aerosols (SSAs) act as nuclei for the growth of polar stratospheric clouds (PSCs). Heterogeneous reactions can occur on these PSCs, leading to chlorine activation and catalytic ozone destruction. This thesis addresses the issue of polar ozone depletion through laboratory studies which examine the nucleation of PSCs on sulfuric acid. In addition, chemistry which occurs directly on sulfate aerosols may impact ozone at midlatitudes, and studies describing one such reaction are presented as well. To study the growth of type I PSCs on sulfuric acid, thin H2SO4 films were exposed to water and nitric acid vapors at stratospheric temperatures. Fourier transform infrared spectroscopy was used to probe the phase of the sulfuric acid and to identify the HNO3/H2O films which condensed. Supercooled liquid sulfuric acid films showed uptake of HNO3 to form ternary solutions, followed by crystallization of nitric acid trihydrate (NAT). When crystalline sulfuric acid tetrahydrate (SAT) films were exposed to nitric acid and water, condensation of a supercooled HNO3/H2O layer was often observed. As predicted by theory, some of the SAT crystal then dissolved, creating a ternary H2SO4/HNO3/H2O solution. From this solution, NAT nearly always crystallized, halting the phase change of sulfuric acid. If a supercooled nitric acid layer did not condense on frozen sulfuric acid, crystalline NAT was not deposited from the gas phase when SNAT/leq41. At significantly higher supersaturations, NAT could be forced to condense on sulfuric acid, regardless of its phase. Calculations of the contact parameter from experimental data indicate that m<0.79 for NAT on SAT, predicting a significant barrier to nucleation of NAT from the gas phase. While PSCs can form only in the cold polar regions of the stratosphere, sulfuric

  18. VizieR Online Data Catalog: ExoMol line lists for HNO3 (Pavlyuchko+, 2015)

    NASA Astrophysics Data System (ADS)

    Pavlyuchko, A. I.; Yurchenko, S. N.; Tennyson, J.

    2015-05-01

    The data for each isotopologue are in two parts. The first, HNO3.states contains a list of rovibronic states. Each state is labelled with the total angular momentum, state degeneracy, total parity, vibrational quantum number, projection of the electronic, spin and total angular momenta. Each state has a unique number, which is the number of the row in which it appears in the file. This number is the means by which the state is related to the second part of the data system, the transitions files. Because of their size, the transitions are listed in 71 separate files, each containing all the transitions in a 100cm-1 wavenumber range. These and their contents are ordered by increasing frequency. The name of the file includes the lowest frequency in the range; thus the a-00500.dat file contains all the transitions in the frequency range 500-600cm-1. The transition files a-*.dat contain three columns: the reference number in the energy file of the upper state; that of the lower state; and the Einstein A coefficient of the transition. (3 data files).

  19. Potential heat exchange fluids for use in sulfuric acid vaporizers

    NASA Technical Reports Server (NTRS)

    Lawson, D. D.; Petersen, G. R.

    1981-01-01

    A series of liquids have been screened as candidate heat exchange fluids for service in thermochemical cycles that involve the vaporization of sulfuric acid. The required chemical and physical criteria of the liquids is described with the results of some preliminary high temperature test data presented.

  20. A TUNABLE DIODE LASER STACK MONITOR FOR SULFURIC ACID VAPOR

    EPA Science Inventory

    A field prototype instrument for continuous in-situ monitoring of sulfuric acid vapor in industrial smoke stacks has been developed. The method of detection is dual wavelength differential absorption in the infrared. Two tunable diode lasers are locked to two specific frequencies...

  1. Temperature dependences of saturated vapor pressure and the enthalpy of vaporization of n-pentyl esters of dicarboxylic acids

    NASA Astrophysics Data System (ADS)

    Portnova, S. V.; Krasnykh, E. L.; Levanova, S. V.

    2016-05-01

    The saturated vapor pressures and enthalpies of vaporization of n-pentyl esters of linear C2-C6 dicarboxylic acids are determined by the transpiration method in the temperature range of 309.2-361.2 K. The dependences of enthalpies of vaporization on the number of carbon atoms in the molecule and on the retention indices have been determined. The predictive capabilities of the existing calculation schemes for estimation of enthalpy of vaporization of the studied compounds have been analyzed.

  2. Analysis of fish otoliths by electrothermal vaporization inductively coupled plasma mass spectrometry: aspects of precipitating otolith calcium with hydrofluoric acid for trace element determination.

    PubMed

    Arslan, Zikri

    2005-03-15

    A method is developed for determination of trace elements, including Ag, As, Cd, Co, Cr, Cu, Mn, Ni, Se, Tl and Zn, in fish otoliths by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS). Hydrofluoric acid was used to precipitate calcium resulting from acid dissolution of otolith calcium carbonate. Initial acidity of the sample solution influenced the precipitation efficiency of calcium fluoride. Up to 99.5% of Ca was precipitated in solutions that contained less than 2% (v/v) HNO(3). Recoveries of the elements obtained from spiked artificial otolith solutions were between 90 and 103%. Stabilization of the elements within the ETV cell was achieved with 0.3mug Pd/0.2mug Rh chemical modifier that also afforded optimum sensitivity for multielement determination. The method was validated by the analysis of a fish otolith reference material (CRM) of emperor snapper, and then applied to the determination of the trace elements in otoliths of several fish species captured in Raritan Bay, New Jersey. Results indicated that fish physiology and biological processes could influence the levels of Cu, Mn, Se and Zn in the otoliths of fish inhabiting a similar aqueous environment. Otolith concentrations of Cr and Ni did not show any significant differences among different species. Concentrations for Ag, As, Cd, Co and Tl were also not significantly different, but were very low indicating low affinity of otolith calcium carbonate to these elements. PMID:18969949

  3. Analysis of seasonal variation of stratospheric nitric acid

    NASA Astrophysics Data System (ADS)

    Gruzdev, A. N.

    1998-11-01

    Data from the draft COSPAR reference model for stratospheric nitric acid (HNO3) are analysed. Eight months of LIMS HNO3 measurements allow the analysis of dynamics of regimes associated with the annual HNO3 maximum followed by the HNO3 decrease in the Northern Hemisphere and the annual HNO3 minimum followed by the HNO3 increase in the Southern Hemisphere. The HNO3 minimum is noted earlier (in November) in the Southern Hemisphere subtropical upper stratosphere, from where the regime of minimum HNO3 values propagates to the southern high-latitude middle stratosphere, and then (in Austral summer) the equatorward propagation of the regime is observed, with a persistent downward component. The regime of the HNO3 annual maximum in the Northern Hemisphere propagates from the Arctic lower stratosphere (in autumn) and from the tropical middle stratosphere (in late summer), so that in the mid-latitude middle stratosphere the downward propagation of the regime is observed. Evolution of areas with HNO3 increase and decrease by 1 ppbv against the January HNO3 distribution quantifies intensity of the HNO3 decrease in winter-spring in the Northern Hemisphere and the HNO3 increase in Austral summer-autumn in the Southern Hemisphere.

  4. High resolution, balloon-borne emission spectroscopy of trace species in the lower stratosphere - N2O5, HNO3

    NASA Technical Reports Server (NTRS)

    Brasunas, J.; Herman, J.; Kunde, V.; Maguire, W.; Herath, L.; Shaffer, W.; Abbas, M.; Massie, S.

    1988-01-01

    A liquid-nitrogen cooled Fourier transform spectrometer (SIRIS) measures thermal limb-emission of the stratosphere from a balloon platform at a nominal altitude of 40 km, under night and day conditions, with a 3 km vertical resolution. N2O5 and HNO3 mixing ratios inferred from emission spectra are compared with previous measurements and with the predictions from a one-dimensional photochemical model.

  5. HNO3, N2O5 and CIONO2 Enhancements after the October-November 2003 Solar Proton Events

    NASA Technical Reports Server (NTRS)

    Lopez-Puertas, M.; Funke, B.; Gil-Lopez, S.; Tsidu, G. Mengistu; Fischer, H.; Jackman, C. H.

    2005-01-01

    The large solar storm in October-November 2003 produced enormous amounts of high-energy protons which reached the Earth and penetrated into the middle atmosphere in the polar regions. At this time, the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on board the Environmental Satellite (ENVISAT) was observing the atmosphere in the 6-68 km altitude range. MIPAS observed significant enhancements of the NO(y) components HNO3, N2O5 and CIONO2 in the Northern polar stratosphere after the intense solar proton events. Two distinct HNO3 enhancements were observed. An instantaneous increase of 1-2 ppbv was observed immediately after the SPEs and is attributed to gas-phase chemistry: NO2 + OH + M yields HNO3 + M, accelerated by SPE-produced excess OH. A very large second increase of 1- 5 ppbv started around 10 November and lasted until the end of December. It is attributed to NO(x) (NO+NO2) produced in the mesosphere during the major SPEs in late October/early November and then transported downwards during November and December, partially converted to N2O5 in the upper stratosphere, which finally formed HNO3 via ion cluster reactions. N2O5 was observed to increase by 0.1-0.4 ppbv 1-3 days after the major SPEs and reached down to 30 km altitude. A second, more pronounced N2O5 enhancement of up to 1.2 ppbv at 40 km appeared about 12-13 days after the major SPEs. With a delay of 1-2 days after the major SPEs CIONO2 increased by up to 0.4 ppbv (40%) at 32 km altitude. NO(y) enhancements in the Southern hemisphere were generally less pronounced.

  6. Lifetime Extension of Cirrus Cloud Ice Particles upon Contamination with HCl and HNO3 under conditions of the Upper Troposphere and Lower Stratosphere

    NASA Astrophysics Data System (ADS)

    Rossi, Michel J.; Delval, Christophe

    2016-04-01

    Ice particles in the Upper Troposphere/Lower Stratosphere (UT/LS) are the seat of heterogeneous chemical processes that are important in polar ozone chemistry. Estimated evaporative lifetimes of typical pure ice particles of a few micrometers radius in Cirrus clouds are on the order of a minute or so at 80% relative humidity, too short to allow significant heterogeneous processing. We took this as a motivation to systematically measure absolute rates of evaporation and condensation of H2O in 1 to 2 micrometer thick ice films taken as proxies for small atmospheric ice particles under controlled conditions of HCl and HNO3 trace gas contamination. We have used a multidiagnostic reaction vessel equipped with residual gas mass spectrometry (MS), FTIR absorption spectroscopy in transmission and a quartz crystal microbalance (QCMB) in order to simultaneously observe both the gas and condensed phases under relevant atmospheric conditions. The rates (Rev(H2O)) or fluxes of evaporation (Jev(H2O)) of H2O from thin ice films contaminated by a measured amount of HCl in the range of 10% of a formal monolayer to 20 formal monolayers decreased by factors of between 2 and 50 depending on parameters such as temperature of deposition (Tdep), rate (RHCl) and dose (NHCl) of contaminant doping. Experiments with HCl fell into two categories as far as the decrease of Jev with the average mole fraction of contaminant (χHCl) in the remaining ice slab was concerned: one group where Jev(H2O) decreased gradually after pure ice evaporated, and another group where Jev(H2O) abruptly changes with χHCl after evaporation of excess ice. FTIR spectroscopy revealed an unknown, yet crystalline form of HCl hydrate upon HCl doping that does not correspond to a known crystalline hydrate. Of importance is the observation, that the equilibrium vapor pressure of these contaminated ices correspond to that of pure ice even after evaporation of excess ice at the characteristic rate of pure ice evaporation

  7. Balloon-borne radiometer measurement of Northern Hemisphere mid-latitude stratospheric HNO3 profiles spanning 12 years

    NASA Astrophysics Data System (ADS)

    Toohey, M.; Quine, B. M.; Strong, K.; Bernath, P. F.; Boone, C. D.; Jonsson, A. I.; McElroy, C. T.; Walker, K. A.; Wunch, D.

    2007-08-01

    Low-resolution atmospheric thermal emission spectra collected by balloon-borne radiometers over the time span of 1990-2002 are used to retrieve vertical profiles of HNO3, CFC-11 and CFC-12 volume mixing ratios between approximately 10 and 35 km altitude. All of the data analyzed have been collected from launches from a Northern Hemisphere mid-latitude site, during late summer, when stratospheric dynamic variability is at a minimum. The retrieval technique incorporates detailed forward modeling of the instrument and the radiative properties of the atmosphere, and obtains a best fit between modeled and measured spectra through a combination of onion-peeling and global optimization steps. The retrieved HNO3 profiles are consistent over the 12-year period, and are consistent with recent measurements by the Atmospheric Chemistry Experiment-Fourier transform spectrometer satellite instrument. This suggests that, to within the errors of the 1990 measurements, there has been no significant change in the HNO3 summer mid-latitude profile.

  8. Balloon-borne radiometer measurements of Northern Hemisphere mid-latitude stratospheric HNO3 profiles spanning 12 years

    NASA Astrophysics Data System (ADS)

    Toohey, M.; Quine, B. M.; Strong, K.; Bernath, P. F.; Boone, C. D.; Jonsson, A. I.; McElroy, C. T.; Walker, K. A.; Wunch, D.

    2007-12-01

    Low-resolution atmospheric thermal emission spectra collected by balloon-borne radiometers over the time span of 1990-2002 are used to retrieve vertical profiles of HNO3, CFC-11 and CFC-12 volume mixing ratios between approximately 10 and 35 km altitude. All of the data analyzed have been collected from launches from a Northern Hemisphere mid-latitude site, during late summer, when stratospheric dynamic variability is at a minimum. The retrieval technique incorporates detailed forward modeling of the instrument and the radiative properties of the atmosphere, and obtains a best fit between modeled and measured spectra through a combination of onion-peeling and optimization steps. The retrieved HNO3 profiles are consistent over the 12-year period, and are consistent with recent measurements by the Atmospheric Chemistry Experiment-Fourier transform spectrometer satellite instrument. We therefore find no evidence of long-term changes in the HNO3 summer mid-latitude profile, although the uncertainty of our measurements precludes a conclusive trend analysis.

  9. Coupled aerosol-chemical modeling of UARS HNO3 and N2O5 measurements in the Arctic upper stratosphere

    NASA Astrophysics Data System (ADS)

    Bekki, S.; Chipperfield, M. P.; Pyle, J. A.; Remedios, J. J.; Smith, S. E.; Grainger, R. G.; Lambert, A.; Kumer, J. B.; Mergenthaler, J. L.

    1997-04-01

    Gas-phase photochemical models do not account for the formation of a secondary altitude HNO3 maximum in the upper stratosphere at high latitudes during winter, suggesting that some processes are missing in the currently accepted chemistry of reactive nitrogen species [Kawa et al, 1995]. Heterogeneous chemistry on aerosol particles had been discounted as the cause because the aerosol surface area is expected to be very low at these altitudes. We have coupled a sulphate aerosol microphysical model to a chemical transport model to investigate this model deficiency in the Arctic during January 1992. The aerosol model predicts the formation of small sulphate particles at 1100 K. Comparisons with cryogenic limb array etalon spectrometer (CLAES) HNO3 and improved stratospheric and mesospheric sounder (ISAMS) N2O5 observations show that the heterogeneous conversion of N2O5 to HNO3 on the modeled small sulphate particles can account for some of the unexpected features seen in Upper Atmosphere Research Satellite (UARS) observations.

  10. Analysis of the ν 8+ ν 9Band of HNO 3, Line Positions and Intensities, and Resonances Involving the v6= v7= 1 Dark State

    NASA Astrophysics Data System (ADS)

    Perrin, A.; Flaud, J.-M.; Keller, F.; Goldman, A.; Blatherwick, R. D.; Murcray, F. J.; Rinsland, C. P.

    1999-03-01

    Using a high-resolution (R= 0.0025 cm-1) Fourier transform spectrum of nitric acid recorded at room temperature in the 1100-1240 cm-1region, it has been possible to perform a more extended analysis of the ν8+ ν9band of HNO3centered at 1205.7075 cm-1. As in a recent analysis of this band [W. F. Wang, P. P. Ong, T. L. Tan, E. C. Looi, and H. H. Teo,J. Mol. Spectrosc.183, 407-413 (1997)], the Hamiltonian used for the line positions calculation takes into account, for the upper state, the ΔK= ±2 anharmonic resonance linking the rotational levels of thev8=v9= 1 "bright" vibrational state and those of the "dark"v6=v7= 1 vibrational state. More than 4800 lines were assigned in the ν8+ ν9band, which involve significantly higher rotational quantum numbers than in previous works. On the other hand, and surprisingly as compared to previous studies, the ν8+ ν9band appears to be a hybrid band. In fact, nonnegligibleB-type transitions could be clearly identified among the much strongerA-type lines. Accordingly, a set of individual line intensities were measured for lines of both types and were introduced in a least-squares fit to get theA- andB-type components of the transition moment operator. Finally, a synthetic spectrum of the 8.3-μm region of HNO3has been generated, using for the line positions and line intensities the Hamiltonian constants and the expansion of the transition moment operator which were determined in this work. In this way, theB-type and theA-type components of the ν8+ ν9band appear to contribute for about {1}/{4} and {3}/{4}, respectively, to the total band intensity.

  11. Molecular weight of aquatic fulvic acids by vapor pressure osmometry

    USGS Publications Warehouse

    Aiken, G.R.; Malcolm, R.L.

    1987-01-01

    The molecular weights of aquatic fulvic acids extracted from five rivers were determined by vapor pressure osmometry with water and tetrahydrofuran as solvents. The values obtained ranged from 500 to 950 dallons, indicating that the molecular weights of aquatic fulvic acids are not as great as has been suggested in some other molecular weight studies. The samples were shown to be relatively monodisperse from radii of gyration measurements determined by small angle x-ray scattering. THF affords greater precision and accuracy than H2O in VPO measurements, and was found to be a suitable solvent for the determination of molecular weight of aquatic fulvic acid because it obviates the dissociation problem. An inverse correlation was observed with these samples between the concentration of Ca++ and Mg++ in the river water and the radii of gyration and molecular weights of the corresponding fulvic acid samples. ?? 1987.

  12. Commercial Alloys for Sulfuric Acid Vaporization in Thermochemical Hydrogen Cycles

    SciTech Connect

    Thomas M. Lillo; Karen M. Delezene-Briggs

    2005-10-01

    Most thermochemical cycles being considered for producing hydrogen include a processing stream in which dilute sulfuric acid is concentrated, vaporized and then decomposed over a catalyst. The sulfuric acid vaporizer is exposed to highly aggressive conditions. Liquid sulfuric acid will be present at a concentration of >96 wt% (>90 mol %) H2SO4 and temperatures exceeding 400oC [Brown, et. al, 2003]. The system will also be pressurized, 0.7-3.5 MPa, to keep the sulfuric acid in the liquid state at this temperature and acid concentration. These conditions far exceed those found in the commercial sulfuric acid generation, regeneration and handling industries. Exotic materials, e.g. ceramics, precious metals, clad materials, etc., have been proposed for this application [Wong, et. al., 2005]. However, development time, costs, reliability, safety concerns and/or certification issues plague such solutions and should be considered as relatively long-term, optimum solutions. A more cost-effective (and relatively near-term) solution would be to use commercially-available metallic alloys to demonstrate the cycle and study process variables. However, the corrosion behavior of commercial alloys in sulfuric acid is rarely characterized above the natural boiling point of concentrated sulfuric acid (~250oC at 1 atm). Therefore a screening study was undertaken to evaluate the suitability of various commercial alloys for concentration and vaporization of high-temperature sulfuric acid. Initially alloys were subjected to static corrosion tests in concentrated sulfuric acid (~95-97% H2SO4) at temperatures and exposure times up to 200oC and 480 hours, respectively. Alloys with a corrosion rate of less than 5 mm/year were then subjected to static corrosion tests at a pressure of 1.4 MPa and temperatures up to 375oC. Exposure times were shorter due to safety concerns and ranged from as short as 5 hours up to 144 hours. The materials evaluated included nickel-, iron- and cobalt

  13. Acid Vapor Weathering of Apatite and Implications for Mars

    NASA Technical Reports Server (NTRS)

    Hausrath, E. M.; Golden, D. C.; Morris, R. V.; Ming, D. W.

    2008-01-01

    Phosphorus is an essential nutrient for terrestrial life, and therefore may be important in characterizing habitability on Mars. In addition, phosphate mobility on Mars has been postulated as an indicator of early aqueous activity [1]. Rock surfaces analyzed by the Spirit Mars Exploration Rover indicate elemental concentrations consistent with the loss of a phosphate-containing mineral [2], and the highly altered Paso Robles deposit contains 5% P2O5, modeled as 8-10 % phosphate [3]. Depending on the pH of the solution, phosphate can exist as one of four charge states, which can affect its solubility, reactivity and mobility. Phosphate may therefore prove a useful and interesting tracer of alteration conditions on Mars. Acid vapor weathering has been previously studied as a potentially important process on Mars [4-6], and Paso Robles may have been formed by reaction of volcanic vapors with phosphate-bearing rock [3, 7]. Here we present preliminary results of acid vapor reactions in a Parr vessel [6] using fluorapatite, olivine and glass as single phases and in a mixture.

  14. Structural Characteristics of Homogeneous Hydrophobic Ionic Liquid-HNO3-H2O Ternary System: Experimental Studies and Molecular Dynamics Simulations.

    PubMed

    Fu, Jing; Yang, Y Isaac; Zhang, Jun; Chen, Qingde; Shen, Xinghai; Gao, Yi Qin

    2016-06-16

    The solubility of water in the hydrophobic ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) increases significantly in the presence of HNO3. [C2mim][NTf2] is completely miscible with HNO3 but immiscible with water. The triangular phase diagram of the ternary system [C2mim][NTf2]-HNO3-H2O was determined at 300.1 K. The homogeneous [C2mim][NTf2]-HNO3-H2O phase is thermodynamically stable, while it can be separated into two phases with an increase of water content. Experiments (electrospray ionization mass spectrometry, Fourier transform infrared spectrometry, and (1)H-nuclear magnetic resonance spectrometry) and molecular dynamics simulations were carried out to investigate the interaction between [C2mim][NTf2], HNO3, and water in the homogeneous phase. It was found that NO3(-) ions interact with both C2mim(+) and water via H-bonding and act as a "bridge" to induce a large amount of water to be dissolved in the hydrophobic IL phase. This confirms that the complexes [C2mim-NTf2-C2mim](+) and [NTf2-C2mim-NTf2](-) exist in the homogeneous [C2mim][NTf2]-HNO3-H2O system at the concentration of HNO3 up to 27.01 wt % and of water as high as 20.74 wt %. PMID:27196811

  15. Evaluation of sampling methods for measuring exposure to volatile inorganic acids in workplace air. Part 2: Sampling capacity and breakthrough tests for sodium carbonate-impregnated filters.

    PubMed

    Demange, Martine; Oury, Véronique; Rousset, Davy

    2011-11-01

    In France, the MétroPol 009 method used to measure workplace exposure to inorganic acids, such as HF, HCl, and HNO3, consists of a closed-face cassette fitted with a prefilter to collect particles, and two sodium carbonate-impregnated filters to collect acid vapor. This method was compared with other European methods during the development of a three-part standard (ISO 21438) on the determination of inorganic acids in workplace air by ion chromatography. Results of this work, presented in a companion paper, led to a need to go deeper into the performance of the MétroPol 009 method regarding evaluation of the breakthrough of the acids, both alone and in mixtures, interference from particulate salts, the amount of sodium carbonate required to impregnate the sampling filter, the influence of sampler components, and so on. Results enabled improvements to be made to the sampling device with respect to the required amount of sodium carbonate to sample high HCl or HNO3 concentrations (500 μL of 5% Na2CO3 on each of two impregnated filters). In addition, a PVC-A filter used as a prefilter in a sampling device showed a propensity to retain HNO3 vapor so a PTFE filter was considered more suitable for use as a prefilter. Neither the material of the sampling cassette (polystyrene or polypropylene) nor the sampling flowrate (1 L/min or 2 L/min) influenced the performance of the sampling device, as a recovery of about 100% was achieved in all experiments for HNO3, HCl, and HF, as well as HNO3+HF and HNO3+HCl mixtures, over a wide range of concentrations. However, this work points to the possibility of interference between an acid and salts of other acids. For instance, interference can occur through interaction of HNO3 with chloride salts: the stronger the acid, the greater the interference. Methods based on impregnated filters are reliable for quantitative recovery of inorganic volatile acids in workplace atmosphere but are valuable only in the absence of interferents. PMID

  16. Use of HNO(3) as the source of NO to prepare a nitric oxide complex of ruthenium.

    PubMed

    Drew, Michael G B; Nag, Samik; Datta, Dipankar

    2008-05-01

    Reaction of cis-Ru(bisox)(2)Cl(2), where bisox is 4,4,4',4'-tetramethyl-2,2'-bisoxazoline, with HNO(3) in 1 : 4 molar proportion in boiling water under N(2) atmosphere and subsequent addition of an excess of NaClO(4).H(2)O yields [Ru(bisox)(HL)(NO)](ClO(4))(NO(3)) (1). HL is a hydrolysed form of bisox where one of the oxazoline rings opens up. X-Ray crystallography shows that 1 contains an octahedral RuN(5)O core. HL binds the metal through an imino N, an amide N and an alcoholic O atom. Reaction of cis-Ru(bisox)(2)Cl(2) with an excess of NaNO(2) in water gives cis-Ru(bisox)(2)(NO(2))(2) (2). On acidification by HClO(4) in methanol, is smoothly converted to cis-[Ru(bisox)(2)(NO(2))(NO)](ClO(4))(2) (3) due to equilibrium (1). [Formula: see text] (1) The X-ray crystal structures of 2 and 3 have also been determined. NO binds Ru in 1 and 3 linearly. The Ru-NO bond length in 1 is 1.764(13) A and that in 3 is approximately 1.78 A. All the three complexes have been characterised by FTIR, NMR and ESIMS. The NO stretching frequencies in 1 and 3 are 1897 and 1936 cm(-1) respectively. While 3 reverts back to 2 readily in presence of OH(-) [equilibrium (1)], 1 does not react with OH(-). It is concluded that while in the reaction of cis-Ru(bisox)(2)Cl(2) with HNO(3), bisox is hydrolysed following abstraction of NO from HNO(3), generation of the nitrosyl complex 3 via reaction (1) is not accompanied with such hydrolysis. PMID:18414755

  17. Heterogeneous conversion of N2O5 to HNO3 on background stratospheric aerosols - Comparisons of model results with data

    NASA Technical Reports Server (NTRS)

    Considine, David B.; Douglass, Anne R.; Stolarski, Richard S.

    1992-01-01

    The effects of heterogeneous processing by a parameterized lower stratospheric sulfate aerosol layer on model calculations were examined using a 2D photochemical model. Model results were compared with zonally averaged LIMS data on HNO3 and NO2 and in situ measurements of NO, NO(y), and ClO, taken by the ER-2 aircraft. The results obtained are contradictory: some comparisons favor heterogeneous chemistry, and some do not. It is suggested that the assumptions made to parameterize the sulfate aerosol chemistry result in a rate of heterogeneous processing that is too vigorous.

  18. NMR Study of Phase Transitions in Pure Water and Binary H(2)O/HNO(3) Films Adsorbed on Surface of Pyrogenic Silica.

    PubMed

    Bogdan; Kulmala; Gorbunov; Kruppa

    1996-01-15

    Pyrogenic silica (aerosil) was employed as host within which the phase transitions in the adsorbed pure water and binary H(2)O/HNO(3) films have been studied with NMR spectroscopy. The median freezing temperature and freezing temperature region were shown to be highly sensitive both to the average thickness of the adsorbed films and to the amount of adsorbed nitric acid. The molar concentration of nitric acid in the adsorbed films was found to be very small, on the order of 10(-3)-10(-2) (M/liter). The concentration was found to be greater in the layers adjacent to the surface of silica and sharply decreases with distance from the surface. The difference between the median freezing temperatures for adsorbed pure water and for the binary system was found to be about 9 K for films of equal thickness. This is about 150 times greater than the difference between the freezing temperatures of bulk pure water and a solution with the same concentration of nitric acid. PMID:10479419

  19. Interaction of Ethyl Alcohol Vapor with Sulfuric Acid Solutions

    NASA Technical Reports Server (NTRS)

    Leu, Ming-Taun

    2006-01-01

    We investigated the uptake of ethyl alcohol (ethanol) vapor by sulfuric acid solutions over the range approx.40 to approx.80 wt % H2SO4 and temperatures of 193-273 K. Laboratory studies used a fast flow-tube reactor coupled to an electron-impact ionization mass spectrometer for detection of ethanol and reaction products. The uptake coefficients ((gamma)) were measured and found to vary from 0.019 to 0.072, depending upon the acid composition and temperature. At concentrations greater than approx.70 wt % and in dilute solutions colder than 220 K, the values approached approx.0.07. We also determined the effective solubility constant of ethanol in approx.40 wt % H2SO4 in the temperature range 203-223 K. The potential implications to the budget of ethanol in the global troposphere are briefly discussed.

  20. Relationship Between HNO3, NO, NO2 and HONO Fluxes Above Snow Surfaces at Ny- Aalesund, Svalbard (Arctic)

    NASA Astrophysics Data System (ADS)

    Amoroso, A.; Beine, H. J.; Esposito, G.; Nardino, M.; Montagnoli, M.; Ianniello, A.

    2006-12-01

    Deposition of NO3- in and on snow surfaces is not the final sink for atmospheric N-species; nitrates can be photochemically re-activated in the snow: this leads to the release of the more reactive species NO, NO2, and HONO back into the atmosphere. Surface flux measurements of HONO, HNO3, NO and NO2 were made above the snow surface near the Italian Station "Dirigibile Italia" at the Kongsfjorden International Research Base at Ny-Aalesund, Svalbard (79 N), between February 20, 2006 and April 20, 2006 During a few defined episodes the maximum fluxes observed were 40 nmol m-2h-1 for HONO, 50 and 150 nmol m-2h-1 for NO and NO2 , respectively, and -350 nmol m-2h-1 for HNO3 . However, for the most part the fluxes were much smaller at this Arctic marine site, in accord with earlier observations. These observations help us understand the nitrogen exchange processes between snow surfaces and the atmosphere. In this work we explore the chemical and physical snow and light conditions necessary for NOx and HONO release.

  1. Unusually low ozone, HCl, and HNO3 column measurements at Eureka, Canada during winter/spring 2011

    NASA Astrophysics Data System (ADS)

    Lindenmaier, R.; Strong, K.; Batchelor, R. L.; Chipperfield, M. P.; Daffer, W. H.; Drummond, J. R.; Duck, T. J.; Fast, H.; Feng, W.; Fogal, P. F.; Kolonjari, F.; Manney, G. L.; Manson, A.; Meek, C.; Mittermeier, R. L.; Nott, G. J.; Perro, C.; Walker, K. A.

    2012-04-01

    As a consequence of dynamically variable meteorological conditions, springtime Arctic ozone levels exhibit significant interannual variability in the lower stratosphere. In winter 2011, the polar vortex was strong and cold for an unusually long time. Our research site, located at Eureka, Nunavut, Canada (80.05° N, 86.42° W), was mostly inside the vortex from October 2010 until late March 2011. The Bruker 125HR Fourier transform infrared spectrometer installed at the Polar Environment Atmospheric Research Laboratory at Eureka acquired measurements from 23 February to 6 April during the 2011 Canadian Arctic Atmospheric Chemistry Experiment Validation Campaign. These measurements showed unusually low ozone, HCl, and HNO3 total columns compared to the previous 14 yr. To remove dynamical effects, we normalized these total columns by the HF total column. The normalized values of the ozone, HCl, and HNO3 total columns were smaller than those from previous years, and confirmed the occurrence of chlorine activation and chemical ozone depletion. To quantify the chemical ozone loss, a three-dimensional chemical transport model, SLIMCAT, and the passive subtraction method were used. The chemical ozone depletion was calculated as the mean percentage difference between the measured ozone and the SLIMCAT passive ozone, and was found to be 35%.

  2. Unusually low ozone, HCl, and HNO3 column measurements at Eureka, Canada during winter/spring 2011

    NASA Astrophysics Data System (ADS)

    Lindenmaier, R.; Strong, K.; Batchelor, R. L.; Chipperfield, M. P.; Daffer, W. H.; Drummond, J. R.; Duck, T. J.; Fast, H.; Feng, W.; Fogal, P. F.; Kolonjari, F.; Manney, G. L.; Manson, A.; Meek, C.; Mittermeier, R. L.; Nott, G. J.; Perro, C.; Walker, K. A.

    2012-01-01

    As a consequence of dynamically variable meteorological conditions, springtime Arctic ozone levels exhibit significant interannual variability in the lower stratosphere. In winter 2011, the polar vortex was strong and cold for an unusually long time. Our research site, located at Eureka, Nunavut, Canada (80.05° N, 86.42° W), was mostly inside the vortex from October 2010 until late March 2011. The Bruker 125HR Fourier transform infrared spectrometer installed at the Polar Environment Atmospheric Research Laboratory at Eureka acquired measurements from 23 February to 6 April during the 2011 Canadian Arctic Atmospheric Chemistry Experiment Validation Campaign. These measurements showed unusually low ozone, HCl, and HNO3 total columns compared to the previous 14 yr. To remove dynamical effects, we normalized these total columns by the HF total column. The normalized values of the ozone, HCl, and HNO3 total columns were smaller than those from previous years, and confirmed the occurrence of chlorine activation and chemical ozone depletion. To quantify the chemical ozone loss, a three-dimensional chemical transport model, SLIMCAT, and the passive subtraction method were used. The chemical ozone depletion was calculated as the mean percentage difference between the measured ozone and the SLIMCAT passive ozone, and was found to be 35%.

  3. Partitioning of HNO3, H2O2 and SO2 to cloud ice: Simulations with CMAQ

    NASA Astrophysics Data System (ADS)

    Marmo, Brain P.; Carlton, Annmarie G.; Henderson, Barron H.

    2014-05-01

    In the upper troposphere, gas phase species can partition to cloud ice, undergo chemical reaction and contribute to particle mass aloft, affecting chemical cycling in the atmosphere. This manuscript describes the first implementation of gas-to-cloud ice partitioning of three inorganic gases, HNO3, SO2 and H2O2, along with subsequent SO2 oxidation in the Community Multiscale Air Quality (CMAQ) chemical transport model. Four simulations are performed with CMAQv4.7.1 that include lightning production of NO for August 12th-25th of 2005 to investigate the impacts of ice chemistry on CMAQ-predicted gas phase mixing ratios and particle mass concentrations of associated species. Considerable episodic decreases, greater than 25%, in gas phase HNO3 are noted at pressures of 200-600 mb, with the largest changes at 300-400 mb. Effects are also induced on other gases in the nitrogen budget. NOx and HONO mixing ratios decrease up to 20%, but changes are generally less than 10%. Nitrate aerosol mass concentrations increase up to 0.15 μg m-3 for the highest model layers (100 mb). We find that phase changes in nitrogen species induced by ice partitioning are sensitive to CMAQ predictions of the aerosol phase accumulation mode ammonium to sulfate ratios [NH]:[SO]. Predicted O3 concentrations do not change (<1%). No changes in H2O2, SO2, or sulfate aerosol concentrations are observed.

  4. Evidence That Nitric Acid Increases Relative Humidity in Low-Temperature Cirrus Clouds

    NASA Technical Reports Server (NTRS)

    Gao, R. S.; Popp, P. J.; Fahey, D. W.; Marcy, T. P.; Herman, R. L.; Weinstock, E. M.; Baumgardner, D. G.; Garrett, T. J.; Rosenlof, K. H.; Thompson, T. L.

    2004-01-01

    In situ measurements of the relative humidity with respect to ice (RH(sub(i)) and of nitric acid (HNO3) were made in both natural and contrail cirrus clouds in the upper troposphere. At temperatures lower than 202 kelvin, RH(sub i) values show a sharp increase to average values of over 130% in both cloud types. These enhanced RH(sub i) values are attributed to the presence of a new class of NHO3- containing ice particles (Delta-ice). We propose that surface HNO3 molecules prevent the ice/vapor system from reaching equilibrium by a mechanism similar to that of freezing point depression by antifreeze proteins. Delta-ice represents a new link between global climate and natural and anthropogenic nitrogen oxide emissions. Including Delta-ice in climate models will alter simulated cirrus properties and the distribution of upper tropospheric water vapor.

  5. Aerosol chamber study of optical constants and N2O5 uptake on supercooled H2SO4/H2O/HNO3 solution droplets at polar stratospheric cloud temperatures.

    PubMed

    Wagner, Robert; Naumann, Karl-Heinz; Mangold, Alexander; Möhler, Ottmar; Saathoff, Harald; Schurath, Ulrich

    2005-09-15

    The mechanism of the formation of supercooled ternary H(2)SO(4)/H(2)O/HNO(3) solution (STS) droplets in the polar winter stratosphere, i.e., the uptake of nitric acid and water onto background sulfate aerosols at T < 195 K, was successfully mimicked during a simulation experiment at the large coolable aerosol chamber AIDA of Forschungszentrum Karlsruhe. Supercooled sulfuric acid droplets, acting as background aerosol, were added to the cooled AIDA vessel at T = 193.6 K, followed by the addition of ozone and nitrogen dioxide. N(2)O(5), the product of the gas phase reaction between O(3) and NO(2), was then hydrolyzed in the liquid phase with an uptake coefficient gamma(N(2)O(5)). From this experiment, a series of FTIR extinction spectra of STS droplets was obtained, covering a broad range of different STS compositions. This infrared spectra sequence was used for a quantitative test of the accuracy of published infrared optical constants for STS aerosols, needed, for example, as input in remote sensing applications. The present findings indicate that the implementation of a mixing rule approach, i.e., calculating the refractive indices of ternary H(2)SO(4)/H(2)O/HNO(3) solution droplets based on accurate reference data sets for the two binary H(2)SO(4)/H(2)O and HNO(3)/H(2)O systems, is justified. Additional model calculations revealed that the uptake coefficient gamma(N(2)O(5)) on STS aerosols strongly decreases with increasing nitrate concentration in the particles, demonstrating that this so-called nitrate effect, already well-established from uptake experiments conducted at room temperature, is also dominant at stratospheric temperatures. PMID:16834200

  6. Revising the retrieval technique of a long-term stratospheric HNO3 data set: from a constrained matrix inversion to the optimal estimation algorithm

    NASA Astrophysics Data System (ADS)

    Fiorucci, I.; Muscari, G.; de Zafra, R. L.

    2011-07-01

    The Ground-Based Millimeter-wave Spectrometer (GBMS) was designed and built at the State University of New York at Stony Brook in the early 1990s and since then has carried out many measurement campaigns of stratospheric O3, HNO3, CO and N2O at polar and mid-latitudes. Its HNO3 data set shed light on HNO3 annual cycles over the Antarctic continent and contributed to the validation of both generations of the satellite-based JPL Microwave Limb Sounder (MLS). Following the increasing need for long-term data sets of stratospheric constituents, we resolved to establish a long-term GMBS observation site at the Arctic station of Thule (76.5° N, 68.8° W), Greenland, beginning in January 2009, in order to track the long- and short-term interactions between the changing climate and the seasonal processes tied to the ozone depletion phenomenon. Furthermore, we updated the retrieval algorithm adapting the Optimal Estimation (OE) method to GBMS spectral data in order to conform to the standard of the Network for the Detection of Atmospheric Composition Change (NDACC) microwave group, and to provide our retrievals with a set of averaging kernels that allow more straightforward comparisons with other data sets. The new OE algorithm was applied to GBMS HNO3 data sets from 1993 South Pole observations to date, in order to produce HNO3 version 2 (v2) profiles. A sample of results obtained at Antarctic latitudes in fall and winter and at mid-latitudes is shown here. In most conditions, v2 inversions show a sensitivity (i.e., sum of column elements of the averaging kernel matrix) of 100 ± 20 % from 20 to 45 km altitude, with somewhat worse (better) sensitivity in the Antarctic winter lower (upper) stratosphere. The 1σ uncertainty on HNO3 v2 mixing ratio vertical profiles depends on altitude and is estimated at ~15 % or 0.3 ppbv, whichever is larger. Comparisons of v2 with former (v1) GBMS HNO3 vertical profiles, obtained employing the constrained matrix inversion method, show that

  7. Atmospheric gaseous HNO 3, particulate nitrate, and aerosol size distributions of major ionic species at a rural site in western Germany

    NASA Astrophysics Data System (ADS)

    Mehlmann, Alois; Warneck, Peter

    Nitric acid and particulate nitrate in addition to other trace species were measured in the air at Deuselbach, a rural site in western Germany, in June and July 1985 under background atmospheric conditions. High-volume open face triple filter packs and cascade impactors were used together with ion-chromatographic analyses. Laboratory tests showed good correspondence between gaseous nitric acid and nitrate deposited on nylon back-up filters for low ambient aerosol concentrations as observed in the field. High aerosol loadings typically found in Mainz caused part of nitric acid to be retained together with particulate nitrate on the teflon front filter. The concentration of nitric acid observed in the field went through a maximum during the day and a minimum at night with a clear anti-correlation with relative humidity. For r.h. ⩽ 60% the average fraction of gaseous to total nitrate was 39 ± 8%. The average fraction from all data was 22%. The molar fraction of total nitrate to nitrogen dioxide was 24%. It is shown that the diurnal variation of HNO 3 is partly due to absorption by liquid water associated with the aerosol, which increases with rising relative humidity (at night). The absorption is significant only because solution pH is buffered by the presence of sulfate and the formation of bisulfate. Most of the field data showed particulate nitrate to occur primarily in the coarse size range ( ⩾ 2 μm diameter) with sodium providing the main cation. Sea salt was identified as the principal source of sodium. Ammonium nitrate occurred only sporadically in the fine particle mode ( ⩽ 2 pm diameter). Ammonium nitrate was largely absent because the product of the concentrations of nitric acid (observed) and ammonia (inferred) was below the minimum required for equilibrium concentrations of particulate NH 4NO 3 to form. In addition, there often was insufficient ammonium (and other measurable cations) present in fine particles to balance the amount of sulfate.

  8. Effects of Acid Vapor, Basic Vapor and Heat Treatments on the Properties of Langmuir-Blodgett Films of Divalent Metal Salts of Fatty Acids

    NASA Astrophysics Data System (ADS)

    Saito, Mitsuyoshi; Sugi, Michio; Ikegami, Keiichi; Yoneyama, Mitsuru; Iizima, Sigeru

    1986-06-01

    When LB films are exposed to the atmosphere vaporized from acid at room temperature, the X-ray diffraction peaks attributed to the lamellar structure disappear and new peaks appear depending on the metal ion species of the salt, whereas such noticeable change is not observed by basic vapor treatment and heat treatment. Diffraction patterns for LB films of free fatty acids are not influenced by these three treatments.

  9. The effect of ultrasonic and HNO3 treatment of activated carbon from fruit stones on capacitive and pseudocapacitive energy storage in electrochemical supercapacitors.

    PubMed

    Venhryn, B Ya; Stotsko, Z A; Grygorchak, I I; Bakhmatyuk, B P; Mudry, S I

    2013-09-01

    The effect of ultrasonic treatment and modification with nitric acid of activated carbon obtained from fruit stones, on the parameters of electric double-layer (EDL) as well as on farad-volt characteristics of its boundary with electrolyte 7.6 m KОН, 4 m KI and 2 m ZnI2 aqueous solutions has been studied by means of precision porometry, cyclic voltamperometry, electrochemical impedance spectroscopy and computer simulation methods. It is shown that HNO3 treatment results in an increase of the electrostatic capacitance up to 202 F/g in 7.6 m KОН-solution as well as pseudocapacitance up to 1250 F/g in 4 m KI. This increase is supposed to be related both with hydrophilicity and with an increase of the density of states on Fermi level. The ultrasonic treatment enables one to significantly increase (more than 200 times) the density of states on Fermi level which in turn causes both quantitative and qualitative changes in farad-volt dependences. A hybrid supercapacitor with specific capacitance of 1100 F/g and specific energy of 49 Wh/kg per active mass of two electrodes was developed. PMID:23541908

  10. HNO 3 fluxes to a deciduous forest derived using gradient and REA methods

    NASA Astrophysics Data System (ADS)

    Pryor, S. C.; Barthelmie, R. J.; Jensen, B.; Jensen, N. O.; Sørensen, L. L.

    Summertime nitric acid concentrations over a deciduous forest in the midwestern United States are reported, which range between 0.36 and 3.3 μg m -3. Fluxes to the forest are computed using the relaxed eddy accumulation technique and gradient methods. In accord with previous studies, the results indicate substantial uncertainties in the gradient-based calculations. The relaxed eddy accumulation (REA) derived fluxes are physically reasonable and are shown to be of similar magnitude to dry deposition estimates from gradient sampling. The REA derived mean deposition velocity is approximately 3 cm s -1, which is also comparable to growing season estimates derived by Meyers et al. for a similar deciduous forest. Occasional inverted concentration gradients and fluxes are observed but most are not statistically significant. Data are also presented that indicate substantial through canopy penetration of nitric acid.

  11. Kinetics of the Reactions of F((sup 2)P) and Cl((sup 2)P) with HNO3

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Wells, J. R.; Nicovich, J. M.

    1997-01-01

    The kinetics of the reactions of HNO3 with fluorine (k(sub 1)) and Chlorine (k(sub 2)) atoms have been studied by using a time-resolved long-path laser absorption technique to monitor the appearance of product NO3 radicals following 351-nm pulsed laser photolysis of X2/HNO3/He mixtures (X = F,Cl). Absolute rate coefficients for the F((sup 2)P) + HNO reaction have been determined over the temperature range 260-373 K. Between 260 and 320 K, the data are adequately represented by the Arrhenius expression k(sub 1)(T) = (6.0 +/- 2.6) x 10(exp -12) exp[(40 +/- 120)/T]cu cm/(molecule.s). Between 335 and 373 K, the rate coefficient is found to be (2.0 +/- 0.3) x 10(exp -11)cu cm/(molecule.s) independent of temperature. The observed temperature dependence suggests that reaction proceeds via competing direct abstraction and complex pathways. No NO3 production was observed in the experiments with X equals Cl, thus establishing that k(sub 2)(298 K) is less than 2 x 10(exp -16) cu cm/(molecule.s). The Cl((sup 2)P) + HNO reaction was also investigated by using a pulsed laser photolysis-resonance fluorescence technique to monitor the decay of Cl((sup 2)P). Upper limit values for k(sub 2) obtained from these experiments, in units of 10(exp -16)cu cm/(molecule.s), are 13 at 298 K and 10 at 400 K.

  12. Balloon profiles of stratospheric NO2 and HNO3 for testing the heterogeneous hydrolysis of N2O5 on sulfate aerosols

    NASA Technical Reports Server (NTRS)

    Webster, C. R.; May, R. D.; Allen, M.; Jaegle, L.; Mccormick, M. P.

    1994-01-01

    Simultaneous in situ measurements of stratospheric NO2, HNO3, HCl, and CH4 from 34 to 24 km were made in August 1992 from Palestine, Texas, using the Balloon-borne Laser In-Situ Sensor (BLISS) tunable diode laser spectrometer. Although the measurements of NO2, HNO3, and NO2/HNO3 agree well with gas-phase model calculations near 34 km where Stratospheric Aerosol and Gas Experiment (SAGE) 2 data show little sulfate aerosol, this is not true at the lower altitudes where SAGE 2 shows high aerosol loadings. At 24 km the BLISS NO2 and HNO3 measurements are 70% lower and 50% higher, respectively, than the gas phase model predictions, with a measured NO2/HNO3 ratio 5 times smaller. When the heterogeneous hydrolysis of N2O5 and ClONO2 on sulfate aerosol of surface area densities matching the SAGE 2 measurements is added to the model, good agreement with the BLISS measurements is found over the whole altitude range.

  13. Experimental plant for simultaneous production of (14)N and (15)N by (15)N/(14)N exchange in NO, NO(2)-HNO(3) system under pressure.

    PubMed

    Axente, Damian; Marcu, Cristina; Muresan, Ancuţa; Kaucsar, Martin; Misan, Ioan; Popeneciu, Gabriel; Gligan, Nicolae; Cristea, Gabriela

    2010-06-01

    An experimental study on (14)N and (15)N simultaneous separation using the chemical exchange in NO, NO(2)-HNO(3) system under pressure is presented. The influence of the pressure and of the interstage 10 M HNO(3) flow rate on the separation of (14)N and (15)N was measured on a packed column with product and waste refluxers. At steady state and 1.8 atm (absolute), the isotopic concentration at the bottom of the separation column was 0.563 at% (15)N, and in the top of the column was 0.159 at% (15)N. The height equivalent to a theoretical plate and interstage 10 M HNO(3) flow rate values, obtained in these experimental conditions, allows the separation of (14)N highly depleted of (15)N and of (15)N at 99 at% (15)N concentration. PMID:20582793

  14. New analysis of the ν3 and ν4 bands of HNO3 in the 7.6 μm region.

    PubMed

    Perrin, Agnès

    2013-12-19

    A new line position analysis of the ν3 and ν4 bands of nitric acid (HNO3) at 1326.186 and 1303.072 cm(-1) together with its associated interacting bands is presented. The 3(1) and 4(1) energy levels were obtained from an extended analysis of high-resolution Fourier transform spectra recorded at Giessen in the 7.6 μm region. The energy levels of 3(1) and 4(1) upper states of nitric acid are strongly interacting with those of the 9(3), 6(2), 5(1)9(1), and 7(1)8(1) dark states centered at 1288.899, 1289.46, 1341.05, and 1343.78 cm(-1), respectively. Informations on these perturbing dark states were achieved through previous partial investigations of hot bands in high-resolution Fourier transform spectra recorded at 22 μm in Giessen (for 3ν9-2ν9 and 3ν9-ν5), at 12 μm in Denver (for 3ν9-ν9), and at 11 μm in Orsay (for ν5+ν9-ν9). The energy levels calculation accounts for the various Fermi, anharmonic, A-type, B-type, and C-type Coriolis resonances, which couple together the {6(2),9(3),4(1),3(1),5(1)9(1),7(1)8(1)} interacting energy levels. For nitric acid, the ν9 mode (OH torsion relative to the -NO2 moiety) is a large amplitude motion. The theoretical model used in this work accounts also for large amplitude effects in the 9(3) dark state, which lead to a splitting of the 9(3) energy levels of about 0.060 cm(-1). In this way, the existence of torsional splittings for several ν4 perturbed lines was explained by the occurrence of local A-type and B-type Coriolis resonances coupling the 4(1) energy levels with those of 9(3). Because four dark bands had to be accounted for in the model, the results of the energy level calculations are reasonable, although not perfect. However, a very significant improvement was achieved in terms of understanding the 7.6 μm absorbing bands of nitric acid as compared to the analysis of the ν3 and ν4 bands performed several years ago [Perrin, A.; Lado-Bordowski, O.; Valentin, A. Mol. Phys. 1989, 67, 249-267]. Finally, the

  15. Direct bonding for dissimilar metals assisted by carboxylic acid vapor

    NASA Astrophysics Data System (ADS)

    Song, Jenn-Ming; Huang, Shang-Kun; Akaike, Masatake; Suga, Tadatomo

    2015-03-01

    This study developed a low-temperature low-vacuum direct bonding process for dissimilar metals via surface modification with formic acid vapor. Robust Cu/Ag and Cu/Zn bonding with a shear strength higher than 25 MPa can be achieved by thermal compression at 275 and 300 °C, respectively. CuZn5 and Cu5Zn8 formed at the interface of Cu/Zn joints, while no distinct interdiffusion layers appeared at the Cu/Ag interface. At elevated temperatures, the shear strength of Cu/Zn joints decreased significantly and turned to be weaker than Cu/Ag at 250 °C due to the softening of Zn. All the joints performed well subjected to thermal cycling up to 1000 times. However, compared with Cu/Ag joints with stable mechanical performance suffering aging at 250 °C, the shear strength of Cu/Zn degraded drastically up to 200 h, and after that it remained almost constant, which can be ascribed to the competitive growth between CuZn5 and Cu5Zn8, resulting in collapse and oxidation of CuZn5.

  16. Observations and Modeling of Composition of Upper Troposphere/Lower Stratosphere (UTILS): Isentropic Mixing Events and Morphology of HNO3 as Observed by HIRDLS and Comparison with Results from Global Modeling Initiative

    NASA Technical Reports Server (NTRS)

    Rodriquez, J. M.; Douglass, A.R.; Yoshida, Y.; Strahan, S.; Duncan, B.; Olsen, M.; Gille, J.; Yudin, V.; Nardi, B.

    2008-01-01

    isentropic exchange of air masses between the tropical upper troposphere and mid-latitude lowermost stratosphere (the so-called "middle world") is an important pathway for stratospheric-tropospheric exchange. A seasonal, global view of this process has been difficult to obtain, in part due to the lack of the vertical resolution in satellite observations needed to capture the laminar character of these events. Ozone observations at a resolution of about 1 km from the High Resolution Dynamic Limb Sounder (HIRDLS) on NASA's Aura satellite show instances of these intrusions. Such intrusions should also be observable in HN03 observations; however, the abundances of nitric acid could be additionally controlled by chemical processes or incorporation and removal into ice clouds. We present a systematic examination of the HIRDLS data on O3 and HNO3 to determine the seasonal and spatial characteristics of the distribution of isentropic intrusions. At the same time, we compare the observed distributions with those calculated by the Global Modeling Initiative combined tropospheric-stratospheric model, which has a vertical resolution of about I km. This Chemical Transport Model (CTM) is driven by meteorological fields obtained from the GEOS-4 system of NASA/Goddard Global Modeling and Assimilation Office (GMAO), for the Aura time period, at a vertical resolution of about 1 km. Such comparison brings out the successes and limitations of the model in representing isentropic stratospheric-tropospheric exchange, and the different processes controlling HNO3 in the UTAS.

  17. Measurements of NO2, SO2, NH3, HNO3 and O3 in West African urban environments

    NASA Astrophysics Data System (ADS)

    Adon, Marcellin; Yoboué, Véronique; Galy-Lacaux, Corinne; Liousse, Catherine; Diop, Babakar; Doumbia, El Hadji Thierno; Gardrat, Eric; Ndiaye, Seydi Ababacar; Jarnot, Christian

    2016-06-01

    In this paper, we present the measurements of atmospheric gas concentrations of NO2, SO2, NH3, HNO3, and O3 performed at two traffic sites in the context of the POLCA (Pollution of African Capitals) program. These gases were measured using a passive sampling technique from Jan. 2008 to Dec. 2009 at Dakar and from Jun. 2008 to Dec. 2009 at Bamako. In addition, during these periods there were two intensive measurement campaigns (from 19 Jan. to 2 Feb. 2009 at Bamako and from 30 Nov. to 13 Dec. 2009 at Dakar) where real-time active analysers were used to measure NO2 and SO2. Results show that Dakar has a pollution level for NO2 and SO2 higher than that of Bamako, whereas it is lower for NH3 concentrations. Monthly values of NO2 range between 21.1 and 43.5 ppb in Dakar with an annual mean concentration of 31.7 ppb (59.6 μg/m3). NO2 values in Bamako are 9.4-22.6 ppb with a mean of 16.2 ppb. At Dakar, the mean annual NO2 limit value (21.3 ppb or 40 μg/m3) recommended by the World Health Organization (WHO) is widely exceeded. The mean annual concentration of SO2 is 15.9 ppb in Dakar and 3.6 ppb in Bamako. These differences may be explained by different sources of traffic between Bamako (with mainly gasoline vehicles) and Dakar (with mainly diesel vehicles). The annual mean NH3 concentration is about two times higher in Bamako (46.7 ppb) than in Dakar (21.1 ppb). In addition to other possible sources, we assume that the ammonia from domestic fires and uncontrolled garbage incineration may have more influence at Bamako than at Dakar. The mean annual concentrations of HNO3 and O3 are 1.3 ppb and 7.7 ppb in Dakar and 0.6 ppb and 5.1 ppb in Bamako, respectively. Seasonal variation in measured gas concentrations are low in Bamako and more pronounced in Dakar, except for HNO3 and NH3. At Dakar, NO2 and SO2 daily mean concentrations are higher during the weekdays than on weekends, when urban activities are reduced, whereas at Bamako, no significant difference was observed

  18. A multifacet mechanism for the OH+HNO3 reaction: An ab initio molecular orbital/statistical theory study

    NASA Astrophysics Data System (ADS)

    Xia, W. S.; Lin, M. C.

    2001-03-01

    The mechanism for the OH+HNO3 reaction has been studied by ab initio molecular orbital calculations at the G2M(cc3) level of theory. Four complexes and four transition states have been found and confirmed by intrinsic reaction coordinate analyses. The commonly assumed six-membered ring complex formed by hydrogen bonding of the OH radical with HNO3, -ON(O)OH…OH-, was found to be stable by 8.1 kcal/mol; its decomposition producing NO3+H2O was predicted to have a barrier of 11.6 kcal/mol. A five-membered ring complex, -ON(O)OH…O(H)-, with the H atom of the OH radical placed out of the ring plane, was found to have a stability of 5.3 kcal/mol; it fragments to form NO3+H2O with a barrier of 6.6 kcal/mol. Two additional complexes, which are the mirror image of each other with a 7.4 kcal/mol binding energy, were found to be related to the OH exchange reaction with a 13.3 kcal/mol barrier above the complexes. The direct abstraction process producing H2O2 and NO2 was predicted to have a large barrier of 24.4 kcal/mol, insignificant to atmospheric chemistry. The rate constant has been calculated at 200-1500 K and 0-760 Torr. The results show that the reaction has strong pressure and tunneling effects below room temperature. In addition, the rate constants for the decay of OH and OD (in OD+DNO3) evaluated by kinetic modeling compare reasonably well with experimental data below room temperature. The unusually pronounced kinetic isotope effect observed experimentally, kH/kD⩾10, could be accounted for by the combination of the greater tunneling rate in the H system and the large redissociation rate of stabilized complexes in the D system. The rate constant predicted for the production of H2O and NO3 in the temperature range 750-1500 K can be effectively represented by the expression k=1.45×10-23 T3.5 exp(+839/T) cm3/s.

  19. Gas Cluster Ion Beam Etching under Acetic Acid Vapor for Etch-Resistant Material

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Akira; Hinoura, Ryo; Toyoda, Noriaki; Hara, Ken-ichi; Yamada, Isao

    2013-05-01

    Gas cluster ion beam (GCIB) etching of etch-resistant materials under acetic acid vapor was studied for development of new manufacturing process of future nonvolatile memory. Etching depths of various etch-resistant materials (Pt, Ru, Ta, CoFe) with acetic acid vapor during O2-GCIB irradiations were 1.8-10.7 times higher than those without acetic acid. Also, etching depths of Ru, Ta, CoFe by Ar-GCIB with acetic acid vapor were 2.2-16.1 times higher than those without acetic acid. Even after etching of Pt, smoothing of Pt was realized using O2-GCIB under acetic acid. From XPS and angular distribution of sputtered Pt, it was shown that PtOx layer was formed on Pt after O2-GCIB irradiation. PtOx reacted with acetic acid by GCIB bombardments; as a result, increase of etching depth was observed.

  20. Stratospheric HNO3 measurements from 0.002/cm resolution solar occultation spectra and improved spectroscopic line parameters in the 5.8-micron region

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Murcray, F. J.; Blatherwick, R. D.; Kosters, J. J.; Murcray, D. G.; Rinsland, C. P.; Flaud, J.-M.; Camy-Peyret, C.

    1992-01-01

    Very-high-resolution FWHM solar-occultation spectra are investigated with a balloon-borne interferometer using revised spectroscopic line parameters for HNO3, O3, and H2O. The O3 and H2O data are evaluated to determine their capacity for interference in the HNO3 line which is studied in the nu sub 2 band at 5.8 microns. The line parameters developed with the stratospheric data are compared to data based on a HITRAN compilation as well as laboratory spectra with a 0.002/cm resolution. The line list is calculated and shown to include J and Ka transitions which improve the line parameters for HNO3 by accounting for the weaker absorption features in the stratospheric spectra. The stratospheric HNO3 profile developed analytically is compared to those based on reported measurements, and the one developed with the stratospheric solar spectra is found to be consistent with the measurements and confirm inherent measurement biases.

  1. Intercomparison of Clean Air Status and Trends Network (CASTNET) NO3 - and HNO3 Measurements with Data from Other Monitoring Programs

    EPA Science Inventory

    The EPA Clean Air Status and Trends Network (CASTNET) utilizes an open face filter pack system to measure concentrations of atmospheric sulfur and nitrogen species. The purpose of this study was to estimate the uncertainty in seasonal and annual concentrations of HNO3, NO3 - , ...

  2. Stratospheric HNO3 measurements from 0.002/cm resolution solar occultation spectra and improved spectroscopic line parameters in the 5.8-micron region

    NASA Astrophysics Data System (ADS)

    Goldman, A.; Murcray, F. J.; Blatherwick, R. D.; Kosters, J. J.; Murcray, D. G.; Rinsland, C. P.; Flaud, J.-M.; Camy-Peyret, C.

    1992-02-01

    Very-high-resolution FWHM solar-occultation spectra are investigated with a balloon-borne interferometer using revised spectroscopic line parameters for HNO3, O3, and H2O. The O3 and H2O data are evaluated to determine their capacity for interference in the HNO3 line which is studied in the nu sub 2 band at 5.8 microns. The line parameters developed with the stratospheric data are compared to data based on a HITRAN compilation as well as laboratory spectra with a 0.002/cm resolution. The line list is calculated and shown to include J and Ka transitions which improve the line parameters for HNO3 by accounting for the weaker absorption features in the stratospheric spectra. The stratospheric HNO3 profile developed analytically is compared to those based on reported measurements, and the one developed with the stratospheric solar spectra is found to be consistent with the measurements and confirm inherent measurement biases.

  3. Measurements of HNO3 and N2O5 using Ion drift - Chemical Ionization Mass Spectrometry during the MCMA - 2006 Campaign

    NASA Astrophysics Data System (ADS)

    Zheng, J.; Zhang, R.; Fortner, E. C.; Molina, L.; Aiken, A. C.; Jimenez, J. L.; Gäggeler, K.; Dommen, J.; Dusanter, S.; Stevens, P. S.; Tie, X.

    2008-03-01

    An ion drift - chemical ionization mass spectrometry (ID-CIMS) was deployed in Mexico City between 5 and 31 March to measure HNO3 and N2O5 during the 2006 Mexico City Metropolitan Area (MCMA) field campaign. The observation site, T0, was located at the Instituto Mexicano del Petróleo at the center of the Mexico City Basin with major emissions of pollutants from both domestic and industrial sources. Diurnally, HNO3 was less than 200 parts per trillion (ppt) during the night and in the early morning, increased steadily from around 09:00 a.m. central standard time (CST), reached a peak value of 0.5 to 3 parts per billion (ppb) in the early afternoon, and declined sharply to less than half of the peak value near 05:00 p.m. CST. An inter-comparison between the ID-CIMS and an ion chromatograph/mass spectrometer (ICMS) showed a good correlation in the HNO3 measurements (R2=0.75). The HNO3 mixing ratio was found to anti-correlate with aerosol nitrate, suggesting that the gaseous HNO3 concentration was controlled by the gas-particle partitioning process. During most times of the MCMA 2006 field campaign, N2O5 was found to be under the detection limit (about 20 ppt for a 10 s integration time) of the ID-CIMS, because of high NO mixing ratio (>100 ppb) during the night. With one exception on 26 March 2006, about 40 ppt N2O5 was observed during the late afternoon and early evening hours under a cloudy condition, before NO built up at the surface site. The results revealed that during the 2006 MCMA field campaign HNO3 was primarily produced by the reaction of OH with NO2 and regulated by gas/particle partitioning, and HNO3 production from N2O5 hydrolysis during the nighttime was small because of high NO and low O3 concentrations near the surface.

  4. Covalent functionalization of HiPco single-walled carbon nanotubes: differences in the oxidizing action of H2 SO4 and HNO3 during a soft oxidation process.

    PubMed

    Devaux, Xavier; Vigolo, Brigitte; McRae, Edward; Valsaque, Fabrice; Allali, Naoual; Mamane, Victor; Fort, Yves; Soldatov, Alexander V; Dossot, Manuel; Tsareva, Svetlana Yu

    2015-08-24

    The results of a study on the evolution of HiPco single-walled carbon nanotubes during the oxidizing action of H2 SO4 and HNO3 are presented. The process conditions used have been chosen so as to avoid any significant damage to the nanotube structure. The type and level of functionalization, the location of the grafted functions on the surface of the nanotube and the changes in morphological characteristics of the samples were examined by using a wide and complementary range of analytical techniques. We propose an explanation for the differences in the oxidizing action of sulfuric and nitric acids. The combined results allow us to suggest possible reaction mechanisms that occur on the surface of the nanotube. PMID:26136373

  5. Surface-catalyzed chlorine and nitrogen activation: mechanisms for the heterogeneous formation of ClNO, NO, NO2, HONO, and N2O from HNO3 and HCl on aluminum oxide particle surfaces.

    PubMed

    Rubasinghege, Gayan; Grassian, Vicki H

    2012-05-31

    It is well-known that chlorine active species (e.g., Cl(2), ClONO(2), ClONO) can form from heterogeneous reactions between nitrogen oxides and hydrogen chloride on aerosol particle surfaces in the stratosphere. However, less is known about these reactions in the troposphere. In this study, a potential new heterogeneous pathway involving reaction of gaseous HCl and HNO(3) on aluminum oxide particle surfaces, a proxy for mineral dust in the troposphere, is proposed. We combine transmission Fourier transform infrared spectroscopy with X-ray photoelectron spectroscopy to investigate changes in the composition of both gas-phase and surface-bound species during the reaction under different environmental conditions of relative humidity and simulated solar radiation. Exposure of surface nitrate-coated aluminum oxide particles, from prereaction with nitric acid, to gaseous HCl yields several gas-phase products, including ClNO, NO(2), and HNO(3), under dry (RH < 1%) conditions. Under humid more conditions (RH > 20%), NO and N(2)O are the only gas products observed. The experimental data suggest that, in the presence of adsorbed water, ClNO is hydrolyzed on the particle surface to yield NO and NO(2), potentially via a HONO intermediate. NO(2) undergoes further hydrolysis via a surface-mediated process, resulting in N(2)O as an additional nitrogen-containing product. In the presence of broad-band irradiation (λ > 300 nm) gas-phase products can undergo photochemistry, e.g., ClNO photodissociates to NO and chlorine atoms. The gas-phase product distribution also depends on particle mineralogy (Al(2)O(3) vs CaCO(3)) and the presence of other coadsorbed gases (e.g., NH(3)). These newly identified reaction pathways discussed here involve continuous production of active ozone-depleting chlorine and nitrogen species from stable sinks such as gas-phase HCl and HNO(3) as a result of heterogeneous surface reactions. Given that aluminosilicates represent a major fraction of mineral dust

  6. Vapor pressures of substituted polycarboxylic acids are much lower than previously reported

    NASA Astrophysics Data System (ADS)

    Huisman, A. J.; Krieger, U. K.; Zuend, A.; Marcolli, C.; Peter, T.

    2013-07-01

    The partitioning of compounds between the aerosol and gas phase is a primary focus in the study of the formation and fate of secondary organic aerosol. We present measurements of the vapor pressure of 2-methylmalonic (isosuccinic) acid, 2-hydroxymalonic (tartronic) acid, 2-methylglutaric acid, 3-hydroxy-3-carboxy-glutaric (citric) acid and DL-2,3-dihydroxysuccinic (DL-tartaric) acid, which were obtained from the evaporation rate of supersaturated liquid particles levitated in an electrodynamic balance. Our measurements indicate that the pure component liquid vapor pressures at 298.15 K for tartronic, citric and tartaric acids are much lower than the same quantity that was derived from solid state measurements in the only other room temperature measurement of these materials (made by Booth et al., 2010). This strongly suggests that empirical correction terms in a recent vapor pressure estimation model to account for the inexplicably high vapor pressures of these and similar compounds should be revisited, and that due caution should be used when the estimated vapor pressures of these and similar compounds are used as inputs for other studies.

  7. Vapor pressures of substituted polycarboxylic acids are much lower than previously reported

    NASA Astrophysics Data System (ADS)

    Huisman, A. J.; Krieger, U. K.; Zuend, A.; Marcolli, C.; Peter, T.

    2013-01-01

    The partitioning of compounds between the aerosol and gas phase is a primary focus in the study of the formation and fate of secondary organic aerosol. We present measurements of the vapor pressure of 2-Methylmalonic (isosuccinic) acid, 2-Hydroxymalonic (tartronic) acid, 2-Methylglutaric acid, 3-Hydroxy-3-carboxy-glutaric (citric) acid and 2,3-Dihydroxysuccinic (tartaric) acid which were obtained from the evaporation rate of supersaturated liquid particles levitated in an electrodynamic balance. Our measurements indicate that the pure component liquid vapor pressures at 298.15 K for tartronic, citric and tartaric acids are much lower than the same quantity which was derived from solid state measurements in the only other room temperature measurement of these materials (made by Booth et al., 2010). This strongly suggests that empirical correction terms in vapor pressure estimation models to account for the inexplicably high vapor pressures of these and similar compounds should be revisited, and that due caution should be used when the estimated vapor pressures of these and similar compounds are used as inputs for other studies.

  8. What Is the Boiling Point and Heat of Vaporization of Sulfuric Acid?

    ERIC Educational Resources Information Center

    Myers, R. Thomas

    1983-01-01

    Discusses the values presented in various handbooks for the boiling point and heat of vaporization of sulfuric acid, noting discrepencies. Analyzes various approaches to data presentation, discussing the data on sulfuric acid in light of the Trouton constant. Points out the need for a more critical use of tables. (JM)

  9. Identification of the HNO3 3 nu(sub 9) - nu(sub 9) band Q branch in stratospheric solar occultation spectra

    NASA Technical Reports Server (NTRS)

    Perrin, A.; Flaud, J.-M.; Camy-Peyret, C.; Goldman, A.; Rinsland, C. P.; Gunson, M. R.

    1994-01-01

    The spectroscopic identification for the HNO3 3 nu(sub 9) - nu(sub 9) band Q branch at 830.4/cm is reported based on 0.01/cm resolution solar occultation spectra of the lower stratosphere recorded by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer and a recent analysis of this band. Least-squares fits to 0.0025/cm resolution laboratory spectra in the Q branch region indicate an integrated intensity of 0.529 x 10(exp -18)/cm/mol/sq cm at 296 K for this weak band. Stratospheric HNO3 retrievals derived from the ATMOS data are consistent with this value within its estimated uncertainty of about +/- 30%. A set of spectroscopic line parameters suitable for atmospheric studies has been generated.

  10. In situ stratospheric measurements of HNO3 and HCl near 30 km using the balloon-borne laser in situ sensor tunable diode laser spectrometer

    NASA Technical Reports Server (NTRS)

    May, R. D.; Webster, C. R.

    1989-01-01

    In situ stratospheric measurements of the concentrations of the reservoir species HNO3 and HCl made during two flights of the high-resolution (0.0005/cm) balloon-borne laser in situ sensor instrument from Palestine, Texas, are reported. A measured HNO3 volume mixing ratio of 4.3 parts per billion by volume (ppbv) at 31 km altitude is about 1 ppbv larger than previously reported measurements at 32 deg N. An HCl mixing ratio of 1.6 ppbv at 29 km is in agreement with values obtained from earlier remote sensing techniques within the experimental uncertainties. Upper limits at 31 km of 0.4 ppbv for H2O2 and 0.2 ppbv for HOCl are also derived from analyses of spectra recorded near 1252/cm.

  11. Comparison of correlative data with HNO3 version 7 from the CLAES instrument deployed on the NASA Upper Atmosphere Research Satellite

    NASA Astrophysics Data System (ADS)

    Kumer, J. B.; Mergenthaler, J. L.; Roche, A. E.; Nightingale, R. W.; Ely, G. A.; Uplinger, W. G.; Gille, J. C.; Massie, S. T.; Bailey, P. L.; Gunson, M. R.; Abrams, M. C.; Toon, G. C.; Sen, B.; Blavier, J.-F.; Stachnik, R. A.; Webster, C. R.; May, R. D.; Murcray, D. G.; Murcray, F. J.; Goldman, A.; Traub, W. A.; Jucks, K. W.; Johnson, D. G.

    1996-04-01

    The cryogenic limb array etalon spectrometer (CLAES) aboard UARS made near-global measurements of HNO3 and 388 days from January 9, 1992, to April 25, 1993, have been processed to data version 7 (V7). Results from UARS instruments, including CLAES, the improved stratospheric and mesospheric sounder, and the microwave limb sounder, provide the first near-global documentation of the evolution of denitrification in the Antarctic 1992 winter and spring vortex. We provide a description of the CLAES HNO3 V7 quality that includes comparisons with correlative measurements to assess overall quality, accuracy, and precision. Correlative profiles of volume mixing ratio (vmr) included those obtained by the space shuttle deployed ATMOS in two missions, March-April 1992 and April 1993, data from a variety of balloon-borne instruments at midlatitude (11 profiles), and in high-latitude northern winter (six profiles), and LIMS data. In general, the CLAES V7 HNO3 maximum values of vmr were of the order of 6-15% less than correlative for CLAES values ≤8 parts per billion by volume (ppbv). However, when CLAES peak vmr values were 10 to 13 ppbv, then CLAES values exceeded correlative by 0-7%. The comparisons were within the combined instrumental error estimates, or observed measurement variability, for the large majority of comparisons. As discussed, the retrieval of future versions will utilize updated spectral parameters and will also correct for a small uncompensated drift in radiometric calibration that occurred in the latter part of the mission. This is expected to improve the comparisons in the ≤8 ppbv range, perhaps at the expense of those in the ≥8 ppbv range. The data obtained January 9 to April 15, 1992, in comparison with data obtained January 9 to April 15, 1993, reveal strikingly evident 1-year period deseasonalized trends on a global basis. These trends agree quantitatively with available correlative data suitable for trend analysis. These include ATMOS in the

  12. Structure-property relationships in halogenbenzoic acids: Thermodynamics of sublimation, fusion, vaporization and solubility.

    PubMed

    Zherikova, Kseniya V; Svetlov, Aleksey A; Kuratieva, Natalia V; Verevkin, Sergey P

    2016-10-01

    Temperature dependences of vapor pressures for 2-, 3-, and 4-bromobenzoic acid, as well as for five isomeric bromo-methylbenzoic acids were studied by the transpiration method. Melting temperatures and enthalpies of fusion for all isomeric bromo-methylbenzoic acids and 4-bromobenzoic acid were measured with a DSC. The molar enthalpies of sublimation and vaporization were derived. These data together with results available in the literature were collected and checked for internal consistency using a group-additivity procedure and results from X-ray structural diffraction studies. Specific (hydrogen bonding) interactions in the liquid and in the crystal phase of halogenbenzoic acids were quantified based on experimental values of vaporization and sublimation enthalpies. Structure-property correlations of solubilities of halogenobenzoic acids with sublimation pressures and sublimation enthalpies were developed and solubilities of bromo-benzoic acids were estimated. These new results resolve much of the ambiguity in the available thermochemical and solubility data on bromobenzoic acids. The approach based on structure property correlations can be applied for the assessment of water solubility of sparingly soluble drugs. PMID:27424058

  13. LIMS Instrument Package (LIP) balloon experiment: Nimbus 7 satellite correlative temperature, ozone, water vapor, and nitric acid measurements

    NASA Technical Reports Server (NTRS)

    Lee, R. B., III; Gandrud, B. W.; Robbins, D. E.; Rossi, L. C.; Swann, N. R. W.

    1982-01-01

    The Limb Infrared Monitor of the Stratosphere (LIMS) LIP balloon experiment was used to obtain correlative temperature, ozone, water vapor, and nitric acid data at altitudes between 10 and 36 kilometers. The performance of the LIMS sensor flown on the Nimbus 7 Satellite was assessed. The LIP consists of the modified electrochemical concentration cell ozonesonde, the ultraviolet absorption photometric of ozone, the water vapor infrared radiometer sonde, the chemical absorption filter instrument for nitric acid vapor, and the infrared radiometer for nitric acid vapor. The limb instrument package (LIP), its correlative sensors, and the resulting data obtained from an engineering and four correlative flights are described.

  14. VAPOR PRESSURE AND MELTING BEHAVIOR OF SULFURIC ACID-WATER SYSTEMS

    EPA Science Inventory

    An experimental apparatus was designed and constructed to use high vacuum and mass spectrometric techniques to determine total and partial vapor pressures above bulk liquid samples in the temperature range between -65C and 25C. Observations on the sulfuric acid-water system revea...

  15. Evaluation of sampling methods for measuring exposure to volatile inorganic acids in workplace air. Part 1: sampling hydrochloric acid (HCl) and nitric acid (HNO₃) from a test gas atmosphere.

    PubMed

    Howe, Alan; Musgrove, Darren; Breuer, Dietmar; Gusbeth, Krista; Moritz, Andreas; Demange, Martine; Oury, Véronique; Rousset, Davy; Dorotte, Michel

    2011-08-01

    Historically, workplace exposure to the volatile inorganic acids hydrochloric acid (HCl) and nitric acid (HNO(3)) has been determined mostly by collection on silica gel sorbent tubes and analysis of the corresponding anions by ion chromatography (IC). However, HCl and HNO(3) can be present in workplace air in the form of mist as well as vapor, so it is important to sample the inhalable fraction of airborne particles. As sorbent tubes exhibit a low sampling efficiency for inhalable particles, a more suitable method was required. This is the first of two articles on "Evaluation of Sampling Methods for Measuring Exposure to Volatile Inorganic Acids in Workplace Air" and describes collaborative sampling exercises carried out to evaluate an alternative method for sampling HCl and HNO(3) using sodium carbonate-impregnated filters. The second article describes sampling capacity and breakthrough tests. The method was found to perform well and a quartz fiber filter impregnated with 500 μL of 1 M Na(2)CO(3) (10% (m/v) Na(2)CO(3)) was found to have sufficient sampling capacity for use in workplace air measurement. A pre-filter is required to remove particulate chlorides and nitrates that when present would otherwise result in a positive interference. A GSP sampler fitted with a plastic cone, a closed face cassette, or a plastic IOM sampler were all found to be suitable for mounting the pre-filter and sampling filter(s), but care has to be taken with the IOM sampler to ensure that the sampler is tightly closed to avoid leaks. HCl and HNO(3) can react with co-sampled particulate matter on the pre-filter, e.g., zinc oxide, leading to low results, and stronger acids can react with particulate chlorides and nitrates removed by the pre-filter to liberate HCl and HNO(3), which are subsequently collected on the sampling filter, leading to high results. However, although there is this potential for both positive and negative interferences in the measurement, these are unavoidable

  16. Topical and vapor toxicity of saturated fatty acids to the German cockroach (Dictyoptera: Blattellidae).

    PubMed

    Sims, Steven R; Balusu, Rammohan R; Ngumbi, Esther N; Appel, Arthur G

    2014-04-01

    Topical and fumigant toxicity of saturated aliphatic fatty acids with chain lengths of C1 through C14 were determined against the German cockroach, Blattella germanica (L.). In the C1 to C11 series, topical toxicity (LD50 in milligram per adult male) ranged from 0.145 (C1) to 0.322 mg (C2). Toxicity declined dramatically with C12 and C14 acids whose LD50 values could not be calculated. The relative fumigation toxicity (LC50 in microliter per liter) of C1 through C5 acids was positively correlated with topical toxicity with values ranging from 6.159 (C3) to 12.302 microl/liter (C2). Fumigant toxicity decreased sharply with C6 (LC50 = 37.691 microl/liter) and there was no mortality of cockroaches exposed to vapors from C7 to C14 acids. The low fumigant toxicity of the C6 to C11 acids was correlated with their relatively low vapor pressure, but differences in diffusion of the vapors into the spiracles and subsequent passage to the target sites may have also been involved. PMID:24772558

  17. Modulation of size and viscosity of Ni/Zn ferrites: Effect of doping with βCD and chemical treatment with HNO3 and NaOH

    NASA Astrophysics Data System (ADS)

    Corrêa, Jéssyca M. L.; Abrishamkar, Afshin; Da Silva, Jeferson G.; Pereira, Juliano Rocha; de Oliveira, Fernando C.; Denadai, Ângelo M. L.

    2015-11-01

    In this work, we have studied the rheological properties of nickel-zinc and nickel-zinc-β-cyclodextrin (Fe-Ni/Zn and Fe-Ni/Zn/βCD) ferrite suspensions as a function of temperature, solids content, shear rate and NaOH/HNO3 concentration. The goal was to investigate the conditions where the particle size and viscosity are both lower. In both suspensions, temperature had insignificant impact on viscosity, suggesting no destructive effect on the particles. The Fe-Ni/Zn/βCD suspension exhibited lower viscosity, Newtonian profile and lower dependence of viscosity upon the solids content in comparison with Fe-Ni/Zn, which was pseudoplastic and thixotropic. These differences were ascribed to the lower particle size caused by incorporation of βCD. Considering both ferrites, HNO3 was more efficient in reducing the particles size and viscosity than NaOH, which affected only the Fe-Ni/Zn. This behavior was rationalized in terms of chemical equilibrium of FeOOH at the surface of particles, which was supported by structural characterization as well as elementary analysis.

  18. Comparing data obtained from ground-based measurements of the total contents of O3, HNO3,HCl, and NO2 and from their numerical simulation

    NASA Astrophysics Data System (ADS)

    Virolainen, Ya. A.; Timofeyev, Yu. M.; Polyakov, A. V.; Ionov, D. V.; Kirner, O.; Poberovskii, A. V.; Imhasin, H. Kh.

    2016-01-01

    Chemistry climate models of the gas composition of the atmosphere make it possible to simulate both space and time variations in atmospheric trace-gas components (TGCs) and predict their changes. Both verification and improvement of such models on the basis of a comparison with experimental data are of great importance. Data obtained from the 2009-2012 ground-based spectrometric measurements of the total contents (TCs) of a number of TGCs (ozone, HNO3, HCl, and NO2) in the atmosphere over the St. Petersburg region (Petergof station, St. Petersburg State University) have been compared to analogous EMAC model data. Both daily and monthly means of their TCs for this period have been analyzed in detail. The seasonal dependences of the TCs of the gases under study are shown to be adequately reproduced by the EMAC model. At the same time, a number of disagreements (including systematic ones) have been revealed between model and measurement data. Thus, for example, the EMAC model underestimates the TCs of NO2, HCl, and HNO3, when compared to measurement data, on average, by 14, 22, and 35%, respectively. However, the TC of ozone is overestimated by the EMAC model (on average, by 12%) when compared to measurement data. In order to reveal the reasons for such disagreements between simulated and measured data on the TCs of TGCs, it is necessary to continue studies on comparisons of the contents of TGCs in different atmospheric layers.

  19. ReaxFF molecular dynamics simulations of intermediate species in dicyanamide anion and nitric acid hypergolic combustion

    NASA Astrophysics Data System (ADS)

    Weismiller, Michael R.; Junkermeier, Chad E.; Russo, Michael F., Jr.; Salazar, Michael R.; Bedrov, Dmitry; van Duin, Adri C. T.

    2015-10-01

    Ionic liquids based on the dicyanamide anion (DCA) are of interest as replacements for current hypergolic fuels, which are highly toxic. To better understand the reaction dynamics of these ionic liquid fuels, this study reports the results of molecular dynamics simulations performed for two predicted intermediate compounds in DCA-based ionic liquids/nitric acid (HNO3) combustion, i.e. protonated DCA (DCAH) and nitro-dicyanamide-carbonyl (NDC). Calculations were performed using a ReaxFF reactive force field. Single component simulations show that neat NDC undergo exothermic decomposition and ignition. Simulations with HNO3 were performed at both a low (0.25 g ml-1) and high (1.00 g ml-1) densities, to investigate the reaction in a dense vapor and liquid phase, respectively. Both DCAH and NDC react hypergolically with HNO3, and increased density led to shorter times for the onset of thermal runaway. Contrary to a proposed mechanism for DCA combustion, neither DCAH nor NDC are converted to 1,5-Dinitrobiuret (DNB) before thermal runaway. Details of reaction pathways for these processes are discussed.

  20. Improvement of microwave-assisted digestion of milk powder with diluted nitric acid using oxygen as auxiliary reagent

    NASA Astrophysics Data System (ADS)

    Bizzi, Cezar A.; Barin, Juliano S.; Garcia, Edivaldo E.; Nóbrega, Joaquim A.; Dressler, Valderi L.; Flores, Erico M. M.

    2011-05-01

    The feasibility of using diluted HNO 3 solutions under oxygen pressure for decomposition of whole and non-fat milk powders and whey powder samples has been evaluated. Digestion efficiency was evaluated by determining the carbon content in solution (digests) and the determination of Ca, Cd, Cu, Fe, K, Mg, Mn, Mo, Na, Pb and Zn was performed by inductively coupled plasma optical emission spectrometry and Hg by chemical vapor generation coupled to inductively coupled plasma mass spectrometry. Samples (up to 500 mg) were digested using HNO 3 solutions (1 to 14 mol L - 1 ) and the effect of oxygen pressure was evaluated between 2.5 and 20 bar. It was possible to perform the digestion of 500 mg of milk powder using 2 mol L - 1 HNO 3 with oxygen pressure ranging from 7.5 to 20 bar with resultant carbon content in digests lower than 1700 mg L - 1 . Using optimized conditions, less than 0.86 mL of concentrated nitric acid (14 mol L - 1 ) was enough to digest 500 mg of sample. The accuracy was evaluated by determination of metal concentrations in certified reference materials, which presented an agreement better than 95% (Student's t test, P < 0.05) for all the analytes.

  1. Copper corrosion mechanism in the presence of formic acid vapor for short exposure times

    SciTech Connect

    Bastidas, J.M.; Lopez-Delgado, A.; Cano, E.; Polo, J.L.; Lopez, F.A.

    2000-03-01

    The rate of copper corrosion originated by the action of formic acid vapors at 100% relative humidity was studied. Five formic vapor concentration levels (10, 50, 100, 200, and 300 ppm) were used. A copper corrosion rate of up to 1,300 mg/m{sup 2} d was measured for a period of 21 days using a gravimetric method. The patina layers were characterized using cathodic reduction, X-ray powder diffraction. Fourier transform infrared spectrometry, and scanning electron microscopy techniques. Some of the components identified in the corrosion-product layers were cuprite (Cu{sub 2}O), cupric hydroxide hydrate [Cu(OH){sub 2}{sm_bullet}H{sub 2}O], and copper formate hydrate [Cu(HCOO){sub 2}{sm_bullet}4H{sub 2}O]. The latter was formed by both cupric hydroxide and formic acid-cuprous ion complex mechanisms.

  2. An intercomparison of measurement systems for vapor and particulate phase concentrations of formic and acetic acids

    NASA Technical Reports Server (NTRS)

    Keene, William C.; Talbot, Robert W.; Andreae, Meinrat O.; Beecher, Kristene; Berresheim, Harold

    1989-01-01

    During June 1986, eight systems for measuring vapor phase and four for measuring particulate phase concentrations of formic acid (HCOOH) and acetic acid (CH3COOH) were intercompared in central Virginia. HCOOH and CH3COOH vapors were sampled by condensate, mist, Chromosorb 103 GC resin, NaOH-coated annular denuders, NaOH-impregnated quartz filters, K2CO3 and NaCO3-impregnated cellulose filters, and Nylasorb membranes. Atmospheric aerosol was collected on Teflon and Nuclepore filters using both hi-vol and lo-vol systems to measure particulate phase concentrations. Performances of the mist chamber and K2CO3-impregnated filter techniques were evaluated using zero air and ambient air spiked with HCOOH(g) and CH3COOH(g), and formaldehyde from permeation sources. The advantages and drawbacks of these methods are reported and discussed.

  3. The variation of nitric acid vapor and nitrate aerosol concentrations near the island of Hawaii

    SciTech Connect

    Lee, G.

    1992-01-01

    Anthropogenic emissions of nitrogen oxides (NO + NO[sub 2]) are estimated to be half of the global emissions to the atmosphere. To understand the effect of increasing anthropogenic reactive nitrogen inputs to the global atmosphere, one needs to monitor their long-term variations. This dissertation examines the variations of total nitrate (nitric acid vapor and nitrate aerosol) at the Mauna Loa Observatory (MLO), Hawaii. During the Mauna Loa Observatory Photochemistry Experiment (MLOPEX) in May, 1988, six different air types were identified at MLO with statistical analysis. They were: (1) volcano influenced air, (2) stratosphere-like air, (3) boundary-layer air with recent anthropogenic influence, (4) photochemical haze, (5) marine boundary-layer air, (6) well-aged and modified marine air. Samples that might be influenced by marine air or human activity from local islands were eliminated with three meterological criteria (wind direction, condensation nuclei, and dew point). To examine the negative sampling artifacts of nitric acid vapor due to ground loss, mixing ratio gradients with height were measured during August of 1991. The observed gradients of nitric acid vapor indicated that the long-term samplers at 8 m at MLO may underestimate the free tropospheric nitric acid vapor mixing ratio by about 20%. The three year mean and median of free tropospheric total nitrate during long-term measurements were 113 pptv and 93 pptv, respectively. Each year, the total nitrate mixing ratios at MLO during the spring and summer were increased by more than a factor of two higher than fall and winter. NO[sub y] from remote continents (Asia and North America) are likely sources of these increased total nitrate at MLO during these seasons. However, other processes govern the total nitrate mixing ratios, e.g., degree of mixing between free tropospheric air and boundary air at source regions, stratospheric injection, and wet removal of total nitrate.

  4. Vapor-liquid equilibria for nitric acid-water and plutonium nitrate-nitric acid-water solutions

    SciTech Connect

    Maimoni, A.

    1980-01-01

    The liquid-vapor equilibrium data for nitric acid and nitric acid-plutnonium nitrate-water solutions were examined to develop correlations covering the range of conditions encountered in nuclear fuel reprocessing. The scanty available data for plutonium nitrate solutions are of poor quality but allow an order of magnitude estimate to be made. A formal thermodynamic analysis was attempted initially but was not successful due to the poor quality of the data as well as the complex chemical equilibria involved in the nitric acid and in the plutonium nitrate solutions. Thus, while there was no difficulty in correlating activity coefficients for nitric acid solutions over relatively narrow temperature ranges, attempts to extend the correlations over the range 25/sup 0/C to the boiling point were not successful. The available data were then analyzed using empirical correlations from which normal boiling points and relative volatilities can be obtained over the concentration ranges 0 to 700 g/l Pu, 0 to 13 M nitric acid. Activity coefficients are required, however, if estimates of individual component vapor pressures are needed. The required ternary activity coefficients can be approximated from the correlations.

  5. Measurements of HNO3, SO2 High Resolution Aerosol SO4 (sup 2-), and Selected Aerosol Species Aboard the NASA DC-8 Aircraft: During the Transport and Chemical Evolution Over the Pacific Airborne Mission (TRACE-P)

    NASA Technical Reports Server (NTRS)

    Talbot, Robert W.; Dibb, Jack E.

    2004-01-01

    The UNH investigation during TRACE-P provided measurements of selected acidic gases and aerosol species aboard the NASA DC-8 research aircraft. Our investigation focused on measuring HNO3, SO2, and fine (less than 2 microns) aerosol SO4(sup 2-) with two minute time resolution in near-real-time. We also quantified mixing ratios of aerosol ionic species, and aerosol (210)Pb and (7)Be collected onto bulk filters at better than 10 minute resolution. This suite of measurements contributed extensively to achieving the principal objectives of TRACE-P. In the context of the full data set collected by experimental teams on the DC-8, our observations provide a solid basis for assessing decadal changes in the chemical composition and source strength of Asian continental outflow. This region of the Pacific should be impacted profoundly by Asian emissions at this time with significant degradation of air quality over the next few decades. Atmospheric measurements in the western Pacific region will provide a valuable time series to help quantify the impact of Asian anthropogenic activities. Our data also provide important insight into the chemical and physical processes transforming Asian outflow during transport over the Pacific, particularly uptake and reactions of soluble gases on aerosol particles. In addition, the TRACE-P data set provide strong constraints for assessing and improving the chemical fields simulated by chemical transport models.

  6. H 2SO 4/HNO 3/HCl—Functionalization and its effect on dispersion of carbon nanotubes in aqueous media

    NASA Astrophysics Data System (ADS)

    Osorio, A. G.; Silveira, I. C. L.; Bueno, V. L.; Bergmann, C. P.

    2008-12-01

    Chemical functionalization is a procedure used in materials science to oxidize the surface of materials. Several researchers use this technique to improve carbon nanotubes (CNTs) interaction and dispersion. The present article evaluates the effect of different functionalization methodologies on dispersion of CNTs in aqueous media. Sulfuric, nitric and chloridric acids were used on the first functionalization. For the second procedure tested the addition of chloridric acid was eliminated; and the third functionalization was done using only nitric acid. Experimental results obtained by Raman spectroscopy indicated the maintenance of the structure of CNTs after all oxidations. The presence of other structures was proved by thermogravimetry decomposition and the addition of functional groups was confirmed by transform Fourier infrared spectroscopy. From these experimental results, we conclude that all methodologies used showed a percentage of adsorption of functional groups on the CNTs. However, based on dispersion analysis in aqueous media, it is observed that this adsorption showed more efficiency on the first functionalization method, followed by the second method.

  7. The effect of fatty acid surfactants on the uptake of nitric acid to deliquesced NaCl aerosol

    NASA Astrophysics Data System (ADS)

    Stemmler, K.; Vlasenko, A.; Guimbaud, C.; Ammann, M.

    2008-01-01

    Surface active organic compounds have been observed in marine boundary layer aerosol. Here, we investigate the effect such surfactants have on the uptake of nitric acid (HNO3), an important removal reaction of nitrogen oxides in the marine boundary layer. The uptake of gaseous HNO3 on deliquesced NaCl aerosol was measured in a flow reactor using HNO3 labelled with the short-lived radioactive isotope 13N. The uptake coefficient γ on pure deliquesced NaCl aerosol was γ=0.5±0.2 at 60% relative humidity and 30 ppb HNO3(g). The uptake coefficient was reduced by a factor of 5-50 when the aerosol was coated with saturated linear fatty acids with carbon chain lengths of 18 and 15 atoms in monolayer quantities. In contrast, neither shorter saturated linear fatty acids with 12 and 9 carbon atoms, nor coatings with the unsaturated oleic acid (C18, cis-double bond) had a detectable effect on the rate of HNO3 uptake. It is concluded that it is the structure of the monolayers formed, which determines their resistance towards HNO3 uptake. Fatty acids (C18 and C15), which form a highly ordered film in the so-called liquid condensed state, represent a significant barrier towards HNO3 uptake, while monolayers of shorter-chain fatty acids (C9, C12) and of the unsaturated oleic acid form a less ordered film in the liquid expanded state and do not hinder the uptake. Similarly, high contents of humic acids in the aerosol, a structurally inhomogeneous, quite water soluble mixture of oxidised high molecular weight organic compounds did not affect HNO3 uptake. As surfactant films on naturally occurring aerosol are expected to be less structured due to their chemical inhomogeneity, it is likely that their inhibitory effect on HNO3 uptake is smaller than that observed here for the C15 and C18 fatty acid monolayers.

  8. The effect of fatty acid surfactants on the uptake of nitric acid to deliquesced NaCl aerosol

    NASA Astrophysics Data System (ADS)

    Stemmler, K.; Vlasenko, A.; Guimbaud, C.; Ammann, M.

    2008-09-01

    Surface active organic compounds have been observed in marine boundary layer aerosol. Here, we investigate the effect such surfactants have on the uptake of nitric acid (HNO3), an important removal reaction of nitrogen oxides in the marine boundary layer. The uptake of gaseous HNO3 on deliquesced NaCl aerosol was measured in a flow reactor using HNO3 labelled with the short-lived radioactive isotope 13N. The uptake coefficient γ on pure deliquesced NaCl aerosol was γ=0.5±0.2 at 60% relative humidity and 30 ppb HNO3(g). The uptake coefficient was reduced by a factor of 5 50 when the aerosol was coated with saturated linear fatty acids with carbon chain lengths of 18 and 15 atoms in monolayer quantities. In contrast, neither shorter saturated linear fatty acids with 12 and 9 carbon atoms, nor coatings with the unsaturated oleic acid (C18, cis-double bond) had a detectable effect on the rate of HNO3 uptake. It is concluded that it is the structure of the monolayers formed, which determines their resistance towards HNO3 uptake. Fatty acids (C18 and C15), which form a highly ordered film in the so-called liquid condensed state, represent a significant barrier towards HNO3 uptake, while monolayers of shorter-chain fatty acids (C9, C12) and of the unsaturated oleic acid form a less ordered film in the liquid expanded state and do not hinder the uptake. Similarly, high contents of humic acids in the aerosol, a structurally inhomogeneous, quite water soluble mixture of oxidised high molecular weight organic compounds did not affect HNO3 uptake. As surfactant films on naturally occurring aerosol are expected to be less structured due to their chemical inhomogeneity, it is likely that their inhibitory effect on HNO3 uptake is smaller than that observed here for the C15 and C18 fatty acid monolayers.

  9. HCl Vapour Pressures and Reaction Probabilities for ClONO2 + HCl on Liquid H2SO4-HNO3-HCl-H20 Solutions

    NASA Technical Reports Server (NTRS)

    Elrod, M. J.; Koch, R. E.; Kim, J. E.; Molina, M. J.

    1995-01-01

    Henry's Law solubility constants for HCl have been measured for liquid H2SO4-HNO3-HCl-H2O solutions; the results are in good agreement with predictions from published semiempirical models. The ClONO2 + HCl reaction on the surfaces of such solutions with compositions simulating those of stratospheric aerosols has been investigated; as the composition changes following the temperature drop characteristic of the high-latitude stratosphere the reaction probability gamma increases rapidly. Furthermore, the gamma values remain essentially unchanged when HN03 uptake is neglected; the controlling factor appears to be the solubility of HCl. These results corroborate our earlier suggestion that supercooled liquid sulfate aerosols promote chlorine activation at low temperatures as efficiently as solid polar stratospheric cloud particles.

  10. Laboratory studies of the formation of polar stratospheric clouds: Nitric acid condensation on thin sulfuric acid films

    NASA Astrophysics Data System (ADS)

    Iraci, Laura T.; Middlebrook, Ann M.; Tolbert, Margaret A.

    1995-10-01

    Thin sulfuric acid films were exposed to 5 × 10-8 - 8 × 10-7 torr HNO3 and 2 - 3 × 10-4 torr H2O and cooled to temperatures near the ice frost point. Fourier transform infrared (FTIR) spectroscopy was used to probe the condensed-phase species during isothermal experiments, and gas pressures were monitored with mass spectrometry. Supercooled liquid sulfuric acid films exposed to HNO3 (6 ≤ SNAT ≤ 114) showed indications of HNO3 uptake to form ternary solutions of approximately 4 wt % HNO3, 38 wt % H2SO4, and 59 wt % H2O, followed by crystallization of nitric acid trihydrate (NAT). NAT crystallization did not initiate significant crystallization of the supercooled H2SO4, but the H2SO4 often crystallized to sulfuric acid tetrahydrate (SAT) upon warming. In contrast, when crystalline SAT films were exposed to HNO3 and water, NAT did not condense within several hours, even at HNO3 saturation ratios of 30 or higher. Calculations of the contact parameter from experimental data indicate that m <0.76 for NAT on SAT. Our film studies suggest that crystalline polar stratospheric cloud (PSC) growth is most easily accomplished when stratospheric sulfate aerosols (SSAs) remain liquid, absorb HNO3, and produce crystalline nitric acid trihydrate via heterogeneous nucleation. If SSAs crystallize to SAT at some point during the winter, nitric acid condensation is hindered, and PSC formation could become more difficult.

  11. A laboratory study of the effect of acetic acid vapor on atmospheric copper corrosion

    SciTech Connect

    Lopez-Delgado, A.; Cano, E.; Bastidas, J.M.; Lopez, F.A.

    1998-12-01

    A study was made of the copper corrosion rate and corrosion products originated by the action of acetic acid vapor at 100% relative humidity. Copper plates were exposed to an acetic acid contaminated atmosphere for a period of 21 days. Five acetic vapor concentration levels were used. The copper corrosion rate was in the range of 1 to 23 mg/dm{sup 2} day. The corrosion-product layers were characterized using electrochemical, X-ray powder diffraction, Fourier transform infrared spectrometry, and scanning electron microscopy techniques. Thermal and calorimetric studies were also performed. Some of the compounds identified were cuprite (Cu{sub 2}O), copper acetate hydrate [Cu(CH{sub 3}COO){sub 2}{center_dot}2H{sub 2}O], and copper hydroxide acetate [Cu{sub 4}(OH)(CH{sub 3}COO){sub 7}{center_dot}2H{sub 2}O]. This last compound was also characterized. The thickness of the patina layers was 4 to 8 nm for amorphous cuprite, 11 to 48 nm for cuprite, and 225 nm for copper acetate. The patina, in which the cementation process of different corrosion-product layers plays an important role, is formed by the reaction of acetic vapor with copper through porous cuprite paths.

  12. Acid effects on the measurement of mercury by cold vapor atomic absorption spectrometry

    SciTech Connect

    Adeloju, S.B.; Mann, T.F.

    1987-07-01

    The influence of nitric, hydrochloric and sulfuric acids on the measurement of mercury by cold vapor atomic absorption spectrometry has been investigated. Small pre-reduction peaks associated with the instability of mercury were observed in solutions containing less than or equal to 12.5, < 2 and less than or equal to 12.5% v/v of each acid, respectively. Mercury was found to be most stable in greater than or equal to 2% v/v hydrochloric acid and the measured absorbance was not greatly influenced by varying concentration of the acid. The mercury absorbance measurements were more sensitive in solutions containing less than or equal to 6.3% v/v hydrochloric acid than in similar concentrations of nitric and sulfuric acids. The use of the three acids as a digestion mixture result in serious interference from nitrogen oxides. The interference was removed by use of expelling agents such as urea and sulfamic acid or overcome by use of excess stannous chloride, prior to the reduction of mercury(II) ions. The determination of mercury in NBS albacore tuna using both of these approaches to overcome the interference problem proved to be successful.

  13. Use of a solution cathode glow discharge for cold vapor generation of mercury with determination by ICP-atomic emission spectrometry.

    PubMed

    Zhu, Zhenli; Chan, George C-Y; Ray, Steven J; Zhang, Xinrong; Hieftje, Gary M

    2008-09-15

    A novel vapor-generation technique is described for mercury determination in aqueous solutions. Without need for a chemical reducing agent, dissolved mercury species are converted to volatile Hg vapor in a solution cathode glow discharge. The generated Hg vapor is then transported to an inductively coupled plasma for determination by atomic emission spectrometry. Mercury vapor is readily generated from a background electrolyte containing 0.1 M HNO 3. Vapor generation efficiency was found to be higher by a factor of 2-3 in the presence of low molecular weight organic acids (formic or acetic acids) or alcohols (ethanol). Optimal conditions for discharge-induced vapor generation and reduced interference from concomitant inorganic ions were also identified. However, the presence of chloride ion reduces the efficiency of Hg-vapor generation. In the continuous sample introduction mode, the detection limit was found to be 0.7 microg L (-1), and repeatability was 1.2% RSD ( n = 11) for a 20 microg L (-1) standard. In comparison with other vapor generation methods, it offers several advantages: First, it is applicable to both inorganic and organic Hg determination; organic mercury (thiomersal) can be directly transformed into volatile Hg species without the need for prior oxidation. Second, the vapor-generation efficiency is high; the efficiency (with formic acid as a promoter) is superior to that of conventional SnCl 2-HCl reduction. Third, the vapor generation is extremely rapid and therefore is easy to couple with flow injection. The method is sensitive and simple in operation, requires no auxiliary reagents, and serves as a useful alternative to conventional vapor generation for ultratrace Hg determination. PMID:18710258

  14. Strong Fluorescent Smart Organogel as a Dual Sensing Material for Volatile Acid and Organic Amine Vapors.

    PubMed

    Xue, Pengchong; Yao, Boqi; Wang, Panpan; Gong, Peng; Zhang, Zhenqi; Lu, Ran

    2015-11-23

    An L-phenylalanine derivative (C12PhBPCP) consisting of a strong emission fluorophore with benzoxazole and cyano groups is designed and synthesized to realize dual responses to volatile acid and organic amine vapors. The photophysical properties and self-assembly of the said derivative in the gel phase are also studied. C12PhBPCP can gelate organic solvents and self-assemble into 1 D nanofibers in the gels. UV/Vis absorption spectral results show H-aggregate formation during gelation, which indicates strong exciton coupling between fluorophores. Both wet gel and xerogel emit strong green fluorescence because the cyano group suppresses fluorescence quenching in the self-assemblies. Moreover, the xerogel film with strong green fluorescence can be used as a dual chemosensor for quantitative detection of volatile acid and organic amine vapors with fast response times and low detection limits owing to its large surface area and amplified fluorescence quenching. The detection limits are 796 ppt and 25 ppb for gaseous aniline and trifluoroacetic acid (TFA), respectively. PMID:26449736

  15. Photolysis of Nitric Acid and Nitrate on Natural and Artificial Surfaces.

    PubMed

    Ye, Chunxiang; Gao, Honglian; Zhang, Ning; Zhou, Xianliang

    2016-04-01

    Photolysis of nitric acid and nitrate (HNO3/nitrate) was investigated on the surfaces of natural and artificial materials, including plant leaves, metal sheets, and construction materials. The surfaces were conditioned in the outdoor air prior to experiments to receive natural depositions of ambient HNO3/nitrate and other atmospheric constituents. The photolysis rate constant (JHNO3(s)) of the surface HNO3/nitrate was measured based on the production rates of nitrous acid (HONO) and nitrogen oxides (NOx). The JHNO3(s) values, from 6.0 × 10(-6) s(-1) to 3.7 × 10(-4) s(-1), are 1 to 3 orders of magnitude higher than that of gaseous HNO3. The HONO was the major product from photolysis of HNO3/nitrate on most plant leaves, whereas NOx was the major product on most artificial surfaces. The JHNO3(s) values decreased with HNO3/nitrate surface density and could be described by a simple analytical equation. Within a typical range of HNO3/nitrate surface density in the low-NOx forested areas, photolysis of HNO3/nitrate on the forest canopy can be a significant source for HONO and NOx for the overlying atmosphere. PMID:26936001

  16. An Investigation of Solid-State Amidization and Imidization Reactions in Vapor Deposited Poly (amic acid)

    SciTech Connect

    Anthamatten, M; Letts, S A; Day, K; Cook, R C; Gies, A P; Hamilton, T P; Nonidez, W K

    2004-06-28

    The condensation polymerization reaction of 4,4'-oxydianiline (ODA) with pyromellitic dianhydride (PMDA) to form poly(amic acid) and the subsequent imidization reaction to form polyimide were investigated for films prepared using vapor deposition polymerization techniques. Fourier-transform infrared spectroscopy (FT-IR), thermal analysis, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) of films at different temperatures indicate that additional solid-state polymerization occurs prior to imidization reactions. Experiments reveal that, upon vapor deposition, poly(amic acid) oligomers form that have a number-average molecular weight of about 1500 Daltons. Between 100 - 130 C these chains undergo additional condensation reaction to form slightly higher molecular weight oligomers. Calorimetry measurements show that this reaction is exothermic ({Delta}H {approx} -30 J/g) with an activation energy of about 120 kJ/mol. Experimental reaction enthalpies are compared to results from ab initio molecular modeling calculations to estimate the number of amide groups formed. At higher temperatures (150 - 300 C) imidization of amide linkages occurs as an endothermic reaction ({Delta}H {approx} +120 J/g) with an activation energy of about 130 kJ/mol. Solid-state kinetics were found to depend on reaction conversion as well as the processing conditions used to deposit films.

  17. Strong emissive nanofibers of organogels for the detection of volatile acid vapors.

    PubMed

    Xue, Pengchong; Sun, Jiabao; Yao, Boqi; Gong, Peng; Zhang, Zhenqi; Qian, Chong; Zhang, Yuan; Lu, Ran

    2015-03-16

    Two L-phenylalanine derivatives with 5,8-bis(2-(carbazol-3-yl)vinyl)quinoxaline (PCQ) and 5,8-bis[2-(carbazol-3-yl)]-2,3-dimethylquinoxaline (DCQ) as fluorophores were synthesized, and their photophysical properties were measured and compared. The two compounds were found to gelate some organic solvents and self-assemble into 1D nanofibers in gels. The wet gel of PCQ emitted a weak orange fluorescence, but the DCQ gel had a strong green one. This result can be due to the presence of two methyl groups and the nonplanar conformation of fluorophore in DCQ. The gel film of DCQ also showed significantly stronger fluorescence than that of PCQ. Thus, the wet gel and xerogel film of DCQ were selected to study their sensing properties to acids. The yellow wet gel of DCQ transformed into a brown sol upon the addition of 0.2 equiv trifluoroacetic acid (TFA), accompanied by emission quenching. The xerogel film of DCQ rapidly responded to volatile acids, such as TFA, HCl, and HOAc. The fluorescence of the xerogel film was gradually quenched with increased concentration of volatile acid vapors. The fibrous film exhibited low detection limits for volatile acid. The detection limits of the thin films for TFA, HCl, and HOAc reached 43, 122, and 950 ppb, respectively. PMID:25393379

  18. Vapor Phase Dehydration of Glycerol to Acrolein Over SBA-15 Supported Vanadium Substituted Phosphomolybdic Acid Catalyst.

    PubMed

    Viswanadham, Balaga; Srikanth, Amirineni; Kumar, Vanama Pavan; Chary, Komandur V R

    2015-07-01

    Vapor phase dehydration of glycerol to acrolein was investigated over heteropolyacid (HPA) catalysts containing vanadium substituted phosphomolybdic acid (H4PMo11VO40) supported on mesoporous SBA-15. A series of HPA catalysts with HPA loadings varying from 10-50 wt% were prepared by impregnation method on SBA-15 support. The catalysts were characterized by X-ray diffraction, Raman spectroscopy, Fourier Transform infrared spectroscopy, temperature-programmed desorption of NH3, pyridine adsorbed FT-IR spectroscopy, scanning electron microscopy, pore size distribution and specific surface area measurements. The nature of acidic sites was examined by pyridine adsorbed FT-IR spectroscopy. XRD results suggest that the active phase containing HPA was highly dispersed at lower loadings on the support. FT-IR and Raman spectra results confirm that the presence of primary Keggin ion structure of HPA on the support and it was not affected during the preparation of catalysts. Pore size distribution results reveal that all the samples show unimodel pore size distribution with well depicted mesoporous structure. NH3-TPD results suggest that the acidity of catalysts increased with increase of HPA loading. The findings of acidity measurements by FT-IR spectra of pyridine adsorption reveals that the catalysts consist both the Brønsted and Lewis acidic sites and the amount of Brønsted acidic sites are increasing with HPA loading. SBA-15 supported vanadium substituted phosphomolybdic acid catalysts are found to be highly active during the dehydration reaction and exhibited 100% conversion of glycerol (10 wt% of glycerol) and the acrolein selectivity was appreciably changed with HPA active phase loading. The catalytic functionalities during glycerol dehydration are well correlated with surface acidity of the catalysts. PMID:26373149

  19. A new reference state and climatology of O3, N2O, CH4 and HNO3 in the summer stratosphere

    NASA Astrophysics Data System (ADS)

    Payan, S.; Bureau, J.; Thieblemont, R.; Jegou, F.; Camy-Peyret, C.; Huret, N.

    2011-12-01

    The polar stratosphere in the summertime remains largely unexplored. In the framework of the International Polar Year, the STRAPOLETE project started on January 2009. It is associated with a successful balloon borne campaign which took place close to Kiruna (Sweden) from 2 August 2009 to 12 September 2009 with eight balloon flights. During this campaign the main characteristics of the summertime arctic stratosphere have been captured. The data set obtained using UV-visible and infrared instruments, remote and in situ sensing embarked spectrometers provided detailed information on vertical distributions of more than fifteen chemical tracers and reactive species from the upper troposphere to the middle stratosphere. A climatology over the 3 summer months and for 2 degrees latitude bins has been derived from MIPAS-IMK, MLS data and REPROBUS output, for CO, H2O, HCl, HNO3, N2O and O3. From this climatology, a reference state for these species has been determined. It has been compared to the balloon measurements obtained performed during the StraPolEte campaign. The statistical approach used in this study will be presented, as well as the corresponding results.

  20. New Experimental and Theoretical Approach to the Heterogeneous Hydrolysis of NO2: Key Role of Molecular Nitric Acid and Its Complexes

    SciTech Connect

    Ramazan, K A.; Wingen, Lisa M.; Miller, Y; Chaban, Galina M.; Gerber, Robert B.; Xantheas, Sotiris S.; Finlayson-Pitts, Barbara J.

    2006-06-01

    Although heterogeneous chemistry on surfaces in the troposphere is known to be important, there are currently only a few techniques available for studying the nature of surface-adsorbed species as well as their chemistry and photochemistry under atmospheric conditions of 1 atm pressure and in the presence of water vapor. We report here a new laboratory approach using a combination of long path FTIR to identify gases and attenuated total reflectance (ATR)-FTIR that allows the simultaneous observation and quantification of gases and surface species. Theory is used to identify the surface-adsorbed intermediates and products, and to quantify their relative concentrations. At intermediate relative humidities typical of the tropospheric boundary layer, the nitric acid formed in the NO2 heterogeneous hydrolysis is shown to exist as both nitrate ions from the dissociation of nitric acid formed on the surface, and as molecular nitric acid. In both cases, the ions and HNO3 are complexed to water molecules. Upon pumping, water is selectively removed, shifting the NO3- - HNO3(H2O)y equilibria towards more dehydrated forms of HNO3. Photolysis of the nitric acid-water film using 300-400 nm radiation generates gaseous NO, while photolysis at 254 nm generates both NO and HONO, resulting in conversion of surface-adsorbed nitrogen oxides into photochemically active NOx. This suggests that the assumption that deposition or formation of nitric acid provides a permanent removal mechanism from the atmosphere may not be correct. Furthermore, a potential role of surface-adsorbed nitric acid and other species formed during the heterogeneous hydrolysis of NO2 on the oxidation of organics on surfaces, and on the generation of gas phase HONO on local to global scales, should be considered.

  1. SIMULTANEOUS QUANTIFICATION OF JASMONIC ACID AND SALICYLIC ACID IN PLANTS BY VAPOR PHASE EXTRACTION AND GAS CHROMATOGRAPHY-CHEMICAL IONIZATION-MASS SPECTROMETRY

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Jasmonic acid and salicylic acid represent important signaling compounds in plant defensive responses against other organisms. Here, we present a new method for the easy, sensitive and reproducible quantification of both compounds by vapor phase extraction and gas chromatography-positive ion chemic...

  2. Sulfuric acid vapor and other cloud-related gases in the Venus atmosphere - Abundances inferred from observed radio opacity

    NASA Technical Reports Server (NTRS)

    Steffes, P. G.; Eshleman, V. R.

    1982-01-01

    It is suggested that the absorbing characteristics of sulfuric acid vapor appear to reconcile what had been thought to be an inconsistency among measurements and deductions regarding the constituents of the Venus atmosphere and radio occultation, radar reflection, and radio emission measurements of its opacity. Laboratory measurements of sulfuric acid, sulfur dioxide, water vapor, and carbon dioxide are used to model relative contributions to opacity as a function of height in a way that is consistent with observations of the constituents and absorbing properties of the atmosphere. It is concluded that sulfuric acid vapor is likely to be the principal microwave absorber in the 30-50 km altitude range of the middle atmosphere of Venus.

  3. Penetration of methyl isocyanate through organic vapor and acid gas respirator cartridges.

    PubMed

    Moyer, E S; Berardinelli, S P

    1987-04-01

    Methyl isocyanate (MIC) is a volatile, toxic chemical [Threshold Limit Value (TLV) = 0.02 ppm] used to manufacture carbamate pesticides. The principal manufacturer of MIC is Union Carbide, and the site of production is Institute, West Virginia. In light of the December 1984 Bhopal, India disaster and possible safety problems at the Institute facility, NIOSH conducted this research as a basis upon which to recommend protective equipment that might be used in an emergency situation where extremely high MIC concentrations might be encountered. Both protective clothing and respirators were evaluated. In particular, NIOSH studied air-purifying respirators in order to assess their effectiveness against MIC vapor penetration. NIOSH does not recommend any air purifying respirator for MIC because of its high toxicity and lack of warning properties and because no effective end of service life indicator currently is available for MIC. This report addresses only MIC penetration through air-purifying cartridges at challenge concentrations designed to simulate emergency escape conditions. Another report addresses the protective clothing issue. The results presented are for two different manufacturers' organic vapor (OV) and acid gas cartridges. Penetration tests were conducted at three or four MIC challenge concentrations and at three different humidity conditions. In general, breakthrough times (1% of challenge concentration) were very short (less than 20 min). Also, high relative humidity was found to decrease the breakthrough time of MIC. PMID:3591646

  4. Simulating the phase partitioning of NH3, HNO3, and HCl with size-resolved particles over northern Colorado in winter

    NASA Astrophysics Data System (ADS)

    Kelly, James T.; Baker, Kirk R.; Nolte, Christopher G.; Napelenok, Sergey L.; Keene, William C.; Pszenny, Alexander A. P.

    2016-04-01

    Numerical modeling of inorganic aerosol processes is useful in air quality management, but comprehensive evaluation of modeled aerosol processes is rarely possible due to the lack of comprehensive datasets. During the Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT) campaign in February and March 2011, the phase partitioning of soluble trace gases with size-resolved particles and related meteorological conditions were measured continuously at a site in Colorado about 33 km north of Denver. These size-resolved measurements of particulate SO4 2 - , NH4+,NO3- , Cl-, Na+, Ca2+, Mg2+, and K+ and inorganic gases are used here to assess the ability of a continental U.S. modeling platform to simulate the gas-particle partitioning of NH3, HNO3, and HCl at this location. Modeling is based on the Community Multiscale Air Quality (CMAQ) model with 12 km horizontal resolution. Baseline, sensitivity, and source apportionment simulations are conducted to fully characterize the model predictions. Considering the limitations in representing regional terrain features in the national 12 km modeling, predictions agree reasonably well with measured concentrations and gas-particle partitioning at this location. However, the median sum of NH4+ and NH3 is underpredicted in the baseline simulation by a factor of four suggesting a need for improved bottom-up NH3 emissions inventories in this area. The median sum of Cl- and HCl is underpredicted by a factor of 2.8, while levels of Ca2+, Mg2+, and K+ are overpredicted. Improvements in windblown and fugitive dust emissions may improve and/or better constrain these predictions. Mass size distributions for inorganic particle constituents are generally simulated well, although the modeled fine particle mode is shifted to slightly larger diameters relative to measurements. Source apportionment modeling estimates of source sector and boundary contributions to air quality at the site are provided.

  5. Simulating the phase partitioning of NH3, HNO3, and HCl with size-resolved particles over northern Colorado in winter

    NASA Astrophysics Data System (ADS)

    Kelly, James T.; Baker, Kirk R.; Nolte, Christopher G.; Napelenok, Sergey L.; Keene, William C.; Pszenny, Alexander A. P.

    2016-04-01

    Numerical modeling of inorganic aerosol processes is useful in air quality management, but comprehensive evaluation of modeled aerosol processes is rarely possible due to the lack of comprehensive datasets. During the Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT) campaign in February and March 2011, the phase partitioning of soluble trace gases with size-resolved particles and related meteorological conditions were measured continuously at a site in Colorado about 33 km north of Denver. These size-resolved measurements of particulate SO42- , NH4+, NO3- , Cl-, Na+, Ca2+, Mg2+, and K+ and inorganic gases are used here to assess the ability of a continental U.S. modeling platform to simulate the gas-particle partitioning of NH3, HNO3, and HCl at this location. Modeling is based on the Community Multiscale Air Quality (CMAQ) model with 12 km horizontal resolution. Baseline, sensitivity, and source apportionment simulations are conducted to fully characterize the model predictions. Considering the limitations in representing regional terrain features in the national 12 km modeling, predictions agree reasonably well with measured concentrations and gas-particle partitioning at this location. However, the median sum of NH4+ and NH3 is underpredicted in the baseline simulation by a factor of four suggesting a need for improved bottom-up NH3 emissions inventories in this area. The median sum of Cl- and HCl is underpredicted by a factor of 2.8, while levels of Ca2+, Mg2+, and K+ are overpredicted. Improvements in windblown and fugitive dust emissions may improve and/or better constrain these predictions. Mass size distributions for inorganic particle constituents are generally simulated well, although the modeled fine particle mode is shifted to slightly larger diameters relative to measurements. Source apportionment modeling estimates of source sector and boundary contributions to air quality at the site are provided.

  6. Vapor phase ketonization of acetic acid on ceria based metal oxides

    SciTech Connect

    Liu, Changjun; Karim, Ayman M.; Lebarbier, Vanessa MC; Mei, Donghai; Wang, Yong

    2013-12-01

    The activities of CeO2, Mn2O3-CeO2 and ZrO2-CeO2 were measured for acetic acid ketonization under reaction conditions relevant to pyrolysis vapor upgrading. We show that the catalyst ranking changed depending on the reaction conditions. Mn2O3-CeO2 was the most active catalyst at 350 oC, while ZrO2 - CeO2 was the most active catalyst at 450 oC. Under high CO2 and steam concentration in the reactants, Mn2O3-CeO2 was the most active catalyst at 350 and 450 °C. The binding energies of steam and CO2 with the active phase were calculated to provide the insight into the tolerance of Mn2O3-CeO2 to steam and CO2.

  7. MW Spectroscopy Coupled with Ultrafast UV Laser Vaporization: Succinic Acid in the Gas Phase

    NASA Astrophysics Data System (ADS)

    Mendez, Estibaliz; Ecija, Patricia; Cocinero, Emilio J.; Castano, Fernando; Basterretxea, Francisco J.; Godfrey, Peter D.; McNaughton, Don; Jahn, Michaela K.; Nair, K. P. Rajappan; Grabow, Jens-Uwe

    2013-06-01

    Recent lab and field measurements have indicated critical roles of organic acids in enhancing new atmospheric aerosol formation. In order to understand the nucleation process, here we report an experimental and theoretical investigation of chemical structure of succinic acid. We have used the technique of Fourier Transform Microwave Spectroscopy (FTMW). Succinic acid was vaporized by UV ultrafast laser ablation to suppress thermal decomposition processes^a and seeded into an expanding stream of Ne forming a supersonic jet. The rotational spectrum detected the presence of a single most stable conformation in the cm- mm- wave regions for which accurate rotational and centrifugal distortion parameters have been determined. The study was extended to all monosubstituted isotopic species (^{13}C, ^{18}O, D(O)), which were positively identified, leading to an accurate determination of the effective and substitution structures of the molecule. The experimental study was supplemented by ab initio (MP2) and DFT (M06-2X and B3LYP) calculations. ^{a} E. J. Cocinero, A. Lesarri, P. écija, F. J. Basterretxea, J. U. Grabow, J. A. Fernández and F. Castaño, Angew. Chem. Int. Ed., 51, 3119-3124, 2012.

  8. A model of vapor-liquid equilibria for acid gas-alkanolamine-water systems

    SciTech Connect

    Austgen, D.M. Jr.

    1989-01-01

    A physico-chemical model was developed for representing liquid phase chemical equilibria and vapor-liquid (phase) equilibria of H{sub 2}SCO{sub 2}-alkanolamine-water systems. The equilibrium composition of the liquid phase is determined by minimization of the Gibbs free energy. Activity coefficients are represented with the Electrolyte-NRTL equation treating both long-range electrostatic interactions and short-range binary interactions between liquid phase species. Vapor phase fugacity coefficients are calculated using the Redlich-Kwong-Soave Equation of State. Adjustable parameters of the model, binary interaction parameters and carbamate stability constants, were fitted on published binary system alkanolamine-water and ternary system (H{sub 2}S-alkanolamine-water, CO{sub 2}-alkanolamine-water) VLE data. The Data Regression System of ASPEN PLUS, based upon the Maximum Likelihood Principle, was used to estimate adjustable parameters. Ternary system measurements used in parameter estimation ranged in temperature from 25 to 120{degree}C in alkanolamine concentration from 1 to 5 M, in acid gas loading from 0 to 1.5 moles per mole alkanolamine, and in acid gas partial pressure from 0.1 to 1,000 kPa. Maximum likelihood estimates of ternary system H{sub 2} or CO{sub 2} equilibrium partial pressures and liquid phase concentrations were found to be in good agreement with measurements for aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), diglycolamine (DGA), and methyldiethanolamine (MDEA) indicating that the model successfully represents ternary system data. The model was extended to represent CO{sub 2} solubility in aqueous mixtures of MDEA with MEA or DEA. The solubility was measured at 40 and 80{degree}C over a wide range of CO{sub 2} partial pressures. These measurements were used to estimate additional binary parameters of the mixed solvent systems.

  9. Measurement of vapor pressures and heats of sublimation of dicarboxylic acids using atmospheric solids analysis probe mass spectrometry.

    PubMed

    Bruns, Emily A; Greaves, John; Finlayson-Pitts, Barbara J

    2012-06-21

    Vapor pressures of low volatility compounds are important parameters in several atmospheric processes, including the formation of new particles and the partitioning of compounds between the gas phase and particles. Understanding these processes is critical for elucidating the impacts of aerosols on climate, visibility, and human health. Dicarboxylic acids are an important class of compounds in the atmosphere for which reported vapor pressures often vary by more than an order of magnitude. In this study, atmospheric solids analysis probe mass spectrometry (ASAP-MS), a relatively new atmospheric pressure ionization technique, is applied for the first time to the measurement of vapor pressures and heats of sublimation of a series of dicarboxylic acids. Pyrene was also studied because its vapor pressures and heat of sublimation are relatively well-known. The heats of sublimation measured using ASAP-MS were in good agreement with published values. The vapor pressures, assuming an evaporation coefficient of unity, were typically within a factor of ∼3 lower than published values made at similar temperatures for most of the acids. The underestimation may be due to diffusional constraints resulting from evaporation at atmospheric pressure. However, this study establishes that ASAP-MS is a promising new technique for such measurements. PMID:22432524

  10. Measurements of tropospheric nitric acid over the Western United States and Northeastern Pacific Ocean

    NASA Technical Reports Server (NTRS)

    Lebel, P. J.; Huebert, B. J.; Schiff, H. I.; Vay, S. A.; Vanbramer, S. E.; Hastie, D. R.

    1990-01-01

    Over 240 measurements of nitric acid (HNO3) were made in the free troposphere as well as in the boundary layer. Marine HNO3 measurement results were strikingly similar to results from GAMETAG and other past atmospheric field experiments. The marine boundary layer HNO3 average, 62 parts-per-trillion by volume (pptv), was 1/3 lower than the marine free tropospheric average, 108 pptv, suggesting that the boundary layer is a sink for tropospheric nitric acid, probably by dry deposition. Nitric acid measurements on a nighttime continental flight gave a free tropospheric average of 218 pptv, substantially greater than the daytime continental free tropospheric 5-flight average of 61 pptv. However, the nighttime results may be influenced by highly convective conditions that existed from thunderstorms in the vicinity during that night flight. The continental boundary layer HNO3 average of 767 pptv is an order of magnitude greater than the free tropospheric average, indicating that the boundary layer is a source of free tropospheric HNO3. The distribution of continental boundary layer HNO3 data, from averages of 123 over rural Nevada and Utah to 1057 pptv in the polluted San Joaquin Valley of California suggest a close tie between boundary layer HNO3 and anthropogenic activity.

  11. SMILES zonal and diurnal variation climatology of stratospheric and mesospheric trace gasses: O3, HCl, HNO3, ClO, BrO, HOCl, HO2, and temperature

    NASA Astrophysics Data System (ADS)

    Kreyling, Daniel; Sagawa, Hideo; Wohltmann, Ingo; Lehmann, Ralph; Kasai, Yasuko

    2013-10-01

    We present a climatology of the diurnal variation of short-lived atmospheric compounds, such as ClO, BrO, HO2, and HOCl, as well as longer-lived species: O3, the hydrogen chloride isotopes H35Cl and H37Cl, and HNO3. Measurements were taken by the Superconducting Submillimeter-wave Limb-Emission Sounder (SMILES). This spectrally resolving radiometer, with very low observation noise and altitude range from the lower stratosphere to the lower thermosphere (20-100km), was measuring vertical profiles of absorption spectra along a non-sun-synchronous orbit, thus observing at all local times. We used the retrieved volume mixing ratio profiles to compile climatologies that are a function of pressure, a horizontal coordinate (latitude or equivalent latitude), and a temporal coordinate (solar zenith angle or local solar time). The main product presented are climatologies with a high resolution of the temporal coordinate (diurnal variation climatologies). In addition, we provide climatologies with a high resolution of the horizontal coordinate (zonal climatologies).The diurnal variation climatologies are based on data periods of 2 months and the zonal climatologies on monthly data periods. Consideration of the SMILES time-space sampling patterns with respect to the averaging coordinates is a key issue for climatology creation, especially in case of diurnal variation climatologies. Biases induced by inhomogeneous sampling are minimized by carefully choosing the size of averaging bins. The sampling biases of the diurnal variation climatology of ClO and BrO are investigated in a comparison of homogeneously sampled model data versus SMILES-sampled model data from the stratospheric Lagrangian chemistry and transport model Alfred Wegener Institute Lagrangian Chemisrty/Transport System. In most cases, the relative sampling error is in the range of 0-20%. The strongest impact of sampling biases is found where the species' temporal gradients are strongest (mostly at sunrise and sunset

  12. Comment on “Observations of ammonia, nitric acid, and fine particles in a rural gas production region” by Yi Li, Florian M. Schwandnera, H. James Sewell, Angela Zivkovich, Mark Tigges, Suresh Raja, Stephen Holcomb, John V. Molenar, Lincoln Sherman, Cassie Archuleta, Taehyoung Lee and Jeffrey L. Collett Jr. Atmospheric Environment (in press)

    NASA Astrophysics Data System (ADS)

    Phillips, Gavin J.

    2014-05-01

    An artefact of the detection of nitric acid (HNO3) by denuder methods is discussed. This artefact arises from the likely reaction of dinitrogen pentoxide (N2O5) on the denuder train resulting in the report of some fraction of N2O5 as HNO3.

  13. Sources of atmospheric acidity in an agricultural-industrial region of São Paulo State, Brazil

    NASA Astrophysics Data System (ADS)

    Da Rocha, G. O.; Franco, A.; Allen, A. G.; Cardoso, A. A.

    2003-04-01

    Surface-based measurements of atmospheric formic acid (HCOOH), acetic acid (CH3COOH), sulfur dioxide (SO2), hydrogen chloride (HCl), and nitric acid (HNO3) were made in central São Paulo State, Brazil, between April 1999 and March 2000. Mean concentrations were 9.0 ppb (HCOOH), 1.3 ppb (CH3COOH), 4.9 ppb (SO2), 0.3 ppb (HCl), and 0.5 ppb (HNO3). Concentrations in sugar cane burning plumes were 1160-4230 ppb (HCOOH), 360-1750 ppb (CH3COOH), 10-630 ppb (SO2), 4-210 ppb (HCl), and 14-90 ppb (HNO3). Higher ambient concentrations of SO2, HCl and HNO3 were measured during the burning season (May-November). Concentrations of SO2 and HCl increased during the evening, and of HCOOH and CH3COOH were lowest in the morning, with peak levels in the afternoon. Ratios obtained between different species showed either nighttime maxima (SO2/HCOOH, SO2/CH3COOH, SO2/HNO3, CH3COOH/HNO3, SO2/HCl and HCOOH/HNO3), daytime maxima (HCOOH/HCl, CH3COOH/HCl and HNO3/HCl), or no clear trends (HCOOH/CH3COOH). Correlation analysis showed that SO2 and HCl were primary emissions from biomass burning and road transport; HCOOH, HNO3 and CH3COOH were products of photochemistry; HCOOH and CH3COOH were emitted directly during combustion as well as from biogenic sources. Biomass burning affected atmospheric acidity on a regional scale, while vehicular emissions had greater impact in urban and adjacent areas. Atmospheric ammonia levels were insufficient to neutralize atmospheric acidity, which was mainly removed by deposition to the surface.

  14. Unravelling the potential of nitric acid as a surface modifier for improving the hemocompatibility of metallocene polyethylene for blood contacting devices

    PubMed Central

    Vellayappan, Muthu Vignesh; Muhamad, Ida Idayu

    2016-01-01

    Design of blood compatible surfaces is obligatory to minimize platelet surface interactions and improve the thromboresistance of foreign surfaces when they are utilized as biomaterials particularly for blood contacting devices. Pure metallocene polyethylene (mPE) and nitric acid (HNO3) treated mPE antithrombogenicity and hydrophilicity were investigated. The contact angle of the mPE treated with HNO3 decreased. Surface of mPE and HNO3 treated mPE investigated with FTIR revealed no major changes in its functional groups. 3D Hirox digital microscopy, SEM and AFM images show increased porosity and surface roughness. Blood coagulation assays prothrombin time (PT) and activated partial thromboplastin time (APTT) were delayed significantly (P < 0.05) for HNO3 treated mPE. Hemolysis assay and platelet adhesion of the treated surface resulted in the lysis of red blood cells and platelet adherence, respectively indicating improved hemocompatibility of HNO3 treated mPE. To determine that HNO3 does not deteriorate elastic modulus of mPE, the elastic modulus of mPE and HNO3 treated mPE was compared and the result shows no significant difference. Hence, the overall observation suggests that the novel HNO3 treated mPE may hold great promises to be exploited for blood contacting devices like grafts, catheters, and etc. PMID:26819837

  15. Unravelling the potential of nitric acid as a surface modifier for improving the hemocompatibility of metallocene polyethylene for blood contacting devices.

    PubMed

    Vellayappan, Muthu Vignesh; Jaganathan, Saravana Kumar; Muhamad, Ida Idayu

    2016-01-01

    Design of blood compatible surfaces is obligatory to minimize platelet surface interactions and improve the thromboresistance of foreign surfaces when they are utilized as biomaterials particularly for blood contacting devices. Pure metallocene polyethylene (mPE) and nitric acid (HNO3) treated mPE antithrombogenicity and hydrophilicity were investigated. The contact angle of the mPE treated with HNO3 decreased. Surface of mPE and HNO3 treated mPE investigated with FTIR revealed no major changes in its functional groups. 3D Hirox digital microscopy, SEM and AFM images show increased porosity and surface roughness. Blood coagulation assays prothrombin time (PT) and activated partial thromboplastin time (APTT) were delayed significantly (P < 0.05) for HNO3 treated mPE. Hemolysis assay and platelet adhesion of the treated surface resulted in the lysis of red blood cells and platelet adherence, respectively indicating improved hemocompatibility of HNO3 treated mPE. To determine that HNO3 does not deteriorate elastic modulus of mPE, the elastic modulus of mPE and HNO3 treated mPE was compared and the result shows no significant difference. Hence, the overall observation suggests that the novel HNO3 treated mPE may hold great promises to be exploited for blood contacting devices like grafts, catheters, and etc. PMID:26819837

  16. Heterogeneous reactions of HNO3(g) + NaCl(s) yields HCl(g) + NaNO3(s) and N2O5(g) + NaCl(s) yields ClNO2(g) + NaNO3(s)

    NASA Technical Reports Server (NTRS)

    Leu, Ming-Taun; Timonen, Raimo S.; Keyser, Leon F.; Yung, Yuk L.

    1995-01-01

    The heterogeneous reactions of HNO3(g) + NaCl(s) yields HCl(g) + NaNO3(s) (eq 1) and N2O5(g) + NaCl(s) yields ClNO2(g) + NaNO3(S) (eq 2) were investigated over the temperature range 223-296 K in a flow-tube reactor coupled to a quadrupole mass spectrometer. Either a chemical ionization mass spectrometer (CIMS) or an electron-impact ionization mass spectrometer (EIMS) was used to provide suitable detection sensitivity and selectivity. In order to mimic atmospheric conditions, partial pressures of HNO3 and N2O5 in the range 6 x 10(exp -8) - 2 x 10(exp -6) Torr were used. Granule sizes and surface roughness of the solid NaCl substrates were determined by using a scanning electron microscope. For dry NaCl substrates, decay rates of HNO3 were used to obtain gamma(1) = 0.013 +/- 0.004 (1sigma) at 296 K and > 0.008 at 223 K, respectively. The error quoted is the statistical error. After all corrections were made, the overall error, including systematic error, was estimated to be about a factor of 2. HCl was found to be the sole gas-phase product of reaction 1. The mechanism changed from heterogeneous reaction to predominantly physical adsorption when the reactor was cooled from 296 to 223 K. For reaction 2 using dry salts, gamma(2) was found to be less than 1.0 x 10(exp -4) at both 223 and 296 K. The gas-phase reaction product was identified as ClNO2 in previous studies using an infrared spectrometer. An enhancement in reaction probability was observed if water was not completely removed from salt surfaces, probably due to the reaction of N2O5(g) + H2O(s) yields 2HNO3(g). Our results are compared with previous literature values obtained using different experimental techniques and conditions. The implications of the present results for the enhancement of the hydrogen chloride column density in the lower stratosphere after the El Chichon volcanic eruption and for the chemistry of HCl and HNO3 in the marine troposphere are discussed.

  17. SIMULATED ACID RAIN ON CROPS

    EPA Science Inventory

    In 1981, simulated H2SO4 acid rain was applied to alfalfa and tall fescue and a 2:1 ratio of H2SO4:HNO3 acid rain was applied to alfalfa, tall fescue, barley, wheat, potato, tomato, radish, and corn crops growing in the open field at Corvallis, Oregon. Careful attention was given...

  18. Improvements in the profiles and distributions of nitric acid and nitrogen dioxide with the LIMS version 6 dataset

    NASA Astrophysics Data System (ADS)

    Remsberg, E.; Natarajan, M.; Marshall, T.; Gordley, L. L.; Thompson, R. E.; Lingenfelser, G.

    2010-02-01

    The quality of the Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) nitric acid (HNO3) and nitrogen dioxide (NO2) profiles and distributions of 1978/1979 is described after their processing with an updated, Version 6 (V6) algorithm and subsequent archival in 2002. Estimates of the precision and accuracy of both of those species are developed and provided herein. The character of the V6 HNO3 profiles is relatively unchanged from that of the earlier LIMS Version 5 (V5) profiles, except in the upper stratosphere where the interfering effects of CO2 are accounted for better with V6. The accuracy of the retrieved V6 NO2 is also significantly better in the middle and upper stratosphere, due to improvements in its spectral line parameters and in the reduced biases for the accompanying V6 temperature and water vapor profiles. As a result of these important updates, there is better agreement with theoretical calculations for profiles of the HNO3/NO2 ratio, day-to-night NO2 ratio, and with estimates of the production of NO2 in the mesosphere and its descent to the upper stratosphere during polar night. The improved precisions and more frequent retrievals of the profiles along the LIMS orbit tracks provide for better continuity and detail in map analyses of these two species on pressure surfaces. It is judged that the chemical effects of the oxides of nitrogen on ozone can be examined quantitatively throughout the stratosphere with the LIMS V6 data, and that the findings will be more compatible with those obtained from measurements of the same species from subsequent satellite sensors.

  19. Improvements in the profiles and distributions of nitric acid and nitrogen dioxide with the LIMS version 6 dataset

    NASA Astrophysics Data System (ADS)

    Remsberg, E.; Natarajan, M.; Marshall, B. T.; Gordley, L. L.; Thompson, R. E.; Lingenfelser, G.

    2010-05-01

    The quality of the Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) nitric acid (HNO3) and nitrogen dioxide (NO2) profiles and distributions of 1978/1979 are described after their processing with an updated, Version 6 (V6) algorithm and subsequent archival in 2002. Estimates of the precision and accuracy of both of those species are developed and provided herein. The character of the V6 HNO3 profiles is relatively unchanged from that of the earlier LIMS Version 5 (V5) profiles, except in the upper stratosphere where the interfering effects of CO2 are accounted for better with V6. The accuracy of the retrieved V6 NO2 is also significantly better in the middle and upper stratosphere, due to improvements in its spectral line parameters and in the reduced biases for the accompanying V6 temperature and water vapor profiles. As a result of these important updates, there is better agreement with theoretical calculations for profiles of the HNO3/NO2 ratio, day-to-night NO2 ratio, and with estimates of the production of NO2 in the mesosphere and its descent to the upper stratosphere during polar night. In particular, the findings for middle and upper stratospheric NO2 should also be more compatible with those obtained from more recent satellite sensors because the effects of the spin-splitting of the NO2 lines are accounted for now with the LIMS V6 algorithm. The improved precisions and more frequent retrievals of the LIMS profiles along their orbit tracks provide for better continuity and detail in map analyses of these two species on pressure surfaces. It is judged that the chemical effects of the oxides of nitrogen on ozone can be studied quantitatively throughout the stratosphere with the LIMS V6 data.

  20. Acidity of vapor plume from cooling tower mixed with flue gases emitted from coal-fired power plant.

    PubMed

    Hlawiczka, Stanislaw; Korszun, Katarzyna; Fudala, Janina

    2016-06-01

    Acidity of products resulting from the reaction of flue gas components emitted from a coal-fired power plant with water contained in a vapor plume from a wet cooling tower was analyzed in a close vicinity of a power plant (710 m from the stack and 315 m from the cooling tower). Samples of this mixture were collected using a precipitation funnel where components of the mixed plumes were discharged from the atmosphere with the rainfall. To identify situations when the precipitation occurred at the same time as the wind directed the mixed vapor and flue gas plumes above the precipitation funnel, an ultrasound anemometer designed for 3D measurements of the wind field located near the funnel was used. Precipitation samples of extremely high acidity were identified - about 5% of samples collected during 12 months showed the acidity below pH=3 and the lowest recorded pH was 1.4. During the measurement period the value of pH characterizing the background acidity of the precipitation was about 6. The main outcome of this study was to demonstrate a very high, and so far completely underestimated, potential of occurrence of episodes of extremely acid depositions in the immediate vicinity of a coal-fired power plant. PMID:26950639

  1. Vapor pressures and calculated heats of vaporization of concentrated nitric acid solutions in the composition range 71 to 89 percent nitrogen dioxide, 1 to 10 percent water, and in the temperature range 10 to 60 degrees C

    NASA Technical Reports Server (NTRS)

    Mckeown, A B; Belles, Frank E

    1954-01-01

    Total vapor pressures were measured for 16 acid mixtures of the ternary system nitric acid, nitrogen dioxide, and water within the temperature range 10 degrees to 60 degrees Celsius, and with the composition range 71 to 89 weight percent nitric acid, 7 to 20 weight percent nitrogen dioxide, and 1 to 10 weight percent water. Heats of vaporization were calculated from the vapor pressure measurements for each sample for the temperatures 25, 40, and 60 degrees Celsius. The ullage of the apparatus used for the measurements was 0.46. Ternary diagrams showing isobars as a function of composition of the system were constructed from experimental and interpolated data for the temperatures 25, 40, 45, and 60 degrees C and are presented herein.

  2. Optimum condition to fabricate 5-10 nm SiO2/Si structure using advanced nitric acid oxidation of Si method with Si source

    NASA Astrophysics Data System (ADS)

    Imamura, Kentaro; Matsumoto, Taketoshi; Kobayashi, Hikaru

    2012-12-01

    A low temperature (≦120 °C) fabrication method to form relatively thick SiO2/Si structure with a Si source has been developed using the advanced nitric acid oxidation of Si (NAOS) method, and the formation mechanism has been investigated. The reaction mechanism consists of direct oxidation of Si, dissolution of Si sources, and surface reaction of the dissolved Si species. The dissolved Si species is present in HNO3 solutions as mono-silicic acid and reacts with oxidizing species formed by decomposition of HNO3 on an ultrathin SiO2 layer (i.e., 1.4 nm) produced by the direct oxidation of Si substrates with HNO3 solutions. To achieve a uniform thickness of SiO2 layer with a smooth surface, HNO3 solutions with concentrations higher than 60 wt. % are needed because the dissolved Si species polymerizes in HNO3 solutions when the concentration is below 60 wt. %, resulting in the formation of SiO2 particles in HNO3, which are deposited afterwards on the SiO2 layer. In spite of the low temperature formation at 120 °C, the electrical characteristics of the advanced NAOS SiO2 layer formed with 68 wt. % HNO3 and subsequent post-metallization anneal at 250 °C are nearly identical to those of thermal oxide formed at 900 °C.

  3. Ozone, nitric acid, and ammonia air pollution is unhealthy for people and ecosystems in southern Sierra Nevada, California.

    PubMed

    Cisneros, Ricardo; Bytnerowicz, Andrzej; Schweizer, Donald; Zhong, Sharon; Traina, Samuel; Bennett, Deborah H

    2010-10-01

    Two-week average concentrations of ozone (O3), nitric acid vapor (HNO3) and ammonia (NH3) were measured with passive samplers during the 2002 summer season across the central Sierra Nevada Mountains, California, along the San Joaquin River drainage. Elevated concentrations of the pollutants were determined with seasonal means for individual sites ranging between 62 and 88 ppb for O3, 1.0-3.8 microg m(-3) for HNO3, and 2.6-5.2 microg m(-3) for NH3. Calculated O3 exposure indices were very high, reaching SUM00-191 ppm h, SUM60-151 ppm h, and W126-124 ppm h. Calculated nitrogen (N) dry deposition ranged from 1.4 to 15 kg N ha(-1) for maximum values, and 0.4-8 kg N ha(-1) for minimum values; potentially exceeding Critical Loads (CL) for nutritional N. The U.S., California, and European 8 h O3 human health standards were exceeded during 104, 108, and 114 days respectively, indicating high risk to humans from ambient O3. PMID:20708832

  4. Vapor-pressure osmometric study of the molecular weight and aggregation tendency of a reference-soil fulvic acid

    USGS Publications Warehouse

    Marinsky, J.A.; Reddy, M.M.

    1990-01-01

    The molecular weight and aggregation tendency of a reference-soil fulvic acid in Armadale horizon Bh were determined by vapor-pressure osmometry using tetrahydrofuran and water as solvents. With tetrahydrofuran, number-average molecular weight values of 767 ?? 34 and 699 ?? 8 daltons were obtained from two separate sets of measurements. Two sets of measurements with water also yielded values within this range (754 ?? 70 daltons) provided that the fulvic acid concentration in water did not exceed 7 mg ml-1; at higher concentrations (9.1-13.7 mg ml-1) a number-average molecular weight of 956 ?? 25 daltons was resolved, providing evidence of molecular aggregation. Extension of these studies to 80% neutralized fulvic acid showed that a sizeable fraction of the sodium counter ion is not osmotically active.

  5. Vapor-phase esterification of acetic acid with ethanol catalyzed by a macroporous sulfonated styrene-divinylbenzene (20%) resin

    SciTech Connect

    Gimenez, J.; Costa, J.; Cervera, S.

    1987-02-01

    The kinetics of the vapor-phase (85-120/sup 0/C) esterification of acetic acid with ethyl alcohol, at atmospheric pressure, catalyzed by a macroporous sulfonated styrene-divinylbenzene (DVB;20%) resin, has been studied. A simple first-order model (r = kp/sub 1/) fits experimental kinetic data properly for a constant reactants ratio. Discussion by means of L-H-H-W models shows that the rate-controlling step is the surface reaction with a single-site mechanism. The apparent activation energy is 4000 cal/mol.

  6. Molecular interactions between organized surface-confined monolayers and vapor-phase probe molecules. 8. Reactions between acid-terminated self-assembled monolayers and vapor-phase bases

    SciTech Connect

    Yang, H.C.; Dermody, D.L.; Xu, C.; Crooks, R.M.; Ricco, A.J.

    1996-02-07

    We present the results of a study of the interactions between three different acid-terminated self-assembled monolayer(SAM) surfaces and three basic vapor-phase probe molecules. The SAMs are composed of 4-mercaptobenzoic acid (MBA), 3-mercaptopropionic acid(MPA), and 11-mercaptoundecanoic acid (MUA), and the vapor-phase probes are, in order of increasing solution-phase acidity, decylamine, pyridine, and pyrazine. Our results are based on data from surface infrared spectroscopy and thickness-shear mode mass sensors. We find that all three SAMs irreversibly bind approximately one monolayer of decylamine, although there are slight differences that correlate with the structural nuances of the SAMs. The MPA and MBA SAMs bind decylamine through an electrostatic interaction brought about by transfer of a proton from the acid to the base. Because the MUA SAM is more impenetrable than the others, complete proton transfer is hindered, and binding of decylamine arises through a combination of proton transfer and strong hydrogen bonding. In the presence of its vapor, pyridine adsorbs to MBA surfaces at near-monolayrer coverage, but upon N{sub 2} purging about two-thirds of it desorbs. Only one-half monolayer of pyrazine, which is less basic than pyridine, adsorbs to the MBA SAM, and upon N{sub 2} purging, about two-thirds of it desorbs. The aliphatic acid SAMs follow a similar trend. 40 refs., 10 figs., 2 tabs.

  7. Study of the liquid vapor equilibrium in the bromine-hydrobromic acid-water system

    NASA Technical Reports Server (NTRS)

    Benizri, R.; Lessart, P.; Courvoisier, P.

    1984-01-01

    A glass ebullioscope was built and at atmospheric pressure, liquid-vapor equilibria relative to the Br2-HBr-H2O system, in the concentration range of interest for evaluation of the Mark 13 cycle was studied. Measurements were performed for the brome-azeotrope (HBr-H2O) pseudo-binary system and for the ternary system at temperatures lower than 125 C and in the bromine concentration range up to 13% wt.

  8. Ultrasound-promoted cold vapor generation in the presence of formic acid for determination of mercury by atomic absorption spectrometry.

    PubMed

    Gil, Sandra; Lavilla, Isela; Bendicho, Carlos

    2006-09-01

    A new cold vapor technique within the context of green chemistry is described for determination of mercury in liquid samples following high-intensity ultrasonication. Volatile Hg evolved in a sonoreactor without the use of a chemical reducing agent is carried to a quartz cell kept at room temperature for measurement of the atomic absorption. The mechanism involved lies in the reduction of Hg(II) to Hg(0) by reducing gases formed upon sonication and subsequent volatilization of Hg(0) due to the degassing effect caused by the cavitation phenomenon. Addition of a low molecular weight organic acid such as formic acid favors the process, but vapor generation also occurs from Hg solutions in ultrapure water. The detection limit of Hg was 0.1 microg/L, and the repeatability, expressed as relative standard deviation, was 4.4% (peak height). Addition of small amounts of oxidizing substances such as the permanganate or dichromate anions completely suppressed the formation of Hg(0), which confirms the above mechanism. Effect of other factors such as ultrasound irradiation time, ultrasound amplitude, and the presence of concomitants are also investigated. Some complexing anions such as chloride favored the stabilization of Hg(II) in solution, hence causing an interference effect on the ultrasound-assisted reduction/volatilization process. PMID:16944910

  9. Effect the conditions of the acid-thermal modification of clinoptilolite have on the catalytic properties of palladium-copper complexes anchored on it in the reaction of carbon monoxide oxidation

    NASA Astrophysics Data System (ADS)

    Rakitskaya, T. L.; Kiose, T. A.; Ennan, A. A.; Golubchik, K. O.; Oleksenko, L. P.; Gerasiova, V. G.

    2016-06-01

    The dependence of the physicochemical and structural-adsorption properties of natural and acid-thermal modified clinoptilolite, and of Pd(II)-Cu(II) catalysts based on them, on the duration of acid-thermal modification is investigated. The samples under study are described via XRD and thermal gravimetric (DTG and DTA) analysis, IR, DR UV-Vis, EPR spectroscopy, and water vapor adsorption. Values of both the specific surface area ( S sp) and pH of aqueous suspensions are determined. The resulting catalysts are tested in the reaction of low-temperature carbon monoxide oxidation with air oxygen. A conclusion is drawn about the nature of surface bimetallic Pd(II)-Cu(II) complexes. The greatest catalytic activity is shown by complexes based on clinoptilolite and modified with 3 M HNO3 for 0.5 and 1 h.

  10. Energetic particle-induced enhancements of stratospheric nitric acid

    NASA Technical Reports Server (NTRS)

    Aikin, Arthur C.

    1994-01-01

    Inclusion of complete ion chemistry in the calculation of minor species production during energetic particle deposition events leads to significant enhancement in the calculated nitric acid concentration during precipitation. An ionization rate of 1.2 x 10(exp 3)/cu cm/s imposed for 1 day increases HNO3 from 3 x 10(exp 5) to 6 x 10(exp 7)/cu cm at 50 km. With an ionization rate of 600 cu cm/s, the maximum HNO3 is 3 x 10(exp 7)/cu cm. Calculations which neglect negative ions predict the nitric acid will fall during precipitation events. The decay time for converting HNO3 into odd nitrogen and hydrogen is more than 1 day for equinoctial periods at 70 deg latitude. Examination of nitric acid data should yield important information on the magnitude and frequency of charged particle events.

  11. Aircraft simultaneous measurements of NO2, total peroxy nitrate, total alkyl nitrate, and HNO3: observations and main results from UK, Boreal forest and Central Italy

    NASA Astrophysics Data System (ADS)

    Di Carlo, Piero; Aruffo, Eleonora; Busilacchio, Marcella; Giammaria, Franco; Dari-Salisburgo, Cesare; Biancofiore, Fabio; Visconti, Guido; Lee, James; Moller, Sarah; Reeves, Claire C.; Bauguitte, Stephane; Forster, Grant; Jones, Roderic; Ouyang, Bin; Palmer, Paul I.; Parrington, Mark; McQuaid, Jim; Krejci, Radek

    2013-04-01

    A four-channel thermal dissociation laser induced fluorescence (TD-LIF) instrument for simultaneous measurements of nitrogen dioxide (NO2), total peroxy nitrate, total alkyl nitrate and nitric acid, was installed three years ago on the UK Facility for Airborne Atmospheric Measurements (FAAM) BAe 146-301 atmospheric research aircraft. Since summer 2010 the TD-LIF has successfully flown in five field campaigns: RONOCO I (summer 2010, UK), SeptEx (summer 2010, UK), RONOCO II (winter 2011, UK), BORTAS (summer 2012, Canada) and SONATA (summer 2012, Italy). In this presentation will be show the main characteristics of the TD-LIF and the observations collected during the five campaigns above. The main results achieved in each campaign will be reported and emphasis will be given to the role of NOx, total peroxy and total alkyl nitrates in the different environments observed to date.

  12. Absorption cross section for the 5νOH stretch of acetic acid and peracetic acid

    NASA Astrophysics Data System (ADS)

    Begashaw, I. G.; Collingwood, M.; Bililign, S.

    2009-12-01

    We report measurements of the absorption cross sections for the vibrational O-H stretch (5νOH) overtone transitions in glacial acetic acid and peracetic acid. The photochemistry that results from overtone excitation has been shown to lead to OH radical production in molecules containing O-H (HNO3, H2O2). In addition the overtone excitation has been observed to result in light initiated chemical reaction. A Cavity ring-down spectroscopy (CRDS) instrument comprising of an Nd:YAG pumped dye laser and 620nm high reflectivity mirrors (R=99.995%) was used to measure the cross sections. The dye laser wavelength was calibrated using water vapor spectrum and the HITRAN 2008 database. The instrument’s minimum detectable absorption is αmin =4.5 *10-9cm-1 Hz-1/2 at 2σ noise level near the peak of the absorption feature. This measurement is the first for acetic acid at this excitation level. Preliminary results for acetic acid show the peak occurs near 615nm. Procedures for separating the monomer and dimer contribution will be presented. We would like to acknowledge support from NSF award #0803016 and NOAA-EPP award #NA06OAR4810187.

  13. Ship-based nitric acid measurements in the Gulf of Maine during New England Air Quality Study 2002

    NASA Astrophysics Data System (ADS)

    Dibb, Jack E.; Scheuer, Eric; Whitlow, Sallie I.; Vozella, Marcy; Williams, Eric; Lerner, Brian M.

    2004-10-01

    Gas phase nitric acid (HNO3) was measured at 5-min resolution on board the National Oceanographic and Atmospheric Administration (NOAA) research vessel Ronald H. Brown during the second leg (29 July to 10 August) of the New England Air Quality Study (NEAQS) 2002 cruise. A primary objective of the cruise was to improve understanding of the oxidation of NOx in, and removal of the oxidation products from, the polluted marine boundary layer east of northeastern North America. For the first 9 days of this leg the ship remained north of Cape Cod, and the cruise track did not extend much farther north than the New Hampshire-Maine border. During this period, HNO3 averaged 1.1 ppb and accounted for 19% of total reactive nitrogen oxides (measured NOy). On all days, peak HNO3 mixing ratios were observed in the early afternoon (average 2.3 ppb), at levels twofold to fourfold higher than the minima around sunrise and sunset. In these daytime peaks, HNO3/NOy averaged 28%. There were secondary nighttime peaks of HNO3 (0.9 ppb average), when HNO3 accounted for 16% of total reactive nitrogen oxides. This pronounced diurnal pattern confirms that production, and subsequent deposition, of HNO3 in the polluted marine boundary layer downwind of New England removes a significant fraction of the NOx exported to the atmosphere over the Gulf of Maine. Nitric acid was correlated with O3, particularly during the early afternoon interval when both molecules reached maximum mixing ratios (R2 = 0.66). The ozone production efficiency (OPE) inferred from the slope (10 ppb O3/ppb HNO3) was similar to the OPE of 9 estimated at the Atmospheric Investigation, Regional Modeling, Analysis and Prediction (AIRMAP) Thompson Farm station in coastal New Hampshire during the study period.

  14. Collection of VLE data for acid gas---alkanolamine systems using fourier transform infrared spectroscopy. [Vapor-liquid equilibrium

    SciTech Connect

    Bullin, J.A.; Frazier, R.E.

    1992-01-01

    The industrial standard process for the purification of natural gas is to remove acid gases, mainly hydrogen sulfide and carbon dioxide, by the absorption and reaction of these gases with alkanolamines. Inadequate data for vapor--liquid equilibrium (VLE) hinder the industry from converting operations to more energy efficient amine mixtures and conserving energy. Some energy reductions have been realized in the past decade by applying such amine systems as hindered'' amines, methyldiethanolamine (MDEA), and MDEA based amine mixtures. However, the lack of reliable and accurate fundamental VLE data impedes the commercial application of these more efficient alkanolamine systems. The first project objective is to improve the accuracy of vapor--liquid equilibrium measurements at low hydrogen sulfide concentrations. The second project objective is to measure the VLE for amine mixtures. By improving the accuracy of the VLE measurements on MDEA and mixtures with other amines, energy saving can be quickly and confidently implemented in the many existing absorption units already in use. If about 25% of the existing 95.3 billion SCFD gas purification capacity is converted to these new amine systems, the energy savings are estimated to be about 3 [times] 10[sup 14] BTU/yr.

  15. Vapor-liquid equilibria in the system ethanethiol + methyldiethanolamine + water in the presence of acid gases

    SciTech Connect

    Jou, F.Y.; Mather, A.E.; Schmidt, K.A.G.; Ng, H.J.

    1999-07-01

    This investigation was carried out to determine the solubility of ethanethiol in a methyldiethanolamine (MDEA) solution. Measurements were made in the absence of acid gases, H{sub 2}H and CO{sub 2}, with individual acid gases present, and with mixtures of acid gases present. Experiments with an aqueous solution of 50 mass % MDEA were carried out at 40 and 70 C. The total pressure for most of the experiments was 6,890 kPa, which was maintained by methane. Partial pressures of ethanethiol ranged from 0.2 to 15 kPa.

  16. Determination of Activity Coefficients of di-(2-ethylhexyl) Phosphoric Acid Dimer in Select Organic Solvents Using Vapor Phase Osmometry

    SciTech Connect

    Michael F. Gray; Peter Zalupski; Mikael Nilsson

    2013-08-01

    Effective models for solvent extraction require accurate characterization of the nonideality effects for each component, including the extractants. In this study, the nonideal behavior of the industrial extractant di(2-ethylhexyl) phosphoric acid has been investigated using vapor pressure osmometry (VPO). From the osmometry data, activity coefficients for the HDEHP dimer were obtained based on a formulation of the regular solution theory of Scatchard and Hildebrand, and the Margules two- and three-suffix equations. The results show similarity with a slope-analysis based relation from previous literature, although important differences are highlighted. The work points towards VPO as a useful technique for this type of study, but care must be taken with the choice of standard and method of analysis.

  17. Electrical conductivity measurements of aqueous boric acid at 25--350{degree}C at saturation vapor pressure. Final report

    SciTech Connect

    Ho, P.C.; Palmer, D.A.

    1995-09-01

    Electrical conductance measurements of aqueous boric acid solutions (15-110 g/kg-H{sub 2}O {equivalent_to} 0.251--1.815 mol/kg-H{sub 2}O) were measured over the temperature range 25 to 75 C at saturation vapor pressures in glass cells with parallel platinum electrodes. Sixteen series of measurements were made involving three samples of boric acid from different sources. Conductance measurements were also made at 15.5 and 30.5 g/kg-H{sub 2}O over the temperature range 100 to 350 C at 50 C intervals with a metallic cell fitted with concentric platinum electrodes. The specific conductances of H{sub 3}BO{sub 3} (aq)were calculated after correction for the conductance of the solvent (water) and are tabulated in this report. At the specific conditions requested in the project description, namely a concentration of 110 g/kg-H{sub 2}O and 65 C, the specific conductance of boric acid is 293.2 {+-} 1.8 microSiemens/cm based on duplicate measurements of four independent solutions. The results from these tests will be utilized by the Tokamak Physics Experimental Project (TPX).

  18. Determination of Water Vapor Pressure Over Corrosive Chemicals Versus Temperature Using Raman Spectroscopy as Exemplified with 85.5% Phosphoric Acid.

    PubMed

    Rodier, Marion; Li, Qingfeng; Berg, Rolf Willestofte; Bjerrum, Niels Janniksen

    2016-07-01

    A method to determine the water vapor pressure over a corrosive substance was developed and tested with 85.5 ± 0.4% phosphoric acid. The water vapor pressure was obtained at a range of temperatures from ∼25 ℃ to ∼200 ℃ using Raman spectrometry. The acid was placed in an ampoule and sealed with a reference gas (either hydrogen or methane) at a known pressure (typically ∼0.5 bar). By comparing the Raman signals from the water vapor and the references, the water pressure was determined as a function of temperature. A considerable amount of data on the vapor pressure of phosphoric acid are available in the literature, to which our results could successfully be compared. A record value of the vapor pressure, 3.40 bar, was determined at 210 ℃. The method required a determination of the precise Raman scattering ratios between the substance, water, and the used reference gas, hydrogen or methane. In our case the scattering ratios between water and reference ν1 Q-branches were found to be 1.20 ± 0.03 and 0.40 ± 0.02 for H2 and CH4, respectively. PMID:27273974

  19. Competition between Displacement and Dissociation of a Strong Acid Compared to a Weak Acid Adsorbed on Silica Particle Surfaces: The Role of Adsorbed Water.

    PubMed

    Fang, Yuan; Tang, Mingjin; Grassian, Vicki H

    2016-06-16

    The adsorption of nitric (HNO3) and formic (HCOOH) acids on silica particle surfaces and the effect of adsorbed water have been investigated at 296 K using transmission FTIR spectroscopy. Under dry conditions, both nitric and formic acids adsorb reversibly on silica. Additionally, the FTIR spectra show that both of these molecules remain in the protonated form. At elevated relative humidities (RH), adsorbed water competes both for surface adsorption sites with these acids as well as promotes their dissociation to hydronium ions and the corresponding anions. Compared to HNO3, the extent of dissociation is much smaller for HCOOH, very likely because it is a weaker acid. This study provides valuable insights into the interaction of HNO3 and HCOOH with silica surface on the molecular level and further reveals the complex roles of surface-adsorbed water in atmospheric heterogeneous chemistry of mineral dust particles-many of these containing silica. PMID:27220375

  20. Thermodynamic Phase And Chemical Equilibrium At 0-110 C For The H+-K+-Na+-Cl--H2O System Up To 16 Molal And The HNO3-H2O System Up To 20 Molal Using An Association-Based Pitzer Model Compatible With ASPEN Plus

    SciTech Connect

    Nichols,T.T.; Taylor,D.D.

    2003-09-26

    A status is presented of the parameterization during FY2003 of an association-based Pitzer model to simulate chemical and phase equilibria of acid-chloride-nitrate-mercury aqueous electrolyte systems at 0-100 C within the industry-standard process simulator, ASPEN Plus. Compatibility with ASPEN Plus requires that the Pitzer model used be limited to the third virial coefficient and have the values of b and a1 as originally proposed by Pitzer. Two aqueous models for 0-110 C at atmospheric pressure were parameterized in FY03. The model for the aqueous H+-K+-Na+-Cl- system is applicable for 0-16 molal, and the HNO3-H2O for 0-20 molal. An association-based Pitzer activity coefficient model is combined with Henry's law to predict activity/osmotic coefficient and VLE. The chloride model also predicts KCl and NaCl solubility, while the nitric acid model has the unique capability of predicting extent of dissociation with an average absolute deviation of 1.43%. The association-based approach presented here extends the utility of the molality-based Pitzer model past 6 molal to predict activity/osmotic coefficients up to 16-20 molal. The association-based approach offers the additional benefits of predicting extent of dissociation and of allowing the Pitzer model to be fully utilized in commercial simulators, such as ASPEN Plus, that require accounting for association to implement Henry's law. The Pitzer models presented here provide the chemical process simulation engineer with a superior alternative to the Electrolyte NRTL model that can easily be used in ASPEN Plus.

  1. Heterogeneous interactions of chlorine nitrate, hydrogen chloride, and nitric acid with sulfuric acid surfaces at stratospheric temperatures

    NASA Technical Reports Server (NTRS)

    Tolbert, Margaret A.; Rossi, Michel J.; Golden, David M.

    1988-01-01

    The heterogeneous interactions of ClONO2, HCl, and HNO3 with sulfuric acid surfaces were studied using a Knudsen cell flow reactor. The surfaces studied, chosen to simulate global stratospheric particulate, were composed of 65-75 percent H2SO4 solutions at temperatures in the range -63 to -43 C. Heterogeneous loss, but not reaction, of HNO3 and HCl occurred on these surfaces; the measured sticking coefficients are reported. Chlorine nitrate reacted on the cold sulfuric acid surfaces, producing gas-phase HOCl and condensed HNO3. CLONO2 also reacted with HCl dissolved in the 65-percent H2SO4 solution at -63 C, forming gaseous Cl2. In all cases studied, the sticking and/or reaction coefficients were much larger for the 65-percent H2SO4 solution at -63 C than for the 75-percent solution at -43 C.

  2. Delayed production of sulfuric acid condensation nuclei in the polar stratosphere from El Chichon volcanic vapors

    NASA Technical Reports Server (NTRS)

    Hofmann, D. J.; Rosen, J. M.; Gringel, W.

    1985-01-01

    It is pointed out that measurements of the vertical profiles of atmospheric condensation nuclei (CN) have been conducted since 1973. Studies with a new instrument revealed that the CN concentration undergoes a remarkable annual variation in the 30-km region characterized by a large increase in the late winter/early spring period with a subsequent decay during the remainder of the year. The event particles are observed to be volatile at 150 C, suggesting a sulfuric acid-water composition similar to that found in the normal 20 km aerosol layer. The development of about 10 to the 7th metric tons of sulfuric acid aerosol following the injection of sulfurous gases by El Chichon in April 1982, prompted Hofmann and Rosen (1983) to predict a very large CN event for 1983. The present investigation is concerned with the actual observation of the predicted event. Attention is given to the observation of a very large increase of what appear to be small sulfuric acid droplets at 30-km altitude in January 1983 over Laramie, WY, in January 1983.

  3. Quantum chemical modeling of humic acid/air equilibrium partitioning of organic vapors.

    PubMed

    Niederer, Christian; Goss, Kai-Uwe

    2007-05-15

    Classical approaches for predicting soil organic matter partition coefficients of organic compounds require a calibration with experimental partition data and, for good accuracy, experimental compound descriptors. In this study we evaluate the quantum chemical model COSMO-RS in its COSMOtherm implementation for the prediction of about 200 experimental Leonardite humic acid/air partition coefficients without calibration or experimental compound descriptors, but simply based on molecular structures. For this purpose a Leonardite Humic Acid model monomer limited to 31 carbon atoms was derived from 13C NMR analysis, elemental analysis, and acidic function analysis provided in the literature. Altogether the COSMOtherm calculations showed a good performance and we conclude that it may become a very promising tool for the prediction of sorption in soil organic matter for compounds for which the molecular structure is the only reliable information available. COSMOtherm can be expected to be very robust with respectto new and complex compound structures because its calculations are based on a fundamental assessment of the underlying intermolecular forces. In contrast, other empirical models that are also based on the molecular structure of the sorbate have an application domain that is limited by their calibration data set that is often unknown to the user. PMID:17547191

  4. C3HNO 3-Oxo-2-propenenitrile

    NASA Astrophysics Data System (ADS)

    Demaison, J.

    This document is part of Part 2 of Subvolume D 'Asymmetric Top Molecules' of Volume 29 'Molecular Constants Mostly from Microwave, Molecular Beam, and Sub-Doppler Laser Spectroscopy' of Landolt-Börnstein - Group II 'Molecules and Radicals'.

  5. Diurnal variations in H2O2, O3, PAN, HNO3 and aldehyde concentrations and NO/NO2 ratios at Rishiri Island, Japan: potential influence from iodine chemistry.

    PubMed

    Kanaya, Yugo; Tanimoto, Hiroshi; Matsumoto, Jun; Furutani, Hiroshi; Hashimoto, Shigeru; Komazaki, Yuichi; Tanaka, Shigeru; Yokouchi, Yoko; Kato, Shungo; Kajii, Yoshizumi; Akimoto, Hajime

    2007-04-15

    The presence of iodine chemistry, hypothesized due to the overprediction of HO(2) levels by a photochemical box model at Rishiri Island in June 2000, was quantitatively tested against the observed NO/NO(2) ratios and the net production rates of ozone. The observed NO/NO(2) ratios were reproduced reasonably well by considering the conversion of NO to NO(2) by IO, whose amount was calculated so as to reproduce the observed HO(2) levels. However, the net production rates of ozone were calculated to be negative when such high mixing ratios of IO were considered, which was inconsistent with the observed buildup of ozone during daytime. These results suggest that iodine chemistry may not be the sole mechanism for the reduced mixing ratios of HO(2), or that "hot spots" for iodine chemistry were present. Diurnal variations in the mixing ratios of HCHO, CH(3)CHO, peroxy acetyl nitrate (PAN) and HNO(3) observed during the study are presented along with the simulated ones. The box model simulations suggest that the effect of iodine chemistry on these concentrations is small and that important sources of CH(3)CHO and sinks of PAN are probably missing from our current understanding of the tropospheric chemistry mechanism. PMID:17306859

  6. Improvement in electrochemical capacitance of activated carbon from scrap tires by nitric acid treatment

    NASA Astrophysics Data System (ADS)

    Han, Yan; Zhao, Ping-Ping; Dong, Xiao-Ting; Zhang, Cui; Liu, Shuang-Xi

    2014-12-01

    Activated carbon (AC) obtained from the industrial pyrolytic tire char is treated by concentrated nitric acid (AC-HNO3) and then used as the electrode material for supercapacitors. Surface properties and electrochemical capacitances of AC and ACHNO3 are studied. It is found that the morphology and the porous texture for AC and AC-HNO3 have little difference, while the oxygen content increases and functional groups change after the acid treatment. Electrochemical results demonstrate that the AC-HNO3 electrode displays higher specific capacitance, better stability and cycling performance, and lower equivalent series resistance, indicating that AC obtained from the industrial pyrolytic tire char treated by concentrated nitric acid is applicable for supercapacitors.

  7. Speciated fine-particle (<2.5 {micro}m aerodynamic diameter) and vapor-phase acid concentrations in southern California

    SciTech Connect

    Taylor, C.A. Jr.; Stover, C.A.; Westerdahl, F.D.

    1998-12-31

    A fine-particle (<2.5 {micro}m aerodynamic diameter) and vapor-phase acid sampling network has been in operation among 12 communities in southern California since late 1993. The data from this network consists of concentrations of particulate matter <10 {micro}m in aerodynamic diameter (PM10), nitrogen dioxide, ozone, vapor-phase hydrochloric, nitric, acetic, and formic acids, particulate matter <2.5 {micro}m in aerodynamic diameter (PM2.5), and the chloride, nitrate, sulfate, and ammonium components of PM2.5. These measurements are the basis of the exposure assessment estimates of the Children`s Health Study, a multi-year study, mainly of lung function development and respiratory illness, taking place in southern California. One of the goals of the Children`s Health Study is to utilize a cost-effective means of obtaining continuous fine-particle and vapor-phase acid data for a multi-year study with enough time resolution to allow seasonal estimates of exposure. A two-week sampler was developed to meet these needs. Four continuous years of vapor-phase acid and PM2.5 mass, chloride, nitrate, sulfate, and ammonium data have been collected. During this time, the sampler has proven to be reliable. A decline in PM2.5 mass, nitrate, and ammonium ions in most of the communities from 1994 to 1997 was observed. In contrast, very little change in vapor-phase acids was observed. There has been increased interest at the national level in fine particles and their characteristics. The network provides a rich database that can be used to characterize southern California communities on the basis of their level of fine particles (and their components) and vapor-phase acids and should prove valuable with respect to both prospective and retrospective health studies. The database also provides a general characterization of the levels of PM2.5 affecting 25 million people in southern California.

  8. Deposition kinetics and characterization of stable ionomers from hexamethyldisiloxane and methacrylic acid by plasma enhanced chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Urstöger, Georg; Resel, Roland; Koller, Georg; Coclite, Anna Maria

    2016-04-01

    A novel ionomer of hexamethyldisiloxane and methacrylic acid was synthesized by plasma enhanced chemical vapor deposition (PECVD). The PECVD process, being solventless, allows mixing of monomers with very different solubilities, and for polymers formed at high deposition rates and with high structural stability (due to the high number of cross-links and covalent bonding to the substrate) to be obtained. A kinetic study over a large set of parameters was run with the aim of determining the optimal conditions for high stability and proton conductivity of the polymer layer. Copolymers with good stability over 6 months' time in air and water were obtained, as demonstrated by ellipsometry, X-Ray reflectivity, and FT-IR spectroscopy. Stable coatings showed also proton conductivity as high as 1.1 ± 0.1 mS cm-1. Chemical analysis showed that due to the high molecular weight of the chosen precursors, it was possible to keep the plasma energy-input-per-mass low. This allowed limited precursor fragmentation and the functional groups of both monomers to be retained during the plasma polymerization.

  9. Laboratory measurements of the microwave opacity and vapor pressure of sulfuric acid vapor under simulated conditions for the middle atmosphere of Venus

    NASA Technical Reports Server (NTRS)

    Steffes, P. G.

    1985-01-01

    Microwave absorption measurements at wavelengths of 13.4 and 3.6 cm were made in gaseous H2SO4 in a CO2 atmosphere under simulated conditions for the Venus middle atmosphere. The results suggest that abundances of gaseous H2SO4 on the order of 15-30 ppm could account for the absorption observed by radio occultation measurements at these wavelengths. They also imply that such abundances would correspond to saturation vapor pressure existing at or above the 46-48-km range, which correlates with the observed cloud base.

  10. Density functional studies of the formation of nitrous acid from the reaction of nitrogen dioxide and water vapor

    SciTech Connect

    Chou, A.; Li, Z.; Tao, F.M.

    1999-09-30

    Nitrous acid (HONO) has long been recognized as an important trace gas in the troposphere where its rapid photolysis represents a significant source of hydroxy (OH) radicals. During the night, HONO has been observed to accumulate to concentrations up to 15 ppb, and this accumulation of HONO has a profound impact on the daytime chemistry of the troposphere. Reaction mechanisms for the production of nitrous acid (HONO ) from the homogeneous gas-phase hydrolysis of nitrogen dioxide (NO{sub 2}) are examined by density functional theory calculations. The molecular structures and energies of the NO{sub 2}-(H{sub 2}O){sub n} (n = 1, 2, 3) and N{sub 2}O{sub 4}-(H{sub 2} O){sub n}(n = 1, 2) systems corresponding to the stationary points on the potential energy surface along the reaction pathways are calculated using the B3LYP method with the 6-311+G(2d,p) basis set. These reaction pathways represent the homogeneous hydrolysis of NO{sub 2} or N{sub 2}O{sub 4} with a varying number of water (H{sub 2}O) molecules. The reactions of NO{sub 2} with water produce HONO, along with the OH radical which was postulated to combine in the next step with a second NO{sub 2} to form nitric acid (HNO{sub 3}). The simple NO{sub 2} + H{sub 2}O bimolecular reaction leads to the highly unstable OH radical which reacts reversibly with HONO without an energy barrier. The introduction of single solvating H{sub 2}O molecule appears to stabilize the transition state as well as an intermediate that contains the OH radical. However, the energy barrier is found to be near 30 kcal mol{sup {minus}1} and is not affected by multiple additional H{sub 2}O molecules. On the other hand, the reaction of N{sub 2}O{sub 4} with water lead directly to HONO and HNO{sub 3}. the energy barrier for the N{sub 2}O{sub 4} reaction is above 30 kcal mol{sup {minus}1} and is also unaffected by additional H{sub 2}O molecules. The study demonstrates that the gas-phase hydrolysis of NO{sub 2} or N{sub 2}O{sub 4} is

  11. Nitric acid and ammonia emissions from a mid-latitude prescribed wetlands fire

    NASA Astrophysics Data System (ADS)

    LeBel, P. J.; Cofer, W. R., III; Levine, J. S.; Vay, S. A.; Roberts, P. D.

    1988-08-01

    We have obtained the first simultaneous measurements of gaseous nitric acid (HNO3) and ammonia (NH3) in the smoke plume of a wetlands biomass burn. These measurements were made using tungsten oxide-coated diffusion denuder tubes from a helicopter during a prescribed burn at the Merritt Island National Wildlife Refuge, located at the NASA John F. Kennedy Space Center, Florida, on November 9, 1987. The mean NH3 and HNO3 mixing ratios measured in the smoke plume were 19 ppbv and 14 ppbv, respectively, both significantly higher than background mixing ratios. Nitric acid correlated well with carbon dioxide (CO2) produced by the combustion. The mean CO2-normalized emission ratio for HNO3 was found to be 1.2 × 10-4. Ammonia, however, did not correlate well with CO2 suggesting a more complex relationship between combustion and production/release of NH3.

  12. SPODOSOL VARIABILITY AND ASSESSMENT OF RESPONSE TO ACIDIC DEPOSITION

    EPA Science Inventory

    Variability in forest soils makes it difficult to observe short-term changes in chemical properties under field conditions. uried soil-bag technique was developed to examine the chemical response of a Maine forest soil to loadings of strong acids (HNO3 and H2SO4). cids were added...

  13. POLLUTANT SAMPLER FOR MEASUREMENTS OF ATMOSPHERIC ACIDIC DRY DEPOSITION

    EPA Science Inventory

    An acidic pollutant sampler for dry deposition monitoring has been designed and evaluated in laboratory and field studies. The system, which is modular and simple to operate, samples gaseous HNO3, NH3, SO2 and NO2 and particulate SO4(-2), NO3(1-) and NH4(1+) and is made of Teflon...

  14. Rational Design of a Nile Red/Polymer Composite Film for Fluorescence Sensing of Organophosphonate Vapors using Hydrogen Bond Acidic Polymers

    SciTech Connect

    Levitsky, Igor; Krivoshlykov, Sergei G.; Grate, Jay W. )

    2000-12-01

    The solvatochromic dye Nile Red dispersed in selected hydrogen-bond acidic polymer matrices demonstrated strong fluorescence enhancement at the presence of dimethyl methylphosphonate (DMMP) vapors. Two hydrogen bond acidic polymers were examined as dye matrices, one with fluorinated alcohol groups on a polystyrene backbone (PSFA), and the other with fluorinated bisphenol groups alternating with oligodimethylsiloxane segments (BSP3). The combination of hydrogen-bond acidic polymer (a strong sorbent for DMMP) with the solvatochromic dye led to initial depression of the dye fluorescence and a significant red shift in the absorbance and fluorescence spectra. DMMP sorption changed the dye environment and dramatically altered the fluorescence spectrum and intensity, resulting in a strong fluorescence enhancement. It is proposed that this fluorescence enhancement is due to the competition set up between the dye and the sorbed vapor for polymeric hydrogen bonding sites. The highest responses were obtained with BSP3. DMMP detection has been demonstrated at sub-ppm DMMP concentrations, indicating very low detection limits compared to previous Nile Red/polymer matrix fluorescence vapor sensors. Nile Red/poly(methyl methacrylate) films prepared for comparisons exhibited substantially lower response to DMMP. Rational selection of polymers providing high sorption for DMMP and competition for hydrogen-bonding interactions with Nile Red yielded fluorescent films with high sensitivity.

  15. Development of the detection threshold concept from a close look at sorption occurrence inside a glass vial based on the in-vial vaporization of semivolatile fatty acids.

    PubMed

    Kim, Yong-Hyun; Kim, Ki-Hyun; Szulejko, Jan E; Parker, David

    2014-07-01

    Headspace (HS) analysis has been recommended as one of the most optimal methods for extracting and analyzing volatile organic compounds from samples in diverse media such as soil and water. Short-chain volatile fatty acids (VFA, C3-C7) with strong adsorptivity were selected as the target compounds to assess the basic characteristics of the HS analysis through simulation of HS conditions by in-vial vaporization of liquid-phase standards (VL) in 25 mL glass vials. The reliability of the VL approach was assessed by apportioning the in-vial VFA mass into three classes: (1) vaporized fraction, (2) dynamic adsorption on the vial walls (intermediate stage between vaporization and irreversible absorption), and (3) irreversible absorptive loss (on the vial wall). The dynamic adsorption partitioning inside the vial increased with n-VFA carbon number, e.g., 43% (C2: acetic acid, extrapolated value), 65% (C3: propanoic acid), and 98% (C7: heptanoic acid). The maximum irreversible losses for the studied n-VFAs exhibited a quadratic relationship with carbon number. If the detection threshold limit (DTL: the onset of mass detection after attaining the maximum irreversible loss) is estimated, the DTL values for target VFAs were in the range of 101 ng for i-valeric acid to 616 ng for propionic acid, which are larger than the method detection limit by about 3 orders of magnitude. Consequently, quantitation of VFAs using the VL approach should be critically assessed by simultaneously considering the DTL criterion and the initial VFA masses loaded into the vial. PMID:24881858

  16. FIELD METHOD COMPARISON FOR THE CHARACTERIZATION OF ACID AEROSOLS AND GASES

    EPA Science Inventory

    This paper presents findings from two intercomparison studies of acid aerosol measurement systems, which were conducted in Uniontown and State College, PA, during the summers of 1990 and 1991, respectively. s part of these studies, acid aerosol and gas concentrations (NH3, HNO3, ...

  17. Direct real-time detection of vapors from explosive compounds.

    PubMed

    Ewing, Robert G; Clowers, Brian H; Atkinson, David A

    2013-11-19

    The real-time detection of vapors from low volatility explosives including PETN, tetryl, RDX, and nitroglycerine along with various compositions containing these substances was demonstrated. This was accomplished with an atmospheric flow tube (AFT) using a nonradioactive ionization source coupled to a mass spectrometer. Direct vapor detection was accomplished in less than 5 s at ambient temperature without sample preconcentration. The several seconds of residence time of analytes in the AFT provided a significant opportunity for reactant ions to interact with analyte vapors to achieve ionization. This extended reaction time, combined with the selective ionization using the nitrate reactant ions (NO3(-) and NO3(-)·HNO3), enabled highly sensitive explosives detection from explosive vapors present in ambient laboratory air. Observed signals from diluted explosive vapors indicated detection limits below 10 ppqv using selected ion monitoring (SIM) of the explosive-nitrate adduct at m/z 349, 378, 284, and 289 for tetryl, PETN, RDX, and NG, respectively. Also provided is a demonstration of the vapor detection from 10 different energetic formulations sampled in ambient laboratory air, including double base propellants, plastic explosives, and commercial blasting explosives using SIM for the NG, PETN, and RDX product ions. PMID:24090362

  18. Nitric Acid-Sea Salt Reactions: Implications for Nitrogen Deposition to Water Surfaces.

    NASA Astrophysics Data System (ADS)

    Pryor, S. C.; Sørensen, L. L.

    2000-05-01

    Many previous studies have indicated the importance of nitric acid (HNO3) reactions on sea salt particles for flux divergence of HNO3 in the marine surface layer. The potential importance of this reaction in determining the spatial and temporal patterns of nitrogen dry deposition to marine ecosystems is investigated using models of sea spray generation and particle- and gas-phase dry deposition. Under horizontally homogeneous conditions with near-neutral stability and for wind speeds between 3.5 and 10 m s1, transfer of HNO3 to the particle phase to form sodium nitrate may decrease the deposition velocity of nitrogen by over 50%, leading to greater horizontal transport prior to deposition to the sea surface. Conversely, for wind speeds above 10 m s1, transfer of nitrogen to the particle phase would increase the deposition rate and hence decrease horizontal transport prior to surface removal.

  19. Recycling of metal-organic chemical vapor deposition waste of GaN based power device and LED industry by acidic leaching: Process optimization and kinetics study

    NASA Astrophysics Data System (ADS)

    Swain, Basudev; Mishra, Chinmayee; Kang, Leeseung; Park, Kyung-Soo; Lee, Chan Gi; Hong, Hyun Seon; Park, Jeung-Jin

    2015-05-01

    Recovery of metal values from GaN, a metal-organic chemical vapor deposition (MOCVD) waste of GaN based power device and LED industry is investigated by acidic leaching. Leaching kinetics of gallium rich MOCVD waste is studied and the process is optimized. The gallium rich waste MOCVD dust is characterized by XRD and ICP-AES analysis followed by aqua regia digestion. Different mineral acids are used to find out the best lixiviant for selective leaching of the gallium and indium. Concentrated HCl is relatively better lixiviant having reasonably faster kinetic and better leaching efficiency. Various leaching process parameters like effect of acidity, pulp density, temperature and concentration of catalyst on the leaching efficiency of gallium and indium are investigated. Reasonably, 4 M HCl, a pulp density of 50 g/L, 100 °C and stirring rate of 400 rpm are the effective optimum condition for quantitative leaching of gallium and indium.

  20. The formation of acid rain in the atmosphere, adjacent to the TTP with the joint-condensing of sulfur dioxide and water vapor

    NASA Astrophysics Data System (ADS)

    Gvozdyakov, D. V.; Gubin, V. E.; Matveeva, A. A.

    2014-08-01

    Presents the results of mathematical simulation of the condensation process of sulphur dioxide and water vapor on the condensation nuclei surface under the action of natural factors. Numerical investigations were carried out for the summer at a moderate speed of the wind. The influence of the parameter of condensation on the speed of the process of sulfuric acid drops formation in the air space was analyzed. Time ranges, sufficient for the formation of the acid rain sedimentation in the atmosphere, adjacent to the areas of thermal power station work were established. It is shown that the speed of air masses movement effects on the process of acid anthropogenic admixtures dispersion in the atmosphere. Approbation of the obtained results was carried out by checking the difference scheme conservative and solution of test problems.

  1. Determination of inorganic and total mercury by vapor generation atomic absorption spectrometry using different temperatures of the measurement cell

    NASA Astrophysics Data System (ADS)

    Kaercher, Luiz Eduardo; Goldschmidt, Fabiane; Paniz, José Neri Gottfried; de Moraes Flores, Érico Marlon; Dressler, Valderi Luiz

    2005-06-01

    A simple and inexpensive laboratory-built flow injection vapor generation system coupled to atomic absorption spectrometry (FI-VG AAS) for inorganic and total mercury determination has been developed. It is based on the vapor generation of total mercury and a selective detection of Hg 2 + or total mercury by varying the temperature of the measurement cell. Only the inorganic mercury is measured when the quartz cell is at room temperature, and when the cell is heated to 650 °C or higher the total Hg concentration is measured. The organic Hg concentration in the sample is calculated from the difference between the total Hg and Hg 2 + concentrations. Parameters such as the type of acid (HCl or HNO 3) and its concentration, reductant (NaBH 4) concentration, carrier solution (HCl) flow rate, carrier gas flow rate, sample volume and quartz cell temperature, which influence FI-VG AAS system performance, were systematically investigated. The optimized conditions for Hg 2 + and total Hg determinations were: 1.0 mol l - 1 HCl as carrier solution, carrier flow rate of 3.5 ml min - 1 , 0.1% (m/v) NaBH 4, reductant flow rate of 1.0 ml min - 1 and carrier gas flow rate of 200 ml min - 1 . The relative standard deviation (RSD) is lower than 5.0% for a 1.0 μg l - 1 Hg solution and the limit of quantification (LOQ, 10 s) is 55 ng g - 1 . Certified samples of dogfish muscle (DORM-1 and DORM-2) and non-certified fish samples were analyzed, using a 6.0 mol l - 1 HCl solution for analyte extraction. The Hg 2 + and CH 3Hg + concentrations found were in agreement with certified ones.

  2. Surface morphology study of Zr-based amorphous alloys after immersion in boiling nitric acid medium

    NASA Astrophysics Data System (ADS)

    Sharma, Poonam; Dhawan, Anil; Sharma, S. K.

    2016-05-01

    Weight loss studies have been performed to determine the corrosion resistance of amorphous Zr60Nb2Al10Ni8Cu20 and Zr59Nb3Al10Ni8Cu20 alloys in aqueous HNO3 media at boiling temperature. The FESEM micrographs has been obtained to know the surface morphology of specimens after immersion in 11.5M boiling aqueous HNO3 media. Zr59Nb3Al10Ni8Cu20 alloy shows better corrosion resistance in nitric acid media than Zr60Nb2Al10Ni8Cu20 alloy.

  3. Sorption of vapors of some organic liquids on soil humic acid and its relation to partitioning of organic compounds in soil organic matter

    USGS Publications Warehouse

    Chlou, G.T.; Kile, D.E.; Malcolm, R.L.

    1988-01-01

    Vapor sorption of water, ethanol, benzene, hexane, carbon tetrachloride, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene, and 1,2-dibromoethane on (Sanhedron) soil humic acid has been determined at room temperature. Isotherms for all organic liquids are highly linear over a wide range of relative pressure (P/P??), characteristic of the partitioning (dissolution) of the organic compounds in soil humic acid. Polar liquids exhibit markedly greater sorption capacities on soil humic acid than relatively nonpolar liquids, in keeping with the polar nature of the soil humic acid as a partition medium. The limiting sorption (partition) capacities of relatively non-polar liquids are remarkably similar when expressed in terms of volumes per unit weight of soil humic acid. The soil humic acid is found to be about half as effective as soil organic matter in sorption of relatively nonpolar organic compounds. The nearly constant limiting sorption capacity for nonpolar organic liquids with soil humic acid on a volume-to-weight basis and its efficiency in sorption relative to soil organic matter provide a basis for predicting the approximate sorption (partition) coefficients of similar compounds in uptake by soil in aqueous systems.

  4. Simultaneous desulfurization and denitrification of flue gas by ·OH radicals produced from O2+ and water vapor in a duct.

    PubMed

    Bai, Mindi; Zhang, Zhitao; Bai, Mindong

    2012-09-18

    In the present study, simultaneous flue gas desulfurization and denitrification are achieved with ·OH radicals generated from O(2)(+) reacting with water vapor in a duct. The O(2)(+) ions are generated by a strong ionization dielectric barrier discharge and then injected into the duct. Compared with conventional gas discharge treatment, the present method does not need a plasma reaction reactor, additional catalysts, reductants, or oxidants. The main recovered products are the liquids H(2)SO(4) and HNO(3), which can be used in many processes. Removal rates of 97% for NO and 82% for SO(2) are obtained under the following optimal experimental conditions: molar ratio of reactive oxygen species (O(2)(+), O(3)) to SO(2) and NO, 5; inlet flue gas temperature, 65 °C; reaction time, 0.94 s; and H(2)O volume fraction, 8%. Production of O(2)(+) and the plasma reaction mechanisms are discussed, and the recovered acid is characterized. The experimental results show that the present method performs better for denitrification than for desulfurization. Compared with conventional air discharge flue gas treatments, the present method has lower initial investment and operating costs, and the equipment is more compact. PMID:22891818

  5. REACTIONS OF OXIDES OF NITROGEN (NOX) LEADING TO THE FORMATION OF NITRIC ACID (HNO3) IN NON-THERMAL PLASMAS (NTPS): WHITE PAPER FOR THE STRATEGIC ENVIRONMENTAL RESEARCH AND DEVELOPMENT PROGRAM (SERDP)

    EPA Science Inventory

    Electrical energy coupled into an NTP can be used to create highly reactive species, e.g., oxygen atoms O(3P), OH radicals, N-radicals, electrons, and other free radicals, ions, and active species in gaseous media at near-ambient temperatures and pressures. These active species ...

  6. Vapor phase oxidation of benzoic acid to phenol over a novel catalyst system consisting of NiO and NiFe{sub 2}O{sub 4}

    SciTech Connect

    Miki, Jun; Asanuma, Minoru; Tachibana, Yakudo

    1995-02-01

    NiO and Fe{sub 2}O{sub 3} were found to show the catalytic activities for the vapor phase oxidation of benzoic acid to form phenol. Furthermore, the enhancement of the activity and phenol selectivity were achieved by combined Ni and Fe components prepared by precipitation. The calcination temperature and the atomic ratio of Ni to Fe were found to be important for the enhancement of activity. The homogeneous distribution profile of NiO and NiFe{sub 2}O{sub 4} on the surface and in the bulk of the catalyst is essential for the optimization of phenol formation. 32 refs., 7 figs., 4 tabs.

  7. Extraction of rare earth oxides using supercritical carbon dioxide modified with Tri-n-butyl phosphate–nitric acid adducts

    DOE PAGESBeta

    Baek, Donna L.; Fox, Robert V.; Case, Mary E.; Sinclair, Laura K.; Schmidt, Alex B.; McIlwain, Patrick R.; Mincher, Bruce J.; Wai, Chien M.

    2016-06-14

    A new tri-n-butylphosphate–nitric acid (TBP–HNO3) adduct was prepared by combining TBP and fuming (90%) HNO3. The adduct was characterized, and its phase-equilibrium behavior in supercritical carbon dioxide is reported. Supercritical carbon dioxide (sc-CO2) was modified with this new adduct [TBP(HNO3)5.2(H2O)1.7], and the extraction efficacies of selected rare earth oxides (Y, Ce, Eu, Tb, and Dy) at 338 K and 34.5 MPa were compared with those obtained using an adduct formed from concentrated (70%) HNO3 and TBP [TBP(HNO3)1.7(H2O)0.6]. All rare earth oxides tested with both adduct species could be extracted with the exception of cerium oxide. Furthermore, the water and acidmore » concentrations in the different adducts were found to play a significant role in rare earth oxide extraction efficiency.« less

  8. Balloon-Borne Measurements of Total Reactive Nitrogen, Nitric Acid, and Aerosol in the Cold Arctic Stratosphere

    NASA Technical Reports Server (NTRS)

    Kondo, Y.; Aimedieu, P.; Matthews, W. A.; Fahey, D. W.; Murcray, D. G.; Hofmann, D. J.; Johnston, P. V.; Iwasaka, Y.; Iwata, A.; Sheldon, W. R.

    1990-01-01

    Total reactive nitrogen (NO(Y)) between 15 and 29 km was measured for the first time on board a balloon within the Arctic cold vortex. Observations of HNO3, aerosol, and ozone were made by instruments on the same balloon gondola which was launched from Esrange, Sweden (68 deg N, 20 deg E) on January 23, 1989. The NO(y) mixing ratio was observed to increase very rapidly from 6 ppbv at 18 km altitude to a maximum of 21 ppbv at 21 km, forming a sharp layer with a thickness of about 2 km. A minimum in the NO(y) mixing ratio of 5 ppbv was found at 27 km. The measured HNO3 profile shows broad similarities to that of NO(y). This observation, together with the observed very low column amount of NO2, shows that NO(x) had been almost totally converted to HNO3, and that NO(y) was composed mainly of HNO3. The enhanced aerosol concentration between 19 and 22 km suggests that the maximum abundance of HNO3 trapped in the form of nitric acid trihydrate (NAT) was about 6 ppbv at 21 km. The sampled air parcels were highly supersaturated with respect to NAT. Although extensive denitrification throughout the stratosphere did not prevail, an indication of denitrification was found at altitudes of 27 and 22 km, and between 18 and 15 km.

  9. Direct Real-Time Detection of Vapors from Explosive Compounds

    SciTech Connect

    Ewing, Robert G.; Clowers, Brian H.; Atkinson, David A.

    2013-10-03

    The real-time detection of vapors from low volatility explosives including PETN, tetryl, RDX and nitroglycerine along with various compositions containing these substances is demonstrated. This was accomplished with an atmospheric flow tube (AFT) using a non-radioactive ionization source and coupled to a mass spectrometer. Direct vapor detection was demonstrated in less than 5 seconds at ambient temperature without sample pre-concentration. The several seconds of residence time of analytes in the AFT provides a significant opportunity for reactant ions to interact with analyte vapors to achieve ionization. This extended reaction time, combined with the selective ionization using the nitrate reactant ions (NO3- and NO3-•HNO3), enables highly sensitive explosives detection. Observed signals from diluted explosive vapors indicate detection limits below 10 ppqv using selected ion monitoring (SIM) of the explosive-nitrate adduct at m/z 349, 378, 284 and 289 for tetryl, PETN, RDX and NG respectively. Also provided is a demonstration of the vapor detection from 10 different energetic formulations, including double base propellants, plastic explosives and commercial blasting explosives using SIM for the NG, PETN and RDX product ions.

  10. Direct Real-Time Detection of RDX Vapors Under Ambient Conditions

    SciTech Connect

    Ewing, Robert G.; Atkinson, David A.; Clowers, Brian H.

    2013-01-15

    The results in this manuscript represent a demonstration of RDX vapor detection in real time at ambient temperature without sample pre-concentration. The detection of vapors from the low volatility explosive compound RDX was achieved through selective atmospheric pressure chemical ionization using nitrate reactant ions (NO3-), and NO3-•HNO3 adducts generated in an electrical discharge source. The RDX vapors were ionized in a reaction region, which provided a variable (up to several seconds) reaction time. The reaction times were controlled by either flow in an atmospheric flow tube (AFT) or by electric field in an atmospheric drift tube (ADT). Both AFT and ADT were interfaced to a quadrupole mass spectrometer for ion detection and identification. Recorded signals were observed for RDX concentrations below 25 ppq using selected ion monitoring (SIM) of the RDX-nitrate adduct at m/z 284.

  11. Oxidative degradation of bis (2,4,4-trimethylpentyl) dithiophosphinic acid in nitric acid studied by electrospray ionization mass spectrometry

    SciTech Connect

    G. S. Groenewold; D. R. Peterman

    2012-10-01

    Samples of bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex-301) were analyzed using direct infusion electrospray ionization mass spectrometry. Positive ion spectra of standard and stereo-pure acids displayed ions typical of the unmodified compound, cationized monomeric and dimeric cluster ion species. In addition, a significant ions 2 u less than the dimeric clusters were seen, that correspond to an oxidatively coupled species designated Cyx2 that is observed as H- or Na-cationized species in the electrospray analyses. Based on uncorrected ion intensities, Cyx2 is estimated to account for about 20% of the total in the standard materials. When samples that were contacted with 3 M HNO3 were analyzed, the positive ion spectrum consisted nearly entirely of ions derived from the oxidatively coupled product, indicating that the acid promotes coupling. The negative ion spectra of the standard acids consisted nearly entirely of the conjugate base that is formed by deprotonation of the acids, and cluster ions containing multiple acid molecules. The negative spectra of the HNO3-contacted samples also contained the conjugate base of the unmodified acid, but also two other species that correspond to the dioxo- and perthio- derivatives. It is concluded that HNO3 contact causes significant oxidation, forming at least three major products, Cyx2, the perthio-acid, and the dioxo-acid.

  12. PH BUFFERING IN FOREST SOIL ORGANIC HORIZONS: RELEVANCE TO ACID PRECIPITATION

    EPA Science Inventory

    Samples of organic surface horizons (Oi, Oe, Oa) from New York State forest soils were equilibrated with 0 to 20 cmol HNO3 Kg(-1) soil in the laboratory by a batch technique designed to simulate reactions of acid precipitation with forest floors. Each organic horizon retained a c...

  13. Polymorph-dependent titanium dioxide nanoparticle dissolution in acidic and alkali digestions

    EPA Science Inventory

    Multiple polymorphs (anatase, brookite and rutile) of titanium dioxide nanoparticles (TiO2-NPs) with variable structures were quantified in environmental matrices via microwave-based hydrofluoric (HF) and nitric (HNO3) mixed acid digestion and muffle furnace (MF)-based potassium ...

  14. Corrosion resistant performances of alkanoic and phosphonic acids derived self-assembled monolayers on magnesium alloy AZ31 by vapor-phase method.

    PubMed

    Ishizaki, Takahiro; Okido, Masazumi; Masuda, Yoshitake; Saito, Naobumi; Sakamoto, Michiru

    2011-05-17

    Alkanoic and phosphonic acid derived self-assembled monolayers (SAMs) were formed on magnesium alloy by the vapor phase method. AFM and XPS studies showed that SAMs were formed on Mg alloy. The chemical and anticorrosive properties of the SAMs prepared on magnesium alloys were characterized using contact angle measurements, X-ray photoelectron spectroscopy (XPS), and electrochemical measurements. Water contact angle measurements revealed that, although SA and ISA have the same headgroup to anchor to the magnesium alloy surface, the packing density on the magnesium alloy surface could be considerably different. The contact angle hysteresis of SAMs with a carboxylate headgroup is much larger than that of SAMs with a phosphonic acid group. The XPS O 1s peaks indicated more likely a mix of mono-, bi-, or tridentate binding of phosphonic acid SAM to the oxide or hydroxide surface of the Mg alloy. The electrochemical measurements showed that the phosphonic acid derived SAM had better corrosion resistance compared to alkanoic acid derived SAM. The chemical stability of SAMs modified magnesium alloy was investigated using water contact angle and XPS measurements. The water contact angle and XPS measurements revealed that the molecular density of OP and PFEP on magnesium alloy would be higher than those of SA and ISA on magnesium alloy. PMID:21504153

  15. Advanced zirconia-coated carbonyl-iron particles for acidic magnetorheological finishing of chemical-vapor-deposited ZnS and other IR materials

    NASA Astrophysics Data System (ADS)

    Salzman, S.; Giannechini, L. J.; Romanofsky, H. J.; Golini, N.; Taylor, B.; Jacobs, S. D.; Lambropoulos, J. C.

    2015-10-01

    We present a modified version of zirconia-coated carbonyl-iron (CI) particles that were invented at the University of Rochester in 2008. The amount of zirconia on the coating is increased to further protect the iron particles from corrosion when introduced to an acidic environment. Five low-pH, magnetorheological (MR) fluids were made with five acids: acetic, hydrochloric, nitric, phosphoric, and hydrofluoric. All fluids were based on the modified zirconia-coated CI particles. Off-line viscosity and pH stability were measured for all acidic MR fluids to determine the ideal fluid composition for acidic MR finishing of chemical-vapor-deposited (CVD) zinc sulfide (ZnS) and other infrared (IR) optical materials, such as hot-isostatic-pressed (HIP) ZnS, CVD zinc selenide (ZnSe), and magnesium fluoride (MgF2). Results show significant reduction in surface artifacts (millimeter-size, pebble-like structures on the finished surface) for several standard-grade CVD ZnS substrates and good surface roughness for the non-CVD MgF2 substrate when MR finished with our advanced acidic MR fluid.

  16. Tuning the acid/metal balance of carbon nanofiber-supported nickel catalysts for hydrolytic hydrogenation of cellulose.

    PubMed

    Van de Vyver, Stijn; Geboers, Jan; Schutyser, Wouter; Dusselier, Michiel; Eloy, Pierre; Dornez, Emmie; Seo, Jin Won; Courtin, Christophe M; Gaigneaux, Eric M; Jacobs, Pierre A; Sels, Bert F

    2012-08-01

    Carbon nanofibers (CNFs) are a class of graphitic support materials with considerable potential for catalytic conversion of biomass. Earlier, we demonstrated the hydrolytic hydrogenation of cellulose over reshaped nickel particles attached at the tip of CNFs. The aim of this follow-up study was to find a relationship between the acid/metal balance of the Ni/CNFs and their performance in the catalytic conversion of cellulose. After oxidation and incipient wetness impregnation with Ni, the Ni/CNFs were characterized by various analytical methods. To prepare a selective Ni/CNF catalyst, the influences of the nature of oxidation agent, Ni activation, and Ni loading were investigated. Under the applied reaction conditions, the best result, that is, 76 % yield in hexitols with 69 % sorbitol selectivity at 93 % conversion of cellulose, was obtained on a 7.5 wt % Ni/CNF catalyst prepared by chemical vapor deposition of CH(4) on a Ni/γ-Al(2)O(3) catalyst, followed by oxidation in HNO(3) (twice for 1 h at 383 K), incipient wetness impregnation, and reduction at 773 K under H(2). This preparation method leads to a properly balanced Ni/CNF catalyst in terms of Ni dispersion and hydrogenation capacity on the one hand, and the number of acidic surface-oxygen groups responsible for the acid-catalyzed hydrolysis on the other. PMID:22730195

  17. Stratospheric aerosol acidity, density, and refractive index deduced from SAGE 2 and NMC temperature data

    NASA Technical Reports Server (NTRS)

    Yue, G. K.; Poole, L. R.; Wang, P.-H.; Chiou, E. W.

    1994-01-01

    Water vapor concentrations obtained by the Stratospheric Aerosol and Gas Experiment 2 (SAGE 2) and collocated temperatures provided by the National Meteorological Center (NMC) from 1986 to 1990 are used to deduce seasonally and zonally averaged acidity, density, and refractive index of stratospheric aerosols. It is found that the weight percentage of sulfuric acid in the aerosols increases from about 60 just above the tropopause to about 86 at 35 km. The density increases from about 1.55 to 1.85 g/cu cm between the same altitude limits. Some seasonal variations of composition and density are evident at high latitudes. The refractive indices at 1.02, 0.694, and 0.532 micrometers increase, respectively, from about 1.425, 1.430, and 1.435 just above the tropopause to about 1.445, 1.455, and 1.458 at altitudes above 27 km, depending on the season and latitude. The aerosol properties presented can be used in models to study the effectiveness of heterogeneous chemistry, the mass loading of stratospheric aerosols, and the extinction and backscatter of aerosols at different wavelengths. Computed aerosol surface areas, rate coefficients for the heterogeneous reaction ClONO2 + H2O yields HOCl + HNO3 and aerosol mass concentrations before and after the Pinatubo eruption in June 1991 are shown as sample applications.

  18. Reactions Between Water Soluble Organic Acids and Nitrates in Atmospheric Aerosols: Recycling of Nitric Acid and Formation of Organic Salts

    SciTech Connect

    Wang, Bingbing; Laskin, Alexander

    2014-03-25

    Atmospheric particles often include a complex mixture of nitrate and secondary organic materials accumulated within the same individual particles. Nitrate as an important inorganic component can be chemically formed in the atmosphere. For instance, formation of sodium nitrate (NaNO3) and calcium nitrate Ca(NO3)2 when nitrogen oxide and nitric acid (HNO3) species react with sea salt and calcite, respectively. Organic acids contribute a significant fraction of photochemically formed secondary organics that can condense on the preexisting nitrate-containing particles. Here, we present a systematic microanalysis study on chemical composition of laboratory generated particles composed of water soluble organic acids and nitrates (i.e. NaNO3 and Ca(NO3)2) investigated using computer controlled scanning electron microscopy with energy dispersive analysis of X-rays (CCSEM/EDX) and Fourier transform infrared micro-spectroscopy (micro-FTIR). The results show that water-soluble organic acids can react with nitrates releasing gaseous HNO3 during dehydration process. These reactions are attributed to acid displacement of nitrate with weak organic acids driven by the evaporation of HNO3 into gas phase due to its relatively high volatility. The reactions result in significant nitrate depletion and formation of organic salts in mixed organic acids/nitrate particles that in turn may affect their physical and chemical properties relevant to atmospheric environment and climate. Airborne nitrate concentrations are estimated by thermodynamic calculations corresponding to various nitrate depletions in selected organic acids of atmospheric relevance. The results indicate a potential mechanism of HNO3 recycling, which may further affect concentrations of gas- and aerosol-phase species in the atmosphere and the heterogeneous reaction chemistry between them.

  19. Field test of four methods for gas-phase ambient nitric acid

    NASA Astrophysics Data System (ADS)

    Arnold, J. R.; Hartsell, Benjamin E.; Luke, Winston T.; Rahmat Ullah, S. M.; Dasgupta, Purnendu K.; Greg Huey, L.; Tate, Paul

    Three semi-continuous methods for detecting nitric acid (HNO 3) were tested against the annular denuder + filter pack (ADS) integrated collection technique at the Tampa Bay Regional Atmospheric Chemistry Experiment (BRACE) Sydney research station ˜20km downwind of the Tampa, Florida, urban core. The semi-continuous instruments included: two slightly differing implementations of the NOY-NO (total oxides of nitrogen minus that total denuded of HNO 3) denuder difference technique, one from the NOAA Air Resources Lab (ARL), and one from Atmospheric Research and Analysis, Inc. (ARA); the parallel plate wet diffusion scrubber + online ion chromatography technique from Texas Tech University (TTU); and the chemical ionization mass spectrometer from the Georgia Institute of Technology (GIT). Twelve hour ADS samples were collected by the University of South Florida (USF). Results for 10 min samples computed from the various higher sampling frequencies of each semi-continuous instrument showed good agreement (R2>0.7) for afternoon periods of the highest production and accumulation of HNO 3. Further, agreement was within ±30% for these instruments even at HNO 3 concentrations <0.30ppb. The USF ADS results were biased low, however, by 44%, on average, compared to the corporate 12 h aggregated means from the semi-continuous methods, and by >60% for the nighttime samples; ADS results were below the corporate mean maximum HNO 3 concentration by >30% as well. The four instruments using semi-continuous methods, by contrast, were all within 10% of each other's 12 h mean mixing ratios. While only ARA employed a formal minimum detection limit at 0.050 ppb, error analysis with the other techniques established that at the same level of precision, TTU's effective limit was approximately the same as ARA's and that ARL's limit was 0.030 ppb; analysis for GIT showed no apparent effective limit at the levels of HNO 3 encountered in this field study. The importance of sample inlet height for

  20. The Effect of Incorporation of HNO(sub 3) Into Liquid Sulfuric Acid on Heterogeneous Reaction Probabilities

    NASA Technical Reports Server (NTRS)

    Zhang, R.; Leu, M-T.; Keyser, L.

    1994-01-01

    Using a fast-flow reactor coupled to a quadrupole mass spectrometer, the heterogeneous reactions of C1ONO2 + HCl and HOCl + HCl as well as hydrolysis of N2O5 and C1ONO2 were investigated on liquid sulfuric acid, with particular emphasis on the effect of incorporation of HNO3 on the reaction probabilities.

  1. The effects of acid treatment on the thermoelectric power of multiwalled carbon nanotubes synthesized by chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Hewitt, Corey A.; Carroll, David L.

    2013-08-01

    Acid treatment of carbon nanotubes is a post synthesis processing step used to clean carbon nanotubes. We show that exposure of the nanotubes to oxygen rich reagents including nitric and sulfuric acid results in an increase of the thermoelectric power. Improving dispersion through the use of the surfactant triton-x results in a further increase in TEP of up to 21%. Additionally, refluxing in an oxygen rich acidic solution results in improved dispersion and an increased TEP. These results indicate that improved dispersion of the nanotubes by either sonication or reflux leads to increased oxygenation and thermopower.

  2. Chemical Degradation Studies on a Series of Dithiophosphinic Acids

    SciTech Connect

    Freiderich, Melissa E; Delmau, Laetitia Helene; Peterman, D. R.; Marc, Philippe L; Klaehn, John D.

    2014-01-01

    In this study a significant increase in the stability of a series of dithiophosphinic acids (DPAHs) under oxidizing acidic conditions was achieved. The degradation behavior of a series of DPAHs, designed for lanthanide/actinide separation, was examined. The stability of the DPAHs, when contacted with varying nitric acid concentrations, was tested and monitored using 31P {1H} NMR. Changes in the functional groups of the DPAHs resulted in substantial increases in the stability. However, all the DPAHs eventually showed signs of degradation when placed in contact with 2 M HNO3. The addition of a radical scavenger, hydrazine, inhibited the degradation of the DPAHs. With small amounts of hydrazine, five of the DPAHs remained stable for over a month in direct contact with 2 M HNO3.

  3. Chemical Degradation Studies on a Series of Dithiophosphinic Acids

    SciTech Connect

    Melissa E. Freiderich; Dean R. Peterman; John R. Klaehn; Philippe Marc; Laetitia H. Delmau

    2014-04-01

    A significant increase in the stability of a series of dithiophosphinic acids (DPAHs) under oxidizing acidic conditions was achieved. The degradation behavior of a series of DPAHs, designed for lanthanide/actinide separation, was examined. The stability of the DPAHs, when contacted with varying nitric acid concentrations, was tested and monitored using 31P {1H} NMR. Changes in the functional groups of the DPAHs resulted in substantial increases in the stability. However, when placed in contact with 2 M HNO3 all the DPAHs eventually showed signs of degradation. The addition of a radical scavenger, hydrazine, inhibited the degradation of the DPAHs. In the presence of a small concentration of hydrazine, five of the DPAHs remained stable for over a month in direct contact with 2 M HNO3.

  4. Amaranthus cruentus flour edible films: influence of stearic acid addition, plasticizer concentration, and emulsion stirring speed on water vapor permeability and mechanical properties.

    PubMed

    Colla, Eliane; do Amaral Sobral, Paulo J; Menegalli, Florencia Cecília

    2006-09-01

    Films forming solutions composed of Amaranth (Amaranthus cruentus) flour (4.0 g/100 mL), stearic acid (5-15 g/100 g of flour), and glycerol (25-35 g/100 g of flour) were prepared by an emulsification process, with varying stirring speed values (6640-13360 rpm). The influence of these parameters (stearic acid and glycerol concentrations and stirring speed) on the water vapor barrier and mechanical properties of films was evaluated using the response surface methodology (RSM). Other characterizations, including microstructure, water solubility, and oxygen permeability, were performed in optimized films. According to statistical analysis results, the optimized conditions corresponded to 10 g of stearic acid/100 g of flour, 26 g of glycerol/100 g of flour, and a stirring speed of 12 000 rpm. The films produced under these conditions exhibited superior mechanical properties (2.5 N puncture force, 2.6 MPa tensile strength, and 148% elongation at break) in comparison to those of other protein and polysaccharide composite films, low solubility (15.2%), and optimal barrier properties (WVP of 8.9 x 10(- 11) g m(- 1) s(- 1) Pa(- 1) and oxygen permeability of 2.36 x 10(- 13) cm3 m(-1) s(-1) Pa(-1)). PMID:16939322

  5. Application of Lactobacillus immobilized by Activated Carbon Fiber in Fermentation of Lactic Acid in Starch Wastewater

    NASA Astrophysics Data System (ADS)

    Xu, Wei; Wang, Peng; Chi, Guoda; Huang, Chenyong

    2010-11-01

    Activated carbon fibers (ACF) as the carrier of Lactobacillus was introduced into fermenting system, and a method of modifying the surface of ACF by HNO3-Fe (III) was established. Factors that affect ACF carrier's effect on immobilization of Lactobacillus were studied. HCl, H2SO4, HNO3 and FeCl3 solutions were respectively used to modify the surface properties of ACF. The amount of Fe (III) carried on ACF surface was 0.1563 mol/kg after ACF surface was modified by HNO3 for 5 h and then by 0.1 mol/L FeCl3 for 4 h, when the thickness of Lactobacillus on a single silk of carrier reached 40 μm. When ACF modified by HNO3-Fe (III) was applied in the fermentation of lactic acid in starch industry wastewater, the fermentation period reduced by 8 h and the output of L-lactic acid was 65.5 g/L, which was 3.3% more than that fermented without the carrier.

  6. Incorporation of stratospheric acids into water ice

    NASA Technical Reports Server (NTRS)

    Elliott, Scott; Turco, Richard P.; Toon, Owen B.; Hamill, Patrick

    1990-01-01

    Hydrochloric and hydrofluoric acids are absorbed within the water ice lattice at mole fractions maximizing below 0.00001 and 0.0001 in a variety of solid impurity studies. The absorption mechanism may be substitutional or interstitial, leading in either case to a weak permeation of stratospheric ices by the acids at equilibrium. Impurities could also inhabit grain boundaries, and the acid content of atmospheric ice crystals will then depend on details of their surface and internal microstructures. Limited evidence indicates similar properties for the absorption of HNO3. Water ice lattices saturated with acid cannot be a significant local reservoir for HCl in the polar stratosphere.

  7. Sorption equilibrium of a wide spectrum of organic vapors in Leonardite humic acid: modeling of experimental data.

    PubMed

    Niederer, Christian; Goss, Kai-Uwe; Schwarzenbach, Renè P

    2006-09-01

    In a recent publication we presented experimental Leonardite humic acid/air partition coefficients for 188 polar and nonpolar organic compounds measured with one consistent method. In this paper these experimental data are evaluated with various model predictions. For the PcKocWIN model some major shortcomings become apparent. The octanol-based Karickhoff-model exhibits a good performance for the nonpolar compounds but not for the polar ones. A good description of the whole data set is achieved with a polyparameter linear free energy relationship (pp-LFER) that explicitly accounts for the nonpolar (van der Waals and cavity formation) and polar (electron donor/acceptor) interactions between the sorbate molecule and the sorbent phase. With this pp-LFER model, most of the humic acid/air partition coefficients could be predicted within a factor of 2. The pp-LFER model also successfully predicts organic-C/water partition coefficients (K(ioc)) collected from the literature when it is combined with a pp-LFER for air/water partition coefficients. This supports our earlier conclusion that the thermodynamic cycle is applicable in the humic acid/water/air system. Based on our experimental data, we present a pp-LFER-model for humic acid/air and humic acid/water partitioning at any ambient temperatures. PMID:16999113

  8. Electrolyte vapor condenser

    DOEpatents

    Sederquist, Richard A.; Szydlowski, Donald F.; Sawyer, Richard D.

    1983-01-01

    A system is disclosed for removing electrolyte from a fuel cell gas stream. The gas stream containing electrolyte vapor is supercooled utilizing conventional heat exchangers and the thus supercooled gas stream is passed over high surface area passive condensers. The condensed electrolyte is then drained from the condenser and the remainder of the gas stream passed on. The system is particularly useful for electrolytes such as phosphoric acid and molten carbonate, but can be used for other electrolyte cells and simple vapor separation as well.

  9. Electrolyte vapor condenser

    DOEpatents

    Sederquist, R.A.; Szydlowski, D.F.; Sawyer, R.D.

    1983-02-08

    A system is disclosed for removing electrolyte from a fuel cell gas stream. The gas stream containing electrolyte vapor is supercooled utilizing conventional heat exchangers and the thus supercooled gas stream is passed over high surface area passive condensers. The condensed electrolyte is then drained from the condenser and the remainder of the gas stream passed on. The system is particularly useful for electrolytes such as phosphoric acid and molten carbonate, but can be used for other electrolyte cells and simple vapor separation as well. 3 figs.

  10. Graphene decorated microelectrodes for simultaneous detection of ascorbic, dopamine, and folic acids by means of chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Namdar, N.; Hassanpour Amiri, M.; Dehghan Nayeri, F.; Gholizadeh, A.; Mohajerzadeh, S.

    2015-09-01

    In this paper, high quality and large area graphene layers were synthesized using thermal chemical vapour deposition on copper foil substrates. We use graphene incorporated electrodes to measure simultaneously ascorbic acid, dopamine and folic acid. Cyclic voltammetry and differential pulse voltammetry methods were used to evaluate electrochemical behaviour of the grown graphene layers. The graphene-modified electrode shows large electrochemical potential difference compared to bare gold electrodes with higher current responses. Also our fabricated electrodes configuration can be used easily for microfluidic analysis.

  11. Sorption equilibrium of a wide spectrum of organic vapors in Leonardite humic acid: experimental setup and experimental data

    SciTech Connect

    Christian Niederer; Kai-Uwe Goss; Rene P. Schwarzenbach

    2006-09-01

    The environmental fate of volatile and semivolatile organic compounds is determined by their partitioning between air and soil constituents, in particular soil organic matter (SOM). While there are many studies on the partitioning of nonpolar compounds between water and SOM, data on sorption of polar compounds and data for sorption from the gas phase are rather limited. In this study, Leonardite humic acid/air partition coefficients for 188 polar and nonpolar organic compounds at temperatures between 5 and 75{sup o}C and relative humidities between {lt}0.01% and 98% have been determined using a dynamic flow-through technique. The Leonardite used is a standard humic acid produced by the natural oxidation of expose lignite originating from the Gascoyne Mine in North Dakota. To the best of our knowledge, this is by far the largest and most diverse and consistent data set for sorption into humic material published so far. The major results are as follows: the relative humidity affected the experimental partition coefficients by up to a factor of 3; polar compounds generally sorbed more strongly than nonpolar compounds due to H-bonding (electron donor/acceptor interactions) with the humic acid; no glass transitions in the range of 5-75{sup o}C that would be relevant with respect to the sorption behavior of hydrated Leonardite humic acid were observed; our experimental data agree well with experimental partition coefficients from various literature sources. 42 refs., 2 figs., 2 tabs.

  12. Thermal Decomposition of Gaseous Ammonium Nitrate at Low Pressure: Kinetic Modeling of Product Formation and Heterogeneous Decomposition of Nitric Acid

    NASA Astrophysics Data System (ADS)

    Park, J.; Lin, M. C.

    2009-10-01

    The thermal decomposition of ammonium nitrate, NH4NO3 (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH4NO3 at 423 K was proposed to produce equal amounts of NH3 and HNO3, followed by the decomposition reaction of HNO3, HNO3 + M → OH + NO2 + M (where M = third-body and reactor surface). The absolute yields of N2, N2O, H2O, and NH3, which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH3-NO2 (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO3 itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO3 in our kinetic modeling. The heterogeneous decomposition rate of HNO3, HNO3 + (B2O3/SiO2) → OH + NO2 + (B2O3/SiO2), was determined by varying its rate to match the modeled result to the measured concentrations of NH3 and H2O; the rate could be represented by k2b = 7.91 × 107 exp(-12 600/T) s-1, which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO3 decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

  13. Microbial Community Structure and Arsenic Biogeochemistry in an Acid Vapor-Formed Spring in Tengchong Geothermal Area, China.

    PubMed

    Jiang, Zhou; Li, Ping; Jiang, Dawei; Dai, Xinyue; Zhang, Rui; Wang, Yanhong; Wang, Yanxin

    2016-01-01

    Arsenic biogeochemistry has been studied extensively in acid sulfate-chloride hot springs, but not in acid sulfate hot springs with low chloride. In this study, Zhenzhuquan in Tengchong geothermal area, a representative acid sulfate hot spring with low chloride, was chosen to study arsenic geochemistry and microbial community structure using Illumina MiSeq sequencing. Over 0.3 million 16S rRNA sequence reads were obtained from 6-paired parallel water and sediment samples along its outflow channel. Arsenic oxidation occurred in the Zhenxhuquan pool, with distinctly high ratios of arsenate to total dissolved arsenic (0.73-0.86). Coupled with iron and sulfur oxidation along the outflow channel, arsenic accumulated in downstream sediments with concentrations up to 16.44 g/kg and appeared to significantly constrain their microbial community diversity. These oxidations might be correlated with the appearance of some putative functional microbial populations, such as Aquificae and Pseudomonas (arsenic oxidation), Sulfolobus (sulfur and iron oxidation), Metallosphaera and Acidicaldus (iron oxidation). Temperature, total organic carbon and dissolved oxygen significantly shaped the microbial community structure of upstream and downstream samples. In the upstream outflow channel region, most microbial populations were microaerophilic/anaerobic thermophiles and hyperthermophiles, such as Sulfolobus, Nocardia, Fervidicoccus, Delftia, and Ralstonia. In the downstream region, aerobic heterotrophic mesophiles and thermophiles were identified, including Ktedonobacteria, Acidicaldus, Chthonomonas and Sphingobacteria. A total of 72.41-95.91% unassigned-genus sequences were derived from the downstream high arsenic sediments 16S rRNA clone libraries. This study could enable us to achieve an integrated understanding on arsenic biogeochemistry in acid hot springs. PMID:26761709

  14. Microbial Community Structure and Arsenic Biogeochemistry in an Acid Vapor-Formed Spring in Tengchong Geothermal Area, China

    PubMed Central

    Jiang, Zhou; Li, Ping; Jiang, Dawei; Dai, Xinyue; Zhang, Rui; Wang, Yanhong; Wang, Yanxin

    2016-01-01

    Arsenic biogeochemistry has been studied extensively in acid sulfate-chloride hot springs, but not in acid sulfate hot springs with low chloride. In this study, Zhenzhuquan in Tengchong geothermal area, a representative acid sulfate hot spring with low chloride, was chosen to study arsenic geochemistry and microbial community structure using Illumina MiSeq sequencing. Over 0.3 million 16S rRNA sequence reads were obtained from 6-paired parallel water and sediment samples along its outflow channel. Arsenic oxidation occurred in the Zhenxhuquan pool, with distinctly high ratios of arsenate to total dissolved arsenic (0.73–0.86). Coupled with iron and sulfur oxidation along the outflow channel, arsenic accumulated in downstream sediments with concentrations up to 16.44 g/kg and appeared to significantly constrain their microbial community diversity. These oxidations might be correlated with the appearance of some putative functional microbial populations, such as Aquificae and Pseudomonas (arsenic oxidation), Sulfolobus (sulfur and iron oxidation), Metallosphaera and Acidicaldus (iron oxidation). Temperature, total organic carbon and dissolved oxygen significantly shaped the microbial community structure of upstream and downstream samples. In the upstream outflow channel region, most microbial populations were microaerophilic/anaerobic thermophiles and hyperthermophiles, such as Sulfolobus, Nocardia, Fervidicoccus, Delftia, and Ralstonia. In the downstream region, aerobic heterotrophic mesophiles and thermophiles were identified, including Ktedonobacteria, Acidicaldus, Chthonomonas and Sphingobacteria. A total of 72.41–95.91% unassigned-genus sequences were derived from the downstream high arsenic sediments 16S rRNA clone libraries. This study could enable us to achieve an integrated understanding on arsenic biogeochemistry in acid hot springs. PMID:26761709

  15. Sorption equilibrium of a wide spectrum of organic vapors in Leonardite humic acid: experimental setup and experimental data.

    PubMed

    Niederer, Christian; Goss, Kai-Uwe; Schwarzenbach, René P

    2006-09-01

    The environmental fate of volatile and semivolatile organic compounds is determined by their partitioning between air and soil constituents, in particular soil organic matter (SOM). While there are many studies on the partitioning of nonpolar compounds between water and SOM, data on sorption of polar compounds and data for sorption from the gas phase are rather limited. In this study, Leonardite humic acid/air partition coefficients for 188 polar and nonpolar organic compounds at temperatures between 5 and 75 degrees C and relative humidities between < 0.01% and 98% have been determined using a dynamic flow-through technique. To the best of our knowledge, this is by far the largest and most diverse and consistent data set for sorption into humic material published so far. The major results are as follows: the relative humidity affected the experimental partition coefficients by up to a factor of 3; polar compounds generally sorbed more strongly than nonpolar compounds due to H-bonding (electron donor/ acceptor interactions) with the humic acid; no glass transitions in the range of 5-75 degrees C that would be relevant with respect to the sorption behavior of hydrated Leonardite humic acid were observed; our experimental data agree well with experimental partition coefficients from various literature sources. PMID:16999112

  16. Nitric acid dry deposition to conifer forests: Niwot Ridge spruce-fir-pine study

    USGS Publications Warehouse

    Sievering, H.; Kelly, T.; McConville, G.; Seibold, C.; Turnipseed, A.

    2001-01-01

    The dry deposition velocity of nitric acid, Vd(HNO3), over a 12-m (mean height) spruce-fir forest at Niwot Ridge, Colorado was estimated during 13 daytime periods using the flux-gradient approach. Turbulence intensity at this site is high (mean u* of 0.65ms-1 with u of 2.9ms-1) and contributed to the large observed Vd(HNO3). The overriding contributor is identified to be the small aerodynamic needle width of the conifer trees. Two cases had inflated Vd(HNO3) due to height-differentiated nitric acid loss to soil-derived particle surfaces. Not considering these cases, the mean Vd(HNO3) was 7.6cms-1. The mean laminar boundary layer resistance (Rb) was found to be 7.8sm-1 (of similar magnitude to that of the aerodynamic resistance, 8.5sm-1). The data-determined Rb is bracketed by two theoretical estimates of the mean Rb, 5.9 and 8.6sm-1, that include consideration of the small canopy length scale (aerodynamic needle width), 1mm or less, at this conifer forest. However, the poor correlation of data-determined Rb values with both sets of theoretical estimates indicates that measurement error needs to be reduced and/or improved formulations of theoretical Rb values are in order. The large observed Vd(HNO3) at this conifer forest site is attributed to high turbulence intensity, and, especially, to small aerodynamic needle width. Copyright ?? 2001 Elsevier Science Ltd.

  17. Sulfuric acid vapor in the atmosphere of Venus as observed by the Venus Express Radio Science experiment VeRa

    NASA Astrophysics Data System (ADS)

    Oschlisniok, Janusz; Pätzold, Martin; Häusler, Bernd; Tellmann, Silvia; Bird, Mike; Andert, Tom

    2016-04-01

    The cloud deck within Venus' atmosphere, which covers the entire planet between approx. 50 and 70 km altitude, consists mostly of liquid and gaseous sulfuric acid. The gaseous part increases strongly just below the main clouds and builds an approx. 15 km thick haze layer of H2SO4. This region is responsible for a strong absorption of radio waves as seen in VeRa radio science observations. The amount of the absorption, which is used to derive the abundance of gaseous sulfuric acid, depends on the signal frequency. VeRa probed the atmosphere of Venus between 2006 and 2015 with radio signals at 13 cm (S-band) and 3.6 cm (X-band) wavelengths. We present H2SO4 profiles derived from S-band and X-band absorption during the first occultation season in 2006. The comparison of the H2SO4 profiles derived from both frequency bands provides a reliable picture of the H2SO4 abundance. Distinct differences in the S- and X-band profiles may give a clue to increased SO2 abundances. The derived VeRa results shall be compared with results provided by other experiments onboard Venus Express as well as with previous missions.

  18. Vaporizer performance

    NASA Astrophysics Data System (ADS)

    Liu, C. H.; Perez-Ortiz, B. M.; Whitelaw, J. H.

    This paper examines the nature of the flow leaving a vaporizer, its dependence on the flowrates of air and kerosene fuel, the inlet air temperature, and the possible consequences for the performance of a combustor fueled by the vaporizer. A phase Doppler velocimeter was used to examine the distribution of droplet diameters, velocities of the droplets, and the liquid-fuel flux at the exit. Measurements are also reported which show the nature of the two-phase flow away from the vaporizer exits and in important regions within a combustor corresponding to a one-sixth annular sector of a reverse-flow arrangement. The distribution of droplets within the combustor was observed and photographs of the combusting flow are presented.

  19. Vapor fragrancer

    NASA Astrophysics Data System (ADS)

    Sang, Q. Tran; Bryant, Timothy D.

    1987-05-01

    This invention relates to a vapor fragrancer for continuously, uniformly, and economically odorizing or deodorizing an environment. Homes, offices, automobiles, and space stations require either odorizing or deodorizing of the atmosphere to create pleasant conditions for work or leisure. A vapor fragrancer is provided to accomplish these goals. A supplier continuously supplies a predetermined amount of desired liquid fragrance from a container to a retaining material, which is positioned in the circulation path of the atmosphere. The supplier is either a low powered pump or a gravity dispenser. The atmosphere flowing in a circulation path passes over the retaining material containing the liquid fragrance and lifts a fragrant vapor from the retaining material. The atmosphere is thereby continuously and uniformly fragranced.

  20. The Consistency of Isotopologues of Ambient Atmospheric Nitric Acid in Passively Collected Samples

    NASA Astrophysics Data System (ADS)

    Bell, M. D.; Sickman, J. O.; Bytnerowicz, A.; Padgett, P.; Allen, E. B.

    2012-12-01

    Anthropogenic sources of nitrogen oxides have previously been shown to have distinctive isotopic signatures of oxygen and nitrogen. Nylon filters are currently used in passive sampling arrays to measure ambient atmospheric nitric acid concentrations and estimate deposition rates. This experiment measured the ability of nylon filters to consistently collect isotopologues of atmospheric nitric acid in the same ratios as they are present in the atmosphere. Samplers were deployed in continuous stirred tank reactors (CSTR) and at field sites across a nitrogen deposition gradient in Southern California. Filters were exposed over a four week period with individual filters being subjected to 1-4 week exposure times. Extracted nitric acid were measured for δ18O and δ15N ratios and compared for consistency based on length of exposure and amount of HNO3 collected. Filters within the CSTRs collected HNO3 at a consistent rate in both high and low concentration chambers. After two weeks of exposure, the mean δ18O values were within 0.5‰ of the δ18O of the source HNO3 solution. The mean of all weekly exposures were within 0.5‰ of the δ15N of the source solution, but after three weeks, the mean δ15N of adsorbed HNO3 was within 0.2‰. As the length of the exposure increased, the variability of measured delta values decreased for both elements. The field samplers collected HNO3 consistent with previously measured values along a deposition gradient. The mean δ18O at high deposition sites was 52.2‰ compared to 35.7‰ at the low deposition sites. Mean δ15N values were similar at all sites across the deposition gradient. Due to precipitation events occurring during the exposure period, the δ15N and δ18O of nitric acid were highly variable at all field sites. At single sites, changes in δ15N and δ18O were negatively correlated, consistent with two-sourcing mixing dynamics, but the slope of the regressions differed between high and low deposition sites. Anthropogenic

  1. Dispersibility of vapor phase oxygen and nitrogen functionalized multi-walled carbon nanotubes in various organic solvents

    NASA Astrophysics Data System (ADS)

    Khazaee, Maryam; Xia, Wei; Lackner, Gerhard; Mendes, Rafael G.; Rümmeli, Mark; Muhler, Martin; Lupascu, Doru C.

    2016-05-01

    The synthesis and characterization of gas phase oxygen- and nitrogen-functionalized multi-walled carbon nanotubes (OMWCNTs and NMWCNTs) and the dispersibility of these tubes in organic solvents were investigated. Recently, carbon nanotubes have shown supreme capacity to effectively enhance the efficiency of organic solar cells (OSCs). A critical challenge is to individualize tubes from their bundles in order to provide homogenous nano-domains in the active layer of OSCs. OMWCNTs and NMWCNTs were synthesized via HNO3 vapor and NH3 treatments, respectively. Surface functional groups and the structure of the tubes were analyzed by temperature-programmed desorption, Fourier transform infrared spectroscopy, transmission electron microscopy, and Raman spectroscopy which confirmed the formation of functional groups on the tube surface and the enhancement of surface defects. Elemental analysis demonstrated that the oxygen and nitrogen content increased with increasing treatment time of the multi-walled carbon nanotube (MWCNT) in HNO3 vapor. According to ultra-violet visible spectroscopy, modification of the MWCNT increased the extinction coefficients of the tubes owing to enhanced compatibility of the functionalized tubes with organic matrices.

  2. Dispersibility of vapor phase oxygen and nitrogen functionalized multi-walled carbon nanotubes in various organic solvents

    PubMed Central

    Khazaee, Maryam; Xia, Wei; Lackner, Gerhard; Mendes, Rafael G.; Rümmeli, Mark; Muhler, Martin; Lupascu, Doru C.

    2016-01-01

    The synthesis and characterization of gas phase oxygen- and nitrogen-functionalized multi-walled carbon nanotubes (OMWCNTs and NMWCNTs) and the dispersibility of these tubes in organic solvents were investigated. Recently, carbon nanotubes have shown supreme capacity to effectively enhance the efficiency of organic solar cells (OSCs). A critical challenge is to individualize tubes from their bundles in order to provide homogenous nano-domains in the active layer of OSCs. OMWCNTs and NMWCNTs were synthesized via HNO3 vapor and NH3 treatments, respectively. Surface functional groups and the structure of the tubes were analyzed by temperature-programmed desorption, Fourier transform infrared spectroscopy, transmission electron microscopy, and Raman spectroscopy which confirmed the formation of functional groups on the tube surface and the enhancement of surface defects. Elemental analysis demonstrated that the oxygen and nitrogen content increased with increasing treatment time of the multi-walled carbon nanotube (MWCNT) in HNO3 vapor. According to ultra-violet visible spectroscopy, modification of the MWCNT increased the extinction coefficients of the tubes owing to enhanced compatibility of the functionalized tubes with organic matrices. PMID:27188622

  3. Dispersibility of vapor phase oxygen and nitrogen functionalized multi-walled carbon nanotubes in various organic solvents.

    PubMed

    Khazaee, Maryam; Xia, Wei; Lackner, Gerhard; Mendes, Rafael G; Rümmeli, Mark; Muhler, Martin; Lupascu, Doru C

    2016-01-01

    The synthesis and characterization of gas phase oxygen- and nitrogen-functionalized multi-walled carbon nanotubes (OMWCNTs and NMWCNTs) and the dispersibility of these tubes in organic solvents were investigated. Recently, carbon nanotubes have shown supreme capacity to effectively enhance the efficiency of organic solar cells (OSCs). A critical challenge is to individualize tubes from their bundles in order to provide homogenous nano-domains in the active layer of OSCs. OMWCNTs and NMWCNTs were synthesized via HNO3 vapor and NH3 treatments, respectively. Surface functional groups and the structure of the tubes were analyzed by temperature-programmed desorption, Fourier transform infrared spectroscopy, transmission electron microscopy, and Raman spectroscopy which confirmed the formation of functional groups on the tube surface and the enhancement of surface defects. Elemental analysis demonstrated that the oxygen and nitrogen content increased with increasing treatment time of the multi-walled carbon nanotube (MWCNT) in HNO3 vapor. According to ultra-violet visible spectroscopy, modification of the MWCNT increased the extinction coefficients of the tubes owing to enhanced compatibility of the functionalized tubes with organic matrices. PMID:27188622

  4. A broadband cavity enhanced absorption spectrometer for aircraft measurements of glyoxal, methylglyoxal, nitrous acid, nitrogen dioxide, and water vapor

    NASA Astrophysics Data System (ADS)

    Min, K.-E.; Washenfelder, R. A.; Dubé, W. P.; Langford, A. O.; Edwards, P. M.; Zarzana, K. J.; Stutz, J.; Lu, K.; Rohrer, F.; Zhang, Y.; Brown, S. S.

    2015-10-01

    We describe a two-channel broadband cavity enhanced absorption spectrometer (BBCEAS) for aircraft measurements of glyoxal (CHOCHO), methylglyoxal (CH3COCHO), nitrous acid (HONO), nitrogen dioxide (NO2), and water (H2O). The instrument spans 361-389 and 438-468 nm, using two light emitting diodes (LEDs) and a grating spectrometer with a charge-coupled device (CCD) detector. Robust performance is achieved using a custom optical mounting system, high power LEDs with electronic on/off modulation, state-of-the-art cavity mirrors, and materials that minimize analyte surface losses. We have successfully deployed this instrument during two aircraft and two ground-based field campaigns to date. The demonstrated precision (2σ) for retrievals of CHOCHO, HONO and NO2 are 34, 350 and 80 pptv in 5 s. The accuracy is 5.8, 9.0 and 5.0 % limited mainly by the available absorption cross sections.

  5. A broadband cavity enhanced absorption spectrometer for aircraft measurements of glyoxal, methylglyoxal, nitrous acid, nitrogen dioxide, and water vapor

    NASA Astrophysics Data System (ADS)

    Min, K.-E.; Washenfelder, R. A.; Dubé, W. P.; Langford, A. O.; Edwards, P. M.; Zarzana, K. J.; Stutz, J.; Lu, K.; Rohrer, F.; Zhang, Y.; Brown, S. S.

    2016-02-01

    We describe a two-channel broadband cavity enhanced absorption spectrometer (BBCEAS) for aircraft measurements of glyoxal (CHOCHO), methylglyoxal (CH3COCHO), nitrous acid (HONO), nitrogen dioxide (NO2), and water (H2O). The instrument spans 361-389 and 438-468 nm, using two light-emitting diodes (LEDs) and a single grating spectrometer with a charge-coupled device (CCD) detector. Robust performance is achieved using a custom optical mounting system, high-power LEDs with electronic on/off modulation, high-reflectivity cavity mirrors, and materials that minimize analyte surface losses. We have successfully deployed this instrument during two aircraft and two ground-based field campaigns to date. The demonstrated precision (2σ) for retrievals of CHOCHO, HONO and NO2 are 34, 350, and 80 parts per trillion (pptv) in 5 s. The accuracy is 5.8, 9.0, and 5.0 %, limited mainly by the available absorption cross sections.

  6. Quantitative analysis of mixed hydrofluoric and nitric acids using Raman spectroscopy with partial least squares regression.

    PubMed

    Kang, Gumin; Lee, Kwangchil; Park, Haesung; Lee, Jinho; Jung, Youngjean; Kim, Kyoungsik; Son, Boongho; Park, Hyoungkuk

    2010-06-15

    Mixed hydrofluoric and nitric acids are widely used as a good etchant for the pickling process of stainless steels. The cost reduction and the procedure optimization in the manufacturing process can be facilitated by optically detecting the concentration of the mixed acids. In this work, we developed a novel method which allows us to obtain the concentrations of hydrofluoric acid (HF) and nitric acid (HNO(3)) mixture samples with high accuracy. The experiments were carried out for the mixed acids which consist of the HF (0.5-3wt%) and the HNO(3) (2-12wt%) at room temperature. Fourier Transform Raman spectroscopy has been utilized to measure the concentration of the mixed acids HF and HNO(3), because the mixture sample has several strong Raman bands caused by the vibrational mode of each acid in this spectrum. The calibration of spectral data has been performed using the partial least squares regression method which is ideal for local range data treatment. Several figures of merit (FOM) were calculated using the concept of net analyte signal (NAS) to evaluate performance of our methodology. PMID:20441916

  7. Modification of the surface chemistry of single- and multi-walled carbon nanotubes by HNO3 and H2SO4 hydrothermal oxidation for application in direct contact membrane distillation.

    PubMed

    Morales-Torres, Sergio; Silva, Tânia L S; Pastrana-Martínez, Luisa M; Brandão, Ana T S C; Figueiredo, José L; Silva, Adrián M T

    2014-06-28

    A specific methodology based on nitric acid hydrothermal oxidation was used to control the surface chemistry of multi-walled (MWCNTs) and single-walled (SWCNTs) carbon nanotubes (CNTs) with different lengths, and this methodology was adapted to the use of sulphuric acid containing ammonium persulfate as an oxidizing agent. The amount of oxygen-containing surface groups depends on the number and length of the graphene layers of the CNTs, thicker and shorter CNTs having more reactive sites for surface functionalization. In particular, the oxidation of MWCNTs was more pronounced than that of short SWCNTs and less surface groups were introduced into long SWCNTs, regardless of the acid used at any fixed concentration. It was also possible to tailor the surface chemistry of both SWCNTs and MWCNTs by using the adopted methodologies, and the amount of both oxygen- and sulphur-containing functional groups was correlated with the concentration of each oxidizing agent used. Mathematical functions that allow precise control of the amount and type of the surface groups introduced into carbon nanotubes were obtained. Buckypapers were also prepared over a polytetrafluoroethylene commercial membrane. These membranes were tested in direct contact membrane distillation and, under salinity conditions, the membrane prepared using oxidized MWCNTs (instead of SWCNTs) was the most efficient, the permeate flux of the commercial membrane significantly increasing in the presence of these CNTs, while completely rejecting chloride ions. In addition, the permeate flux was precisely correlated with the amount of oxygenated functional surface groups (as well as with the pH of point of zero charge) of the oxidized MWCNTs. PMID:24821484

  8. Effect of acid vapor etching on morphological and opto-electric properties of flat silicon and silicon nanowire arrays: A comparative study

    NASA Astrophysics Data System (ADS)

    Amri, Chohdi; Ouertani, Rachid; Hamdi, Abderrahmen; Ezzaouia, Hatem

    2016-03-01

    In this paper, we report a comparative study between porous silicon (pSi) and porous silicon nanowires (pSiNWs). Acid Vapor Etching (AVE) treatment has been used to perform porous structure on flat Si and SiNWs array substrates respectively. SiNW structure is prepared by the widely used Silver catalyzed etching method. SEM and TEM images show that AVE treatment induces porous structure in the whole Si wafer and the SiNW sidewall. Comparatively to pSi, pSiNWs exhibit a low reflectivity in the whole spectral range which decreases with etching duration. However, the reflectivity of pSi changes with porous layer thickness. Both pSi and pSiNWs exhibit a significant PL peak situated at 2 eV. PL peaks are attributed to the quantum confinement effect in the silicon nanocrystallites (SiNCs). We discussed the significant enhancement in the peak intensities and a shift toward lower energy displayed in Raman spectra for both pSi and pSiNWs. We reported a correlative study of the AVE treatment effect on the minority carrier life time of flat silicon and SiNW arrays with the passivation effect of chemical induced silicon oxides highlighted by FTIR spectra.

  9. Water vapor diffusion membranes, 2

    NASA Technical Reports Server (NTRS)

    Holland, F. F.; Klein, E.; Smith, J. K.; Eyer, C.

    1976-01-01

    Transport mechanisms were investigated for the three different types of water vapor diffusion membranes. Membranes representing porous wetting and porous nonwetting structures as well as dense diffusive membrane structures were investigated for water permeation rate as a function of: (1) temperature, (2) solids composition in solution, and (3) such hydrodynamic parameters as sweep gas flow rate, solution flow rate and cell geometry. These properties were measured using nitrogen sweep gas to collect the effluent. In addition, the chemical stability to chromic acid-stabilized urine was measured for several of each type of membrane. A technology based on the mechanism of vapor transport was developed, whereby the vapor diffusion rates and relative susceptibility of membranes to fouling and failure could be projected for long-term vapor recovery trials using natural chromic acid-stabilized urine.

  10. XPS and STEM studies of Allende acid insoluble residues

    NASA Technical Reports Server (NTRS)

    Housley, R. M.; Clarke, D. R.

    1980-01-01

    Data on Allende acid residues obtained both before and after etching with hot HNO3 are presented. X-ray photoelectron spectra show predominantly carbonaceous material plus Fe-deficient chromite in both cases. The HNO3 oxidizes the carbonaceous material to some extent. The small chromites in these residues have a wide range of compositions somewhat paralleling those observed in larger Allende chromites and in Murchison chromites, especially in the high Al contents; however, they are deficient in divalent cations, which makes them metastable and indicates that they must have formed at relatively low temperatures. It is suggested that they formed by precipitation of Cr(3+) and Fe(3+) from olivine at low temperature or during rapid cooling.

  11. Nitric acid measurements at Eureka obtained in winter 2001-2002 using solar and lunar Fourier transform infrared absorption spectroscopy: Comparisons with observations at Thule and Kiruna and with results from three-dimensional models

    NASA Astrophysics Data System (ADS)

    Farahani, Elham; Fast, H.; Mittermeier, R. L.; Makino, Y.; Strong, K.; McLandress, C.; Shepherd, T. G.; Chipperfield, M. P.; Hannigan, J. W.; Coffey, M. T.; Mikuteit, S.; Hase, F.; Blumenstock, T.; Raffalski, U.

    2007-01-01

    For the first time, vertical column measurements of nitric acid (HNO3) above Eureka (80.1°N, 86.4°W), Canada, have been made during polar night using lunar spectra recorded with a Fourier transform infrared (FTIR) spectrometer, from October 2001 to March 2002. This site is part of the primary Arctic station of the Network for the Detection of Stratospheric Change. These measurements were compared with FTIR measurements at two other Arctic sites: Thule, Greenland (76.5°N, 68.8°W), and Kiruna, Sweden (67.8°N, 20.4°E). Eureka lunar measurements are in good agreement with solar ones made with the same instrument. Eureka and Thule HNO3 columns are consistent within measurement error. Differences between HNO3 columns at Kiruna and those at Eureka and Thule can be explained on the basis of available sunlight hours and location of the polar vortex. The measurements were also compared with results from a chemistry-climate model, the Canadian Middle Atmosphere Model (CMAM), and from a three-dimensional chemical transport model, SLIMCAT. This is the first time that CMAM HNO3 columns have been compared with observations in the Arctic. The comparison of CMAM HNO3 columns with Eureka and Kiruna data shows good agreement. The warm 2001-2002 winter with almost no polar stratospheric clouds makes the comparison with this version of CMAM, which has a known warm bias, a good test for CMAM under these conditions. SLIMCAT captures the magnitude of HNO3 columns at Eureka, and the day-to-day variability, but generally reports higher values than were measured at Thule and Kiruna.

  12. Influence of gas-particle partitioning on ammonia and nitric acid fluxes above a deciduous forest in the Midwestern USA

    NASA Astrophysics Data System (ADS)

    Hansen, K.; Sørensen, L. L.; Hornsby, K. E.; Boegh, E.; Pryor, S. C.

    2013-12-01

    Quantifying the atmosphere-biosphere exchange of reactive nitrogen gasses (including ammonia (NH3) and nitric acid (HNO3)) is crucial to assessing the impact of anthropogenic activities on natural and semi-natural ecosystems. However, measuring the deposition of reactive nitrogen is challenging due to bi-directionality of the flux, and the dynamics of the chemical gas/aerosol equilibrium of NH3 and HNO3 (or other atmospheric acids) with aerosol-phase ammonium (NH4+) and nitrate (NO3-). NH3 and HNO3 are both very reactive and typically exhibit higher deposition velocities than aerosol NH4+. Therefore, the phase partitioning between gas and aerosol phases can have a significant effect on local budgets and atmospheric transport distances (Nemitz et al., Atmos. Chem. Phys., 2004). In this study, fluxes of NH3, HNO3 and carbon dioxide (CO2) along with size-resolved N-aerosol concentrations are measured above the deciduous forest, Morgan Monroe State Forest (MMSF) in south-central Indiana (39°53'N, 86°25'W) during a field campaign. Two relaxed eddy accumulation (REA) systems are used to measure fluxes and concentrations of NH3 and HNO3 at 44 m. The NH3 REA system operates based on wet effluent diffusion denuders with detection by florescence and half-hourly flux measurements are calculated. HNO3 REA system is based on gas capture on sodium chloride (NaCl) coated denuders with subsequent analysis by ion-chromatography, and the resulting fluxes have a resolution of 3-4 hours. CO2 fluxes are measured by eddy covariance using a closed-path Licor LI-7500, while two MSP MOUDI-110 impactors are used to measure the 24-hourly average inorganic and 48 hourly averaged organic ion concentrations in 11 size bins, respectively, just above the canopy level (28 m). The results of this field campaign are used to quantify the fluxes of NH3, HNO3, CO2 to/from the forest during the transition towards senescence, and to investigate process-level controls (e.g. the role of phase

  13. Laboratory measurements of heterogeneous reactions on sulfuric acid surfaces

    NASA Technical Reports Server (NTRS)

    Williams, Leah R.; Manion, Jeffrey A.; Golden, David M.; Tolbert, Margaret A.

    1994-01-01

    Increasing evidence from field, modeling, and laboratory studies suggests that heterogeneous reactions on stratospheric sulfate aerosol particles may contribute to global ozone depletion. Using a Knudsen cell reactor technique, the authors have studied the uptake, reactivity, and solubility of several trace atmospheric species on cold sulfuric acid surfaces representative of stratospheric aerosol particles. The results suggest that the heterogeneous conversion of N2O5 to HNO3 is fast enough to significantly affect the partitioning of nitrogen species in the global stratosphere and thus contribute to global ozone depletion. The hydrolysis of ClONO2 is slower and unlikely to be important under normal conditions at midlatitudes. The solubilities of HCl and HNO3 in sulfuric acid down to 200 K were found to be quite low. For HCl, this means that little HCl is available for reaction on the surfaces of stratospheric sulfate aerosol particles. The low solubility of HNO3 means that this product of heterogeneous reactions will enter the gas phase, and the denitrification observed in polar regions is unlikely to occur in the global stratosphere.

  14. Thermal hazard evaluation of lauroyl peroxide mixed with nitric acid.

    PubMed

    Tsai, Lung-Chang; You, Mei-Li; Ding, Mei-Fang; Shu, Chi-Min

    2012-01-01

    Many thermal runaway incidents have been caused by organic peroxides due to the peroxy group, -O-O-, which is essentially unstable and active. Lauroyl peroxide (LPO) is also sensitive to thermal sources and is incompatible with many materials, such as acids, bases, metals, and ions. From the thermal decomposition reaction of various concentrations of nitric acid (HNO3) (from lower to higher concentrations) with LPO, experimental data were obtained as to its exothermic onset temperature (T0), heat of decomposition (ΔHd), isothermal time to maximum rate (TMRiso), and other safety parameters exclusively for loss prevention of runaway reactions and thermal explosions. As a novel finding, LPO mixed with HNO3 can produce the detonation product of 1-nitrododecane. We used differential scanning calorimetry (DSC), thermal activity monitor III (TAM III), and gas chromatography/mass spectrometer (GC/MS) analyses of the reactivity for LPO and itself mixed with HNO3 to corroborate the decomposition reactions and reaction mechanisms in these investigations. PMID:22763742

  15. In situ measurements of carbon dioxide, 0.37-4.0 μm particles, and water vapor in the stratospheric plumes of small rockets

    NASA Astrophysics Data System (ADS)

    Gates, Amelia M.; Avallone, Linnea M.; Toohey, Darin W.; Rutter, Andrew P.; Whitefield, Philip D.; Hagen, Donald E.; Hopkins, A. Raymond; Ross, Martin N.; Zittel, Paul F.; Thompson, Thomas L.; Herman, Robert L.; Friedl, Randall R.

    2002-11-01

    Carbon dioxide (CO2) and large particles (0.37-4.0 μm) were measured in the stratospheric plume wakes of three rockets, an Atlas IIAS, a Delta II, and an Athena II. The correlations between CO2 mass and particle number densities in each plume are consistent with the unique combination of solid and liquid engine emissions of each rocket. Measured size distributions indicate a 1.1 μm mode with density of 2 g cm-3, consistent with spherical alumina particles emitted by solid rocket motors. Disagreement between the measured size distributions and the mean sizes inferred from the known alumina and CO2 emission indices and an observed increase in the particle number emission index with altitude are evidence for large particle oversampling effects and the presence of condensed volatile compounds within the particle population. Direct evidence for the latter is a persistent ~0.5-1 part per million (ppm) shortfall of water vapor relative to CO2 measured in the plume of the Athena II rocket based on the expected H2O/CO2 emission ratio. Although pure ice particles would not persist at the conditions of the measurements, a more stable coating of HNO3 (as either nitric acid trihydrate or as a liquid layer) could have reduced the sublimation rate of the underlying ice, thereby increasing the lifetimes of volatile particles within the plume. If confirmed, such a process would have important implications for the radiative and chemical properties of rocket plumes, including global ozone depletion associated with rocket launch activities.

  16. In situ measurements of carbon dioxide, 0.37-4.0 μm particles, and water vapor in the stratospheric plumes of small rockets

    NASA Astrophysics Data System (ADS)

    Gates, Amelia M.; Avallone, Linnea M.; Toohey, Darin W.; Rutter, Andrew P.; Whitefield, Philip D.; Hagen, Donald E.; Hopkins, A. Raymond; Ross, Martin N.; Zittel, Paul F.; Thompson, Thomas L.; Herman, Robert L.; Friedl, Randall R.

    2002-11-01

    Carbon dioxide (CO2) and large particles (0.37-4.0 μm) were measured in the stratospheric plume wakes of three rockets, an Atlas IIAS, a Delta II, and an Athena II. The correlations between CO2 mass and particle number densities in each plume are consistent with the unique combination of solid and liquid engine emissions of each rocket. Measured size distributions indicate a 1.1 μm mode with density of 2 g cm-3, consistent with spherical alumina particles emitted by solid rocket motors. Disagreement between the measured size distributions and the mean sizes inferred from the known alumina and CO2 emission indices and an observed increase in the particle number emission index with altitude are evidence for large particle oversampling effects and the presence of condensed volatile compounds within the particle population. Direct evidence for the latter is a persistent ˜0.5-1 part per million (ppm) shortfall of water vapor relative to CO2 measured in the plume of the Athena II rocket based on the expected H2O/CO2 emission ratio. Although pure ice particles would not persist at the conditions of the measurements, a more stable coating of HNO3 (as either nitric acid trihydrate or as a liquid layer) could have reduced the sublimation rate of the underlying ice, thereby increasing the lifetimes of volatile particles within the plume. If confirmed, such a process would have important implications for the radiative and chemical properties of rocket plumes, including global ozone depletion associated with rocket launch activities.

  17. Interaction of mineral dust with gas phase nitric acid and sulfur dioxide during the MINATROC II field campaign: First estimate of the uptake coefficient from atmospheric data

    NASA Astrophysics Data System (ADS)

    Umann, B.; Arnold, F.; Schaal, C.; Hanke, M.; Uecker, J.; Aufmhoff, H.; Balkanski, Y.; van Dingenen, R.

    2005-11-01

    Mineral dust, one of the most abundant aerosols by mass in the atmosphere, may have a lasting but to date almost unexplored effect on the trace gases nitric acid (HNO3) and sulfur dioxide (SO2). These gases have an important influence on, for example, the tropospheric ozone cycle, aerosol formation or acid rain. Within the second part of the MINATROC project (Mineral Dust and Tropospheric Chemistry) we investigated the interaction of mineral dust with gaseous HNO3 and SO2. The measurements were performed on a high mountain plateau (Izaña, Tenerife, 2367 m asl) using the highly sensitive CIMS (Chemical Ionization Mass Spectrometry) technique. During five periods of medium and one period of high atmospheric dust load, the HNO3 concentration decreased with increasing dust concentrations, and in all cases the HNO3 detection limit was reached. From the HNO3 decrease the uptake coefficient ? was calculated for the first time on the basis of in situ measurements. For the observed events, ? varied between 0.017 and 0.054. Moreover, during the dust events a significant decrease of ozone (O3) of the order of 30% was detected. The measurements and the analyses made in this paper show that the direct uptake of O3 on dust is a minor pathway for O3 depletion compared to the indirect effect, i.e., HNO3 depletion on dust which takes away a source of the O3 precursors nitrogen oxides. In contrast, a general interaction between SO2 and mineral dust was not observed. Positive as well as negative and no correlations between SO2 and mineral dust were detected.

  18. [Determination of trace mercury in coal by microwave digestion and cold vapor atomic fluorescence spectrometry].

    PubMed

    Liu, Jing; Zheng, Chu-guang; Xu, Jie-ying

    2004-09-01

    A method of determining trace Hg in coal by microwave digestion and cold vapor atomic fluorescence spectrometry is reported. The digestion system of HNO3-HCl-HF was evaluated. The experimental conditions of microwave digestion, including pressure, temperature, power and time of digestion were evaluated. The operating conditions such as flow rate of carrier gas, flow rate of shield gas and negative high voltage, and interference were also investigated. Testing results show that the detection limit is 0.03 ng x mL(-1) and RSD (n = 7) is below 5%. This method is simple and rapid. The treatment method was applicable to determining trace Hg in coal and gave results that were in good agreement with the certified values of the standard reference material. PMID:15762543

  19. Nitric acid and ammonia emissions from a mid-latitude prescribed wetlands fire

    NASA Technical Reports Server (NTRS)

    Lebel, P. J.; Cofer, W. R., III; Levine, J. S.; Vay, S. A.; Roberts, P. D.

    1988-01-01

    The first simultaneous measurements of gaseous nitric acid and ammonia in the smoke plume of a wetlands biomass burn were obtained. The measurements were made using tungsten oxide-coated diffusion denuder tubes from a helicopter during a prescribed burn on November 9, 1987, at the Merritt Island National Wildlife Refuge, located at the NASA John F. Kennedy Space Center, Florida. The mean NH3 and HNO3 mixing ratios measured in the smoke plume were 19 ppbv and 14 ppbv, respectively, both significantly higher than background mixing ratios. Nitric acid correlated well with carbon dioxide produced by the combustion. The mean CO2-normalized emission ratio for HNO3 was found to be 0.00012. Ammonia, however, dit not correlate well with CO2, suggesting a more complex relationship between combustion and production/release of NH3.

  20. Enhancement of acidic gases in biomass burning impacted air masses over Canada

    NASA Technical Reports Server (NTRS)

    Lefer, B. L.; Talbot, R. W.; Harriss, R. C.; Bradshaw, J. D.; Sandholm, S. T.; Olson, J. O.; Sachse, G. W.; Collins, J.; Shipham, M. A.; Blake, D. R.

    1994-01-01

    Biomass-burning impacted air masses sampled over central and eastern Canada during the summer of 1990 as part of ABLE 3B contained enhanced mixing ratios of gaseous HNO3, HCOOH, CH3COOH, and what appears to be (COOH)2. These aircraft-based samples were collected from a variety of fresh burning plumes and more aged haze layers from different source regions. Values of the enhancement factor, delta X/delta CO, where X represents an acidic gas, for combustion-impacted air masses sampled both near and farther away from the fires, were relatively uniform. However, comparison of carboxylic acid emission ratios measured in laboratory fires to field plume enhancement factors indicates significant in-plume production of HCOOH. Biomass-burning appears to be an important source of HNO3, HCOOH, and CH3COOH to the troposphere over subarctic Canada.

  1. Acid sulfate alteration of fluorapatite, basaltic glass and olivine by hydrothermal vapors and fluids: Implications for fumarolic activity and secondary phosphate phases in sulfate-rich Paso Robles soil at Gusev Crater, Mars

    NASA Astrophysics Data System (ADS)

    Hausrath, E. M.; Golden, D. C.; Morris, R. V.; Agresti, D. G.; Ming, D. W.

    2013-01-01

    Phosphate-rich rocks and a nearby phosphate-rich soil, Paso Robles, were analyzed in Gusev Crater, Mars, by the Mars Exploration Rover Spirit and interpreted to be highly altered, possibly by hydrothermal or fumarolic alteration of primary, phosphate-rich material. To test mineral phases resulting from such alteration, we performed hydrothermal acid-vapor and acid-fluid experiments on olivine (Ol), fluorapatite (Ap), and basaltic glass (Gl) as single phases and a mixture of phases. Minerals formed include Ca-, Al-, Fe- and Mg-sulfates with different hydration states (anhydrite, bassanite, gypsum; alunogen; hexahydrite, and pentahydrite). Phosphate-bearing minerals formed included monocalcium phosphate monohydrate (MCP) (acid-vapor and acid-fluid alteration of fluorapatite only) and ferrian giniite (acid-fluid alteration of the Ol + Gl + Ap mixture). MCP is likely present in Paso Robles if primary Ca-phosphate minerals reacted with sulfuric acid with little transport of phosphate. Under fluid:rock ratios allowing transport of phosphate, a ferric phosphate phase such as ferrian giniite might form instead. Mössbauer measurements of ferrian giniite-bearing alteration products and synthetic ferrian giniite are consistent with Spirit's Mössbauer measurements of the ferric-bearing phase in Paso Robes soil, but are also consistent with ferric sulfate phases in the low-P soil Arad_Samra. Therefore, Mössbauer data alone do not constrain the fluid:rock ratio. However, the excess iron (hematite) in Paso Robles soil, which implies aqueous transport, combined with our laboratory experiments, suggest acid-sulfate alteration in a hydrothermal (fumarolic) environment at fluid:rock ratios sufficient to allow dissolution, transport, and precipitation of secondary chemical components including a ferric phosphate such as ferrian giniite.

  2. Heterogeneous Reactions of ClONO2, HCl, and HOCl on Liquid Sulfuric Acid Surfaces

    NASA Technical Reports Server (NTRS)

    Zhang, Renyi; Leu, Ming-Taun; Keyser, Leon F.

    1994-01-01

    The heterogeneous reactions of ClONO2 + H2O yields HNO3 + HOCl (1), ClONO2 + HCl yields C12 + HNO3 (2), and HOCl + HCl yields Cl2 + H2O (3) on liquid sulfuric acid surfaces have been studied using a fast flow reactor coupled to a quadrupole mass spectrometer. The main objectives of the study are to investigate: (a) the temperature dependence of these reactions at a fixed H2O partial pressure typical of the lower stratosphere (that is, by changing temperature at a constant water partial pressure, the H2SO4 content of the surfaces is also changed), (b) the relative importance or competition between reactions 1 and 2, and (c) the effect of HNO3 on the reaction probabilities due to the formation of a H2SO4/HNO3/H2O ternary system. The measurements show that all the reactions depend markedly on temperature at a fixed H2O partial pressure: they proceed efficiently at temperatures near 200 K and much slower at temperatures near 220 K. The reaction probability (gamma(sub 1)) for ClONO2 hydrolysis approaches 0.01 at temperatures below 200 K, whereas the values for gamma(sub 2) and gamma(sub 3) are on the order of a few tenths at 200 K. Although detailed mechanisms for these reactions are still unknown, the present data indicate that the competition between ClONO2 hydrolysis and ClONO2 reaction with HCl may depend on temperature (or H2SO4 Wt %): in the presence of gaseous HCl at stratospheric concentrations, reaction 2 is dominant at lower temperatures (less than 200 K), but reaction 1 becomes important at temperatures above 210 K. Furthermore, reaction probability measurements performed on the H2SO4/HNO3/ H2O ternary solutions do not exhibit noticeable deviation from those performed on the H2SO4/H2O binary system, suggesting little effect of HNO3 in sulfate aerosols on the ClONO2 and HOCl reactions with HCl. The results reveal that significant reductions in the chlorine-containing reservoir species (such as ClONO2 and HCl) can take place on stratospheric sulfate aerosols at

  3. Long-term variations in abundance and distribution of sulfuric acid vapor in the Venus atmosphere inferred from Pioneer Venus and Magellan radio occultation studies

    NASA Technical Reports Server (NTRS)

    Jenkins, J. M.; Steffes, P. G.

    1992-01-01

    Radio occultation experiments have been used to study various properties of planetary atmospheres, including pressure and temperature profiles, and the abundance profiles of absorbing constituents in those planetary atmospheres. However, the reduction of amplitude data from such experiments to determine abundance profiles requires the application of the inverse Abel transform (IAT) and numerical differentiation of experimental data. These two operations preferentially amplify measurement errors above the true signal underlying the data. A new technique for processing radio occultation data has been developed that greatly reduces the errors in the derived absorptivity and abundance profiles. This technique has been applied to datasets acquired from Pioneer Venus Orbiter radio occultation studies and more recently to experiments conducted with the Magellan spacecraft. While primarily designed for radar studies of the Venus surface, the high radiated power (EIRP) from the Magellan spacecraft makes it an ideal transmitter for measuring the refractivity and absorptivity of the Venus atmosphere by such experiments. The longevity of the Pioneer Venus Orbiter has made it possible to study long-term changes in the abundance and distribution of sulfuric acid vapor, H2SO4(g), in the Venus atmosphere between 1979 and 1992. The abundance of H2SO4(g) can be inferred from vertical profiles of 13-cm absorptivity profiles retrieved from radio occultation experiments. Data from 1979 and 1986-87 suggest that the abundance of H2SO4(g) at latitudes northward of 70 deg decreased over this time period. This change may be due to a period of active volcanism in the late 1970s followed by a relative quiescent period, or some other dynamic process in the Venus atmosphere. While the cause is not certain, such changes must be incorporated into dynamic models of the Venus atmosphere. Potentially, the Magellan spacecraft will extend the results of Pioneer Venus Orbiter and allow the continued

  4. Heterogeneous reactions of chlorine nitrate and hydrogen chloride on type I polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Leu, Ming-Taun; Moore, Steven B.; Keyser, Leon F.

    1991-01-01

    A fast-flow reactor coupled with a quadrupole mass spectrometer was used to study the heterogeneous reactions ClONO2 + HCl yields Cl2 + HNO3 (1) and ClONO2 + H2O yields HOCl + HNO3 (2) on vapor-deposited HNO3-H2O ice substrates. It was found that the sticking coefficient of HCl on these substrates was a strong function of the substrate composition, ranging from about 2 x 10 exp -5 at nitric acid trihydrate composition to 6 x 10 exp -3 at 45 wt pct HNO3. The HNO3-H2O ice substrates were found to have large internal surface areas, and corrections for gas-phase diffusion within the porous ices were applied to observed loss rates.

  5. Fourier transform infrared studies of model polar stratospheric cloud surfaces - Growth and evaporation of ice and nitric acid/ice

    NASA Technical Reports Server (NTRS)

    Tolbert, Margaret A.; Middlebrook, Ann M.

    1990-01-01

    Fourier-transform infrared surface studies are used to probe the microphysical properties of nitric acid trihydrate (NAT) and ice films representative of type I and II polar stratospheric clouds (PSC). Experiments indicate that, on initial exposure to 1.8 microtorr of HNO3, a layer of ice is quantitatively converted to NAT. However, conversion of ice to NAT does not proceed indefinitely, but rather the system reaches saturation. For longer exposures or higher HNO3 pressures, NAM becomes the dominant nitric acid containing species on the surface. Evaporation studies were performed to test the feasibility of a recent denitrification mechanism. The results indicate that ice coated with 0.20 micron of NAT evaporates at a temperature of about 4 C higher than uncoated ice.

  6. Densities and apparent molar volumes of atmospherically important electrolyte solutions. 1. The solutes H2SO4, HNO3, HCl, Na2SO4, NaNO3, NaCl, (NH4)2SO4, NH4NO3, and NH4Cl from 0 to 50 °C, including extrapolations to very low temperature and to the pure liquid state, and NaHSO4, NaOH, and NH3 at 25 °C.

    PubMed

    Clegg, S L; Wexler, A S

    2011-04-21

    Calculations of the size and density of atmospheric aerosols are complicated by the fact that they can exist at concentrations highly supersaturated with respect to dissolved salts and supercooled with respect to ice. Densities and apparent molar volumes of solutes in aqueous solutions containing the solutes H(2)SO(4), HNO(3), HCl, Na(2)SO(4), NaNO(3), NaCl, (NH(4))(2)SO(4), NH(4)NO(3), and NH(4)Cl have been critically evaluated and represented using fitted equations from 0 to 50 °C or greater and from infinite dilution to concentrations saturated or supersaturated with respect to the dissolved salts. Using extrapolated densities of high-temperature solutions and melts, the relationship between density and concentration is extended to the hypothetical pure liquid solutes. Above a given reference concentration of a few mol kg(-1), it is observed that density increases almost linearly with decreasing temperature, and comparisons with available data below 0 °C suggest that the fitted equations for density can be extrapolated to very low temperatures. As concentration is decreased below the reference concentration, the variation of density with temperature tends to that of water (which decreases as temperature is reduced below 3.98 °C). In this region below the reference concentration, and below 0 °C, densities are calculated using extrapolated apparent molar volumes which are constrained to agree at the reference concentrations with an equation for the directly fitted density. Calculated volume properties agree well with available data at low temperatures, for both concentrated and dilute solutions. Comparisons are made with literature data for temperatures of maximum density. Apparent molar volumes at infinite dilution are consistent, on a single ion basis, to better than ±0.1 cm(3) mol(-1) from 0 to 50 °C. Volume properties of aqueous NaHSO(4), NaOH, and NH(3) have also been evaluated, at 25 °C only. In part 2 of this work (ref 1 ) an ion interaction (Pitzer

  7. Acid retardation method in analysis of strongly acidic solutions by inductively coupled plasma mass-spectrometry.

    PubMed

    Seregina, I F; Perevoznik, O A; Bolshov, M A

    2016-10-01

    Acid retardation on the sorbents as a technique for reduction of the acidity of the solutions prior to their analysis by inductively coupled plasma mass spectrometry was proposed and investigated. The proposed scheme provides substantial separation of the analytes and nitric acid, which allows direct introduction of the eluates in plasma without dilution. Two sorbents were examined - AV-17 anion-exchange resin and the Stirosorb 584 sorbent. Sorption and desorption of 38 elements on these sorbents were investigated. The efficiencies of the REEs' sorption on the anion-exchange and neutral sorbents were compared. The higher efficiency of the REEs and HNO3 separation was revealed for the neutral Stirosorb 584 sorbent. It was also found that most elements come out quantitatively of the column filled with the AV-17 resin after pumping 2-4mL of the solution. Wherein, the concentration of nitric acid decreased by 20 times. The anomalous behaviour of Ag, Pb, Th and U on the AV-17 resin was found. These analytes were eluted only after pumping 4 column volumes of deionized water. Na, K, Fe, Al and Li in concentrations within (50-1000mgL(-1)) range did not affect the recovery of REEs. The potential of ARM technique was demonstrate by the analysis of puriss. HNO3 and silverware. ARM enables to avoid dilution of highly acidic solutions prior to their introduction in ICP-MS. PMID:27474322

  8. Ultrafine aerosol size distributions and sulfuric acid vapor pressures: Implications for new particle formation in the atmosphere. Year 2 progress report

    SciTech Connect

    McMurry, P.H.

    1993-07-01

    This project has two components: (1) measurement of H{sub 2}SO{sub 4} vapor pressures in air under temperature/relative humidity conditions similar to atmospheric, and (2) measurement of ultrafine aerosol size distributions. During Year 2, more effort was put on size distribution measurements. 4 figs.

  9. Scandium separation from tungsten crucibles : preliminary investigation into the separation of scandium metal from tungsten metal crucibles using an acid soak process.

    SciTech Connect

    Boyle, Timothy J.; Hess, Ryan Falcone; Neville, Michael Luke; Howard, Panit Clifton

    2013-02-01

    The first step in an attempt to isolate Sco from a Wo crucible was explored by soaking the samples in a series of organic (HOAc) and inorganic (HCl, H2SO4, H3PO4, HNO3) acids. All samples, except the HOAc, yielded a powder. The weight loss suggests that HNO3 is the most efficient solvent; however, the powders were tentatively identified by PXRD and found to contain both W and Sc by-products. The higher weight loss may also indicate dissolution of the Wo crucible, which was further evidenced upon visual inspection of the crucible. The H3PO4 acid soak yielded the cleanest removal of Sc from the crucible. More work to understand the separation of the Sco from the Wo crucible is necessary but the acid routes appear to hold promise under not as of yet established criteria.

  10. Wintertime nitric acid chemistry - Implications from three-dimensional model calculations

    NASA Technical Reports Server (NTRS)

    Rood, Richard B.; Kaye, Jack A.; Douglass, Anne R.; Allen, Dale J.; Steenford, Stephen

    1990-01-01

    A three-dimensional simulation of the evolution of HNO3 has been run for the winter of 1979. Winds and temperatures are taken from a stratospheric data assimilation analysis, and the chemistry is based on Limb Infrared Monitor of the Stratosphere (LIMS) observations. The model is compared to LIMS observations to investigate the problem of 'missing' nitric acid chemistry in the winter hemisphere. Both the model and observations support the contention that a nitric acid source is needed outside of the polar vortex and north of the subtropics. Observations suggest that HNO3 is not dynamically controlled in middle latitudes. The model shows that given the time scales of conventional chemistry, dynamical control is expected. Therefore, an error exists in the conventional chemistry or additional processes are needed to bring the model and data into agreement. Since the polar vortex is dynamically isolated from the middle latitudes, and since the highest HNO3 values are observed in October and November, a source associated solely with polar stratospheric clouds cannot explain the deficiencies in the chemistry. The role of heterogeneous processes on background aerosols is reviewed in light of these results.

  11. Calibrated vapor generator source

    DOEpatents

    Davies, J.P.; Larson, R.A.; Goodrich, L.D.; Hall, H.J.; Stoddard, B.D.; Davis, S.G.; Kaser, T.G.; Conrad, F.J.

    1995-09-26

    A portable vapor generator is disclosed that can provide a controlled source of chemical vapors, such as, narcotic or explosive vapors. This source can be used to test and calibrate various types of vapor detection systems by providing a known amount of vapors to the system. The vapor generator is calibrated using a reference ion mobility spectrometer. A method of providing this vapor is described, as follows: explosive or narcotic is deposited on quartz wool, placed in a chamber that can be heated or cooled (depending on the vapor pressure of the material) to control the concentration of vapors in the reservoir. A controlled flow of air is pulsed over the quartz wool releasing a preset quantity of vapors at the outlet. 10 figs.

  12. Calibrated vapor generator source

    DOEpatents

    Davies, John P.; Larson, Ronald A.; Goodrich, Lorenzo D.; Hall, Harold J.; Stoddard, Billy D.; Davis, Sean G.; Kaser, Timothy G.; Conrad, Frank J.

    1995-01-01

    A portable vapor generator is disclosed that can provide a controlled source of chemical vapors, such as, narcotic or explosive vapors. This source can be used to test and calibrate various types of vapor detection systems by providing a known amount of vapors to the system. The vapor generator is calibrated using a reference ion mobility spectrometer. A method of providing this vapor is described, as follows: explosive or narcotic is deposited on quartz wool, placed in a chamber that can be heated or cooled (depending on the vapor pressure of the material) to control the concentration of vapors in the reservoir. A controlled flow of air is pulsed over the quartz wool releasing a preset quantity of vapors at the outlet.

  13. Interactions of Gas-Phase Nitric/Nitrous Acids and Primary Organic Aerosol in the Atmosphere of Houston, TX

    NASA Astrophysics Data System (ADS)

    Ziemba, L. D.; Griffin, R. J.; Dibb, J. E.; Anderson, C. H.; Whitlow, S. I.; Lefer, B. L.; Flynn, J.; Rappenglück, B.

    2007-12-01

    Concentrations of aerosol and gas-phase pollutants were measured on the roof of an 18-story building during the Texas Air Quality Study II Radical and Aerosol Measurement Project (TRAMP) from August 15 through September 28, 2006. Aerosol measurements included size-resolved, non-refractory mass concentrations of ammonium, nitrate, sulfate, chloride, and organic aerosol in submicron particles using an Aerodyne quadrupole aerosol mass spectrometer (Q-AMS). Particulate water-soluble organic carbon (PWSOC) was quantified using a mist chamber/total organic carbon analysis system. Concentration data for gas-phase pollutants included those for nitric acid (HNO3), nitrous acid (HONO), and hydrochloric acid (HCl) collected using a mist chamber/ion chromatographic technique, oxides of nitrogen (NOx) collected using a chemiluminescent method, and carbon monoxide (CO) collected using an infrared gas correlation wheel instrument. Coincident increases in nitrate and organic aerosol mass concentrations were observed on many occasions throughout the measurement campaign, most frequently during the morning rush hour. Based on the lack of organic aerosol processing (defined by the ratio of m/z = 44/57 in the Q-AMS spectra), strong correlation with NOx and CO, and a lack of significant increase in PWSOC concentration, the spikes in organic aerosol were likely associated with primary organic aerosol (POA). During these events, gas-phase HNO3 concentration decreases were observed simultaneously with increases in gas-phase HONO concentrations. These data likely indicate uptake of HNO3 and subsequent heterogeneous conversion to HONO involving POA. Preliminary calculations show that HNO3 partitioning could account for the majority of the observed HONO and aerosol nitrate concentrations during these events. Q-AMS chloride and HCl data also indicate uptake of chloride by particles during these events. This phenomenon was also observed during the night, but these nocturnal events were less

  14. High-quality, 2-inch-diameter m-plane GaN substrates grown by hydride vapor phase epitaxy on acidic ammonothermal seeds

    NASA Astrophysics Data System (ADS)

    Tsukada, Yusuke; Enatsu, Yuuki; Kubo, Shuichi; Ikeda, Hirotaka; Kurihara, Kaori; Matsumoto, Hajime; Nagao, Satoru; Mikawa, Yutaka; Fujito, Kenji

    2016-05-01

    In this paper, we discusse the origin of basal-plane stacking faults (BSFs) generated in the homoepitaxial hydride vapor phase epitaxy (HVPE) growth of m-plane gallium nitride (GaN). We investigated the effects of seed quality, especially dislocation density, on BSF generation during homoepitaxy. The results clearly identify basal-plane dislocation in the seed as a cause of BSF generation. We realized high-quality m-plane GaN substrates with a 2-in. diameter using HVPE on low-dislocation-density m-plane seeds.

  15. The Effects of Gaseous Ozone and Nitric Acid Deposition on two Crustose Lichen Species From Joshua Tree National Park

    NASA Astrophysics Data System (ADS)

    Hessom, Elizabeth Curie

    Lichens are dependent on atmospheric deposition for much of their water and nutrients, and due to their sensitivity to pollutants, are commonly used as bioindicators for air quality. While studies have focused on epiphytic (tree dwelling) lichens as bioindicators, virtually nothing is known about crustose (rock dwelling) lichens. The atmospheric pollutants ozone (O 3) and nitric acid (HNO3) are two major pollutants found within the Los Angeles Basin. While recent O3 research suggests it does not significantly affect lichen growth, HNO3 appears to be phytotoxic to some lichens. As both of these pollutants are deposited downwind from the L.A. basin into Joshua Tree National Park (JOTR), lichen species located in the park may provide a sensitive indicator of pollution effects. This research studied two lichen species of particular interest from Joshua Tree National Park, Lobothallia praeradiosa (Nyl.) Hafellner, and Acarospora socialis H. Magn., both of which are crustose species with unknown sensitivities to O3, as well as hypothesized and unknown sensitivities to nitrogen compounds, respectively. Little research exists for either species, possibly because of the difficulty in working with crustose lichens. This research attempted to expand the background knowledge of these species by exposing them to varying levels of O3 and HNO3, to ascertain their physiological responses. Physiological measures of chlorophyll fluorescence, dark respiration, microscopic imaging, and lichen washes (as a proxy for membrane leakage), were measured throughout the exposure period. Results indicated that both species had similar sensitivities to O3 and HNO3. Both species registered physical damage during the O3 fumigation, as well as a decrease in respiration. Neither species showed major physical damage to HNO3, but both manifested a decrease in chlorophyll fluorescence, suggesting damage to the photosynthetic systems of the algae symbiont. These results suggest that both of these

  16. Application of hydrocyanic acid vapor generation via focused microwave radiation to the preparation of industrial effluent samples prior to free and total cyanide determinations by spectrophotometric flow injection analysis.

    PubMed

    Quaresma, Maria Cristina Baptista; de Carvalho, Maria de Fátima Batista; Meirelles, Francis Assis; Santiago, Vânia Maria Junqueira; Santelli, Ricardo Erthal

    2007-02-01

    A sample preparation procedure for the quantitative determination of free and total cyanides in industrial effluents has been developed that involves hydrocyanic acid vapor generation via focused microwave radiation. Hydrocyanic acid vapor was generated from free cyanides using only 5 min of irradiation time (90 W power) and a purge time of 5 min. The HCN generated was absorbed into an accepting NaOH solution using very simple glassware apparatus that was appropriate for the microwave oven cavity. After that, the cyanide concentration was determined within 90 s using a well-known spectrophotometric flow injection analysis system. Total cyanide analysis required 15 min irradiation time (90 W power), as well as chemical conditions such as the presence of EDTA-acetate buffer solution or ascorbic acid, depending on the effluent to be analyzed (petroleum refinery or electroplating effluents, respectively). The detection limit was 0.018 mg CN l(-1) (quantification limit of 0.05 mg CN l(-1)), and the measured RSD was better than 8% for ten independent analyses of effluent samples (1.4 mg l(-1) cyanide). The accuracy of the procedure was assessed via analyte spiking (with free and complex cyanides) and by performing an independent sample analysis based on the standard methodology recommended by the APHA for comparison. The sample preparation procedure takes only 10 min for free and 20 min for total cyanide, making this procedure much faster than traditional methodologies (conventional heating and distillation), which are time-consuming (they require at least 1 h). Samples from oil (sour and stripping tower bottom waters) and electroplating effluents were analyzed successfully. PMID:17143595

  17. Double liquid membrane system for the removal of actinides and lanthanides from acidic nuclear wastes

    SciTech Connect

    Chiarizia, R.; Danesi, P.R.

    1987-01-01

    Supported liquid membranes (SLM), consisting of an organic solution of n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and tributyl-phosphate (TBP) in decalin are able to perform selective separation and concentration of actinide and lanthanide ions from aqueous nitrate feed solutions and synthetic nuclear wastes. In the membrane process a possible strip solution is a mixture of formic acid and hydroxylammonium formate (HAF). The effectiveness of this strip solution is reduced and eventually nullified by the simultaneous transfer through the SLM of HNO3 which accumulates in the strip solution. A possible way to overcome this drawback is to make use of a second SLM consisting of a primary amine which is able to extract only HNO3 from the strip solution. In this work the results obtained by experimentally studying the membrane system: synthetic nuclear waste/CMPO-TBP membrane/HCOOH-HAF strip solution/primary amine membrane/NaOH solution, are reported. They show that the use of a second liquid membrane is effective in controlling the HNO3 concentration in the strip solution, thus allowing the actinide and lanthanide ions removal from the feed solution to proceed to completion.

  18. Annular denuders for use in global climate and stratospheric measurements of acidic gases and particles

    NASA Astrophysics Data System (ADS)

    Stevens, Robert K.

    1991-02-01

    Measurements of acidic and basic gases that coexist with fine particle (less than 2.5 micron) may be useful for determining the impact of these species on global climate changes and determining species that influence stratospheric ozone levels. Annular denuders are well suited for this purpose. A new concentric annular denuder system, consisting of a three channel denuder, a Teflon coated cyclone preseparator, and a multistage filter pack was developed, evaluated, and shown to provide reliable atmospheric measurements of SO2, HNO2, HNO3, NH3, SO4(=), NH4(+), NO3(-), and H(+). For example, the precision of the annular denuder for the ambient measurements of HNO3 and nitrates at concentrations between 0.1 to 3 microgram/cu m was + or - 12 and 16 pct., respectively. The 120 x 25 mm three channel denuder is encased in a stainless steel sheath and has annular spaces that are 1 mm wide. This design was shown to have nearly identical capacity for removal of SO2 as conventional 210 x 25 mm single channel denuder configurations. The cyclone preseparator was designed and tested to have a D sub 50 cutoff diameter of 2.5 micron and minimal retention of HNO3.

  19. Decay Mechanism of NO3(•) Radical in Highly Concentrated Nitrate and Nitric Acidic Solutions in the Absence and Presence of Hydrazine.

    PubMed

    Garaix, Guillaume; Horne, Gregory P; Venault, Laurent; Moisy, Philippe; Pimblott, Simon M; Marignier, Jean Louis; Mostafavi, Mehran

    2016-06-01

    The decay mechanism of NO3(•) has been determined through a combination of experiment and calculation for 7 mol dm(-3) solutions of deaerated aqueous LiNO3 and HNO3, in the absence and presence of hydrazine (N2H4, N2H5(+), and N2H6(2+)). In the absence of hydrazine, the predominant NO3(•) decay pathways are strongly dependent upon the pH of the solution. For neat, neutral pH LiNO3 solutions (7 mol dm(-3)), NO3(•) produced by the pulse is fully consumed within 160 μs by OH(•) (37%), H2O (29%), NO2(-) (17%), and NO2 (17%). For acidic HNO3 solutions (7 mol dm(-3)), radiolytically produced NO3(•) is predominantly consumed within 1 ms by HNO2 (15%) and NO2 (80%). Intervening formulations exhibit the mechanistic transition from neat LiNO3 to neat HNO3. In highly acidic nitric acid solution, hydrazine exists mainly as N2H5(+) and N2H6(2+), both of which rapidly consume NO3(•) in addition to other decay mechanisms, with rate constants of 2.9 (±0.9) × 10(7) and 1.3 (±0.3) × 10(6) dm(3) mol(-1) s(-1), respectively. PMID:27171587

  20. Structure of a Microbial Community in Soil after Prolonged Addition of Low Levels of Simulated Acid Rain

    PubMed Central

    Pennanen, Taina; Fritze, Hannu; Vanhala, Pekka; Kiikkilä, Oili; Neuvonen, Seppo; Bååth, Erland

    1998-01-01

    Humus samples were collected 12 growing seasons after the start of a simulated acid rain experiment situated in the subarctic environment. The acid rain was simulated with H2SO4, a combination of H2SO4 and HNO3, and HNO3 at two levels of moderate acidic loads close to the natural anthropogenic pollution levels of southern Scandinavia. The higher levels of acid applications resulted in acidification, as defined by humus chemistry. The concentrations of base cations decreased, while the concentrations of exchangeable H+, Al, and Fe increased. Humus pH decreased from 3.83 to 3.65. Basal respiration decreased with decreasing humus pH, and total microbial biomass, measured by substrate-induced respiration and total amount of phospholipid fatty acids (PLFA), decreased slightly. An altered PLFA pattern indicated a change in the microbial community structure at the higher levels of acid applications. In general, branched fatty acids, typical of gram-positive bacteria, increased in the acid plots. PLFA analysis performed on the bacterial community growing on agar plates also showed that the relative amount of PLFA specific for gram-positive bacteria increased due to the acidification. The changed bacterial community was adapted to the more acidic environment in the acid-treated plots, even though bacterial growth rates, estimated by thymidine and leucine incorporation, decreased with pH. Fungal activity (measured as acetate incorporation into ergosterol) was not affected. This result indicates that bacteria were more affected than fungi by the acidification. The capacity of the bacterial community to utilize 95 different carbon sources was variable and only showed weak correlations to pH. Differences in the toxicities of H2SO4 and HNO3 for the microbial community were not found. PMID:9603831

  1. Immobilization of EAFD heavy metals using acidic materials.

    PubMed

    Mitrakas, Manassis G; Sikalidis, Constantinos A; Karamanli, Theoktisti P

    2007-03-01

    This study was undertaken to determine the chemical and leaching characteristics of the Electric Arc Furnace Dust (EAFD) generated by a Greek plant and to investigate various acidic materials efficiency on the EAFD stabilization. In order to investigate how [OH(-)] neutralization influences EAFD heavy metals leachability, Na HCO3(-), HNO3 and H3PO4 were used as acidic materials. The concentration of Pb in leachate was found between 40 and 3.7 x 10(3) mg Pb/kg of EAFD, exceeding in all EAFD samples the maximum acceptable limit (MAL) 25 mg/kg for landfill disposal. Neutralization of [OH(-)] with HCO3(-) decreased Pb concentration in leachate at 350 mg Pb/kg of EAFD, while excess over a stoichiometry in HCO3(-) addition increased leachability of Pb, Cd, Cr, Cu as well as F. Using HNO3 as an acidic material decreased leachability of almost all the parameters concerning the EC directive 33/19-01-2003 in a pH value up to 7.2, in exception of Zn. Zinc leachability showed a U shape curve as a function of pH value. The concentration of Zn was minimized in a concentration lower than 1 mg Zn/kg EAFD in a pH range 10.5 to 9 and exceeded the MAL 90 mg/kg at a pH value 7.2. However, the major disadvantage of HNO3 was proved to be its leachability, since NO3(-) concentration in leachate was equal to HNO3 dose. H3PO4 was found the most promising acidic material for the chemical immobilization of heavy metals, since it decreased their leachability in a concentration significantly lower than MAL at a pH value up to 7.1. Finally, the concentration of Cl(-) ranged between 18 and 33 x 10(3) mg Cl(-)/kg EAFD exceeding in all EAFD samples the MAL 17 x 10(3) mg/kg. This high concentration of Cl(-) is attributed to the scrap and it could be reduced only by modification of its composition. PMID:17365324

  2. Vapor phase pyrolysis

    NASA Technical Reports Server (NTRS)

    Steurer, Wolfgang

    1992-01-01

    The vapor phase pyrolysis process is designed exclusively for the lunar production of oxygen. In this concept, granulated raw material (soil) that consists almost entirely of metal oxides is vaporized and the vapor is raised to a temperature where it dissociates into suboxides and free oxygen. Rapid cooling of the dissociated vapor to a discrete temperature causes condensation of the suboxides, while the oxygen remains essentially intact and can be collected downstream. The gas flow path and flow rate are maintained at an optimum level by control of the pressure differential between the vaporization region and the oxygen collection system with the aid of the environmental vacuum.

  3. Evaluation of oxygen pressurized microwave-assisted digestion of botanical materials using diluted nitric acid.

    PubMed

    Bizzi, Cezar Augusto; Barin, Juliano Smanioto; Müller, Edson Irineu; Schmidt, Lucas; Nóbrega, Joaquim A; Flores, Erico Marlon Moraes

    2011-02-15

    The feasibility of diluted nitric acid solutions for microwave-assisted decomposition of botanical samples in closed vessels was evaluated. Oxygen pressurized atmosphere was used to improve the digestion efficiency and Al, Ca, K, Fe, Mg and Na were determined in digests by inductively coupled plasma optical emission spectrometry (ICP OES). Efficiency of digestion was evaluated taking into account the residual carbon content (RCC) and residual acidity in digests. Samples were digested using nitric acid solutions (2, 3, 7, and 14 mol L(-1) HNO(3)) and the effect of gas phase composition inside the reaction vessels by purging the vessel with Ar (inert atmosphere, 1 bar), air (20% of oxygen, 1 bar) and pure O(2) (100% of oxygen, 1 bar) was evaluated. The influence of oxygen pressure was studied using pressures of 5, 10, 15 and 20 bar. It was demonstrated that a diluted nitric acid solution as low as 3 mol L(-1) was suitable for an efficient digestion of sample masses up to 500 mg of botanical samples using 5 bar of oxygen pressure. The residual acidities in final digests were lower than 45% in relation to the initial amount of acid used for digestion (equivalent to 1.3 mol L(-1) HNO(3)). The accuracy of the proposed procedure was evaluated using certified reference materials of olive leaves, apple leaves, peach leaves and pine needles. Using the optimized conditions for sample digestion, the results obtained were in agreement with certified values. The limit of quantification was improved up to a factor of 14.5 times for the analytes evaluated. In addition, the proposed procedure was in agreement with the recommendations of the green chemistry once it was possible to obtain relatively high digestion efficiency (RCC<5%) using only diluted HNO(3), which is important to minimize the generation of laboratory residues. PMID:21238716

  4. Tuning the work function of monolayer graphene on 4H-SiC (0001) with nitric acid.

    PubMed

    Günes, Fethullah; Arezki, Hakim; Pierucci, Debora; Alamarguy, David; Alvarez, José; Kleider, Jean-Paul; Dappe, Yannick J; Ouerghi, Abdelkarim; Boutchich, Mohamed

    2015-11-01

    Chemical doping of graphene is a key process for the modulation of its electronic properties and the design and fabrication of graphene-based nanoelectronic devices. Here, we study the adsorption of diluted concentrations of nitric acid (HNO3) onto monolayer graphene/4H-SiC (0001) to induce a variation of the graphene work function (WF). Raman spectroscopy indicates an increase in the defect density subsequent to the doping. Moreover, ultraviolet photoemission spectroscopy (UPS) was utilized to quantify the WF shift. UPS data show that the WF of the graphene layer decreased from 4.3 eV (pristine) down to 3.8 eV (30% HNO3) and then increased to 4.4 eV at 100% HNO3 concentration. These observations were confirmed using density functional theory (DFT) calculations. This straightforward process allows a large WF modulation, rendering the molecularly modified graphene/4H-SiC(0001) a highly suitable electron or hole injection electrode. PMID:26457876

  5. Effects of acid fog and dew on materials. Final report

    SciTech Connect

    Mansfeld, F.; Henry, R.; Vijayakumar, R.

    1989-10-01

    Field exposure tests have been carried out in order to separate the effects of acidic fog on materials damage from those caused by rain, dew and natural weathering. The test sites were McKittrick and Visalia in the Central Valley and West Casitas Pass in Ventura County. The field tests have been supported by laboratory tests in which materials damage has been determined during exposure to carefully controlled fog water chemistry. Analysis of the field exposure results for galvanized steel and the paint samples shows that the corrosivity of the atmosphere at the three test sites have been very low. The result is confirmed by the ACRM data which show very low corrosion activity. Since corrosion rates were so low approaching those for natural weathering, it was not possible to determine the effects of acidic fog. Based on the aerometric data and the observed corrosion behavior, it is doubtful that acidic fog conditions prevailed for significant times during the exposure period of 1/87 - 3/88 at Visalia and McKittrick. The results of the laboratory tests show that exposure to HNO3 at low pH and to high pollutant concentration increased the corrosion rate of galvanized steel to over 10 micro m/year. Exposure to HNO3 caused serious corrosion damage to anodized aluminum and the paint.

  6. Vapor spill monitoring method

    DOEpatents

    Bianchini, Gregory M.; McRae, Thomas G.

    1985-01-01

    Method for continuous sampling of liquified natural gas effluent from a spill pipe, vaporizing the cold liquified natural gas, and feeding the vaporized gas into an infrared detector to measure the gas composition. The apparatus utilizes a probe having an inner channel for receiving samples of liquified natural gas and a surrounding water jacket through which warm water is flowed to flash vaporize the liquified natural gas.

  7. Supplemental fuel vapor system

    SciTech Connect

    Foster, P.M.

    1991-01-08

    This patent describes a supplemental fuel system utilizing fuel vapor. It comprises: an internal combustion engine including a carburetor and an intake manifold; a fuel tank provided with air vents; a fuel conduit having a first end connected to the fuel tank and in communication with liquid fuel in the tank and a second end connected to the carburetor; the fuel conduit delivering the liquid fuel to the carburetor from the fuel tank; a fuel vapor conduit having a first end connected to the fuel tank at a location displaced from contact with the liquid fuel and a second end connected to a carbon canister; a PCV conduit having a first end connected to a pollution control valve and a second end connected to the intake manifold; and, an intermediate fuel vapor conduit having a first end connected to the fuel vapor conduit and a second end connected to the PCV conduit; wherein the air vents continuously provide air to the tank to mix with the liquid fuel and form fuel vapor. The fuel vapor drawn from the fuel tank by vacuum developed in the intake manifold and flows through the fuel vapor conduit. The intermediate fuel vapor conduit and the intake manifold to combustion chambers of the internal combustion engine so as to supplement fuel delivered to the engine by the fuel conduit. The liquid fuel and the fuel vapor constantly delivered to the engine during normal operation.

  8. Quantum mechanical study of atmospheric nitrogen oxides and nitric acid: Implications on acid rain

    SciTech Connect

    Richardson, M.D.; Davey, C.A.; Evanseck, J.D.

    1996-12-31

    The energetics of the nonhydrated and monohydrated reaction NO2 + OH {r_arrow} HNO3 were studied using computational methods. Energetic and structural data were obtained using high level ab initio calculations (up to MP4 for energetics). The activation energy was calculated to be around 8 kcal/mol for the nonhydrated system, but the presence of a single water molecule completely eliminated the barrier to nitric acid formation. The hydration of this atmospheric reaction significantly stabilizes the transition structure, leading to an activation energy of about -1 kcal/mol for the reaction. This suggests that enthalpically the reactants may spontaneously form nitric acid in the lower atmosphere where water is available for catalysis, resulting in further production of acid rain.

  9. Dissolution of sulfuric acid tetrahydrate at low temperatures and subsequent growth of nitric acid trihydrate

    NASA Astrophysics Data System (ADS)

    Iraci, Laura T.; Fortin, Tara J.; Tolbert, Margaret A.

    1998-04-01

    Crystalline sulfuric acid tetrahydrate (SAT) has been observed to change phase at temperatures below its melting point, in agreement with recent theoretical predictions of deliquescence. Dissolution of SAT was observed in 63% of experiments expected to show a phase change, leading to formation of a ternary HNO3/H2SO4/H2O solution. This solution, which still contained a portion of the original solid SAT, crystallized to form nitric acid trihydrate (NAT). NAT then continued to grow by condensation of additional nitric acid and water at temperatures several degrees above the ice frost point. This process of SAT dissolution followed by NAT crystallization and growth may offer a mechanism for the formation of type Ia polar stratospheric clouds on frozen sulfate aerosols when SNAT>15.

  10. An intercomparison of airborne nitric acid measurements

    NASA Astrophysics Data System (ADS)

    Gregory, G. L.; Hoell, J. M.; Huebert, B. J.; van Bramer, S. E.; Lebel, P. J.; Vay, S. A.; Marinaro, R. M.; Schiff, H. I.; Hastie, D. R.; Mackay, G. I.; Karecki, D. R.

    1990-06-01

    Results from an airborne intercomparison of techniques to measure tropospheric levels of nitric acid are discussed. The intercomparison was part of the National Aeronautics and Space Administration's Global Tropospheric Experiment and was conducted during the summer of 1986. Instruments intercompared included a denuder tube collection system (DENUDER) with chemiluminescent detection, a niylon filter collection system (FILTER) with ion chromatography detection, and a tunable diode laser (TDLAS) multipath absorption system. Intercomparison of investigators' calibration standards were also performed as part of the test protocol. While results were somewhat "soft" and data sparse, these tests suggested that the TDLAS measurements might be high compared to the other techniques. Airborne intercomparisons were conducted predominately in the free troposphere and included encounters with marine and continental air masses. While the intercomparisons included mixing ratios to 1000 parts per trillion by volume (pptv), the majority of the results were for mixing ratios of <300 pptv. The TDLAS participated in an intercomparison of NO2 instruments (major focus) that was also conducted during the same flights. As a result the TDLAS data set is limited. Further, a significant fraction of the nitric acid measurements were below the TDLAS detection limit (75 pptv as configured for these tests). While the lack of simultaneous measurements from the three instruments limits the conclusions that can be drawn, it is clear that there can be substantial disagreement among the three techniques, even at mixing ratios above their respective detection limits. Equally clear is that at mixing ratios below 150 pptv there is very little correlation between their results. Based on these observations, an overall conclusion from the intercomparison is that none of the HNO3 techniques can be identified to unambiguously (e.g., 20% accuracy) provide measurements of HNO3 at levels often encountered in the

  11. Solubility and equilibrium vapor pressures of HC1 dissolved in polar stratospheric cloud materials - Ice and the trihydrate of nitric acid

    NASA Technical Reports Server (NTRS)

    Hanson, David; Mauersberger, Konrad

    1988-01-01

    Measurements of the pressure-solubility behavior of HC1 in water ice and in the nitric acid trihydrate (NAT) crystal at 200 K are reported. It was found that HC1 is about 20 times more soluble in NAT than in ice for stratospheric conditions. A relation between HC1 pressure and substrate composition based on the Gibbs-Duhem equation is developed. This relation, along with other thermodynamic data, can be used to obtain the HC1 pressure-solubility behavior at different temperatures. Implications of these results for the south polar ozone hole are discussed.

  12. Speciation in aqueous solutions of nitric acid.

    PubMed

    Hlushak, S; Simonin, J P; De Sio, S; Bernard, O; Ruas, A; Pochon, P; Jan, S; Moisy, P

    2013-02-28

    In this study, speciation in aqueous solutions of nitric acid at 25 °C was assessed in two independent ways. First, Raman experiments were carried out and interpreted in terms of free nitrate ions, ion pairs and neutral HNO(3) molecules. In parallel, a model was developed to account for the formation of these two kinds of pairs. It was based on an extension of the binding mean spherical approximation (BiMSA), or associative MSA (AMSA), in which the size and the charge of the ions in the chemical pair may differ from those of the free ions. A simultaneous fit of the osmotic coefficient and of the proportion of free ions (obtained from Raman spectroscopy experiments) led to an estimation of the speciation in nitric acid solutions. The result obtained using this procedure was compared with the estimation obtained from the Raman experiments. PMID:23258765

  13. Nylon Dissolution in Nitric Acid Solutions

    SciTech Connect

    KESSINGER, GLENF.

    2004-06-16

    H Area Operations is planning to process Pu-contaminated uranium scrap in support of de-inventory efforts. Nylon bags will be used to hold materials to be dissolved in H-Canyon. Based on this set of twelve nylon dissolutions, it is concluded that (when other variables are held constant): increased acid concentration results in increased dissolution rates; increased acid concentration results in a lower dissolution onset temperature; little, if any, H plus is consumed during the depolymerization process; and 2.0-3.0 M HNO3, with 0.025 M KF and 2 g/L B, is satisfactory for the dissolution of nylon bag materials to be used during H-Canyon processing.

  14. Petroleum Vapor - Field Technical

    EPA Science Inventory

    The screening approach being developed by EPA OUST to evaluate petroleum vapor intrusion (PVI) requires information that has not be routinely collected in the past at vapor intrusion sites. What is the best way to collect this data? What are the relevant data quality issues and ...

  15. Water vapor pressure calculation.

    PubMed

    Hall, J R; Brouillard, R G

    1985-06-01

    Accurate calculation of water vapor pressure for systems saturated with water vapor can be performed using the Goff-Gratch equation. A form of the equation that can be adapted for computer programming and for use in electronic databases is provided. PMID:4008425

  16. Stratospheric water vapor feedback

    PubMed Central

    Dessler, A. E.; Schoeberl, M. R.; Wang, T.; Davis, S. M.; Rosenlof, K. H.

    2013-01-01

    We show here that stratospheric water vapor variations play an important role in the evolution of our climate. This comes from analysis of observations showing that stratospheric water vapor increases with tropospheric temperature, implying the existence of a stratospheric water vapor feedback. We estimate the strength of this feedback in a chemistry–climate model to be +0.3 W/(m2⋅K), which would be a significant contributor to the overall climate sensitivity. One-third of this feedback comes from increases in water vapor entering the stratosphere through the tropical tropopause layer, with the rest coming from increases in water vapor entering through the extratropical tropopause. PMID:24082126

  17. Stratospheric water vapor feedback.

    PubMed

    Dessler, A E; Schoeberl, M R; Wang, T; Davis, S M; Rosenlof, K H

    2013-11-01

    We show here that stratospheric water vapor variations play an important role in the evolution of our climate. This comes from analysis of observations showing that stratospheric water vapor increases with tropospheric temperature, implying the existence of a stratospheric water vapor feedback. We estimate the strength of this feedback in a chemistry-climate model to be +0.3 W/(m(2)⋅K), which would be a significant contributor to the overall climate sensitivity. One-third of this feedback comes from increases in water vapor entering the stratosphere through the tropical tropopause layer, with the rest coming from increases in water vapor entering through the extratropical tropopause. PMID:24082126

  18. Nitric Acid Particles in Cold Thick Ice Clouds Observed at Global Scale: Link with Lightning, Temperature, and Upper Tropospheric Water Vapor

    NASA Technical Reports Server (NTRS)

    Chepfer, H.; Minnis, P.; Dubuisson, P.; Chiriaco, M.; Sun-Mack, S.; Riviere, E. D.

    2007-01-01

    Signatures of nitric acid particles (NAP) in cold thick ice clouds have been derived from satellite observations. Most NAP are detected in the Tropics (9 to 20% of clouds with T less than 202.5 K). Higher occurrences were found in the rare mid-latitudes very cold clouds. NAP occurrence increases as cloud temperature decreases and NAP are more numerous in January than July. Comparisons of NAP and lightning distributions show that lightning is the main source of the NOx, which forms NAP in cold clouds. Qualitative comparisons of NAP with upper tropospheric humidity distributions suggest that NAP play a role in the dehydration of the upper troposphere when the tropopause is colder than 195K.

  19. Electronic and optical characteristics of an m-plane GaN single crystal grown by hydride vapor phase epitaxy on a GaN seed synthesized by the ammonothermal method using an acidic mineralizer

    NASA Astrophysics Data System (ADS)

    Kojima, Kazunobu; Tsukada, Yusuke; Furukawa, Erika; Saito, Makoto; Mikawa, Yutaka; Kubo, Shuichi; Ikeda, Hirotaka; Fujito, Kenji; Uedono, Akira; Chichibu, Shigefusa F.

    2016-05-01

    Fundamental electronic and optical properties of a low-resistivity m-plane GaN single crystal, which was grown by hydride vapor phase epitaxy on a bulk GaN seed crystal synthesized by the ammonothermal method in supercritical ammonia using an acidic mineralizer, were investigated. The threading dislocation and basal-plane staking-fault densities of the crystal were around 104 cm-2 and less than 100 cm-1, respectively. Oxygen doping achieved a high electron concentration of 4 × 1018 cm-3 at room temperature. Accordingly, a photoluminescence (PL) band originating from the recombination of hot carriers was observed at low temperatures, even under weak excitation conditions. The simultaneous realization of low-level incorporation of Ga vacancies (VGa) less than 1016 cm-3 was confirmed by using the positron annihilation technique. Consistent with our long-standing claim that VGa complexes are the major nonradiative recombination centers in GaN, the fast-component PL lifetime of the near-band-edge emission at room temperature longer than 2 ns was achieved.

  20. The interaction of propionic and butyric acids with ice and HNO₃-doped ice surfaces at 195-212 K.

    PubMed

    Romanias, Manolis N; Papadimitriou, Vassileios C; Papagiannakopoulos, Panos

    2014-12-01

    The interaction of propionic and butyric acids on ice and HNO3-doped ice were studied between 195 and 212 K and low concentrations, using a Knudsen flow reactor coupled with a quadrupole mass spectrometer. The initial uptake coefficients (γ0) of propionic and butyric acids on ice as a function of temperature are given by the expressions: γ0(T) = (7.30 ± 1.0) × 10(-10) exp[(3216 ± 478)/T] and γ0(T) = (6.36 ± 0.76) × 10(-11) exp[(3810 ± 434)/T], respectively; the quoted error limits are at 95% level of confidence. Similarly, γ0 of propionic acid on 1.96 wt % (A) and 7.69 wt % (B) HNO3-doped ice with temperature are given as γ(0,A)(T) = (2.89 ± 0.26) × 10(-8) exp[(2517 ± 266)/T] and γ(0,B)(T) = (2.77 ± 0.29) × 10(-7) exp[(2126 ± 206)/T], respectively. The results show that γ0 of C1 to C4 n-carboxylic acids on ice increase with the alkyl-group length, due to lateral interactions between alkyl-groups that favor a more perpendicular orientation and well packing of H-bonded monomers on ice. The high uptakes (>10(15) molecules cm(-2)) and long recovery signals indicate efficient growth of random multilayers above the first monolayer driven by significant van der Waals interactions. The heterogeneous loss of both acids on ice and HNO3-doped ice particles in dense cirrus clouds is estimated to take a few minutes, signifying rapid local heterogeneous removal by dense cirrus clouds. PMID:25384192

  1. Vacuum vapor deposition

    NASA Technical Reports Server (NTRS)

    Poorman, Richard M. (Inventor); Weeks, Jack L. (Inventor)

    1995-01-01

    A method and apparatus is described for vapor deposition of a thin metallic film utilizing an ionized gas arc directed onto a source material spaced from a substrate to be coated in a substantial vacuum while providing a pressure differential between the source and the substrate so that, as a portion of the source is vaporized, the vapors are carried to the substrate. The apparatus includes a modified tungsten arc welding torch having a hollow electrode through which a gas, preferably inert, flows and an arc is struck between the electrode and the source. The torch, source, and substrate are confined within a chamber within which a vacuum is drawn. When the arc is struck, a portion of the source is vaporized and the vapors flow rapidly toward the substrate. A reflecting shield is positioned about the torch above the electrode and the source to ensure that the arc is struck between the electrode and the source at startup. The electrode and the source may be confined within a vapor guide housing having a duct opening toward the substrate for directing the vapors onto the substrate.

  2. Vapor resistant arteries

    NASA Technical Reports Server (NTRS)

    Shaubach, Robert M. (Inventor); Dussinger, Peter M. (Inventor); Buchko, Matthew T. (Inventor)

    1989-01-01

    A vapor block resistant liquid artery structure for heat pipes. A solid tube artery with openings is encased in the sintered material of a heat pipe wick. The openings are limited to that side of the artery which is most remote from the heat source. The liquid in the artery can thus exit the artery through the openings and wet the sintered sheath, but vapor generated at the heat source is unlikely to move around the solid wall of the artery and reverse its direction in order to penetrate the artery through the openings. An alternate embodiment uses finer pore size wick material to resist vapor entry.

  3. Size-controlled synthesis and formation mechanism of manganese oxide OMS-2 nanowires under reflux conditions with KMnO4 and inorganic acids

    NASA Astrophysics Data System (ADS)

    Zhang, Qin; Cheng, Xiaodi; Qiu, Guohong; Liu, Fan; Feng, Xionghan

    2016-05-01

    This study presents a simplified approach for size-controlled synthesis of manganese oxide octahedral molecular sieve (OMS-2) nanowires using potassium permanganate (KMnO4) and different inorganic acids (HCl, HNO3, and H2SO4) under reflux conditions. The morphology and nanostructure of the synthesized products are characterized by X-ray diffraction, Ar adsorption, and electron microscopy analysis, in order to elucidate the controlling effects of acid concentration and type as well as the formation mechanism of OMS-2 nanowires. The concentration of inorganic acid is a crucial factor controlling the phase of the synthesized products. OMS-2 nanowires are obtained with HCl at the concentration ≥0.96 mol/L or with HNO3 and H2SO4 at the concentrations ≥0.72 mol/L. Differently, the type of inorganic acid effectively determines the particle size of OMS-2 nanowires. When the acid is changed from HCl to HNO3 and H2SO4 in the reflux system, the average length of OMS-2 declines significantly by 60-70% (1104-442 and 339 nm), with minor decreased in the average width (43-39 and 34 nm). The formation of OMS-2 nanowires under reflux conditions with KMnO4 and inorganic acids involves a two-step process, i.e., the initial formation of layered manganese oxides, and subsequent transformation to OMS-2 via a dissolution-recrystallization process under acidic conditions. The proposed reflux route provides an alternative approach for synthesizing OMS-2 nanowires as well as other porous nano-crystalline OMS materials.

  4. AMTEC vapor-vapor series connected cells

    NASA Technical Reports Server (NTRS)

    Underwood, Mark L. (Inventor); Williams, Roger M. (Inventor); Ryan, Margaret A. (Inventor); Nakamura, Barbara J. (Inventor); Oconnor, Dennis E. (Inventor)

    1995-01-01

    An alkali metal thermoelectric converter (AMTEC) having a plurality of cells structurally connected in series to form a septum dividing a plenum into two chambers, and electrically connected in series, is provided with porous metal anodes and porous metal cathodes in the cells. The cells may be planar or annular, and in either case a metal alkali vapor at a high temperature is provided to the plenum through one chamber on one side of the wall and returned to a vapor boiler after condensation at a chamber on the other side of the wall in the plenum. If the cells are annular, a heating core may be placed along the axis of the stacked cells. This arrangement of series-connected cells allows efficient generation of power at high voltage and low current.

  5. Second Vapor-Level Sensor For Vapor Degreaser

    NASA Technical Reports Server (NTRS)

    Painter, Nance M.; Burley, Richard K.

    1990-01-01

    Second vapor-level sensor installed at lower level in vapor degreaser makes possible to maintain top of vapor at that lower level. Evaporation reduced during idle periods. Provides substantial benefit, without major capital cost of building new vapor degreaser with greater freeboard height.

  6. Gasoline Vapor Recovery

    NASA Technical Reports Server (NTRS)

    1979-01-01

    Gasoline is volatile and some of it evaporates during storage, giving off hydrocarbon vapor. Formerly, the vapor was vented into the atmosphere but anti-pollution regulations have precluded that practice in many localities, so oil companies and storage terminals are installing systems to recover hydrocarbon vapor. Recovery provides an energy conservation bonus in that most of the vapor can be reconverted to gasoline. Two such recovery systems are shown in the accompanying photographs (mid-photo at right and in the foreground below). They are actually two models of the same system, although.configured differently because they are customized to users' needs. They were developed and are being manufactured by Edwards Engineering Corporation, Pompton Plains, New Jersey. NASA technological information proved useful in development of the equipment.

  7. Large-Scale Distributions of Tropospheric Nitric, Formic, and Acetic acids Over the Westerm Pacific Basin During Wintertime

    NASA Technical Reports Server (NTRS)

    Talbot, R. W.; Dibb, J. E.; Lefer, B. L.; Scheuer, E. M.; Bradshaw, J. D.; Sandholm, S. T.; Smyth, S.; Blake, D. R.; Blake, N. J.; Sachse, G. W.; Collins, J. E.; Gregory, G. L.

    1997-01-01

    We report here measurements of the acidic gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) over the western Pacific basin during the February-March 1994 Pacific Exploratory Mission-West (PEM-West B). These data were obtained aboard the NASA DC-8 research aircraft as it flew missions in the altitude range of 0.3 - 12.5 km over equatorial regions near Guam and then further westward encompassing the entire Pacific Rim arc. Aged marine air over the equatorial Pacific generally exhibited mixing ratios of acidic gases less than 100 parts per trillion by volume (pptv). Near the Asian continent, discrete plumes encountered below 6 km altitude contained up to 8 parts per billion by volume (ppbv) HNO3 and 10 ppbv HCOOH and CH3COOH. Overall there was a general correlation between mixing ratios of acidic gases with those of CO, C2H2, and C2Cl4, indicative of emissions from combustion and industrial sources. The latitudinal distributions of HNO3 and CO showed that the largest mixing ratios were centered around 15 deg N, while HCOOH, CH3COOH, and C2Cl4 peaked at 25 deg N. The mixing ratios of HCOOH and CH3COOH were highly correlated (r(sup 2) = 0.87) below 6 km altitude, with a slope (0.89) characteristic of the nongrowing season at midlatitudes in the northern hemisphere. Above 6 km altitude, HCOOH and CH3COOH were marginally correlated (r(sup 2) = 0.50), and plumes well defined by CO, C2H2, and C2Cl4 were depleted in acidic gases, most likely due to scavenging during vertical transport of air masses through convective cloud systems over the Asian continent. In stratospheric air masses, HNO, mixing ratios were several parts per billion by volume (ppbv), yielding relationships with 03 and N2O consistent with those previously reported for NO(y).

  8. Sporicidal Activity of the KMT reagent in its vapor phase against Geobacillus stearothermophilus Spores.

    PubMed

    Kida, Nori; Mochizuki, Yasushi; Taguchi, Fumiaki

    2007-01-01

    In an investigation of the sporicidal activity of the KMT reagent, a vapor phase study was performed using five kinds of carriers contaminated with Geobacillus stearothermophilus spores. When 25 ml of the KMT reagent was vaporized in a chamber (capacity; approximately 95 liters), the 2-step heating method (vaporization by a combination of low temperature and high temperature) showed the most effective sporicidal activity in comparison with the 1-step heating method (rapid vaporization). The 2-step heating method appeared to be related to the sporicidal activity of vaporized KMT reagent, i.e., ethanol and iodine, which vaporized mainly when heated at a low temperature such as 55 C, and acidic water, which vaporized mainly when heated at a high temperature such as 300 C. We proposed that the KMT reagent can be used as a new disinfectant not only in the liquid phase but also in the vapor phase in the same way as peracetic acid and hydrogen peroxide. PMID:17237604

  9. Raman spectroscopy of vapors at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Laane, Jaan; Haller, Kristjan; Sakurai, Sachie; Morris, Kevin; Autrey, Daniel; Arp, Zane; Chiang, Whe-Yi; Combs, Amanda

    2003-05-01

    The most effective way to obtain high quality vapor-phase Raman spectra is to heat the samples to increase their vapor pressure. Many samples can be heated to 350 °C and higher without decomposition. We have designed a simple Raman cell to allow these high temperature studies to be carried out. The high-temperature Raman spectra of nine molecules will be presented and discussed. Most of these are non-rigid molecules containing aromatic rings for which vibrational potential energy surfaces have been determined from their spectra. Two molecules ( p-cresol and 3-methylindole) are model compounds for amino acids and their vapor-phase spectra are characteristic of environments with no hydrogen bonding.

  10. Infrared spectrum of nitric acid dihydrate: Influence of particle shape.

    PubMed

    Wagner, Robert; Möhler, Ottmar; Saathoff, Harald; Stetzer, Olaf; Schurath, Ulrich

    2005-03-24

    In situ Fourier transform infrared (FTIR) extinction spectra of airborne alpha-NAD microparticles generated by two different methods were recorded in the large coolable aerosol chamber AIDA of Forschungszentrum Karlsruhe. The extinction spectrum of alpha-NAD crystals obtained by shock freezing of a HNO3/H2O gas mixture could be accurately reproduced using Mie theory with published refractive indices of alpha-NAD as input. In contrast, Mie theory proved to be inadequate to properly reproduce the infrared extinction spectrum of alpha-NAD crystals which were formed via homogeneous nucleation of supercooled HNO3/H2O solution droplets, evaporating slowly on a time scale of several hours at about 195 K. Much better agreement between measured and calculated extinction spectra was obtained by T-matrix calculations assuming oblate particles with aspect ratios greater than five. This indicates that strongly aspherical alpha-NAD crystals are obtained when supercooled nitric acid solution droplets freeze and grow slowly, a process which has been discussed as a potential pathway to the formation of crystalline polar stratospheric cloud (PSC) particles. PMID:16833561

  11. Retention behavior of common mono- and divalent cations on calcinated silica gel columns in ion chromatography with conductimetric detection and the use of nitric acid, containing crown ethers, as eluents.

    PubMed

    Ohta, Kazutoku; Kusumoto, Keiji; Takao, Yasumasa; Towata, Atsuya; Kawakami, Shoji; Murase, Yoshio; Ohashi, Masayoshi

    2002-05-17

    Ion chromatographic behavior of common mono- and divalent cations (Li+, Na+, NH4+, K+, Mg2+ and Ca2+) on columns packed with silica gels (Super Micro Bead Silica Gel B-5, SMBSG B-5) calcinated at 200, 400, 600, 800 and 1000 degrees C for 5 h was investigated using nitric acid containing crown ethers [18-crown-6 (1,4,7,10,13,15-hexaoxacyclooctadecane) and 15-crown-5 (1,4,7,10,13-pentaoxacyclopentadecane)] as eluent. When using 0.5 mM HNO3 as the eluent, the calcination had almost no effect on the improvement of peak resolution between these mono- and divalent cations. In contrast, when using 0.5 mM HNO3 containing crown ethers as the eluent, with increasing the calcinating temperature, the amount of crown ethers adsorbed on the corresponding calcinated SMBSG B-5 silica gels columns increased and, as a consequence, peak resolution between these mono- and divalent cations was quite improved. Excellent simultaneous separation of these mono- and divalent cations was achieved on column (150x4.6 mm I.D.) packed with the SMBSG B-5 silica gel calcinated at 1000 degrees C by elution with 0.5 mM HNO3 containing either 1.0 mM 18-crown-6 or 5.0 mM 15-crown-5. PMID:12108647

  12. pH-dependent immobilization of proteins on surfaces functionalized by plasma-enhanced chemical vapor deposition of poly(acrylic acid)- and poly(ethylene oxide)-like films.

    PubMed

    Belegrinou, Serena; Mannelli, Ilaria; Lisboa, Patricia; Bretagnol, Frederic; Valsesia, Andrea; Ceccone, Giacomo; Colpo, Pascal; Rauscher, Hubert; Rossi, François

    2008-07-15

    The interaction of the proteins bovine serum albumin (BSA), lysozyme (Lys), lactoferrin (Lf), and fibronectin (Fn) with surfaces of protein-resistant poly(ethylene oxide) (PEO) and protein-adsorbing poly(acrylic acid) (PAA) fabricated by plasma-enhanced chemical vapor deposition has been studied with quartz crystal microbalance with dissipation monitoring (QCM-D). We focus on several parameters which are crucial for protein adsorption, i.e., the isoelectric point (pI) of the proteins, the pH of the solution, and the charge density of the sorbent surfaces, with the zeta-potential as a measure for the latter. The measurements reveal adsorption stages characterized by different segments in the plots of the dissipation vs frequency change. PEO remains protein-repellent for BSA, Lys, and Lf at pH 4-8.5, while weak adsorption of Fn was observed. On PAA, different stages of protein adsorption processes could be distinguished under most experimental conditions. BSA, Lys, Lf, and Fn generally exhibit a rapid initial adsorption phase on PAA, often followed by slower processes. The evaluation of the adsorption kinetics also reveals different adsorption stages, whereas the number of these stages does not always correspond to the structurally different phases as revealed by the D- f plots. The results presented here, together with information obtained in previous studies by other groups on the properties of these proteins and their interaction with surfaces, allow us to develop an adsorption scenario for each of these proteins, which takes into account electrostatic protein-surface and protein-protein interaction, but also the pH-dependent properties of the proteins, such as shape and exposure of specific domains. PMID:18549295

  13. Determination of mercury in gasoline by cold vapor atomic absorption spectrometry with direct reduction in microemulsion media

    NASA Astrophysics Data System (ADS)

    Brandão, Geisamanda Pedrini; de Campos, Reinaldo Calixto; Luna, Aderval Severino

    2005-06-01

    The determination of Hg in gasoline by cold vapor atomic absorption spectrometry, after direct aqueous NaBH 4 reduction in a three-component (microemulsion) medium, was investigated. Microemulsions were prepared by mixing gasoline with propan-1-ol and 50% v / v HNO 3 at a 20 : 15 : 1 volume ratio. A long-term homogeneous system was immediately formed this way. After reduction, the Hg vapor generated in a reaction flask was transported to an intermediate K 2Cr 2O 7/H 2SO 4 trap solution in order to avoid poisoning of the Au-Pt trap by the gasoline vapors. A second reduction step was then conducted and the generated Hg vapor transported to the Au-Pt trap, followed by thermal release of Hg 0 and atomic absorption measurement. Purified N 2 was used as purge and transport gas. After multivariate optimization by central composite design calibration graphs showed coefficients of correlation of 0.9999 and a characteristic mass of 2 ng was obtained. Typical coefficients of variation of 5% and 6% were found for ten consecutive measurements at concentration levels of 1 and 8 μg L -1 of Hg 2+, respectively. The limit of detection was 0.10 μg L -1 (0.14 μg kg -1) in the original sample. A total measurement cycle took 11 min, permitting duplicate analysis of 3 samples per hour. The results obtained with the proposed procedure in the analysis of commercial gasoline samples were in agreement with those obtained by a comparative procedure. Gasoline samples of the Rio de Janeiro city have shown Hg concentrations below 0.27 μg L -1.

  14. Seasonal and diurnal cycles of ammonia, nitrous acid and nitric acid at a forest site in Finland

    NASA Astrophysics Data System (ADS)

    Virkkula, A.; Makkonen, U.; Mäntykenttä, J.; Hakola, H.

    2012-04-01

    Background In July - August 2010 a large campaign "Hyytiälä United Measurements of Photochemistry and Particles in Air - Comprehensive Organic Precursor Emission Concentration 2010 (HUMPPA - COPEC-10)", was conducted in a boreal forest at the SMEAR II station in Hyytiälä, southwestern central Finland. The general goal was to study links between gas phase oxidation chemistry and particle properties and processes. The Finnish Meteorological Institute contributed to the campaign with an on-line analyzer MARGA 2S (Ten Brink et al., 2007) for semi-continuous (1-hr time resolution) measurement of water-soluble gases and ions. Concentrations of gases (HCl, HNO3, HNO2, NH3, SO2) and major ions in particles (Cl, NO3, SO4, NH4, Na, K, Mg, Ca) were measured in two size fractions: PM2.5 and PM10. The MARGA was kept running at SMEAR II also after the campaign. Here we discuss data collected until 30 April, 2011, and restrict the analysis to the nitrogen-containing gases. Ammonia plays a key role in neutralizing acidic atmospheric compounds and in aerosol formation. The concentration of semi-volatile aerosol species such as ammonium nitrate and ammonium chloride is strongly dependent on the gas phase precursors, NH3, HNO3 and HCl. HONO is of atmospheric importance due to its expected significant contribution to the production of OH radicals. Results and discussion The median concentrations of ammonia (NH3), nitrous acid (HONO) and nitric acid (HNO3) during whole period of 21 June 2010 - 30 April 2011 were 85, 54, and 57 ppt, respectively. The seasonal cycle was such that in summer the concentrations of all of these gases were the highest, the respective medians were 356, 70, and 81 ppt in June 21 - August 12, and lowest in winter (December - February), the respective medians were 38, 54, and 52 ppt. A very clear diurnal cycle of all these gases was observed, especially in July. In December there were no cyclic diurnal variation of these but in spring, especially in April the

  15. Acidity decline in Antarctic ice cores during the Little Ice Age linked to changes in atmospheric nitrate and sea salt concentrations

    NASA Astrophysics Data System (ADS)

    Pasteris, Daniel; McConnell, Joseph R.; Edwards, Ross; Isaksson, Elizabeth; Albert, Mary R.

    2014-05-01

    Acidity is an important chemical variable that impacts atmospheric and snowpack chemistry. Here we describe composite time series and the spatial pattern of acidity concentration (Acy = H+ - HCO3-) during the last 2000 years across the Dronning Maud Land region of the East Antarctic Plateau using measurements in seven ice cores. Coregistered measurements of the major ion species show that sulfuric acid (H2SO4), nitric acid (HNO3), and hydrochloric acid (HCl) determine greater than 98% of the acidity value. The latter, also described as excess chloride (ExCl-), is shown mostly to be derived from postdepositional diffusion of chloride with little net gain or loss from the snowpack. A strong inverse linear relationship between nitrate concentration and inverse accumulation rate provides evidence of spatially homogenous fresh snow concentrations and reemission rates of nitrate from the snowpack across the study area. A decline in acidity during the Little Ice Age (LIA, 1500-1900 Common Era) is observed and is linked to declines in HNO3 and ExCl- during that time. The nitrate decline is found to correlate well with published methane isotope data from Antarctica (δ13CH4), indicating that it is caused by a decline in biomass burning. The decrease in ExCl- concentration during the LIA is well correlated to published sea surface temperature reconstructions in the Atlantic Ocean, which suggests increased sea salt aerosol production associated with greater sea ice extent.

  16. Electrical resistance response of polyaniline films to water, ethanol, and nitric acid solution

    NASA Astrophysics Data System (ADS)

    Yin, Hong-Xing; Li, Meng-Meng; Yang, H.; Long, Yun-Ze; Sun, Xin

    2010-08-01

    This paper reports on electrical resistance vs. aging time for the response of polyaniline films under exposure to water, ethanol and nitric acid (HNO3) solution. Camphor sulfonic acid-doped polyaniline films were prepared by a “doping-dedoping-redoping" method, the morphology and microstructures of the films were characterized by a scanning electron microscope and an x-ray diffractometer, the electrical resistance was measured by a four-probe method. It was found that a lower amount of water molecules infiltrating the film can decrease the film's resistance possibly due to an enhancement of charge carrier transfer between polyaniline chains, whereas excessive water molecules can swell inter-chain distances and result in a quick increase of resistance. The resistance of the film under exposure to ethanol increases and becomes much larger than the original value. However, HNO3 solution can decrease the film's resistance sharply possibly owing to doping effect of protonic acid. These results can help to understand the conduction mechanism in polyaniline films, and also indicate that the films have potential application in chemical sensors.

  17. Large discharge capacity from carbon electrodes in sulfuric acid with oxidant

    NASA Astrophysics Data System (ADS)

    Inagaki, M.; Iwashita, N.

    The discharge performance of the graphite intercalation compounds in sulfuric acid containing nitric acid (H 2SO 4-GICs) was studied by focusing on the effects of oxidant and carbon nanotexture. A large discharge capacity from H 2SO 4-GICs synthesized by using an excess amount of HNO 3, more than 150 times of the theoretical value (93 mAh/g carbon), was obtained depending on the amount of oxidant added, the discharge current, and the nanotexture of carbon electrode. The experimental results are explained in terms of competition between the de-intercalation of sulfuric acid due to galvanostatic reduction and the re-intercalation due to chemical oxidation by HN03 during discharging. However, a subsidiary reaction decreases the effective amount of HNO 3 on the discharge by a small current and also on the cycle of chemical charging and electrochemical discharging. The oxidant KMnO 4 gave only a little larger capacity for discharge than the theoretical one, because it was reduced to the manganese oxide precipitates during the oxidation of the carbon electrode.

  18. Vapor core propulsion reactors

    NASA Technical Reports Server (NTRS)

    Diaz, Nils J.

    1991-01-01

    Many research issues were addressed. For example, it became obvious that uranium tetrafluoride (UF4) is a most preferred fuel over uranium hexafluoride (UF6). UF4 has a very attractive vaporization point (1 atm at 1800 K). Materials compatible with UF4 were looked at, like tungsten, molybdenum, rhenium, carbon. It was found that in the molten state, UF4 and uranium attacked most everything, but in the vapor state they are not that bad. Compatible materials were identified for both the liquid and vapor states. A series of analyses were established to determine how the cavity should be designed. A series of experiments were performed to determine the properties of the fluid, including enhancement of the electrical conductivity of the system. CFD's and experimental programs are available that deal with most of the major issues.

  19. Fuel Vaporization Effects

    NASA Technical Reports Server (NTRS)

    Bosque, M. A.

    1983-01-01

    A study of the effects of fuel-air preparation characteristics on combustor performance and emissions at temperature and pressure ranges representative of actual gas turbine combustors is discussed. The effect of flameholding devices on the vaporization process and NOx formation is discussed. Flameholder blockage and geometry are some of the elements that affect the recirculation zone characteristics and subsequently alter combustion stability, emissions and performance. A water cooled combustor is used as the test rig. Preheated air and Jet A fuel are mixed at the entrance of the apparatus. A vaporization probe is used to determine percentage of vaporization and a gas sample probe to determine concentration of emissions in the exhaust gases. The experimental design is presented and experimental expected results are discussed.

  20. Proton transfer reactions between nitric acid and acetone, hydroxyacetone, acetaldehyde and benzaldehyde in the solid phase.

    PubMed

    Lasne, Jérôme; Laffon, Carine; Parent, Philippe

    2012-12-01

    The heterogeneous and homogeneous reactions of acetone, hydroxyacetone, acetaldehyde and benzaldehyde with solid nitric acid (HNO(3)) films have been studied with Reflection-Absorption Infrared Spectroscopy (RAIRS) under Ultra-High Vacuum (UHV) conditions in the 90-170 K temperature range. In the bulk or at the surface of the films, nitric acid transfers its proton to the carbonyl function of the organic molecules, producing protonated acetone-H(+), hydroxyacetone-H(+), acetaldehyde-H(+) and benzaldehyde-H(+), and nitrate anions NO(3)(-), a reaction not observed when nitric acid is previously hydrated [J. Lasne, C. Laffon and Ph. Parent, Phys. Chem. Chem. Phys., 2012, 14, 697]. This provides a molecular-scale description of the carbonyl protonation reaction in an acid medium, the first step of the acid-catalyzed condensation of carbonyl compounds, fuelling the growth of secondary organic aerosols (SOA) in the atmosphere. PMID:23090634

  1. Vapor concentration monitor

    DOEpatents

    Bayly, John G.; Booth, Ronald J.

    1977-01-01

    An apparatus for monitoring the concentration of a vapor, such as heavy water, having at least one narrow bandwidth in its absorption spectrum, in a sample gas such as air. The air is drawn into a chamber in which the vapor content is measured by means of its radiation absorption spectrum. High sensitivity is obtained by modulating the wavelength at a relatively high frequency without changing its optical path, while high stability against zero drift is obtained by the low frequency interchange of the sample gas to be monitored and of a reference sample. The variable HDO background due to natural humidity is automatically corrected.

  2. Simultaneous measurements of ammonia and nitric acid over a coniferous forest, Germany

    NASA Astrophysics Data System (ADS)

    Plessow, K.; Zimmermann, F.; Matschullat, J.; Köstner, B.

    2003-04-01

    The atmospheric nitrogen input on an ecosystem consists of the wet deposition of nitrate (NO3-) and ammonium (NH4+) ions via rain, fog, and snow and the dry deposition of N-containing particles and gases, e.g., gaseous nitric acid (HNO3) and ammonia (NH3). Particularly dry deposition represents a significant pathway for the removal of pollutant species from the atmosphere and the addition of nutrients to ecosystems. But inherent problems in quantifying ambient concentrations and the deposition of highly reactive N gases and aerosols often leads to omission of these components from flux studies. Typical concentration ranges and seasonal variability of nitrogen species are quantified at the forest research site Oberbärenburg (Eastern Erzgebirge, Germany). Ambient air concentrations of nitric acid (HNO3), ammonia (NH3) are determined using a honeycomb denuder system as a part of the Partisol 2300 ChemComb 3500 Speciation Sampler (Rupprecht &Patashnick, USA). Aerosol concentrations of nitrate and ammonium are measured using the filter pack unit of the speciation sampler. As additional information concentrations of SO2 and sulphate aerosol are determined simultaneously.Average NH3-N, HNO3-N, and SO2-S ambient concentrations are about 0.4 µg m-3, 0.15 µg m-3, and 1.0 µg m-3, respectively. However, the particulate nitrogen species dominate the studied atmospheric compounds with an overall fraction of 70% to 90%. Ambient ammonia concentrations are strongly dependent on meteorological conditions like air temperature, global radiation, wind speed, relative air and leaf surface humidity. Higher concentrations in the range of 0.75 - 1.25 µg m-3 are found in warm (> 15°C) and dry summer conditions. Smaller values between 0.1 to 0.75 µg m-3 are measured during colder, specially humid and windy conditions. This corresponds to a distinct seasonal variation with average NH3-N-concentrations of 0.2 µg m-3 in autumn and winter, and 0.7 µg m-3 NH3-N in spring and summer. In a

  3. BTSC VAPOR INSTRUSION PRIMER "VAPOR INTRUSION CONSIDERATION FOR REDEVELOPMENT"

    EPA Science Inventory

    This primer is designed for brownfields stakeholders concerned about vapor intrusion, including property owners, real estate developers, and contractors performing environmental site investigations. It provides an overview of the vapor intrusion issue and how it can impact the ap...

  4. Thermogravimetric study of vapor pressure of TATP synthesized without recrystallization.

    PubMed

    Mbah, Jonathan; Knott, Debra; Steward, Scott

    2014-11-01

    This study aims at characterizing the vapor pressure signatures generated by triacetone triperoxide (TATP) that was synthesized without recrystallization by thermogravimmetric analysis (TGA) for exploitation by standoff detection technologies of explosive devices. The thermal behavior of the nonrecrystallized sample was compared with reported values. Any phase change, melting point and decomposition identification were studied by differential scanning calorimeter. Vapor pressures were estimated by the Langmuir method of evaporation from an open surface in a vacuum. Vapor pressures of TATP at different temperatures were calculated using the linear logarithmic relationship obtained from benzoic acid reference standard. Sublimation of TATP was found to follow apparent zero-order kinetics and sublimes at steady rates at 298 K and above. While the enthalpy of sublimation found, 71.7 kJ mol(-1), is in agreement with reported values the vapor pressures deviated significantly. The differences in the vapor pressures behavior are attributable to the synthesis pathway chosen in this study. PMID:25127637

  5. Passive Vaporizing Heat Sink

    NASA Technical Reports Server (NTRS)

    Knowles, TImothy R.; Ashford, Victor A.; Carpenter, Michael G.; Bier, Thomas M.

    2011-01-01

    A passive vaporizing heat sink has been developed as a relatively lightweight, compact alternative to related prior heat sinks based, variously, on evaporation of sprayed liquids or on sublimation of solids. This heat sink is designed for short-term dissipation of a large amount of heat and was originally intended for use in regulating the temperature of spacecraft equipment during launch or re-entry. It could also be useful in a terrestrial setting in which there is a requirement for a lightweight, compact means of short-term cooling. This heat sink includes a hermetic package closed with a pressure-relief valve and containing an expendable and rechargeable coolant liquid (e.g., water) and a conductive carbon-fiber wick. The vapor of the liquid escapes when the temperature exceeds the boiling point corresponding to the vapor pressure determined by the setting of the pressure-relief valve. The great advantage of this heat sink over a melting-paraffin or similar phase-change heat sink of equal capacity is that by virtue of the =10x greater latent heat of vaporization, a coolant-liquid volume equal to =1/10 of the paraffin volume can suffice.

  6. Water vapor lidar

    NASA Technical Reports Server (NTRS)

    Ellingson, R.; Mcilrath, T.; Schwemmer, G.; Wilkerson, T. D.

    1976-01-01

    The feasibility was studied of measuring atmospheric water vapor by means of a tunable lidar operated from the space shuttle. The specific method evaluated was differential absorption, a two-color method in which the atmospheric path of interest is traversed by two laser pulses. Results are reported.

  7. Water vapor diffusion membranes

    NASA Technical Reports Server (NTRS)

    Holland, F. F., Jr.; Smith, J. K.

    1974-01-01

    The program is reported, which was designed to define the membrane technology of the vapor diffusion water recovery process and to test this technology using commercially available or experimental membranes. One membrane was selected, on the basis of the defined technology, and was subjected to a 30-day demonstration trial.

  8. Solvent vapor collector

    DOEpatents

    Ellison, Kenneth; Whike, Alan S.

    1979-01-30

    A solvent vapor collector is mounted on the upstream inlet end of an oven having a gas-circulating means and intended for curing a coating applied to a strip sheet metal at a coating station. The strip sheet metal may be hot and solvent vapors are evaporated at the coating station and from the strip as it passes from the coating station to the oven. Upper and lower plenums within a housing of the collector are supplied with oven gases or air from the gas-circulating means and such gases or air are discharged within the collector obliquely in a downstream direction against the strip passing through that collector to establish downstream gas flows along the top and under surfaces of the strip so as, in turn, to induct solvent vapors into the collector at the coating station. A telescopic multi-piece shroud is usefully provided on the housing for movement between an extended position in which it overlies the coating station to collect solvent vapors released thereat and a retracted position permitting ready cleaning and adjustment of that coating station.

  9. Inorganic acid-catalyzed tautomerization of vinyl alcohol to acetaldehyde

    NASA Astrophysics Data System (ADS)

    Karton, Amir

    2014-01-01

    The vinyl alcohol-acetaldehyde tautomerization reaction has recently received considerable attention as a potential route for the formation of organic acids in the troposphere (Andrews et al., 2012 [7]). We examine the catalytic effect of inorganic acids in the troposphere (e.g. HNO3, H2SO4 and HClO4) on the vinyl alcohol-acetaldehyde tautomerization reaction, by means high-level thermochemical procedures. We show that H2SO4 and HClO4 catalysts lead to near-zero reaction barrier heights for the vinyl alcohol → acetaldehyde reaction, and to low reaction barrier heights in the reverse direction (ΔH298‡=40.6 and 39.5 kJ mol, respectively).

  10. The decrease in Greenland ice-core δ15N of nitrate in the industrial period: influenced by changes in atmospheric acidity?

    NASA Astrophysics Data System (ADS)

    Geng, L.; Cole-Dai, J.; Alexander, B.; Steig, E. J.; Schauer, A. J.; Savarino, J.

    2012-12-01

    Previous study in a central Greenland ice core has revealed a decreasing trend in δ15N of nitrate (δ15N (nitrate)) starting as early as 1850 C.E.. Lake sediment cores from North America show a similar trend in δ15N of total nitrogen starting around 1895 C.E.. The decrease in δ15N has been proposed to be due to the increasing deposition of anthropogenically derived (i.e., fossil fuel combustion) nitrate in the industrial period. However, this interpretation is questioned by measurements of δ15N in NOx and atmospheric nitrate. Here, we present new, annually-resolved records of δ15N (nitrate) and major ion concentrations (Cl-, NO3-, SO42-, Na+, NH4+, K+, Mg2+, and Ca2+) obtained from two central Greenland ice cores. The results (Figure 1) indicate that the significant decrease in δ15N is coincident with an increase in acidity (H+ concentration estimated based on ionic balance) beginning around 1895 C.E., which is about 50 years earlier than the start of the increase in nitrate concentration (~1945 C.E.) . This observation suggests that it is likely the acidity change, instead of the input of anthropogenic nitrate, triggered the decrease in ice-core δ15N (nitrate). Atmospheric aerosol acidity influences the partitioning of atmospheric nitrate between its gaseous (HNO3) and particulate (p-NO3-) phases, resulting in a depletion of δ15N in HNO3 relative to p-NO3-. If atmospheric nitrate is transported to central Greenland preferentially in its gaseous form (HNO3), which is an open question, a decrease in ice-core δ15N (nitrate) would be expected with an increase in atmospheric acidity. We will examine the relationships between δ15N (nitrate) and the ice-core records of acidity, and HNO3, to discern the processes from changes in atmospheric acidity to the observed variability in ice core δ15N (nitrate) during the Industrial era.igure 1. The annual NO3- (blue curve), H+ (black curve) concentrations, and annual δ15N (nitrate) (red curve, y-axis is reversely

  11. Enthalpy of Vaporization and Vapor Pressures: An Inexpensive Apparatus

    ERIC Educational Resources Information Center

    Battino, Rubin; Dolson, David A.; Hall, Michael A.; Letcher, Trevor M.

    2007-01-01

    A simple and inexpensive method to determine the enthalpy of vaporization of liquids by measuring vapor pressure as a function of temperature is described. The vapor pressures measured with the stopcock cell were higher than the literature values and those measured with the sidearm rubber septum cell were both higher and lower than literature…

  12. BioVapor Model Evaluation

    EPA Science Inventory

    General background on modeling and specifics of modeling vapor intrusion are given. Three classical model applications are described and related to the problem of petroleum vapor intrusion. These indicate the need for model calibration and uncertainty analysis. Evaluation of Bi...

  13. Daily Changes in CO2 and Water Vapor Exchange, Chlorophyll Fluorescence, and Leaf Water Relations in the Halophyte Mesembryanthemum crystallinum during the Induction of Crassulacean Acid Metabolism in Response to High NaCl Salinity 1

    PubMed Central

    Winter, Klaus; Gademann, Rolf

    1991-01-01

    Simultaneous measurements of net CO2 exchange, water vapor exchange, and leaf water relations were performed in Mesembryanthemum crystallinum during the development of crassulacean acid metabolism (CAM) in response to high NaCl salinity in the rooting medium. Determinations of chlorophyll a fluorescence were used to estimate relative changes in electron transport rate. Alterations in leaf mass per unit area, which—on a short-term basis—largely reflect changes in water content, were recorded continuously with a beta-gauge. Turgor pressure of mesophyll cells was determined with a pressure probe. As reported previously (K Winter, DJ von Willert [1972] Z Pflanzenphysiol 67: 166-170), recently expanded leaves of plants grown under nonsaline conditions showed gas-exchange characteristics of a C3 plant. Although these plants were not exposed to any particular stress treatment, water content and turgor pressure regularly decreased toward the end of the 12 hour light periods and recovered during the following 12 hours of darkness. When the NaCl concentration of the rooting medium was raised to 400 millimolar, in increments of 100 millimolar given at the onset of the photoperiods for 4 consecutive days, leaf water content and turgor pressure decreased by as much as 30 and 60%, respectively, during the course of the photoperiods. These transient decreases probably triggered the induction of the biochemical machinery which is required for CAM to operate. After several days at 400 millimolar NaCl, when leaves showed features typical of CAM, overall turgor pressure and leaf mass per unit area had increased above the levels before onset of the salt treatment, and diurnal alterations in leaf water content were reduced. Net carbon gain during photoperiods and average intercellular CO2 partial pressures at which net CO2 uptake occurred, progressively decreased upon salinization. Reversible diurnal depressions in leaf conductance and net CO2 uptake, with minima recorded in the

  14. Aircraft measurements of ammonia and nitric acid in the lower troposphere

    NASA Astrophysics Data System (ADS)

    Lebel, P. J.; Hoell, J. M.; Levine, J. S.; Vay, S. A.

    1985-06-01

    The first simultaneous measurements of ammonia and nitric acid in the troposphere have been made from an aircraft using a tungsten oxide denuder system. Vertical profiles of NH3 and HNO3 taken over coastal Virginia and Maryland in March and September, 1983, at altitudes from 150 m to 3000 m, show mixing ratios that decrease with altitude. Ammonia profiles show substantial seasonal variation, while nitric acid profiles do not. Using the measured profiles and a one-dimensional photochemical model, lifetimes due to heterogeneous loss of one day for HNO3 and ten days for NH3 are calculated. In contrast, NH3 profiles up to 5300 m over the North Atlantic Ocean during August 1982 show mixing ratios that increase slightly with altitude. These data represent the first ammonia profiles measured over the ocean. It is suggested that the increase in NH3 with altitude is a result of an ammonia-rich continental air mass advected over the ocean, followed by the dissolution of NH3 in the marine boundary layer on water-covered sea salt particles.

  15. Study of the effect of the acid-base surface properties of ZnO, Fe{sub 2}O{sub 3} and ZnFe{sub 2}O{sub 4} oxides on their gas sensitivity to ethanol vapor

    SciTech Connect

    Karpova, S. S. Moshnikov, V. A.; Maksimov, A. I.; Mjakin, S. V.; Kazantseva, N. E.

    2013-08-15

    Binary (ZnO, Fe{sub 2}O{sub 3}) and ternary (ZnFe{sub 2}O{sub 4}) gas-sensitive oxide materials are synthesized, and the correlation between their sensitivity to ethanol vapor and the functional chemical composition of the surface is studied by X-ray photoelectron spectroscopy and by the technique of the adsorption of acid-base indicators. It is found that the sensitivity to ethanol increases with increasing content of Broensted acid sites with the acidity index pK{sub a} Almost-Equal-To 2.5 and with increasing percentage of surface oxygen involved in OH/CO{sub 3}/C-O groups. This interrelation is attributed to the specific features of interaction between ethanol molecules and hydroxyl groups on the surface of the oxides.

  16. Effects of acid on the microstructures and properties of three-dimensional TiO2 hierarchical structures by solvothermal method

    PubMed Central

    2012-01-01

    Three-dimensional (3D) TiO2 hierarchical structures with various microstructures have been successfully synthesized via a surfactant-free and single-step solvothermal route, in which hydrochloric acid (HCl), nitric acid (HNO3), and acetic acid (HAc) are employed as the acid medium, respectively. The effects of acid medium on the microstructures and properties of 3D TiO2 hierarchical structure have been studied. The results indicate that 3D dandelion-like microspheres assembled of radial rutile nanorods are obtained in the sample prepared with HCl. Both the fraction of rutile and the diameter of nanorod enhance with the increasing HCl concentration. For the products derived from either HNO3 or HAc, 3D spheres composed of anatase nanoparticles are present. The 3D dandelion-like TiO2 hierarchical structures show low reflectance and efficient light harvesting since this ordered rod geometry offers a light-transfer path for incident light as well as multiple reflective and scattering effects. Moreover, 3D TiO2 with this unique topology shows superior photocatalytic activity despite low surface area, which can be ascribed to the enhanced light harvesting, fast electron transport, and low electron/hole recombination loss. PMID:22500985

  17. A new method for measuring vapor emissions

    SciTech Connect

    Knaebel, K.S.; Yeoman, L.D.

    1996-12-31

    A new approach for measuring point-source emissions of volatile organic compounds, acidic vapors, and other species is presented. The basic principle is that the amount emitted is determined directly, by mass, and is cumulative rather than intermittent. As a result, wide fluctuations of concentration and erratic flow behavior are accommodated without affecting the accuracy of the measured emission rate. The vapors are retained by a sorbent, such as activated carbon, ion exchange resin, or zeolite, or a combination of those. Validation tests have been conducted in which a known quantity of vapor in a carrier gas was admitted to the test unit, and that was compared with the amount measured. The vapor comprised a single VOC, a mixture of VOCs, or a mixture of a VOC with water. Conditions studied were: the compound or mixture of compounds, concentration, carrier gas, flow rate, and adsorbent. In some tests the VOC was admitted intermittently. The VOCs included: hexane, acetone, toluene, vinyl acetate, and 1,1,1 trichloroethane. The average absolute error of the delivered and measured VOC emission rates was 6.8% and the standard deviation was 3.4%. 6 refs., 6 figs., 3 tabs.

  18. Stratified vapor generator

    DOEpatents

    Bharathan, Desikan; Hassani, Vahab

    2008-05-20

    A stratified vapor generator (110) comprises a first heating section (H.sub.1) and a second heating section (H.sub.2). The first and second heating sections (H.sub.1, H.sub.2) are arranged so that the inlet of the second heating section (H.sub.2) is operatively associated with the outlet of the first heating section (H.sub.1). A moisture separator (126) having a vapor outlet (164) and a liquid outlet (144) is operatively associated with the outlet (124) of the second heating section (H.sub.2). A cooling section (C.sub.1) is operatively associated with the liquid outlet (144) of the moisture separator (126) and includes an outlet that is operatively associated with the inlet of the second heating section (H.sub.2).

  19. Chemical vapor deposition growth

    NASA Technical Reports Server (NTRS)

    Ruth, R. P.; Manasevit, H. M.; Kenty, J. L.; Moudy, L. A.; Simpson, W. I.; Yang, J. J.

    1976-01-01

    A chemical vapor deposition (CVD) reactor system with a vertical deposition chamber was used for the growth of Si films on glass, glass-ceramic, and polycrystalline ceramic substrates. Silicon vapor was produced by pyrolysis of SiH4 in a H2 or He carrier gas. Preliminary deposition experiments with two of the available glasses were not encouraging. Moderately encouraging results, however, were obtained with fired polycrystalline alumina substrates, which were used for Si deposition at temperatures above 1,000 C. The surfaces of both the substrates and the films were characterized by X-ray diffraction, reflection electron diffraction, scanning electron microscopy optical microscopy, and surface profilometric techniques. Several experiments were conducted to establish baseline performance data for the reactor system, including temperature distributions on the sample pedestal, effects of carrier gas flow rate on temperature and film thickness, and Si film growth rate as a function of temperature.

  20. Water vaporization on Ceres

    NASA Technical Reports Server (NTRS)

    A'Hearn, Michael F.; Feldman, Paul D.

    1992-01-01

    A search is presently conducted for OH generated by the photodissociation of atmospheric water vapor in long-exposure IUE spectra of the region around Ceres. A statistically significant detection of OH is noted in an exposure off the northern limb of Ceres after perihelion. The amount of OH is consistent with a polar cap that might be replenished during winter by subsurface percolation, but which dissipates in summer.

  1. Filter vapor trap

    DOEpatents

    Guon, Jerold

    1976-04-13

    A sintered filter trap is adapted for insertion in a gas stream of sodium vapor to condense and deposit sodium thereon. The filter is heated and operated above the melting temperature of sodium, resulting in a more efficient means to remove sodium particulates from the effluent inert gas emanating from the surface of a liquid sodium pool. Preferably the filter leaves are precoated with a natrophobic coating such as tetracosane.

  2. [Determination of Sb and Bi in 24 international geological reference materials by using pressurized acid digestion-ICP-MS].

    PubMed

    Hu, Zhao-chu; Gao, Shan; Liu, Xiao-ming; Yuan, Hong-lin; Liu, Ye; Diwu, Chun-rong

    2007-12-01

    The authors studied in detail the memory effect of Bi, Sb, As and Te in ICP-MS. The produced memory effects of these element were in the order of Bi>Sb>Te>As. Bi was seriously adsorbed by the polypropylene sample storing bottle and the sample introduction system in the low nitric acid medium (0.01%-1% HNO3). The washout effect of 0.1% HF was found to be better than those of 6% HNO3 and 0.1% HClO4. Under the given experiment conditions, the instrumental limit of detection was 0.001 and 0.0001 ng x mL(-1) for Sb and Bi, respectively. The authors report the determination of Sb and Bi in 24 international geological reference materials by using pressurized acid digestion-ICP-MS (including AGV-2, BHVO-2, BCR-2, etc.). Most of the results were found to be in reasonable agreement with the reported values in the literature. The authors' determined values of Sb for GSR-1 (granite; 0.30 microg x g(-1)) and JP-1 (peridotite; 0.045 microg x g(-1)) are obviously higher than those reported values. This is attributed to the efficient pressurized acid digestion, which is generally much more efficient than conventional wet digestions for insoluble minerals. PMID:18330312

  3. The vapor pressures of explosives

    SciTech Connect

    Ewing, Robert G.; Waltman, Melanie J.; Atkinson, David A.; Grate, Jay W.; Hotchkiss, Peter

    2013-01-05

    The vapor pressures of many explosive compounds are extremely low and thus determining accurate values proves difficult. Many researchers, using a variety of methods, have measured and reported the vapor pressures of explosives compounds at single temperatures, or as a function of temperature using vapor pressure equations. There are large variations in reported vapor pressures for many of these compounds, and some errors exist within individual papers. This article provides a review of explosive vapor pressures and describes the methods used to determine them. We have compiled primary vapor pressure relationships traceable to the original citations and include the temperature ranges for which they have been determined. Corrected values are reported as needed and described in the text. In addition, after critically examining the available data, we calculate and tabulate vapor pressures at 25 °C.

  4. Removing perfluorooctane sulfonate and perfluorooctanoic acid from solid matrices, paper, fabrics, and sand by mineral acid suppression and supercritical carbon dioxide extraction.

    PubMed

    Chen, Hsiang-Yu; Liao, Weisheng; Wu, Ben-Zen; Nian, Hungchi; Chiu, KongHwa; Yak, Hwa-Kwang

    2012-09-01

    The removal of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) from solid matrices has received considerable attention because of the environmental persistence, bioaccumulation, and potential toxicity of these compounds. This study presents a simple method using concentrated HNO(3) as a suppression agent, and methanol-modified supercritical carbon dioxide (Sc-CO(2)) extraction for removing PFOS and PFOA from solid matrices. The optimal conditions were 16 M HNO(3) and 20% (v/v) methanol containing Sc-CO(2), under a pressure of 20.3 MPa and a temperature of 50 °C. Extraction time was set at 70 min (40 min for static and 30 min for dynamic extraction). PFOA and PFOS were identified and quantitated by liquid chromatography/mass spectrometry. The extraction efficiencies (with double extractions) were close to 100% for PFOA and 80% for PFOS for both paper and fabric matrices. The extraction efficiencies for sand were approximately 77% for PFOA and 59% for PFOS. The results show that this method is accurate, and effective, and that it provides a promising and convenient approach to remediate the environment of hazardous PFOA and PFOS contamination. PMID:22748389

  5. VAPOR PRESSURES AND HEATS OF VAPORIZATION OF PRIMARY COAL TARS

    SciTech Connect

    Eric M. Suuberg; Vahur Oja

    1997-07-01

    This project had as its main focus the determination of vapor pressures of coal pyrolysis tars. It involved performing measurements of these vapor pressures and from them, developing vapor pressure correlations suitable for use in advanced pyrolysis models (those models which explicitly account for mass transport limitations). This report is divided into five main chapters. Each chapter is a relatively stand-alone section. Chapter A reviews the general nature of coal tars and gives a summary of existing vapor pressure correlations for coal tars and model compounds. Chapter B summarizes the main experimental approaches for coal tar preparation and characterization which have been used throughout the project. Chapter C is concerned with the selection of the model compounds for coal pyrolysis tars and reviews the data available to us on the vapor pressures of high boiling point aromatic compounds. This chapter also deals with the question of identifying factors that govern the vapor pressures of coal tar model materials and their mixtures. Chapter D covers the vapor pressures and heats of vaporization of primary cellulose tars. Chapter E discusses the results of the main focus of this study. In summary, this work provides improved understanding of the volatility of coal and cellulose pyrolysis tars. It has resulted in new experimentally verified vapor pressure correlations for use in pyrolysis models. Further research on this topic should aim at developing general vapor pressure correlations for all coal tars, based on their molecular weight together with certain specific chemical characteristics i.e. hydroxyl group content.

  6. Role of Co-Vapors in Vapor Deposition Polymerization

    NASA Astrophysics Data System (ADS)

    Lee, Ji Eun; Lee, Younghee; Ahn, Ki-Jin; Huh, Jinyoung; Shim, Hyeon Woo; Sampath, Gayathri; Im, Won Bin; Huh, Yang–Il; Yoon, Hyeonseok

    2015-02-01

    Polypyrrole (PPy)/cellulose (PPCL) composite papers were fabricated by vapor phase polymerization. Importantly, the vapor-phase deposition of PPy onto cellulose was assisted by employing different co-vapors namely methanol, ethanol, benzene, water, toluene and hexane, in addition to pyrrole. The resulting PPCL papers possessed high mechanical flexibility, large surface-to-volume ratio, and good redox properties. Their main properties were highly influenced by the nature of the co-vaporized solvent. The morphology and oxidation level of deposited PPy were tuned by employing co-vapors during the polymerization, which in turn led to change in the electrochemical properties of the PPCL papers. When methanol and ethanol were used as co-vapors, the conductivities of PPCL papers were found to have improved five times, which was likely due to the enhanced orientation of PPy chain by the polar co-vapors with high dipole moment. The specific capacitance of PPCL papers obtained using benzene, toluene, water and hexane co-vapors was higher than those of the others, which is attributed to the enlarged effective surface area of the electrode material. The results indicate that the judicious choice and combination of co-vapors in vapor-deposition polymerization (VDP) offers the possibility of tuning the morphological, electrical, and electrochemical properties of deposited conducting polymers.

  7. The toxicity of inhaled methanol vapors

    SciTech Connect

    Kavet, R.; Nauss, K.M. )

    1990-01-01

    Methanol could become a major automotive fuel in the U.S., and its use may result in increased exposure of the public to methanol vapor. Nearly all of the available information on methanol toxicity in humans relates to the consequences of acute, rather than chronic, exposures. Acute methanol toxicity evolves in a well-understood pattern and consists of an uncompensated metabolic acidosis with superimposed toxicity to the visual system. The toxic properties of methanol are rooted in the factors that govern both the conversion of methanol to formic acid and the subsequent metabolism of formate to carbon dioxide in the folate pathway. In short, the toxic syndrome sets in if formate generation continues at a rate that exceeds its rate of metabolism. Current evidence indicates that formate accumulation will not challenge the metabolic capacity of the folate pathway at the anticipated levels of exposure to automotive methanol vapor.117 references.

  8. The toxicity of inhaled methanol vapors.

    PubMed

    Kavet, R; Nauss, K M

    1990-01-01

    Methanol could become a major automotive fuel in the U.S., and its use may result in increased exposure of the public to methanol vapor. Nearly all of the available information on methanol toxicity in humans relates to the consequences of acute, rather than chronic, exposures. Acute methanol toxicity evolves in a well-understood pattern and consists of an uncompensated metabolic acidosis with superimposed toxicity to the visual system. The toxic properties of methanol are rooted in the factors that govern both the conversion of methanol to formic acid and the subsequent metabolism of formate to carbon dioxide in the folate pathway. In short, the toxic syndrome sets in if formate generation continues at a rate that exceeds its rate of metabolism. Current evidence indicates that formate accumulation will not challenge the metabolic capacity of the folate pathway at the anticipated levels of exposure to automotive methanol vapor. PMID:2264926

  9. The NH4--NO3--Cl--SO42--H2O Aerosol System and its Gas Phase Precursors at a Rural Site in the Amazon Basin: How Relevant are Mineral Cations and Soluble Organic Acids?

    NASA Astrophysics Data System (ADS)

    Helas, G.; Trebs, I.; Metzger, S.; Meixner, F. X.; Hoffer, A.; Moura, M. A.; da Silva, R. S.; Rudich, Y.; Falkovich, A.; Artaxo, P.; Slanina, J.; Andreae, M. O.

    2004-12-01

    We performed real-time measurements of ammonia (NH3), nitric acid (HNO3), hydrochloric acid (HCl), sulfur dioxide (SO2) and the water-soluble inorganic aerosol species, ammonium (NH4+), nitrate (NO3-), chloride (Cl-), and sulfate (SO42-) at a pasture site in the Amazon Basin (Rondônia, Brazil). The measurements were made during the closing of the dry season (biomass burning), the transition period, and the onset of the wet season (clean conditions) (12 Sep. to 14 Nov. 2002, LBA-SMOCC*), using a wet-annular denuder (WAD) in combination with a Steam-Jet Aerosol Collector (SJAC). Real-time data were combined with measurements of mineral cations (K+ , Ca2+ , Mg2+) and low-molecular weight (LMW) polar organic acids on 12-, 24- and 48-hours integrated filter samples. The contribution of inorganic species to the fine particulate mass (Dp < 2.5 um)was frequently below 20 % by mass, indicating the preponderance of organic matter. The high abundance of NH3 at the sampling site substantially influenced gas/aerosol partitioning processes, being responsible for complete acid neutralization through the aerosol phase forming aerosol NH4+. Balances of aerosol fine mode inorganic ionic charges indicated the role of dissociated low-molecular weight (LMW) polar organic acids, which were apparently neutralized by excess NH3. The measured concentration products of NH3 x HNO3 and NH3 x HCl persistently remained below the theoretical equilibrium dissociation constants of the NH3/HNO3/NH4NO3 and NH3/HCl/NH4Cl systems during daytime (RH < 90 %). The application of thermodynamic equilibrium models (EQMs), namely EQSAM, ISORROPIA, GEFMN and SCAPE2 indicated that balancing of aerosol NO3-, Cl- and SO42- preferentially proceeded via mineral cations (particularly pyrogenic K+) during daytime. At nighttime (RH > 90 %) NH4NO3 and NH4Cl were predicted to be formed in the aqueous aerosol phase. Cl- was largely driven out of the aerosol phase by reaction of KCl with HNO3 and H2SO4. As shown by an

  10. Hydrazine-Vapor Samplers

    NASA Technical Reports Server (NTRS)

    Young, Rebecca; Mcbrearty, Charles; Curran, Dan; Leavitt, Nilgun

    1994-01-01

    Active sampling unit capable of detecting hydrazine and monomethyl hydrazine vapors at levels as low as 10 ppb in air developed. Includes detachable badge holder and pump which draws air through badge holder at selectable rate of 1 or 2 L/min. Coated strip in each badge designed to align with air passage in badge holder. Two types of badge holders constructed: one has open-face design for general monitoring of air in open spaces, while other has closed-face design with viewing window and intended for sampling through small openings to detect leaks.

  11. Warm Vapor Atom Interferometer

    NASA Astrophysics Data System (ADS)

    Biedermann, Grant; Wheeler, David; Jau, Yuan-Yu; McGuinness, Hayden

    2014-05-01

    We present a light pulse atom interferometer using room temperature rubidium vapor. Doppler sensitive stimulated Raman transitions forming the atom optical elements inherently select a cold velocity group for the interferometer. The interferometer is configured to be sensitive to accelerations. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  12. Enhancement of volatile fatty acids production from rice straw via anaerobic digestion with chemical pretreatment.

    PubMed

    Park, Gwon Woo; Kim, Ilgook; Jung, Kwonsu; Seo, Charles; Han, Jong-In; Chang, Ho Nam; Kim, Yeu-Chun

    2015-08-01

    Rice straw is one of the most abundant renewable biomass sources and was selected as the feedstock for the production of volatile fatty acids (VFAs) from which microbial biodiesel can be produced. Two kinds of chemical pretreatments involving nitric acid and sodium hydroxide were investigated at 150 °C with 20 min of reaction time. The nitric acid pretreatment generated the most hemicellulose hydrolyzate, while significant reduction of the lignin occurred with sodium hydroxide pretreatment. Anaerobic digestion of 20 g/L rice straw yielded 6.00 and 7.09 g VFAs/L with 0.5% HNO3 and 2% NaOH, respectively. The VFAs yield with 2% NaOH was 0.35 g/g. PMID:25764527

  13. Kinetics of the reaction of hydroxyl radicals with nitric acid

    NASA Technical Reports Server (NTRS)

    Margitan, J. J.; Watson, R. T.

    1982-01-01

    An extensive study was made of the reaction of hydroxyl radicals with nitric acid in a laser photolysis-resonance fluorescence system. A 266 nm laser was used to photolyze HNO3 in the temperature range 225-415 K at pressures of 20-300 torr. A temperature dependence was detected below room temperature, with a leveling off at 298 K and a wide spread in the rate constants. A pressure dependence was observed over the entire range and was more pronounced at lower temperatures. The results are noted to be in agreement with those of previous investigations. However, the wide range of rate constants are suggested to be a problem for stratospheric HO(x) modeling for anthropogenic effects. No explanation could be given of the varying results obtained by other investigators regarding the kinetics of the reactions.

  14. Hydrolysis kinetics of lead silicate glass in acid solution

    NASA Astrophysics Data System (ADS)

    Rahimi, Rafi Ali; Sadrnezhaad, Sayed Khatibuleslam; Raisali, Gholamreza; Hamidi, Amir

    2009-06-01

    Hydrolysis kinetics of the lead silicate glass (LSG) with 40 mol% PbO in 0.5 N HNO 3 aqueous acid solution was investigated. The surface morphology and the gel layer thickness were studied by scanning electron microscopy (SEM) micrographs. Energy dispersive X-ray spectroscopy (EDS) and inductively coupled plasma spectroscopy (ICP) were used to determine the composition of the gel layer and the aqueous solution, respectively. The silicon content of the dissolution products was determined by using weight-loss data and compositions of the gel layer and the solution. The kinetic parameters were determined using the shrinking-core-model (SCM) for rate controlling step. The activation energy obtained for hydrolysis reaction was Qche = 56.07 kJ/mole. The diffusion coefficient of the Pb ions from the gel layer was determined by using its concentration in solution and in LSG. The shrinkage of the sample and the gel layer thickness during dissolution process were determined.

  15. 137Cs desorption from lichen using acid solutions

    NASA Astrophysics Data System (ADS)

    Čučulović, A. A.; Veselinović, D.; Miljanić, S. S.

    2009-09-01

    Desoprtion of 137Cs from samples of Cetraria islandica lichen using HCl ( A) and HNO3 ( B) acid solutions with pH values from 2.00 to 3.75 was investigated. After five consecutive desorptions lasting 24 h it was shown that between 52.2% (solution B pH 3.28) and 72.2% (solution A pH 2.00) of 137Cs was desorbed from the lichen and the initial desorptions were the most successful. Lichen desorbed with the stated solutions did not undergo structural changes. The amount of absorbed water from solutions A and B, used for desorption from lichen, in relation to the starting volume (expressed in %) showed that solution concentration did not take place. Lichen act as neutralizing agents because the pH of the lichen thallus is higher than the pH value of the solution used

  16. The effect of the Mt. Pinatubo aerosol on the NHO3 column over Mauna Loa, Hawaii

    NASA Technical Reports Server (NTRS)

    David, Shelle J.; Murcray, Frank J.; Goldman, Aaron; Rinsland, Curtis P.; Murcray, David G.

    1994-01-01

    A very high resolution infrared solar spectrometer system for the Network for Detection of Stratospheric Change has been routinely operated at the Mauna Loa Observatory in Hawaii since November, 1991. Solar absorption spectra are normally taken one day a week at sunrise. We report the analysis of these spectra for the vertical column amount of nitric acid (HNO3) vapor. The observations began four months after the arrival of volcanic aerosols from Mt. Pinatubo over the site. Although quite variable, total HNO3 columns were initially about 7 x 10(exp 15) molecules/sq cm and have decreased about 30% in the following two years.

  17. Vapor spill pipe monitor

    NASA Astrophysics Data System (ADS)

    Bianchini, G. M.; McRae, T. G.

    1983-06-01

    The invention is a method and apparatus for continually monitoring the composition of liquefied natural gas flowing from a spill pipe during a spill test by continually removing a sample of the LNG by means of a probe, gasifying the LNG in the probe, and sending the vaporized LNG to a remote IR gas detector for analysis. The probe comprises three spaced concentric tubes surrounded by a water jacket which communicates with a flow channel defined between the inner and middle, and middle and outer tubes. The inner tube is connected to a pump for providing suction, and the probe is positioned in the LNG flow below the spill pipe with the tip oriented partly downward so that LNG is continuously drawn into the inner tube through a small orifice. The probe is made of a high thermal conductivity metal. Hot water is flowed through the water jacket and through the flow channel between the three tubes to provide the necessary heat transfer to flash vaporize the LNG passing through the inner channel of the probe. The gasified LNG is transported through a connected hose or tubing extending from the probe to a remote IR sensor which measures the gas composition.

  18. Vapor spill pipe monitor

    DOEpatents

    Bianchini, G.M.; McRae, T.G.

    1983-06-23

    The invention is a method and apparatus for continually monitoring the composition of liquefied natural gas flowing from a spill pipe during a spill test by continually removing a sample of the LNG by means of a probe, gasifying the LNG in the probe, and sending the vaporized LNG to a remote ir gas detector for analysis. The probe comprises three spaced concentric tubes surrounded by a water jacket which communicates with a flow channel defined between the inner and middle, and middle and outer tubes. The inner tube is connected to a pump for providing suction, and the probe is positioned in the LNG flow below the spill pipe with the tip oriented partly downward so that LNG is continuously drawn into the inner tube through a small orifice. The probe is made of a high thermal conductivity metal. Hot water is flowed through the water jacket and through the flow channel between the three tubes to provide the necessary heat transfer to flash vaporize the LNG passing through the inner channel of the probe. The gasified LNG is transported through a connected hose or tubing extending from the probe to a remote ir sensor which measures the gas composition.

  19. Biofiltration of methanol vapor

    SciTech Connect

    Shareefdeen, Z.; Baltzis, B.C. ); Oh, Youngsook; Bartha, R. )

    1993-03-05

    Biofiltration of solvent and fuel vapors may offer a cost-effective way to comply with increasingly strict air emission standards. An important step in the development of this technology is to derive and validate mathematical models of the biofiltration process for predictive and scaleup calculations. For the study of methanol vapor biofiltration, an 8-membered bacterial consortium was obtained from methanol-exposed soil. The bacteria were immobilized on solid support and packed into a 5-cm diameter, 60-cm-high column provided with appropriate flowmeters and sampling ports. The solid support was prepared by mixing two volumes of peat with three volumes of perlite particles. Two series of experiments were performed. In the first, the inlet methanol concentration was kept constant while the superficial air velocity was varied from run to run. In the second series, the air flow rate (velocity) was kept constant while the inlet methanol concentration was varied. The unit proved effective in removing methanol at rates up to 112.8 g h[sup [minus]1] m[sup [minus]3] packing. A mathematical model has been derived and validated. The model described and predicted experimental results closely. Both experimental data and model predictions suggest that the methanol biofiltration process was limited by oxygen diffusion and methanol degradation kinetics.

  20. INTERCOMPARISON OF ATMOSPHERIC NITRIC ACID MEASUREMENTS AT ELEVATED AMBIENT CONCENTRATIONS

    EPA Science Inventory

    Several methods for measurement of ambient HNO3 were compared over a 9-day period during the Carbonaceous Species Methods Comparison Study at Glendora, CA, in August 1986. ourly averaged HNO3 concentrations were in the range 0.5-25 ppbv, with hourly maxima each day in excess of 1...

  1. NITRIC ACID-AIR DIFFUSION COEFFICIENT: EXPERIMENTAL DETERMINATION

    EPA Science Inventory

    Trace gaseous HNO3 in air is removed in a laminar flow nylon tube. The HNO3 deposition pattern was obtained by sectioning the tube, extracting with an aqueous solution, and measuring the concentration by ion chromatography. Mass transport analysis of the deposition pattern demons...

  2. Detection of explosives, narcotics, and taggant vapors by an ion mobility spectrometry particle detector

    NASA Astrophysics Data System (ADS)

    Ritchie, Robert K.; Thomson, Paul C.; DeBono, Reno F.; Danylewich-May, Lucy L.; Kim, Lena

    1994-03-01

    Methods of analyzing vapors in an IMS explosives/narcotics detector that is primarily designed for particle collection were investigated, with emphasis on nitroglycerin explosive, and acetic and benzoic acid contaminants in narcotics. A preconcentration step is required because expected vapor concentrations are low. NG adsorption and retention behavior on coated teflon filters that are compatible with the IMS sample desorption system is reported, including the effects of adsorbent, and sampling flow rate, time and volume. Similar investigations were carried out for acetic and benzoic acid vapors, and a gold-plated nickel mesh was selected as the most appropriate IMS-compatible filter for these materials. Vapor sampling flow rates and volumes are much lower than those used in particle sampling. Examples of NG and benzoic acid vapor detection in real and simulated applications are discussed.

  3. Chemical vapor deposition growth

    NASA Technical Reports Server (NTRS)

    Ruth, R. P.; Manasevit, H. M.; Kenty, J. L.; Moudy, L. A.; Simpson, W. I.; Yang, J. J.

    1976-01-01

    The chemical vapor deposition (CVD) method for the growth of Si sheet on inexpensive substrate materials is investigated. The objective is to develop CVD techniques for producing large areas of Si sheet on inexpensive substrate materials, with sheet properties suitable for fabricating solar cells meeting the technical goals of the Low Cost Silicon Solar Array Project. Specific areas covered include: (1) modification and test of existing CVD reactor system; (2) identification and/or development of suitable inexpensive substrate materials; (3) experimental investigation of CVD process parameters using various candidate substrate materials; (4) preparation of Si sheet samples for various special studies, including solar cell fabrication; (5) evaluation of the properties of the Si sheet material produced by the CVD process; and (6) fabrication and evaluation of experimental solar cell structures, using standard and near-standard processing techniques.

  4. Vapor compression distillation module

    NASA Technical Reports Server (NTRS)

    Nuccio, P. P.

    1975-01-01

    A Vapor Compression Distillation (VCD) module was developed and evaluated as part of a Space Station Prototype (SSP) environmental control and life support system. The VCD module includes the waste tankage, pumps, post-treatment cells, automatic controls and fault detection instrumentation. Development problems were encountered with two components: the liquid pumps, and the waste tank and quantity gauge. Peristaltic pumps were selected instead of gear pumps, and a sub-program of materials and design optimization was undertaken leading to a projected life greater than 10,000 hours of continuous operation. A bladder tank was designed and built to contain the waste liquids and deliver it to the processor. A detrimental pressure pattern imposed upon the bladder by a force-operated quantity gauge was corrected by rearranging the force application, and design goals were achieved. System testing has demonstrated that all performance goals have been fulfilled.

  5. THERMALLY OPERATED VAPOR VALVE

    DOEpatents

    Dorward, J.G. Jr.

    1959-02-10

    A valve is presented for use in a calutron to supply and control the vapor to be ionized. The invention provides a means readily operable from the exterior of the vacuum tank of the apparatuss without mechanical transmission of forces for the quick and accurate control of the ionizing arc by a corresponding control of gas flow theretos thereby producing an effective way of carefully regulating the operation of the calutron. The invention consists essentially of a tube member extending into the charge bottle of a calutron devices having a poppet type valve closing the lower end of the tube. An electrical heating means is provided in the valve stem to thermally vary the length of the stem to regulate the valve opening to control the flow of material from the charge bottle.

  6. Constrained Vapor Bubble

    NASA Technical Reports Server (NTRS)

    Huang, J.; Karthikeyan, M.; Plawsky, J.; Wayner, P. C., Jr.

    1999-01-01

    The nonisothermal Constrained Vapor Bubble, CVB, is being studied to enhance the understanding of passive systems controlled by interfacial phenomena. The study is multifaceted: 1) it is a basic scientific study in interfacial phenomena, fluid physics and thermodynamics; 2) it is a basic study in thermal transport; and 3) it is a study of a heat exchanger. The research is synergistic in that CVB research requires a microgravity environment and the space program needs thermal control systems like the CVB. Ground based studies are being done as a precursor to flight experiment. The results demonstrate that experimental techniques for the direct measurement of the fundamental operating parameters (temperature, pressure, and interfacial curvature fields) have been developed. Fluid flow and change-of-phase heat transfer are a function of the temperature field and the vapor bubble shape, which can be measured using an Image Analyzing Interferometer. The CVB for a microgravity environment, has various thin film regions that are of both basic and applied interest. Generically, a CVB is formed by underfilling an evacuated enclosure with a liquid. Classification depends on shape and Bond number. The specific CVB discussed herein was formed in a fused silica cell with inside dimensions of 3x3x40 mm and, therefore, can be viewed as a large version of a micro heat pipe. Since the dimensions are relatively large for a passive system, most of the liquid flow occurs under a small capillary pressure difference. Therefore, we can classify the discussed system as a low capillary pressure system. The studies discussed herein were done in a 1-g environment (Bond Number = 3.6) to obtain experience to design a microgravity experiment for a future NASA flight where low capillary pressure systems should prove more useful. The flight experiment is tentatively scheduled for the year 2000. The SCR was passed on September 16, 1997. The RDR is tentatively scheduled for October, 1998.

  7. Student Exposure to Mercury Vapors.

    ERIC Educational Resources Information Center

    Weber, Joyce

    1986-01-01

    Discusses the problem of mercury vapors caused by spills in high school and college laboratories. Describes a study which compared the mercury vapor levels of laboratories in both an older and a newer building. Concludes that the mercurial contamination of chemistry laboratories presents minimal risks to the students. (TW)

  8. SOFIA Water Vapor Monitor Design

    NASA Technical Reports Server (NTRS)

    Cooper, R.; Roellig, T. L.; Yuen, L.; Shiroyama, B.; Meyer, A.; Devincenzi, D. (Technical Monitor)

    2002-01-01

    The SOFIA Water Vapor Monitor (WVM) is a heterodyne radiometer designed to determine the integrated amount of water vapor along the telescope line of sight and directly to the zenith. The basic technique that was chosen for the WVM uses radiometric measurements of the center and wings of the 183.3 GHz rotational line of water to measure the water vapor. The WVM reports its measured water vapor levels to the aircraft Mission Controls and Communication System (MCCS) while the SOFIA observatory is in normal operation at flight altitude. The water vapor measurements are also available to other scientific instruments aboard the observatory. The electrical, mechanical and software design of the WVM are discussed.

  9. Biofiltration of solvent vapors from air

    SciTech Connect

    Oh, Young-sook.

    1993-01-01

    For various industrial solvent vapors, biofiltration promises to offer a cost-effective emission control technology. Exploiting the full potential of this technology will help attain the goals of the Clean Air Act Amendments of 1990. Concentrating on large volumes of volatile industrial solvents, stable multicomponent microbial enrichments capable of growing a mineral medium with solvent vapors as their only source of carbon and energy were obtained from soil and sewage sludge. These consortia were immobilized on an optimized porous solid support (ground peat moss and perlite). The biofilter material was packed in glass columns connected to an array of pumps and flow meters that allowed the independent variation of superficial velocity and solvent vapor concentrations. In various experiments, single solvents, such as methanol, butanol, acetonitrile, hexane and nitrobenzene, and solvent mixtures, such as benzene-toluene-xylene (BTX) and chlorobenzene-o-dichlorobenzene (CB/DCB) were biofiltered with rates ranging from 15 to334 g solvent removed per m[sup 3] filter volume /h. Pressure drops were low to moderate (0-10 mmHg/m) and with periodic replacement of moisture, the biofiltration activity could be maintained for a period of several months. The experimental data on methanol biofiltration were subjected to mathematical analysis and modeling by the group of Dr. Baltzis at NJIT for a better understanding and a possible scale up of solvent vapor biofilters. In the case of chlorobenzenes and nitrobenzene, the biofilter columns had to be operated with water recirculation in a trickling filter mode. To prevent inactivation of the trickling filter by acidity during CB/DCB removal, pH control was necessary, and the removal rate of CB/DCB was strongly influenced by the flow rate of the recyling water. Nitrobenzene removal in a trickling filter did not require pH control, since the nitro group was reduced and volatilized as ammonia.

  10. 40 CFR 721.10412 - Phosphonic acid ester (generic) (P-07-706).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... appropriate gas/vapor cartridges (organic vapor, acid gas, or substance-specific); NIOSH-certified powered air... (organic vapor, acid gas, or substance-specific); NIOSH-certified powered air-purifying respirator with a... Specific Chemical Substances § 721.10412 Phosphonic acid ester (generic) (P-07-706). (a) Chemical...

  11. 40 CFR 721.10412 - Phosphonic acid ester (generic) (P-07-706).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... appropriate gas/vapor cartridges (organic vapor, acid gas, or substance-specific); NIOSH-certified powered air... (organic vapor, acid gas, or substance-specific); NIOSH-certified powered air-purifying respirator with a... Specific Chemical Substances § 721.10412 Phosphonic acid ester (generic) (P-07-706). (a) Chemical...

  12. 40 CFR 721.10412 - Phosphonic acid ester (generic) (P-07-706).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... appropriate gas/vapor cartridges (organic vapor, acid gas, or substance-specific); NIOSH-certified powered air... (organic vapor, acid gas, or substance-specific); NIOSH-certified powered air-purifying respirator with a... Specific Chemical Substances § 721.10412 Phosphonic acid ester (generic) (P-07-706). (a) Chemical...

  13. Influence of crustal dust and sea spray supermicron particle concentrations and acidity on inorganic NO3- aerosol during the 2013 Southern Oxidant and Aerosol Study

    SciTech Connect

    Allen, Hannah M.; Draper, Danielle C.; Ayres, Benjamin R.; Ault, Andrew P.; Bondy, Amy L.; Takahama, S.; Modini, Robert; Baumann, K.; Edgerton, Eric S.; Knote, Christoph; Laskin, Alexander; Wang, Bingbing; Fry, Juliane L.

    2015-09-25

    The inorganic aerosol composition was measured in the southeastern United States, a region that exhibits high aerosol mass loading during the summer, as part of the 1 June to 15 July 2013 Southern Oxidant and Aerosol Study (SOAS) campaign. Measurements using a Monitor for AeRosols and GAses (MARGA), an ion chromatograph coupled with a wet rotating denuder and a steam-jet aerosol collector for monitoring of ambient inorganic gas and aerosol species, revealed two periods of high aerosol nitrate (NO3 ) concentrations during the campaign. These periods of high nitrate were correlated with increased concentrations of coarse mode mineral or sea spray aerosol species, particularly Na+ and Ca2+, and with a shift towards aerosol with larger (1 to 2.5 um) diameters. We suggest this nitrate aerosol forms by multiphase reactions of HNO3 and particles, reactions that are facilitated by transport of mineral dust and sea spray aerosol from a source within the United States. The observed high aerosol acidity prevents the formation of NH4NO3, the inorganic nitrogen species often dominant in fine-mode aerosol at higher pH. Calculation of the rate of the heterogeneous uptake of HNO3 on mineral aerosol supports the conclusion that aerosol NO3 is produced primarily by this process, and is likely limited by the availability of mineral dust surface area. Modeling of NO3 and HNO3 by thermodynamic equilibrium models (ISORROPIA II and E-AIM) reveals the importance of including mineral cations in the southeastern United States to accurately balance ion species and predict gas/aerosol phase partitioning.

  14. Heterogeneous reactions of gaseous hydrogen peroxide on pristine and acidic gas-processed calcium carbonate particles: Effects of relative humidity and surface coverage of coating

    NASA Astrophysics Data System (ADS)

    Zhao, Yue; Chen, Zhongming; Shen, Xiaoli; Huang, Dao

    2013-03-01

    Atmospheric aging appears to alter physical and chemical properties of mineral dust aerosol and thus its role as reactive surface in the troposphere. Yet, previous studies in the atmosphere have mainly focused on the pristine surfaces of mineral dust aerosol, and the reactivity of aged mineral dust toward atmospheric trace gases is poorly recognized. This work presents the first laboratory investigation of heterogeneous reactions of gaseous hydrogen peroxide (H2O2), an important atmospheric oxidant, on the surfaces of HNO3 and SO2-processed calcium carbonate particles as surrogates of atmospheric mineral dust aged by acidic trace gases. It is found that the processing of the calcium carbonate particles with HNO3 and SO2 has a strong impact on their reactivity toward H2O2. On HNO3-processed particles, the presence of nitrate acts to either decrease or increase H2O2 uptake, greatly depending on RH and surface coverage of nitrate. On SO2-processed particles, the presence of surface sulfite appears to enhance the intrinsic reactivity of the mineral particles due to its affinity for H2O2, and the uptake of H2O2 increases significantly relative to the pristine particles, in particular at high RH. The mechanisms for heterogeneous reactions of H2O2 with these processed particles are discussed, as well as their potential implications on tropospheric chemistry. The results of our study suggest that the reactivity of mineral dust aerosol toward H2O2 and maybe other trace gases is markedly dependent on the chemical composition and coverage of the coatings as well as ambient RH, and thus will vary considerably in different polluted air masses.

  15. Condensed Acids In Antartic Stratospheric Clouds

    NASA Technical Reports Server (NTRS)

    Pueschel, R. F.; Snetsinger, K. G.; Toon, O. B.; Ferry, G. V.; Starr, W. L.; Oberbeck, V. R.; Chan, K. R.; Goodman, J. K.; Livingston, J. M.; Verma, S.; Fong, W.

    1992-01-01

    Report dicusses nitrate, sulfate, and chloride contents of stratospheric aerosols during 1987 Airborne Antarctic Ozone Experiment. Emphasizes growth of HNO3*3H2O particles in polar stratospheric clouds. Important in testing theories concerning Antarctic "ozone hole".

  16. Tested Demonstrations. Gasoline Vapor: An Invisible Pollutant

    ERIC Educational Resources Information Center

    Stephens, Edgar R.

    1977-01-01

    Describes a demonstration concerning the air pollution aspects of gasoline vapor which provides an estimation of the vapor pressure of test fuel, the molecular weight of the vapor, and illustrates a method of controlling the pollution. (SL)

  17. Vapor pressure measured with inflatable plastic bag

    NASA Technical Reports Server (NTRS)

    1965-01-01

    Deflated plastic bag in a vacuum chamber measures initial low vapor pressures of materials. The bag captures the test sample vapors and visual observation of the vapor-inflated bag under increasing external pressures yields pertinent data.

  18. Quantifying vapor drift of dicamba herbicides applied to soybean.

    PubMed

    Egan, J Franklin; Mortensen, David A

    2012-05-01

    Recent advances in biotechnology have produced cultivars of corn, soybean, and cotton resistant to the synthetic-auxin herbicide dicamba. This technology will allow dicamba herbicides to be applied in new crops, at new periods in the growing season, and over greatly expanded areas, including postemergence applications in soybean. From past and current use in corn and small grains, dicamba vapor drift and subsequent crop injury to sensitive broadleaf crops has been a frequent problem. In the present study, the authors measured dicamba vapor drift in the field from postemergence applications to soybean using greenhouse-grown soybean as a bioassay system. They found that when the volatile dimethylamine formulation is applied, vapor drift could be detected at mean concentrations of 0.56 g acid equivalent dicamba/ha (0.1% of the applied rate) at 21 m away from a treated 18.3 × 18.3 m plot. Applying the diglycolamine formulation of dicamba reduced vapor drift by 94.0%. With the dimethylamine formulation, the extent and severity of vapor drift was significantly correlated with air temperature, indicating elevated risks if dimethylamine dicamba is applied early to midsummer in many growing regions. Additional research is needed to more fully understand the effects of vapor drift exposures to nontarget crops and wild plants. PMID:22362509

  19. Liquid-phase and vapor-phase dehydration of organic/water solutions

    DOEpatents

    Huang, Yu; Ly, Jennifer; Aldajani, Tiem; Baker, Richard W.

    2011-08-23

    Processes for dehydrating an organic/water solution by pervaporation or vapor separation using fluorinated membranes. The processes are particularly useful for treating mixtures containing light organic components, such as ethanol, isopropanol or acetic acid.

  20. Vapor Pressure, Vapor Composition and Fractional Vaporization of High Temperature Lavas on Io

    NASA Technical Reports Server (NTRS)

    Fegley, B., Jr.; Schaefer, L.; Kargel, J. S.

    2003-01-01

    Observations show that Io's atmosphere is dominated by SO2 and other sulfur and sulfur oxide species, with minor amounts of Na, K, and Cl gases. Theoretical modeling and recent observations show that NaCl, which is produced volcanically, is a constituent of the atmosphere. Recent Galileo, HST and ground-based observations show that some volcanic hot spots on Io have extremely high temperatures, in the range 1400-1900 K. At similar temperatures in laboratory experiments, molten silicates and oxides have significant vapor pressures of Na, K, SiO, Fe, Mg, and other gases. Thus vaporization of these species from high temperature lavas on Io seems likely. We therefore modeled the vaporization of silicate and oxide lavas suggested for Io. Our results for vapor chemistry are reported here. The effects of fractional vaporization on lava chemistry are given in a companion abstract by Kargel et al.

  1. Passive vapor extraction feasibility study

    SciTech Connect

    Rohay, V.J.

    1994-06-30

    Demonstration of a passive vapor extraction remediation system is planned for sites in the 200 West Area used in the past for the disposal of waste liquids containing carbon tetrachloride. The passive vapor extraction units will consist of a 4-in.-diameter pipe, a check valve, a canister filled with granular activated carbon, and a wind turbine. The check valve will prevent inflow of air that otherwise would dilute the soil gas and make its subsequent extraction less efficient. The granular activated carbon is used to adsorb the carbon tetrachloride from the air. The wind turbine enhances extraction rates on windy days. Passive vapor extraction units will be designed and operated to meet all applicable or relevant and appropriate requirements. Based on a cost analysis, passive vapor extraction was found to be a cost-effective method for remediation of soils containing lower concentrations of volatile contaminants. Passive vapor extraction used on wells that average 10-stdft{sup 3}/min air flow rates was found to be more cost effective than active vapor extraction for concentrations below 500 parts per million by volume (ppm) of carbon tetrachloride. For wells that average 5-stdft{sup 3}/min air flow rates, passive vapor extraction is more cost effective below 100 ppm.

  2. The lithium vapor box divertor

    NASA Astrophysics Data System (ADS)

    Goldston, R. J.; Myers, R.; Schwartz, J.

    2016-02-01

    It has long been recognized that volumetric dissipation of the plasma heat flux from a fusion power system is preferable to its localized impingement on a material surface. Volumetric dissipation mitigates both the anticipated very high heat flux and intense particle-induced damage due to sputtering. Recent projections to a tokamak demonstration power plant suggest an immense upstream parallel heat flux, of order 20 GW m-2, implying that fully detached operation may be a requirement for the success of fusion power. Building on pioneering work on the use of lithium by Nagayama et al and by Ono et al as well as earlier work on the gas box divertor by Watkins and Rebut, we present here a concept for a lithium vapor box divertor, in which lithium vapor extracts momentum and energy from a fusion-power-plant divertor plasma, using fully volumetric processes. At the high powers and pressures that are projected this requires a high density of lithium vapor, which must be isolated from the main plasma in order to avoid lithium build-up on the chamber walls or in the plasma. Isolation is achieved through a powerful multi-box differential pumping scheme available only for condensable vapors. The preliminary box-wise calculations are encouraging, but much more work is required to demonstrate the practical viability of this scheme, taking into account at least 2D plasma and vapor flows within and between the vapor boxes and out of the vapor boxes to the main plasma.

  3. Corrosion investigations on zircaloy-4 and titanium dissolver materials for MOX fuel dissolution in concentrated nitric acid containing fluoride ions

    NASA Astrophysics Data System (ADS)

    Jayaraj, J.; Krishnaveni, P.; Krishna, D. Nanda Gopala; Mallika, C.; Mudali, U. Kamachi

    2016-05-01

    Aqueous reprocessing of plutonium-rich mixed oxide fuels require fluoride as a dissolution catalyst in boiling nitric acid for an effective dissolution of the spent fuel. High corrosion rates were obtained for the candidate dissolver materials zircaloy-4 (Zr-4) and commercial pure titanium (CP-Ti grade 2) in boiling 11.5 M HNO3 + 0.05 M NaF. Complexing the fluoride ions either with Al(NO3)3 or ZrO(NO3)2 aided in decreasing the corrosion rates of Zr-4 and CP-Ti. From the obtained corrosion rates it is concluded that CP-Ti is a better dissolver material than Zr-4 for extended service life in boiling 11.5 M HNO3 + 0.05 M NaF, when complexed with 0.15 M ZrO(NO3)2. XPS analysis confirmed the presence of TiO2 and absence of fluoride on the surface of CP-Ti samples, indicating that effective complexation had occurred in solution leading to passivation of the metal and imparting high corrosion resistance.

  4. IMPROVED O3, SO2 AND HNO3 VEGETATION-ATMOSPHERE EXCHANGE MODELING FOR NETWORK APPLICATIONS

    EPA Science Inventory

    A long term goal of multimedia environmental management is to achieve sustainable ecological resources. Progress towards this goal rests on a foundation of science-based methods and data integrated into predictive multimedia, multi-stressor open architecture modeling systems. The...

  5. CORRECTION FACTORS FOR COVARIANCE BETWEEN CONCENTRATION AND DEPOSITION VELOCITY ON CASTNET HNO3 DEPOSITION ESTIMATES

    EPA Science Inventory

    The covariance between hourly concentration (C) and deposition velocity (V) for various atmospheric; species may act to bias the, deposition (D) computed from the product of the weekly average C and 'V. This is a potential problem for the CASTNet filter pack (FP) species, nitric...

  6. Medicinal Cannabis: In Vitro Validation of Vaporizers for the Smoke-Free Inhalation of Cannabis.

    PubMed

    Lanz, Christian; Mattsson, Johan; Soydaner, Umut; Brenneisen, Rudolf

    2016-01-01

    Inhalation by vaporization is a promising application mode for cannabis in medicine. An in vitro validation of 5 commercial vaporizers was performed with THC-type and CBD-type cannabis. Gas chromatography/mass spectrometry was used to determine recoveries of total THC (THCtot) and total CBD (CBDtot) in the vapor. High-performance liquid chromatography with photodiode array detection was used for the quantitation of acidic cannabinoids in the residue and to calculate decarboxylation efficiencies. Recoveries of THCtot and CBDtot in the vapor of 4 electrically-driven vaporizers were 58.4 and 51.4%, 66.8 and 56.1%, 82.7 and 70.0% and 54.6 and 56.7% for Volcano Medic®, Plenty Vaporizer®, Arizer Solo® and DaVinci Vaporizer®, respectively. Decarboxylation efficiency was excellent for THC (≥ 97.3%) and CBD (≥ 94.6%). The gas-powered Vape-or-Smoke™ showed recoveries of THCtot and CBDtot in the vapor of 55.9 and 45.9%, respectively, and a decarboxylation efficiency of ≥ 87.7 for both cannabinoids. However, combustion of cannabis was observed with this device. Temperature-controlled, electrically-driven vaporizers efficiently decarboxylate inactive acidic cannabinoids and reliably release their corresponding neutral, active cannabinoids. Thus, they offer a promising application mode for the safe and efficient administration of medicinal cannabis. PMID:26784441

  7. Medicinal Cannabis: In Vitro Validation of Vaporizers for the Smoke-Free Inhalation of Cannabis

    PubMed Central

    Lanz, Christian; Mattsson, Johan; Soydaner, Umut; Brenneisen, Rudolf

    2016-01-01

    Inhalation by vaporization is a promising application mode for cannabis in medicine. An in vitro validation of 5 commercial vaporizers was performed with THC-type and CBD-type cannabis. Gas chromatography/mass spectrometry was used to determine recoveries of total THC (THCtot) and total CBD (CBDtot) in the vapor. High-performance liquid chromatography with photodiode array detection was used for the quantitation of acidic cannabinoids in the residue and to calculate decarboxylation efficiencies. Recoveries of THCtot and CBDtot in the vapor of 4 electrically-driven vaporizers were 58.4 and 51.4%, 66.8 and 56.1%, 82.7 and 70.0% and 54.6 and 56.7% for Volcano Medic®, Plenty Vaporizer®, Arizer Solo® and DaVinci Vaporizer®, respectively. Decarboxylation efficiency was excellent for THC (≥ 97.3%) and CBD (≥ 94.6%). The gas-powered Vape-or-Smoke™ showed recoveries of THCtot and CBDtot in the vapor of 55.9 and 45.9%, respectively, and a decarboxylation efficiency of ≥ 87.7 for both cannabinoids. However, combustion of cannabis was observed with this device. Temperature-controlled, electrically-driven vaporizers efficiently decarboxylate inactive acidic cannabinoids and reliably release their corresponding neutral, active cannabinoids. Thus, they offer a promising application mode for the safe and efficient administration of medicinal cannabis. PMID:26784441

  8. Archimedes Mass Filter Vaporizer

    NASA Astrophysics Data System (ADS)

    Putvinski, S.; Agnew, A. F.; Cluggish, B. P.; Ohkawa, T.; Sevier, L.; Umstadter, K. R.; Dresvin, S. V.; Kuteev, B. V.; Feygenson, O. N.; Ivanov, D. V.; Zverev, S. G.; Miroshnikov, I. V.; Egorov, S. M.; Kiesewetter, D. V.; Maliugin, V. I.

    2001-10-01

    Archimedes Technology Group, Inc., is developing a plasma mass separator called the Archimedes Filter that separates waste oxide mixtures ion by ion into two mass groups: light and heavy. Since high-level waste at Hanford has 99.9its radioactivity associated with heavy elements, the Archimedes Filter can effectively decontaminate over three-quarters of that waste. The Filter process involves some preprocessing followed by volatilization and separation by the magnetic and electric fields of the main plasma. This presentation describes the approach to volatilization of the waste oxy-hydroxide mixture by means of a very high heat flux (q > 10 MW/m2). Such a high heat flux is required to ensure congruent evaporation of the complex oxy-hydroxide mixture and is achieved by injection of small droplets of molten waste into an inductively coupled plasma (ICP) torch. This presentation further addresses different issues related to evaporation of the waste including modeling of droplet evaporation, estimates of parameters of plasma torch, and 2D modeling of the plasma. The experimental test bed for oxide vaporization and results of the initial experiments on oxide evaporation in 60 kW ICP torch will also be described.

  9. Chemical vapor deposition growth

    NASA Technical Reports Server (NTRS)

    Ruth, R. P.; Manasevit, H. M.; Campbell, A. G.; Johnson, R. E.; Kenty, J. L.; Moudy, L. A.; Shaw, G. L.; Simpson, W. I.; Yang, J. J.

    1978-01-01

    The objective was to investigate and develop chemical vapor deposition (CVD) techniques for the growth of large areas of Si sheet on inexpensive substrate materials, with resulting sheet properties suitable for fabricating solar cells that would meet the technical goals of the Low Cost Silicon Solar Array Project. The program involved six main technical tasks: (1) modification and test of an existing vertical-chamber CVD reactor system; (2) identification and/or development of suitable inexpensive substrate materials; (3) experimental investigation of CVD process parameters using various candidate substrate materials; (4) preparation of Si sheet samples for various special studies, including solar cell fabrication; (5) evaluation of the properties of the Si sheet material produced by the CVD process; and (6) fabrication and evaluation of experimental solar cell structures, using impurity diffusion and other standard and near-standard processing techniques supplemented late in the program by the in situ CVD growth of n(+)/p/p(+) sheet structures subsequently processed into experimental cells.

  10. Supercritical microgravity droplet vaporization

    NASA Technical Reports Server (NTRS)

    Hartfield, J.; Curtis, E.; Farrell, P.

    1990-01-01

    Supercritical droplet vaporization is an important issue in many combustion systems, such as liquid fueled rockets and compression-ignition (diesel) engines. In order to study the details of droplet behavior at these conditions, an experiment was designed to provide a gas phase environment which is above the critical pressure and critical temperature of a single liquid droplet. In general, the droplet begins as a cold droplet in the hot, high pressure environment. In order to eliminate disruptions to the droplet by convective motion in the gas, forced and natural convection gas motion are required to be small. Implementation of this requirement for forced convection is straightforward, while reduction of natural convection is achieved by reduction in the g-level for the experiment. The resulting experiment consists of a rig which can stably position a droplet without restraint in a high-pressure, high temperature gas field in microgravity. The microgravity field is currently achieved by dropping the device in the NASA Lewis 2.2 second drop tower. The performance of the experimental device and results to date are presented.

  11. Precision ozone vapor pressure measurements

    NASA Technical Reports Server (NTRS)

    Hanson, D.; Mauersberger, K.

    1985-01-01

    The vapor pressure above liquid ozone has been measured with a high accuracy over a temperature range of 85 to 95 K. At the boiling point of liquid argon (87.3 K) an ozone vapor pressure of 0.0403 Torr was obtained with an accuracy of + or - 0.7 percent. A least square fit of the data provided the Clausius-Clapeyron equation for liquid ozone; a latent heat of 82.7 cal/g was calculated. High-precision vapor pressure data are expected to aid research in atmospheric ozone measurements and in many laboratory ozone studies such as measurements of cross sections and reaction rates.

  12. VAPOR SHIELD FOR INDUCTION FURNACE

    DOEpatents

    Reese, S.L.; Samoriga, S.A.

    1958-03-11

    This patent relates to a water-cooled vapor shield for an inductlon furnace that will condense metallic vapors arising from the crucible and thus prevent their condensation on or near the induction coils, thereby eliminating possible corrosion or shorting out of the coils. This is accomplished by placing, about the top, of the crucible a disk, apron, and cooling jacket that separates the area of the coils from the interior of the cruclbIe and provides a cooled surface upon whlch the vapors may condense.

  13. Simultaneous airborne nitric acid and formic acid measurements using a chemical ionization mass spectrometer around the UK: Analysis of primary and secondary production pathways

    NASA Astrophysics Data System (ADS)

    Le Breton, Michael; Bacak, Asan; Muller, Jennifer B. A.; Xiao, Ping; Shallcross, Beth M. A.; Batt, Rory; Cooke, Michael C.; Shallcross, Dudley E.; Bauguitte, S. J.-B.; Percival, Carl J.

    2014-02-01

    The first simultaneous measurements of formic and nitric acid mixing ratios around the United Kingdom were measured on the FAAM BAe-146 research aircraft with a chemical ionization mass spectrometer using I- reagent ions at 0.8 Hz. Analysis of the whole dataset shows that formic acid and nitric acid are positively correlated as illustrated by other studies (e.g. Veres et al., 2011). However, initial evidence indicates a prominent direct source of formic acid and also a significant source when O3 levels are high, suggesting the importance of the ozonolysis of 1-alkenes. A trajectory model was able to reproduce the formic acid concentrations by both the inclusion of a primary vehicle source and production via ozonolysis of propene equivalent 1-alkene levels. Inspection of data archives implies these levels of 1-alkene are possible after 11 am, but formic acid and nitric acid plumes early in the flight are too high for the model to replicate. These data show the relationship between nitric acid and formic acid cannot solely be attributed to related photochemical production. The simultaneous measurement of HCOOH and HNO3 has been implemented to estimate OH levels along the flight track assuming a relationship between formic and nitric acid in photochemical plumes and a constant source of 1-alkene.

  14. CAPSULE REPORT: CONTROL OF ACIDIC AIR POLLUTANTS BY COATED BAGHOUSES

    EPA Science Inventory

    Emissions from the aluminum, glass, phosphate, fertilizer, and sulfuric acid industries and from waste incineration share several common problems, including combined particulate, corrosive acid vapor, and acid mist emissions. his capsule report presents an approach to alleviate t...

  15. The nature of nitrate at the ice surface studied by XPS and NEXAFS.

    PubMed

    Krepelová, Adéla; Newberg, John; Huthwelker, Thomas; Bluhm, Hendrik; Ammann, Markus

    2010-08-21

    Trace contaminants such as strong acids have been suggested to affect the thickness of the quasi-liquid layer at the ice/air interface, which is at the heart of heterogeneous chemical reactions between snowpacks or cirrus clouds and the surrounding air. We used X-ray photoelectron spectroscopy (XPS) and electron yield near edge X-ray absorption fine structure (NEXAFS) spectroscopy at the Advanced Light Source (ALS) to probe the ice surface in the presence of HNO(3) formed from the heterogeneous hydrolysis of NO(2) at 230 K. We studied the nature of the adsorbed species at the ice/vapor interfaces as well as the effect of HNO(3) on the hydrogen bonding environment at the ice surface. The NEXAFS spectrum of ice with adsorbed HNO(3) can be represented as linear combination of the clean ice and nitrate solution spectrum, thus indicating that in the presence of HNO(3) the ice surface consists of a mixture of clean ice and nitrate ions that are coordinated as in a concentrated solution at the same temperature but higher HNO(3) pressures. PMID:20532376

  16. Finding organic vapors - a Monte Carlo approach

    NASA Astrophysics Data System (ADS)

    Vuollekoski, Henri; Boy, Michael; Kerminen, Veli-Matti; Kulmala, Markku

    2010-05-01

    Aerosols have an important role in regulating the climate both directly by absorbing and scattering solar radiation, as well as indirectly by acting as cloud condensation nuclei. While it is known that their net effect on radiative forcing is negative, several key aspects remain mysterious. There exist plenty of known primary sources of particles due to both natural and man-made origin - for example desert dust, volcanic activity and tire debris. On the other hand, it has been shown that the formation of secondary particles, by nucleation from precursor vapors, is a frequent, global phenomenon. However, the very earliest steps in new particle formation - nucleation and early growth by condensation - have many big question marks on them. While several studies have indicated the importance of a sufficient concentration of sulphuric acid vapor for the process, it has also been noted that this is usually not enough. Heads have therefore turned to organic vapors, which in their multitude could explain various observed characteristics of new particle formation. But alas, the vast number of organic compounds, their complex chemistry and properties that make them difficult to measure, have complicated the quantifying task. Nevertheless, evidence of organic contribution in particles of all size classes has been found. In particular, a significant organic constituent in the very finest particles suggests the presence of a high concentration of very low-volatile organic vapors. In this study, new particle formation in the boreal forest environment of Hyytiälä, Finland, is investigated in a process model. Our goal is to quantify the concentration, to find the diurnal profile and to get hints of the identity of some organic vapors taking part in new particle formation. Previous studies on the subject have relied on data analysis of the growth rate of the observed particles. However, due to the coarse nature of the methods used to calculate growth rates, this approach has its

  17. A stratospheric water vapor feedback

    NASA Astrophysics Data System (ADS)

    Dessler, A. E.; Schoeberl, M. R.; Wang, T.; Davis, S. M.; Rosenlof, K. H.

    2013-12-01

    Variations in stratospheric water vapor play a role in the evolution of our climate. We show here that variations in water vapor since 2004 can be traced to tropical tropopause layer (TTL) temperature perturbations from at least three processes: the quasi-biennial oscillation, the strength of the Brewer-Dobson circulation, and the temperature of the troposphere. The connection between stratospheric water vapor and the temperature of the troposphere implies the existence of a stratospheric water vapor feedback. We estimate the feedback in a chemistry-climate model to have a magnitude of +0.3 W/m2/K, which could be a significant contributor to the overall climate sensitivity. About two-thirds of the feedback comes from the extratropical stratosphere below ~16 km (the lowermost stratosphere), with the rest coming from the stratosphere above ~16 km (the overworld).

  18. Tubing For Sampling Hydrazine Vapor

    NASA Technical Reports Server (NTRS)

    Travis, Josh; Taffe, Patricia S.; Rose-Pehrsson, Susan L.; Wyatt, Jeffrey R.

    1993-01-01

    Report evaluates flexible tubing used for transporting such hypergolic vapors as those of hydrazines for quantitative analysis. Describes experiments in which variety of tubing materials, chosen for their known compatibility with hydrazine, flexibility, and resistance to heat.

  19. Understanding Latent Heat of Vaporization.

    ERIC Educational Resources Information Center

    Linz, Ed

    1995-01-01

    Presents a simple exercise for students to do in the kitchen at home to determine the latent heat of vaporization of water using typical household materials. Designed to stress understanding by sacrificing precision for simplicity. (JRH)

  20. Portable vapor diffusion coefficient meter

    DOEpatents

    Ho, Clifford K.

    2007-06-12

    An apparatus for measuring the effective vapor diffusion coefficient of a test vapor diffusing through a sample of porous media contained within a test chamber. A chemical sensor measures the time-varying concentration of vapor that has diffused a known distance through the porous media. A data processor contained within the apparatus compares the measured sensor data with analytical predictions of the response curve based on the transient diffusion equation using Fick's Law, iterating on the choice of an effective vapor diffusion coefficient until the difference between the predicted and measured curves is minimized. Optionally, a purge fluid can forced through the porous media, permitting the apparatus to also measure a gas-phase permeability. The apparatus can be made lightweight, self-powered, and portable for use in the field.

  1. Packed Alumina Absorbs Hypergolic Vapors

    NASA Technical Reports Server (NTRS)

    Thomas, J. J.; Mauro, D. M.

    1984-01-01

    Beds of activated alumina effective as filters to remove hypergolic vapors from gas streams. Beds absorb such substances as nitrogen oxides and hydrazines and may also absorb acetylene, ethylene, hydrogen sulfide, benzene, butadiene, butene, styrene, toluene, and xoylene. Bed has no moving parts such as pumps, blowers and mixers. Reliable and energy-conservative. Bed readily adapted to any size from small portable units for use where little vapor release is expected to large stationary units for extensive transfer operations.

  2. Vapor deposition of hardened niobium

    DOEpatents

    Blocher, Jr., John M.; Veigel, Neil D.; Landrigan, Richard B.

    1983-04-19

    A method of coating ceramic nuclear fuel particles containing a major amount of an actinide ceramic in which the particles are placed in a fluidized bed maintained at ca. 800.degree. to ca. 900.degree. C., and niobium pentachloride vapor and carbon tetrachloride vapor are led into the bed, whereby niobium metal is deposited on the particles and carbon is deposited interstitially within the niobium. Coating apparatus used in the method is also disclosed.

  3. Chemical vapor deposition sciences

    SciTech Connect

    1992-12-31

    Chemical vapor deposition (CVD) is a widely used method for depositing thin films of a variety of materials. Applications of CVD range from the fabrication of microelectronic devices to the deposition of protective coatings. New CVD processes are increasingly complex, with stringent requirements that make it more difficult to commercialize them in a timely fashion. However, a clear understanding of the fundamental science underlying a CVD process, as expressed through computer models, can substantially shorten the time required for reactor and process development. Research scientists at Sandia use a wide range of experimental and theoretical techniques for investigating the science of CVD. Experimental tools include optical probes for gas-phase and surface processes, a range of surface analytic techniques, molecular beam methods for gas/surface kinetics, flow visualization techniques and state-of-the-art crystal growth reactors. The theoretical strategy uses a structured approach to describe the coupled gas-phase and gas-surface chemistry, fluid dynamics, heat and mass transfer of a CVD process. The software used to describe chemical reaction mechanisms is easily adapted to codes that model a variety of reactor geometries. Carefully chosen experiments provide critical information on the chemical species, gas temperatures and flows that are necessary for model development and validation. This brochure provides basic information on Sandia`s capabilities in the physical and chemical sciences of CVD and related materials processing technologies. It contains a brief description of the major scientific and technical capabilities of the CVD staff and facilities, and a brief discussion of the approach that the staff uses to advance the scientific understanding of CVD processes.

  4. Use of Ni/NixB Nanoparticles as a Novel Adsorbent for the Preconcentration of Mercury Species prior to Cold Vapor-Atomic Fluorescence Spectrometric Determination.

    PubMed

    Yayayürük, Onur; Henden, Emür

    2016-01-01

    A selective matrix separation/enrichment method, utilizing a simple batch procedure with nickel/nickel boride (Ni/NixB) nanoparticles was proposed for the determination of inorganic mercury(II), Hg(2+) and methyl mercury(I), CH3Hg(+) in waters prior to cold vapor-atomic fluorescence spectrometry (CV-AFS). The Ni/NixB nanoparticles, were synthesized by the chemical reduction of Ni(II) to Ni/NixB. The novel adsorbent was selective to Hg(2+) and CH3Hg(+) species between pH values of 4 - 10. Both of the mercury species were recovered from the adsorbent using 1.0 mol L(-1) hot HNO3 with high efficiency. It was observed that the adsorbent selectively removed Hg(2+) and CH3Hg(+) from the bulk solution in the presence of several competitor ions (As(3+), Sb(3+), Pb(2+), Zn(2+), Cu(2+), Cd(2+) and Fe(3+)) with ≥96% adsorption. The limit of detection (3σ above blank) was found to be 1.8 ng L(-1) with a preconcentration factor of 20. The validation of the method was tested through spike recovery experiments with several water samples (tap and seawater) at μg L(-1) concentration levels, and all recovery values were found to vary between 95 and 105%. PMID:27506713

  5. Impact Vaporization of Planetesimal Cores

    NASA Astrophysics Data System (ADS)

    Kraus, R. G.; Root, S.; Lemke, R. W.; Stewart, S. T.; Jacobsen, S. B.; Mattsson, T. R.

    2013-12-01

    The degree of mixing and chemical equilibration between the iron cores of planetesimals and the mantle of the growing Earth has important consequences for understanding the end stages of Earth's formation and planet formation in general. At the Sandia Z machine, we developed a new shock-and-release technique to determine the density on the liquid-vapor dome of iron, the entropy on the iron shock Hugoniot, and the criteria for shock-induced vaporization of iron. We find that the critical shock pressure to vaporize iron is 507(+65,-85) GPa and show that decompression from a 15 km/s impact will initiate vaporization of iron cores, which is a velocity that is readily achieved at the end stages of planet formation. Vaporization of the iron cores increases dispersal of planetesimal cores, enables more complete chemical equilibration of the planetesimal cores with Earth's mantle, and reduces the highly siderophile element abundance on the Moon relative to Earth due to the expanding iron vapor exceeding the Moon's escape velocity. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Securities Administration under Contract No. DE-AC04-94AL85000.

  6. 21 CFR 868.5880 - Anesthetic vaporizer.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Anesthetic vaporizer. 868.5880 Section 868.5880...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5880 Anesthetic vaporizer. (a) Identification. An anesthetic vaporizer is a device used to vaporize liquid anesthetic and deliver a...

  7. 21 CFR 868.5880 - Anesthetic vaporizer.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Anesthetic vaporizer. 868.5880 Section 868.5880...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5880 Anesthetic vaporizer. (a) Identification. An anesthetic vaporizer is a device used to vaporize liquid anesthetic and deliver a...

  8. 21 CFR 868.5880 - Anesthetic vaporizer.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Anesthetic vaporizer. 868.5880 Section 868.5880...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5880 Anesthetic vaporizer. (a) Identification. An anesthetic vaporizer is a device used to vaporize liquid anesthetic and deliver a...

  9. 21 CFR 868.5880 - Anesthetic vaporizer.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Anesthetic vaporizer. 868.5880 Section 868.5880...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5880 Anesthetic vaporizer. (a) Identification. An anesthetic vaporizer is a device used to vaporize liquid anesthetic and deliver a...

  10. 21 CFR 868.5880 - Anesthetic vaporizer.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Anesthetic vaporizer. 868.5880 Section 868.5880...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5880 Anesthetic vaporizer. (a) Identification. An anesthetic vaporizer is a device used to vaporize liquid anesthetic and deliver a...

  11. Generation of organic acids and monosaccharides by hydrolytic and oxidative transformation of food processing residues.

    PubMed

    Fischer, Klaus; Bipp, Hans-Peter

    2005-05-01

    Carbohydrate-rich biomass residues, i.e. sugar beet molasses, whey powder, wine yeast, potato peel sludge, spent hops, malt dust and apple marc, were tested as starting materials for the generation of marketable chemicals, e.g. aliphatic acids, sugar acids and mono-/disaccharides. Residues were oxidized or hydrolyzed under acidic or alkaline conditions applying conventional laboratory digestion methods and microwave assisted techniques. Yields and compositions of the oxidation products differed according to the oxidizing agent used. Main products of oxidation by 30% HNO(3) were acetic, glucaric, oxalic and glycolic acids. Applying H(2)O(2)/CuO in alkaline solution, the organic acid yields were remarkably lower with formic, acetic and threonic acids as main products. Gluconic acid was formed instead of glucaric acid throughout. Reaction of a 10% H(2)O(2) solution with sugar beet molasses generated formic and lactic acids mainly. Na(2)S(2)O(8) solutions were very inefficient at oxidizing the residues. Glucose, arabinose and galactose were formed during acidic hydrolysis of malt dust and apple marc. The glucose content reached 0.35 g per gram of residue. Important advantages of the microwave application were lower reaction times and reduced reagent demands. PMID:15607197

  12. Catalytic Ethanol Dehydration over Different Acid-activated Montmorillonite Clays.

    PubMed

    Krutpijit, Chadaporn; Jongsomjit, Bunjerd

    2016-01-01

    In the present study, the catalytic dehydration of ethanol to obtain ethylene over montmorillonite clays (MMT) with mineral acid activation including H2SO4 (SA-MMT), HCl (HA-MMT) and HNO3 (NA-MMT) was investigated at temperature range of 200 to 400°C. It revealed that HA-MMT exhibited the highest catalytic activity. Ethanol conversion and ethylene selectivity were found to increase with increased reaction temperature. At 400°C, the HA-MMT yielded 82% of ethanol conversion having 78% of ethylene yield. At lower temperature (i.e. 200 to 300°C), diethyl ether (DEE) was a major product. The highest activity obtained from HA-MMT can be attributed to an increase of weak acid sites and acid density by the activation of MMT with HCl. It can be also proven by various characterization techniques that in most case, the main structure of MMT did not alter by acid activation (excepted for NA-MMT). Upon the stability test for 72 h during the reaction, the MMT and HA-MMT showed only slight deactivation due to carbon deposition. Hence, the acid activation of MMT by HCl is promising to enhance the catalytic dehydration of ethanol. PMID:27041515

  13. Nitric Acid Uptake on Subtropical Cirrus Cloud Particles

    NASA Technical Reports Server (NTRS)

    2004-01-01

    The redistribution of HNO3 via uptake and sedimentation by cirrus cloud particles is considered an important term in the upper tropospheric budget of reactive nitrogen. Numerous cirrus cloud encounters by the NASA WB-57F high-altitude research aircraft during CRYSTAL-FACE were accompanied by the observation of condensed-phase HNO3 with the NOAA chemical ionization mass spectrometer. The instrument measures HNO3 with two independent channels of detection connected to separate forward- and downward-facing inlets that allow a determination of the amount of HNO3 condensed on ice particles. Subtropical cirrus clouds, as indicated by the presence of ice particles, were observed coincident with condensed-phase HNO3 at temperatures of 197 K - 224 K and pressures of 122 hPa - 224 hPa. Maximum levels of condensed-phase HNO3 approached the gas-phase equivalent of 0.8 ppbv. Ice particle surface coverages as high as 1.4- 10(exp 14) molecules/sq cm were observed. A dissociative Langmuir adsorption model, when using an empirically derived HNO3 adsorption enthalpy of -11.0 kcal/mol, effectively describes the observed molecular coverages to within a factor of 5. The percentage of total HNO3 in the condensed phase ranged from near zero to 100% in the observed cirrus clouds. With volume-weighted mean particle diameters up to 700 pm and particle fall velocities up to 10 m/s, some observed clouds have significant potential to redistribute HNO3 in the upper troposphere.

  14. Nitric Acid Uptake on Subtropical Cirrus Cloud Particles

    NASA Technical Reports Server (NTRS)

    Popp, P. J.; Gao, R. S.; Marcy, T. P.; Fahey, D. W.; Hudson, P. K.; Thompson, T. L.; Kaercher, B.; Ridley, B. A.; Weinheimer, A. J.; Knapp, D. J.; Montzka, D. D.; Baumgardner, D.; Garrett, T. J.; Weinstock, E. M.; Smith, J. B.; Sayres, D. S.; Pittman, J. V.; Dhaniyala, S.; Bui, T. P.; Mahoney, M. J.

    2004-01-01

    The redistribution of HNO3 via uptake and sedimentation by cirrus cloud particles is considered an important term in the upper tropospheric budget of reactive nitrogen. Numerous cirrus cloud encounters by the NASA WB-57F high-altitude research aircraft during the Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE) were accompanied by the observation of condensed-phase HNO3 with the NOAA chemical ionization mass spectrometer. The instrument measures HNO3 with two independent channels of detection connected to separate forward and downward facing inlets that allow a determination of the amount of HNO3 condensed on ice particles. Subtropical cirrus clouds, as indicated by the presence of ice particles, were observed coincident with condensed-phase HNO3 at temperatures of 197-224 K and pressures of 122-224 hPa. Maximum levels of condensed-phase HNO3 approached the gas-phase equivalent of 0.8 ppbv. Ice particle surface coverages as high as 1.4 # 10(exp 14) molecules/ square cm were observed. A dissociative Langmuir adsorption model, when using an empirically derived HNO3 adsorption enthalpy of -11.0 kcal/mol, effectively describes the observed molecular coverages to within a factor of 5. The percentage of total HNO3 in the condensed phase ranged from near zero to 100% in the observed cirrus clouds. With volume-weighted mean particle diameters up to 700 ?m and particle fall velocities up to 10 m/s, some observed clouds have significant potential to redistribute HNO3 in the upper troposphere.

  15. Summer-time distribution of air pollutants in Sequoia National Park, California.

    PubMed

    Bytnerowicz, Andrzej; Tausz, Michael; Alonso, Rocio; Jones, David; Johnson, Ronald; Grulke, Nancy

    2002-01-01

    Concentrations of air pollutants were monitored during the May November 1999 period on a network of forested sites in Sequoia National Park, California. Measurements were conducted with: (1) active monitors for nitric oxide (NO), nitrogen dioxide (NO2) and ozone (O3); (2) honeycomb denuder/filter pack systems for nitric acid vapor (HNO3), nitrous acid vapor (HNO2), ammonia (NH3), sulfur dioxide (SO2), particulate nitrate (NO3-), ammonium (NH4+), and sulfate (SO4(2-)); and (3) passive samplers for O3, HNO3 and NO2. Elevated concentrations of O3 (seasonal means 41-71 ppb), HNO3 (seasonal means 0.4-2.9 microg/m3), NH3 (seasonal means 1.6-4.5 microg/m3), NO3 (1.1-2.0 microg/m3) and NH4+ (1.0-1.9 microg/m3) were determined. Concentrations of other pollutants were low. With increasing elevation and distance from the pollution source area of O3, NH3 and HNO3 concentrations decreased. Ammonia and NH4+ were dominant N pollutants indicating strong influence of agricultural emissions on forests and other ecosystems of the Sequoia National Park. PMID:11939282

  16. Vapor pressures of new fluorocarbons

    SciTech Connect

    Kubota, H.; Yamashita, T.; Tanaka, Y.; Makita, T. )

    1989-05-01

    The vapor pressures of four fluorocarbons have been measured at the following temperature ranges: R123 (2,2-dichloro-1,1,1-trifluoroethane), 273-457 K; R123a (1,2-dichloro-1,1,2-trifluoroethane), 303-458 K; R134a (1,1,1,2-tetrafluoroethane), 253-373 K; and R132b (1,2-dichloro-1,1-difluoroethane), 273-398 K. Determinations of the vapor pressure were carried out by a constant-volume apparatus with an uncertainty of less than 1.0%. The vapor pressures of R123 and R123a are very similar to those of R11 over the whole experimental temperature range, but the vapor pressures of R134a and R132b differ somewhat from those of R12 and R113, respectively, as the temperature increases. The numerical vapor pressure data can be fitted by an empirical equation using the Chebyshev polynomial with a mean deviation of less than 0.3%.

  17. The Lithium Vapor Box Divertor

    NASA Astrophysics Data System (ADS)

    Goldston, Robert; Hakim, Ammar; Hammett, Gregory; Jaworski, Michael; Myers, Rachel; Schwartz, Jacob

    2015-11-01

    Projections of scrape-off layer width to a demonstration power plant suggest an immense parallel heat flux, of order 12 GW/m2, which will necessitate nearly fully detached operation. Building on earlier work by Nagayama et al. and by Ono et al., we propose to use a series of differentially pumped boxes filled with lithium vapor to isolate the buffering vapor from the main plasma chamber, allowing stable detachment. This powerful differential pumping is only available for condensable vapors, not conventional gases. We demonstrate the properties of such a system through conservation laws for vapor mass and enthalpy, and then include plasma entrainment and ultimately an estimate of radiated power. We find that full detachment should be achievable with little leakage of lithium to the main plasma chamber. We also present progress towards solving the Navier-Stokes equation numerically for the chain of vapor boxes, including self-consistent wall boundary conditions and fully-developed shocks, as well as concepts for an initial experimental demonstration-of-concept. This work supported by DOE Contract No. DE-AC02-09CH11466.

  18. Measurements of Acidic Gases and Aerosol Species Aboard the NASA DC-8 Aircraft During the Pacific Exploratory Mission in the Tropics (PEM-Tropics A)

    NASA Technical Reports Server (NTRS)

    Talbot, Robert W.; Dibb, Jack E.

    1999-01-01

    We received funding to provide measurements of nitric acid (HNO3), formic acid (HCOOH), acetic acid (CH3COOH), and the chemical composition of aerosols aboard the NASA Ames DC-8 research aircraft during the PEM-Tropics A mission. These measurements were successfully completed and the final data resides in the electronic archive (ftp-gte.larc.nasa.gov) at NASA Langley Research Center. For the PEM-Tropics A mission the University of New Hampshire group was first author of four different manuscripts. Three of these have now appeared in the Journal of Geophysical Research-Atmospheres, included in the two section sections on PEM-Tropics A. The fourth manuscript has just recently been submitted to this same journal as a stand alone paper. All four of these papers are included in this report. The first paper (Influence of biomass combustion emissions on the distribution of acidic trace gases over the Southern Pacific basin during austral springtime) describes the large-scale distributions of HNO3, HCOOH, and CH3COOH. Arguments were presented to show, particularly in the middle tropospheric region, that biomass burning emissions from South America and Africa were a major source of acidic gases over the South Pacific basin. The second paper (Aerosol chemical composition and distribution during the Pacific Exploratory Mission (PEM) Tropics) covers the aerosol aspects of our measurement package. Compared to acidic gases, O3, and selected hydrocarbons, the aerosol chemistry showed little influence from biomass burning emissions. The data collected in the marine boundary layer showed a possible marine source of NH3 to the troposphere in equatorial areas. This source had been speculated on previously, but our data was the first collected from an airborne platform to show its large-scale features. The third paper (Constraints on the age and dilution of Pacific Exploratory Mission-Tropics biomass burning plumes from the natural radionuclide tracer Pb-210) utilized the unexpectedly

  19. The effects of acid leaching on 40Ar/39Ar age dating results using samples from the Walvis Ridge hotspot trail

    NASA Astrophysics Data System (ADS)

    Klath, J. F.; Koppers, A. A.; Heaton, D. E.; Schnur, S.

    2013-12-01

    In this study we systematically explore how acid leaching can be used to reduce the negative effects of seawater alteration on the 40Ar/39Ar age dating of submarine basalts. Koppers et al (2000) showed that acid leaching of groundmass samples generated more consistent ages as well as ages more concordant with phenocrystic mineral phases, compared to samples that were left untreated. By studying the effects of progressively increasing the strength and length of acid treatment, we will show how acid leaching of groundmass separates reduces alteration while leaving the initial eruption signature intact. Samples were chosen from the Walvis ridge hotspot trail in the southeast Atlantic. Three samples were selected based on degree and style of alteration. Two samples (basalt and basaltic andesite) appear highly altered in thin section. The basalt contains diffuse iddingsite alteration that is pervasive throughout the groundmass. The basaltic andesite displays focused secondary mineral phases within and around abundant vesicles. The third sample, a trachyte, shows relatively minor degrees of alteration in thin section. These groundmass separates were divided into four splits and treated with a progressively stronger acid and for longer duration. One split from each rock was left untreated to act as a baseline. Of the other three splits from each sample, one was treated with a mild leach (1N HCl and 1N HNO3), one a strong leach (1N HCl, 1N HNO3, 6N HCl, and 3N HNO3), and lastly the strong leach performed twice. The samples were then handpicked to remove any remaining visible alteration. The untreated samples were picked as well, removing the most distinctly altered grains. All splits were analyzed by electron microprobe, x-ray fluorescence (XRF) and the incremental heating 40Ar/39Ar dating method. We will report on the results of an image analysis of microprobe backscatter images and elemental maps taken of individual groundmass grains. This analysis will show the location

  20. Potentiometric detection of chemical vapors using molecularly imprinted polymers as receptors

    PubMed Central

    Liang, Rongning; Chen, Lusi; Qin, Wei

    2015-01-01

    Ion-selective electrode (ISE) based potentiometric gas sensors have shown to be promising analytical tools for detection of chemical vapors. However, such sensors are only capable of detecting those vapors which can be converted into ionic species in solution. This paper describes for the first time a polymer membrane ISE based potentiometric sensing system for sensitive and selective determination of neutral vapors in the gas phase. A molecularly imprinted polymer (MIP) is incorporated into the ISE membrane and used as the receptor for selective adsorption of the analyte vapor from the gas phase into the sensing membrane phase. An indicator ion with a structure similar to that of the vapor molecule is employed to indicate the change in the MIP binding sites in the membrane induced by the molecular recognition of the vapor. The toluene vapor is used as a model and benzoic acid is chosen as its indicator. Coupled to an apparatus manifold for preparation of vapor samples, the proposed ISE can be utilized to determine volatile toluene in the gas phase and allows potentiometric detection down to parts per million levels. This work demonstrates the possibility of developing a general sensing principle for detection of neutral vapors using ISEs. PMID:26215887

  1. Potentiometric detection of chemical vapors using molecularly imprinted polymers as receptors.

    PubMed

    Liang, Rongning; Chen, Lusi; Qin, Wei

    2015-01-01

    Ion-selective electrode (ISE) based potentiometric gas sensors have shown to be promising analytical tools for detection of chemical vapors. However, such sensors are only capable of detecting those vapors which can be converted into ionic species in solution. This paper describes for the first time a polymer membrane ISE based potentiometric sensing system for sensitive and selective determination of neutral vapors in the gas phase. A molecularly imprinted polymer (MIP) is incorporated into the ISE membrane and used as the receptor for selective adsorption of the analyte vapor from the gas phase into the sensing membrane phase. An indicator ion with a structure similar to that of the vapor molecule is employed to indicate the change in the MIP binding sites in the membrane induced by the molecular recognition of the vapor. The toluene vapor is used as a model and benzoic acid is chosen as its indicator. Coupled to an apparatus manifold for preparation of vapor samples, the proposed ISE can be utilized to determine volatile toluene in the gas phase and allows potentiometric detection down to parts per million levels. This work demonstrates the possibility of developing a general sensing principle for detection of neutral vapors using ISEs. PMID:26215887

  2. Potentiometric detection of chemical vapors using molecularly imprinted polymers as receptors

    NASA Astrophysics Data System (ADS)

    Liang, Rongning; Chen, Lusi; Qin, Wei

    2015-07-01

    Ion-selective electrode (ISE) based potentiometric gas sensors have shown to be promising analytical tools for detection of chemical vapors. However, such sensors are only capable of detecting those vapors which can be converted into ionic species in solution. This paper describes for the first time a polymer membrane ISE based potentiometric sensing system for sensitive and selective determination of neutral vapors in the gas phase. A molecularly imprinted polymer (MIP) is incorporated into the ISE membrane and used as the receptor for selective adsorption of the analyte vapor from the gas phase into the sensing membrane phase. An indicator ion with a structure similar to that of the vapor molecule is employed to indicate the change in the MIP binding sites in the membrane induced by the molecular recognition of the vapor. The toluene vapor is used as a model and benzoic acid is chosen as its indicator. Coupled to an apparatus manifold for preparation of vapor samples, the proposed ISE can be utilized to determine volatile toluene in the gas phase and allows potentiometric detection down to parts per million levels. This work demonstrates the possibility of developing a general sensing principle for detection of neutral vapors using ISEs.

  3. Evaluation of ionic pollutants of acid fog and rain using a factor analysis and back trajectories.

    PubMed

    Adzuhata, T; Inotsume, J; Okamura, T; Kikuchi, R; Ozeki, T; Kajikawa, M; Ogawa, N

    2001-01-01

    Fog and rain water samples were collected at the same time in the Akita Hachimantai mountain range in northern Japan from June to September in 1998 and 1999. The various ion concentrations in these samples were analyzed, and the fog droplet sizes were measured for each fog event. As the fog droplet size increased, the ion concentration decreased. The slope of log-log plots of the concentration versus the droplet size differed with the kind of ion. In order to characterize the air pollutant, moreover, these data were quantitatively analyzed by an oblique rotational factor analysis. We found that three factors were extracted as the air pollutant source: (NH4)2SO4, acids (HNO3 + H2SO4) and sea-salt. Combining the factor analysis with the 72 h back-trajectory at 850 hPa level, we found that the contribution of each factor varied with the transport pattern of air masses. PMID:11993680

  4. Laboratory Experiments on Nitric Acid Uptake by a Meteoric Smoke Analogue

    NASA Astrophysics Data System (ADS)

    James, A.; Frankland, V. L.; Plane, J. M.

    2013-12-01

    Amorphous olivine particles have been synthesised using the sol-gel technique to provide analogues of meteoric smoke particles. A Knudsen cell was used to measure an uptake coefficient of nitric acid on meteoric smoke of 3 × 4 x 10-3. Employing this parameter in an atmospheric model of smoke transport suggests that in the polar winter vortex, where meteoric smoke is concentrated (and photolysis is negligible) the lifetime of HNO3 with respect to heterogeneous removal is around 4 months, which is similar to the length of the polar winter. One uncertainty in this estimate is the size of the cosmic dust input to the atmosphere (assumed here to be 20 t d-1, one quarter of which ablates).

  5. Impact of stratospheric aircraft on calculations of nitric acid trihydrate cloud surface area densities using NMC temperatures and 2D model constituent distributions

    NASA Technical Reports Server (NTRS)

    Considine, David B.; Douglass, Anne R.

    1994-01-01

    A parameterization of NAT (nitric acid trihydrate) clouds is developed for use in 2D models of the stratosphere. The parameterization uses model distributions of HNO3 and H2O to determine critical temperatures for NAT formation as a function of latitude and pressure. National Meteorological Center temperature fields are then used to determine monthly temperature frequency distributions, also as a function of latitude and pressure. The fractions of these distributions which fall below the critical temperatures for NAT formation are then used to determine the NAT cloud surface area density for each location in the model grid. By specifying heterogeneous reaction rates as functions of the surface area density, it is then possible to assess the effects of the NAT clouds on model constituent distributions. We also consider the increase in the NAT cloud formation in the presence of a fleet of stratospheric aircraft. The stratospheric aircraft NO(x) and H2O perturbations result in increased HNO3 as well as H2O. This increases the probability of NAT formation substantially, especially if it is assumed that the aircraft perturbations are confined to a corridor region.

  6. The effect of heating temperature and nitric acid treatments on the performance of Cu- and Zn-based broad spectrum respirator carbons.

    PubMed

    Smith, J W H; Romero, J V; Dahn, T R; Dunphy, K; Sullivan, B; Mallay, M; Croll, L M; Reynolds, J H; Andress, C; Dahn, J R

    2011-12-01

    Impregnated activated carbons (IACs) that are used in broad spectrum gas mask applications have historically contained copper and/or zinc impregnants. The addition of an oxidizing agent, such as nitric acid (HNO(3)) can be useful in distributing the metallic impregnants uniformly on the activated carbon substrate. In this work, we study IACs prepared from copper nitrate (Cu(NO(3))(2)) and zinc nitrate (Zn(NO(3))(2)) precursors as a function of HNO(3) content present in the impregnating solution and as a function of heating temperature. The gas adsorption capacity of the IACs was determined by dynamic flow testing using sulfur dioxide (SO(2)), ammonia (NH(3)), hydrogen cyanide (HCN) and cyclohexane (C(6)H(12)) challenge gases under dry and humid conditions. The thermal decomposition and distribution of the impregnant on the activated carbon substrate is studied using X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermal analysis techniques. Relationships between gas adsorption capacity, impregnant distribution and the species of surface impregnants are discussed. PMID:21911221

  7. Marine loading vapor control systems

    SciTech Connect

    Babet, F.H.

    1996-09-01

    The EPA and State air quality control boards have mandated the collection and destruction or recovery of vapors generated by the loading of some hydrocarbons and chemicals into marine vessels. This is a brief overview of the main US Coast Guard requirements for marine vapor control systems. As with most regulations, they are open to interpretation. In an attempt to more clearly define the intent of the regulations, the US Coast Guard has issued guidelines to assist the certifying entities in ensuring compliance with intended regulations. If a company is contemplating the installation of a marine loading vapor control system, the authors strongly recommend that one engage the services of a certifying entity, either as the designer, or an advisor and ultimately the certifier of the system. This should be done well up front in the design of the system to avoid costly mistakes which can occur as a result of lack of knowledge or misinterpretation of the regulations and guidelines.

  8. Vapor deposition of thin films

    DOEpatents

    Smith, David C.; Pattillo, Stevan G.; Laia, Jr., Joseph R.; Sattelberger, Alfred P.

    1992-01-01

    A highly pure thin metal film having a nanocrystalline structure and a process of preparing such highly pure thin metal films of, e.g., rhodium, iridium, molybdenum, tungsten, rhenium, platinum, or palladium by plasma assisted chemical vapor deposition of, e.g., rhodium(allyl).sub.3, iridium(allyl).sub.3, molybdenum(allyl).sub.4, tungsten(allyl).sub.4, rhenium(allyl).sub.4, platinum(allyl).sub.2, or palladium(allyl).sub.2 are disclosed. Additionally, a general process of reducing the carbon content of a metallic film prepared from one or more organometallic precursor compounds by plasma assisted chemical vapor deposition is disclosed.

  9. Dissociative attachment reactions of electrons with strong acid molecules

    NASA Astrophysics Data System (ADS)

    Adams, Nigel G.; Smith, David; Viggiano, A. A.; Paulson, John F.; Henchman, Michael J.

    1986-06-01

    Using the flowing afterglow/Langmuir probe (FALP) technique, we have determined (at variously 300 and 570 K) the dissociative attachment coefficients β for the reactions of electrons with the common acids HNO3 (producing NO-2) and H2SO4 (HSO-4), the superacids FSO3H (FSO-3), CF3SO3H (CF3SO-3), ClSO3H (ClSO-3,Cl-), the acid anhydride (CF3SO2)2O (CF3SO-3), and the halogen halides HBr (Br-) and HI (I-). The anions formed in the reactions are those given in the parentheses. The reactions with HF and HCl were investigated, but did not occur at a measurable rate since they are very endothermic. Dissociative attachment is rapid for the common acids, the superacids, and the anhydride, the measured β being appreciable fractions of the theoretical maximum β for such reactions, βmax. The HI reaction is very fast ( β˜βmax) but the HBr reaction occurs much more slowly because it is significantly endothermic. The data indicate that the extreme acidity of the (Bronsted-type) superacids has its equivalence in the very efficient gas-phase dissociative attachment which these species undergo when reacting with free electrons. The anions of the superacids generated in these reactions, notably FSO-3 and CF3SO-3, are very stable (unreactive) implying exceptionally large electron affinities for the FSO3 and CF3SO3 radicals.

  10. Sensitivity of the Contact Chemoreceptors of the Blowfly to Vapors

    PubMed Central

    Dethier, V. G.

    1972-01-01

    Contact chemoreceptors on the mouthparts and legs of the blowfly Phormia regina that normally respond to aqueous solutions of sapid substances also respond to compounds in the gaseous state. Effective vapors include organic and inorganic acids and various unrelated nonpolar compounds. In general, the acids stimulate the salt receptor. Some nonpolar compounds stimulate the salt receptor while others inhibit it. Others stimulate the water, sugar, or “fifth” receptor. Differential action cannot be attributed to pH or solubility. Not all compounds that are irritating to mammalian mucous membranes or amphibian skin stimulate the contact chemoreceptors of the fly. Sensitivity to these vapors is a phenomenon analogous to the common chemical sense of vertebrates. Images PMID:16592005

  11. Low level vapor verification of monomethyl hydrazine

    NASA Technical Reports Server (NTRS)

    Mehta, Narinder

    1990-01-01

    The vapor scrubbing system and the coulometric test procedure for the low level vapor verification of monomethyl hydrazine (MMH) are evaluated. Experimental data on precision, efficiency of the scrubbing liquid, instrument response, detection and reliable quantitation limits, stability of the vapor scrubbed solution, and interference were obtained to assess the applicability of the method for the low ppb level detection of the analyte vapor in air. The results indicated that the analyte vapor scrubbing system and the coulometric test procedure can be utilized for the quantitative detection of low ppb level vapor of MMH in air.

  12. Waste Tank Vapor Project: Tank vapor database development

    SciTech Connect

    Seesing, P.R.; Birn, M.B.; Manke, K.L.

    1994-09-01

    The objective of the Tank Vapor Database (TVD) Development task in FY 1994 was to create a database to store, retrieve, and analyze data collected from the vapor phase of Hanford waste tanks. The data needed to be accessible over the Hanford Local Area Network to users at both Westinghouse Hanford Company (WHC) and Pacific Northwest Laboratory (PNL). The data were restricted to results published in cleared reports from the laboratories analyzing vapor samples. Emphasis was placed on ease of access and flexibility of data formatting and reporting mechanisms. Because of time and budget constraints, a Rapid Application Development strategy was adopted by the database development team. An extensive data modeling exercise was conducted to determine the scope of information contained in the database. a A SUN Sparcstation 1000 was procured as the database file server. A multi-user relational database management system, Sybase{reg_sign}, was chosen to provide the basic data storage and retrieval capabilities. Two packages were chosen for the user interface to the database: DataPrism{reg_sign} and Business Objects{trademark}. A prototype database was constructed to provide the Waste Tank Vapor Project`s Toxicology task with summarized and detailed information presented at Vapor Conference 4 by WHC, PNL, Oak Ridge National Laboratory, and Oregon Graduate Institute. The prototype was used to develop a list of reported compounds, and the range of values for compounds reported by the analytical laboratories using different sample containers and analysis methodologies. The prototype allowed a panel of toxicology experts to identify carcinogens and compounds whose concentrations were within the reach of regulatory limits. The database and user documentation was made available for general access in September 1994.

  13. New Approaches to Measuring Sticky Molecules: Improvement of Instrumental Response Times Using Active Passivation.

    PubMed

    Roscioli, J R; Zahniser, M S; Nelson, D D; Herndon, S C; Kolb, C E

    2016-03-10

    A novel method has been developed to improve sampling system response times for nominally "sticky" molecules such as HNO3 and NH3. The method reported here makes use of active, continuous passivation, where the instrument interfaces are continuously exposed to 0.01-1 ppm of fluorinated acidic or basic surfactants. To reduce HNO3 response times, perfluoroheptanoic acid and perfluorobutanesulfonic acid vapors are evaluated as passivation species. 1H,1H-perfluorooctylamine is used to improve NH3 response times. The resulting time responses using the perfluoroalkanoic acids are on the order of 0.4-0.7 s for a 75% quantitative recovery of HNO3, and 1-5 s for 90% recovery. Similar response time improvements are seen in detection of NH3 using perfluorooctylamine (<1 s for a 75% recovery, ∼2 s for 90% recovery). This generally applicable methodology significantly improves the capability of eddy covariance flux and real-time plume-based measurements of highly polar molecules that have historically been hampered by slow response times due to adsorption on sampling system surfaces. The utility of this approach is demonstrated by field measurements of HNO3 eddy covariance fluxes in a central U.S. prairie. PMID:26106902

  14. Stratospheric Sulfuric Acid and Black Carbon Aerosol Measured During POLARIS and its Role in Ozone Chemistry

    NASA Technical Reports Server (NTRS)

    Strawa, Anthony W.; Pueschel, R. F.; Drdla, K.; Verma, S.; Gore, Warren J. (Technical Monitor)

    1998-01-01

    Stratospheric aerosol can affect the environment in three ways. Sulfuric acid aerosol have been shown to act as sites for the reduction of reactive nitrogen and chlorine and as condensation sites to form Polar Stratospheric Clouds, under very cold conditions, which facilitate ozone depletion. Recently, modeling studies have suggested a link between BCA (Black Carbon Aerosol) and ozone chemistry. These studies suggest that HNO3, NO2, and O3 may be reduced heterogeneously on BCA particles. The ozone reaction converts ozone to oxygen molecules, while HNO3 and NO2 react to form NOx. Finally, a buildup of BCA could reduce the single-scatter albedo of aerosol below a value of 0.98, a critical value that has been postulated to change the effect of stratospheric aerosol from cooling to warming. Correlations between measured BCA amounts and aircraft usage have been reported. Attempts to link BCA to ozone chemistry and other stratospheric processes have been hindered by questions concerning the amount of BCA that exists in the stratosphere, the magnitude of reaction probabilities, and the scarcity of BCA measurements. The Ames Wire Impactors (AWI) participated in POLARIS as part of the complement of experiments on the NASA ER-2. One of our main objectives was to determine the amount of aerosol surface area, particularly BCA, available for reaction with stratospheric constituents and assess if possible, the importance of these reactions. The AWI collects aerosol and BCA particles on thin Palladium wires that are exposed to the ambient air in a controlled manner. The samples are returned to the laboratory for subsequent analysis. The product of the AWI analysis is the size, surface area, and volume distributions, morphology and elemental composition of aerosol and BCA. This paper presents results from our experiments during POLARIS and puts these measurements in the context of POLARIS and other missions in which we have participated. It describes modifications to the AWI data

  15. Transport of Elements By Geothermal And Volcanic Vapor

    NASA Astrophysics Data System (ADS)

    Kaasalainen, H. S.; Stefánsson, A.; Prapaipong, P.; Giroud, N.; Arnórsson, S.; Shock, E.

    2009-12-01

    Volatile species provide information on physical and chemical origin and processes in volcanic geothermal systems. Volatile metals and metalloids may be transported by both liquid and vapor phases that are often present in these systems, and some elements (e.g. As, Hg, Pb) may even be enriched in the vapor phases. The speciation and transport mechanism, as well as the origin of the elements in vapor is often poorly understood. Our aim is to characterize elemental concentrations and transport mechanism in the vapor phase in active geothermal systems. Samples of geothermal and volcanic vapor were collected from two-phase well discharges from Iceland and high temperature fumaroles in Vulcano Island and Solfatara field in Italy. Vapor and liquid phases were analyzed for major components and trace elements. Single phase volcanic vapor discharges had temperatures between 144 and 407°C. Their composition was dominated by H2O, but contained significant amounts of CO2 and acid gases (SO2, HCl, HF) whereas also H2S, H2 and N2 were present. In geothermal steam, with discharge pressures up to 42 bars, acid gases were absent and the steam consisted of 99% H2O, the rest being CO2, H2S, N2, and H2. Volcanic vapor condensates were analyzed for over 50 trace elements. Precipitation of condensate samples upon sampling and storage is commonly encountered problem. Different sampling protocols and sample treatments were tested to avoid and study their effects on the measured concentrations. The measured concentrations of some elements (e.g. Mg, Al, Sb) were found to show significant differences depending on the treatment, where as others (e.g. B, Ni, Zn) were not affected. In volcanic vapor, metals and metalloids were found in concentrations from lower ppb level up to tens of ppm. B shows highest concentrations followed by e.g. As, Pb, Zn, Mn, Ni, and Cu. In two phase well discharges, however, metals and metalloids were observed to be depleted in vapor compared to the liquid phase

  16. Vapor generation methods for explosives detection research

    SciTech Connect

    Grate, Jay W.; Ewing, Robert G.; Atkinson, David A.

    2012-12-01

    The generation of calibrated vapor samples of explosives compounds remains a challenge due to the low vapor pressures of the explosives, adsorption of explosives on container and tubing walls, and the requirement to manage (typically) multiple temperature zones as the vapor is generated, diluted, and delivered. Methods that have been described to generate vapors can be classified as continuous or pulsed flow vapor generators. Vapor sources for continuous flow generators are typically explosives compounds supported on a solid support, or compounds contained in a permeation or diffusion device. Sources are held at elevated isothermal temperatures. Similar sources can be used for pulsed vapor generators; however, pulsed systems may also use injection of solutions onto heated surfaces with generation of both solvent and explosives vapors, transient peaks from a gas chromatograph, or vapors generated by s programmed thermal desorption. This article reviews vapor generator approaches with emphasis on the method of generating the vapors and on practical aspects of vapor dilution and handling. In addition, a gas chromatographic system with two ovens that is configurable with up to four heating ropes is proposed that could serve as a single integrated platform for explosives vapor generation and device testing. Issues related to standards, calibration, and safety are also discussed.

  17. Method and apparatus for vapor detection

    NASA Technical Reports Server (NTRS)

    Lerner, Melvin (Inventor); Hood, Lyal V. (Inventor); Rommel, Marjorie A. (Inventor); Pettitt, Bruce C. (Inventor); Erikson, Charles M. (Inventor)

    1980-01-01

    The method disclosed herein may be practiced by passing the vapors to be sampled along a path with halogen vapor, preferably chlorine vapor, heating the mixed vapors to halogenate those of the sampled vapors subject to halogenation, removing unreacted halogen vapor, and then sensing the vapors for organic halogenated compounds. The apparatus disclosed herein comprises means for flowing the vapors, both sample and halogen vapors, into a common path, means for heating the mixed vapors to effect the halogenation reaction, means for removing unreacted halogen vapor, and a sensing device for sensing halogenated compounds. By such a method and means, the vapors of low molecular weight hydrocarbons, ketones and alcohols, when present, such as methane, ethane, acetone, ethanol, and the like are converted, at least in part, to halogenated compounds, then the excess halogen removed or trapped, and the resultant vapors of the halogenated compounds sensed or detected. The system is highly sensitive. For example, acetone in a concentration of 30 parts per billion (volume) is readily detected.

  18. Hydrazine vapor inactivates Bacillus spores

    NASA Astrophysics Data System (ADS)

    Schubert, Wayne W.; Engler, Diane L.; Beaudet, Robert A.

    2016-05-01

    NASA policy restricts the total number of bacterial spores that can remain on a spacecraft traveling to any planetary body which might harbor life or have evidence of past life. Hydrazine, N2H4, is commonly used as a propellant on spacecraft. Hydrazine as a liquid is known to inactivate bacterial spores. We have now verified that hydrazine vapor also inactivates bacterial spores. After Bacillus atrophaeus ATCC 9372 spores deposited on stainless steel coupons were exposed to saturated hydrazine vapor in closed containers, the spores were recovered from the coupons, serially diluted, pour plated and the surviving bacterial colonies were counted. The exposure times required to reduce the spore population by a factor of ten, known as the D-value, were 4.70 ± 0.50 h at 25 °C and 2.85 ± 0.13 h at 35 °C. These inactivation rates are short enough to ensure that the bioburden of the surfaces and volumes would be negligible after prolonged exposure to hydrazine vapor. Thus, all the propellant tubing and internal tank surfaces exposed to hydrazine vapor do not contribute to the total spore count.

  19. Acoustic Behavior of Vapor Bubbles

    NASA Technical Reports Server (NTRS)

    Prosperetti, Andrea; Oguz, Hasan N.

    1996-01-01

    In a microgravity environment vapor bubbles generated at a boiling surface tend to remain near it for a long time. This affects the boiling heat transfer and in particular promotes an early transition to the highly inefficient film boiling regime. This paper describes the physical basis underlying attempts to remove the bubbles by means of pressure radiation forces.

  20. INDOOR AIR VAPOR INTRUSION SEMINAR

    EPA Science Inventory

    This seminar is sponsored by the ORD in collaboration with the Office of Solid Waste and Emergency Response. The goal of this seminar is to present information and guidance to evaluate, assess and characterize chemical vapor pathways migrating into structures resulting from conta...