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Sample records for acid hno3 ozone

  1. Antarctic ozone - Meteoric control of HNO3

    NASA Astrophysics Data System (ADS)

    Prather, Michael J.; Rodriguez, Jose M.

    1988-01-01

    Atmospheric circulation leads to an accumulation of debris from meteors in the Antarctic stratosphere at the beginning of austral spring. The major component of meteoric material is alkaline, comprised predominantly of the oxides of magnesium and iron. These metals may neutralize the natural acidity of stratospheric aerosols, remove nitric acid from the gas phase, and bond it as metal nitrates in the aerosol phase. Removal of nitric acid vapor has been previously shown to be a critical link in the photochemical depletion of ozone in the Antarctic spring, by allowing for increased catalytic loss from chlorine and bromine.

  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. 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.

  4. Passive sampler for measurements of atmospheric nitric acid vapor (HNO3) concentrations.

    PubMed

    Bytnerowicz, A; Padgett, P E; Arbaugh, M J; Parker, D R; Jones, D P

    2001-12-01

    Nitric acid (HNO3) vapor is an important nitrogenous air pollutant responsible for increasing saturation of forests with nitrogen and direct injury to plants. The USDA Forest Service and University of California researchers have developed a simple and inexpensive passive sampler for monitoring air concentrations of HNO3. Nitric acid is selectively absorbed on 47-mm Nylasorb nylon filters with no interference from particulate NO3-. Concentrations determined with the passive samplers closely corresponded with those measured with the co-located honeycomb annular denuder systems. The PVC protective caps of standardized dimensions protect nylon filters from rain and wind and allow for reliable measurements of ambient HNO3 concentrations. The described samplers have been successfully used in Sequoia National Park, the San Bernardino Mountains, and on Mammoth Mountain in California.

  5. 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.

  6. Dissociation of strong acid revisited: X-ray photoelectron spectroscopy and molecular dynamics simulations of HNO3 in water

    SciTech Connect

    Lewis, Tanza; Winter, Berndt; Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J.; Tobias, Douglas J.; Hemminger, J. C.

    2011-08-04

    Molecular-level insight into the dissociation of nitric acid in water is obtained from photoelectron X-ray spectroscopy and first-principles molecular dynamics (MD) simulations. Our combined studies reveal surprisingly abrupt changes in solvation configurations of undissociated nitric acid at approximately 4 M concentration. Experimentally, this is inferred from N1s binding energy shifts of HNO3(aq) as a function of concentration, and is associated with variations in the local electronic structure of the nitrogen atom. It also shows up as a discontinuity in the degree of dissociation as a function of concentration, determined here from the N1s photoelectron signal intensity, which can be separately quantified for undissociated HNO3(aq) and dissociated NO3-(aq). Intermolecular interactions within the nitric acid solution are discussed on the basis of MD simulations, which reveal that molecular HNO3 interacts remarkably weakly with solvating water molecules at low concentration; around 4 M there is a turnover to a more structured solvation shell, accompanied by an increase in hydrogen bonding between HNO3 and water. We suggest that the driving force behind the more structured solvent configuration of HNO3 is the overlap of nitric acid solvent shells that sets in around 4 M concentration. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  7. 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.

  8. 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

  9. 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.

  10. The influence of treatment temperature on the acidity of MWCNT oxidized by HNO 3 or a mixture of HNO 3/H 2SO 4

    NASA Astrophysics Data System (ADS)

    Saleh, Tawfik A.

    2011-06-01

    The nature of multi-walled carbon nanotubes (MWCNTs) varies with the change in oxidation conditions. In this work, the effect of treatment temperatures on the acidity of MWCNTs was studied. Oxidation was performed by refluxing the MWCNTs in nitric acid or mixtures of sulfuric acid and nitric acid at different temperatures. After oxidative treatment, a quantitative characterization of o-MWCNTs has been performed using acid-base titrations which show that the number of surface acidic functional groups increased by increasing the treatment temperatures. Energy dispersive X-ray (EDX) measurements show that the oxygen content increased with increasing treatment temperatures. Fourier transform infrared absorption spectroscopy (FTIR) was used for qualitative characterization. It has been demonstrated that the acidity is a function of the type of oxidizing agent used and the treatment temperatures. Due to the importance in attachment strategies and functionalization, this study adds to the global discussion of the possibility of controlling the MWCNTs' surface chemistry which plays a crucial role in determining its reactivity.

  11. The use of NO y , H2O2, and HNO3 as indicators for ozone-NO x -hydrocarbon sensitivity in urban locations

    NASA Astrophysics Data System (ADS)

    Sillman, Sanford

    1995-07-01

    Correlations are presented between model predictions for O3-NOx-hydrocarbon sensitivity and afternoon concentrations of four "indicator species": NOy, O3/(NOy-NOx), HCHO/NOy, and H2O2/HNO3. The indicator species correlations are based on a series of photochemical simulations with varying rates of anthropogenic and biogenic emissions and meteorology. Hydrocarbon-sensitive chemistry in models is shown to be linked to afternoon NOy > 20 ppb, O3/(NOy - NOx) < 7, HCHO/NOy < 0.28, and H2O2/HNO3 < 0.4. Lower NOy and higher ratios correspond with NOx-sensitive ozone. The correlation between NOx-hydrocarbon sensitivity and indicator species remains, even when model emission rates and hydrocarbon/NOx ratios are changed by a factor of 2. Methods are developed for evaluating the goodness of fit between model NOx-hydrocarbon sensitivity and indicator values. Ozone chemistry is also analyzed in terms of fundamental properties of odd hydrogen, and theoretical criteria for the transition between NOx- and hydrocarbon-sensitive regimes are derived. A theoretical correlation between O3 and H2O2 + NOy - NOx is developed as a way to extend rural O3-NOy correlations into urban locations. Measured indicator values during pollution events in Los Angeles, Atlanta, and rural Virginia are used to illustrate the range of observed values under different environmental conditions.

  12. Dry deposition of nitrogen compounds (NO2, HNO3, NH3), sulfur dioxide and ozone in West and Central African ecosystems using the inferential method

    NASA Astrophysics Data System (ADS)

    Adon, M.; Galy-Lacaux, C.; Yoboue, V.; Delon, C.; Solmon, F.; Kaptue Tchuente, A. T.

    2013-05-01

    This work is part of the IDAF program (IGAC-DEBITS-AFRICA) and is based on the long term monitoring of gas concentrations (1998-2007) established on seven remote sites representative of major African ecosystems. Dry deposition fluxes were estimated by the inferential method using on one hand surface measurements of gas concentrations (NO2, HNO3, NH3, SO2, and O3) and on the other hand simulated dry deposition velocities (Vd). Vd were calculated using the big-leaf model of Zhang et al. (2003b). In the model of deposition, surface and meteorological conditions specific to IDAF sites have been adapted in order to simulate Vd representative of major African ecosystems. The monthly, seasonal and annual mean variations of gaseous dry deposition fluxes (NO2, HNO3, NH3, O3, and SO2) are analyzed. Along the latitudinal transect of ecosystems, the annual mean dry deposition fluxes of nitrogen compounds range from 0.4 ± 0.0 to 0.8 ± 0.2 kg N ha-1 yr-1 for NO2, from 0.7 ± 0.1 to 1.0 ± 0.3 kg N ha-1 yr-1 for HNO3, and from 2.3 ± 0.8 to 10.5 ± 5.0 kg N ha-1 yr-1 for NH3 over the study period (1998-2007). The total nitrogen dry deposition flux (NO2+HNO3+NH3) is more important in forests (11.2-11.8 kg N ha-1 yr-1) than in wet and dry savannas (3.4-5.3 kg N ha-1 yr-1). NH3 dominated nitrogen dry deposition, representing 67-80% of the total. The annual mean dry deposition fluxes of ozone range between 11.3 ± 4.7 and 17.5 ± 3.0 kg ha-1 yr-1 in dry savannas, 17.5 ± 3.0 and 19.2 ± 2.9 kg ha-1 yr-1 in wet savannas, and 10.6 ± 2.0 and 13.2 ± 3.6 kg ha-1 yr-1 in forests. Lowest O3 dry deposition fluxes in forests are correlated to low measured O3 concentrations, lower of a factor of 2-3, compared to others ecosystems. Along the ecosystem transect, annual mean of SO2 dry deposition fluxes present low values and a small variability (0.5 to 1 kg S ha-1 yr-1). No specific trend in the interannual variability of these gaseous dry deposition fluxes is observed over the study period.

  13. Dry deposition of nitrogen compounds (NO2, HNO3, NH3), sulfur dioxide and ozone in west and central African ecosystems using the inferential method

    NASA Astrophysics Data System (ADS)

    Adon, M.; Galy-Lacaux, C.; Delon, C.; Yoboue, V.; Solmon, F.; Kaptue Tchuente, A. T.

    2013-11-01

    This work is part of the IDAF program (IGAC-DEBITS-AFRICA) and is based on the long-term monitoring of gas concentrations (1998-2007) established at seven remote sites representative of major African ecosystems. Dry deposition fluxes were estimated by the inferential method using on the one hand surface measurements of gas concentrations (NO2, HNO3, NH3, SO2 and O3) and on the other hand modeled exchange rates. Dry deposition velocities (Vd) were calculated using the big-leaf model of Zhang et al. (2003b). The bidirectional approach is used for NH3 surface-atmosphere exchange (Zhang et al., 2010). Surface and meteorological conditions specific to IDAF sites have been used in the models of deposition. The seasonal and annual mean variations of gaseous dry deposition fluxes (NO2, HNO3, NH3, O3 and SO2) are analyzed. Along the latitudinal transect of ecosystems, the annual mean dry deposition fluxes of nitrogen compounds range from -0.4 to -0.8 kg N ha-1 yr-1 for NO2, from -0.7 to -1.0 kg N ha-1 yr-1 for HNO3 and from -0.7 to -8.3 kg N ha-1 yr-1 for NH3 over the study period (1998-2007). The total nitrogen dry deposition flux (NO2+HNO3+NH3) is more important in forests (-10 kg N ha-1 yr-1) than in wet and dry savannas (-1.6 to -3.9 kg N ha-1 yr-1). The annual mean dry deposition fluxes of ozone range between -11 and -19 kg ha-1 yr-1 in dry and wet savannas, and -11 and -13 kg ha-1 yr-1 in forests. Lowest O3 dry deposition fluxes in forests are correlated to low measured O3 concentrations, lower by a factor of 2-3, compared to other ecosystems. Along the ecosystem transect, the annual mean of SO2 dry deposition fluxes presents low values and a small variability (-0.5 to -1 kg S ha-1 yr-1). No specific trend in the interannual variability of these gaseous dry deposition fluxes is observed over the study period.

  14. 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.

  15. 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.

  16. Thermochemical Kinetics of H2O and HNO3 on crystalline Nitric Acid Hydrates (alpha-, beta-NAT, NAD) in the range 175-200 K

    NASA Astrophysics Data System (ADS)

    Rossi, Michel J.; Iannarelli, Riccardo

    2015-04-01

    The growth of NAT (Nitric Acid Trihydrate, HNO3x3H2O) and NAD (Nitric Acid Dihydrate, HNO3x2H2O) on an ice substrate, the evaporative lifetime of NAT and NAD as well as the interconversion of alpha- and beta-NAT competing with evaporation and growth under UT/LS conditions depends on the interfacial kinetics of H2O and HNO3 vapor on the condensed phase. Despite the existence of some literature results we have embarked on a systematic investigation of the kinetics using a multidiagnostic experimental approach enabled by the simultaneous observation of both the gas (residual gas mass spectrometry) as well as the condensed phase (FTIR absorption in transmission). We report on thermochemically consistent mass accommodation coefficients alpha and absolute evaporation rates Rev/molecule s-1cm-3 as a function of temperature which yields the corresponding vapor pressures of both H2O and HNO3 in equilibrium with the crystalline phases, hence the term thermochemical kinetics. These results have been obtained using a stirred flow reactor (SFR) using a macroscopic pure ice film of 1 micron or so thickness as a starting substrate mimicking atmospheric ice particles and are reported in a phase diagram specifically addressing UT (Upper Troposphere)/LS (Lower Stratosphere) conditions as far as temperature and partial pressures are concerned. The experiments have been performed either at steady-state flow conditions or in transient supersaturation using a pulsed solenoid valve in order to generate gas pulses whose decay were subsequently monitored in real time. Special attention has been given to the effect of the stainless-steel vessel walls in that Langmuir adsorption isotherms for H2O and HNO3 have been used to correct for wall-adsorption of both probe gases. Typically, the accommodation coefficients of H2O and HNO3 are similar throughout the temperature range whereas the rates of evaporation Rev of H2O are significantly larger than for HNO3 thus leading to the difference in

  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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. First characterization and validation of FORLI-HNO3 vertical profiles retrieved from IASI/Metop

    NASA Astrophysics Data System (ADS)

    Ronsmans, Gaétane; Langerock, Bavo; Wespes, Catherine; Hannigan, James W.; Hase, Frank; Kerzenmacher, Tobias; Mahieu, Emmanuel; Schneider, Matthias; Smale, Dan; Hurtmans, Daniel; De Mazière, Martine; Clerbaux, Cathy; Coheur, Pierre-François

    2016-09-01

    Knowing the spatial and seasonal distributions of nitric acid (HNO3) around the globe is of great interest and allows us to comprehend the processes regulating stratospheric ozone, especially in the polar regions. Due to its unprecedented spatial and temporal sampling, the nadir-viewing Infrared Atmospheric Sounding Interferometer (IASI) is capable of sounding the atmosphere twice a day globally, with good spectral resolution and low noise. With the Fast Optimal Retrievals on Layers for IASI (FORLI) algorithm, we are retrieving, in near real time, columns as well as vertical profiles of several atmospheric species, among which is HNO3. We present in this paper the first characterization of the FORLI-HNO3 profile products, in terms of vertical sensitivity and error budgets. We show that the sensitivity of IASI to HNO3 is highest in the lower stratosphere (10-20 km), where the largest amounts of HNO3 are found, but that the vertical sensitivity of IASI only allows one level of information on the profile (degrees of freedom for signal, DOFS; ˜ 1). The sensitivity near the surface is negligible in most cases, and for this reason, a partial column (5-35 km) is used for the analyses. Both vertical profiles and partial columns are compared to FTIR ground-based measurements from the Network for the Detection of Atmospheric Composition Change (NDACC) to characterize the accuracy and precision of the FORLI-HNO3 product. The profile validation is conducted through the smoothing of the raw FTIR profiles by the IASI averaging kernels and gives good results, with a slight overestimation of IASI measurements in the upper troposphere/lower stratosphere (UTLS) at the six chosen stations (Thule, Kiruna, Jungfraujoch, Izaña, Lauder and Arrival Heights). The validation of the partial columns (5-35 km) is also conclusive with a mean correlation of 0.93 between IASI and the FTIR measurements. An initial survey of the HNO3 spatial and seasonal variabilities obtained from IASI

  3. 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

  4. 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

  5. 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.

  6. 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.

  7. Effects of nitric acid gas alone or in combination with ozone on healthy volunteers

    SciTech Connect

    Aris, R.; Christian, D.; Tager, I.; Ngo, L.; Finkbeiner, W.E.; Balmes, J.R. )

    1993-10-01

    Nitric acid (HNO3) is the most prevalent acid air pollutant in the western United States and has the potential to cause adverse respiratory effects through both acidification and oxidation reactions. To study this potential, we measured physiologic (specific airway resistance, SRaw, FEV1, and FVC) and bronchoalveolar lavage (total and differential cell counts, LDH, fibronectin, and total protein) end points in a group of 10 healthy, athletic subjects who were exposed to 500 micrograms/m3 of HNO3 gas or filtered air for 4 h during moderate exercise (ventilatory rate, 40 L/min) and underwent bronchoscopy 18 h later. Under an identical protocol, 10 healthy subjects were exposed to 500 micrograms/m3 of HNO3 gas plus 0.20 ppm ozone (O3) or 0.20 ppm O3 alone to determine if HNO3 might enhance the toxicity of O3. In addition to bronchoalveolar lavage (BAL), we employed the techniques of isolated left mainstem bronchial lavage and bronchial biopsy to determine if proximal airway injury was caused by pollutant exposure and whether there was any correlation with the degree of distal lung injury as assessed by BAL. We found no significant differences in pulmonary function tests or in the cellular or biochemical constituents in either the BAL or the left mainstem lavage fluids between the HNO3 and the air exposures. Similarly, there were no differences in these end points between the HNO3/O3 and the O3 exposures. Furthermore, there were no significant differences in the bronchial biopsy specimens between the HNO3 and air exposures or between the HNO3/O3 and O3 exposures.

  8. NARSTO EPA SS HOUSTON NH3 HNO3 DATA

    Atmospheric Science Data Center

    2014-04-25

    NARSTO EPA SS HOUSTON NH3 HNO3 DATA Project Title:  NARSTO Discipline:  ... Parameters:  Ammonia Nitric Acid Order Data:  ASDC Order Tool:   Order Data Guide Documents:  ... Earth Related Data:  Environmental Protection Agency Supersites Houston, Texas SCAR-B Block:  ...

  9. 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

  10. 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

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. Laboratory studies of HNO3/H2O mixtures at low temperatures

    NASA Technical Reports Server (NTRS)

    Hanson, David; Mauersberger, Konrad

    1988-01-01

    The possibility of stratospheric HN3 condensing out of the gas-phase at low temperatures has become important in the chemical explanations of the rapid loss of Antarctic ozone in spring. Consequently, knowledge about the behavior of the vapor pressures of water and HNO3 over HNO3/water mixtures at stratospheric temperatures is needed to determine if HNO3 could condense, and by how much the HNO3 vapor pressure could be depressed. Laboratory investigations of vapor pressures above HNO3/water mixtures are described. Vapor pressures were initially measured over liquid and frozen bulk mixtures contained in a glass still which was attached to a stainless steel vacuum chamber. The total pressure in the chamber was monitored with a precision pressure sensor, and the vapor pressures of HNO3, water and impurities were analyzed with a mass spectrometer beam system. In a second set of experiments, vapor deposits were made to produce ice and the mono- and trihydrate of HNO3. Further data and conclusions are presented.

  17. 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

  18. 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

  19. 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

  20. 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.

  1. 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.

  2. A Study on the Passivation Behavior and Semiconducting Properties of Gamma Titanium Aluminide in 0.1 N H2SO4, HNO3, and HClO4 Acidic Solutions

    NASA Astrophysics Data System (ADS)

    Memarbashi, S.; Saebnoori, E.; Shahrabi, T.

    2014-03-01

    The study focuses on the passivation behavior of single-gamma-phase titanium aluminide in acidic solutions with a particular emphasis on the role of oxidizing strength in characteristics of passive layer. The report includes potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies along with Mott-Schottky analysis in order to determine the corrosion behavior of the alloy and the semiconducting properties of the scale formed during exposure to acidic environment. Passive current density measured from potentiodynamic polarization curve, polarization resistance ( R p) estimated by EIS, defect density, and flatband potential drawn from Mott-Schottky analysis are mainly used in estimating the ability of passive film formed on alloy in protecting it against high corrosion rates in Sulfuric acid (a non-oxidizing acid), perchloric acid, and nitric acid (oxidizing acid with different oxidizing strength). The results show that passive current density ( i pass) in Sulfuric acid is 2.67 × 10-5 A cm-2, which is 2.5 and 3 times greater than the values obtained in perchloric acid ( i pass = 9.91 × 10-6) and nitric acid ( i pass = 7.98 × 10-6), respectively. EIS data reveal that the value of R p in sulfuric acid (20 kΩ cm2) is about three and five times smaller than that its value in perchloric acid and Nitric acid, respectively. Mott-Schottky analysis shows that the passive layer exhibits an n-type semiconducting characteristics irrespective of acidic environment. The greatest and the smallest values of donor density ( N D) are obtained for the passive scale formed in sulfuric acid ( N D, H2SO4 = 18.36 × 1019) and nitric acid ( N D, HNO3 = 13.13 × 1019), respectively. The report concludes that characteristics of the passive scale are directly affected by reduction potential of the acid, which is the criterion of its oxidizing strength. An increase in the oxidizing strength of the acidic solution results in formation of more protective and less

  3. 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.

  4. Effects of HNO3 concentration on the pit morphologies of aluminum foil etched in HNO3-HCl and HNO3-H2SO4-HCl solutions

    NASA Astrophysics Data System (ADS)

    Yi, Quan-xiu; He, Ye-dong; Peng, Ning; Song, Hong-zhou; Yang, Xiao-fei; Cai, Xiao-yu

    2016-01-01

    In this work, the effects of HNO3 concentration on the pit morphologies of high-cubic-texture aluminum foil etched in HNO3-HCl and HNO3-H2SO4-HCl solutions were investigated. When the aluminum foil was etched in HNO3-HCl solutions, the morphologies of pits transformed from irregular tunnels to typical tunnels (as inverted pyramids) and shallow cuboids as the HNO3 concentration in the etchant solution was increased. However, as the HCl concentration in the etchant solution was increased, the morphologies of pits transformed from shallow cuboids to typical tunnels (as inverted pyramids) and irregular tunnels. When the aluminum foil was etched in n N HNO3-(7.2- n) N H2SO4-0.8 N HCl solutions, the morphologies of the pits transformed from typical tunnels (i.e., the number of sub-tunnels formed on the main tunnels increased) to irregular tunnels (corrugated tunnels and polyline tunnels) as the HNO3 concentration in the etchant solution was increased. These effects are attributed primarily to corrosion on the (100) and (010) faces of pits being accelerated and to the (001) faces being prone to passivation to different degrees when various concentrations of HNO3 are added to the etchant solutions.

  5. Heterogeneous kinetics of H2O, HNO3 and HCl on HNO3 hydrates (α-NAT, β-NAT, NAD) in the range 175-200 K

    NASA Astrophysics Data System (ADS)

    Iannarelli, Riccardo; Rossi, Michel J.

    2016-09-01

    Experiments on the title compounds have been performed using a multidiagnostic stirred-flow reactor (SFR) in which the gas phase as well as the condensed phase has been simultaneously investigated under stratospheric temperatures in the range 175-200 K. Wall interactions of the title compounds have been taken into account using Langmuir adsorption isotherms in order to close the mass balance between deposited and desorbed (recovered) compounds. Thin solid films at 1 µm typical thickness have been used as a proxy for atmospheric ice particles and have been deposited on a Si window of the cryostat, with the optical element being the only cold point in the deposition chamber. Fourier transform infrared (FTIR) absorption spectroscopy in transmission as well as partial and total pressure measurement using residual gas mass spectrometry (MS) and sensitive pressure gauges have been employed in order to monitor growth and evaporation processes as a function of temperature using both pulsed and continuous gas admission and monitoring under SFR conditions. Thin solid H2O ice films were used as the starting point throughout, with the initial spontaneous formation of α-NAT (nitric acid trihydrate) followed by the gradual transformation of α- to β-NAT at T > 185 K. Nitric acid dihydrate (NAD) was spontaneously formed at somewhat larger partial pressures of HNO3 deposited on pure H2O ice. In contrast to published reports, the formation of α-NAT proceeded without prior formation of an amorphous HNO3 / H2O layer and always resulted in β-NAT. For α- and β-NAT, the temperature-dependent accommodation coefficient α(H2O) and α(HNO3), the evaporation flux Jev(H2O) and Jev(HNO3) and the resulting saturation vapor pressure Peq(H2O) and Peq(HNO3) were measured and compared to binary phase diagrams of HNO3 / H2O in order to afford a thermochemical check of the kinetic parameters. The resulting kinetic and thermodynamic parameters of activation energies for evaporation (Eev) and

  6. Investigations on HONO formation from photolysis of adsorbed HNO3 on quartz glass surfaces.

    PubMed

    Laufs, Sebastian; Kleffmann, Jörg

    2016-04-14

    During the last few decades, nitrous acid (HONO) has attracted significant attention as a major source of the OH radical, the detergent of the atmosphere. However, the different daytime sources identified in the laboratory are still the subject of controversial discussion. In the present study, one of these postulated HONO sources, the heterogeneous photolysis of nitric acid (HNO3), was studied on quartz glass surfaces in a photo flow-reactor under atmospherically relevant conditions. In contrast to other investigations, a very low HNO3 photolysis frequency for HONO formation of J(HNO3→ HONO) = 2.4 × 10(-7) s(-1) (0° SZA, 50% r.h.) was determined. If these results can be translated to atmospheric surfaces, HNO3 photolysis cannot explain the significant HONO levels in the daytime atmosphere. In addition, it is demonstrated that even the small measured yields of HONO did not result from the direct photolysis of HNO3 but rather from the consecutive heterogeneous conversion of the primary photolysis product NO2 on the humid surfaces. The secondary NO2 conversion was not photo-enhanced on pure quartz glass surfaces in good agreement with former studies. A photolysis frequency for the primary reaction product NO2 of J(HNO3→ NO2) = 1.1 × 10(-6) s(-1) has been calculated (0° SZA, 50% r.h.), which indicates that renoxification by photolysis of adsorbed HNO3 on non-reactive surfaces is also a minor process in the atmosphere. PMID:26997156

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. Temporal variation in daily concentrations of ozone and acid-related substances at Saturna Island, British Columbia.

    PubMed

    Vingarzan, Roxanne; Thomson, Bruce

    2004-04-01

    A multiple linear regression model was used to investigate seasonal and long-term trends in concentrations of ozone (O3) and acid-related substances at the Saturna Island monitoring station in southwestern British Columbia from 1991 to 2000. Statistically significant primary (dominant) cycles with a period of 1 yr were found for O3, sulfur dioxide (SO2), nitric acid (HNO3), and aerosol concentrations of sulfate (SO4(2-)), calcium (Ca2+) and chloride (Cl-). Of these, peak median concentrations occurred during the spring for O3 and Ca2+, during the warmer, drier months (April-September) for SO4(2-) and HNO3, and during the cooler, wetter months (October-March) for SO2 and Cl-. Statistically significant secondary cycles of 6 months duration were seen for concentrations of O3, SO4(2-), HNO3, Ca2+, and Cl-. Daily maximum O3 concentrations exhibited a statistically significant increase over the period of record of 0.33 +/- 0.26 ppb/yr. Statistically significant declines were found for concentrations of SO2, SO4(2-), HNO3, Ca2+, and potassium, ranging from 20 to 36% from levels at the start of the sampling period. Declines in ambient concentrations of SO2, SO4(2-), and HNO3 reflect local declines in anthropogenic emissions of the primary precursors SO2 and NOx over the past decade. Trends in Ca2+ and potassium ion concentrations are in line with a broader North American declining trend in acid-neutralizing cations.

  12. Nucleation and growth of HNO3-3H2O particles in the polar stratosphere

    NASA Technical Reports Server (NTRS)

    Wofsy, Steven C.; Gobbi, Gian Paolo; Salawitch, Ross J.; Mcelroy, Michael B.

    1990-01-01

    Growth of nitric acid trihydrate (NAT) particles on background stratospheric aerosols is examined for an isolated air parcel cooled at a uniform rate. During the process of nucleation, the saturation ratio of HNO3 vapor reaches a maximum value between 2 and 15, corresponding to supercooling by 1-4 K. If cooling rates exceed 0.5-1 K/day, small particles of NAT are produced. A major fraction of the available condensation nuclei is activated and removal of HNO3 by gravitational settling is slow. If cooling rates are less than 0.5-1 K/day, the number of aerosols that nucleate is reduced, leading to differential growth of large NAT particles. Observations of 5 micron radius particles in clouds at temperatures above the water frost point may reflect condensation of NAT on ice particles that fall through a column of air as it is cooled. Rapid condensation of HNO3 on ice particles is promoted by the high supersaturation attained during nucleation and maintained during subsequent cooling. This process provides a mechanism for irreversible removal of HNO3.

  13. Growth of upper tropospheric aerosols due to uptake of HNO3

    NASA Astrophysics Data System (ADS)

    Romakkaniemi, S.; Kokkola, H.; Petzold, A.; Laaksonen, A.

    2004-01-01

    The effect of nitric acid on the equilibrium size distributions of upper tropospheric aerosols is calculated as a function of relative humidity. It is shown that HNO3 concentrations above a few tenths of a ppb can cause substantial increases in haze mode particle concentrations at relative humidities at about 60% and above. The effect can be strongly magnified when letovicite particles are present in addition to sulfuric acid aerosols. This is mainly due to the lowering of the deliquescence RH of letovicite in the presence of gaseous nitric acid at low temperatures. We have also compared equilibrium calculations of the HNO3 effect with observations of increased haze mode concentrations at relative humidities above 50% (Petzold et al., 2000). Nitric acid mixing ratios on the order of 0.5-2 ppb may explain the observed increase of haze mode particles at least partially.

  14. 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.

  15. Morphological modification of MWCNT functionalized with HNO3/H2SO4 mixtures.

    PubMed

    Pistone, A; Ferlazzo, A; Lanza, M; Milone, C; Iannazzo, D; Piperno, A; Piperopoulos, E; Galvagno, S

    2012-06-01

    The acidic oxidation with HNO3/H2SO4 mixtures is widely reported as an effective method to functionalize multi-walled carbon nanotubes (MWCNT). Although effective, a bad control of the oxidation conditions frequently cause serious modifications of carbon nanotube network, limiting further potential applications. Investigations about the effect of functionalization operating conditions on the morphological, chemical and chemical-physical properties of MWCNT can be useful for a proper setting of oxidation reactions of MWCNT according to their specific applications. In this work the effect of HNO3/H2SO4 ratio on the morphological and chemical-physical properties and on the degree of functionalization of MWCNT was investigated. Electron microscopy, thermogravimetric, X-ray diffraction, titration and water dispersion analyses clearly revealed that the increase of the amount of concentrated sulphuric acid in the HNO3/H2SO4 mixture lead to an increase of the amount of functional groups on the MWCNT surface but also to an increase of structural damage in terms of tube cutting and generation of additional defects in the graphitic network of pristine PMID:22905576

  16. 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

  17. 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

  18. Influence of ozone and simulated acidic rain on microorganisms in the rhizosphere of Sorghum.

    PubMed

    Shafer, S R

    1988-01-01

    Seedlings of a sorghum x sudangrass hybrid in pots of non-sterile soil-sand mix were exposed to ozone (O(3)) at 0, 0.15, or 0.30 microl litre(-1) (7 h day(-1), 3 days week(-1)) and simulated rain (SR) adjusted with H(2)SO(4) + HNO(3) to pH 5.5, 4.0, or 2.5 (2 cm in 1.5 h per event; 2 events week(-1)) over 3 weeks in a greenhouse. Ozone suppressed shoot and root growth, but increased acid content (i.e. pH < 5.5) of SR stimulated shoot growth and had inconsistent effects on root growth. Ozone x SR chemistry interactions significantly affected plant growth. Data for 'total' bacterial populations in the rhizosphere (number of colony-forming units per gram of rhizosphere soil) exhibited a curvilinear relationship with O(3) (maximum at 0.15 microl liter(-1)). Increased acid content of SR stimulated numbers of 'total' bacteria but suppressed populations of amylolytic bacteria. Ozone and acid content of SR tended to stimulate numbers of fungal propagules in the rhizosphere, but this effect was not significant. Numbers of rhizosphere bacteria capable of phosphatase activity increased linearly with O(3), but only when SR chemistry was characterised by pH 4.0. Data for other populations of rhizosphere microorganisms did not exhibit significant relationships to O3 x SR chemistry interactions.

  19. Growth of upper tropospheric aerosols due to uptake of HNO3

    NASA Astrophysics Data System (ADS)

    Romakkaniemi, S.; Kokkola, H.; Petzold, A.; Laaksonen, A.

    2004-03-01

    The effect of nitric acid on the equilibrium size distributions of upper tropospheric aerosols is calculated as a function of relative humidity. It is shown that HNO3 concentrations above a few tenths of a ppb can cause substantial increases in haze mode particle concentrations at relative humidities at about 60% and above. The effect can be strongly magnified when letovicite particles are present in addition to sulfuric acid aerosols. Letovicite particles are less acidic than the sulfuric acid particles and so more nitric acid can be absorbed. This effect can be seen even at RH below 50% due to the lowering of the deliquescence RH of letovicite in the presence of gaseous nitric acid at low temperatures. We have also compared equilibrium calculations of the HNO3 effect with observations of increased haze mode concentrations at relative humidities above 50% (Petzold et al., 2000). Nitric acid mixing ratios on the order of 0.5-2ppb may explain the observed increase of haze mode particles at least partially.

  20. 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

  1. 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

  2. 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

  3. 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.

  4. 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

  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. Aircraft measurements of O3, HNO3, and N2O in the winter Arctic lower stratosphere during the Stratosphere-Troposphere Experiment by Aircraft Measurements (STREAM) 1

    NASA Astrophysics Data System (ADS)

    Bregman, A.; van Velthoven, P. F. J.; Wienhold, F. G.; Fischer, H.; Zenker, T.; Waibel, A.; Frenzel, A.; Arnold, F.; Harris, G. W.; Bolder, M. J. A.; Lelieveld, J.

    1995-06-01

    Simultaneous in situ measurements of O3, HNO3, and N2O were performed in the Arctic (68°-74°N) lower stratosphere during February 1993 on board a Cessna Citation aircraft up to 12.5 km altitude, during the first Stratosphere-Troposphere Experiment by Aircraft Measurements (STREAM) campaign. Strong variations in the concentrations, distributions, and ratios of these trace gases were found from the maximum altitude down to the tropopause. Close to the tropopause, vortex air was present with relatively low N2O concentrations. The observed N2O-HNO3 relation agrees with earlier measurements of total nitrogen and N2O inside the vortex, suggesting subsidence of vortex air across the bottom of the vortex. This air also contained low O3 concentrations relative to N2O, indicating enhanced O3 loss by chemical reactions involving stratospheric particles. Based on trajectory calculations and assuming a potential temperature cooling rate of 0.6 K d-1, we estimate an O3 loss of 4-7 ppbv d-1 (0.9-1.2% d-1), in the Arctic lower stratosphere for the period January-February 1993. Air parcels originating from middle latitudes, containing relatively low O3 and N2O concentrations, may have originated from the vortex earlier in the winter. In addition, the results also show high HNO3 concentrations relative to O3 and N2O. Air parcels originating from high latitudes may have been enriched in HNO3 by sedimentation and evaporation of nitric acid containing particles, which would explain the relatively high HNO3 concentrations and HNO3/O3 ratios measured. Heterogeneous chemistry on sulfuric acid particles, probably enhanced in concentration by gravitational settling of the Pinatubo aerosol, is the most plausible explanation for the observed high HNO3 concentrations relative to N2O in air parcels originating from midlatitudes.

  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. Model development for naphthenic acids ozonation process.

    PubMed

    Al Jibouri, Ali Kamel H; Wu, Jiangning

    2015-02-01

    Naphthenic acids (NAs) are toxic constituents of oil sands process-affected water (OSPW) which is generated during the extraction of bitumen from oil sands. NAs consist mainly of carboxylic acids which are generally biorefractory. For the treatment of OSPW, ozonation is a very beneficial method. It can significantly reduce the concentration of NAs and it can also convert NAs from biorefractory to biodegradable. In this study, a factorial design (2(4)) was used for the ozonation of OSPW to study the influences of the operating parameters (ozone concentration, oxygen/ozone flow rate, pH, and mixing) on the removal of a model NAs in a semi-batch reactor. It was found that ozone concentration had the most significant effect on the NAs concentration compared to other parameters. An empirical model was developed to correlate the concentration of NAs with ozone concentration, oxygen/ozone flow rate, and pH. In addition, a theoretical analysis was conducted to gain the insight into the relationship between the removal of NAs and the operating parameters. PMID:25189805

  9. Freezing temperatures of H2SO4/HNO3/H2O mixtures: Implications for polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Song, Naihui

    1994-01-01

    The freezing temperatures of H2SO4/HNO3/H2O mixtures were systematically documented. Nitric acid was found to affect freezing significantly. Measurements show that nitric acid can cause substantial supercooling over a broad composition range. However, some ternary compositions, like to those in polar stratospheric clouds (PSCs), have high freezing temperatures. The freezing of PSC particles could be controlled by the temperature and vapor pressure of both nitric acid and water in a non-linear way. Formation of polar stratospheric clouds may be forecasted on the basic of conditions of temperature and vapor contents of water and nitric acid.

  10. 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.

  11. 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

  12. 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.

  13. Interaction of acetone, hydroxyacetone, acetaldehyde and benzaldehyde with the surface of water ice and HNO3·3H2O ice.

    PubMed

    Lasne, Jérôme; Laffon, Carine; Parent, Philippe

    2012-01-14

    Oxygenated volatile organic compounds (OVOCs) influence the oxidative properties of the atmosphere, and their transport from the ground may occur by scavenging by the HNO(3)-rich supercooled water droplets found in polluted convective air masses. With infrared spectroscopy, we have studied the interactions of four typical atmospheric OVOCs (acetone, hydroxyacetone, acetaldehyde and benzaldehyde) with model surfaces of water ice and of trihydrated nitric acid (NAT) ice. We show that these molecules weakly adsorb on water ice and NAT by hydrogen bonding. No chemical reaction occurs between the molecules and the NAT substrate, the OVOCs remaining intact when in contact with hydrated HNO(3) in atmospheric ice clouds.

  14. 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.

  15. Ozonization of humic acids in brown coal oxidized in situ

    SciTech Connect

    S.A. Semenova; Yu.F. Patrakov; M.V. Batina

    2008-10-15

    The effect of the ozonization of humic acids in chloroform and glacial acetic acid media on the yield and component composition of the resulting products was studied. The high efficiency of ozonization in acetic acid was found. Water-soluble low-molecular-weight substances were predominant among the ozonization products.

  16. Laboratory Evaluation of the Effect of HNO3 Uptake on Frost Point Hygrometer Measurement of Water Vapor under UT/LS Conditions

    NASA Astrophysics Data System (ADS)

    Thornberry, T.; Gierczak, T.; Gao, R.; Voemel, H.; Watts, L.; Burkholder, J. B.; Fahey, D. W.

    2010-12-01

    Chilled mirror hygrometers (CMH) are widely used to measure water vapor in the troposphere and lower stratosphere from balloon-borne sondes. Systematic discrepancies among in situ water vapor instruments have been observed at low water vapor mixing ratios (< 5 ppm) in the upper troposphere and lower stratosphere (UT/LS). Understanding the source of the measurement discrepancies is important for a more accurate and reliable determination of water vapor abundance in this region. We have conducted a laboratory study to investigate the potential interference of gas-phase nitric acid (HNO3) with the measurement of frost point temperature, and consequently the water vapor mixing ratio, determined by CMH under conditions representative of operation in the UT/LS. No detectable interference in the measured frost point temperature was found for HNO3 mixing ratios of up to 2 ppb for exposure times up to 150 minutes. HNO3 was observed to co-condense on the mirror frost, with the adsorbed mass increasing linearly with time at constant exposure levels. Over the duration of a typical balloon sonde ascent (90-120 min), the maximum accumulated HNO3 amounts were comparable to monolayer coverage of the geometric mirror surface area, which likely corresponds to small fractional coverage of the actual frost layer surface area. This small amount of co-condensed HNO3 is consistent with the observed lack of HNO3 interference in the frost point measurement because the CMH utilizes significant reductions (>10%) in surface reflectivity by the condensate for the determination of H2O.

  17. [Degradation of oxytetracycline with ozonation in acetic acid solvent].

    PubMed

    Li, Shi-Yin; Li, Xiao-Rong; Zhu, Yi-Ping; Zhu, Jiang-Peng; Wang, Guo-Xiang

    2012-12-01

    Use acetic acid as the media of ozone degradation of oxytetracycline (OTC), and effects of the initial dosing ratio of ozone/OTC, ozone flow, free radical scavenger, metal ions on the removal rate of OTC were investigated respectively. The results showed that acetic acid had a high ozone stability and solubility. OTC had a high removal rate and degradation rate in acetic acid solution. With the increase of OTC dosage, the removal rate of OTC decreased in acetic acid. Removal rate of OTC was increased distinctly when ozone flow increased properly. It was also observed that free radical scavenger had a significantly negative effect on OTC ozonation degradation in acetic acid. Furthermore the main reactions of OTC ozone oxidation were direct oxidation and indirect oxidation in acetic acid. When Fe3+ and Co2+ were existent in acetic acid, the degradation of OTC was inhibited significantly.

  18. 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

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. Theoretical study of atmospheric clusters: HNO3-HCl-H2O.

    PubMed

    Gómez, P C; Gálvez, O; Escribano, R

    2009-11-14

    Nitric acid, hydrochloric acid and water can form stable aggregates with atmospheric implications, for instance at the surface of polar stratospheric clouds. The structure, stability and chemical properties of these ternary complexes are studied by means of high level theoretical calculations (hybrid DFT B3LYP method along with aug-cc-pVQZ basis set). From the many possible systems that these molecules could form, only 15 are found to yield stable structures, well characterized by a minimum in their potential energy surfaces. These aggregates are studied in detail. They can be collected in three families, according to the role played by each species in the different hydrogen bonding links that result and provide the basis for the stabilization of the clusters. Water and HCl can be H-donors to almost every O atom of HNO(3), which in turn can donate its H atom to the other two molecules. Two special cases are found, one in which H(2)O plays a central role, and another with a three-dimensional structure, in contrast to the basically planar frame of the other clusters. Bonding properties are investigated for the whole series using AIM methods. The elongation of the H-Cl bond as a consequence of the aggregate creation is inspected in detail, as it may provide a clue to the lability of this molecule with implications in atmospheric processes. The Gibbs free energy calculated for these clusters shows that some of them could form spontaneously in the range of temperatures of the stratosphere.

  4. Improvement of oxygen-containing functional groups on olive stones activated carbon by ozone and nitric acid for heavy metals removal from aqueous phase.

    PubMed

    Bohli, Thouraya; Ouederni, Abdelmottaleb

    2016-08-01

    Recently, modification of surface structure of activated carbons in order to improve their adsorption performance toward especial pollutants has gained great interest. Oxygen-containing functional groups have been devoted as the main responsible for heavy metal binding on the activated carbon surface; their introduction or enhancement needs specific modification and impregnation methods. In the present work, olive stones activated carbon (COSAC) undergoes surface modifications in gaseous phase using ozone (O3) and in liquid phase using nitric acid (HNO3). The activated carbon samples were characterized using N2 adsorption-desorption isotherm, SEM, pHpzc, FTIR, and Boehm titration. The activated carbon parent (COSAC) has a high surface area of 1194 m(2)/g and shows a predominantly microporous structure. Oxidation treatments with nitric acid and ozone show a decrease in both specific surface area and micropore volumes, whereas these acidic treatments have led to a fixation of high amount of surface oxygen functional groups, thus making the carbon surface more hydrophilic. Activated carbon samples were used as an adsorbent matrix for the removal of Co(II), Ni(II), and Cu(II) heavy metal ions from aqueous solutions. Adsorption isotherms were obtained at 30 °C, and the data are well fitted to the Redlich-Peterson and Langmuir equation. Results show that oxidized COSACs, especially COSAC(HNO3), are capable to remove more Co(II), Cu(II), and Ni(II) from aqueous solution. Nitric acid-oxidized olive stones activated carbon was tested in its ability to remove metal ions from binary systems and results show an important maximum adsorbed amount as compared to single systems.

  5. Uric acid protects erythrocytes from ozone-induced changes

    SciTech Connect

    Meadows, J.; Smith, R.C.

    1987-08-01

    Uric acid effectively reduced hemolysis and methemoglobin formation in bovine and swine erythrocytes bubbled with ozone in vitro. In bovine erythrocytes, formation of thiobarbituric acid-reactive material was inhibited by uric acid, but there was little immediate protection for the swine cells. Antioxidant protection was due to preferential degradation of the uric acid by ozone. These results provide evidence to support the hypothesis that in plasma, uric acid can provide antioxidant protection for erythrocytes.

  6. 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.

  7. 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.

  8. 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.

  9. Relative stabilities of HCl•H2SO4•HNO3 aggregates in polar stratospheric clouds.

    PubMed

    Verdes, Marian; Paniagua, M

    2015-04-01

    Strong acids such as HCl (C), HNO3 (N) and H2SO4 (S) acquire relevance in Polar Stratospheric Clouds (PSCs) and aerosols in which nucleation processes occur. Ab initio quantum chemical studies of aggregates were performed for these strong acids. Structures were calculated using DFT methods with the B3LYP hybrid functional and aug-cc-pVTZ basis set. As an initial constraint, an H2SO4 moiety was placed in all candidate structures. A total of 11 optimized structures was found: a global minimum (CSN-a) plus ten local minima on the Potential Energy Surface (PES). The global minimum aggregate gave four hydrogen bonds, yielding a hexagonal ring in its structure. HNO3 acts as proton donor in all clusters; nevertheless, using trans-H2SO4 as the proton donor yielded the most stable structures, whereas HCl acts mainly as a proton donor/acceptor. Real harmonic frequencies, IR spectra, and inter-monomeric parameters were obtained. CSN-a symmetric stretching modes were shifted to 2805.56 cm(-1) and 3520.00 cm(-1) for H-Cl modes, while O-H modes shifted to 3256.87 cm(-1) and 3362.47 cm(-1). On the other hand, relative stabilities improved for 5 of the 11 aggregates when the temperature decreased from 298 K to 210 K, 195 K and 188 K. The aggregate CSN-f remained unstable only at 210 K. Moreover, the relative Gibbs free energy, ΔG(0-298K) was -9.26 kcalmol(-1) with respect to CSN-a; relative reaction Gibbs free energy [Δ(ΔG)] values ranged from 0.0 at 298 K, to -6.9 kcalmol(-1) at 188 K. It seems that CSN aggregates remain slightly more stable than CNS aggregates with a HNO3 moiety when the temperature decreases from 298 to 188 K. Five structures remained relatively stable under both study conditions.

  10. The ozone hole - The role of polar stratospheric cloud particles

    NASA Technical Reports Server (NTRS)

    Hamill, Patrick; Turco, R. P.

    1988-01-01

    The role of polar stratospheric clouds in the formation of the Antarctic ozone hole is considered. Several researchers have suggested that the decrease in ozone over Antarctica is related to the polar stratospheric clouds (PSCs) which had been observed in the antarctic winter stratosphere. Some of the pertinent characteristics of polar stratospheric clouds are discussed, and it is shown how these clouds may participate in the ozone destruction process. The satellite data for PSCs is analyzed, and statistical information regarding the number and maximum extinctions of these clouds is presented. Evidence that the polar stratospheric clouds are composed of frozen nitric acid is considered. It is suggested that the evaporation of the clouds, in late August and September, will release HOCl and HNO3 to the environment. This could be followed by the photodissociation of HOCl to OH and Cl, which would very effectively destroy ozone. However, the ozone destruction mechanism could be halted when enough of the evaporated nitric acid is photolized.

  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. 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.

  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. Variable temperature pressure broadening of HNO3 in the millimeter wave spectral region

    NASA Technical Reports Server (NTRS)

    Goyette, Thomas M.; Guo, Wei; Delucia, Frank C.; Helminger, Paul

    1991-01-01

    Measurements were performed for both O2 and N2 broadening in the 100-380 K temperature range by using a heated equilibrium cell for elevated temperatures and the utilization of a collisionally cooled cell at the lower temperatures where HNO3 has a small vapor pressure. Observed pressure-broadening data can be fit to the normal empirical law, giving n values between 0.62 and 0.84.

  17. 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.

  18. 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

  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. Inactivation of H1N1 viruses exposed to acidic ozone water

    NASA Astrophysics Data System (ADS)

    Uhm, Han S.; Lee, Kwang H.; Seong, Baik L.

    2009-10-01

    The inactivation of H1N1 viruses upon exposure to acidic ozone water was investigated using chicken allantoic fluids of different dilutions, pH values, and initial ozone concentrations. The inactivation effect of the acidic ozone water was found to be stronger than the inactivation effect of the ozone water combined with the degree of acidity, indicating a synergic effect of acidity on ozone decay in water. It is also shown that acidic ozone water with a pH value of 4 or less is very effective means of virus inactivation if provided in conjunction with an ozone concentration of 20 mg/l or higher.

  1. Simultaneous ozonation kinetics of phenolic acids present in wastewaters

    SciTech Connect

    Benitez, F.J.; Beltran-Heredia, J.; Acero, J.L.; Pinilla, M.L.

    1996-12-31

    Among the several chemical processes conducted for the removal of organic matter present in wastewaters coming from some agro-industrial plants (wine distilleries, olive oil mills, etc), the oxidation by ozone has shown a great effectiveness in the destruction of specially refractory pollutants: it is demonstrated that the biodegradability of those wastewaters increases aflcer an ozonation pretreatment. Their great pollutant character is imputed to the presence of some organic compounds, like phenols and polyphenols, which are toxic and inhibit the latter biological treatments. In this research, a competitive kinetic procedure reported by Clurol and Nekouinaini is applied to determine the degradation rate constants by ozone of several phenolic acids which are present in the wastewaters from the olive oil obtaining process. The resulting kinetic expressions for the ozonation reactions are useful for the successful design and operation of ozone reactors in water and wastewaters treatment plants.

  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. Composition-dependent freezing nucleation rates for HNO3/H2O aerosols resembling gravity-wave-perturbed stratospheric particles

    NASA Astrophysics Data System (ADS)

    Prenni, Anthony J.; Onasch, Timothy B.; Tisdale, Robert T.; Siefert, Ronald L.; Tolbert, Margaret A.

    1998-11-01

    Laboratory measurements are presented for the freezing kinetics of H2O/HNO3 aerosols over the temperature range of 188-204 K. For 2:1 H2O:HNO3 aerosols crystallizing to NAD we observed a maximum nucleation rate of J = 9.3×109 cm-3 s-1 at 194 K. This temperature is between the glass point of 161 K [Ji et al., 1993] and the melting point of 235.5 K [Ji et al., 1996]. This can be compared to a previous measurement of J = 6.7×109 cm-3 s-1 at 193 K [Disselkamp et al., 1996] and lower temperature measurements of J ≈ 1010-1012 cm-3 s-1 at 178.8 - 175.8 K [Bertram and Sloan, 1998a]. Measured nucleation rates decrease as the aerosol becomes dilute, but NAD formation is still observable for 2.5:1 H2O:HNO3 at temperatures near 195 K. In contrast, freezing of 3:1 H2O:HNO3 aerosol was not observed for constant temperature experiments throughout this temperature range, yielding an upper limit of J<1.5×109 cm-3 s-1. This is the lowest experimental value determined for 3:1 H2O:HNO3 freezing rates at these temperatures. From the measured freezing rates and knowledge of the free energy of diffusion the average interfacial free energy for NAD in a 2:1 H2O:HNO3 solution was determined to be σ = 25.2 ergs cm-2. A limit for the interfacial free energy was placed on 3:1 H2O:HNO3 particles, for which freezing was not observed. These data imply that if aerosols reach compositions more concentrated than 3:1 H2O:HNO3 in the atmosphere, NAD may play a role in polar stratospheric cloud formation.

  5. 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.

  6. Removal of oxalic acid, oxamic acid and aniline by a combined photolysis and ozonation process.

    PubMed

    Orge, C A; Faria, J L; Pereira, M F R

    2015-01-01

    Aniline (ANL), an aromatic amine, oxalic acid (OXA) and oxamic acid (OMA), short-chain carboxylic acids, were chosen as model organic pollutants for testing the combined effect of neat photolysis and ozonation in the treatment of aqueous effluents. In order to better understand the results, single ozonation and neat photolysis were also carried out. OXA has a high refractory character relatively to single ozonation and neat photolysis only accounted for 26% conversion of OXA after 2 h of reaction. On the other hand, OXA complete degradation was observed in less than an hour when ozone and light were used simultaneously. Despite OMA, a compound never studied before by a combined ozonation and photolysis treatment, being highly refractory to oxidation, more than 50% was removed by photo-ozonation after 3 h of reaction. In the case of ANL, both single ozonation and photo-ozonation resulted in 100% removal in a short reaction period due to the high reactivity of ozone to attack this type of molecules; however, only the combined method leads to efficient mineralization (89%) after 3 h of reaction. A significant synergetic effect was observed in the degradation of the selected contaminants by the simultaneous use of ozone and light, since the mineralization rate of combined method is higher than the sum of the mineralization rates of the individual treatments. The promising results observed in the degradation of the selected contaminants are paving the way to the application of photo-ozonation in the treatment of wastewater containing this type of pollutants.

  7. [Characteristics of acid red 3R wastewater treatment by ozone microbubbles].

    PubMed

    Zhang, Jing; Du, Ya-Wei; Liu, Xiao-Jing; Zhou, Yu-Wen; Liu, Chun; Yang, Jing-Liang; Zhang, Lei

    2015-02-01

    The application of microbubble technology for ozonation wastewater treatment could enhance ozone mass transfer, improve ozonation performance and increase ozone utilization efficiency. The ozone microbubbles were used to treat synthetic acid red 3R wastewater in the present study, and compared to ozone conventional bubbles. The ozone mass transfer and ozonation characteristics of acid red 3R were investigated when ozone microbubbles and ozone conventional bubbles were applied. The results confirmed the enhanced ozone mass transfer using microbubbles. The ozone mass transfer coefficient using microbubbles was 3.6 times higher than that using conventional bubbles under the same conditions. Simultaneously, the ozone decomposition coefficient using microbubbles was 6.2 times higher than that using conventional bubbles, which would be favorable for *OH generation. The ozonation rate and mineralization efficiency of acid red 3R could be improved significantly using ozone microbubbles. A TOC removal efficiency of 78.0% was achieved using ozone microbubbles, which was about 2 times higher than that using ozone conventional bubbles. The ozone utilization efficiency using microbubbles was much higher that using conventional bubbles during ozonation treatment of acid red 3R. The average ozone utilization efficiencies were 97.8% and 69.3% when microbubbles and conventional bubbles were used, respectively. The oxidative ability of ozone microbubbles could be increased by enhancing *OH generation, and as a result, the oxidative reaction of degradation intermediates was accelerated by ozone microbubbles. Especially, the mineralization ability of small organic acid intermediates using ozone microbubbles was about 1.6 times higher than that using ozone conventional bubbles.

  8. Increase in the ozone decay time in acidic ozone water and its effects on sterilization of biological warfare agents.

    PubMed

    Uhm, Han S; Hong, Yi F; Lee, Han Y; Park, Yun H

    2009-09-15

    The sterilization properties of ozone in acidic water are investigated in this study. Acidification of water increases the ozone decay time by several times compared to the decay time in neutral water, thereby enhancing the sterilization strength of ozone in acidic water. A simple analytical model involving the viable microbial counts after contact with acidic ozone water was derived, and a sterilization experiment was conducted on bacterial cells using the acidic ozone water. The acidic ozone water was found to kill very effectively endospores of Bacillus atrophaeus ATCC 9372, thereby demonstrating the potential for disinfection of a large surface area in a very short time and for reinstating the contaminated environment as free from toxic biological agents.

  9. 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

  10. 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.

  11. Uptake measurements of acetaldehyde on solid ice surfaces and on solid/liquid supercooled mixtures doped with HNO3 in the temperature range 203-253 K.

    PubMed

    Petitjean, M; Mirabel, Ph; Le Calvé, S

    2009-04-30

    Uptake of acetaldehyde on ice surfaces has been investigated over the temperature range 203-253 K using a coated wall flow tube coupled to a mass spectrometric detection. The experiments were conducted on pure ice surfaces and on liquid/solid ice mixture both doped with nitric acid (0.063, 0.63, and 6.3 wt %). Uptake of acetaldehyde on these surfaces was always found to be totally reversible whatever the experimental conditions were. The number of acetaldehyde molecules adsorbed per surface unit was conventionally plotted as a function of acetaldehyde concentration in the gas phase. Although the amounts of acetaldehyde adsorbed on solid ice surfaces (pure and HNO(3)-doped ice) were approximately similar and rather limited, the number of acetaldehyde molecules taken up on the HNO(3)-doped solid ice/liquid mixtures are significantly higher, up to 1 or 2 orders of magnitudes compared to pure ice surfaces. At 213 K for example and for low concentrations of acetaldehyde (<1 x 10(13) molecule cm(-3)), the amount of acetaldehyde molecules taken up on solid/liquid doped surfaces is 3.3 and 8.8 times higher than those measured on pure ice respectively for 0.063 and 0.63 wt % of HNO(3). The huge quantities of acetaldehyde taken up by liquid-/solid-doped mixtures are likely dissolved in the nonhomogeneous liquid part of the surfaces according to the Henry's law equilibrium. As a consequence, up to about 10% of acetaldehyde may be scavenged by supercooled liquid droplets of convective clouds in the upper troposphere.

  12. Determination of total fluoride in HF/HNO3/H2SiF6 etch solutions by new potentiometric titration methods.

    PubMed

    Weinreich, Wenke; Acker, Jörg; Gräber, Iris

    2007-03-30

    In the photovoltaic industry the etching of silicon in HF/HNO(3) solutions is a decisive process for cleaning wafer surfaces or to produce certain surface morphologies like polishing or texturization. With regard to cost efficiency, a maximal utilisation of etch baths in combination with highest quality and accuracy is strived. To provide an etch bath control realised by a replenishment with concentrated acids the main constituents of these HF/HNO(3) etch solutions including the reaction product H(2)SiF(6) have to be analysed. Two new methods for the determination of the total fluoride content in an acidic etch solution based on the precipitation titration with La(NO(3))(3) are presented within this paper. The first method bases on the proper choice of the reaction conditions, since free fluoride ions have to be liberated from HF and H(2)SiF(6) at the same time to be detected by a fluoride ion-selective electrode (F-ISE). Therefore, the sample is adjusted to a pH of 8 for total cleavage of the SiF(6)(2-) anion and titrated in absence of buffers. In a second method, the titration with La(NO(3))(3) is followed by a change of the pH-value using a HF resistant glass-electrode. Both methods provide consistent values, whereas the analysis is fast and accurate, and thus, applicable for industrial process control. PMID:19071540

  13. The de Haas-van Alphen effect of graphite intercalation compounds with SbCl 5 and HNO 3

    NASA Astrophysics Data System (ADS)

    Takahashi, Otofumi; Iye, Yasuhiro; Tanuma, Sei-ichi

    1981-03-01

    The de Haas-van Alphen (dHvA) effect of SbCl 5-graphite intercalation compounds of stage 2, 3 and 4, and residual HNO 3-compound of stage 3 has been studied. The dHvA spectra are stage dependent, and no combination frequency relations are found, which are in disagreement with Batallan et al.'s report. The amount of charge transfer per intercalant estimated on the basis of the rigid band model is 0.44, 0.49 and 0.43 for stage 4, 3 and 2 SbCl 5-compounds and is 0.14 for stage 3 HNO 3-compound.

  14. Retrieval of stratospheric O3, HNO3, and ClONO2 profiles from 1992 MIPAS-B limb emission spectra: method, results, and error analysis

    NASA Astrophysics Data System (ADS)

    Clarmann, T. von; Fischer, H.; Friedl-Vallon, F.; Linden, A.; Oelhaf, H.; Piesch, C.; Seefeldner, M.; Völker, W.

    1993-11-01

    Within the framework of the European Arctic Stratospheric Ozone Experiment, two flights of the balloon-borne MIPAS-B limb emission spectrometer were performed in the Arctic stratosphere from Kiruna, northern Sweden. During the early hours of January 13 and the night from March 14 to March 15, 1992, several limb sequences of infrared spectra were recorded which have permitted the retrieval of vertical profiles of many trace gases relevant for ozone chemistry. In the present work, the retrieval strategy, error estimation strategy, and resulting profiles of O3, HNO3, and ClONO2 are reported. The data analysis procedure, consisting of data preprocessing including calibration, analysis of auxiliary data including temperature profiles and line of sight determination, and retrieval of trace gas profiles, is described in detail. The last is carried out by means of multiparameter nonlinear least squares fitting in combination with onion peeling. An astonishingly high ClONO2 amount of 2.6 ppb by volume at about 19-km altitude was inferred for the March flight. A rigorous error analysis, which takes into account systematic and random errors and their often nonlinear impact on the results, proves the significance of the retrieved trace gas profiles.

  15. Effects of acidity and ozone on airway epithelium. Final report

    SciTech Connect

    Sheppard, D.; Wang, A.; Cone, R.; Cohen, S.

    1991-12-01

    The study examined the in vitro effects of acidity and/or ozone on primary cultures of guinea pig airway epithelial cells. Surface acidification to pH 6 or pH 5, reduced protein synthesis and induced the synthesis of two stress proteins: hsp 72 and grp 78. No such effect was produced by nitric acid vapor (50 to 18,000 micrograms/cum). Acid exposure did not affect cytotoxicity or glycoconjugate, fibronectin or TGF(beta) synthesis or secretion. Exposure of these cells to ozone (0.05 - 0.2 ppm) caused concentration-dependent cytotoxicity and decreased protein synthesis, but produced no other detectable effects on cellular metabolism.

  16. 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.

  17. 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

  18. Measurements of Nitric Acid and Aerosol Species Aboard the NASA DC-8 Aircraft During the SASS OZone and Nitrogen Oxide Experiment (SONEX)

    NASA Technical Reports Server (NTRS)

    Talbot, Robert W.; Dibb, Jack E.

    1999-01-01

    The SASS Ozone and Nitrogen Oxides Experiment (SONEX) over the north Atlantic during October/November 1997 offered an excellent opportunity to examine the budget of total reactive nitrogen (NO(y)) in the upper troposphere (8 - 12 km altitude). The median measured NO(y) mixing ratio was 425 parts per trillion by volume (pptv). Two different methods were used to measure HNO3: (1) the mist chamber technique and, (2) chemical ionization mass spectrometry. Two merged data sets using these HNO3 measurements were used to calculate NO(y) by summing the reactive nitrogen species (a combination of measured plus modeled results) and comparing the resultant values to measured NO(y) (gold catalytic reduction method). Both comparisons showed good agreement in the two quantities (slope greater than 0.9 and r(sup 2) greater than 0.9). Thus, the total reactive nitrogen budget in the upper troposphere over the North Atlantic can be explained in a general manner as a simple mixture of NO(x). (NO + NO2), HNO3, and PAN. Median values of NO(x)/NO(y) were approx. = 0.25, HNO3/NO(y) approx. = 0.35 and PAN/NO(y) approx. = 0.17. Particulate NO3 and alkyl nitrates together composed less than 10% of NO(y), while model estimated HNO4 averaged 12%.

  19. Measurements of Nitric Acid and Aerosol Species Aboard the NASA DC-8 Aircraft During the SASS Ozone and Nitrogen Oxide Experiment (SONEX)

    NASA Technical Reports Server (NTRS)

    Talbot, Robert W.; Dibb, Jack E.

    1999-01-01

    The SASS Ozone and Nitrogen Oxides Experiment (SONEX) over the North Atlantic during October/November 1997 offered an excellent opportunity to examine the budget of total reactive nitrogen (NO(sub y)) in the upper troposphere (8 - 12 km altitude). The median measured NO(sub y) mixing ratio was 425 parts per trillion by volume (pptv). Two different methods were used to measure HNO3: (1) the mist chamber technique and, (2) chemical ionization mass spectrometry. Two merged data sets using these HNO3 measurements were used to calculate NO(sub y) by summing the reactive nitrogen species (a combination of measured plus modeled results) and comparing the resultant values to measured NO(sub y) (gold catalytic reduction method). Both comparisons showed good agreement in the two quantities (slope > 0.9 and r(exp 2) > 0.9). Thus, the total reactive nitrogen budget in the upper troposphere over the North Atlantic can be explained in a general manner as a simple mixture of NO(sub x). (NO + NO2), HNO3, and PAN. Median values of NO(sub x)/NO(sub y) were approximately equal to 0.25, HNO3/NO(sub y) were approximately equal to 0.35 and Peroxyacetyl Nitrate (PAN)/NO(sub y) were approximately equal to 0. 17. Particulate NO3 and alkyl nitrates together composed <10 % of NO(sub y), while model estimated HNO4 averaged 12%.

  20. Effects of ozone and sulfuric acid aerosol on gas trapping in the guinea pig lung

    SciTech Connect

    Silbaugh, S.A.; Mauderly, J.L.

    1986-01-01

    Four groups of 20 guinea pigs were sequentially exposed by inhalation to either air followed by sulfuric acid aerosol, ozone followed by sulfuric acid aerosol, ozone followed by air, or air followed by air to determine whether ozone preexposure sensitizes guinea pigs to the airway constrictive effects of sulfuric acid aerosol. All first exposures to ozone or air were 2 h in duration; all second exposures to sulfuric acid or air were for 1 h. All ozone and sulfuric acid exposures were 0.8 ppm and 12 mg/m3, respectively. Animals were observed for respiratory distress during exposure, and excised lungs were quantitated for trapped gas and wet/dry ratios. None of the guinea pigs developed dyspnea, and wet/dry ratios were not altered. Ozone significantly (p less than 0.05) increased trapped gas volumes, which were 44% (ozone-acid) to 68% (ozone-air) greater than in the air-air group. Trapped gas volume was 23% greater in the ozone-acid group than in the air-acid group, but the difference was not statistically significant (p less than 0.20). Thus, ozone increased gas trapping but did not significantly sensitize guinea pigs to the bronchoconstrictive action of sulfuric acid.

  1. Study on the kinetics and transformation products of salicylic acid in water via ozonation.

    PubMed

    Hu, Ruikang; Zhang, Lifeng; Hu, Jiangyong

    2016-06-01

    As salicylic acid is one of widely used pharmaceuticals, its residue has been found in various environmental water systems e.g. wastewater, surface water, treated water and drinking water. It has been reported that salicylic acid can be efficiently removed by advanced oxidation processes, but there are few studies on its transformation products and ozonation mechanisms during ozonation process. The objective of this study is to characterize the transformation products, investigate the degradation mechanisms at different pH, and propose the ozonation pathways of salicylic acid. The results showed that the rate of degradation was about 10 times higher at acidic condition than that at alkaline condition in the first 1 min when 1 mg L(-1) of ozone solution was added into 1 mg L(-1) of salicylic acid solution. It was proposed that ozone direct oxidation mechanism dominates at acidic condition, while indirect OH radical mechanism dominates at alkaline condition. A two stages pseudo-first order reaction was proposed at different pH conditions. Various hydroxylation products, carbonyl compounds and carboxylic acids, such as 2,5-dihydroxylbenzoic acid, 2,3-dihydroxylbenzoic acid, catechol, formaldehyde, glyoxal, acetaldehyde, maleic acid, acetic acid and oxalic acid etc. were identified as ozonation transformation products. In addition, acrylic acid was identified, for the first time, as ozonation transformation products through high resolution liquid chromatography-time of flight mass spectrometer. The information demonstrated in this study will help us to better understand the possible effects of ozonation products on the water quality. The degradation pathways of salicylic acid by ozonation in water sample were proposed. As both O3 and OH radical were important in the reactions, the degradation pathways of salicylic acid by ozonation in water sample were proposed at acidic and basic conditions. To our knowledge, there was no integrated study reported on the ozonation of

  2. Study on the kinetics and transformation products of salicylic acid in water via ozonation.

    PubMed

    Hu, Ruikang; Zhang, Lifeng; Hu, Jiangyong

    2016-06-01

    As salicylic acid is one of widely used pharmaceuticals, its residue has been found in various environmental water systems e.g. wastewater, surface water, treated water and drinking water. It has been reported that salicylic acid can be efficiently removed by advanced oxidation processes, but there are few studies on its transformation products and ozonation mechanisms during ozonation process. The objective of this study is to characterize the transformation products, investigate the degradation mechanisms at different pH, and propose the ozonation pathways of salicylic acid. The results showed that the rate of degradation was about 10 times higher at acidic condition than that at alkaline condition in the first 1 min when 1 mg L(-1) of ozone solution was added into 1 mg L(-1) of salicylic acid solution. It was proposed that ozone direct oxidation mechanism dominates at acidic condition, while indirect OH radical mechanism dominates at alkaline condition. A two stages pseudo-first order reaction was proposed at different pH conditions. Various hydroxylation products, carbonyl compounds and carboxylic acids, such as 2,5-dihydroxylbenzoic acid, 2,3-dihydroxylbenzoic acid, catechol, formaldehyde, glyoxal, acetaldehyde, maleic acid, acetic acid and oxalic acid etc. were identified as ozonation transformation products. In addition, acrylic acid was identified, for the first time, as ozonation transformation products through high resolution liquid chromatography-time of flight mass spectrometer. The information demonstrated in this study will help us to better understand the possible effects of ozonation products on the water quality. The degradation pathways of salicylic acid by ozonation in water sample were proposed. As both O3 and OH radical were important in the reactions, the degradation pathways of salicylic acid by ozonation in water sample were proposed at acidic and basic conditions. To our knowledge, there was no integrated study reported on the ozonation of

  3. Study of enhanced low-quality coal oxidative desulphurization and deashing by using HNO3 and microwave pretreatment.

    PubMed

    Ma, Xiangmei; Zhang, Mingxu; Min, Fanfei

    2014-01-01

    In this paper, the effect of urea-hydrogen peroxide (UHP) solution on desulphurization and demineralization of coal with high sulphur and high ash by using HNO3 and microwave pretreatment was investigated. The oxidation process is strongly dependent on irradiation power and time for microwave pretreatment, UHP concentration, leaching time and temperature of the UHP solution. X-ray diffraction and Fourier transform infrared technique have been performed for the raw and treated coals. Compared with the UHP alone, successive treatments with HNO3 and microwave pretreatment resulted in the significant removal of total sulphur and mineral matter from the coal. The proposed experimental method has the meaning of practical guide to the desulphurization and deashing of coal by microwave.

  4. Ozone

    MedlinePlus

    ... reactive form of oxygen. In the upper atmosphere, ozone forms a protective layer that shields us from the sun’s ultraviolet rays. At ground level, ozone is a harmful air pollutant and a primary ...

  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. Ozone, hydroperoxides, oxides of nitrogen, and hydrocarbon budgets in the marine boundary layer over the South Atlantic

    NASA Astrophysics Data System (ADS)

    Heikes, Brian; Lee, Meehye; Jacob, Daniel; Talbot, Robert; Bradshaw, John; Singh, Hanwant; Blake, Donald; Anderson, Bruce; Fuelberg, Henry; Thompson, Anne M.

    1996-10-01

    The NASA GTE TRACE A mission sampled air over the South Atlantic and western Indian Oceans. Thirteen flight legs were flown within the marine boundary layer (MBL). The MBL was typically the cleanest air sampled (e.g., CH4 < 1680 ppb, CO < 70 ppb, C2H6 < 400 ppt, C3H8 < 40 ppt, NOx < 15 ppt, and midday NO < 5 ppt) but was overlain by polluted air. The photochemistry of the MBL was influenced by oceanic emissions, surface deposition, and entrainment of pollutants from aloft. Chemical budgets were constructed for several species in the MBL in order to investigate these effects and are presented for ethane, ethylene, propane, propylene, n-butane, formic acid (HFo), methylhydroperoxide (CH3OOH), oxides of nitrogen (i.e., NO, NO2, PAN, HNO3), hydrogen peroxide (H2O2), and ozone (O3). A photochemical point model was used to evaluate local chemical production and loss. An entrainment model was used to assess material exchange between the lower free troposphere (FT) and the MBL and a resistance deposition model was used to evaluate material exchange across the air-sea interface. The results suggested the ocean to be the source of measured alkenes in the MBL and to be the most likely source of the shorter-lived alkanes: propane and n-butane. Ethane was the only hydrocarbon for which input from aloft may have exceeded its photochemical destruction. The estimated hydrocarbon sources from the ocean were in agreement with prior analyses. Transport from the lower FT together with surface loss could not account for measured concentrations of CH2O, HFo, and HNO3. The transport of peroxyacetylnitrate (PAN) from the FT to the MBL exceeded the rate of HNO3 production and was more than sufficient to maintain observed NOx levels without having to invoke an oceanic source for NO. The flux of NOx, PAN, and HNO3 was in balance with the surface deposition flux of HNO3. However, the predicted rates of HNO3 formation from the oxidation of NO2 and HNO3 entrainment from aloft were inadequate to

  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. Ozone

    MedlinePlus

    Ozone is a gas. It can be good or bad, depending on where it is. "Good" ozone occurs naturally about 10 to 30 miles above ... the sun's ultraviolet rays. Part of the good ozone layer is gone. Man-made chemicals have destroyed ...

  10. Comparison of six denuder methods and a filter pack for the collection of ambient HNO 3(g), HNO 2(g) and SO 2(g) in the 1985 NSMC study

    NASA Astrophysics Data System (ADS)

    Eatough, Norman L.; McGregor, Scott; Lewis, Edwin A.; Eatough, Delbert J.; Huang, Andrew A.; Ellis, Elizabeth C.

    The concentrations of HNO 2(g), HNO 2(g), particle nitrate and particle nitrite have been determined using annular denuders (AD), nylon denuders (ND), short nylon denuders (SD), tungstic acid denuders (TD), cylindrical carbonate denuders (CD), a filter pack (FP), and a denuder difference method (DD) in field tests during the 1985 NSMCS. Concentrations of SO 2(g) and particle sulfate were measured by the annular denuder (AD) and cylindrical carbonate denuder (CD) systems. The results of linear regression comparison of various collection methods for total nitrate, HNO 3(g) and HNO 2(g), and results calculated as the denuder difference between nitrate and nitrite collected on the FP sampler and on the filter pack after the AD are presented. Results for HNO 3(g) and particle nitrate measured by the different sampling systems compared well with the exception of the TD and CD systems. The AD, FP and SD samplers showed the best consistency in results presumably because they operate at higher flow rates and give more sample with correspondingly lower analytical errors. The results obtained for the nitrogenous species studied are also correlated with other atmospheric parameters which might be related to the formation of HNO 3(g) and/or HNO 2(g) in the atmosphere. Concentrations of SO 2(g) measured by the annular denuder (AD) are compared to values determined by flame photometry.

  11. 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

  12. [Catalytic ozonation by ceramic honeycomb for the degradation of oxalic acid in aqueous solution].

    PubMed

    Zhao, Lei; Sun, Zhi-Zhong; Ma, Jun

    2007-11-01

    Comparative experiments for the degradation of oxalic acid in aqueous solution were carried out in the three processes of ozonation alone, ceramic honeycomb-catalyzed ozonation and ceramic honeycomb adsorption. The results show that the degradation rates of oxalic acid in the ceramic honeycomb-catalyzed ozonation, ozonation alone and ceramic honeycomb adsorption systems are 37.6%, 2.2% and 0.4%, and the presence of ceramic honeycomb catalyst significantly improves the degradation rate of oxalic acid compared to the results from non-catalytic ozonation and adsorption. With the addition of tert-butanol, the degradation rates of oxalic acid in catalytic ozonation system decrease by 24.1%, 29.0% and 30.1%, respectively, at the concentration of 5, 10 and 15 mg x L(-1). This phenomenon indicates that ceramic honeycomb-catalyzed ozonation for the degradation of oxalic acid in aqueous solution follows the mechanism of *OH oxidation, namely the heterogeneous surface of catalyst enhances the initiation of *OH. The results of TOC analysis demonstrate that the process of ceramic honeycomb-catalyzed ozonation can achieve the complete mineralization level without the formation of intermediary degradation products. The experimental results suggest that the reaction temperature has positive relationship with the degradation rate of oxalic acid. The degradation rates of oxalic acid in the ceramic honeycomb-catalyzed ozonation system are 16.4%, 37.6%, 61.3% and 68.2%, at the respective reaction temperature of 10, 20, 30 and 40 degrees C.

  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. Effects of acid fog and ozone on conifers. Final report

    SciTech Connect

    Bytnerowicz, A.; Olszyk, D.M.; Takemoto, B.K.; McCool, P.M.; Musselman, R.C.

    1989-05-01

    This study evaluated the effects of acidic fog (pH 2.0, 3.0, or 4.0) on the physiological, biochemical, and growth responses of two coniferous tree species (Pinus ponderosa and Abies concolor), and determined if exposure to acidic fog predisposed the tree seedlings to the phytotoxic effects of ozone (O{sub 3}). Results provide evidence that the growth and metabolic responses of two coniferous tree species could be altered by multiple applications of acidic fog, and by exposure to ambient O{sub 3}. In general, the alterations were slight to modest, which may be attributed to the low degree of stress severity, and the slow rate of tree growth. The findings indicate that exposure to acidic fog followed by O{sub 3} does not cause detectable changes in conifer seedling growth within a single-growing season. Nevertheless, it is clear that acidic fog and O{sub 3} cause temporal alterations in seedling physiology and biochemistry.

  15. Acid aerosol measurements at a suburban Connecticut site

    NASA Astrophysics Data System (ADS)

    Keeler, Gerald J.; Spengler, John D.; Castillo, Raymond A.

    Atmospheric acidity data were gathered during a year-long field project investigating the possible health effects of acid aerosol in a rural community in southwestern Connecticut. This site was chosen because the air quality is frequently influenced by pollutants transported from the New York-New Jersey corridor as well as from the Midwest U.S. An annular denuder filter-pack system utilized to obtain daily measurements of gaseous HNO 3, HONO, SO 2, and NH 3; plus fine particle SO 42-, NO 3-, and H +. Fine particle mass ( d ⩽ 2.1 μm) and PM10 (particles d ⩽ 10 μm) were also measured. Ozone concentrations and basic meteorological data were also obtained continuously. The atmosphere was acidic with average concentrations of HONO (16 nmol m -3), HNO 3 (42 nmol m -3), and H + (42 nmol m -3), observed from May to September 1988. Atmospheric ammonia concentrations were fairly low averaging 34 nmol m -3 during the same period, and suggesting the neutralizing capacity of the air was significant to neutralize all the acidic species present. Neutralization of acidic particles by reactions on the filter media after collection resulted in a loss of approximately 10% of the measured particle strong acidity for the summertime period investigated. Concentrations of ozone and acidic gases tended to peak with mixed layer flow from the south-southwest while particulate acidity was highest with flow predominantly from the west-soutwest. Hourly ozone concentrations greater than 100 ppb were observed on 31 different days during the monitoring, and concentrations greater than 150 ppb measured on 14 days. HNO 3 and aerosol strong acidity (H +) concentrations reached 174 and 199 nmol m -3, respectively during the summer months.

  16. Wastewater disinfection alternatives: chlorine, ozone, peracetic acid, and UV light.

    PubMed

    Mezzanotte, V; Antonelli, M; Citterio, S; Nurizzo, C

    2007-11-01

    Disinfection tests were carried out at pilot scale to compare the disinfection efficiency of ozone, sodium hypochlorite (NaOCl), peracetic acid (PAA), and UV irradiation. Total coliforms, fecal coliforms, and Escherichia coli were monitored as reference microorganisms. Total heterotrophic bacteria (THB) were also enumerated by cytometry. At similar doses, NaOCl was more effective than PAA, and its action was less affected by contact time. The results obtained by ozonation were comparable for total coliforms, fecal coliforms, and E. coli. On the contrary, some differences among the three indicators were observed for NaOCl, PAA, and UV. Differences increased with increasing values of the disinfectant concentration times contact time (C x t) and were probably the result of different initial counts, as total coliforms include fecal coliforms, which include E. coli. The UV irradiation lead to complete E. coli removals, even at low doses (10 to 20 mJ/cm2). Total heterotrophic bacteria appeared to be too wide a group to be a good disinfection indicator; no correlation was found among THB inactivation, dose, and contact time.

  17. Kinetic Study of Heterogeneous Reaction of Deliquesced NaCI Particles with Gaseous HNO3 Using Particle-on-Substrate Stagnation Flow Reactor Approach

    SciTech Connect

    Liu, Yong; Cain, Jeremy P.; Wang, Hai; Laskin, Alexander

    2007-10-11

    Heterogeneous reaction kinetics of gaseous nitric acid with deliquesced sodium chloride particles were investigated with a novel Particle-on-Substrate Stagnation Flow Reactor (PS-SFR) approach under conditions, including particle size, relative humidity and reaction time, directly relevant to the atmospheric chemistry of sea salt particles. Particles deposited onto an electron microscopy grid substrate were exposed to the reacting gas at atmospheric pressure and room temperature by impingement via a stagnation flow inside the reactor. The reactor design and choice of flow parameters were guided by computational fluid dynamics results to ensure uniformity of the diffusion flux to all particles undergoing reaction. The chloride depletion in the particles was followed by computer-controlled scanning electron microscopy with energy-dispersive X-ray analysis (CCSEM/EDX). The validity of the current approach was examined first by conducting experiments with median dry particle diameter = 0.82 μm, 80% relative humidity, particle loading densities 4×104 ≤ Ns ≤ 7×106 cm–2 and free stream HNO3 concentrations 2, 7 and 22 ppb. Upon deliquescence the droplet diameter approximately doubles. The apparent, pseudo first-order rate constant determined in these experiments varied with particle loading and HNO3 concentration in a manner consistent with a diffusion-kinetic analysis reported earlier (Laskin, A.; Wang, H.; Robertson, W. H.; Cowin, J. P.; Ezell, M. J.; Finlayson-Pitts, B. J. J. Phys. Chem. A 2006, 110, 10619). The intrinsic, second-order rate constant was obtained as kII = 5.7×10–15 cm3molecule–1s–1 in the limit of zero particle loading and by assuming that the substrate is inert to HNO3. Under this loading condition the experimental, net reaction uptake coefficient was found to be γnet = 0.11 with an uncertainty factor of 3. Additional experiments examined the variations of HNO3 uptake on pure NaCl, a sea salt-like mixture of NaCl and MgCl2 (Mg

  18. Catalytic ozonation of sulfosalicylic acid over manganese oxide supported on mesoporous ceria.

    PubMed

    Xing, Shengtao; Lu, Xiaoyang; Liu, Jia; Zhu, Lin; Ma, Zichuan; Wu, Yinsu

    2016-02-01

    Manganese oxide supported on mesoporous ceria was prepared and used as catalyst for catalytic ozonation of sulfosalicylic acid (SA). Characterization results indicated that the manganese oxide was mostly incorporated into the pores of ceria. The synthesized catalyst exhibited high activity and stability for the mineralization of SA in aqueous solution by ozone, and more than 95% of total organic carbon was removed in 30 min under various conditions. Mechanism studies indicated that SA was mainly degraded by ozone molecules, and hydroxyl radical reaction played an important role for the degradation of its ozonation products (small molecular organic acids). The manganese oxide in the pores of CeO2 improved the adsorption of small molecular organic acids and the generation of hydroxyl radicals from ozone decomposition, resulting in high TOC removal efficiency.

  19. Antarctic ozone depletion chemistry - Reactions of N2O5 with H2O and HCl on ice surfaces

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

    In a study concerning Antarctic ozone depletion, reactions of dinitrogen pentoxide with water and hydrochloric acid were studied on ice surfaces in a Knudsen cell flow reactor. The N2O5 reacted on ice at 185 K to form condensed-phase nitric acid (HNO3). This reaction may provide a sink for odd nitrogen, NO(x), during the polar winter, a requirement in nearly all models of Antarctic ozone depletion. The reaction of N2O5 on HCl-ice surfaces at 185 K produced gaseous nitryl chloride (ClNO2) and condensed-phase HNO3 and proceeded until all of the HCl within the ice was depleted. The ClNO2 which did not react or condense on ice at 185 K, can be readily photolyzed in the Antarctic spring to form atomic chlorine for catalytic ozone destruction cycles. The other photolysis product, gaseous nitrogen dioxide may be important in the partitioning of NO(x) between gaseous and condensed phases in the Antarctic winter.

  20. Reactive nitrogen partitioning and its relationship to winter ozone events in Utah

    NASA Astrophysics Data System (ADS)

    Wild, R. J.; Edwards, P. M.; Bates, T. S.; Cohen, R. C.; de Gouw, J. A.; Dubé, W. P.; Gilman, J. B.; Holloway, J.; Kercher, J.; Koss, A. R.; Lee, L.; Lerner, B. M.; McLaren, R.; Quinn, P. K.; Roberts, J. M.; Stutz, J.; Thornton, J. A.; Veres, P. R.; Warneke, C.; Williams, E.; Young, C. J.; Yuan, B.; Zarzana, K. J.; Brown, S. S.

    2016-01-01

    High wintertime ozone levels have been observed in the Uintah Basin, Utah, a sparsely populated rural region with intensive oil and gas operations. The reactive nitrogen budget plays an important role in tropospheric ozone formation. Measurements were taken during three field campaigns in the winters of 2012, 2013 and 2014, which experienced varying climatic conditions. Average concentrations of ozone and total reactive nitrogen were observed to be 2.5 times higher in 2013 than 2012, with 2014 an intermediate year in most respects. However, photochemically active NOx (NO + NO2) remained remarkably similar all three years. Nitric acid comprised roughly half of NOz ( ≡ NOy - NOx) in 2013, with nighttime nitric acid formation through heterogeneous uptake of N2O5 contributing approximately 6 times more than daytime formation. In 2012, N2O5 and ClNO2 were larger components of NOz relative to HNO3. The nighttime N2O5 lifetime between the high-ozone year 2013 and the low-ozone year 2012 is lower by a factor of 2.6, and much of this is due to higher aerosol surface area in the high-ozone year of 2013. A box-model simulation supports the importance of nighttime chemistry on the reactive nitrogen budget, showing a large sensitivity of NOx and ozone concentrations to nighttime processes.

  1. Foliar nutrient status of Pinus ponderosa exposed to ozone and acid rain

    SciTech Connect

    Anderson, P.D.; Houpis, J.L.J. )

    1991-05-01

    A direct effect of foliar exposure to acid rain may be increased leaching of nutrient elements. Ozone exposure, through degradation of the cuticle and cellular membranes, may also result in increased nutrient leaching. To test these hypotheses, the foliar concentrations of 13 nutrient elements were monitored for mature branches of three clones of Pinus ponderosa exposed to ozone and/or acid rain. The three clones represented three distinct levels of phenotypic vigor. Branches were exposed to charcoal filtered, ambient, or 2 x ambient concentrations of ozone and received no acid rain (NAP), pH 5.1 rain (5.1), or pH 3.0 (3.0) rain. Following 10 months of continuous ozone exposure and 3 months of weekly rain applications, the concentrations of P and Mg differed significantly among rain treatments with a ranking of: 5.1 < NAP < 3.0. The S concentration increased with rain application regardless of pH. For the clones of moderate and low vigor, the concentration of N decreased with increasing rain acidity. There was no evidence of significant ozone or ozone x acid rain response. Among the three families, high phenotypic vigor was associated with significantly greater concentrations of N, P, K, Mg, B and An. These results indicate generally negligible leaching as a result of exposure to acid rain and/or ozone for one growing season. Increases in foliar concentrations of S, Mg and P are possibly the result of evaporative surface deposition from the rain solution.

  2. Effects of ozone and acid aerosol exposures on surfactant-associated protein A in the lung

    SciTech Connect

    Su, W.Y.

    1993-01-01

    This study examined the effect of ozone and/or acid aerosol exposure on the level of surfactant associated protein A (SP-A), its gene expression and functionality in the lung. Guinea pigs were exposed to (1) a single exposure to 0.2 to 0.8 ppm ozone for 6 hr and sacrificed at 0 to 120 hr postexposure, (2) 0.8 ppm ozone, 6 hr/day for 3 to 5 days and sacrificed immediately postexposure, or (3) 0.8 ppm ozone, 600 [mu]g/m[sup 3] sulfuric acid, or ozone plus acid for 6 hr and sacrificed at 72 hr postexposure. The concentration of SP-A was determined by ELISA in lavage fluid, lavage cell pellets, and lung tissue compartments. SP-A gene expression was examined in lung tissue by Northern and slot blot analysis. Effect of ozone exposure on functionality of surfactant was tested by its ability to modulate phagocytic cell respiratory burst in a luminol-amplified chemiluminescence (CL) assay of phagocytic cells simulated by PMA or opsonized-zymosan. There were isolated, but significant, changes in SP-A concentrations in the lavage cell and the lavage fluid compartments at 24 and 48 hr after single exposure to 0.8 ppm ozone, respectively. Exposure to ozone and ozone plus acid also slightly increased total SP-A level in the lung. No change in SP-A gene expression was detected under the exposure conditions examined. However, surfactant from ozone exposed animals significantly enhanced CL response of phagocytic cells stimulated by either PMA or opsonized-zymosan. Blocking of the enhancement of CL by a rabbit anti-human SP-A antibody strongly suggested that SP-A may contribute in the altered respiratory burst of phagocytic cells induced by surfactant from ozone exposed animals.

  3. Using ozonation and amino acids to change pasting properties of rice starch.

    PubMed

    An, H J; King, J M

    2009-04-01

    In this study, the effects of ozonation and the addition of amino acids on rice starches were determined in terms of pasting properties using a rapid visco-analyzer. Results from viscosity analysis showed that 30-min ozone treatment on commercial rice starch exhibited the greatest swelling extent among the treatments and least retrogradation tendency. The control pure oxygen treated sample had the best cooking stability. The addition of lysine (6%) to 30-min ozonated commercial rice starch significantly reduced peak viscosity (PV), minimum viscosity (MV), and final viscosity (FV) by 918, 1024, and 1023 cP, respectively. Moreover, it decreased Ptime, resulting in the faster swelling upon heating and less rigid gel formation upon cooling. Furthermore, the presence of lysine in 30-min ozonated starch isolate (WSI) also significantly reduced PV, MV, FV, pasting time, and total setback (TSB) and produced starch gel with the best cooking stability and the least retrogradation tendency. Ozonated starch exhibited similar pasting properties to those from oxidized starches treated with low concentrations of chemical oxidizing agents. The combination of lysine with ozonation resulted in pasting properties similar to starches treated with high levels of chemical oxidizing agents. The ozonated starch could be used as a thickening agent, whereas ozonated starch with lysine might be an alternative for a highly chemically oxidized starch. Therefore, ozonation alone or the combination of ozonation and addition of lysine might be used to develop new starch ingredients with various functionalities without using typical chemical modifications.

  4. Kinetics of electron attachment to OH and HNO3 and mutual neutralization of Ar+ with NO2- and NO3- at 300 and 500 K

    NASA Astrophysics Data System (ADS)

    Shuman, Nicholas S.; Miller, Thomas M.; Viggiano, A. A.

    2012-03-01

    The electron attachment rate constant to nitric acid (HNO3) has been measured in a flowing afterglow-Langmuir probe (FALP) apparatus at 300 and 500 K using three independent methods: the traditional FALP technique of monitoring electron depletion, "one-gas" VENDAMS (variable electron and neutral density attachment mass spectrometry), and "two-gas" VENDAMS. The three measurements are in agreement with a 300 K weighted average of 1.4 ± 0.3 × 10-7 cm3 s-1, 2 to 10 times higher than previously reported values. Attachment is primarily dissociative yielding NO2- as previously reported, but for the first time a small endothermic channel to produce OH- was also observed at 500 K. From the one-gas VENDAMS data, associative attachment to the OH produced in the primary attachment was found to occur with an effective two body rate constant of 1.2 ± _{0.7}^3 × 10-11 cm3 s-1 at 300 K, the first reported rate constant for this radical species. Finally, ion-ion neutralization rate constants of NO2- and NO3- with Ar+ were determined to be 5.2 ± _{2.5}^{1.5} × 10-8 and 4.5 ± 2.5 × 10-8 cm3 s-1 at 300 K, respectively.

  5. A theoretical investigation of gaseous absorption by water droplets from SO2-HNO3-NH3-CO2-HCl mixtures

    NASA Technical Reports Server (NTRS)

    Adewuyi, Y. G.; Carmichael, G. R.

    1982-01-01

    A physical-chemical model is developed and used to investigate gaseous absorption by water droplets from trace gas mixtures. The model is an extension of that of Carmichael and Peters (1979) and includes the simultaneous absorption of SO2, NH3, HNO3, CO2, and HCl. Gas phase depletion is also considered. Presented results demonstrate that the absorption behavior of raindrops is strongly dependent on drop size, fall distance, trace gas concentrations, and the chemical and physical properties of the constituents of the mixture. In addition, when gas phase depletion is considered, the absorption rates and equilibrium values are also dependent on the precipitation rate itself. Also, the trace constituents liquid phase concentrations may be a factor of six or more lower when gas depletion is considered then when the depletion is ignored. However, the hydrogen ion concentration may be insensitive to the gas phase depletion.

  6. Enhanced ozonation of dichloroacetic acid in aqueous solution using nanometer ZnO powders.

    PubMed

    Zhai, Xu; Chen, Zhonglin; Zhao, Shuqing; Wang, He; Yang, Lei

    2010-01-01

    Nanometer zinc oxide (ZnO) powders were used as a catalyst to enhance the ozonation for the degradation of dichloroacetic acid (DCAA) in aqueous solution. The batch experiments were carried out to investigate the effects of key factors such as catalyst dosage, ozone dosage, solution pH and tert-butyl alcohol (t-BuOH) on the degradation efficiency of DCAA. Density functional theory (DFT) was adopted to explore the mechanism of generating hydroxyl radical (*OH) on the ZnO surface. The results showed that adsorption and ozonation processes were not effective for DCAA removal, and the addition of ZnO catalyst improved the degradation efficiency of DCAA during ozonation, which caused an increase of 22.8% for DCAA decomposition compared to the case of ozonation alone after 25 min. Under the same experimental conditions, the DCAA decomposition was enhanced by increasing catalyst dosage from 100 to 500 mg/L and ozone dosage from 0.83 to 3.2 mg/L. The catalytic ozonation process is more pronounced than the ozonation process alone at pH 3.93, 6.88, and 10. With increasing the concentration of t-BuOH from 10 to 200 mg/L, the degradation of DCAA was significantly inhibited in the process of catalytic ozonation, indicating that ZnO catalytic ozonation followed *OH reaction mechanism. Based on the experimental results and DFT analysis, it is deduced that the generation of *OH on the ZnO surface is ascribed to the adsorption of molecule ozone followed by the interaction of adsorbed ozone with active sites of the catalyst surface. It is also concluded that ZnO may be an effective catalyst for DCAA removal, which could promote the formation of *OH derived from the catalytic decomposition of ozone. PMID:21235181

  7. 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.

  8. Removal of dicyclohexyl acetic acid from aqueous solution using ultrasound, ozone and their combination.

    PubMed

    Kumar, Pardeep; Headley, John; Peru, Kerry; Bailey, Jon; Dalai, Ajay

    2014-01-01

    Naphthenic acids are a complex mixture of organic components, some of which include saturated alkyl-substituted cycloaliphatic carboxylic acids and acyclic aliphatic acids. They are naturally found in hydrocarbon deposits like oil sand, petroleum, bitumen and crude oil. In this study, the oxidation of a relatively high molecular weight naphthenic acid (Dicyclohexyl acetic acid) was investigated using ozonation, ultrasonication and hydrogen peroxide alone and their combinations. Effects on oxidation of dicyclohexyl acetic acid (DAA) were measured for different concentrations of ozone ranging between 0.7 to 3.3 mg L(-1) and pH in the range 6 to 10. Ultrasonication and hydrogen peroxide alone were not effective to oxidize dicyclohexyl acetic acid, but combining ultrasonication with H2O2 had a significant effect on oxidation of dicyclohexyl acetic acid with maximum removal reaching to 84 ± 2.2% with 81 ± 2.1% reduction in chemical oxygen demand (COD). Synergistic effects were observed for combining ultrasonication with ozonation and resulted in 100% DAA removal with 98 ± 0.8% reduction in COD within 15 min at 3.3 mg L(-1) ozone concentration and 130 Watts ultrasonication power. The reaction conditions obtained for the maximum oxidation of DAA and COD removal were used for the degradation of naphthenic acids mixture extracted from oil sands process water (OSPW). The percentage oxidation of NAs mixture extracted from OSPW was 89.3 ± 1.1% in ozonation and combined ozonation and ultrasonication, but COD removal observed was 65 ± 1.2% and 78 ± 1.4% for ozonation and combined ozonation and ultrasonication treatments, respectively.

  9. 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.

  10. Response of total tannins and phenolics in loblolly pine foliage exposed to ozone and acid rain.

    PubMed

    Jordan, D N; Green, T H; Chappelka, A H; Lockaby, B G; Meldahl, R S; Gjerstad, D H

    1991-03-01

    Tannin and total phenolic levels in the foliage of loblolly pine (Pinus taeda L.) were examined in order to evaluate the effect of atmospheric pollution on secondary plant metabolism. The trees were exposed to four ozone concentrations and three levels of simulated acid rain. Tannin concentration (quantity per gram) and content (quantity per fascicle) were increased in foliage exposed to high concentrations of ozone in both ozone-sensitive and ozone-tolerant families. No effect of acid rain on tannins was observed. Neither total phenolic concentration nor content was significantly affected by any treatment, indicating that the ozone-related increase in foliar tannins was due to changes in allocation within the phenolic group rather than to increases in total phenolics. The change in allocation of resources in the production of secondary metabolites may have implications in herbivore defense, as well as for the overall energy balance of the plant.

  11. Ozonation of oil sands process water removes naphthenic acids and toxicity.

    PubMed

    Scott, Angela C; Zubot, Warren; MacKinnon, Michael D; Smith, Daniel W; Fedorak, Phillip M

    2008-03-01

    Naphthenic acids are naturally-occurring, aliphatic or alicyclic carboxylic acids found in petroleum. Water used to extract bitumen from the Athabasca oil sands becomes toxic to various organisms due to the presence of naphthenic acids released from the bitumen. Natural biodegradation was expected to be the most cost-effective method for reducing the toxicity of the oil sands process water (OSPW). However, naphthenic acids are poorly biodegraded in the holding ponds located on properties leased by the oil sands companies. In the present study, chemical oxidation using ozone was investigated as an option for mitigation of this toxicity. Ozonation of sediment-free OSPW was conducted using proprietary technology manufactured by Seair Diffusion Systems Inc. Ozonation for 50min generated a non-toxic effluent (based on the Microtox bioassay) and decreased the naphthenic acids concentration by approximately 70%. After 130min of ozonation, the residual naphthenic acids concentration was 2mgl(-1): <5% of the initial concentration in the filtered OSPW. Total organic carbon did not change with 130min of ozonation, whereas chemical oxygen demand decreased by approximately 50% and 5-d biochemical oxygen demand increased from an initial value of 2mgl(-1) to a final value of 15mgl(-1). GC-MS analysis showed that ozonation resulted in an overall decrease in the proportion of high molecular weight naphthenic acids (n> or = 22).

  12. Environmental Externalities in Electric Power Markets: Acid Rain, Urban Ozone, and Climate Change

    EIA Publications

    1995-01-01

    This article discusses the emissions resulting from the generation of electricity by utilities and their role in contributing to the environmental problems of acid rain, urban ozone, and climate change.

  13. Effect of metal ions on decomposition of chlorinated organic substances by ozonation in acetic acid.

    PubMed

    Okawa, Kiyokazu; Tsai, Tsung-Yueh; Nakano, Yoichi; Nishijima, Wataru; Okada, Mitsumasa

    2005-01-01

    The objective of this study is to find metal ions that enhance the ozone decomposition of chlorinated organic substances in acetic acid. Although the pseudo-first order degradation rate constant for 2,4-DCP by ozone in acetic acid in addition of Ca2+, Mg2+, Al3+ and Fe2+ were almost the same as that with no metal ion, the degradation rate in addition of Mn2+ and Fe3+ were 2.4 and 4.5 times as high as that with no metal ion, respectively. The presence of Fe3+ enhanced the degradation of 2,4-DCP by ozone in acetic acid because Fe3+-phenolate complex which have high reactivity with ozone was produced by the reaction between 2,4-DCP and Fe3+ in acetic acid. PMID:15620744

  14. Laboratory studies of chemical and photochemical processes relevant to stratospheric ozone

    NASA Technical Reports Server (NTRS)

    Zahniser, Mark S.; Nelson, David D.; Worsnop, Douglas R.; Kolb, Charles E.

    1994-01-01

    The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HO(sub x) and NO(sub x) species in the temperature range 200 K to 240 K relevant to the lower stratosphere. Other areas of study have included infrared spectroscopic studies of the HO2 radical, measurements of OH radical reactions with alternative fluorocarbons, and determination of the vapor pressures of nitric acid hydrates under stratospheric conditions. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences. In this annual report, we focus on our recent accomplishments in the quantitative spectroscopy of the HO2 radical. This report details the measurements of the broadening coefficients for the v(sub 2) vibrational band. Further measurements of the vapor pressures of nitric acid hydrates relevant to the polar stratospheric cloud formation indicate the importance of metastable crystalline phases of H2SO4, HNO3, and H2O. Large particles produced from these metastable phases may provide a removal mechanism for HNO3 in the polar stratosphere.

  15. Experimental study of humic acid degradation and theoretical modelling of catalytic ozonation.

    PubMed

    Turkay, Ozge; Inan, Hatice; Dimoglo, Anatoli

    2015-01-01

    The efficiency of TiO2 as a catalyst in the ozonation of humic acid (HA) was evaluated in a comprehensive manner. Ozonation, catalytic ozonation and adsorption experiments were conducted using both synthetic HA solution and natural water. HA degradation was evaluated in terms of DOC, VIS400 and UV254. It was shown that the addition of catalyst positively affects the mechanism of ozonation. An increase in HA degradation was observed for all these parameters. The impact of catalyst dose and initial pH value of HA on the efficacy of catalytic ozonation was investigated. The highest removal efficiencies were achieved with the dose of 1 g l(-1) of TiO2 (Degussa P-25) and in the acidic pH region. The catalytic ozonation process was efficient also on natural water component although not at the same level as it was on synthetic water. The adsorptive feature of P-25 was considered to have a clear evidence of the catalytic ozonation mechanism. The mechanism of catalysis on the surface of metal oxides was elucidated with the help of quantum-chemical calculations. In the framework of Density Function Theory (DFT), the O3 decomposition was calculated in the catalytic and non-catalytic processes. Donor-acceptor properties of the frontier (highest occupied and lowest unoccupied molecular orbitals, HOMO/LUMO) orbitals are discussed. Electron density distribution and reaction mechanism of superoxide particles formation, which participate in the process of HA ozonation are analyzed. PMID:25056748

  16. A chemiluminescence-based continuous flow aqueous ozone analyzer using photoactivated chromotropic acid.

    PubMed

    Takayanagi, Toshio; Dasgupta, Purnendu K

    2005-05-15

    Ozone has become the oxidant of choice for water disinfection, especially in large water treatment facilities. This paper describes a fast and sensitive method for the determination of ozone content by reaction with photoactivated chromotropic acid (CA, 4,5-dihydroxynaphthalene-2,7-disulfonic acid), which results in intense chemiluminescence (CL). Freshly ozonated water from a recirculating ozonizer/reservoir is injected into a carrier stream of deionized water in the flow-injection mode. This flow mixes with a stream of photoactivated CA solution in a spiral cell placed directly on top of an inexpensive miniature (8mm diameter active area) photomultiplier tube (PMT). Alkaline CA is photoactivated by passing it through a FEP-Teflon((R)) coil (residence time approximately 50s) wrapped around a 1W UV lamp emitting at 254nm; without photoactivation, the signal is approximately 70-fold lower. The S/N=3 limit of detection for aqueous ozone is 3mugl(-1) and good response slope is obtained up to an ozone concentration of 1.4mgl(-1), the highest that could be made in this study. The response obeyed a quadratic equation with r(2)=0.9984. No interference from permanganate ion is observed. The proposed system was applied to the monitoring of ozonation status of a playa lake water that exhibited significant ozone demand.

  17. The impact of high altitude aircraft on the ozone layer in the stratosphere

    NASA Technical Reports Server (NTRS)

    Tie, Xue XI; Brasseur, Guy; Lin, Xing; Friedlingstein, P.; Granier, Claire; Rasch, Philip

    1994-01-01

    The paper discusses the potential effects on the ozone layer of gases released by the engines of proposed high altitude supersonic aircraft. The major problem arises from the emissions of nitrogen oxides which have the potential to destroy significant quantities of ozone in the stratosphere. The magnitude of the perturbation is highly dependent on the cruise altitude of the aircraft. Furthermore, the depletion of ozone is substantially reduced when heterogeneous conversion of nitrogen oxides into nitric acid on sulfate aerosol particles is taken into account in the calculation. The sensitivity of the aerosol load on stratospheric ozone is investigated. First, the model indicates that the aerosol load induced by the SO2 released by aircraft is increased by about 10-20% above the background aerosols at mid-high latitude of the Northern Hemisphere at 15 km for the NASA emission scenario A (the NASA emission scenarios are explained in Tables I to III). This increase in aerosol has small effects on stratospheric ozone. Second, when the aerosol load is increased following a volcanic eruption similar to the eruption of El Chichon (Mexico, April 1982), the ozone column in spring increases by as much as 9% in response to the injection of NOx from the aircraft with the NASA emission scenario A. Finally, the modeled suggests that significant ozone depletion could result from the formation of additional polar stratospheric clouds produced by the injection of H2O and HNO3 by the aircraft engines.

  18. Ozone

    SciTech Connect

    Not Available

    1988-06-01

    The author discusses the debate over whether concern about a hole in the ozone layer in Antarctic is real or science fiction. There is a growing consensus that efforts must be taken to protect the ozone layer. The issue now is not whether chlorofluorocarbons (CFCs) should be controlled and regulated but how much and how soon. The United States has urged that the production of dangerous CFCs, and any other chemicals that affect the ozone layer, be restricted immediately to current levels and that their use be reduced 95 percent over the next decade. The American position was too strong for many European nations and the Japanese. Negotiations at an international conference on the matter broke down. The breakdown is due in part to a more acute concern for environmental matters in the United States than exists in many countries. Meanwhile CFCs are linked to another environmental problem that equally threatens the world - the Greenhouse Effect. The earth is in a natural warming period, but man could be causing it to become even warmer. The Greenhouse Effect could have a catastrophic impact on mankind, although nothing has been proven yet.

  19. Economic assessment of acid deposition and ozone damage on the San Joaquin Valley agriculture. Final report

    SciTech Connect

    Howitt, R.

    1993-02-01

    The California Agricultural Resources Model (CARM) was used to estimate the economic impact of acidic deposition and ozone on crops in the San Joaquin Valley. Data on ozone exposure-crop response and agricultural markets are used in the CARM to estimate the potential economic benefits of an improvement in air quality. The study focused on the economic impact of two ozone reduction scenarios in agricultural regions of California. The CARM projected that if growing season concentrations of ozone were reduced to 0.04 ppm, annual benefits to consumers (higher availability and lower prices) and producers (higher production and lower production costs) would be approximately $489 million. In comparison, the benefit projected if statewide levels of ozone were uniformly reduced to 0.025 ppm was approximately $1.5 billion. Although the 0.025 ppm scenario is unlikely, the economic benefits were estimated to be correspondingly large.

  20. Kinetics of heterogeneous reaction of ozone with linoleic acid and its dependence on temperature, physical state, RH, and ozone concentration.

    PubMed

    Zeng, Guang; Holladay, Sara; Langlois, Danielle; Zhang, Yunhong; Liu, Yong

    2013-03-01

    Heterogeneous reaction between ozone and linoleic acid (LA) thin film was investigated by a flow reactor coupled to attenuated total reflection infrared spectroscopy (FR-ATR-IR) over wide ranges of temperature, relative humidity (RH), and ozone concentration under atmospheric pressure condition. Pseudo-first-order rate constants kapp and overall reactive uptake coefficients γ were acquired on the basis of changes in absorbance from peaks located near 1743, 1710, 1172, and 1110 cm(-1), which can be assigned to C═O in ester, C═O in acid, and C-C and C-O stretching modes, respectively. Results showed that the kapp and γ increased nearly by a factor of 6 with increasing temperatures from 258 to 314 K. It was noted the temperature effect on the reaction kinetics was much more pronounced at lower temperatures. Such behavior can be explained by a change in the physical state of LA at lower temperatures. In addition, kapp and γ were enhanced by 2-fold as the RH increased from 0 to 80%. Moreover, the effect of ozone concentration on the reaction kinetics was reported for the first time. kapp was found to display a Langmuir-Hinshelwood dependence on ozone concentration with KO3 = (1.146 ± 0.017) × 10(-15) molecules cm(-3) and k[S] = 0.0522 ± 0.0004 s(-1), where KO3 is a parameter that describes the partitioning of ozone to the thin film surface, and k[S] is the maximum pseudo-first-order coefficient at high ozone concentration. Furthermore, yields and hygroscopic properties of reaction products were also investigated by FTIR spectroscopy. The intensity ratio of two C═O stretching bands, A1743/A1710, which was utilized as an indicator of the product yields, increased sharply with increasing temperatures in the lower temperature region (258-284 K), and then remained nearly constant in the higher temperature region (284-314 K). The product yields showed no significant variation with RH, for the intensity ratio of A1743/A1710 barely changed in the wide RH range 0

  1. Influence of ozone and paracetic acid disinfection on adhesion of resilient liners to acrylic resin

    PubMed Central

    2016-01-01

    PURPOSE The aim of this study was to evaluate the effect of paracetic acid (PAA) and ozone disinfection on the tensile bond strength (TBS) of silicone-based resilient liners to acrylic resins. MATERIALS AND METHODS One hundred and twenty dumbbell shaped heat-polymerized acrylic resins were prepared. From the mid segment of the specimens, 3 mm of acrylic were grinded off and separated parts were reattached by resilient liners. The specimens were divided into 2 control (control1, control7) and 4 test groups of PAA and ozone disinfection (PAA1, PAA7, ozone1 and ozone7; n=10). While control groups were immersed in distilled water for 10 min (control1) and 7 days (control7), test groups were subjected to PAA (16 g/L) or ozone rich water (4 mg/L) for 1 cycle (10 min for PAA and 60 min for ozone) per day for 7 days prior to tensile tests. Measurements of the TBS were analyzed using 3-way ANOVA and Tukey's HSD test. RESULTS Adhesive strength of Mollosil decreased significantly by application of ozone disinfection. PAA disinfection had no negative effect on the TBS values of Mollosil and Molloplast B to acrylic resin. Single application of ozone disinfection did not have any negative effect on TBS values of Molloplast B, but prolonged exposure to ozone decreased its adhesive strength. CONCLUSION The adhesion of resilient liners to acrylic was not adversely affected by PAA disinfection. Immersion in ozonated water significantly decreased TBS of Mollosil. Prolonged exposure to ozone negatively affects adhesion of Molloplast B to denture base materials. PMID:27555898

  2. 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 - , ...

  3. Acid mist and ozone effects on the leaf chemistry of two western conifer species

    NASA Technical Reports Server (NTRS)

    Westman, Walter E.; Temple, Patrick J.

    1989-01-01

    The effects of ozone and acid-mist exposures on the leaf chemistry of Jeffrey pine and giant sequoia seedlings grown in filtered-air greenhouses were investigated. Acid-mist treatments (pH 4.1, 3.4, 2.7, or 2.0) were administered for 3 h, and ozone exposures (0, 0.10, and 0.20 microliter/liter), which followed acid-mist treatments, for 4 h, each for three days a week for six to nine weeks. It was found that seedlings were more susceptible to acid-mist and acid mist/ozone combinations, than to ozone alone. Acid mist treatment resulted in higher levels of nitrogen and sulfur (both present in acid mist) as well as Na. Leaves of giant sequoia exhibited increased K and decreased Mn, while Jeffrey pine showed increases in Fe and Mn. In sequoia leaves, concentrations of Ca, Mg, and Ba decreased. Acid treatment also reduced chlorophyll b concentrations in both conifer species. Extensive changes induced by acid mist are consistent with earlier observations of changes in spectral reflectance of conifer seedlings observed after three weeks of fumigation.

  4. 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.

  5. Ozonation kinetics of phenolic acids present in wastewaters from olive oil mills

    SciTech Connect

    Benitez, F.J.; Beltran-Heredia, J.; Acero, J.L.; Pinilla, M.L.

    1997-03-01

    A kinetic study of the degradation by ozone of eight phenolic acids present in wastewaters from olive oil mills has been performed by using a competition kinetic method. The selected phenolic acids are: caffeic, p-coumaric, syringic, vanillic, 3,4,5-trimethoxybenzoic, veratric, p-hydroxy-benzoic, and protocatechuic. The influence of the operating variables (temperature, pH, and ozone partial pressure in the gas stream) is established, and the stoichiometric ratios for the individual direct reactions between ozone and each acid are determined. Once the reaction rate constants are evaluated, they are correlated as a function of temperature and pH into kinetic expressions which are provided for every phenolic acid. The global process occurs in the fast and pseudo-first-order kinetic regime of absorption, a condition required by the competition model to be used.

  6. Mechanism for enhanced degradation of clofibric acid in aqueous by catalytic ozonation over MnOx/SBA-15.

    PubMed

    Sun, Qiangqiang; Wang, Yu; Li, Laisheng; Bing, Jishuai; Wang, Yingxin; Yan, Huihua

    2015-04-01

    Comparative experiments were conducted to investigate the catalytic ability of MnO(x)/SBA-15 for the ozonation of clofibric acid (CA) and its reaction mechanism. Compared with ozonation alone, the degradation of CA was barely enhanced, while the removal of TOC was significantly improved by catalytic ozonation (O3/MnO(x)/SBA-15). Adsorption of CA and its intermediates by MnO(x)/SBA-15 was proved unimportant in O3/MnO(x)/SBA-15 due to the insignificant adsorption of CA and little TOC variation after ceasing ozone in stopped-flow experiment. The more remarkably inhibition effect of sodium bisulfite (NaHSO3) on the removal of TOC in catalytic ozonation than in ozonation alone elucidated that MnO(x)/SBA-15 facilitated the generation of hydroxyl radicals (OH), which was further verified by electron spin-resonance spectroscopy (ESR). Highly dispersed MnO(x) on SBA-15 were believed to be the main active component in MnO(x)/SBA-15. Some intermediates were indentified and different degradation routes of CA were proposed in both ozonation alone and catalytic ozonation. The amounts of small molecular carboxylic acids (i.e., formic acid (FA), acetic acid (AA) and oxalic acid (OA)) generated in catalytic ozonation were lower than in ozonation alone, resulting from the generation of more OH.

  7. Preparation of low-molecular-weight hyaluronic acid by ozone treatment.

    PubMed

    Wu, Yue

    2012-06-20

    Recently, low-molecular-weight hyaluronic acid has been reported to have novel features, such as free radical scavenging activities, antioxidant activities, promotion of excisional wound healing, etc. In the present work, degradation of native hyaluronic acid by ozone treatment was performed for preparation of low-molecular-weight hyaluronic acid. The molecular weight of native hyaluronic acid was reduced from 1535 to 87 kDa for 120 min at 40°C. The rate of reduction of molecular weight was 94.33%. The FT-IR, 13C NMR, and UV-vis spectra suggested that there was no obvious modification of chemical structure of low-molecular-weight hyaluronic acid. The use of degradation of native hyaluronic acid by ozone treatment can be a useful alternative for production of low-molecular-weight hyaluronic acid.

  8. Uptake of ozone to mixed sodium bromide/ citric acid solutions

    NASA Astrophysics Data System (ADS)

    Lee, Ming-Tao; Steimle, Emilie; Bartels-Rausch, Thorsten; Kato, Shunsuke; Lampimäki, Markus; Brown, Matthew; van Bokhoven, Jeroen; Nolting, Frithjof; Kleibert, Armin; Türler, Andreas; Ammann, Markus

    2013-04-01

    Sea-salt solution - air interfaces play an important role in the chemistry of the marine boundary layer. The reaction of ozone (O3) with bromide is of interest in the context of formation of photolabile halogens (Br2, BrCl) in the marine boundary layer. Recent experiments have suggested that the bromide oxidation rate is related to the surface concentration of bromide [1] and inversely related to the gas phase concentration of O3, an indication for a precursor mediated reaction at the surface [2]. So far, the effect of organics (such as those occurring at the ocean surface or in marine aerosols) on the reaction of O3 with bromide aerosols has not been studied yet. In our study we investigate the uptake kinetics of O3 to a mixed solution of sodium bromide (NaBr) and citric acid (CA), which represents highly oxidized organic compounds present in the environment, with a well-established coated wall flow tube technique, which leads to exposure of the film to O3 allowing the heterogeneous reactions to take place and the loss of O3 being measured. The results indicate that the uptake of O3 to the films with the higher bromide concentrations (0.34M and 4M) is independent of the gas phase concentration and roughly consistent with uptake limited by reaction in the bulk. For the lower bromide concentration (84mM), however, we observe a trend of the uptake coefficient to decrease with increasing O3 concentration, indicating an increasing importance of a surface reaction. In an attempt to constrain the kinetic data, we employed X-ray photoelectron spectroscopy (XPS) to get insight into the surface composition of the aqueous solution - air interface. Previous XPS studies have shown that halide ion concentrations are enhanced at the aqueous solution air interface [3-4], which likely promotes the surface reactions of bromide or iodide with O3. A first XPS study of ternary solutions of KI with butanol indicated the importance of specific interactions of the cation with the alcohol

  9. Temperature thresholds for chlorine activation and ozone loss in the polar stratosphere

    NASA Astrophysics Data System (ADS)

    Drdla, K.; Müller, R.

    2012-07-01

    Low stratospheric temperatures are known to be responsible for heterogeneous chlorine activation that leads to polar ozone depletion. Here, we discuss the temperature threshold below which substantial chlorine activation occurs. We suggest that the onset of chlorine activation is dominated by reactions on cold binary aerosol particles, without the formation of polar stratospheric clouds (PSCs), i.e. without any significant uptake of HNO3 from the gas phase. Using reaction rates on cold binary aerosol in a model of stratospheric chemistry, a chlorine activation threshold temperature, TACL, is derived. At typical stratospheric conditions, TACL is similar in value to TNAT (within 1-2 K), the highest temperature at which nitric acid trihydrate (NAT) can exist. TNAT is still in use to parameterise the threshold temperature for the onset of chlorine activation. However, perturbations can cause TACL to differ from TNAT: TACL is dependent upon H2O and potential temperature, but unlike TNAT is not dependent upon HNO3. Furthermore, in contrast to TNAT, TACL is dependent upon the stratospheric sulfate aerosol loading and thus provides a means to estimate the impact on polar ozone of strong volcanic eruptions and some geo-engineering options, which are discussed. A parameterisation of TACL is provided here, allowing it to be calculated for low solar elevation (or high solar zenith angle) over a comprehensive range of stratospheric conditions. Considering TACL as a proxy for chlorine activation cannot replace a detailed model calculation, and polar ozone loss is influenced by other factors apart from the initial chlorine activation. However, TACL provides a more accurate description of the temperature conditions necessary for chlorine activation and ozone loss in the polar stratosphere than TNAT.

  10. Laboratory studies of potential mechanisms of renoxification of tropospheric nitric acid.

    PubMed

    Rivera-Figueroa, A M; Sumner, A L; Finlayson-Pitts, B J

    2003-02-01

    Laboratory studies of the heterogeneous reactions between HNO3 in thin water films on silica surfaces and gaseous NO, CO, CH4, and SO2, proposed as potential "renoxification" mechanisms in the atmosphere, are reported. Transmission FTIR was used to monitor reactants and products on the silica surface and in the gas phase as a function of time. No reaction of CO, CH4, or SO2 was observed; upper limits to the reaction probabilities (gamma(rxn)) are < or = 10(-10) for CO and SO2 and < or = 10(-12) for CH4. However, the reaction of HNO3 with NO does occur with a lower limit for the reaction probability of gammaNO > or = (6 +/- 2) x 10(-9) (2s). The experimental evidence shows that the chemistry is insensitive to whether the substrate is pure silica or borosilicate glass. Nitric acid in its molecular form, and not the nitrate anion form, was shown to be the reactive species, and NH4NO3 was shown not to react with NO. The HNO3-NO reaction could be a significant means of renoxification of nitric acid on the surfaces of buildings and soils in the boundary layer of polluted urban atmospheres. This chemistry may help to resolve some discrepancies between model-predicted ozone and field observations in polluted urban atmospheres.

  11. Effects of mist acidity and ambient ozone removal on montane red spruce.

    PubMed

    Vann, D R; Strimbeck, G R; Johnson, A H

    1995-10-01

    Recent forest studies have established that high-elevation (> 900 m) populations of red spruce (Picea rubens Sarg.) in the northeastern USA are declining. Because it has been suggested that changes in air quality are responsible for the decline, we examined the effects of acidic mists and ozone on several biochemical and growth parameters in mature montane red spruce. We used branch-sized environmental chambers to introduce mists of controlled composition and exclude ambient clouds and ozone from individual branches within a tree. Mists consisting of distilled water increased the end-of-season pigment concentration and shoot length of enclosed branches relative to ambient or artificial mists. Needle and twig weights and starch concentrations were not significantly altered by the acidic mist treatments. Removal of ambient ozone had no apparent effect on the variables measured.

  12. 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.

  13. The role of ion-molecule reactions in the conversion of N2O5 to HNO3 in the stratosphere

    NASA Astrophysics Data System (ADS)

    Bohringer, H.; Fahey, D. W.; Fehsenfeld, F. C.; Ferguson, E. E.

    1983-02-01

    The role of several ion-molecule reactions in the conversion of N2O5 to HNO3 was investigated. In the proposed conversion, an N2O5 molecule would react with an H2O molecule clustered to an inert ion to produce two HNO3 molecules. Subsequent clustering of an H2O molecule to the inert ion would make the reaction catalytic. If such an ion-catalyzed conversion of N2O5 to HNO3 occurs, it would probably play a role in the stratospheric chemistry at high latitudes in winter. Reaction rate constant measurements made in a flowing afterglow apparatus flor hydrated H3O(+), H(+)(CH3CN)m(m equals 1,2,3), and several negative ions reacting with N2O5 are presented. Slow rate constants were found for these ions for hydration levels that are predominant in the stratosphere. With the known stratospheric ion density, these slow rate constants preclude significant N2O5 conversion by ion-molecule reactions.

  14. Student Teacher Understanding of the Greenhouse Effect, Ozone Layer Depletion, and Acid Rain.

    ERIC Educational Resources Information Center

    Dove, Jane

    1996-01-01

    Describes the results of a survey designed to ascertain details of student teachers' knowledge and misconceptions about the greenhouse effect, acid rain, and ozone layer depletion. Results indicate familiarity with the issues but little understanding of the concepts involved and many commonly held misconceptions. (JRH)

  15. [Catalytic ozonation of oxalic acid in water with Pt/graphite catalyst].

    PubMed

    Liu, Zheng-Qian; Ma, Jun; Zhao, Lei

    2007-06-01

    Pt/graphite catalyst was prepared by incipient wetness impregnation using H2PtCl6 x 6H2O as precursor substance. The removal efficiencies of oxalic acid by Pt/graphite, graphite catalyzed ozonation and ozonation alone were compared. It was found that the removal efficiency of oxalic acid in ozonation alone, graphite and Pt/graphite catalyzed ozonation was 3.0%, 47.6% and 99.3% respectively under the present experimental conditions. Results showed that loading of Pt could significantly increase the catalytic activity of graphite. Taking oxalic acid degradation efficiency as indication, the preparation conditions of Pt/graphite were optimized. The pretreatment of graphite had no favor to improve the activity of Pt/graphite catalyst. The optimal preparation conditions of Pt/graphite catalyst are as follow: impregnant, distilled water; impregnation time, 24 h; the loading amount of Pt, 1.0%; reduction temperature, 35 degrees C. The Pt/graphite catalyst was used for five times with no significant decrease of its activity and more than 90% oxalic acid removal was obtained. PMID:17674732

  16. Acid mist and ozone effects on the leaf chemistry of two western conifer species.

    PubMed

    Westman, W E; Temple, P J

    1989-01-01

    Seedlings of Jeffrey pine (Pinus jeffreyi) and giant sequoia (Sequoiadendron gigantea) were more susceptible to leaf chemical changes following exposure to acid mist (pH 3.4-2.0) or acid mist/ozone combinations, than to ozone alone (0.1-0.2 microl/litre), when plants were exposed to alternating doses of these pollutants for 6-9 weeks. Under acid mist treatment, leaves exhibited higher levels of nitrogen and sulfur, two elements applied in acid mist. In addition, levels of foliar sodium, and, in the case of giant sequia, potassium, as well, increased under acid mist treatment. Iron and manganese were also mobilized, resulting in significant increases in these elements in pine, and decreases in manganese in giant sequoia foliage. The acid treatment also reduced chlorophyll b concentrations in pine, and, to a less significant extent, in giant sequoia. Calcium, magnesium, barium and strontium were differentially accumulated in giant sequoia compared to Jeffrey pine. Under acid mist treatment, all of these elements (except strontium) declined in concentration in giant sequoia, with calcium showing the most significant trend. The more extensive changes in leaf chemistry induced by acid mist are consistent with earlier observations of significant changes in spectral reflectance of these seedlings after 3 weeks of fumigation. Limited foliage samples collected from these two species in 1985 and 1986 in Sequoia/Kings Canyon National Parks in the southern Sierra Nevada do not in themselves indicate any clearcut or severe effects of ozone alone on leaf chemistry of these species, but a mild influence of nitrate-laden acid deposition, possibly in combination with ozone, is consistent with the rise in nitrogen and lignin levels in Jeffrey pine on sites observed to have moderate visible injury symptoms. No firm conclusions about effects of pollutants on leaf chemistry in these field sites is possible without further study.

  17. Acid mist and ozone effects on the leaf chemistry of two western conifer species.

    PubMed

    Westman, W E; Temple, P J

    1989-01-01

    Seedlings of Jeffrey pine (Pinus jeffreyi) and giant sequoia (Sequoiadendron gigantea) were more susceptible to leaf chemical changes following exposure to acid mist (pH 3.4-2.0) or acid mist/ozone combinations, than to ozone alone (0.1-0.2 microl/litre), when plants were exposed to alternating doses of these pollutants for 6-9 weeks. Under acid mist treatment, leaves exhibited higher levels of nitrogen and sulfur, two elements applied in acid mist. In addition, levels of foliar sodium, and, in the case of giant sequia, potassium, as well, increased under acid mist treatment. Iron and manganese were also mobilized, resulting in significant increases in these elements in pine, and decreases in manganese in giant sequoia foliage. The acid treatment also reduced chlorophyll b concentrations in pine, and, to a less significant extent, in giant sequoia. Calcium, magnesium, barium and strontium were differentially accumulated in giant sequoia compared to Jeffrey pine. Under acid mist treatment, all of these elements (except strontium) declined in concentration in giant sequoia, with calcium showing the most significant trend. The more extensive changes in leaf chemistry induced by acid mist are consistent with earlier observations of significant changes in spectral reflectance of these seedlings after 3 weeks of fumigation. Limited foliage samples collected from these two species in 1985 and 1986 in Sequoia/Kings Canyon National Parks in the southern Sierra Nevada do not in themselves indicate any clearcut or severe effects of ozone alone on leaf chemistry of these species, but a mild influence of nitrate-laden acid deposition, possibly in combination with ozone, is consistent with the rise in nitrogen and lignin levels in Jeffrey pine on sites observed to have moderate visible injury symptoms. No firm conclusions about effects of pollutants on leaf chemistry in these field sites is possible without further study. PMID:15092463

  18. 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.

  19. Effects of simulated acid rain and ozone on foliar chemistry of field-grown Pinus ponderosa seedlings and mature trees.

    PubMed

    Momen, B; Helms, J A

    1996-01-01

    We investigated the additive and interactive effects of simulated acid rain and elevated ozone on C and N contents, and the C:N ratio of one-year-old and current-year foliage of field-grown mature trees and their half-sib seedlings of a stress tolerant genotype of ponderosa pine. Acid rain levels (pH 5.1 and 3.0) were applied weekly to foliage only (no soil acidification or N addition), from January to April, 1992. Plants were exposed to two ozone levels (ambient and twice-ambient) during the day from September 1991 to November 1992. The sequential application of acid rain and elevated ozone mimicked the natural conditions. Twice-ambient ozone significantly decreased foliar N content (by 12-14%) and increased the C:N ratio of both one-year-old and current-year foliage of seedlings. Although similar ozone effects were also observed on one-year-old foliage of mature trees, the only statistically significant effect was an increased C:N ratio when twice-ambient ozone combined with pH 3.0 rain (acid rain by ozone interaction). Enhancing the effect of twice-ambient ozone in increasing the C:N ratio of one-year-old foliage of mature trees in June was the only significant effect of acid rain.

  20. Growth response of Pinus ponderosa seedlings and mature tree branches to acid rain and ozone exposure

    SciTech Connect

    Anderson, P.D.; Houpis, J.L.J.; Helms, J.A.

    1994-10-01

    Forests of the central and southern Sierra Nevada in California have been subjected to chronic damage by ozone and other atmospheric pollutants for the past several decades. Until recently, pollutant exposure of northern Sierra Nevada forests has been mild but increasing population and changes in land use throughout the Sacramento Valley and Sierra Nevada foothills may lead to increased pollutant damage in these forests. Although, better documented in other regions of the United States, little is known regarding the potential for acidic precipitation damage to Sierra Nevada forests. Only recently have studies directed towards understanding the potential interactive effects of ozone and acidic precipitation been undertaken. A key issue in resolving potential regional impacts of pollutants on forests is the extent to which research results can be scaled across genotypes and life-stages. Most of the pollution research to date has been performed using seedlings with varying degrees of genetic control. It is important to determine if the results obtained in such studies can be extrapolated to mature trees and to different genetic sources. In this paper, we present results from a one-year study examining the interactive effects of foliar exposure to acidic rain and ozone on the growth of ponderosa pine (Pinus ponderosa), a conifer known to be sensitive to ozone. The response to pollutants is characterized for both seedlings and mature tree branches of three genotypes grown in a common environment.

  1. Carboxylic acids in secondary aerosols from oxidation of cyclic monoterpenes by ozone

    SciTech Connect

    Glasius, M.; Lahaniati, M.; Calogirou, A.; Di Bella, D.; Jensen, N.R.; Hjorth, J.; Kotzias, D.; Larsen, B.R.

    2000-03-15

    A series of smog chamber experiments have been conducted in which five cyclic monoterpenes were oxidized by ozone. The evolved secondary aerosol was analyzed by GC-MS and HPLC-MS for nonvolatile polar oxidation products with emphasis on the identification of carboxylic acids. Three classes of compounds were determined at concentration levels corresponding to low percentage molar yields: i.e., dicarboxylic acids, oxocarboxylic acids, and hydroxyketocarboxylic acids. Carboxylic acids are highly polar and have lower vapor pressures than their corresponding aldehydes and may thus play an important role in secondary organic aerosol formation processes. The most abundant carboxylic acids were the following: cis-pinic acid AB1(cis-3-carboxy-2,2-dimethylcyclobutylethanoic acid) from {alpha} and {beta}-pinene; cis-pinonic acid A3 (cis-3-acetyl-2,2-dimethylcyclobutylethanoic acid) and cis-10-hydroxypinonic acid Ab6 (cis-2,2-dimethyl-3-hydroxyacetylcyclobutyl-ethanoic acid) from {alpha}-pinene and {beta}-pinene; cis-3-caric acid C1 (cis-2,2-dimethyl-1,3-cyclopropyldiethanoic acid), cis-3-caronic acid C3 (2,2-dimethyl-3-(2-oxopropyl)cyclopropanylethanoic acid), and cis-10-hydroxy-3-caronic acid C6 (cis-2,2-dimethyl-3(hydroxy-2-oxopropyl)cyclopropanylethanoic acid) from 3-carene; cis-sabinic acid S1 (cis-2-carboxy-1-isopropylcyclopropylethanoic acid) from sabinene; limonic acid L1 (3-isopropenylhexanedioic acid), limononic acid L3 (3-isopropenyl-6-oxo-heptanoic acid), 7-hydroxy-limononic acid L6 (3-isopropenyl-7-hydroxy-6-oxoheptanoic acid), and 7-hydroxylimononic acid Lg{prime} (7-hydroxy-3-isopropenyl-6-oxoheptanoic acid) from limonene.

  2. One-pot room-temperature conversion of cyclohexane to adipic acid by ozone and UV light.

    PubMed

    Hwang, Kuo Chu; Sagadevan, Arunachalam

    2014-12-19

    Nitric acid oxidation of cyclohexane accounts for ~95% of the worldwide adipic acid production and is also responsible for ~5 to 8% of the annual worldwide anthropogenic emission of the ozone-depleting greenhouse gas nitrous oxide (N2O). Here we report a N2O-free process for adipic acid synthesis. Treatment of neat cyclohexane, cyclohexanol, or cyclohexanone with ozone at room temperature and 1 atmosphere of pressure affords adipic acid as a solid precipitate. Addition of acidic water or exposure to ultraviolet (UV) light irradiation (or a combination of both) dramatically enhances the oxidative conversion of cyclohexane to adipic acid.

  3. Decomposition of dinitrotoluene isomers and 2,4,6-trinitrotoluene in spent acid from toluene nitration process by ozonation and photo-ozonation.

    PubMed

    Chen, Wen-Shing; Juan, Chien-Neng; Wei, Kuo-Ming

    2007-08-17

    Ozone and UV/O3 were employed to mineralize dinitrotoluene (DNT) isomers and 2,4,6-trinitrotoluene (TNT) in spent acid from toluene nitration process. The oxidative degradation tests were carried out to elucidate the influence of various operating variables on the performance of mineralization of total organic compounds (TOC) in spent acid, including reaction temperature, intensity of UV (254 nm) irradiation, dosage of ozone and concentration of sulfuric acid. It is remarkable that the nearly complete mineralization of organic compounds can be achieved by ozonation combined with UV irradiation. Nevertheless, the hydroxyl radicals (*OH) would not be generated by either ozone decomposition or photolysis of ozone under the experimental condition of this study. According to the spectra identified by gas chromatograph/mass spectrometer (GC/MS) and further confirmed by gas chromatograph/flame ionization detector (GC/FID), the multiple oxidation pathways of DNT isomers are given, which include o-, m-, p-mononitrotoluene (MNT) and 1,3-dinitrobenzene, respectively. In addition, oxidative degradation of 2,4,6-TNT leads to a 1,3,5-trinitrobenzene intermediate. PMID:17257749

  4. Decomposition of dinitrotoluene isomers and 2,4,6-trinitrotoluene in spent acid from toluene nitration process by ozonation and photo-ozonation.

    PubMed

    Chen, Wen-Shing; Juan, Chien-Neng; Wei, Kuo-Ming

    2007-08-17

    Ozone and UV/O3 were employed to mineralize dinitrotoluene (DNT) isomers and 2,4,6-trinitrotoluene (TNT) in spent acid from toluene nitration process. The oxidative degradation tests were carried out to elucidate the influence of various operating variables on the performance of mineralization of total organic compounds (TOC) in spent acid, including reaction temperature, intensity of UV (254 nm) irradiation, dosage of ozone and concentration of sulfuric acid. It is remarkable that the nearly complete mineralization of organic compounds can be achieved by ozonation combined with UV irradiation. Nevertheless, the hydroxyl radicals (*OH) would not be generated by either ozone decomposition or photolysis of ozone under the experimental condition of this study. According to the spectra identified by gas chromatograph/mass spectrometer (GC/MS) and further confirmed by gas chromatograph/flame ionization detector (GC/FID), the multiple oxidation pathways of DNT isomers are given, which include o-, m-, p-mononitrotoluene (MNT) and 1,3-dinitrobenzene, respectively. In addition, oxidative degradation of 2,4,6-TNT leads to a 1,3,5-trinitrobenzene intermediate.

  5. Growth response and drought susceptibility of red spruce seedlings exposed to simulated acidic rain and ozone

    SciTech Connect

    Lee, W.S.; Chevone, B.I.; Seiler, J.R. )

    1988-01-01

    Red spruce (Picea rubens Sarg.) is a long-lived, shade-tolerant tree that is commonly present in the cool, moist climates at high elevations of the Appalachian Mountains. Recently, an accelerated decline of red spruce has been reported in the northern Appalachians in the Green Mountains on Camels Hump, Vermont and on Whiteface Mountain in New York as well as in the mid and southern Appalachians. Even though many possible causes of this decline have been suggested, none have been established conclusively at present. High acid inputs and elevated concentrations of heavy metals, in addition to ozone stress, have been strongly suspected as contributing factors for the decline. The objectives of this research is to investigate the efforts of simulated acidic rain and ozone on growth and drought susceptibility of red spruce seedlings by measuring biomass, foliar nutrient status, root hydraulic conductivity, and gas exchange rates.

  6. Relating physical state and reactivity: humidity dependent ozone uptake on tannic and shikimic acid

    NASA Astrophysics Data System (ADS)

    Steimer, S.; Huisman, A.; Krieger, U.; Lampimäki, M.; Marcolli, C.; Peter, T.; Ammann, M.

    2012-04-01

    Atmospheric aerosols are an important focus of environmental research due to their effect on climate and human health. Recent findings show that organic aerosol particles are capable of forming amorphous solids and semi-solids under atmospheric conditions [1]. Such particles should be highly viscous, leading to low diffusivity within the bulk. This would then slow down eventual chemical reactions in the bulk, thereby increasing the lifetime of the organic compounds involved. First indications of such behavior were recently shown for the reaction of thin protein films with ozone [2]. To investigate the influence of the physical state on the reactivity of atmospherically relevant compounds, the uptake of ozone on two different organics was measured using a coated wall flow tube system. The investigated organic compounds are tannic acid, which is a proxy for atmospheric polyphenolic materials, and shikimic acid, a constituent of biomass burning aerosols. The viscosity of the organic film was adjusted by varying the humidity of the system, assuming a correlation between the two parameters due to water acting as a plasticizer. The investigated humidity range was 0% - 95% RH for tannic and 0% - 92% RH for shikimic acid. It was found that both of the compounds show a long term uptake of ozone which lasts for more than 20 h. The uptake coefficient is clearly humidity dependent and increases by close to two orders of magnitude between driest and wettest conditions. At a given humidity, shikimic acid is the more reactive compound. The measured humidity dependence supports the hypothesis that the uptake coefficient is a strong function of the diffusion coefficient of ozone in the organic film. 1. Virtanen, A., et al., An amorphous solid state of biogenic secondary organic aerosol particles. Nature, 2010. 467(7317): p. 824-827. 2. Shiraiwa, M., et al., Gas uptake and chemical aging of semisolid organic aerosol particles. Proceedings of the National Academy of Sciences of the

  7. Reactive nitrogen, ozone, and nitrate aerosols observed in the Arctic stratosphere in January 1990

    NASA Technical Reports Server (NTRS)

    Kondo, Y.; Aimedieu, P.; Koike, M.; Iwasaka, Y.; Newman, P. A.; Schmidt, U.; Matthews, W. A.; Hayashi, M.; Sheldon, W. R.

    1992-01-01

    Ozone mixing ratios in the vicinity of the 525-K potential temperature surface in January and early February of 1990 were observed to decrease sharply across the edge of the vortex boundary, where the vortex position was estimated from Ertel's potential vorticity. The changes in NO(y) mixing ratio with respect to altitude measured on January 18 and 31 were quite well correlated with those of ozone between 15 and 24 km, indicating that NO(y) also had a large gradient across the edge of the vortex. This is interpreted as being mainly due to the significant denitrification that occurred inside the vortex. The total amount of gas and particulate phase HNO3 was close to the NO(y) amount at the altitude of the 22- to 23-km region, suggesting that the conversion of non-HNO3 reactive nitrogen to HNO3 had occurred with a PSC.

  8. 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.

  9. Cryogenic Infrared Radiance Instrumentation for Shuttle (CIRRIS 1A) Earth limb spectral measurements, calibration, and atmospheric O3, HNO3, CFC-12, and CFC-11 profile retrieval

    NASA Astrophysics Data System (ADS)

    Bingham, G. E.; Zhou, D. K.; Bartschi, B. Y.; Anderson, G. P.; Smith, D. R.; Chetwynd, J. H.; Nadile, R. M.

    1997-02-01

    During the Space Transportation System 39 (STS 39) flight of April 28 to May 6, 1991, the Cryogenic Infrared Radiance Instrumentation for Shuttle (CIRRIS 1A) measured spectral and spatial ("Earth limb scan") distributions of the atmospheric infrared (IR) emissions using a Michelson interferometer. The IR spectral radiant emissions from the greenhouse gases were collected at a shuttle altitude of 260 km in the 9-13 μm atmosphere infrared window. Before and after the flight, the response of CIRRIS 1A to the IR spectral emission sources was calibrated using absolute and spectral source types. The Fast Atmospheric Signature Code 3, which used the HITRAN92 database and predetermined temperature-pressure profiles from the National Meteorological Center, was used in an onion-peeling routine to retrieve gas concentrations from absolutely calibrated spectral data (moderate resolution ˜1.0 cm-1). Vertical profiles of O3, HNO3, CFC-12, and CFC-11 are presented. An error analysis is presented to show the quality of the measured spectral data and the accuracy of these retrieval results. The concentrations of CFC-11 (3.0×10-4 ppmv) and CFC-12 (4.9×10-4 ppmv) in the tropopause region are consistent with a global flux increment rate of about 5% yr-1. The observed concentrations of HNO3 are consistent with previous reports for a relatively clean stratosphere.

  10. Effects of Ozone and Peroxyacetyl Nitrate on Polar Lipids and Fatty Acids in Leaves of Morning Glory and Kidney Bean

    PubMed Central

    Nouchi, Isamu; Toyama, Susumu

    1988-01-01

    To compare the effects of ozone and peroxyacetyl nitrate (PAN) on leaf lipids, fatty acids and malondialdehyde (MDA), morning glory (Pharbitis nil Choisy cv Scarlet O'Hara) and kidney bean (Phaseolus vulgaris L. cv Gintebo) plants were exposed to either ozone (0.15 microliter per liter for 8 hours) or PAN (0.10 microliter per liter for up to 8 hours). Ozone increased phospholipids in morning glory and decreased in kidney bean at the initial stage (2-4 hours) of exposure, while it scarcely changed glycolipids, the unsaturated fatty acids, and MDA in both plants. A large reduction of glycolipids occurred 1 day after ozone exposure in both plants. PAN caused marked drops in phospholipids and glycolipids in kidney bean at relatively late stage (6-8 hours) of exposure, while it increased phosphatidic acid and decreased the unsaturated fatty acids, an increase which was accompanied by a large increase in MDA. These results suggest that ozone may not directly oxidize unsaturated fatty acids at the initial stage of exposure, but may alter polar lipid metabolism, particularly phospholipids. On the other hand, PAN may abruptly and considerably degrade phospholipids and glycolipids by peroxidation or hydrolysis at the late stage of exposure. The present study shows that ozone and PAN affect polar lipids in different manners. Images Fig. 2 Fig. 3 PMID:16666199

  11. Modulations of stratospheric ozone by volcanic eruptions

    NASA Technical Reports Server (NTRS)

    Blanchette, Christian; Mcconnell, John C.

    1994-01-01

    We have used a time series of aerosol surface based on the measurements of Hofmann to investigate the modulation of total column ozone caused by the perturbation to gas phase chemistry by the reaction N2O5(gas) + H2O(aero) yields 2HNO3(gas) on the surface of stratospheric aerosols. We have tested a range of values for its reaction probability, gamma = 0.02, 0.13, and 0.26 which we compared to unperturbed homogeneous chemistry. Our analysis spans a period from Jan. 1974 to Oct. 1994. The results suggest that if lower values of gamma are the norm then we would expect larger ozone losses for highly enhanced aerosol content that for larger values of gamma. The ozone layer is more sensitive to the magnitude of the reaction probability under background conditions than during volcanically active periods. For most conditions, the conversion of NO2 to HNO3 is saturated for reaction probability in the range of laboratory measurements, but is only absolutely saturated following major volcanic eruptions when the heterogeneous loss dominates the losses of N2O5. The ozone loss due to this heterogeneous reaction increases with the increasing chlorine load. Total ozone losses calculated are comparable to ozone losses reported from TOMS and Dobson data.

  12. Antarctic Ozone: Theory and Observation.

    NASA Astrophysics Data System (ADS)

    Salawitch, Ross Jay

    The amount of ozone observed in October over Antarctica has fallen steadily and precipitously in the last decade. Observational data describing the phenomenology of the Antarctic ozone reduction are reviewed, followed by the presentation of theories that seek to account for the observed ozone reductions while satisfying other available constraints. We begin with a discussion of the thermodynamic properties of solid phases containing HCl and HNO_3. The presence of clouds in the Antarctic stratosphere, caused be extremely low temperatures during spring, leads to condensation and precipitation of HNO_3, and condensation and reaction of HCl. Both processes lead to the conversion of unreactive forms of chlorine to chlorine oxides, which participate in a sequence of chemical reactions that consume ozone. A chemical model that incorporates the influence of cloud catalyzed heterogeneous reactions is compared in detail to the interferometric measurements of HCl, ClNO_3, HNO_3 , NO_2, and NO obtained over Antarctica during the spring of 1986 (Farmer et al., 1987). Model results are consistent with observed temporal trends of these species and with trends for total column ozone reported by Stolarski et al. (1986). Loss of ozone is attributed to the catalytic influence of chlorine and bromine radicals, in cycles suggested by McElroy et al. (1986b) and Molina and Molina (1987). Constraints are then placed on the abundance of stratospheric bromine by analysis of observations of OClO over Antarctica during the spring of 1986 (Solomon et al., 1987a). The diurnal variation of OClO is consistent with 16 +/- 4 ppt of stratospheric bromine if a fraction of the overall ClO + BrO reaction proceeds through a channel resulting in the production of BrCl. Bromine levels in this range would contribute approximately 20% of the total ozone loss. Finally, it is shown that the production of reactive chlorine oxides by heterogeneous processes depends on the initial concentration of HCl relative

  13. Quantification of jasmonic acid by SPME in tomato plants stressed by ozone.

    PubMed

    Zadra, Claudia; Borgogni, Andrea; Marucchini, Cesare

    2006-12-13

    Jasmonates are signalling molecules induced in plants as a response to various biotic and/or abiotic stresses. As ozone is known to activate defense responses in plants, we have monitored the concentration of jasmonic acid in tomato leaves during and after an acute exposure to this abiotic elicitor. In this experiment, we observed that the maximum induction of jasmonic acid in O3-fumigated plants occurred 9 h after the end of treatment and the concentration of jasmonic acid in stressed plants increased 13-fold. However, the level of endogenous methyl-jasmonate was constant during the observed period. The extraction and quantification of jasmonic acid as its methyl ester was performed by headspace-solid-phase microextraction (or HS-SPME) in combination with GC-FID and GC-MS. The sensitivity (LOD = 2 ng/g) of this method permitted the detection and quantification of jasmonic acid present in plant tissues at very low concentrations. PMID:17147413

  14. Prompt formation of organic acids in pulse ozonation of terpenes on aqueous surfaces

    NASA Astrophysics Data System (ADS)

    Hoffmann, M. R.; Colussi, A. J.; Enami, S.

    2010-12-01

    A major atmospheric process, the gas-phase ozonation of terpenes yields suites of products via a cascade of chemically activated intermediates that ranges from primary ozonides to dioxiranes. If a similar mechanism operated in water, as it is generally assumed, such intermediates would be deactivated within picoseconds and, henceforth, unable to produce carboxylic acids in microseconds. Herein we report the online electrospray mass spectrometric detection of (M + 2O - H+) and (M + 3O - H+) carboxylates on the surface of aqueous β-caryophyllene (C15H24, M = 204 Da) microjets exposed to a few ppmv O3(g) for < 10 μs. Since neither species is formed on dry solvent microjets, and both incorporate deuterium from D2O, we infer that carboxylates ensue from the interaction of nascent intermediates with interfacial water via a heretofore unreported mechanism. These interfacial events proceed much faster than in bulk liquids saturated with ozone.

  15. 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.

  16. Formation of stratospheric nitric acid by a hydrated ion cluster reaction: chemical and dynamical effects of energetic particle precipitation on the middle atmosphere

    NASA Astrophysics Data System (ADS)

    Kvissel, O. K.; Orsolini, Y. J.; Stordal, F.

    2012-04-01

    In order to Improve our understanding of the effects of energetic particle precipitation upon the nitrogen family (NOy) and ozone (O3), we have modelled the chemical and dynamical middle atmosphere response to the introduction of a chemical pathway that produces nitric acid (HNO3) by conversion of dinitrogen pentoxide (N2O5) upon hydrated water clusters H+•(H2O)n. We have used an ensemble of simulations with the National Center for Atmospheric Research (NCAR) Whole-Atmosphere Community Climate Model (WACCM) chemistry-climate model. The introduced chemical pathway alters the internal partitioning of NOy during winter months in both hemispheres, and ultimately triggers statistically significant changes in the climatological distributions of constituents including: i) a cold season production of HNO3 with a corresponding loss of N2O5, and ii) a cold season decrease in NOx/NOy-ratio and an increase of O3, in polar regions. We see an improved seasonal evolution of modelled HNO3 compared to satellite observations from Microwave Limb Sounder (MLS), albeit not enough HNO3 is produced at high altitudes. Through O3 changes, both temperature and dynamics are affected, allowing for complex chemical-dynamical feedbacks beyond the cold season when the introduced pathway is active. Hence, we also find a NOx polar increase in spring-to-summer in the SH, and in spring in the NH. The springtime NOx increase arises from anomalously strong poleward transport associated with a weaker polar vortex. In the southern hemisphere, a statistical significant weakening of the stratospheric jet is altered down to the lower stratosphere, and we argue that it is caused by strengthened planetary waves induced by mid-latitude zonal asymmetries in O3 and short-wave heating.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Catalytic ozonation of 2,4-dichlorophenoxyacetic acid using alumina in the presence of a radical scavenger.

    PubMed

    Guzman-Perez, Carlos A; Soltan, Jafar; Robertson, Jared

    2012-01-01

    Using a laboratory-scale mixed reactor, the performance of alumina in degrading 2,4-Dichlorophenoxyacetic acid with ozone in the presence of tert-butyl alcohol radical scavenger was studied. The operating variables investigated were the dose of alumina catalyst and solution pH. Results showed that using ozone and alumina leads to a significant increase in 2,4-D removal in comparison to non-catalytic ozonation and adsorption processes. The observed reaction rate constants (k(obs)) for 2,4-D during ozonation were found to increase linearly with increasing catalyst dose. At pH 5, the k(obs) value increased from 19.3 to 26 M(-1) s(-1) and 67 M(-1) s(-1) when varying the alumina dose from 1 to 2 and 4 g L(-1), respectively. As pH was increased, higher reaction rates were observed for both non-catalytic ozonation and catalytic ozonation processes. Thus, at pH 3 and using a catalyst dose of 8 g L(-1), the k(obs) values for non-catalytic ozonation and catalytic ozonation processes were 3.4 and 58.9 M(-1) s(-1), respectively, whereas at pH 5 reaction rate constants of 6.5 and 128.5 M(-1) s(-1) were observed, respectively. Analysis of total organic carbon suggested that catalytic ozonation with alumina achieved a considerable level of mineralization of 2,4-D. Adsorption of 2,4-D on alumina was found to play an important role in the catalytic ozonation process.

  3. Design considerations for ozone and acid aerosol exposure and health investigations: the Fairview Lake summer camp - photochemical smog case study

    SciTech Connect

    Lioy, P.J.; Spektor, D.; Thurston, G.; Citak, K.; Lippmann, M.; Bock, N.; Speizer, F.E.; Hayes, C.

    1987-01-01

    The health effects associated with ozone and acidic particulate sulfate exposures to active children have been and are being addressed in field epidemiological studies at summer camps in rural areas of the Northeastern US. The rationale and study design for studies, which have been conducted in Pennsylvania and New Jersey, are developed and reviewed. As background, results are summarized for human clinical and epidemiological studies and animal studies. These provided the basis for selection of health outcomes measured results from chemical characterization and transport studies are reviewed to define the criteria used for selection of a site which is effected by high ozone and acid species during photochemical smog episodes. The integration of the study design is discussed in detail by reviewing its application to the 1984 - Fairview Lake Camp Study (July 8 to August 4). The features of the camp study are reviewed, including the study population, pulmonary function procedures and analyses, air pollution monitoring instrumentation, and the site characteristics. The pollution exposure data are presented, for ozone and acidic sulfates and examined for the range and distribution concentration. Further information is provided on the intensity and duration of episodes encountered over the course of the study. Episodes occurred which had ozone and acid sulfates, ozone alone, and acid sulfates alone. 56 references, 9 figures.

  4. Effects of protein deficiency and food restriction on lung ascorbic acid and glutathione in rats exposed to ozone

    SciTech Connect

    Dubick, M.A.; Heng, H.; Rucker, R.B.

    1985-08-01

    Weanling (52 +/- 4 g) or adult (259 +/- 16 g) male Sprague-Dawley rats were fed ad libitum casein-based diets containing 4 or 16% protein. A third group (food restricted) was fed daily the 16% protein diet, but at the food intake level of the 4% protein group. After 3 wk (weanling) or 5 wk (adults), half of the rats in each group were continuously exposed to 0.64 ppm ozone for 7 d. Ascorbic acid and reduced glutathione levels were then measured. In the heart and liver from weanling rats, ascorbic acid concentrations were lower in the protein-deficient group than in either control group. In the liver from weanling rats glutathione concentrations were also reduced in response to protein deficiency. Exposure to ozone produced no additional response. For adult rats the response for liver glutathione was similar to that of the weanlings. The liver ascorbate concentration, however, was consistently lower in adult rats compared to weanlings exposed to ozone. In lungs from adult rats, the ascorbic acid concentration was lower in the protein-deficient group than in either control group. On a whole-organ basis, both ascorbic acid and glutathione were usually higher in lungs from rats exposed to ozone than from those exposed to air. Interestingly, protein deficiency did not appear to compromise the lung's ability to maintain, in relative terms, the ascorbic acid or glutathione concentration in response to ozone.

  5. α-Tocopherol/Gallic Acid Cooperation in the Protection of Galactolipids Against Ozone-Induced Oxidation.

    PubMed

    Rudolphi-Skórska, Elżbieta; Filek, Maria; Zembala, Maria

    2016-04-01

    The protective ability of α-tocopherol (TOH) and gallic acid (GA) acting simultaneously at the moment of oxidizer application was evaluated by determination of galactolipid layers' oxidation degree. Addition of GA resulted in a significant decrease of ozone-derived radicals shifting the threshold of lipid sensitivity by an amount approximately corresponding to the GA intake in bulk reaction with ozone. TOH presence in lipid layers results in a change of the role of GA which additionally may be involved in the reduction of tocopheroxyl radical formed during oxidation. This leads to a decrease in effectiveness of GA in diminishing the amount of ozone radicals. Such an effect was not observed for mixed layers containing galactolipid and pre-oxidized tocopherol where the ozone threshold level was associated with a stoichiometry of GA + O3 reaction. It was concluded that probably subsequent transformations of tocopheroxyl radical to less reactive forms prevent its reaction with GA the entire quantity of which is used for radicals scavenging. This result shows the role of time parameter in systems where substrates are engaged in various reactions taking place simultaneously. The inactivation of 1,1-diphenyl-2-picrylhydrazyl radical by studied antioxidants in homogeneous system confirmed observations made on the basis of lipid layer properties indicating their antagonistic action (at least at studied conditions). Formation of layers in post-oxidation situation did not depend whether tocopherol was oxidized during oxidation of lipid/tocopherol mixture or was introduced as pre-oxidized. This may be interpreted as indication that products of tocopherol oxidation may stabilize lipid layers. PMID:26498297

  6. Disinfection efficiency of peracetic acid, UV and ozone after enhanced primary treatment of municipal wastewater.

    PubMed

    Gehr, Ronald; Wagner, Monika; Veerasubramanian, Priya; Payment, Pierre

    2003-11-01

    The City of Montreal Wastewater Treatment Plant uses enhanced physicochemical processes (ferric and/or alum coagulation) for suspended solids and phosphorus removal. The objective of this study was to assess the ability of peracetic acid (PAA), UV, or ozone to inactivate the indicator organisms fecal coliforms, Enterococci, MS-2 coliphage, or Clostridium perfringens in the effluent from this plant. PAA doses to reach the target fecal coliform level of 9000 CFU/100mL exceeded 6 mg/L; similar results were obtained for enterococci, and no inactivation of Clostridium perfringens was observed. However a 1-log reduction of MS-2 occurred at PAA doses of 1.5 mg/L and higher. It was expected that this effluent would have a high ozone demand, and would require relatively high UV fluences, because of relatively high effluent COD, iron and suspended solids concentrations, and low UV transmittance. This was confirmed herein. For UV, the inactivation curve for fecal coliforms showed the typical two-stage shape, with the target of 1000 CFU/100 mL (to account for photoreactivation) occurring in the asymptote zone at fluences >20 mJ/cm(2). In contrast, inactivation curves for MS-2 and Clostridium perfringens were linear. Clostridium perfringens was the most resistant organism. For ozone, inactivation was already observed before any residuals could be measured. The transferred ozone doses to reach target fecal coliform levels ( approximately 2-log reduction) were 30-50 mg/L. MS-2 was less resistant, but Clostridium perfringens was more resistant than fecal coliforms. The different behaviour of the four indicator organisms studied, depending on the disinfectant, suggests that a single indicator organism might not be appropriate. The required dose of any of the disinfectants is unlikely to be economically viable, and upstream changes to the plant will be needed. PMID:14568042

  7. α-Tocopherol/Gallic Acid Cooperation in the Protection of Galactolipids Against Ozone-Induced Oxidation.

    PubMed

    Rudolphi-Skórska, Elżbieta; Filek, Maria; Zembala, Maria

    2016-04-01

    The protective ability of α-tocopherol (TOH) and gallic acid (GA) acting simultaneously at the moment of oxidizer application was evaluated by determination of galactolipid layers' oxidation degree. Addition of GA resulted in a significant decrease of ozone-derived radicals shifting the threshold of lipid sensitivity by an amount approximately corresponding to the GA intake in bulk reaction with ozone. TOH presence in lipid layers results in a change of the role of GA which additionally may be involved in the reduction of tocopheroxyl radical formed during oxidation. This leads to a decrease in effectiveness of GA in diminishing the amount of ozone radicals. Such an effect was not observed for mixed layers containing galactolipid and pre-oxidized tocopherol where the ozone threshold level was associated with a stoichiometry of GA + O3 reaction. It was concluded that probably subsequent transformations of tocopheroxyl radical to less reactive forms prevent its reaction with GA the entire quantity of which is used for radicals scavenging. This result shows the role of time parameter in systems where substrates are engaged in various reactions taking place simultaneously. The inactivation of 1,1-diphenyl-2-picrylhydrazyl radical by studied antioxidants in homogeneous system confirmed observations made on the basis of lipid layer properties indicating their antagonistic action (at least at studied conditions). Formation of layers in post-oxidation situation did not depend whether tocopherol was oxidized during oxidation of lipid/tocopherol mixture or was introduced as pre-oxidized. This may be interpreted as indication that products of tocopherol oxidation may stabilize lipid layers.

  8. Disinfection efficiency of peracetic acid, UV and ozone after enhanced primary treatment of municipal wastewater.

    PubMed

    Gehr, Ronald; Wagner, Monika; Veerasubramanian, Priya; Payment, Pierre

    2003-11-01

    The City of Montreal Wastewater Treatment Plant uses enhanced physicochemical processes (ferric and/or alum coagulation) for suspended solids and phosphorus removal. The objective of this study was to assess the ability of peracetic acid (PAA), UV, or ozone to inactivate the indicator organisms fecal coliforms, Enterococci, MS-2 coliphage, or Clostridium perfringens in the effluent from this plant. PAA doses to reach the target fecal coliform level of 9000 CFU/100mL exceeded 6 mg/L; similar results were obtained for enterococci, and no inactivation of Clostridium perfringens was observed. However a 1-log reduction of MS-2 occurred at PAA doses of 1.5 mg/L and higher. It was expected that this effluent would have a high ozone demand, and would require relatively high UV fluences, because of relatively high effluent COD, iron and suspended solids concentrations, and low UV transmittance. This was confirmed herein. For UV, the inactivation curve for fecal coliforms showed the typical two-stage shape, with the target of 1000 CFU/100 mL (to account for photoreactivation) occurring in the asymptote zone at fluences >20 mJ/cm(2). In contrast, inactivation curves for MS-2 and Clostridium perfringens were linear. Clostridium perfringens was the most resistant organism. For ozone, inactivation was already observed before any residuals could be measured. The transferred ozone doses to reach target fecal coliform levels ( approximately 2-log reduction) were 30-50 mg/L. MS-2 was less resistant, but Clostridium perfringens was more resistant than fecal coliforms. The different behaviour of the four indicator organisms studied, depending on the disinfectant, suggests that a single indicator organism might not be appropriate. The required dose of any of the disinfectants is unlikely to be economically viable, and upstream changes to the plant will be needed.

  9. Plant resistance mechanisms to air pollutants: rhythms in ascorbic acid production during growth under ozone stress

    SciTech Connect

    Lee, E.H. )

    1991-01-01

    Relationships between ozone (O3) tolerance and leaf ascorbic acid concentrations in O3-susceptible (O3-S) 'Hark' and O3-resistant (O3-R) 'Hood' soybean, Glycine max (L.) Merr., cultivars were examined with high-performance liquid chromatography (HPLC). Leaf samples were analyzed at 4 intervals during a 24 h period. Soybean cultivars grown in the greenhouse with charcoal filtered (CF) and nonfiltered (NF) air showed daily oscillations in ascorbic acid production. Highest ascorbic acid levels in leaves during light coincided with highest concentrations of photochemical oxidants in the atmosphere at 2:00 p.m. The resistant genotype produced more ascorbic acid in its trifoliate leaves than did the corresponding susceptible genotype. Under CF air (an O3-reduced environment) O3-S and O3-R cultivars showed rhythms in ascorbic acid production. In NF air (an O3 stress environment) the O3-R cultivar alone showed rhythms in ascorbic acid production. Results indicated that superior O3 tolerance in the Hood soybean cultivar (compared with Hark) was associated with a greater increase in endogenous levels of ascorbic acid. Ascorbic acid may scavenge free radicals and thereby protect cells from injury by O3 or other oxyradical products. Plants defend themselves against photochemical oxidant stress, such as O3, by several mechanisms. Experimental evidence indicates that antioxidant defense systems existing in plant tissues may function to protect cellular components from deleterious effects of photochemical oxidants through endogenous and exogenous controls.

  10. The effects of acid rain and ozone on biomass and leaf area parameters of shortleaf pine (Pinus echinata Mill.).

    PubMed

    Shelburne, V B; Reardon, J C; Paynter, V A

    1993-03-01

    Shortleaf pine (Pinus echinata Mill.) seedlings in 24 open-top chambers were exposed to combinations of ozone (carbon-filtered (control), ambient, 1.7 x ambient, and 2.5 x ambient) and acidic precipitation (pH 5.3, 4.3 and 3.3) for 16 months (1989 harvest) or 28 months (1990 harvest). Although the effects of acid rain were generally not significant, there was a trend toward increased aboveground biomass and leaf area in seedlings subjected to the low pH treatments. Because N concentrations in the soils generally increased with decreasing pH, we concluded that the effects of acid rain on aboveground biomass and leaf area were a consequence of an increasing concentration of soil N. In the 1989 harvest, seedlings in the 2.5 x ambient ozone treatment had significantly less biomass in all aboveground plant components and significantly less total leaf area than seedlings in the 1.7 x ambient ozone treatment. In the 1990 harvest, there were no significant effects of ozone on total aboveground biomass, although there was a trend toward reduced biomass in seedlings in the 2.5 x ambient ozone treatment. Both total leaf area and leaf biomass were significantly less in seedlings exposed to 2.5 x ambient ozone for 28 months than in both control seedlings and seedlings in the 1.7 x ambient ozone treatment. The greater, but not always significant, aboveground biomass and leaf area of seedlings in the 1.7 x ambient ozone treatment compared with control seedlings may be associated with the observed increase in soil nitrate concentration as a result of increased rates of leaf senescence and litterfall.

  11. Effects of UV irradiation on humic acid removal by ozonation, Fenton and Fe⁰/air treatment: THMFP and biotoxicity evaluation.

    PubMed

    Wei, Ming-Chi; Wang, Kai-sung; Hsiao, Tung-En; Lin, I-Chen; Wu, Hui-Ju; Wu, Yuh-Luan; Liu, Pey-Horng; Chang, Shih-Hsien

    2011-11-15

    Effects of UV irradiation on humic acid (HA) removal by Fe(0)/air, ozonation and Fenton oxidation were investigated. The trihalomethane forming potential (THMFP) and toxicity of treated solutions were also evaluated. The experimental conditions were ozone of 21 mg min(-1), H(2)O(2) of 8 × 10(-4)M, Fe(0) of 20 g L(-1), air flow of 5 L min(-1), and UVC of 9 W. Results indicated that Fe(0)/air rapidly removed HA color (>99%) and COD (90%) within 9 min. 51-81% of color and 43-50% of COD were removed by ozonation and Fenton oxidation after 60 min. Both UV enhanced ozone and Fenton oxidation removed HA, but the Fe(0)/air process did not. Spectrum results showed all processes effectively diminished UV-vis spectra, except for ozonation. The THMFP of Fe(0)/air-treated solution (114 μg L(-1)) was much lower than those of Fenton- (226 μg L(-1)) and ozonation-treated solutions (499 μg L(-1)). Fe(0)/air with UV irradiation obviously increased the THMFP of treated solution (502 μg L(-1)). The toxicity results obtained from Vibrio fischeri light inhibition test indicated that the toxicity of Fe(0)/air-treated solution (5%) was much lower than that of ozonation- (33%) and Fenton-treated solutions (31%). Chlorination increased the solution toxicity. The correlation between biotoxicity and chloroform in the chlorinated solution was insignificant.

  12. In-situ measurements of chlorine activation, nitric acid redistribution and ozone depletion in the Antarctic lower vortex aboard the German research aircraft HALO during TACTS/ESMVal

    NASA Astrophysics Data System (ADS)

    Jurkat, Tina; Voigt, Christiane; Kaufmann, Stefan; Schlage, Romy; Gottschaldt, Klaus-Dirk; Ziereis, Helmut; Hoor, Peter; Bozem, Heiko; Müller, Stefan; Zahn, Andreas; Schlager, Hans; Oelhaf, Hermann; Sinnhuber, Björn-Martin; Dörnbrack, Andreas

    2016-04-01

    In-situ measurements of stratospheric chlorine compounds are rare and exhibit the potential to gain insight into small scale mixing processes where stratospheric air masses of different origin and history interact. In addition, the relationship with chemically stable trace gases helps to identify regions that have been modified by chemical processing on polar stratospheric clouds. To this end, in-situ measurements of ClONO2, HCl, HNO3, NOy, N2O and O3 have been performed in the Antarctic Polar Vortex in September 2012 aboard the German research aircraft HALO (High Altitude and Long Rang research aircraft) during the TACTS/ESMVal (Transport and Composition in the UTLS/Earth System Model Validation) mission. With take-off and landing in Capetown, HALO sampled vortex air with latitudes down to 65°S, at altitudes between 8 and 14.3 km and potential temperatures between 340 and 390 K. Before intering the vortex at 350 K potential temperature, HALO additionally sampled mid-latitude stratospheric air. The trace gas distributions at the edge of the Antarctic polar vortex show distinct signatures of processed upper stratospheric vortex air and chemically different lower stratospheric / upper tropospheric air. Diabatic descend of the vortex transports processed air into the lower stratosphere. Here small scale filaments of only a few kilometers extension form at the lower vortex boundary due to shear stress, ultimately leading to transport and irreversible mixing. Comparison of trace gas relationships with those at the beginning of the polar winter reveals substantial chlorine activation, ozone depletion de- and renitrification with high resolution. Furthermore, the measurements are compared to the chemistry climate models EMAC and supported by ECMWF analysis. Finally, we compare the Antarctic measurements with new measurements of ClONO2, HCl and HNO3 aboard HALO obtained during the Arctic mission POLSTRACC (POLar STratosphere in a Changing Climate) based in Kiruna (Sveden

  13. Acid rain, ozone depletion, and the climate response to pulsed Siberian Traps magmatism

    NASA Astrophysics Data System (ADS)

    Black, B. A.; Lamarque, J.; Shields, C. A.; Elkins-Tanton, L. T.; Kiehl, J. T.

    2013-12-01

    The Siberian Traps flood basalts have been invoked as a trigger for the catastrophic end-Permian mass extinction. Widespread aberrant plant remains across the Permian-Triassic boundary provide evidence that atmospheric stress contributed to the collapse in terrestrial diversity. Here, we use recent detailed estimates of magmatic degassing from the Siberian Traps to complete the first 3-D global modeling of atmospheric chemistry during eruption of a large igneous province. We also explore the effects of volcanic gases on climate. Our results show that both strongly acidic rain and global ozone collapse are possible transient consequences of episodic pyroclastic volcanism and heating of volatile-rich Siberian country rocks. We suggest that in conjunction with abrupt warming from greenhouse gas emissions, these repeated, rapidly applied atmospheric stresses directly linked Siberian magmatism to end-Permian ecological failure on land. Our comprehensive modeling describes the global distribution and severity of acid rain and ozone depletion, providing testable predictions for the geography of end-Permian environmental proxies.

  14. Coal desulfurization in oxidative acid media using hydrogen peroxide and ozone: a kinetic and statistical approach

    SciTech Connect

    F.R. Carrillo-Pedroza; A. Davalos Sanchez; M. Soria-Aguilar; E.T. Pecina Trevino

    2009-07-15

    The removal of pyritic sulfur from a Mexican sub-bituminous coal in nitric, sulfuric, and hydrochloric acid solutions was investigated. The effect of the type and concentration of acid, in the presence of hydrogen peroxide and ozone as oxidants, in a temperature range of 20-60{sup o}C, was studied. The relevant factors in pyrite dissolution were determined by means of the statistical analysis of variance and optimized by the response surface method. Kinetic models were also evaluated, showing that the dissolution of pyritic sulfur follows the kinetic model of the shrinking core model, with diffusion through the solid product of the reaction as the controlling stage. The results of statistical analysis indicate that the use of ozone as an oxidant improves the pyrite dissolution because, at 0.25 M HNO{sub 3} or H{sub 2}SO{sub 4} at 20{sup o}C and 0.33 g/h O{sub 3}, the obtained dissolution is similar to that of 1 M H{sub 2}O{sub 2} and 1 M HNO{sub 3} or H{sub 2}SO{sub 4} at 40{sup o}C. 42 refs., 9 figs., 3 tabs.

  15. Electrons Mediate the Gas-Phase Oxidation of Formic Acid with Ozone.

    PubMed

    van der Linde, Christian; Tang, Wai-Kit; Siu, Chi-Kit; Beyer, Martin K

    2016-08-26

    Gas-phase reactions of CO3 (.-) with formic acid are studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Signal loss indicates the release of a free electron, with the formation of neutral reaction products. This is corroborated by adding traces of SF6 to the reaction gas, which scavenges 38 % of the electrons. Quantum chemical calculations of the reaction potential energy surface provide a reaction path for the formation of neutral carbon dioxide and water as the thermochemically favored products. From the literature, it is known that free electrons in the troposphere attach to O2 , which in turn transfer the electron to O3 . O3 (.-) reacts with CO2 to form CO3 (.-) . The reaction reported here formally closes the catalytic cycle for the oxidation of formic acid with ozone, catalyzed by free electrons.

  16. Strong wintertime ozone events in the Upper Green River Basin, Wyoming

    NASA Astrophysics Data System (ADS)

    Rappenglück, B.; Ackermann, L.; Alvarez, S.; Golovko, J.; Buhr, M.; Field, R.; Soltis, J.; Montague, D. C.; Hauze, B.; Adamson, S.; Risch, D.; Wilkerson, G.; Bush, D.; Stoeckenius, T.; Keslar, C.

    2013-07-01

    During recent years, elevated ozone (O3) values have been observed repeatedly in the Upper Green River Basin (UGRB), Wyoming during wintertime. This paper presents an analysis of high ozone days in late winter 2011 (1 h average up to 166 ppbv). Intensive Operational Periods (IOPs) of ambient monitoring were performed which included comprehensive surface and boundary layer measurements. On IOP days, maximum O3 values are restricted to a very shallow surface layer. Low wind speeds in combination with low mixing layer heights (~50 m a.g.l. around noontime) are essential for accumulation of pollutants within the UGRB. Air masses contain substantial amounts of reactive nitrogen (NOx) and non-methane hydrocarbons (NMHC) emitted from fossil fuel exploration activities in the Pinedale Anticline. On IOP days in the morning hours in particular, reactive nitrogen (up to 69%), aromatics and alkanes (~10-15%; mostly ethane and propane) are major contributors to the hydroxyl (OH) reactivity. Measurements at the Boulder monitoring site during these time periods under SW wind flow conditions show the lowest NMHC/NOx ratios (~50), reflecting a relatively low NMHC mixture, and a change from a NOx-limited regime towards a NMHC limited regime as indicated by photochemical indicators, e.g. O3/NOy, O3/NOz, and O3/HNO3 and the EOR (Extent of Reaction). OH production on IOP days is mainly due to nitrous acid (HONO). Until noon on IOP days, HONO photolysis contributes between 74-98% of the entire OH-production. Ozone photolysis (contributing 2-24%) is second to HONO photolysis. However, both reach about the same magnitude in the early afternoon (close to 50%). Photolysis of formaldehyde (HCHO) is not important (2-7%). High HONO levels (maximum hourly median on IOP days: 1096 pptv) are favored by a combination of shallow boundary layer conditions and enhanced photolysis rates due to the high albedo of the snow surface. HONO is most likely formed through (i) abundant nitric acid (HNO3

  17. Oxidations of organic matter present in the phosphoric acid 54% by the ozone: characterization of groups carbonyls upstream and downstream of the ozonation

    NASA Astrophysics Data System (ADS)

    Linda, D.; Louati, A.; Chtara, C.; Kabadou, A.

    2012-02-01

    This study was focused on the oxidation of organic matter in phosphoric acid 54% by ozone. In order to understand the mechanisms involved in this process, the identification of this matter upstream and downstream of the ozonation was necessary. For the identification, after an extraction by a mixture (dichloro-methanol), the organic phase was divided into two parts: the residue and the extract:-The residue was studied by infrared spectroscopy Fourier Transform (IR-TF). It contains Kérogène which is a mixture of saturated hydrocarbons with high molecular weights. The absorption bands of the FT-IR showed that the residue contains also quantities of amino that correspond to the remains of dinoflagellate cysts, which are abundant in sediments.-The extract has been the subject of a detailed study by, chromatography on silica column, IR-TF spectroscopy and CG-SM. The passage of this extract on a silica column yielded two fractions (saturated fraction and polar fraction). Both of these fractions were analyzed by CG-SM. The yield of the reduction of the organic matter content in the phosphoric acid 54% could not exceed 29%. Therefore, we can conclude that the reduction in the rate of organic matter remains limited by the fact that some compounds are inert towards ozone.

  18. Evaluation of ozonation technique for pesticide residue removal and its effect on ascorbic acid, cyanidin-3-glucoside, and polyphenols in apple (Malus domesticus) fruits.

    PubMed

    Swami, Saurabh; Muzammil, Raunaq; Saha, Supradip; Shabeer, Ahammed; Oulkar, Dasharath; Banerjee, Kaushik; Singh, Shashi Bala

    2016-05-01

    Ozonated water dip technique was evaluated for the detoxification of six pesticides, i.e., chlorpyrifos, cypermethrin, azoxystrobin, hexaconazole, methyl parathion, and chlorothalonil from apple fruits. Results revealed that ozonation was better than washing alone. Ozonation for 15 min decreased residues of the test pesticides in the range of from 26.91 to 73.58%, while ozonation for 30 min could remove the pesticide residues by 39.39-95.14 % compared to 19.05-72.80 % by washing. Cypermethrin was the least removed pesticide by washing as well as by ozonation. Chlorothalonil, chlorpyrifos, and azoxystrobin were removed up to 71.45-95.14 % in a 30-min ozonation period. In case of methyl parathion removal, no extra advantage could be obtained by ozonation. The HPLC analysis indicated that ozonation also affected adversely the ascorbic acid and cyanidin-3-glucoside content of apples. However, 11 polyphenols studied showed a mixed trend. Gallic acid, 3,4-dihydroxybenzoic acid, catechin, epicatechin, p-coumaric acid, quercetin-3-O-glucoside, quercetin, and kaempferol were found to decrease while syringic acid, rutin, and resveratrol were found to increase in 30-min ozonation.

  19. Evaluation of ozonation technique for pesticide residue removal and its effect on ascorbic acid, cyanidin-3-glucoside, and polyphenols in apple (Malus domesticus) fruits.

    PubMed

    Swami, Saurabh; Muzammil, Raunaq; Saha, Supradip; Shabeer, Ahammed; Oulkar, Dasharath; Banerjee, Kaushik; Singh, Shashi Bala

    2016-05-01

    Ozonated water dip technique was evaluated for the detoxification of six pesticides, i.e., chlorpyrifos, cypermethrin, azoxystrobin, hexaconazole, methyl parathion, and chlorothalonil from apple fruits. Results revealed that ozonation was better than washing alone. Ozonation for 15 min decreased residues of the test pesticides in the range of from 26.91 to 73.58%, while ozonation for 30 min could remove the pesticide residues by 39.39-95.14 % compared to 19.05-72.80 % by washing. Cypermethrin was the least removed pesticide by washing as well as by ozonation. Chlorothalonil, chlorpyrifos, and azoxystrobin were removed up to 71.45-95.14 % in a 30-min ozonation period. In case of methyl parathion removal, no extra advantage could be obtained by ozonation. The HPLC analysis indicated that ozonation also affected adversely the ascorbic acid and cyanidin-3-glucoside content of apples. However, 11 polyphenols studied showed a mixed trend. Gallic acid, 3,4-dihydroxybenzoic acid, catechin, epicatechin, p-coumaric acid, quercetin-3-O-glucoside, quercetin, and kaempferol were found to decrease while syringic acid, rutin, and resveratrol were found to increase in 30-min ozonation. PMID:27098519

  20. Formation of aldehydes and carboxylic acids in ozonated surface water and wastewater: a clear relationship with fluorescence changes.

    PubMed

    Liu, Chen; Tang, Xiangyu; Kim, Jaeshin; Korshin, Gregory V

    2015-04-01

    This study examined the formation of aldehydes and carboxylic acids in ozonated surface water and municipal wastewater secondary effluent and addressed correlations between the generation of these compounds and concurrent changes of the fluorescence of natural/effluent organic matter (NOM/EfOM) substrates. Ozonation was effective in removing fluorophores in all excitation/emission matrix (EEM) regions, with those operationally assigned to humic- and protein-like species showing relatively higher reactivity than fulvic-like species. Examination of HO exposures and attendant changes of fluorescence-based parameters allows establishing strong linear relationships between formation of the aldehydes and carboxylic acids and the relative changes of integrated fluorescence (ΔIF/IF0). This demonstrates the feasibility of surrogate monitoring of the formation of biodegradable ozonation by-products via online measurements of water/wastewater EEM fluorescence.

  1. Photochemical oxidation of chloride ion by ozone in acid aqueous solution.

    PubMed

    Levanov, Alexander V; Isaykina, Oksana Ya; Amirova, Nazrin K; Antipenko, Ewald E; Lunin, Valerii V

    2015-11-01

    The experimental investigation of chloride ion oxidation under the action of ozone and ultraviolet radiation with wavelength 254 nm in the bulk of acid aqueous solution at pH 0-2 has been performed. Processes of chloride oxidation in these conditions are the same as the chemical reactions in the system O3 - OH - Cl(-)(aq). Despite its importance in the environment and for ozone-based water treatment, this reaction system has not been previously investigated in the bulk solution. The end products are chlorate ion ClO3(-) and molecular chlorine Cl2. The ions of trivalent iron have been shown to be catalysts of Cl(-) oxidation. The dependencies of the products formation rates on the concentrations of O3 and H(+) have been studied. The chemical mechanism of Cl(-) oxidation and Cl2 emission and ClO3(-) formation has been proposed. According to the mechanism, the dominant primary process of chloride oxidation represents the complex interaction with hydroxyl radical OH with the formation of Cl2(-) anion-radical intermediate. OH radical is generated on ozone photolysis in aqueous solution. The key subsequent processes are the reactions Cl2(-) + O3 → ClO + O2 + Cl(-) and ClO + H2O2 → HOCl + HO2. Until the present time, they have not been taken into consideration on mechanistic description and modelling of Cl(-) oxidation. The final products are formed via the reactions 2ClO → Cl2O2, Cl2O2 + H2O → 2H(+) + Cl(-) + ClO3(-) and HOCl + H(+) + Cl(-) ⇄ H2O + Cl2. Some portion of chloride is oxidized directly by O3 molecule with the formation of molecular chlorine in the end.

  2. Photochemical oxidation of chloride ion by ozone in acid aqueous solution.

    PubMed

    Levanov, Alexander V; Isaykina, Oksana Ya; Amirova, Nazrin K; Antipenko, Ewald E; Lunin, Valerii V

    2015-11-01

    The experimental investigation of chloride ion oxidation under the action of ozone and ultraviolet radiation with wavelength 254 nm in the bulk of acid aqueous solution at pH 0-2 has been performed. Processes of chloride oxidation in these conditions are the same as the chemical reactions in the system O3 - OH - Cl(-)(aq). Despite its importance in the environment and for ozone-based water treatment, this reaction system has not been previously investigated in the bulk solution. The end products are chlorate ion ClO3(-) and molecular chlorine Cl2. The ions of trivalent iron have been shown to be catalysts of Cl(-) oxidation. The dependencies of the products formation rates on the concentrations of O3 and H(+) have been studied. The chemical mechanism of Cl(-) oxidation and Cl2 emission and ClO3(-) formation has been proposed. According to the mechanism, the dominant primary process of chloride oxidation represents the complex interaction with hydroxyl radical OH with the formation of Cl2(-) anion-radical intermediate. OH radical is generated on ozone photolysis in aqueous solution. The key subsequent processes are the reactions Cl2(-) + O3 → ClO + O2 + Cl(-) and ClO + H2O2 → HOCl + HO2. Until the present time, they have not been taken into consideration on mechanistic description and modelling of Cl(-) oxidation. The final products are formed via the reactions 2ClO → Cl2O2, Cl2O2 + H2O → 2H(+) + Cl(-) + ClO3(-) and HOCl + H(+) + Cl(-) ⇄ H2O + Cl2. Some portion of chloride is oxidized directly by O3 molecule with the formation of molecular chlorine in the end. PMID:26077317

  3. Retrieval of atmospheric O(3), HNO(3), CFC-11, and CFC-12 profiles from MIPAS-B-89 limb emission spectra.

    PubMed

    Clarmann, T V; Oelhaf, H; Fischer, H

    1993-11-20

    During the night from May 17 to May 18, 1989, the first of four flights of the Michelson Interferometer for Passive Atmospheric Sounding, Balloon-borne version (MIPAS-B) instrument took place from the Centre National d'Etudes Spatiales balloon-launching site at Aire-sur-l'Adour (France, 44° N latitude). From approximately 33 km float altitude, stratospheric and tropospheric limb infrared emission spectra have been recorded by this novel type of fast-scanning interferometer. Although the measured spectra did not reach the expected quality and the a priori information on the corresponding viewing directions was coarse, the data were processed successfully with a retrieval algorithm specially adapted for application to noisydata. Mixingratio profiles of ozone, nitric acid, CFC-11, and CFC-12 havebeen retrieved from limb sequences of wide spectral intervals by nonlinear least-squares fitting in combination with a layer-bylayer onion-peeling approach. A rigorous error analysis has been carried out by means of Monte Carlo calculations.

  4. Conversion of iodide to hypoiodous acid and iodine in aqueous microdroplets exposed to ozone.

    PubMed

    Pillar, Elizabeth A; Guzman, Marcelo I; Rodriguez, Jose M

    2013-10-01

    Halides are incorporated into aerosol sea spray, where they start the catalytic destruction of ozone (O3) over the oceans and affect the global troposphere. Two intriguing environmental problems undergoing continuous research are (1) to understand how reactive gas phase molecular halogens are directly produced from inorganic halides exposed to O3 and (2) to constrain the environmental factors that control this interfacial process. This paper presents a laboratory study of the reaction of O3 at variable iodide (I(-)) concentration (0.010-100 μM) for solutions aerosolized at 25 °C, which reveal remarkable differences in the reaction intermediates and products expected in sea spray for low tropospheric [O3]. The ultrafast oxidation of I(-) by O3 at the air-water interface of microdroplets is evidenced by the appearance of hypoiodous acid (HIO), iodite (IO2(-)), iodate (IO3(-)), triiodide (I3(-)), and molecular iodine (I2). Mass spectrometry measurements reveal an enhancement (up to 28%) in the dissolution of gaseous O3 at the gas-liquid interface when increasing the concentration of NaI or NaBr from 0.010 to 100 μM. The production of iodine species such as HIO and I2 from NaI aerosolized solutions exposed to 50 ppbv O3 can occur at the air-water interface of sea spray, followed by their transfer to the gas-phase, where they contribute to the loss of tropospheric ozone.

  5. Effects of ozone and simulated acid rain on birch seedling growth and formation of ectomycorrhizae.

    PubMed

    Keane, K D; Manning, W J

    1988-01-01

    Four-week-old paper birch (Betula papyrifera Marsh.) seedlings, inoculated or non-inoculated with the ectomycorrhizal fungus Pisolithus tinctorius (Pers.) Coker & Couch and grown in steamed or non-steamed soil, were exposed to ozone (O(3)) and/or simulated acid rain (SAR). Plants were exposed to O(3) for 7 h per day on 5 days per week for 12 weeks. O(3) concentrations were maintained between 0.06 and 0.08 ppm. SAR was applied 10 min per day on 2 days per week. O(3), SAR, soil regime and mycorrhizal treatment did not significantly affect any of the measured variables. Interactions between O(3) and SAR, SAR and mycorrhizal treatment, soil regime and mycorrhizal treatment and ozone and soil regime had significant effects. Treatment of seedlings with pH 3.5 SAR caused increases in growth which were more apparent in birch exposed to O(3). Mucorrhizal treatment caused increased growth in non-steamed soil, while growth appeared to decrease in steamed soil. Birch seedlings grew much better in steamed soil. The implications of increased growth in steamed soil may demonstrate the importance of looking at the secondary effects of pollutants on soil-borne organisms.

  6. Determination of Reactive Nitrogen Species (NOx, NOy-HNO3, Peroxyacetyl Nitrates, Total Organic Nitrates) During the PROPHET Summer 2008 Intensive

    NASA Astrophysics Data System (ADS)

    Alaghmand, M.; Slade, N. J.; Mielke, L.; Starn, T.; Carroll, M.; Bertman, S. B.; Stevens, P. S.; Shepson, P. B.

    2008-12-01

    Determinations of NOx, NOy-HNO3, peroxyacetyl nitrates (PANs) and total organic nitrates (∑RONO2) were made during the summer 2008 intensive of the Program for Research on Oxidants: Photochemistry, Emissions and Transport (PROPHET). The Total Reactive Nitrogen Instrument (TRENI), a high sensitivity instrument, is capable of speciating atmospheric nitrogen species. TRENI, a chemiluminescence analyzer with two inlet systems (photolytic cell and heated gold tube) was employed to quantify NO, NO2 and NOy. Another inlet system comprised of thermal dissociation reactors, was employed to speciate NOy components into NOx, PANs and ∑RONO2. The detection limit of TRENI is 5 ppt for NOx and NOy and 20 ppt for total organic nitrates and PANs. In this study, we examine the extent to which we can explain the ∑RONO2 concentrations with known precursors and/or individual RONO2 measurement data. The observed fraction of NOy attributable to the ∑RONO2 is much higher than from previous individual RONO2 measurements. It seems clear that there is a large component of 'missing NOy' in the ∑RONO2 channel, as observed by others using the thermal dissociation inlet approach. We also examine here the potential sources of the frequently observed morning pulse of NOx, and the potential role of the forest canopy in mediating nitrogen chemistry.

  7. Examining the Impact of Nitrous Acid Chemistry on Ozone and PM over the Pearl River Delta Region

    EPA Science Inventory

    The impact of nitrous acid (HONO) chemistry on regional ozone and particulate matter in Pearl River Delta region was investigated using the community multiscale air quality (CMAQ) modeling system and the CB05 mechanism. Model simulations were conducted for a ten-day period in Oct...

  8. 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

  9. Ozone-induced alterations in arachidonic acid metabolism in cultured lung cell types

    SciTech Connect

    Madden, M.C.

    1986-01-01

    One of the most sensitive cells to ozone (O/sub 3/) damage is the pulmonary endothelial cell which may mediate the response of the lung to injury by productions of the autacoid prostacyclin (PGl/sub 2/), a metabolite of arachidonic acid. Exposure of endothelial cell cultures to ozone produced a concentration dependent decreases in the synthesis of PGl/sub 2/. Release of /sup 3/H-arachidonic acid from endothelial cells was increased after two hours of 0.3 and 1.0 ppm O/sub 3/ exposure while incubation of cells with 20 ..mu..M and arachidonate (4 min) after exposure resulted in a decreased PGl/sub 2/ synthesis. Cells exposed to 1.0 ppm O/sub 3/ did not have a decreased PGl/sub 2/ production when incubated with 5 ..mu..M PGH/sub 2/ immediately after exposure. These results are consistent with an O/sub 3/-induced inhibition of cyclooxygenase activity. O/sub 3/ exposure (1.0 ppm) produced a rapid decrease in endothelial PGl/sub 2/ synthesis. The data suggest that cyclooxygenase was not inactivated by increased autooxidation due to metabolism of increased free arachidonate. PGl/sub 2/ synthesis returned to control amounts within 12 hours after ozone exposure similar to the recovery time of irreversibly inhibited cyclooxygenase suggesting that recovery was due to de novo synthesis of enzyme. Lipid peroxides and/or hydrogen peroxide (H/sub 2/O/sub 2/) may have caused the inhibition of cyclooxygenase. Incubation of cells with catalase (5 U/ml) protected against the O/sub 3/-induced depression in PGl/sub 2/ synthesis. Exogenously added H/sub 2/O/sub 2/ (greater than or equal to 75 ..mu..M) caused a stimulation of basal PGl/sub 2/ production but depressed arachidonate-stimulated synthesis. O/sub 3/ exposure (2 hr, 1.0 ppm) produced altered metabolism of arachidonate in other important lung cell types, e.g., a decreased PGl/sub 2/ synthesis in smooth muscle cultures. Exposure of lung macrophages to O/sub 3/ caused an increase in almost all arachidonate metabolites produced.

  10. An investigation of the effects of simulated acid rain and elevated ozone on the physiology of ponderosa pine (Pinus ponderosa Dougl. ex Laws.) seedlings and mature trees

    SciTech Connect

    Momen, B.

    1993-12-31

    This study investigated the combined effects of simulated acid rain and ozone on foliar water relations, carbon and nitrogen contents, gas exchange, and respiration of ponderosa pine seedlings and mature trees grown in the field at the USDA Forest Service Tree Improvement Center in Chico, California. Acid rain levels (pH 5.1 and 3) were applied weekly on foliage only, from January to April, 1992. Plants were exposed to ozone levels (ambient and twice ambient) during the day only, from August to December, 1990, and from September to November, 1992. Results suggested that elevated ozone, particularly in combination with strong acid, caused osmotic adjustment that may benefit plants during drought. The observed effects of pollutants are similar to the reported effects of drought on plant water relations. Elevated ozone decreased foliar nitrogen content and thus increased the C:N ratio, particularly in seedlings. Stomatal conductance was not affected by pollutants but net photosynthesis was decreased by elevated ozone, especially in mature trees. The greater sensitivity of net photosynthesis of mature trees to elevated ozone was contrary to all other plant characteristics investigated. Elevated ozone increased seedling respiration. Under controlled, temperature, light, and vapor pressure deficit conditions, net photosynthesis responded positively to increases in plant age, light intensity, and rain pH, but negatively to increases in tissue age, heat, and ozone concentration. Overall results indicated that acid rain and elevated ozone declined the carbon pool of ponderosa pine due to increased respiration and decreased net photosynthesis. Pollutant effects were more profound in mid-summer when ozone concentrations were highest. On many occasions the effects of acid rain and ozone levels interacted. Seedlings were more sensitive to pollutants than mature trees.

  11. Rat lung phospholipid fatty acid composition in prepregnant, pregnant, and lactating rats: relationship to ozone-induced pulmonary toxicity.

    PubMed

    Gunnison, A F; Finkelstein, I

    1997-01-01

    Our laboratory has demonstrated recently that pulmonary inflammation induced by acute ozone exposure is much more severe in late stage pregnant and lactating rats than in postlactating rats or age-matched virgin females. It is currently widely believed that such pulmonary damage results, at least in part, from the reaction of ozone at sites of unsaturation in phospholipid fatty acid (PLFA) molecules located in the epithelial fluid layer lining the lung surfaces and/or the plasma membranes of epithelial cells underlying this fluid layer. The objective of this study was to compare the PLFA composition of lung tissue and surfactant from ozone-sensitive late stage pregnant and lactating rats with comparable tissue from relatively ozone-insensitive age-matched prepregnant (virgin female) rats to explore the possibility that changes in lung PLFA composition during pregnancy and/or lactation contribute to the enhanced sensitivity of these physiologic states to ozone. In addition, the correlation of changes in plasma PLFA composition with those in lung was investigated. There were minor differences in the composition of lung tissue and surfactant PLFAs between prepregnant rats and pregnant rats at day 17 of gestation and only slightly greater differences between prepregnant and lactating rats. Changes from the prepregnant state in the PLFA composition of lung tissue, but not surfactant, correlated with changes in the plasma only in lactating rats and not in pregnant rats. Overall, the double bond index of PLFAs in surfactant and lung tissue was decreased in pregnant and lactating rats compared with prepregnant rats. Thus, the increased sensitivity of pregnant and lactating rats to ozone-induced lung injury cannot be attributed to an increased availability of unsaturated fatty acids. In addition, the arachidonic acid composition of phospholipids did not appear to explain differences between prepregnant rats and pregnant or lactating rats in their inflammatory response to

  12. Growth responses of 53 open-pollinated loblolly pine families to ozone and acid rain

    SciTech Connect

    McLaughlin, S.B.; Edwards, N.T.; Hanson, P.J.

    1994-03-01

    Field exposures of 9950 containerized 12-wk-old loblolly pine (Pinustaeda L.) seedlings representing 53 commercially important, open-pollinated families were conducted to evaluate individual and interactive effects of acid rain and O{sub 3} on growth response. A 36-plot field research facility comprised of 33 open-top chambers and three open plots was used to test effects of five O{sub 3} levels that included ambient (A) and seasonally integrated levels that were 0.53, 1.10, 1.58, or 2.15 times ambient. Individual effects of three levels of simulated acid rain (pH 3.3, 4.5, and 5.2) as well as their interaction with O{sub 3} at 0.53A, 1.58A, and 2.15A levels were also included. Exposure to ambient air reduced average growth in height (26%), diameter (5%), and volume (14%) compared with growth of seedlings exposed to a 47% lower dose in charcoal filtered (CF) air. Responses to increasing O{sub 3} above ambient levels varied widely between families, became increasingly inhibitory at the highest O{sub 3} levels, but did not significantly exceed growth reductions found in ambient air. Diameter growth was reduced in most families by all levels of O{sub 3} addition. Acid rain caused a general stimulation of height growth at ambient levels (pH 4.5), while both height and diameter growth were reduced at a mean pH of 3.3. Significant antagonism between rainfall acidity and O{sub 3} effects on height and biomass increment was detected with increasing pollutant concentrations. Ozone reduced root/shoot biomass in most families, while acid rain did not. 51 refs., 6 figs., 6 tabs.

  13. The effect of heat treatment on the corrosion resistance of 440C stainless steel in 20% HNO3 + 2.5% Na2Cr2O7 solution

    NASA Astrophysics Data System (ADS)

    Savas, Terence P.; Wang, Allen Yi-Lan; Earthman, James C.

    2003-04-01

    The effect of heat treatment on the corrosion resistance of 440C stainless steel was investigated in a 20% HNO3 + 2.5% Na2Cr2O7 solution using electrochemical noise (ECN) measurements, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) examinations. The noise resistance ( Rn), which has been found to be inversely related to the localized corrosion rate, was measured to be 5.7E + 08 Ω-cm2, 4.2E + 08 Ω-cm2, and 3.7E + 04 Ω-cm2 for the oil-quenched, air-quenched, and vacuum furnace cooled (VFC) samples, respectively, after 1200 s exposures. The Rn for all heat treat conditions stabilized within a range of 1.0E + 07 Ω-cm2 to 3.2E + 08 Ω-cm2 after 2 h exposures. The EIS response showed a polarization resistance ( R p) on the order of 6.6E + 04 Ω-cm2, 5.3E + 04 Ω-cm2, and 1.1E + 04 Ω-cm2 for the oil-quenched, air-quenched, and VFC samples, respectively, after 2 h exposures. The EIS data are in good agreement with ECN data and indicate that after longer exposures, general corrosion mechanisms dominate and the corrosion rates are comparable. SEM examinations of specimens subjected to 1200 s exposures revealed that severity of pitting and intergranular corrosion damage was consistent with trends in the Rn data. Specifically, the electrochemical noise data as well as SEM examinations of specimens revealed a higher localized corrosion resistance of the hardened specimens during the early stages of passivation. This greater resistance to localized corrosion can be attributed to an increased stability of the natural passive film resulting from a higher concentration of chromium atoms in solution for the martensite phase.

  14. 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.

  15. Effects of acidic rain and ozone on nitrogen fixation and photosynthesis in the lichen lobaria pulmonaria (L. ) Hoffm

    SciTech Connect

    Sigal, L.L.; Johnston, J.W.

    1986-01-01

    The lichen Lobaria pulmonaria was subjected to ozone fumigations at 118, 235 and 353 mcg/cu m and simulated acidic rain at pH levels of 2.6, 4.2 and 5.6 for 5 days (M,W,F,M,W) during a 10-day period. Acidic rain at pH 2.6 caused significant reduction in nitrogen fixation and gross photosynthesis of 100 and 90%, respectively, and thallus bleaching was apparent. There were no significant differences between the pH 5.6 and 4.2 treatments in either gross photosynthesis or nitrogen fixation, and the color of the lichen thalli was unchanged. The effect of ozone on nitrogen fixation and photosynthesis over the range of concentrations used was not significant, but there was a trend toward reduced nitrogen fixation with increasing O/sub 3/ concentration. There were no significant ozone-acidic rain interactions. The threshold for response to rain acidity for L. pulmonaria lies between pH 2.6 and 4.2, and the acidity of wet deposition in parts of the United States may fall in the range.

  16. Long-term trends and weekday-to-weekend differences in ozone, its precursors, and other secondary pollutants in Atlanta, Georgia

    NASA Astrophysics Data System (ADS)

    Pollack, I. B.; Ryerson, T. B.; Baumann, K.; Edgerton, E. S.; De Gouw, J. A.; Gilman, J.; Graus, M.; Holloway, J.; Lerner, B. M.; Neuman, J. A.; Roberts, J. M.; Veres, P. R.; Warneke, C.; Trainer, M.; Parrish, D. D.

    2013-12-01

    In an environment rich in biogenic volatile organic compounds (VOCs), decreasing concentrations of ozone (-1.3 % yr-1) and other secondary pollutants (-8.2 % yr-1 for nitric acid, HNO3; and -7.9 % yr-1 for peroxyacetyl nitrate, PAN) in Atlanta, Georgia over the past fifteen years are primarily attributed to decreases in local emissions of nitrogen oxides (NOx=NO+NO2). Large reductions in abundances of NOx in the Southeast U.S. over the years (-8.0 % yr-1 for total reactive nitrogen, NOy) are the direct result of control strategies implemented to reduced emissions from electric-power generation plants and on-road motor vehicles. Here, we compile an extensive historical data set of trace gas measurements spanning fifteen years between 1998 and 2013 from a surface monitoring network site in downtown Atlanta (i.e. the SEARCH network Jefferson Street site) and research aircraft (e.g. the 2013 Southeast Atmosphere Study and 1999 Southern Oxidants Study aboard the NOAA P-3 aircraft). With this data set we confirm and extend long-term trends and weekday-to-weekend differences in ozone, its precursors, and other secondary pollutants during summertime in Atlanta. Long-term changes in abundances and enhancement ratios of secondary oxidation products indicate changes in pollutant formation chemistry in Atlanta resulting from the significant decrease in NOx precursor emissions over the past fifteen years. The most noteworthy changes include: 1) an increase in enhancement ratios of odd oxygen (Ox=O3+NO2) to (PAN+HNO3) of +5.5 % yr-1 indicating an increase in ozone production efficiency by a factor of 2 over the fifteen year period, 2) no significant change in the fraction of oxidized NOx out of NOy over time indicating little change in the extent of photochemical processing of the NOx emissions, and 3) a flip in observed ozone concentrations from higher average ozone on weekends to higher average ozone on weekdays after 2004. The observations for Atlanta will also be contrasted

  17. The potential for ozone depletion in the arctic polar stratosphere.

    PubMed

    Brune, W H; Anderson, J G; Toohey, D W; Fahey, D W; Kawa, S R; Jones, R L; McKenna, D S; Poole, L R

    1991-05-31

    The nature of the Arctic polar stratosphere is observed to be similar in many respects to that of the Antarctic polar stratosphere, where an ozone hole has been identified. Most of the available chlorine (HCl and ClONO(2)) was converted by reactions on polar stratospheric clouds to reactive ClO and Cl(2)O(2) throughout the Arctic polar vortex before midwinter. Reactive nitrogen was converted to HNO(3), and some, with spatial inhomogeneity, fell out of the stratosphere. These chemical changes ensured characteristic ozone losses of 10 to 15% at altitudes inside the polar vortex where polar stratospheric clouds had occurred. These local losses can translate into 5 to 8% losses in the vertical column abundance of ozone. As the amount of stratospheric chlorine inevitably increases by 50% over the next two decades, ozone losses recognizable as an ozone hole may well appear.

  18. The potential for ozone depletion in the Arctic polar stratosphere

    NASA Technical Reports Server (NTRS)

    Brune, W. H.; Anderson, J. G.; Toohey, D. W.; Fahey, D. W.; Kawa, S. R.; Poole, L. R.

    1991-01-01

    The nature of the Arctic polar stratosphere is observed to be similar in many respects to that of the Antarctic polar stratosphere, where an ozone hole has been identified. Most of the available chlorine (CHl and ClONO2) was converted by reactions on polar stratospheric clouds to reactive ClO and Cl2O2 thoroughout the Arctic polar vortex before midwinter. Reactive nitrogen was converted to HNO3, and some, with spatial inhomogeneity, fell out of the stratosphere. These chemical changes ensured characteristic ozone losses of 10 to 15 percent at altitudes inside the polar vortex where polar stratospheric clouds had occurred. These local losses can translate into 5 to 8 percent losses in the vertical column abundance of ozone. As the amount of stratospheric chlorine inevitably increases by 50 percent over the next two decades, ozone losses recognizable as an ozone hole may well appear.

  19. How do background ozone concentrations affect the biosynthesis of rosmarinic acid in Melissa officinalis?

    PubMed

    Döring, Anne S; Pellegrini, Elisa; Della Batola, Michele; Nali, Cristina; Lorenzini, Giacomo; Petersen, Maike

    2014-03-01

    Lemon balm (Melissa officinalis; Lamiaceae) plants were exposed to background ozone (O3) dosages (80ppb for 5h), because high background levels of O3 are considered to be as harmful as episodic O3 peaks. Immediately at the end of fumigation the plants appeared visually symptomless, but necrotic lesions were observed later. The biosynthesis of rosmarinic acid (RA) comprises eight enzymes, among them phenylalanine ammonia-lyase (PAL), 4-coumarate:coenzyme A ligase (4CL), tyrosine aminotransferase (TAT) and rosmarinic acid synthase (RAS). The transcript levels of these genes have been investigated by quantitative RT-PCR. There was a quick up-regulation of all genes at 3h of O3 exposure, but at 24h from beginning of exposure (FBE) only RAS and PAL were up-regulated. The specific activity of RAS was closely correlated with a decrease of RA concentration in lemon balm leaves. The specific activity of PAL increased at 12h FBE to 163% in comparison to control levels. This work provides insight into the effect of O3 stress on the formation of the main phenolic ingredient of the pharmaceutically important plant M. officinalis. PMID:24484956

  20. How do background ozone concentrations affect the biosynthesis of rosmarinic acid in Melissa officinalis?

    PubMed

    Döring, Anne S; Pellegrini, Elisa; Della Batola, Michele; Nali, Cristina; Lorenzini, Giacomo; Petersen, Maike

    2014-03-01

    Lemon balm (Melissa officinalis; Lamiaceae) plants were exposed to background ozone (O3) dosages (80ppb for 5h), because high background levels of O3 are considered to be as harmful as episodic O3 peaks. Immediately at the end of fumigation the plants appeared visually symptomless, but necrotic lesions were observed later. The biosynthesis of rosmarinic acid (RA) comprises eight enzymes, among them phenylalanine ammonia-lyase (PAL), 4-coumarate:coenzyme A ligase (4CL), tyrosine aminotransferase (TAT) and rosmarinic acid synthase (RAS). The transcript levels of these genes have been investigated by quantitative RT-PCR. There was a quick up-regulation of all genes at 3h of O3 exposure, but at 24h from beginning of exposure (FBE) only RAS and PAL were up-regulated. The specific activity of RAS was closely correlated with a decrease of RA concentration in lemon balm leaves. The specific activity of PAL increased at 12h FBE to 163% in comparison to control levels. This work provides insight into the effect of O3 stress on the formation of the main phenolic ingredient of the pharmaceutically important plant M. officinalis.

  1. A study of ozone-induced edema in the isolated rat lung in relation to arachidonic acid metabolism, mixed-function oxidases and angiotensin converting enzyme activities.

    PubMed

    Dutta, S; Chatterjee, M; Teknos, T N; Carlson, R W

    1990-01-01

    In order to elucidate the role of arachidonic acid in the pathogenesis of ozone-induced pulmonary edema, isolated rat lungs were exposed to 14C-arachidonic acid in the presence or absence of ozone and the incorporation of radiolabelled arachidonate into pulmonary cell lipids was studied. The perfusates from these studies were also subjected to differential extraction and thin layer chromatography (t.l.c.) to determine synthesis of both cyclo-oxygenase and lipoxygenase products. In the presence of an edemagenic concentration of ozone, isolated lungs incorporated significantly less exogenous arachidonic acid into phosphatidyl choline and phosphatidyl ethanolamine, whereas incorporation into phosphatidyl inositol or serine was not affected. The edemagenic concentration of ozone also increased production of a variety of arachidonic acid metabolites via cyclo-oxygenase and lipoxygenase pathways. In separate studies, a similar ozone exposure did not affect 14CO2 production, resulting from the metabolism of 14C-antipyrine by mixed function oxidases (MFO). Similarly, an edemagenic concentration of ozone did not affect pulmonary angiotensin converting enzyme activity (ACE) as determined by the rate of formation of 14C-hippuric acid from 14C-hippuryl-histidyl-leucine (14C-HHL). Thus, acute ozone exposure is specifically associated with a reduced incorporation of arachidonate into phospholipids and with an increased conversion of arachidonate into bio-active metabolites.

  2. A heterogeneous chemistry model for acid rain`s effect on ozone

    SciTech Connect

    Ye, Tao

    1995-11-01

    A computer model for simulating heterogeneous reactions in cloud is developed to determine the S(IV) species` effect on ozone. Crutzen claims that NO{sub x}, HO{sub x} families and H{sub 2}CO in the troposphere can decrease ozone by 5 to 10%. However, is this claim valid for a SO{sub x} polluted atmosphere? The SO{sub x} family reacts with the ozone destroyers. These reactions seem to be significant enough to reduce the H{sub 2}CO`s destructive effect on ozone.

  3. Global OZone Chemistry And Related trace gas Data records for the Stratosphere (GOZCARDS)

    NASA Astrophysics Data System (ADS)

    Froidevaux, L.; Fuller, R.; Santee, M. L.; Schwartz, M. J.; Manney, G. L.; Livesey, N. J.; Anderson, J.; Wang, H.; Cunnold, D.; Bernath, P. F.; Walker, K. A.; Salawitch, R. J.; Canty, T. P.; Fiorucci, I.; Muscari, G.; Nedoluha, G. E.; Connor, B. J.; Pawson, S.

    2009-12-01

    The MEaSUREs GOZCARDS project will provide a commonly-formatted Earth system data record (ESDR) for stratospheric composition, of high relevance to the issue of ozone decline and recovery. The data records are drawn primarily from satellite-derived global stratospheric composition measurements from 1979 to the present, including on-going measurements from Aura MLS and ACE-FTS, as well as temperatures and potential vorticity from GSFC's meteorological reanalyses (GMAO MERRA). These data records will provide time series for stratospheric ozone (O3), hydrogen chloride (HCl), chlorine monoxide (ClO), nitric acid (HNO3), water vapor (H2O), nitrous oxide (N2O), nitrogen dioxide (NO2), nitrogen oxide (NO), methane (CH4), and hydrogen fluoride (HF). Additional "derived data records", using a constrained photochemical model, will be provided for active chlorine (ClOx) and odd nitrogen (NOx). The data are zonal means versus latitude on a common vertical grid, with time resolution of one month as a standard, and one day when possible (for emission measurements from the Microwave Limb Sounder on both UARS and Aura satellites). Data records binned in equivalent latitude and potential temperature will also be produced. We will provide both instrument-specific records and merged data records, with community access (website and data center) starting in 2010. We highlight some results and issues in this presentation.

  4. Assessing the Parameterization of Nitric Oxide Emissions By Lightning in a Chemical Transport Model with Nitric Acid Columns from the IASI Satellite Instrument

    NASA Astrophysics Data System (ADS)

    Cooper, M.; Martin, R.; Wespes, C.; Coheur, P. F.; Clerbaux, C.; Murray, L. T.

    2014-12-01

    Nitrogen oxides (NOx ≡ NO + NO2) in the free troposphere largely control the production of ozone (O3), an important greenhouse gas and atmospheric oxidant. As HNO3 is the dominant sink of tropospheric NOx, improved understanding of its production and loss mechanisms can help to better constrain NOx emissions, and in turn improve understanding of ozone production and its effect on climate. However, this understanding is inhibited by the scarcity of direct measurements of free tropospheric HNO3, particularly in the tropics. We interpret tropical tropospheric nitric acid columns from the IASI satellite instrument with a global chemical transport model (GEOS-Chem). Overall GEOS-Chem generally agrees with IASI, however we find that the simulation underestimates IASI nitric acid over Southeast Asia by a factor of two. The bias is confirmed by comparing the GEOS-Chem simulation with additional satellite (HIRDLS, ACE-FTS) and aircraft (PEM-Tropics A and PEM-West B) observations of the middle and upper troposphere. We show that this bias can be explained by the parameterization of lightning NOx emissions, primarily from the misrepresentation of concentrated subgrid lightning NOx plumes. We tested a subgrid lightning plume parameterization and found that an additional 0.5 Tg N with an ozone production efficiency of 15 mol/mol would reduce the regional nitric acid bias from 92% to 6% without perturbing the rest of the tropics. Other sensitivity studies such as modified NOx yield per flash, increased altitude of lightning NOx emissions, or changes to convective mass flux or wet deposition of nitric acid required unrealistic changes to reduce the bias. This work demonstrates the importance of a comprehensive lightning parameterization to constraining NOx emissions.

  5. Products of ozonized arachidonic acid potentiate the formation of DNA single strand breaks in cultured human lung cells

    SciTech Connect

    Kozumbo, W.J.; Hanley, N.M.; Agarwal, S.

    1996-12-31

    In this study we examined the potential for environmental levels of ozone (O{sub 3}) to degrade arachidonic acid (AA), a polyunsaturated fatty acid abundantly present in the lung, into products that can produce DNA single strand breaks (ssb) in cultured human lung cells. Human lung fibroblasts were incubated with 60 {mu}M AA that had been previously exposed to an degraded by 0.4 ppm O{sub 3} (1 hr). Incubation of the cells with O{sub 3}-exposed AA (but not with vehicle alone) for 1 hr at 4{degrees}C and 37{degrees}C produced 555 and 245 rad-equivalents of DNA ssb, respectively, as determined by the DNA alkaline elution technique. These breaks were completely eliminated when the ozonized AA solution was incubated with catalase prior to cell treatment, indicating that H{sub 2}O{sub 2} was solely responsible for damaging DNA. Superoxide dismutase, bovine serum albumin, or heat-inactivated catalase showed little, if any, inhibitory activity. The H{sub 2}O{sub 2} content for only about 40% of the observed breaks. Potentiation of the H{sub 2}O{sub 2}-induced DNA ssb persisted after removal of the carbonyl substances by chromatographic procedures, suggesting that the non-carbonyl component of ozonized AA was the responsible component for inducing augmentation of the observed increases in DNA ssb. Ozonized AA also induced DNA ssb in cultures of the human bronchial epithelial cell line BEAS-2B. Again, these breaks were shown to exceed levels that could be attributed to the presence of H{sub 2}O{sub 2} alone. These results indicate that products of ozonized AA can interact to potentiate DNA ssb in human lung cells. 42 refs., 6 figs., 3 tabs.

  6. 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

  7. Influence of polar stratospheric clouds on the depletion of Antarctic ozone

    NASA Technical Reports Server (NTRS)

    Salawitch, Ross J.; Wofsy, Steven C.; Mcelroy, Michael B.

    1988-01-01

    Precipitation of nitrate in polar stratospheric clouds (PSCs) can provide a significant sink for Antarctic stratospheric odd nitrogen. It is argued that the depth of the Ozone Hole is sensitive to the occurrence of temperatures below about 196 K. An increase in the prevalence of temperatures below 196 K would enhance ozone loss by increasing the spatial extent and persistence of PSCs, and by decreasing the level of HNO3 that remains following PSC evaporation. Concentrations of halogen gases in the 1960s and earlier were insufficient to support major ozone loss, even if thermal conditions were favorable.

  8. Influence of soil substrate and ozone plus acid mist on the frost resistance of young Norway spruce.

    PubMed

    Senser, M

    1990-01-01

    The needles of clonal Norway spruce grown in environmental chambers on two different soils (an acidic soil 1 and a calcareous soil 2) and exposed to two levels of ozone fumigation (a low level combined with neutral mist = control, and an elevated one combined with acid mist = treatment) were analyzed for their frost hardiness. No effect of ozone was observed on either the development of frost resistance during the hardening phase or on the decrease in frost resistance during the dehardening phase. The preliminary results of Brown et al. (1987) and Barnes and Davidson (1988), which indicated that ozone treatment predisposes plants to winter injury, could thus not be confirmed. Frost resistance was, however, distinctly influenced by the content of the mineral nutrients of the soils. The pronounced K(+) deficiency of the needles of the trees growing on the neutral soil (Alps) had less effect on the development of frost resistance than did the Ca(++) and Mg(++) deficiency of the needles of the trees grown on the acidic soil 1 (Bavarian Forest). The variability of frost resistance between the different clones on soil 1 was partly attributed to fluctuations in the mineral nutrient content of the needles, rather than to a genetic predisposition. PMID:15092284

  9. Seasonal variation of gas exchange and pigmentation in branches of three grafted clones of mature ponderosa pine exposed to ozone and acid rain.

    PubMed

    Anderson, P D; Houpis, J L; Helms, J A; Momen, B

    1997-01-01

    Gas exchange and pigmentation responses of mature ponderosa pine (Pinus ponderosa Laws.) branches to ozone and acid rain exposure were investigated using three grafted clones growing in a managed seed orchard. Exposure of one-year-old foliage to twice ambient ozone (2 x AMB) resulted in significant decreases in net photosynthesis (Pn), stomatal conductance (gsw) and pigmentation relative to charcoal-filtered (CF) and ambient (AMB) ozone treatments. Ozone effects on gas exchange and pigmentation were most pronounced during late-season and differed significantly among clones. Environmental parameters (e.g. light, vapor pressure deficit, and temperature) accounted for more variation in Pn than did cumulative ozone exposure. Minimal differences in gsw and Pn among ozone treatments occurred during seasonal periods of high temperature and evaporative demand. Negative effects of 2 x AMB ozone on gsw and pigmentation were greatest for the clones having highest and lowest phenotypic vigor under ambient conditions; the clone of moderate phenotypic vigor under ambient conditions was least sensitive to ozone. Application of simulated acid rain of pH 3.0, pH 5.1 or no rain (NR) had little impact on gas exchange or pigmentation.

  10. Efficient Catalytic Ozonation over Reduced Graphene Oxide for p-Hydroxylbenzoic Acid (PHBA) Destruction: Active Site and Mechanism.

    PubMed

    Wang, Yuxian; Xie, Yongbing; Sun, Hongqi; Xiao, Jiadong; Cao, Hongbin; Wang, Shaobin

    2016-04-20

    Nanocarbons have been demonstrated as promising environmentally benign catalysts for advanced oxidation processes (AOPs) upgrading metal-based materials. In this study, reduced graphene oxide (rGO) with a low level of structural defects was synthesized via a scalable method for catalytic ozonation of p-hydroxylbenzoic acid (PHBA). Metal-free rGO materials were found to exhibit a superior activity in activating ozone for catalytic oxidation of organic phenolics. The electron-rich carbonyl groups were identified as the active sites for the catalytic reaction. Electron spin resonance (ESR) and radical competition tests revealed that superoxide radical ((•)O2(-)) and singlet oxygen ((1)O2) were the reactive oxygen species (ROS) for PHBA degradation. The intermediates and the degradation pathways were illustrated from mass spectroscopy. It was interesting to observe that addition of NaCl could enhance both ozonation and catalytic ozonation efficiencies and make ·O2(-) as the dominant ROS. Stability of the catalysts was also evaluated by the successive tests. Loss of specific surface area and changes in the surface chemistry were suggested to be responsible for catalyst deactivation. PMID:27007603

  11. Description of data on the Nimbus 7 LIMS map archive tape: Ozone and nitric acid

    NASA Technical Reports Server (NTRS)

    Remsberg, E. E.; Kurzeja, R. J.; Haggard, K. V.; Russell, J. M., III; Gordley, L. L.

    1986-01-01

    The Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) data set has been processed into a Fourier coefficient representation with a Kalman filter algorithm applied to profile data at individual latitudes and pressure levels. The algorithm produces synoptic data at noon Greenwich Mean Time (GMT) from the asynoptic orbital profiles. This form of the data set is easy to use and is appropriate for time series analysis and further data manipulation and display. Ozone and nitric acid results are grouped together in this report because the LIMS vertical field of views (FOV's) and analysis characteristics for these species are similar. A comparison of the orbital input data with mixing ratios derived from Kalman filter coefficients indicates errors in mixing ratio of generally less than 5 percent, with 15 percent being a maximum error. The high quality of the mapped data was indicated by coherence of both the phases and the amplitudes of waves with latitude and pressure. Examples of the mapped fields are presented, and details are given concerning the importance of diurnal variations, the removal of polar stratospheric cloud signatures, and the interpretation of bias effects in the data near the tops of profiles.

  12. The effects of sequential exposure to acidic fog and ozone on pulmonary function in exercising subjects

    SciTech Connect

    Aris, R.; Christian, D.; Sheppard, D.; Balmes, J.R. )

    1991-01-01

    In Southern California coastal regions, morning fog is often acidified by the presence of nitric acid (HNO{sub 3}). Peak exposure to ozone (O{sub 3}) usually occurs in the afternoon and evening, after the fog has dissipated. To determine whether fog containing HNO{sub 3} might enhance pulmonary responses to O{sub 3}, we studied a group of healthy, athletic subjects selected for lung function sensitivity to O{sub 3}. On 3 separate days, the subjects exercised for 2 h in atmospheres containing HNO{sub 3} fog (0.5 mg/ml), H{sub 2}O fog, or clean, filtered air. After a 1-h break, they exercised for an additional 3 h in an atmosphere containing 0.20 ppm O{sub 3}. Surprisingly, the mean O{sub 3}-induced decrements in FEV1 and FVC were smaller after exercise in each fog-containing atmosphere than they were after exercise in clean, filtered air. The mean (+/- SEM) O{sub 3}-induced decrements in FEV1 were 26.4 +/- 5.3% after air, 17.1 +/- 3.7% after H{sub 2}O fog, and 18.0 +/- 4.3% after HNO{sub 3} fog, and in FVC they were 19.9 +/- 4.7% after air, 13.6 +/- 2.8% after H{sub 2}O fog, and 13.6 +/- 4.2% after HNO{sub 3} fog.

  13. 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.

  14. Effects of ozone and peroxyacetyl nitrate on polar lipids and fatty acids in leaves of morning glory and kidney bean. [Pharbitis nil; Phaseolus vulgaris

    SciTech Connect

    Nouchi, Isamu; Toyama, Susumu Ochanomizu Univ., Tokyo )

    1988-07-01

    To compare the effects of ozone and peroxyacetyl nitrate (PAN) on leaf lipids, fatty acids and malondialdehyde (MDA), morning glory (Pharbitis nil Choisy cv Scarlet O'Hara) and kidney bean (Phaseolus vulgaris L. cv Gintebo) plants were exposed to either ozone (0.15 microliter per liter for 8 hours) or PAN (0.10 microliter per liter for up to 8 hours). Ozone increased phospholipids in morning glory and decreased in kidney bean at the initial stage (2-4 hours) of exposure, while it scarcely changed glycolipids, the unsaturated fatty acids, and MDA in both plants. A large reduction of glycolipids occurred 1 day after ozone exposure in both plants. PAN caused marked drops in phospholipids and glycolipids in kidney bean at relatively late stage (6-8 hours) of exposure, while it increased phosphatidic acid and decreased the unsaturated fatty acids, an increase which was accompanied by a large increase in MDA. These results suggest that ozone may not directly oxidize unsaturated fatty acids at the initial stage of exposure, but may alter polar lipid metabolism, particularly phospholipids. On the other hand, PAN may abruptly and considerably degrade phospholipids and glycolipids by peroxidation or hydrolysis at the late stage of exposure. The present study shows that ozone and PAN affect polar lipids in different manners.

  15. 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.

  16. Toxicity on aquatic organisms exposed to secondary effluent disinfected with chlorine, peracetic acid, ozone and UV radiation.

    PubMed

    da Costa, Juliana Berninger; Rodgher, Suzelei; Daniel, Luiz Antonio; Espíndola, Evaldo Luiz Gaeta

    2014-11-01

    The toxic potential of four disinfectant agents (chlorine, ozone, peracetic acid and UV radiation), used in the disinfection of urban wastewater, was evaluated with respect to four aquatic organisms. Disinfection assays were carried out with wastewater from the city of Araraquara (São Paulo State, Brazil), and subsequently, toxicity bioassays were applied in order to verify possible adverse effects to the cladocerans (Ceriodaphnia silvestrii and Daphnia similis), midge larvae Chironomus xanthus and fish (Danio rerio). Under the experimental conditions tested, all the disinfectants were capable of producing harmful effects on the test organisms, except for C. xanthus. The toxicity of the effluent to C. silvestrii was observed to increase significantly as a result of disinfection using 2.5 mg L(-1) chlorine and 29.9 mg L(-1) ozone. Ozonation and chlorination significantly affected the survival of D. similis and D. rerio, causing mortality of 60 to 100 % in comparison to the non-disinfected effluent. In experiments with effluent treated with peracetic acid (PAA) and UV radiation, a statistically significant decrease in survival was only detected for D. rerio. This investigation suggested that the study of the ideal concentrations of disinfectants is a research need for ecologically safe options for the treatment of wastewater.

  17. The effect of ambient ozone pollution and acidic rain on the growth and chlorophyll content of green and white ash.

    PubMed

    Elliott, C L; Eberhardt, J C; Brennan, E G

    1987-01-01

    Two- and three-year old green ash (Fraxinus americana L.) and white ash (Fraxinus pennsylvanica Marsh.) seedlings were exposed to combinations of ambient ozone and acidic ambient rainfall in New Brunswick, New Jersey. During the 3-year study the potted seedlings did not develop typical foliar ozone toxicity symptoms, despite the occurrence of as many as 78 h in exceedance of the National Ambient Air Quality Standard of 0.12 ppm. Although the pH of the rainfall was as low as 3.6 and averaged 4.1, no symptoms were observed resulting from the ambient precipitation. The rate of shoot growth in terms of height and diameter was generally not affected by either of the pollutants during the growing season. Although the chlorophyll content of white ash foliage was low following frequent rainfall in the early summer of 1984, there was no statistically significant evidence that acid raid or ambient ozone decreased chlorophyll in ash seedlings during the 3-year study.

  18. Toxicity on aquatic organisms exposed to secondary effluent disinfected with chlorine, peracetic acid, ozone and UV radiation.

    PubMed

    da Costa, Juliana Berninger; Rodgher, Suzelei; Daniel, Luiz Antonio; Espíndola, Evaldo Luiz Gaeta

    2014-11-01

    The toxic potential of four disinfectant agents (chlorine, ozone, peracetic acid and UV radiation), used in the disinfection of urban wastewater, was evaluated with respect to four aquatic organisms. Disinfection assays were carried out with wastewater from the city of Araraquara (São Paulo State, Brazil), and subsequently, toxicity bioassays were applied in order to verify possible adverse effects to the cladocerans (Ceriodaphnia silvestrii and Daphnia similis), midge larvae Chironomus xanthus and fish (Danio rerio). Under the experimental conditions tested, all the disinfectants were capable of producing harmful effects on the test organisms, except for C. xanthus. The toxicity of the effluent to C. silvestrii was observed to increase significantly as a result of disinfection using 2.5 mg L(-1) chlorine and 29.9 mg L(-1) ozone. Ozonation and chlorination significantly affected the survival of D. similis and D. rerio, causing mortality of 60 to 100 % in comparison to the non-disinfected effluent. In experiments with effluent treated with peracetic acid (PAA) and UV radiation, a statistically significant decrease in survival was only detected for D. rerio. This investigation suggested that the study of the ideal concentrations of disinfectants is a research need for ecologically safe options for the treatment of wastewater. PMID:25213288

  19. Analysis of Strong Wintertime Ozone Events in an Area of Extensive Oil and Gas Extraction

    NASA Astrophysics Data System (ADS)

    Rappenglück, Bernhard; Ackermann, Luis; Alvarez, Sergio; Golovko, Julia; Buhr, Martin; Field, Robert; Soltis, Jeff; Montague, Derek C.; Hauze, Bill; Scott, Adamson; Risch, Dan; Wilkerson, George; Bush, David; Stoeckenius, Till; Keslar, Cara

    2015-04-01

    During recent years, elevated ozone (O3) values have been observed repeatedly in the Upper Green River Basin (UGRB), Wyoming during wintertime. This paper presents an analysis of high ozone days in late winter 2011 (1-hour average up to 166 ppbv). Intensive Observational Periods (IOPs) were performed which included comprehensive surface and boundary layer measurements. Low windspeeds in combination with low mixing layer heights (~50 m agl) are essential for accumulation of pollutants. Air masses contain substantial amounts of reactive nitrogen (NOx) and non-methane hydrocarbons (NMHC) emitted from fossil fuel exploration activities in the Pinedale Anticline. On IOP days in the morning hours reactive nitrogen (up to 69%), then aromatics and alkanes (each ~10-15%; mostly ethane and propane) are major contributors to the hydroxyl (OH) reactivity. This time frame largely coincides with lowest NMHC/NOx ratios (~50), reflecting a relatively low NMHC mixture, and a change from a NOx-limited regime towards a NMHC limited regime. OH production on IOP days is mainly due to nitrous acid (HONO). On a 24-hr basis and as determined for a measurement height of 1.80 m above the surface HONO photolysis on IOP days can contribute ~83% to OH production on average, followed by alkene ozonolysis (~9%). Photolysis by ozone and HCHO photolysis contributes about 4% each to hydroxyl formation. High HONO levels (maximum hourly median on IOP days: 1,096 pptv) are favored by a combination of shallow boundary layer conditions and enhanced photolysis rates due to the high albedo of the snow surface. HONO is most likely formed through (i) abundant nitric acid (HNO3) produced in atmospheric oxidation of NOx, deposited onto the snow surface and undergoing photo-enhanced heterogeneous conversion to HONO and (ii) combustion related emission of HONO. HONO production is confined to the lowermost 10 m of the boundary layer. HONO, serves as the most important precursor for OH, strongly enhanced due to

  20. 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

  1. An evaluation of the regional acid deposition model surface module for ozone uptake at three sites in the San Joaquin Valley of California

    NASA Technical Reports Server (NTRS)

    Massman, W. J.; Pederson, J.; Delany, A.; Grantz, D.; Hertog, G. Den; Neumann, H. H.; Oncley, S. P.; Pearson, R., Jr.; Shaw, R. H.

    1994-01-01

    Plants and soils act as major sinks for the destruction of tropospheric ozone, especially during daylight hours when plant stomata open and are thought to provide the dominant pathway for the uptake of ozone. The present study, part of the California Ozone Deposition Experiment, compares predictions of the regional acid deposition model ozone surface conductance module with surface conductance data derived from eddy covariance measurements of ozone flux taken at a grape, a cotton, and a grassland site in the San Joaquin Valley of California during the summer of 1991. Results indicate that the model (which was developed to provide long-term large-area estimates for the eastern United States) significantly overpredicts the surface conductance at all times of the day for at least two important types of plant cover of the San Joaquin Valley and that it incorrectly partitions the ozone flux between transpiring and nontranspiring components of the surface at the third site. Consequently, the model either overpredicts or inaccurately represents the observed deposition velocities. Other results indicate that the presence of dew does not reduce the rate of ozone deposition, contradicting to model assumptions, and that model assumptions involving the dependency of stomata upon environmental temperature are unnecessary. The effects of measurement errors and biases, arising from the presence of the roughness sublayer and possible photochemical reactions, are also discussed. A simpler model for ozone surface deposition (at least for the San Joaquin Valley) is proposed and evaluated.

  2. Kinetics study of heterogeneous reactions of ozone with erucic acid using an ATR-IR flow reactor.

    PubMed

    Leng, Chunbo; Hiltner, Joseph; Pham, Hai; Kelley, Judas; Mach, Mindy; Zhang, Yunhong; Liu, Yong

    2014-03-01

    The ozone initiated heterogeneous oxidation of erucic acid (EA) thin film was investigated using a flow system combined with attenuated total reflection infrared spectroscopy (ATR-IR) over wide ranges of ozone concentrations (0.25-60 ppm), thin film thickness (0.1-1.0 μm), temperatures (263-298 K), and relative humidities (0-80% RH) for the first time. Pseudo-first-order rate constants, kapp, and overall reactive uptake coefficients, γ, were obtained through changes in the absorbance of C[double bond, length as m-dash]O stretching bands at 1695 cm(-1), which is assigned to the carbonyl group in carboxylic acid. Results showed that the reaction followed the Langmuir-Hinshelwood mechanism and kapp was largely dominated by surface reaction over bulk phase reaction. In addition, both the kapp and the γ values showed very strong temperature dependences (∼two orders of magnitude) over the temperature range; in contrast, they only slightly increased with increasing RH values from 0-80%. According to the kapp values as a function of temperature, the activation energy for the heterogeneous reaction was estimated to be 80.6 kJ mol(-1). Our results have suggested that heterogeneous reactions between ozone and unsaturated solid surfaces likely have a substantially greater temperature dependence than liquid ones. Moreover, the hygroscopic properties of EA thin films before and after exposure to ozone were also studied by measurement of water uptake. Based on the hygroscopicity data, the insignificant RH effect on reaction kinetics was probably due to the relatively weak water uptake by the unreacted and reacted EA thin films.

  3. 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.

  4. Mechanisms of ozone toxicity in cultured cells. I. Reduced clonogenic ability of polyunsaturated fatty acid-supplemented fibroblasts. Effect of vitamin E

    SciTech Connect

    Konings, A.W.

    1986-01-01

    The direct action of ozone on viability and survival of normal and modified mouse lung fibroblasts has been studied. By cell manipulation of fibroblasts in culture, the content of polyunsaturated fatty acids (PUFA) in the phospholipids was increased from about 6% to about 40%. The cellular content of alpha-tocopherol (alpha-T) (vitamin E) could be drastically enhanced. Vitamin E supplementation to the cell did not influence the PUFA manipulation. Normal, PUFA, and PUFA(alpha-T) fibroblasts were exposed to ozone by bubbling 10 ppm through the cell suspensions for different periods of time (0-6 h). No significant effects of the ozone exposure could be established when normal fibroblasts were used. The PUFA fibroblasts, however, were very vulnerable to ozone toxicity, both in terms of dye uptake (Trypan blue) and cell death (clonogenic ability). When alpha-tocopherol was present in the cell (200 ng/10(6) cells), a clear protection against ozone toxicity was found. It is concluded that ozone toxicity might be higher under conditions of a relative high amount of polyunsaturated fatty acids in the membrane phospholipids of the cell and a low cellular antioxidant capacity. Cellular membranes are probably an important target for ozone-induced cell death.

  5. Differential Effects of Elevated Ozone on Two Hybrid Aspen Genotypes Predisposed to Chronic Ozone Fumigation. Role of Ethylene and Salicylic Acid1

    PubMed Central

    Vahala, Jorma; Keinänen, Markku; Schützendübel, Andres; Polle, Andrea; Kangasjärvi, Jaakko

    2003-01-01

    The role of ethylene (ET) signaling in the responses of two hybrid aspen (Populus tremula L. × P. tremuloides Michx.) clones to chronic ozone (O3; 75 nL L−1) was investigated. The hormonal responses differed between the clones; the O3-sensitive clone 51 had higher ET evolution than the tolerant clone 200 during the exposure, whereas the free salicylic acid concentration in clone 200 was higher than in clone 51. The cellular redox status, measured as glutathione redox balance, did not differ between the clones suggesting that the O3 lesions were not a result of deficient antioxidative capacity. The buildup of salicylic acid during chronic O3 exposure might have prevented the up-regulation of ET biosynthesis in clone 200. Blocking of ET perception with 1-methylcyclopropene protected both clones from the decrease in net photosynthesis during chronic exposure to O3. After a pretreatment with low O3 for 9 d, an acute 1.5-fold O3 elevation caused necrosis in the O3-sensitive clone 51, which increased substantially when ET perception was blocked. The results suggest that in hybrid aspen, ET signaling had a dual role depending on the severity of the stress. ET accelerated leaf senescence under low O3, but under acute O3 elevation, ET signaling seemed to be required for protection from necrotic cell death. PMID:12746525

  6. Catalytic performance of Fe3O4-CoO/Al2O3 catalyst in ozonation of 2-(2,4-dichlorophenoxy)propionic acid, nitrobenzene and oxalic acid in water.

    PubMed

    Tong, Shaoping; Shi, Rui; Zhang, Hua; Ma, Chunan

    2010-01-01

    Fe3O4-CoO/Al2O3 catalyst was prepared by incipient wetness impregnation using Fe(NO3)3 x 9H2O and Co(NO3)2 x 6H2O as the precursors, and its catalytic performance was investigated in ozonation of 2-(2,4-dichlorophenoxy)propionic acid (2,4-DP), nitrobenzene and oxalic acid. The experimental results indicated that Fe3O4-CoO/Al2O3 catalyst enabled an interesting improvement of ozonation efficiency during the degradation of each organic pollutant, and the Fe3O4-CoO/Al2O3 catalytic ozonation system followed a radical-type mechanism. The kinetics of ozonation alone and Fe3O4-CoO/Al2O3 catalytic ozonation of three organic pollutants in aqueous solution were discussed under the mere consideration of direct ozone reaction and OH radical reaction to well investigate its performance. In the catalytic ozonation of 2,4-DP, the apparent reaction rate constants (k) were determined to be 1.456 x 10(-2) min(-1) for ozonation alone and 4.740 x 10(-2) min(-1) for O3/Fe3O4-CoO/Al203. And O3/Fe3O4-CoO/Al2O3 had a larger R(ct) (6.614 x 10(-9)) calculated by the relative method than O3 did (1.800 x 10(-9)), showing O3/Fe3O4-CoO/Al2O3 generated more hydroxyl radical. Similar results were also obtained in the catalytic ozonation of nitrobenzene and oxalic acid. The above results demonstrated that the catalytic performance of Fe3O4-CoO/Al2O3 in ozonation of studied organic substance was universal to a certain degree. PMID:21235195

  7. Heterogeneous chemistry related to Antarctic ozone depletion: Reaction of ClONO2 and N2O5 on ice surfaces

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

    Laboratory studies of heterogeneous reactions of possible importance for Antarctic ozone depletion were performed. In particular, the reactions of chlorine nitrate (ClONO2) and dinitrogen pentoxide (N2O5) were investigated on ice and HCl/ice surfaces. These reactions occur on the surfaces of polar stratospheric clouds (PSCs) over Antarctica. One reaction transforms the stable chlorine reservoir species (ClONO2 and HCl) into photochemically active chlorine in the form of HOCl and Cl2. Condensation of HNO3 in the reactions removes odd nitrogen from the stratosphere, a requirement in nearly all models of Antarctic ozone depletion. Other reactions may also be important for Antarctic ozone depletion. Like the reactions of chlorine nitrate, these reactions deplete odd nitrogen through HNO3 condensation. In addition, one reaction converts a stable chlorine reservior species (HCl) into photochemically active chlorine (ClNO2). These reactions were studied with a modified version of a Knudsen cell flow reactor.

  8. Vertical distribution of ozone and nitrogenous pollutants in an air quality class I area, the San Gorgonio wilderness, southern California.

    PubMed

    Alonso, Rocío; Bytnerowicz, Andrzej; Arbaugh, Michael

    2002-01-01

    Information about spatial and temporal distribution of air pollutants is essential for better understanding of environmental stresses affecting forests and estimation of potential risks associated with air pollutants. Ozone and nitrogenous air pollutants were monitored along an elevation gradient in the Class I San Gorgonio Wilderness area (San Bernardino Mountains, California, U.S.) during the summer of 2000 (mid-June to mid-October). Passive samplers were exposed for 2-week periods at six sampling sites located at 300 m intervals ranging from 1200 to 2700 m elevation. Elevated concentrations of ozone were found in this area with summer 24-h hourly means ranging from 53 to 59 ppb. The highest ozone concentrations were detected in the period July 25-August 8, reaching values of 64 to 72 ppb expressed as 2-week mean. Passive-sampler ozone data did not show a clear relationship with elevation, although during the periods with higher ozone levels, ozone concentrations were higher at those sites below 2000 m than at sites located above that elevation. All nitrogenous pollutants studied showed a consistent decrease of concentrations with elevation. Nitrogen dioxide (NO2) levels were low, decreasing with increasing elevation from 6.4 to 1.5 ppb summer means. Nitric oxide (NO) concentrations were around 1 to 2 ppb, which is within the range of the detection levels of the devices used. Nitric acid (HNO3) vapor concentrations were lower at higher elevations (summer means 1.9-2.5 microg m(-3) than at lower elevations (summer means 4.3-5.1 microg m(-3). Summer concentrations of ammonia (NH3) were slightly higher than nitric acid ranging from 6 microg m(-3) at the lowest site to 2.5 microg m(-3) registered at the highest elevation. Since complex interactions between ozone and nitrogenous air pollutants have already been described for forests, simultaneous information about the distribution of these pollutants is needed. This is particularly important in mountain terrain where

  9. On the acidity of dew

    NASA Astrophysics Data System (ADS)

    Pierson, William R.; Brachaczek, Wanda W.; Gorse, Robert A.; Japar, Steven M.; Norbeck, Joseph M.

    1986-03-01

    Nightly dew samples were collected on Allegheny Mountain in southwest Pennsylvania in August 1983. The dew was found to be acidic, with mean pH˜4.0. Free H+ comprised >80% of the total acidity, and the composition approximated an H2SO4/HNO3 mixture with average SO42-/NO3- mol ratio ˜1.3. The chemistry of the dew resembled that of rain at Allegheny, though the dew was generally more dilute. Atmospheric HNO3(g) was chiefly responsible for the dew NO3-. SO2 was the source of ˜80% of the dew SO42-. The allocation of dew H+ among atmospheric precursors was HNO3˜30%, SO2 ≥ 60%, aerosol H+ ≤ 10%. The most acidic dews were associated with wind from the west. Average deposition velocities (stated in centimeters per second) to dew were HNO3, 0.24; NO2, <0.02 SO2, ˜0.04; aerosol SO42-, ˜0.02; aerosol NH4+, 0.024; and aerosol species, 0.02-1. Comparison of the HNO3 deposition velocity with ten-fold higher summer daytime values reveals a pronounced diurnal variation. The 0.24 cm/s value for HNO3 may represent a maximum for any gas or submicron aerosol species whenever the atmosphere is strongly stable. Not all of the S(IV) in dew had been converted to SO42- by morning; thus the rate of oxidation must have been on a time scale of hours at nighttime ambient temperatures. In contrast, S(IV) in rain and fog samples was not evident. Deposition fluxes and cumulative deposition totals involving dew, rain, and settled fog water were compared. Rain proved by far the most important for deposition of all solute species, including acid.

  10. Protective effect of Mn(III)-desferrioxamine B upon oxidative stress caused by ozone and acid rain in the Brazilian soybean cultivar Glycine max "Sambaiba".

    PubMed

    Esposito, Jéssica Bordotti Nobre; Esposito, Breno Pannia; Azevedo, Ricardo Antunes; Cruz, Luciano Soares; da Silva, Luzimar Campos; de Souza, Silvia Ribeiro

    2015-04-01

    This study aimed to investigate the effects of the Mn complex (Mn(III)-desferrioxamine B (MnDFB)) on oxidative stress in the Brazilian soybean cultivar Glycine max "Sambaiba" following exposure to ozone and acid rain. We determined the suitable dose of MnDFB to apply to G. max seedlings using a dose-response curve. The highest superoxide dismutase (SOD) activity and Mn content in leaves were found upon the application of 8 μM MnDFB. Thus, G. max seedlings pretreated with 8 μM MnDFB were individually exposed to ozone and acid rain simulated. Pretreatment with MnDFB reduced lipid peroxidation upon ozone exposure and increased SOD activity in leaves; it did not alter the metal content in any part of the plant. Conversely, following acid rain exposure, neither the metal content in leaves nor SOD enzyme activity were directly affected by MnDFB, unlike pH. Our findings demonstrated that exogenous MnDFB application before ozone exposure may modulate the MnSOD, Cu/ZnSOD, and FeSOD activities to combat the ROS excess in the cell. Here, we demonstrated that the applied dose of MnDFB enhances antioxidative defenses in soybean following exposure to acid rain and especially to ozone.

  11. Protective effect of Mn(III)-desferrioxamine B upon oxidative stress caused by ozone and acid rain in the Brazilian soybean cultivar Glycine max "Sambaiba".

    PubMed

    Esposito, Jéssica Bordotti Nobre; Esposito, Breno Pannia; Azevedo, Ricardo Antunes; Cruz, Luciano Soares; da Silva, Luzimar Campos; de Souza, Silvia Ribeiro

    2015-04-01

    This study aimed to investigate the effects of the Mn complex (Mn(III)-desferrioxamine B (MnDFB)) on oxidative stress in the Brazilian soybean cultivar Glycine max "Sambaiba" following exposure to ozone and acid rain. We determined the suitable dose of MnDFB to apply to G. max seedlings using a dose-response curve. The highest superoxide dismutase (SOD) activity and Mn content in leaves were found upon the application of 8 μM MnDFB. Thus, G. max seedlings pretreated with 8 μM MnDFB were individually exposed to ozone and acid rain simulated. Pretreatment with MnDFB reduced lipid peroxidation upon ozone exposure and increased SOD activity in leaves; it did not alter the metal content in any part of the plant. Conversely, following acid rain exposure, neither the metal content in leaves nor SOD enzyme activity were directly affected by MnDFB, unlike pH. Our findings demonstrated that exogenous MnDFB application before ozone exposure may modulate the MnSOD, Cu/ZnSOD, and FeSOD activities to combat the ROS excess in the cell. Here, we demonstrated that the applied dose of MnDFB enhances antioxidative defenses in soybean following exposure to acid rain and especially to ozone. PMID:25510614

  12. Effects of prolonged, sequential exposure to acid fog and ozone on pulmonary function in exercising, normal subjects. Final report, 28 Feb 89-28 Dec 90

    SciTech Connect

    Balmes, J.

    1990-05-01

    Thirty-nine apparently healthy and asymptomatic subjects were selected for a study that screened for sensitivity to ozone. After three hours of ozone exposure (at 0.20 ppm), eighteen of the subjects (46 percent) experienced a 10 percent reduction in forced expiratory volume, an indicator of exhaling ability. After four hours of exposure, 62 percent of the subjects experienced a similar reduction in expiratory volume. Further, narrowing of airways among the sensitive subjects was suggested by results of the methacholine challenge test, a standard test for measuring airway resistance. The lung capacity of all subjects decreased progressively during ozone exposures. Capacity was unchanged during acidic fog and pollutant-free air exposures. No statistically significant differences in airway resistance, airway responsiveness and symptoms that could be attributed to acid fog exposure were observed. The study indicates that exposue to fog containing nitric acid followed by exposure to ozone does not have additive or synergistic acute effects. However, the study confirms earlier indications that many apparently healthy and asymptomatic individuals are susceptible to and adversely affected by ozone at relatively low concentrations.

  13. Ground-based intercomparison of nitric acid measurement techniques

    NASA Astrophysics Data System (ADS)

    Fehsenfeld, Fred C.; Huey, L. Greg; Sueper, Donna T.; Norton, Richard B.; Williams, Eric J.; Eisele, Fred L.; Mauldin, R. Lee; Tanner, David J.

    1998-02-01

    An informal intercomparison of gas-phase nitric acid (HNO3) measuring techniques was carried out. The intercomparison involved two new chemical ionization mass spectrometers (CIMSs) that have been developed for the measurement of HNO3 along with an older, more established filter pack (FP) technique. The filter pack was composed of a teflon prefilter which collected aerosols followed by a nylon filter which collected the gas-phase HNO3. The study was carried out during the late winter and early spring of 1996 at a site located on the western edge of the Denver metropolitan area. Throughout the study the two CIMS techniques were in general agreement. However, under certain conditions the HNO3 levels obtained from the nylon filter of the FP gave values for the gas-phase concentration of HNO3 that were somewhat higher than that recorded by the two CIMS systems. The formation of ammonium nitrate (NH4NO3) containing aerosols is common during the colder months in this area. An analysis of these results suggests that the HNO3 collected by the nylon filter in the FP suffers an interference associated with the disproportionation of NH4NO3 from aerosols containing that compound that were initially collected on the teflon prefilter. This problem with the FP technique has been suggested from results obtained in previous intercomparisons.

  14. The role of EPA`s Acid Rain Division in the Ozone Transport Commission`s NOx budget program

    SciTech Connect

    Schary, C.; Culligan, K.

    1997-12-31

    The Ozone Transport Commission`s (OTC) Nitrogen Oxides (NO{sub x}) Budget Program will implement the emissions reduction goal of the 1994 Memorandum of Understanding between its twelve member states and the District of Columbia. The program will achieve its significant NO{sub x} reductions from electric utilities and industrial boilers using a {open_quotes}cap-and-trade{close_quotes} approach modeled after the US Environmental Protection Agency`s sulfur dioxide emissions trading under the Acid Rain Program. The similarity of the two programs has led to the development of an important partnership between the OTC states and EPA`s Acid Rain Division, Over the past two years, Acid Rain Program staff have shared their technical expertise and assisted extensively in the development of the program`s rules. Leveraging the investment EPA made in the systems used to run the Acid Rain Program, the OTC states have asked the Acid Rain Division to administer the data systems for them, and together are working to expand its existing Emissions Tracking System and to modify a clone of the sulfur dioxide Allowance Tracking System, to fulfill the unique requirements of the NO{sub x} Budget Program. This partnership is an important example of the new type of cooperation and sharing of expertise and resources that should develop between EPA and states as they launch multi-state programs to address regional pollution problems that defy a single-state solution.

  15. The role of isoprene oxidation in the tropospheric ozone budget in the tropics

    NASA Technical Reports Server (NTRS)

    Brewer, D. A.; Levine, J. S.

    1985-01-01

    A comprehensive chemical mechanism for the oxidation of isoprene (a hydrocarbon, C5H8 emitted primarily by vegetation) by OH and O3 in the troposphere was developed and incorporated into a one-dimensional steady-state photochemical model of the troposphere. Flux boundary conditions for NOx (NO + NO2), HNO3, O3, and CO were used to investigate the changes produced in the tropospheric concentrations and integrated column of ozone from including isoprene chemistry in the model. Two calculations were performed at 15 deg N latitude for annual conditions using identical flux boundary conditions for NOx, HNO3, O3, and CO; in one calculation, the chemistry describing isoprene oxidation was included while in the other it was not. Both sets of calculations included reactions describing the chemistry of anthropogenic nonmethane hydrocarbons. The calculations showed decreases in concentrations of ozone throughout the troposphere when isoprene chemistry was included. Concentrations of NOx and HNO3 increased in the lower troposphere and decreased in the upper troposphere while concentrations of CO and PAN increased throughout the troposphere when isoprene chemistry was included. Implications of this study to the budgets of these species in the tropics is discussed.

  16. Stratospheric ozone isotope enrichment studied by submillimeter-wave heterodyne radiometry

    NASA Astrophysics Data System (ADS)

    Kasai, Y.; Urban, J.; Takahashi, K.; JEM/SMILES Science-Team,

    2002-05-01

    Since the discovery of the heavy isotope enrichment of ozone formation in the stratosphere in 1981, considerable progress has been made in understanding the processes that control the isotope enrichment by using mass spectrometry, spectrometric techniques, laboratory measurements, and so on. The detection limit of the mass spectrometers is enough to discuss these isotope enrichments, but symmetric and asymmetric ozone isotopes cannot be distinguished. It is important to observe symmetric and asymmetric ozone isotopes separately with enough accuracy to understand the mechanism of the ozone isotope enrichment for the ozone formation chemistry. Measurements of the ozone isotopes using a new technology of he superconducting submillimeter-wave limb emission spectrometer (SMILES) have been proposed. The instrument is planned to be aboard the Japanese Experiment Module (JEM) at the International Space Station. The SMILES instrument is planned to be launched in 2006. The SMILES instrument measures thermal emissions from ozone isotopes as well as ozone-depletion-related molecules such as ClO, HCl, HO2, HNO3 and BrO in the frequency bands at 624.32-626.32 GHz and 649.12-650.32 GHz. Overview of this experiment, such as new techniques for a high-sensitive sounding, measurement coverage, measurement frequency, is described. The scientific objective of the SMILES experiment, including a brief review on the controversial problem of stratospheric ozone isotope anomaly, is presented. The error analysis of the SMILES measurement is evaluated by using the SMILES simulator for all 5 isotopes of normal ozone, asymmetric-17-ozone, asymmetric-18-ozone, symmetric-17-ozone, symmetric-18-ozone. The evaluation suggests that the global distributions of symmetric-17-ozone, asymmetric-18-ozone, symmetric-17-ozone, as well as normal ozone can be obtained from the single profile, with the errors of less than about 1 % between 20 and 40 km with the partial column about 5 km.

  17. Nitric acid photolysis on surfaces in low-NOx environments: Significant atmospheric implications

    NASA Astrophysics Data System (ADS)

    Zhou, Xianliang; Gao, Honglian; He, Yi; Huang, Gu; Bertman, Steven B.; Civerolo, Kevin; Schwab, James

    2003-12-01

    Nitric acid (HNO3) is the dominant end product of NOx (= NO + NO2) oxidation in the troposphere, and its dry deposition is considered to be a major removal pathway for the atmospheric reactive nitrogen. Here we present both field and laboratory results to demonstrate that HNO3 deposited on ground and vegetation surfaces may undergo effective photolysis to form HONO and NOx, 1-2 orders of magnitude faster than in the gas phase and aqueous phase. With this enhanced rate, HNO3 photolysis on surfaces may significantly impact the chemistry of the overlying atmospheric boundary layer in remote low-NOx regions via the emission of HONO as a radical precursor and the recycling of HNO3 deposited on ground surfaces back to NOx.

  18. A Three-Tier Diagnostic Test to Assess Pre-Service Teachers' Misconceptions about Global Warming, Greenhouse Effect, Ozone Layer Depletion, and Acid Rain

    ERIC Educational Resources Information Center

    Arslan, Harika Ozge; Cigdemoglu, Ceyhan; Moseley, Christine

    2012-01-01

    This study describes the development and validation of a three-tier multiple-choice diagnostic test, the atmosphere-related environmental problems diagnostic test (AREPDiT), to reveal common misconceptions of global warming (GW), greenhouse effect (GE), ozone layer depletion (OLD), and acid rain (AR). The development of a two-tier diagnostic test…

  19. Re-evaluating the role of phenolic glycosides and ascorbic acid in ozone scavenging in the leaf apoplast of Arabidopsis thaliana L

    Technology Transfer Automated Retrieval System (TEKTRAN)

    To determine if membrane-bound G-proteins are involved in the regulation of defense responses against ozone in the leaf apoplast, the apoplastic concentrations of ascorbic acid and phenolic glycosides in Arabidopsis thaliana L. lines with null mutations in the alpha- and beta-subunits were compared ...

  20. An outbreak of illness after occupational exposure to ozone and acid chlorides.

    PubMed Central

    Ng, T P; Tsin, T W; O'Kelly, F J

    1985-01-01

    New labelling processes installed without adequate ventilation control in an electric motor factory exposed production line workers to toxic gases. Symptoms of eye and respiratory tract irritation together with complaints of headache, fever, chills, dizziness, malaise, general weakness, nausea, and vomiting were widespread. Chest signs, radiographic abnormalities, reduction in ventilatory function, and blood gas abnormalities were found in some cases. Epidemiological analysis of the spatial and temporal distribution of cases supported an exposure effect relationship. Investigations suggested ozone and possibly phosgene and associated trichloroacetyl chlorides as the toxic agents that were generated by an ultraviolet print curing arrangement and perchloroethylene used as a cleaning solvent. PMID:4041387

  1. Formation of water-soluble dicarboxylic acids, oxoacids and a-dicarbonyls by ozone oxidation of isoprene

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Tachibana, E.; Sakamoto, Y.; Hirokawa, J.

    2014-12-01

    Water-soluble dicarboxylic acids such as oxalic acid (C2) are the dominant organic compound class in atmospheric aerosols. They can act as cloud condensation nuclei and affect on the Earth climate. Diacids can be primary emitted from fossil fuel combustion and biomass burning and secondarily produced by photochemical oxidations of biogenic and anthropogenic hydrocarbons. However, their sources and formation processes are still not well understood. Recently model and observation studies suggested the importance of isoprene as a precursor of oxalic acid. Isoprene is the most abundant BVOC emitted from terrestrial plants and can serve as important precursors of diacids. We conducted a laboratory oxidation of isoprene (2.0 ppm) with ozone (4.3 ppm) in a Teflon bag for 10 to 480 min. The formed particles were collected with quartz fiber filters and analyzed for diacids, oxoacids and a-dicarbonyls employing water extraction and butyl ester derivatization and using GC and GC/MS techniques. Here, we report the analytical results to better understand the formation process of diacids and related compounds from isoprene. We detected homologous series of saturated diacids (C2-C6), unsaturated diacids (maleic and methylmaleic acids), w-oxocarboxylic acids (C2-C9), pyruvic acid, glyoxal and methylglyoxal. We found that oxalic acid (3000-9700 ngm-3) is the most abundant diacid followed by succinic (C4) or malonic (C3) acid. Their concentrations increased with reaction time showing a maximum in 4 hours. Interestingly, C3/C4 ratios increased with time. The second most abundant species after oxalic acid was generally methylglyoxal (3600-9600 ngm-3), except for the 30 min. sample where methylglyoxal was more abundant than oxalic acid. Glyoxylic acid (wC2) was found as the most abundant oxoacid (1600-3800 ngm-3) followed by wC3 and wC4. Although the concentrations of diacids and related compounds are 1-2 orders magnitude higher than those reported in ambient aerosols, this study

  2. Strong wintertime ozone events in the Upper Green River basin, Wyoming

    NASA Astrophysics Data System (ADS)

    Rappenglück, B.; Ackermann, L.; Alvarez, S.; Golovko, J.; Buhr, M.; Field, R. A.; Soltis, J.; Montague, D. C.; Hauze, B.; Adamson, S.; Risch, D.; Wilkerson, G.; Bush, D.; Stoeckenius, T.; Keslar, C.

    2014-05-01

    During recent years, elevated ozone (O3) values have been observed repeatedly in the Upper Green River basin (UGRB), Wyoming, during wintertime. This paper presents an analysis of high ozone days in late winter 2011 (1 h average up to 166 ppbv - parts per billion by volume). Intensive operational periods (IOPs) of ambient monitoring were performed, which included comprehensive surface and boundary layer measurements. On IOP days, maximum O3 values are restricted to a very shallow surface layer. Low wind speeds in combination with low mixing layer heights (~ 50 m above ground level around noontime) are essential for accumulation of pollutants within the UGRB. Air masses contain substantial amounts of reactive nitrogen (NOx) and non-methane hydrocarbons (NMHC) emitted from fossil fuel exploration activities in the Pinedale Anticline. On IOP days particularly in the morning hours, reactive nitrogen (up to 69%), aromatics and alkanes (~ 10-15%; mostly ethane and propane) are major contributors to the hydroxyl (OH) reactivity. Measurements at the Boulder monitoring site during these time periods under SW wind flow conditions show the lowest NMHC / NOx ratios (~ 50), reflecting a relatively low reactive NMHC mixture, and a change from a NOx-limited regime towards a NMHC-limited regime as indicated by photochemical indicators, e.g., O3 /NOy, O3 /NOz, and O3 / HNO3 and the EOR (extent of reaction). OH production on IOP days is mainly due to nitrous acid (HONO). On a 24 h basis and as determined for a measurement height of 1.80 m above the surface HONO photolysis on IOP days can contribute ~ 83% to OH production on average, followed by alkene ozonolysis (~ 9%). Photolysis by ozone and HCHO photolysis contribute about 4% each to hydroxyl formation. High HONO levels (maximum hourly median on IOP days: 1096 pptv - parts per trillion by volume) are favored by a combination of shallow boundary layer conditions and enhanced photolysis rates due to the high albedo of the snow

  3. Does Nitric Acid Dissociate at the Aqueous Solution Surface?

    SciTech Connect

    Lewis, Tanza; Winter, Berndt; Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J.; Tobias, Douglas J.; Hemminger, J. C.

    2011-11-03

    Nitric acid is a prevalent component of atmospheric aerosols, and the extent of nitric acid dissociation at aqueous interfaces is relevant to its role in heterogeneous atmospheric chemistry. Several experimental and theoretical studies have suggested that the extent of dissociation of nitric acid near aqueous interfaces is less than in bulk solution. Here, dissociation of HNO3 at the surface of aqueous nitric acid is quantified using X-ray photoelectron spectroscopy of the nitrogen local electronic structure. The relative amounts of undissociated HNO3(aq) and dissociated NO3-(aq) are identified by the distinguishable N1s core-level photoelectron spectra of the two species, and we determine the degree of dissociation, αint, in the interface (the first ~3 layers of solution) as a function of HNO3 concentration. Our measurements show that dissociation is decreased by approximately 20% near the solution interface compared with bulk, and furthermore that dissociation occurs even in the top-most solution layer. The experimental results are supported by first-principles MD simulations, which show that hydrogen-bonds between HNO3 and water molecules at the solution surface stabilize the molecular form at low concentration, in analogy to the stabilization of molecular HNO3 that occurs in bulk solution at high concentration. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.

  4. Microbial evolution during storage of seasoned olives prepared with organic acids with potassium sorbate, sodium benzoate, and ozone used as preservatives.

    PubMed

    Arroyo López, F N; Durán Quintana, M C; Garrido Fernández, A

    2006-06-01

    The effect of potassium sorbate, sodium benzoate, and ozone in combination with citric, lactic, and acetic acids on the microbial population of seasoned table olives of the olive 'Aloreña' cultivar was studied in both fresh (FF) and stored fruits (SF). The inactivation/growth curves were modeled and the biological parameters estimated, with yeast used as the target microorganism. Regardless of the acid added, potassium sorbate showed a general inactivation effect on yeasts in the products prepared from both FF and SE Sodium benzoate had a rapid inactivation effect with FF, but with SF, it was effective only in the presence of acetic acid. A strain of Issatchenkia occidentalis was found that was resistant to the combination of this preservative with citric or lactic acids. In FF, ozone showed an initial marked inhibition against yeasts, but later, yeasts were again able to grow. In SF, ozone was a strong inactivating agent when it replaced any of the traditional preservatives. Lactic acid bacteria were always absent in products prepared from FF, and apparently were not affected by the different preservative agents in those prepared from SF. The behavior of yeasts and lactic acid bacteria populations in commercial products were similar to those found in experimental treatments.

  5. Ozonation of Canadian Athabasca asphaltene

    NASA Astrophysics Data System (ADS)

    Cha, Zhixiong

    Application of ozonation in the petrochemical industry for heavy hydrocarbon upgrading has not been sufficiently explored. Among heavy hydrocarbons, asphaltenes are the heaviest and the most difficult fractions for analysis and treatment. Therefore, ozonation of asphaltenes presents an interesting application in the petrochemical industry. Commercial application of ozonation in the petrochemical industry has three obstacles: availability of an ozone-resistant and environmentally friendly solvent, the precipitation of ozonation intermediates during reaction, and recovery of the solvent and separation of the ozonation products. Preliminary ozonation of Athabasca oil sands asphaltene in nonparticipating solvents encountered serious precipitation of the ozonation intermediates. The precipitated intermediates could be polymeric ozonides and intermolecular ozonides or polymeric peroxides. Because the inhomogeneous reaction medium caused low ozone efficiency, various participating solvents such as methanol and acetic acid were added to form more soluble hydroperoxides. The mass balance results showed that on average, one asphaltene molecule reacted with 12 ozone molecules through the electrophilic reaction and the subsequent decomposition of ozonation intermediates generated acetone extractable products. GC/MS analysis of these compounds indicated that the free radical reactions could be important for generation of volatile products. The extensively ozonated asphaltene in the presence of participating solvents were refluxed with methanol to generate more volatile products. GC/MS analysis of the methanol-esterified ozonation products indicated that most volatile products were aliphatic carboxylic acid esters generated through cleavage of substituents. Reaction kinetics study showed that asphaltene ozonation was initially a diffusion rate-controlled reaction and later developed to a chemical reaction rate-controlled reaction after depletion of the reactive aromatic sites

  6. A comparative study on the effectiveness of ozonated water and peracetic acid in the storability of packaged fresh-cut melon.

    PubMed

    Botondi, Rinaldo; Moscetti, Roberto; Massantini, Riccardo

    2016-05-01

    Ozonated water and peracetic acid were tested as sanitizers to enhance the storability of fresh-cut melon cubes. Sanitizers were also combined with suitable packaging materials (polypropylene and polylactic acid based plastic films). Fresh-cut melon cubes were stored at 4 °C for up to 7 days. Ozonated water and peracetic acid treatments were given by dipping cubes into 0.8 ppm O3 and 100 ppm Tsunami 100™ solutions, respectively, for 3 min. Both sanitizers exhibited efficiency in reducing the total microbial counts on melon cubes (< 2 log CFU g(-1)). Respiratory activity and ethylene production were both affected by the interaction between the sanitizer and the packaging used. Carbon dioxide and oxygen reached 9.89 kPa and 12.20 kPa partial pressures, respectively, using peracetic acid treatment in combination with polypropylene film packaging, consequently developing off-odors starting from day 3. Strong color changes were noted in cubes stored in polylactic acid packaging after 7 days of storage, affecting the sensory quality of the melon cubes. Sensory evaluation (overall visual quality) indicated loss in flavor in the polypropylene packaging. The overall visual quality started to decline on 3rd day because of the development of translucency.Overall, the use of ozone in combination with polypropylene packaging provided the best solution to maintain the quality of melon cubes for up to 5 days of storage at 4 °C. PMID:27407201

  7. A comparative study on the effectiveness of ozonated water and peracetic acid in the storability of packaged fresh-cut melon.

    PubMed

    Botondi, Rinaldo; Moscetti, Roberto; Massantini, Riccardo

    2016-05-01

    Ozonated water and peracetic acid were tested as sanitizers to enhance the storability of fresh-cut melon cubes. Sanitizers were also combined with suitable packaging materials (polypropylene and polylactic acid based plastic films). Fresh-cut melon cubes were stored at 4 °C for up to 7 days. Ozonated water and peracetic acid treatments were given by dipping cubes into 0.8 ppm O3 and 100 ppm Tsunami 100™ solutions, respectively, for 3 min. Both sanitizers exhibited efficiency in reducing the total microbial counts on melon cubes (< 2 log CFU g(-1)). Respiratory activity and ethylene production were both affected by the interaction between the sanitizer and the packaging used. Carbon dioxide and oxygen reached 9.89 kPa and 12.20 kPa partial pressures, respectively, using peracetic acid treatment in combination with polypropylene film packaging, consequently developing off-odors starting from day 3. Strong color changes were noted in cubes stored in polylactic acid packaging after 7 days of storage, affecting the sensory quality of the melon cubes. Sensory evaluation (overall visual quality) indicated loss in flavor in the polypropylene packaging. The overall visual quality started to decline on 3rd day because of the development of translucency.Overall, the use of ozone in combination with polypropylene packaging provided the best solution to maintain the quality of melon cubes for up to 5 days of storage at 4 °C.

  8. Prediction of naphthenic acid species degradation by kinetic and surrogate models during the ozonation of oil sands process-affected water.

    PubMed

    Islam, Md Shahinoor; Moreira, Jesús; Chelme-Ayala, Pamela; Gamal El-Din, Mohamed

    2014-09-15

    Oil sands process-affected water (OSPW) is a complex mixture of organic and inorganic contaminants, and suspended solids, generated by the oil sands industry during the bitumen extraction process. OSPW contains a large number of structurally diverse organic compounds, and due to variability of the water quality of different OSPW matrices, there is a need to select a group of easily measured surrogate parameters for monitoring and treatment process control. In this study, kinetic and surrogate correlation models were developed to predict the degradation of naphthenic acids (NAs) species during the ozonation of OSPW. Additionally, the speciation and distribution of classical and oxidized NA species in raw and ozonated OSPW were also examined. The structure-reactivity of NA species indicated that the reactivity of individual NA species increased as the carbon and hydrogen deficiency numbers increased. The kinetic parameters obtained in this study allowed calculating the evolution of the concentrations of the acid-extractable fraction (AEF), chemical oxygen demand (COD), and NA distributions for a given ozonation process. High correlations between the AEF and COD and NA species were found, suggesting that AEF and COD can be used as surrogate parameters to predict the degradation of NAs during the ozonation of OSPW.

  9. 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.

  10. Combined effects of ozone and nitrogen on secondary compounds, amino acids, and aphid performance in Scots pine

    SciTech Connect

    Kainulainen, P.; Holopainen, J.K.; Holopainen, T.

    2000-02-01

    Combined effects of O{sub 3} and N supply on Scots pine (Pinus sylvestris L.) were studied in two separate growth chamber experiments exposing seedlings to 0, 0.075, 0.15, and 0.3 {micro}L/L of O{sub 3} during 8 h/d, 5 d/wk for a period of 5 wk. Seedlings were fertilized with low, medium, and high levels of N. Ozone and N availability affected concentrations of several primary and secondary metabolites. More changes on metabolites were detected in Exp. 1 (with seedlings ceasing their annual growth) than in Exp. 2 (with seedlings actively growing). Overall, high O{sub 3} exposure levels significantly decreased concentrations of monoterpenes and increased concentrations of resin acids. Concentrations of total phenolics were not affected by O{sub 3} exposure. Mostly lower concentrations of monoterpenes and resin acids were found at a medium N-fertilization level than at low and high N-fertilization levels, while total phenolic concentration decreased by enhanced N availability. In Exp. 1, significantly elevated concentrations of free amino acids were found at O{sub 3} concentration of 0.3 {micro}L/L. Nitrogen availability did not have remarkable effects on amino acid concentrations. In Exp. 1, both {sub 3} and N had a significant effect on the MRGR of the aphid Schizolachnus pineti. In Exp. 2, the weight of the females and nymphs and the total number of reproduced nymphs were significantly affected by O{sub 3} and N. Only a few interaction effects were found, suggesting that the N supply does not significantly modify O{sub 3}-induced effects on studied primary and secondary compounds and aphid performance in Scots pine seedlings.

  11. Experimental Study on How Human Lung Surfactant Protein SP-B1-25 is Oxidized by Ozone in the Presence of Fe(II) and Ascorbic Acid

    NASA Astrophysics Data System (ADS)

    Colussi, A. J.; Enami, S.; Hoffmann, M. R.

    2014-12-01

    We will report the results of experiments on the chemical fate of the human lung surfactant protein SP-B1-25 upon exposure to gaseous ozone in realistic aqueous media simulating the conditions prevalent in epithelial lining fluids in polluted ambient air. Our experiments consist of exposing aqueous microjets containing SP-B1-25, the natural antioxidant ascorbic acid, and the Fe2+ carried by most atmospheric fine particulates, under mild acidic conditions, such as those created by the innate lung host defense response. Reactants and the products of such interactions are detected via online electrospray ionization mass spectrometry. We will show that ascorbic acid largely inhibits the ozonation of SP-B1-25 in the absence of Fe2+, leading to the formation of an ascorbic acid ozonide (Enami et al., PNAS 2008). In the presence of Fe2+, however, the ozonide decomposes into reactive intermediates that result in the partial oxidation of SP-B1-25, presumable affecting its function as surfactant. We infer that these experimental results establish a plausible causal link for the observed synergic adverse health effects of ambient ozone and fine particulates

  12. 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.

  13. 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

    Todd T. Nichols; Dean D. Taylor

    2003-09-01

    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.

  14. 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.

  15. Design considerations for ozone and acid-aerosol exposure and health investigations: the Fairview Lake Summer Camp - photochemical smog case study

    SciTech Connect

    Lioy, P.J.; Spektor, D.; Thurston, G.; Citak, K.; Lippmann, M.

    1987-01-01

    The health effects associated with ozone and acidic particulate sulfate exposures to active children have been and are being addressed in field epidemiological studies at summer camps in rural areas of the Northeastern U.S. The rationale and study design for studies, which have been conducted in Pennsylvania and New Jersey, are developed and reviewed. As background, results are summarized for human clinical and epidemiological studies and animal studies. These provided the basis for selection of health outcomes. Measured results from chemical characterization and transport studies are reviewed to define the criteria used for selection of a site affected by high ozone and acid species during photochemical smog episodes. The integration of the study design is discussed in detail by reviewing its application to the 1984 - Fairview Lake Camp Study (July 8 to August 4). The features of the camp study are reviewed, including the study population, pulmonary function procedures and analyses, air pollution monitoring instrumentation, and the site characteristics.

  16. Vitamin C, uric acid, and glutathione gradients in murine stratum corneum and their susceptibility to ozone exposure.

    PubMed

    Weber, S U; Thiele, J J; Cross, C E; Packer, L

    1999-12-01

    The stratum corneum has been recognized as the main cutaneous oxidation target of atmospheric ozone (O3), a major part of photochemical smog. This study reports the presence and distribution of vitamin C, glutathione, and uric acid in murine stratum corneum, and evaluates their susceptibility to acute environmental exposure to O3. Based on tape stripping and a modified extraction method with high performance liquid chromatography electrochemical analysis, we detected vitamin C (208.0 +/- 82.5 pmol per 10 consecutive pooled tapes), glutathione (283.7 +/-96.3), and uric acid (286.4 +/-47.1) in murine stratum corneum as compared with only 16.5 +/- 1.4 pmol alpha-tocopherol. Vitamin C, glutathione (both p < 00.001), and urate (p < 0.01) were found to exhibit a gradient with the lowest concentrations in the outer layers and a steep increase in the deeper layers. To investigate the effect of O3 exposure on hydrophilic antioxidants, we exposed SKH-1 hairless mice to O3 concentrations of 0, 0.8, 1, and 10 p.p.m., and stratum corneum was analyzed before and after exposure. Whereas mock exposure with 0 p.p. m. for 2 h had no significant effect, O3 doses of 1 p.p.m. for 2 h and above showed depletion of all three antioxidants. Vitamin C was decreased to 80% +/- 15% of its pretreatment content (p < 0.05), GSH to 41% +/- 24% (p < 0.01), and uric acid to 44% +/- 28% (p < 0.01). This report demonstrates the previously unrecognized role of hydrophilic antioxidants in the stratum corneum and provides further evidence that O3 induces oxidative stress in this outer skin layer.

  17. a Microwave and AB Initio Study of the Nitric Acid - Trimethylamine Complex

    NASA Astrophysics Data System (ADS)

    Sedo, Galen; Leopold, Kenneth R.

    2009-06-01

    The microwave spectrum of the gas phase nitric acid - trimethylamine complex has been observed using Fourier transform microwave spectroscopy. The experimental rotational constants and (CH{_3}){_3}{^1}{^5}N-HNO{_3} isotope shifts are consistent with a complex in which the nitric acid proton forms a hydrogen bond to the nitrogen of the amine, similar to the experimentally determined structure of H{_3}N-HNO{_3} Analysis of the hyperfine structure in both the parent and (CH{_3}){_3}{^1}{^5}N-HNO{_3} spectra made it possible to determine, unambiguously, the quadrupole coupling constants of the {^1}{^5}N nuclei in both the nitric acid and trimethylamine moieties. Ab initio calculations, using the MP2/6-311++G(2df,2pd) level of theory and basis set, have been performed and are in quantitative agreement with the available experimental data. Both the experimentally determined quadrupole coupling constants and the ab initio structure have been used to assess the degree of proton transfer occurring in the nitric acid - trimethylamine complex. These results will be compared to those obtained for the H{_3}N-HNO{_3} and HNO{_3}-(H{_2}O){_n} [n = 0 - 3] complexes and discussed in terms of how binding partner basicity and the number of solvent molecules influence the incipient ionization of nitric acid moiety. M. E. Ott, and K. R. Leopold, J. Phys. Chem. A 1999, 103,1322-1328.

  18. Ozone and simulated acid rain effects on growth root hydraulic conductivity, and photosynthesis of red spruce

    SciTech Connect

    Lee, W.S.; Chevone, B.I.; Seiler, J.R.

    1987-04-01

    Three-year-old red spruce seedlings were exposed to ozone (O/sub 3/) at 0.00 (control) or 0.10 ppm, 4 hr/d, 3 d/wk in combination with simulated rain (pH 3.0 or 5.6, 1 hr/d, 2 d/wk at 0.75 cm/hr) for 10 wks. All seedlings were submitted to two drought cycles after the 10-wk-treatment. O/sub 3/ significantly decreased root hydraulic conductivity (Lp) by 21% after 10 wks across all rain pHs. The reduction of Lp in seedlings treated with O/sub 3/ was enhanced by drought stress. Rain pH alone did not affect Lp during the 10-wks-exposure and drought cycles. However, the O/sub 3/ effect on Lp was more severe at pH 5.6 than at pH 3.0. Rain at pH 3.0 stimulated shoot height growth by 31% compared with pH 5.6 across all O/sub 3/ treatments. However, root, shoot, and total dry weight of seedlings were not changed by any treatments. Neither O/sub 3/ nor rain pH affected net photosynthetic (P/sub i/) response to branch water potential in plants subjected to one or two drought cycles. However, P/sub i/ was less sensitive to water potential after two drought cycles, indicating physiological adjustment to drought stress.

  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.

  20. 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

  1. 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'.

  2. Hydrofluoric and nitric acid transport through lipid bilayer membranes.

    PubMed

    Gutknecht, J; Walter, A

    1981-06-01

    Hydrofluoric and nitric acid transport through lipid bilayer membranes were studied by a combination of electrical conductance and pH electrode techniques. Transport occurs primarily by nonionic diffusion of molecular HF and HNO3. Membrane permeabilities to HF and HNO3 ranged from 10(-4) to 10(-3) cm . s-1, five to seven orders of magnitude higher than the permeabilities to NO-3, F- and H+. Our results are consistent with the hypothesis that F- transport through biological membranes occurs mainly by nonionic diffusion of HF. Our results also suggest that of the two principal components of 'acid rain', HNO3 may be more toxic than H2SO4.

  3. Direct ab initio dynamics calculations for rates and the kinetic isotope effects of multiproton transfer in ClONO2 + HCl --> HNO3 + Cl2 reactions with water clusters: breakdown of the rule of the geometric mean.

    PubMed

    Nam, Kikyung; Kim, Yongho

    2009-04-14

    We performed high-level quantum mechanical calculations and direct ab initio reaction dynamics calculations for multiple proton transfers in ClONO(2)+HCl-->HNO(3)+Cl(2) with water clusters containing one to two water molecules, which can be used as a model of the reactions occurring on ice surface in stratospheric clouds. The energy barriers of these reactions depend on the number of water molecules involved. Two and three protons in these reactions with one and two water molecules, respectively, were transferred concertedly and asynchronously. The potential energy barrier at the MP2/6-311++(3df,3pd)//MP2/6-31G(d,p) level was 4.8 kcal/mol for the triple proton transfer involving two water molecules with a rate constant of 1.6x10(3) s(-1) at 197 K. The potential energy curve near the saddle points was very flat and the tunneling effect on the proton transfer was negligible. The primary HH/DH kinetic isotope effect for the double proton transfer involving one water molecule was lower than unity due to the enhanced force constant at the transition state. The rule of the geometric mean for the concerted proton transfer does not hold in these reactions because the zero-point energy changes of each proton in flight at the transition state are not the same in the highly asynchronous processes.

  4. 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.

  5. Effects of depletion of ascorbic acid or nonprotein sulfhydryls on the acute inhalation toxicity of nitrogen dioxide, ozone, and phosgene

    SciTech Connect

    Slade, R.; Highfill, J.W.; Hatch, G.E.

    1989-01-01

    The effect of depleting lung ascorbic acid (AH{sub 2}) and nonprotein sulfhydryls (NPSH) on the acute inhalation toxicity of nitrogen dioxide (NO{sub 2}), ozone (O{sub 3}), and phosgene (COCl{sub 2}) was investigated in guinea pigs. The increase in bronchoalveolar lavage (BAL) fluid protein (an indicator of alveolar-capillary damage leading to increased permeability) was measured 16 to 18 hr following a 4 hr exposure to the gas in animals deficient in (AH{sub 2}) or NPSH. Gas concentrations were chosen which produced low but significant increases in BAL protein. Lung (AH{sub 2}) was lowered to about 20% of control by feeding rabbit chow for 2 weeks. Lung NPSH was lowered to about 50% of control by injecting a mixture of buthionine S,R-sulfoximine (BSO) and diethylmaleate (DEM) (2.7 and 1.2 mmol/kg respectively). BSO/DEM did not affect the lung concentrations of (AH{sub 2}) or alpha-tocopherol. AH{sub 2} depletion caused a 6 fold and a 3 fold enhancement in the toxicity of 5 ppm and 10 ppm (NO{sub 2}), and a 6 fold enhancement in the toxicity of 0.5 ppm (O{sub 3}), but did not affect toxicity of 1.0 ppm (O{sub 3}). AH{sub 2} depletion did not affect phosgene toxicity (at 0.25 ppm and 0.5 ppm).

  6. Use of a non-linear model in examining growth responses of loblolly pine to ozone and acid precipitation

    NASA Astrophysics Data System (ADS)

    Somerville, Matthew C.; Shadwick, Douglas S.; Meldahl, Ralph S.; Chappelka, Arthur H.; Lockaby, B. Graeme

    Monthly diameter 2 × height ( d 2h ) data were measured over two years in open-top chambers at Auburn University, Alabama. This study exposed seedlings from two half-sibling loblolly pine ( Pinus taeda L.) families to ozone and acid precipitation treatments. For these data, the accumulation of d 2h ) by individual trees over two years was efficiently represented by a six-parameter non-linear model of ln ( d 2h ) as a function of time. Multivariate analysis of variance using these six estimated parameters for each seedling resulted in greater sensitivity to treatment differences as measured by tests of hypotheses than did analysis of covariance on ln (final d 2h ). This result illustrates the importance of utilizing appropriate analyses that can bring as much of the data as is possible to bear on the question at hand. A test for additional information indicated that five of the six parameters contributed important information concerning treatment differences for at least one of the two families tested. It may be inferred that the treatments have an important effect on the nature of d 2h accumulation within a growing season as well as on the d 2h at the end of the growing season.

  7. Effect of chronic exposure to ozone and nitric acid on cytochrome P450 monooxygenase system of rat lung and liver

    SciTech Connect

    Sindhu, R.K.; Mautz, W.J.; Ichiro Fujita, Nai-San Wang; Yutaka, Kikkawa

    1996-03-08

    Male F344/N rats were exposed to 0.15ppm ozone (O{sub 3}) and 50{mu}g/m{sup 3} nitric acid (HNO{sub 3}) vapor alone and in combination for 4h/day 3days/week for a total of 40 weeks. Exposure to HNO{sub 3} vapor alone caused a significant increase of 7-ethoxyresorufin O-deethylase (EROD) activity in the hepatic microsomes (p{le}0.05). Monoclonal cytochrome P450 aA1/1A2 antibody-precipitable EROD activity in the hepatic microsomes was increased by 59% (p{le}0.01) and 40T (p{le}0.05), respectively, in the HNO{sub 3} vapor and {sub 3}+HNO{sub 3} vapor groups. In the pulmonary microsomes, benzphetamine N-demethylase (BPND) activity was increased by 72% (p{le}0.01), 85% (p{le}0.01) and decreased by 15% (p{le}0.01), respectively, by exposure to O{sub 3}, O{sub 3}+HNO{sub 3} and HNO{sub 3} vapor, but was unaffected in the hepatic microsomes.

  8. Leaf-level and whole-plant gas exchange characteristics of shortleaf pine exposed to ozone and simulated acid rain.

    PubMed

    Flagler, R B; Lock, J E; Elsik, C G

    1994-04-01

    Field-grown shortleaf pine (Pinus echinata Mill.) seedlings were exposed to ozone (O(3)) and simulated acid rain (SAR) in open-top chambers over three growing seasons. Ranges of O(3) and SAR spanned ambient levels found in the southern USA. Effects of O(3) on leaf-level and whole-plant gas exchange were characterized for a single measurement period immediately before the third summer of exposure. Decreased photosynthesis rates were attributed to O(3), but not SAR. Stomatal conductance decreased in response to O(3) exposure, and either increased or was unaffected by SAR. Increased internal CO(2) concentration (c(i)) in response to O(3) treatment indicated a greater effect of O(3) on photosynthetic capacity than stomatal conductance. Whole-seedling gas exchange characteristics indicated that whole-seedling carbon assimilation was more severely affected by O(3) than was evident from leaf-level gas exchange characteristics. Seedlings exposed to O(3) retained fewer flushes than seedlings grown in charcoal-filtered air.

  9. The effect of ozone exposure on rat alveolar macrophage arachidonic acid metabolism

    SciTech Connect

    Madden, M.C.; Eling, T.E.; Dailey, L.A.; Friedman, M. )

    1991-01-01

    Rat alveolar macrophages were prelabeled with {sup 3}H-arachidonic acid ({sup 3}H-AA) and exposed to air or O3 (0.1-1.0 ppm) in vitro for 2 h. Alveolar macrophages released 3.6-fold more tritium at the 1.0 ppm exposure concentration compared with air-exposed macrophages. A significantly increased production of several {sup 3}H-AA metabolites, including 6-keto-PGF1 alpha, thromboxane B2, 12-hydroxy-5,8,10-heptadecatrienoic acid, prostaglandins E2 and D2, leukotrienes B4 and D4, and 15-hydroxyeicosatetraenoic acid was formed by macrophages exposed to 1.0 ppm O3 compared with air-exposed macrophages as determined by high performance liquid chromatography (HPLC) analysis. O3 exposure did not alter macrophage {sup 3}H-AA metabolism in response to calcium ionophore A23187. The largest tritiated peak observed in the HPLC chromatograms of O{sub 3}-exposed cells was a polar complex of products that contained various phospholipids and neutral lipids (including diacylglycerol) and possibly degradation products of {sup 3}H-AA and some of its metabolites. These changes in macrophage arachidonic acid metabolism may play an important role in the lung response to O{sub 3} exposure in vivo.

  10. Uptake of formaldehyde by sulfuric acid solutions - Impact on stratospheric ozone

    NASA Technical Reports Server (NTRS)

    Tolbert, Margaret A.; Pfaff, Jeanne; Jayaweera, Indira; Prather, Michael J.

    1993-01-01

    The study investigates the uptake of CH2O by low temperature sulfuric acid solutions representative of global stratospheric particulate. It is argued that if similar uptake occurs under stratospheric pressures of CH2O, i.e., 1000 times lower than used in the present study, then the removal of CH2O from the gas phase can take away a significant source of odd hydrogen in the mid- and high-latitude lower stratosphere. It is shown that with the inclusion of this reaction, concentrations of OH and H2O are reduced by as much as 4 percent under background levels of aerosols and more than 15 percent under elevated (volcanic) conditions. The accumulation of CH2O in stratospheric aerosols over a season, reaching about 1 M solutions, will alter the composition and may even change the reactivity of these sulfuric acid-water mixtures.

  11. Polar processing and development of the 2004 Antarctic ozone hole : first results from MLS on Aura

    NASA Technical Reports Server (NTRS)

    Santee, M. L.; Manney, G. L.; Livesey, N. J.; Froidevaux, L.; MacKenzie, I. A.; Pumphrey, H. C.; Read, W. G.; Schwartz, M. J.; Waters, J. W.; Harwood, R. S.

    2005-01-01

    The Microwave Limb Sounder (MLS) on Aura is providing an extensive data set on stratospheric winter polar processing, including the first daily global observations of HCl, together with simultaneous measurements of ClO, HNO3, H2O, O3, N2O, and temperature (among others). We present first results charting the evolution of these quantities during the 2004 Antarctic late winter. MLS observations of chlorine deactivation and ozone loss during this period are shown to be consistent with results from the SLIMCAT chemical transport model.

  12. The use of atmospheric measurements to constrain model predictions of ozone change from chlorine perturbations

    NASA Technical Reports Server (NTRS)

    Douglass, Anne R.; Stolarski, Richard S.

    1987-01-01

    Atmospheric photochemistry models have been used to predict the sensitivity of the ozone layer to various perturbations. These same models also predict concentrations of chemical species in the present day atmosphere which can be compared to observations. Model results for both present day values and sensitivity to perturbation depend upon input data for reaction rates, photodissociation rates, and boundary conditions. A method of combining the results of a Monte Carlo uncertainty analysis with the existing set of present atmospheric species measurements is developed. The method is used to examine the range of values for the sensitivity of ozone to chlorine perturbations that is possible within the currently accepted ranges for input data. It is found that model runs which predict ozone column losses much greater than 10 percent as a result of present fluorocarbon fluxes produce concentrations and column amounts in the present atmosphere which are inconsistent with the measurements for ClO, HCl, NO, NO2, and HNO3.

  13. Global simulation of tropospheric O3-NO x -hydrocarbon chemistry: 2. Model evaluation and global ozone budget

    NASA Astrophysics Data System (ADS)

    Wang, Yuhang; Logan, Jennifer A.; Jacob, Daniel J.

    1998-05-01

    Results from a global three-dimensional model for tropospheric O3-NOx-hydrocarbon chemistry are presented and evaluated with surface, ozonesonde, and aircraft measurements. Seasonal variations and regional distributions of ozone, NO, peroxyacetylnitrate (PAN), CO, ethane, acetone, and H2O2 are examined. The model reproduces observed NO and PAN concentrations to within a factor of 2 for a wide range of tropospheric regions including the upper troposphere but tends to overestimate HNO3 concentrations in the remote troposphere (sometimes several fold). This discrepancy implies a missing sink for HNO3 that does not lead to rapid recycling of NOx; only in the upper troposphere over the tropical South Atlantic would a fast conversion of HNO3 to NOx improve the model simulation for NOx. Observed concentrations of acetone are reproduced in the model by including a large biogenic source (15 Tg C yr-1), which accounts for 40% of the estimated global source of acetone (37 Tg C yr-1). Concentrations of H2O2 in various regions of the troposphere are simulated usually to within a factor of 2, providing a test for HOx chemistry in the model. The model reproduces well the observed concentrations and seasonal variations of ozone in the troposphere, with some exceptions including an underestimate of the vertical gradient across the tropical trade wind inversion. A global budget analysis in the model indicates that the supply and loss of tropospheric ozone are dominated by photochemistry within the troposphere and that NOx. emitted in the southern hemisphere is twice as efficient at producing ozone as NOx emitted in the northern hemisphere.

  14. Dobson spectrophotometer total ozone measurement errors caused by interfering absorbing species such as SO2, NO2, and photochemically produced O3 in polluted air

    NASA Astrophysics Data System (ADS)

    Komhyr, W. D.; Evans, R. D.

    1980-02-01

    Total ozone measurements made with Dobson spectrophotometers in polluted air are subject to errors caused by interfering trace gas species that absorb solar ultraviolet radiation. While such interference is probably non-existent or small at the majority of Dobson instrument stations throughout the world, errors of up to 25% and 5%, resulting from absorption by SO2 and NO2 respectively, may occur occasionally at a few stations located in extremely polluted atmospheres. Interference by other absorbers, including N2O5, H2O2, HNO3, acetyldehyde, acetone, and acrolein has been found to be negligible. Ozone produced photochemically in polluted near-surface air may occasionally constitute from 5% to 10% of the atmospheric total ozone column. Such ozone interferes with measurements of atmospheric background total ozone.

  15. Effects of ozone and acidic deposition on carbon allocation and mycorrhizal colonization of Pinus taeda L. seedlings

    SciTech Connect

    Adams, M.B.; O'Neal, E.G.

    1991-03-01

    Patterns of carbon allocation and mycorrhizal colonization were examined in loblolly pine seedlings from two half-sib families exposed to three ozone treatments (charcoal-filtered air, ambient air + 80 ppb O{sub 3}, and ambient air + 160 ppb O{sub 3}) and three rain pH levels (5.2, 4.5, and 3.3) for 12 weeks in open-topped chambers in a field setting. No statistically significant effects of ozone or rain pH were detected on biomass, root:shoot ratios, or carbon allocation; some consistent patterns were observed, however. Coarse root starch concentrations and mycorrhizal infection varied significantly with ozone levels. No significant interactions of ozone, rain pH, or genotype were detected.

  16. Kinetic measurements of the reactivity of hydrogen peroxide and ozone towards small atmospherically relevant aldehydes, ketones and organic acids in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Schöne, L.; Herrmann, H.

    2014-05-01

    Free radical reactions are an important degradation process for organic compounds within the aqueous atmospheric environment. Nevertheless, non-radical oxidants such as hydrogen peroxide and ozone also contribute to the degradation and conversion of these substances (Tilgner and Herrmann, 2010). In this work, kinetic investigations of non-radical reactions were conducted using UV / Vis spectroscopy (dual-beam spectrophotometer and stopped flow technique) and a capillary electrophoresis system applying pseudo-first order kinetics to reactions of glyoxal, methylglyoxal, glycolaldehyde, glyoxylic, pyruvic and glycolic acid as well as methacrolein (MACR) and methyl vinyl ketone (MVK) with H2O2 and ozone at 298 K. The measurements indicate rather small rate constants at room temperature of k2nd < 3 M-1 s-1 (except for the unsaturated compounds exposed to ozone). Compared to radical reaction rate constants the values are about 10 orders of magnitude smaller (kOH • ~109 M-1 s-1). However, when considering the much larger non-radical oxidant concentrations compared to radical concentrations in urban cloud droplets, calculated first-order conversion rate constants change the picture towards H2O2 reactions becoming more important, especially when compared to the nitrate radical. For some reactions mechanistic suggestions are also given.

  17. Kinetic measurements on the reactivity of hydrogen peroxide and ozone towards small atmospherically relevant aldehydes, ketones and organic acids in aqueous solution

    NASA Astrophysics Data System (ADS)

    Schöne, L.; Herrmann, H.

    2013-10-01

    Within the aqueous atmospheric environment free radical reactions are an important degradation process for organic compounds. Nevertheless, non-radical oxidants like hydrogen peroxide and ozone also contribute to the degradation and conversion of this substance group (Tilgner und Herrmann, 2010). In this work kinetic investigations of non-radical reactions were conducted using UV/Vis spectroscopy (dual-beam spectrophotometer and Stopped Flow technique) and a capillary electrophoresis system applying pseudo-first order kinetics of glyoxal, methylglyoxal, glycolaldehyde, glyoxylic, pyruvic and glycolic acids as well as methacrolein (MACR) and methyl vinyl ketone (MVK) towards H2O2 and ozone. The measurements indicate rather small rate constants at room temperature of k2nd < 3 M-1 s-1 (except for the unsaturated compounds exposed to ozone). Compared to radical reaction rate constants the values are about 10 orders of magnitude smaller (kOH· ~ 109 M-1 s-1). However, when considering the much larger non-radical oxidant concentrations compared to radical concentrations in urban cloud droplets, calculated turnovers change the picture to more important H2O2 reactions especially when compared to the nitrate radical. For some reactions also mechanistic suggestions are given.

  18. Mechanisms and reaction pathways for simultaneous oxidation of NOx and SO₂ by ozone determined by in situ IR measurements.

    PubMed

    Sun, Chenglang; Zhao, Nan; Zhuang, Zhuokai; Wang, Haiqiang; Liu, Yue; Weng, Xiaole; Wu, Zhongbiao

    2014-06-15

    Ozone (O3) oxidation combined with wet scrubbing is a promising method for the simultaneous removal of SO2 and NOx in flue gas. In this study, the O3 oxidation processes of NO and SO2, as well as their coexistence, were investigated using an in situ IR spectrometer. Experimental results showed that the O3 concentration and the reaction temperature played critical roles in the O3 oxidation process of NO. Around 80°C, when inlet molar ratio of O3/NO was less than 1, NO was mainly oxidized to NO2, while when the ratio was greater than 1, NO would be further oxidized to NO3, N2O5, and HNO3. NO3 was the key intermediate product for the formation of N2O5 and HNO3. However, the subsequent reactions of NO3 were temperature dependence. With the increase of reaction temperature above 100°C, the concentration of NO2 increased whereas the concentrations of N2O5 and HNO3 decreased. The oxidation of SO2 by O3 was negligible and SO2 had little influence on the oxidation of NO in the simultaneous oxidation of NO and SO2. Finally, based on the in situ IR results, the oxidation mechanism is discussed and the reaction pathways are proposed. PMID:24801895

  19. Mechanisms and reaction pathways for simultaneous oxidation of NOx and SO₂ by ozone determined by in situ IR measurements.

    PubMed

    Sun, Chenglang; Zhao, Nan; Zhuang, Zhuokai; Wang, Haiqiang; Liu, Yue; Weng, Xiaole; Wu, Zhongbiao

    2014-06-15

    Ozone (O3) oxidation combined with wet scrubbing is a promising method for the simultaneous removal of SO2 and NOx in flue gas. In this study, the O3 oxidation processes of NO and SO2, as well as their coexistence, were investigated using an in situ IR spectrometer. Experimental results showed that the O3 concentration and the reaction temperature played critical roles in the O3 oxidation process of NO. Around 80°C, when inlet molar ratio of O3/NO was less than 1, NO was mainly oxidized to NO2, while when the ratio was greater than 1, NO would be further oxidized to NO3, N2O5, and HNO3. NO3 was the key intermediate product for the formation of N2O5 and HNO3. However, the subsequent reactions of NO3 were temperature dependence. With the increase of reaction temperature above 100°C, the concentration of NO2 increased whereas the concentrations of N2O5 and HNO3 decreased. The oxidation of SO2 by O3 was negligible and SO2 had little influence on the oxidation of NO in the simultaneous oxidation of NO and SO2. Finally, based on the in situ IR results, the oxidation mechanism is discussed and the reaction pathways are proposed.

  20. 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.

  1. Polar stratospheric clouds and ozone depletion

    NASA Technical Reports Server (NTRS)

    Toon, Owen B.; Turco, Richard P.

    1991-01-01

    A review is presented of investigations into the correlation between the depletion of ozone and the formation of polar stratospheric clouds (PSCs). Satellite measurements from Nimbus 7 showed that over the years the depletion from austral spring to austral spring has generally worsened. Approximately 70 percent of the ozone above Antarctica, which equals about 3 percent of the earth's ozone, is lost during September and October. Various hypotheses for ozone depletion are discussed including the theory suggesting that chlorine compounds might be responsible for the ozone hole, whereby chlorine enters the atmosphere as a component of chlorofluorocarbons produced by humans. The three types of PSCs, nitric acid trihydrate, slowly cooling water-ice, and rapidly cooling water-ice clouds act as important components of the Antarctic ozone depletion. It is indicated that destruction of the ozone will be more severe each year for the next few decades, leading to a doubling in area of the Antarctic ozone hole.

  2. Effects of hydrocarbon contamination on ozone generation with dielectric barrier discharges

    NASA Astrophysics Data System (ADS)

    Lopez, Jose L.; Vezzu, Guido; Freilich, Alfred; Paolini, Bernhard

    2013-08-01

    The increasing usage of the feed gases of lower grade liquid oxygen (LOX) containing higher levels of trace hydrocarbon impurities in dielectric barrier discharge (DBD) for ozone generation requires a better understanding of the kinetics of the by-product formation resulting from reactions involving these hydrocarbon impurities. As a case study of hydrocarbon impurities, the kinetics of CH4 conversion in DBDs and the subsequent HNO3 formation were investigated by means of gas-phase plasma diagnostics, supported by detailed process modeling, and extensive in-situ and ex-situ by-product analysis. The by-products formation in the plasma with the presence of CH4, were found to differ significantly in oxygen-fed generators as compared to generators fed with oxygen/nitrogen mixtures. The amount of HNO3 formed depends on the concentration of NOx formed in the plasma and the amount of CH4 that is converted, but not on the O3 concentration. In the present work we have investigated CH4 concentrations of up to 1.95 wt% of the feed gas. The rate of deterioration of the overall ozone generator performance was found to be affected by the concentration of nitrogen in the oxygen/nitrogen mixture.

  3. Effects of ozone, ultraviolet and peracetic acid disinfection of a primary-treated municipal effluent on the immune system of rainbow trout (Oncorhynchus mykiss).

    PubMed

    Hébert, N; Gagné, F; Cejka, P; Bouchard, B; Hausler, R; Cyr, D G; Blaise, C; Fournier, M

    2008-08-01

    Municipal sewage effluents are complex mixtures that are known to compromise the health condition of aquatic organisms. The aim of this study was to evaluate the impacts of various wastewater disinfection processes on the immune system of juvenile rainbow trout (Oncorhynchus mykiss). The trout were exposed to a primary-treated effluent for 28 days before and after one of each of the following treatments: ultraviolet (UV) radiation, ozonation and peracetic acid. Immune function was characterized in leucocytes from the anterior head kidney by the following three parameters: phagocytosis activity, natural cytotoxic cells (NCC) function and lymphocyte (B and T) proliferation assays. The results show that the fish mass to length ratio was significantly decreased for the primary-treated and all three disinfection processes. Exposure to the primary-treated effluent led to a significant increase in macrophage-related phagocytosis; the addition of a disinfection step was effective in removing this effect. Both unstimulated and mitogen-stimulated T lymphocyte proliferation in fish decreased dramatically in fish exposed to the ozonated effluent compared to fish exposed to either the primary-treated effluent or to aquarium water. Stimulation of T lymphocytes proliferation was observed with the peracetic acid treatment group. In conclusion, the disinfection strategy used can modify the immune system in fish at the level of T lymphocyte proliferation but was effective to remove the effects on phagocytosis activity.

  4. Growth response of four species of Eastern hardwood tree seedlings exposed to ozone, acidic precipitation, and sulfur dioxide. [Prunus serotina, Acer rubrum, Quercus rubra, Liriodendron tulipifera

    SciTech Connect

    Davis, D.D. Skelly, J.M. )

    1992-03-01

    In 1987 a study was conducted in controlled environment chambers to determine the foliar sensitivity of tree seedlings of eight species to ozone and acidic precipitation, and to determine the influence of leaf position on symptom severity. Jensen and Dochinger conducted concurrent similar studies in Continuously Stirred Tank Reactor (CSTR) chambers with ten species of forest trees. Based on the results of these initial studies, four species representing a range in foliar sensitivity to ozone were chosen: black cherry (Prunus serotina Ehrh.), red maple (Acer rubrum L.), northern red oak (Quercus rubra L.) and yellow-poplar (Liriodendron tulipifera L.). These species were also chosen because of their ecological and/or commercial importance in Pennsylvania. Seedlings were exposed in growth chambers simulated acid rain. In addition acute exposures to sulfur dioxide were conducted in a regime based on unpublished monitoring data collected near coal-fired power plants. The objective of this study was to determine if the pollutant treatments influenced the growth and productivity of seedlings of these four species. This information will help researchers and foresters understand the role of air pollution in productivity of eastern forests.

  5. Nitrous acid in the urban area of Rome

    NASA Astrophysics Data System (ADS)

    Acker, Karin; Febo, Antonio; Trick, Sebastian; Perrino, Cinzia; Bruno, Paolo; Wiesen, Peter; Möller, Detlev; Wieprecht, Wolfgang; Auel, Renate; Giusto, Marco; Geyer, Andreas; Platt, Ulrich; Allegrini, Ivo

    Nitrous acid (HNO 2) and a large variety of other components were simultaneously measured in the city centre of Rome (Italy) during the NITROCAT ground based field experiment in May/June 2001. The highest HNO 2 concentrations were found under high-pressure conditions with high nocturnal atmospheric stability and high values of pollutants. After night time formation and accumulation up to 2 ppb HNO 2 were observed. The measurements confirm that during the first hours after sunrise, when hydroxyl radical (OH) production rates from other sources (photolysis of ozone and formaldehyde (HCHO)) are slow, HNO 2 photolysis is the most important primary OH source in the lowest part of the troposphere; up to 1-4×10 7 OH cm -3 s -1 were estimated for that time from this source. This contributes considerably to the initiation of the photochemistry for the day. The unexpected high daytime concentrations of few hundred ppt observed by DOAS as well as by the two in situ wet collection techniques (wet denuder/IC, coil sampling/HPLC) possibly influence ozone chemistry during the entire day. The heterogeneous on-surface production of HNO 2 (and consequently of HNO 3) provides also a new-type acidity formation influencing directly the biosphere and the materials. About 20% of the total nitrite was found on atmospheric aerosols. The HNO 2 measurements agree well for the different in situ measurement techniques and the spatial integration DOAS simultaneously performed over several weeks in the real atmosphere and during reaction chamber experiments.

  6. Aircraft observations of the lower troposphere above a megacity: Alkyl nitrate and ozone chemistry

    NASA Astrophysics Data System (ADS)

    Aruffo, Eleonora; Di Carlo, Piero; Dari-Salisburgo, Cesare; Biancofiore, Fabio; Giammaria, Franco; Busilacchio, Marcella; Lee, James; Moller, Sarah; Hopkins, James; Punjabi, Shalini; Bauguitte, Stéphane; O'Sullivan, Debbie; Percival, Carl; Le Breton, Michael; Muller, Jennifer; Jones, Rod; Forster, Grant; Reeves, Claire; Heard, Dwayne; Walker, Hannah; Ingham, Trevor; Vaughan, Stewart; Stone, Daniel

    2014-09-01

    Within the framework of the RONOCO (ROle of Nighttime chemistry in controlling the Oxidising Capacity of the atmOsphere) campaign a daytime flight over the metropolitan area of London were carried out to study the nitrogen oxide chemistry and its role in the production and loss of ozone (O3) and alkyl and multifunctional nitrate (ΣANs). The FAAM BAe-146 aircraft, used for these observations, was equipped with instruments to measure the most relevant compounds that control the lower troposphere chemistry, including O3, NO, NO2, NO3, N2O5, HNO3, peroxy nitrates (ΣPNs), ΣANs, OH, and HO2. In the London's flight a strong ozone titration process was observed when flying above Reading (downwind of London) and when intercepting the London plume. The coupled cycles of NOx and HOx can have different terminations forming ΣPNs, ΣANs, HNO3 or peroxides (H2O2, ROOH) altering the O3 production. In the observations reported here, we found that a strong ozone titration (ΔO3 = -16 ppb), due to a rapid increase of NOx (ΔNOx = 27 ppb), corresponds also to a high increase of ΣANs concentrations (ΔΣANs = 3 ppb), and quite stable concentrations of HNO3 and ΣPNs. Unexpectedly, compared with other megacities, the production of ΣANs is similar to that of Ox (O3 + NO2), suggesting that in the London plume, at least during these observations, the formation of ΣANs effectively removes active NOx and hence reduces the amount of O3 production. In fact, we found that the ratio between the ozone production and the alkyl nitrates production (observed) approximate the unity; on the contrary the calculated ratio is 7. In order to explain this discrepancy, we made sensitivity tests changing the alkyl nitrates branching ratio for some VOCs and we investigated the impact of the unmeasured VOCs during the flight, founding that the calculated ratio decreases from 7 to 2 and that, in this condition, the major contribution to the ΣANs production is given by Alkanes. Observations and analysis

  7. IR absorption spectra of cellulose obtained from ozonated wood

    NASA Astrophysics Data System (ADS)

    Mamleeva, N. A.; Autlov, S. A.; Kharlanov, A. N.; Bazarnova, N. G.; Lunin, V. V.

    2015-08-01

    The kinetic curves of ozone absorption by aspen wood were obtained. Processing of wood with peracetic acid gave cellulose samples. The yields of ozonated wood, water-soluble compounds, and cellulose were determined for the samples corresponding to different consumptions of ozone. The IR absorption spectra of wood and cellulose isolated from ozonated wood were analyzed. The supramolecular structure of cellulose can be changed by varying the conditions of wood ozonation.

  8. Combination of ozonation and photocatalysis for purification of aqueous effluents containing formic acid as probe pollutant and bromide ion.

    PubMed

    Parrino, F; Camera-Roda, G; Loddo, V; Palmisano, G; Augugliaro, V

    2014-03-01

    The treatment by advanced oxidation processes (AOPs) of waters contaminated by organic pollutants and containing also innocuous bromide ions may generate bromate ions as a co-product. In the present work heterogeneous photocatalysis and ozonation have individually been applied and in combination (integrated process) to degrade the organic compounds in water containing also bromide anions. The results show that: i) the sole photocatalysis does not produce bromate ions and in the case of its presence, it is able to reduce bromate to innocuous bromide ions; ii) the integration of photocatalysis and ozonation synergistically enhances the oxidation capabilities; and iii) in the integrated process bromate ions are not produced as long as some oxidizable organics are present.

  9. Heterogeneous nucleation of nitric acid trihydrate on clay minerals: relevance to type ia polar stratospheric clouds.

    PubMed

    Hatch, Courtney D; Gough, Raina V; Toon, Owen B; Tolbert, Margaret A

    2008-01-17

    Although critical to atmospheric modeling of stratospheric ozone depletion, selective heterogeneous nuclei that promote the formation of Type Ia polar stratospheric clouds (PSCs) are largely unknown. While mineral particles are known to be good ice nuclei, it is currently not clear whether they are also good nuclei for PSCs. In the present study, a high-vacuum chamber equipped with transmission Fourier transform infrared spectroscopy and a quadrupole mass spectrometer was used to study heterogeneous nucleation of nitric acid trihydrate (NAT) on two clay minerals-Na-montmorillonite and kaolinite-as analogs of atmospheric terrestrial and extraterrestrial minerals. The minerals are first coated with a 3:1 supercooled H2O/HNO3 solution prior to the observed nucleation of crystalline NAT. At 220 K, NAT formation was observed at low SNAT values of 12 and 7 on kaolinite and montmorillonite clays, respectively. These are the lowest SNAT values reported in the literature on any substrate. However, NAT nucleation exhibited significant temperature dependence. At lower temperatures, representative of typical polar stratospheric conditions, much higher supersaturations were required before nucleation was observed. Our results suggest that NAT nucleation on mineral particles, not previously treated with sulfuric acid, may not be an important nucleation platform for Type Ia PSCs under normal polar stratospheric conditions.

  10. Ozone decomposition

    PubMed Central

    Batakliev, Todor; Georgiev, Vladimir; Anachkov, Metody; Rakovsky, Slavcho

    2014-01-01

    Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers). Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates. PMID:26109880

  11. Ozone decomposition.

    PubMed

    Batakliev, Todor; Georgiev, Vladimir; Anachkov, Metody; Rakovsky, Slavcho; Zaikov, Gennadi E

    2014-06-01

    Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers). Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates. PMID:26109880

  12. Polar ozone

    NASA Technical Reports Server (NTRS)

    Solomon, S.; Grose, W. L.; Jones, R. L.; Mccormick, M. P.; Molina, Mario J.; Oneill, A.; Poole, L. R.; Shine, K. P.; Plumb, R. A.; Pope, V.

    1990-01-01

    The observation and interpretation of a large, unexpected ozone depletion over Antarctica has changed the international scientific view of stratospheric chemistry. The observations which show the veracity, seasonal nature, and vertical structure of the Antarctic ozone hole are presented. Evidence for Arctic and midlatitude ozone loss is also discussed. The chemical theory for Antarctic ozone depletion centers around the occurrence of polar stratospheric clouds (PSCs) in Antarctic winter and spring; the climatology and radiative properties of these clouds are presented. Lab studies of the physical properties of PSCs and the chemical processes that subsequently influence ozone depletion are discussed. Observations and interpretation of the chemical composition of the Antarctic stratosphere are described. It is shown that the observed, greatly enhanced abundances of chlorine monoxide in the lower stratosphere are sufficient to explain much if not all of the ozone decrease. The dynamic meteorology of both polar regions is given, interannual and interhemispheric variations in dynamical processes are outlined, and their likely roles in ozone loss are discussed.

  13. Ozone decomposition.

    PubMed

    Batakliev, Todor; Georgiev, Vladimir; Anachkov, Metody; Rakovsky, Slavcho; Zaikov, Gennadi E

    2014-06-01

    Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers). Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates.

  14. 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.

  15. 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

  16. 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.

  17. The relationship between airborne acidity and ammonia in indoor environments.

    PubMed

    Suh, H H; Koutrakis, P; Spengler, J D

    1994-01-01

    Indoor acid aerosol, nitric acid (HNO3), and ammonia (NH3) concentrations were measured in 47 homes in State College, Pennsylvania, during the summer of 1991. From each home, 12-hour indoor, 12- and 24-hour outdoor, and 12-hour air exchange samples were collected continuously over a 5-day period. Additionally, questionnaires were administered daily by field technicians to obtain information on house occupant number, ventilation, gas stove use, pets, and other housing characteristics. In this paper, we discuss the relationship between NH3 and corresponding concentrations of aerosol strong acidity (H+) and HNO3 inside these homes. As part of this analysis, we also examined indoor/outdoor concentration relationships and identified housing factors that may influence indoor levels. In State College, indoor NH3 concentrations were higher than corresponding outdoor levels, with air conditioner use, air exchange rates, and occupant number identified as important determinants of indoor levels. Indoor concentrations of both H+ and HNO3 were substantially lower than outdoor levels, as homes with air exchange rates less than one exchange per hour were found to have essentially no acid indoors. These low H+ and HNO3 levels likely resulted from their reaction with indoor NH3 and with indoor surfaces. Indoor NH3 concentrations were higher than outdoor levels, indicating the presence of indoor NH3 sources; however, correlations between indoor NH3 and both pets and occupants, its primary indoor sources, were weak and negative, respectively. Mass balance models that included an NH3 neutralization term were found to predict indoor H+ concentrations reasonably well, representing a substantial improvement over outdoor concentrations alone. The accumulation of NH3 indoors was found to be the primary determinant of indoor H+ and HNO3 levels.

  18. Ozone variability

    NASA Astrophysics Data System (ADS)

    Duetsch, H. U.

    1983-09-01

    The annual and long-term variations in the atmospheric ozone layer were examined on the basis of 55 yr of data taken at Aroya, Switzerland and 25 yr of data gathered by the global ozone network. Attention was given to annual and biennial variations, which showed that the midlatitude peak concentration was affected by a quasi-biennial variation of the tropical stratospheric circulation. Smaller scale circulation patterns were dominant in the lower stratosphere, although an observed negative trend of the total ozone was equally distributed between the troposphere and 24 km altitude. The global ozone increase detected in the 1960s was possible due to general circulation alterations, but may also have been influenced by injection of NO(x) into the atmosphere during atomic bomb testing.

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

    DOE PAGES

    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

  20. Ozone, Tropospheric

    NASA Technical Reports Server (NTRS)

    Fishman, Jack

    1995-01-01

    In the early part of the 20th century, ground-based and balloon-borne measurements discovered that most of atmosphere's ozone is located in the stratosphere with highest concentrations located between 15 and 30 km (9,3 and 18.6 miles). For a long time, it was believed that tropospheric ozone originated from the stratosphere and that most of it was destroyed by contact with the earth's surface. Ozone, O3, was known to be produced by the photo-dissociation of molecular oxygen, O2, a process that can only occur at wavelengths shorter than 242 nm. Because such short-wave-length radiation is present only in the stratosphere, no tropospheric ozone production is possible by this mechanism. In the 1940s, however, it became obvious that production of ozone was also taking place in the troposphere. The overall reaction mechanism was eventually identified by Arie Haagen-Smit of the California Institute of Technology, in highly polluted southern California. The copious emissions from the numerous cars driven there as a result of the mass migration to Los Angeles after World War 2 created the new unpleasant phenomenon of photochemical smog, the primary component of which is ozone. These high levels of ozone were injuring vegetable crops, causing women's nylons to run, and generating increasing respiratory and eye-irritation problems for the populace. Our knowledge of tropospheric ozone increased dramatically in the early 1950s as monitoring stations and search centers were established throughout southern California to see what could be done to combat this threat to human health and the environment.

  1. Toward a more physical representation of precipitation scavenging in global chemistry models: cloud overlap and ice physics and their impact on tropospheric ozone

    NASA Astrophysics Data System (ADS)

    Neu, J. L.; Prather, M. J.

    2012-04-01

    Uptake and removal of soluble trace gases and aerosols by precipitation represents a major uncertainty in the processes that control the vertical distribution of atmospheric trace species. Model representations of precipitation scavenging vary greatly in their complexity, and most are divorced from the physics of precipitation formation and transformation. Here, we describe a new large-scale precipitation scavenging algorithm, developed for the UCI chemistry-transport model (UCI-CTM), that represents a step toward a more physical treatment of scavenging through improvements in the formulation of the removal in sub-gridscale cloudy and ambient environments and their overlap within the column as well as ice phase uptake of soluble species. The UCI algorithm doubles the lifetime of HNO3 in the upper troposphere relative to a scheme with commonly used fractional cloud cover assumptions and ice uptake determined by Henry's Law and provides better agreement with HNO3 observations. We find that the process of ice phase scavenging of HNO3 is a critical component of the tropospheric O3 budget, but that NOx and O3 mixing ratios are relatively insensitive to large differences in the removal rate. Ozone abundances are much more sensitive to the lifetime of HNO4, highlighting the need for better understanding of its interactions with ice and for additional observational constraints.

  2. Assessment of acidic deposition and ozone effects on conifer forests in the San Bernardino Mountains. Standard operating procedure manual. Volume 1. Final report

    SciTech Connect

    Miller, P.R.; Chow, J.; Watson, J.G.

    1994-11-30

    The purpose of this study was to evaluate the separate and combined effects of ozone and acidic deposition on mixed conifer forests in the San Bernardino mountains of southern California. The primary objectives were to acquire a long-term data base of specified accuracy, precision and validity for atmospheric pollution concentration, local and stand meteorology, wet and dry deposition fluxes to forest canopies, and biological responses of forest vegetation and soils. Some data were used to parameterize and run simulations with the Big Leaf model. Futhermore, to document the procedures used in the project, complete descriptions of measurement techniques, research protocols and quality assurace objectives were compiled in a companion document to the final report. This multi-disciplinary study provides a data base describing many attributes of a California mixed conifer forest ecosystem exposed to a moderate level of gas and particle deposition compared to the highest possible levels in the western portions of the San Bernardino mountains.

  3. Assessment of acidic deposition and ozone effects on conifer forests in the San Bernardino Mountains. Standard operating procedure manual. Volume 2. Final report

    SciTech Connect

    Miller, P.R.; Chow, J.; Watson, J.G.

    1994-11-30

    The purpose of this study was to evaluate the separate and combined effects of ozone and acidic deposition on mixed conifer forests in the San Bernardino mountains of southern California. The primary objectives were to acquire a long-term data base of specified accuracy, precision and validity for atmospheric pollution concentration, local and stand meteorology, wet and dry deposition fluxes to forest canopies, and biological responses of forest vegetation and soils. Some data were used to parameterize and run simulations with the Big Leaf model. Futhermore, to document the procedures used in the project, complete descriptions of measurement techniques, research protocols and quality assurace objectives were compiled in a companion document to the final report. This multi-disciplinary study provides a data base describing many attributes of a California mixed conifer forest ecosystem exposed to a moderate level of gas and particle deposition compared to the highest possible levels in the western portions of the San Bernardino mountains.

  4. Observations of nitrous acid (HONO) and peroxynitric acid (HO2NO2) made during the 2013 and 2014 Uintah Basin Winter Ozone Study (UBWOS)

    NASA Astrophysics Data System (ADS)

    Veres, P. R.; Roberts, J. M.; Alvarez, S. L.; Brown, S. S.; Burkholder, J. B.; De Gouw, J. A.; Edwards, P. M.; Lefer, B. L.; Liggio, J.; Min, K. E.; Stutz, J.; Tsai, J. Y.; Colosimo, S. F.; Wentzell, J. J. B.; Wild, R. J.; Yuan, B.; Flynn, J. H., III

    2014-12-01

    HONO is frequently observed to be the main OH source in the early morning, with more recent urban measurements showing significant rates of daytime production. Quantifying the impact of HONO as a source of daytime oxidant is crucial to forming a more explicit understanding of tropospheric ozone formation. In this work, ambient observations of HONO were made during the 2013 and 2014 Uintah Basin Wintertime Ozone Study (UBWOS) at a field site in Utah using various analytical techniques including chemical ionization mass spectrometry (CIMS), differential optical absorption spectroscopy (DOAS), cavity enhanced absorption spectroscopy (CEAS), and long path absorption photometry (LOPAP). Observations of HONO and HO2NO2 will be presented and compared to model results using a chemical box model applying explicit MCM chemistry to describe an ozone formation event observed during the 2013 wintertime season. Strong inversions leading to a build-up of many primary and secondary pollutants as well as low temperatures drove daytime HO2NO2 observations as high as 1.5 ppbv during the 2013 study. The potential of these high HO2NO2 concentrations as an interference to the various HONO measurements techniques will be discussed. Daytime HONO observations will be presented and analyzed with respect to coinciding vertical gradients, sampling artifacts, and potential instrumental interferences.

  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. 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.

  7. CANOZE measurements of the Arctic ozone hole

    NASA Technical Reports Server (NTRS)

    Evans, W. F. J.; Kerr, J. B.; Fast, H.

    1988-01-01

    In CANOZE 1 (Canadian Ozone Experiment), a series of 20 ozone profile measurements were made in April, 1986 from Alert at 82.5 N. CANOZE is the Canadian program for study of the Arctic winter ozone layer. In CANOZE 2, ozone profile measurements were made at Saskatoon, Edmonton, Churchill and Resolute during February and March, 1987 with ECC ozonesondes. Ground based measurements of column ozone, nitrogen dioxide and hydrochloric acid were conducted at Saskatoon. Two STRATOPROBE balloon flights were conducted on February 26 and March 19, 1987. Two aerosol flights were conducted by the University of Wyoming. The overall results of this study will be reported and compared with the NOZE findings. The results from CANOZE 3 in 1988, are also discussed. In 1988, as part of CANOZE 3, STRATOPROBE balloon flights were conducted from Saskatchewan on January 27 and February 13. A new lightweight infrared instrument was developed and test flown. A science flight was successfully conducted from Alert (82.5 N) on March 9, 1988 when the vortex was close to Alert; a good measurement of the profile of nitric acid was obtained. Overall, the Arctic spring ozone layer exhibits many of the features of the Antarctic ozone phenomenon, although there is obviously not a hole present every year. The Arctic ozone field in March, 1986 demonstrated many similarities to the Antarctic ozone hole. The TOMS imagery showed a crater structure in the ozone field similar to the Antarctic crater in October. Depleted layers of ozone were found in the profiles around 15 km, very similar to those reported from McMurdo. Enhanced levels of nitric acid were measured in air which had earlier been in the vortex. The TOMS imagery for March 1987 did not show an ozone crater, but will be examined for an ozone crater in February and March, 1988, the target date for the CANOZE 3 project.

  8. 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 ...

  9. Polar stratospheric clouds and ozone depletion

    SciTech Connect

    Toon, O.B. ); Turco, R.P. )

    1991-06-01

    During the Antarctic winter, strange and often invisible clouds form in the stratosphere over the pole. These clouds of ice and frozen nitric acid play a crucial role in the chemical cycle responsible for the recent appearance of the annual ozone hole. Their chemistry removes compounds that would normally trap ozone-destroying free chlorine produced by the breakdown of CFCs. The paper describes these clouds, their formation, and the mechanisms by which these clouds help chlorine destroy ozone.

  10. The individual and combined effects of ozone and simulated acid rain on growth, gas exchange rate and water-use efficiency of Pinus armandi Franch.

    PubMed

    Shan, Y; Feng, Z; Izuta, T; Aoki, M; Totsuka, T

    1996-01-01

    The seedlings of Pinus armandi Franch. were exposed to ozone (O(3)) at 300 ppb for 8 h a day, 6 days a week, and simulated acid rain of pH 3.0 or 2.3, 6 times a week, alone or in combination, for 14 weeks from 15 June to 20 September 1993. The control seedlings were exposed to charcoal-filtered air and simulated rain of pH 6.8 during the same period. Significant interactive effects of O(3) and simulated acid rain on whole plant net photosynthetic rate were observed, but not on other determined parameters. The exposure of the seedlings to O(3) caused the reductions in the dry weight growth, root dry weight relative to the whole plant dry weight, net photosynthetic rate, transpiration rate in light, water-use efficiency and root respiration activity, and increases in shoot/root ratio, and leaf dry weight relative to the whole plant dry weight without an appearance of acute visible foliar injury, but did not affect the dark respiration rate and transpiration rate in the darkness. The decreased net photosynthetic rate was considered to be the major cause for the growth reduction of the seedlings exposed to O(3). On the other hand, the exposure of the seedlings to simulated acid rain reduced the net photosynthetic rate per unit chlorophyll a + b content, but did not induce the significant change in other determined parameters.

  11. Nitric acid depressions in and near midlatitude cirrus clouds during TRACE-P

    NASA Astrophysics Data System (ADS)

    Zondlo, M. A.; Cantrell, C. A.; Clarke, A.; Kosciuch, E.; Mauldin, R. L.; Eisele, F. L.

    2003-12-01

    Cirrus cloud ice particles have been implicated in scavenging a wide variety soluble and semisoluble species. Species removed by an ice surface can undergo a number of significant processes including heterogeneous reactions with other adsorbed species, vertical redistribution in the troposphere from sedimenting particles, or modifying the microphysical properties of the ice particle. Nitric acid (HNO3) has been shown in the laboratory to readily adsorb onto ice surfaces, and modeling studies suggest significant perturbations to its distribution can result. Unfortunately, field observations of HNO3 within and near cirrus clouds have shown mixed and sometimes contradictory results. The NASA P-3B aircraft sampled numerous upper tropospheric, mid-latitude ice clouds during Flight 24 of the NASA TRACE-P field experiment. In contrast to tropical cirrus clouds, the cirrus ice clouds sampled by the P-3B were at warmer temperatures of -17 to -32 degrees Celsius and at pressures of 365-436 mb. The clouds' origins ranged from jet stream induced cirrostratus clouds to convectively-induced cirrus anvils. Nitric acid levels decreased 60-70 pptv (35-60%) within the clouds compared to areas just outside of it. Slight asymmetries in the HNO3 profiles around the cloud were noted, with the lee or downwind sides of clouds containing more gradual returns from inside cloud levels to "background" levels, potentially due to greater mixing as the cloud evaporated. If HNO3 removed inside the cloud were distributed evenly onto ice surfaces, approximately one tenth of a monolayer of HNO3 was adsorbed onto ice (based on estimates of ice surface area density of 5000 microns squared per cubic centimeter). The incorporation of HNO3 into existing liquid quaternary NH3/H2SO4/HNO3/H2O aerosols within the cloud could also be important due to the sampling location over central North America where elevated NH3 emissions exist. The midlatitude HNO3/cirrus cases observed on the P-3B will be contrasted to

  12. 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.

  13. Laboratory evaluation of the effect of nitric acid uptake on frost point hygrometer performance

    NASA Astrophysics Data System (ADS)

    Thornberry, T.; Gierczak, T.; Gao, R. S.; Vömel, H.; Watts, L. A.; Burkholder, J. B.; Fahey, D. W.

    2011-02-01

    Chilled mirror hygrometers (CMH) are widely used to measure water vapour in the troposphere and lower stratosphere from balloon-borne sondes. Systematic discrepancies among in situ water vapour instruments have been observed at low water vapour mixing ratios (<5 ppm) in the upper troposphere and lower stratosphere (UT/LS). Understanding the source of the measurement discrepancies is important for a more accurate and reliable determination of water vapour abundance in this region. We have conducted a laboratory study to investigate the potential interference of gas-phase nitric acid (HNO3) with the measurement of frost point temperature, and consequently the water vapour mixing ratio, determined by CMH under conditions representative of operation in the UT/LS. No detectable interference in the measured frost point temperature was found for HNO3 mixing ratios of up to 4 ppb for exposure times up to 150 min. HNO3 was observed to co-condense on the mirror frost, with the adsorbed mass increasing linearly with time at constant exposure levels. Over the duration of a typical balloon sonde ascent (90-120 min), the maximum accumulated HNO3 amounts were comparable to monolayer coverage of the geometric mirror surface area, which corresponds to only a small fraction of the actual frost layer surface area. This small amount of co-condensed HNO3 is consistent with the observed lack of HNO3 interference in the frost point measurement because the CMH utilizes significant reductions (>10%) in surface reflectivity by the condensate to determine H2O.

  14. Laboratory evaluation of the effect of nitric acid uptake on frost point hygrometer performance

    NASA Astrophysics Data System (ADS)

    Thornberry, T.; Gierczak, T.; Gao, R. S.; Vömel, H.; Watts, L. A.; Burkholder, J. B.; Fahey, D. W.

    2010-08-01

    Chilled mirror hygrometers (CMH) are widely used to measure water vapour in the troposphere and lower stratosphere from balloon-borne sondes. Systematic discrepancies among in situ water vapour instruments have been observed at low water vapour mixing ratios (<5 ppm) in the upper troposphere and lower stratosphere (UT/LS). Understanding the source of the measurement discrepancies is important for a more accurate and reliable determination of water vapour abundance in this region. We have conducted a laboratory study to investigate the potential interference of gas-phase nitric acid (HNO3) with the measurement of frost point temperature, and consequently the water vapour mixing ratio, determined by CMH under conditions representative of operation in the UT/LS. No detectable interference in the measured frost point temperature was found for HNO3 mixing ratios of up to 4 ppb for exposure times up to 150 min. HNO3 was observed to co-condense on the mirror frost, with the adsorbed mass increasing linearly with time at constant exposure levels. Over the duration of a typical balloon sonde ascent (90-120 min), the maximum accumulated HNO3 amounts were comparable to monolayer coverage of the geometric mirror surface area, which corresponds to only a small fraction of the actual frost layer surface area. This small amount of co-condensed HNO3 is consistent with the observed lack of HNO3 interference in the frost point measurement because the CMH utilizes significant reductions (>10%) in surface reflectivity by the condensate to determine H2O.

  15. Stratospheric ozone: Impact of human activity

    NASA Astrophysics Data System (ADS)

    McElroy, Michael B.; Salawitch, Ross J.

    1989-12-01

    Current knowledge of the chemistry of the stratosphere is reviewed using measurements from the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment to test the accuracy of our treatment of processes at mid-latitudes, and results from the Airborne Antarctic Ozone Experiment (AAOE) to examine our understanding of processes for the polar environment. It is shown that, except for some difficulties with N 2O 5 and possibly ClNO 3, gas phase models for nitrogen and chlorine species at 30°N in spring are in excellent agreement with the data from ATMOS. Heterogeneous processes may have an influence on the concentrations of NO 2, N 2O 5, HNO 3, and ClNO 3 for the lower stratosphere at 48°S in fall. Comparison of model and observed concentrations of O 3 indicate good agreement at 30°N, with less satisfactory results at 48°S. The discrepancy between the loss rate of O 3 observed over the course of the AAOE mission in 1987 and loss rates calculated using measured concentrations of ClO and BrO is found to be even larger than that reported by Anderson et al. (1989, J. geophys. Res.94, 11480). There appear to be loss processes for removal of O 3 additional to the HOC1 mechanism proposed by Solomon et al. (1986, Nature321, 755), the ClO-BrO scheme favored by McElroy et al. (1986, Nature321, 759), and the ClO dimer mechanism introduced by Molina and Molina (1987, J. phys. Chem.91, 433). There is little doubt that industrial halocarbons have a significant impact on stratospheric O 3. Controls on emissions more stringent than those defined by the Montreal Protocol will be required if the Antarctic Ozone Hole is not to persist as a permanent feature of the stratosphere.

  16. A novel use of TiO2 fiber for photocatalytic ozonation of 2,4-dichlorophenoxyacetic acid in aqueous solution.

    PubMed

    Giri, Raj Rabindra; Ozaki, Hiroaki; Takanami, Ryohei; Taniguchi, Shogo

    2008-01-01

    More efficient oxidation methods are needed to degrade especially newly emerging recalcitrant organic contaminants at low concentrations in the water environment. Reduced photonic efficiency of immobilized TiO2 is a major challenge in TiO2-assisted advanced oxidation processes (AOP). Mineralization of 2,4-dichllorophenoxyacetic acid (2,4-D) in low aqueous solution by O3/UV/TiO2 using the world's first high-strength TiO2 fiber was investigated and compared with O3, UV/TiO2, and O3/TiO2 in laboratory batch experiments. The 2,4-D degradation and total organic carbon (TOC) removal followed pseudo first-order reaction kinetic, while their rates in O3/UV/TiO2 were respectively about 1.5 and 2.4 times larger than the summation of the values in 03 and UV/TiO2. The O3/UV/TiO2 was characterized by few aromatics with very low abundance, fast disappearance of aliphatics and more than 95% dechlorination. The discrepancies in organic carbon mass balance among the intermediates and 2,4-D were attributed mainly to few apparently major unidentified intermediates. The significantly enhanced 2,4-D mineralization in O3/UV/TiO2 was attributed to increased ozone dissolution followed by its decomposition, and reduced electron-hole recombination in presence of dissolved ozone resulting in a large number of hydroxyl radical (*OH) generation from more than one parallel path. The removal efficiencies of the systems can further be enhanced by optimizing design parameters, and O3/UV/TiO2 with the TiO2 fiber is promising to mineralize recalcitrant organic contaminants in water at low concentrations. PMID:19143323

  17. Liquid-phase ozonation of fusainized components of SS coal

    SciTech Connect

    Semenova, S.A.; Patrakov, Y.F.

    2007-11-15

    Stepwise ozonation of leaning fusainized components of fossil coal of SS grade in acetic acid was studied. The dynamics of accumulation of oxygen-containing groups in the course of ozonation was examined, and the main pathways of the reaction of ozone with structural fragments of the coal substance were revealed.

  18. 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

  19. Climate Suite Study for the National Polar-Orbiting Operational Environmental Satellite System Internal Concepts Study. Part A; Ozone Sensors

    NASA Technical Reports Server (NTRS)

    Lucke, R. L.; Planet, Walter G.; Hudson, R. D.

    1995-01-01

    Our recommendations to NPOESS for the sensors it should adopt to meet threshold requirements for global monitoring of ozone and, to some extent, of aerosols and of atmospheric temperature, pressure, and water vapor content are summarized in this report. The degree to which these sensors fulfill other NPOESS requirements than ozone is also summarized. The number of sensors that should be in the constellation is discussed in terms of desired reliability, continuity of coverage, and the ability to cross-calibrate successive sensors. Our recommendations for specific ozone measurement requirements, IORD item 4.1.6.2.28, are given. We make the case that the monitoring of three minor constituents in the upper atmosphere (N20, ClO or ClONO2, and HNO3) should be added to the list of NPOESS requirements because of their importance to long-term ozone studies and the small additional cost required (ozone sensors are already designed to measure them). Specific measurement requirements, which should be regarded as supplementary to the ozone requirement, are given here. The necessity of using two types of sensors, nadir-viewers and limb-scanners, for atmospheric studies is discussed.

  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. Ozonized oils: a qualitative and quantitative analysis.

    PubMed

    Guinesi, Adriana Simionatto; Andolfatto, Carolina; Bonetti Filho, Idomeo; Cardoso, Arnaldo Alves; Passaretti Filho, Juliano; Farac, Roberta Vieira

    2011-01-01

    Most of the problems of endodontic origin have a bacterial etiological agent. Thus, there is a continued interest in seeking more effective chemical substances that can replace the camphorated paramonochiorophenol or antibiotics as intracanal medicaments. Among the possible substances, ozone has some interesting biological characteristics: bactericidal action, debriding effect, angiogenesis stimulation capacity and high oxidizing power. The purpose of this study was to chemically evaluate the presence of ozone in sunflower, castor, olive and almond oil, as well as in propylene glycol and byproducts of ozonation, such as formaldehyde. These compounds were ozonized, inserted into empty and sterile vials, and analyzed by testing the reaction between ozone and indigo, for determining the presence of ozone, and subjected to the chromotropic acid test for determining the presence of formaldehyde. It was observed complete absence of ozone in all samples tested and presence of formaldehyde. The bactericidal and healing action of ozonized oils could be attributed to products formed by the ozonation of mineral oils, such as formaldehyde, not to the ozone itself.

  2. 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.

  3. The Antarctic Ozone Hole

    ERIC Educational Resources Information Center

    Jones, Anna E.

    2008-01-01

    Since the mid 1970s, the ozone layer over Antarctica has experienced massive destruction during every spring. In this article, we will consider the atmosphere, and what ozone and the ozone layer actually are. We explore the chemistry responsible for the ozone destruction, and learn about why conditions favour ozone destruction over Antarctica. For…

  4. Olfactory response of eastern spruce budworm larvae to red spruce needles exposed to acid rain and elevated levels of ozone.

    PubMed

    Cannon, W N

    1990-12-01

    Second-instar eastern spruce budworm larvae,Choristoneura fumiferana (Clem.), were tested in a two-choice, Y-type, wind-tunnel olfactometer for preferences for red spruce,Picea rubens Sarg., needles exposed for eight weeks to charcoal-filtered air (CFA) or 0.15 ppm ozone (O3) in combination with acidified rainfall at pH 4.2 or 3.0. Volatiles from needles treated with CFA plus pH 4.2 rain (control) were preferred over those from needles exposed to pH 3.0 rain + O3 or O3 alone; O3-treated needles were chosen over those exposed to pH 3.0 rain + O3. No preference was shown between the pH 4.2 and 3.0 rain treatments. Larvae chose purified air flowing through the olfactometer in preference to needle volatiles from the pH 3.0 rain + O3 treatment.

  5. A laboratory study of the nucleation kinetics of nitric acid hydrates under stratospheric conditions

    NASA Astrophysics Data System (ADS)

    James, Alexander D.; Murray, Benjamin J.; Plane, John M. C.

    2016-04-01

    Measurements of the kinetics of crystallisation of ternary H2O-H2SO4-HNO3 mixtures to produce nitric acid hydrate phases, as occurs in the lower stratosphere, have been a long-standing challenge for investigators in the laboratory. Understanding polar stratospheric chlorine chemistry and thereby ozone depletion is increasingly limited by descriptions of nucleation processes. Meteoric smoke particles have been considered in the past as heterogeneous nuclei, however recent studies suggest that these particles will largely dissolve, leaving mainly silica and alumina as solid inclusions. In this study the nucleation kinetics of nitric acid hydrate phases have been measured in microliter droplets at polar stratospheric cloud (PSC) temperatures, using a droplet freezing assay. A clear heterogeneous effect was observed when silica particles were added. A parameterisation based on the number of droplets activated per nuclei surface area (ns) has been developed and compared to global model data. Nucleation experiments on identical droplets have been performed in an X-Ray Diffractometer (XRD) to determine the nature of the phase which formed. β-Nitric Acid Trihydrate (NAT) was observed alongside a mixture of Nitric Acid Dihydrate (NAD) phases. It is not possible to determine whether NAT nucleates directly or is formed by a phase transition from NAD (likely requiring the presence of a mediating liquid phase). Regardless, these results demonstrate the possibility of forming NAT on laboratory timescales. In the polar stratosphere, sulfuric acid (present at several weight percent of the liquid under equilibrium conditions) could provide such a liquid phase. This study therefor provides insight into previous discrepancies between phases formed in the laboratory and those observed in the atmosphere. It also provides a basis for future studies into atmospheric nucleation of solid PSCs.

  6. 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.

  7. Aerosol products, mechanisms, and kinetics of heterogeneous reactions of ozone with oleic acid in pure and mixed particles.

    PubMed

    Ziemann, Paul J

    2005-01-01

    Reactions of O3 with pure and mixed oleic acid particles and bulk solutions were investigated using a thermal desorption particle beam mass spectrometer. The results provide information on the effect of particle matrix on reaction products, mechanisms, and kinetics. The major aerosol products are alpha-acyloxyalkyl hydroperoxides, secondary ozonides, alpha-alkoxyalkyl hydroperoxides, and oxocarboxylic acids formed primarily through reactions of Criegee intermediates with products or with particle matrix compounds. For example, it is estimated that for the reaction of pure oleic acid particles with O3 the aerosol products consist of approximately 68% organic peroxides, 28% 9-oxononanoic acid, and 4% azelaic acid. Although the reaction rate of pure oleic acid particles corresponds to an atmospheric lifetime of minutes, reactions in liquid/solid particle matrices can be orders of magnitude slower. The peroxide products are relatively stable when exposed to matrices typical of atmospheric particles, indicating that the lifetimes of these compounds in the atmosphere may be long enough to allow for long-range transport.

  8. 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.

  9. 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.

  10. Earth's Endangered Ozone

    ERIC Educational Resources Information Center

    Panofsky, Hans A.

    1978-01-01

    Included are (1) a discussion of ozone chemistry; (2) the effects of nitrogen fertilizers, fluorocarbons, and high level aircraft on the ozone layer; and (3) the possible results of a decreasing ozone layer. (MR)

  11. Ozone crisis

    SciTech Connect

    Roan, S.

    1989-01-01

    The author presents an account of the depletion of the atmosphere's ozone layer since the discovery of the phenomenon 15 years ago. The book recounts the flight to ban chlorofluorocarbons (CFC's) and describes the science, the people, and the politics involved, up to the March 1988 international treaty restricting CFC production. It surveys the media's coverage, describes the struggle for remedies, and offers a prognosis for the future.

  12. The Effects of Acid Passivation, Tricresyl Phosphate Presoak, and UV/Ozone Treatment on the Tribology of Perfluoropolyether-Lubricated 440C Stainless Steel Couples

    NASA Technical Reports Server (NTRS)

    Shogrin, Bradley A.; Jones, William R., Jr.; Herrera-Fierro, Pilar; Jansen, Mark J.

    2001-01-01

    The boundary-lubrication performance of two perfluoropolyether (PFPE) thin films in the presence of passivated 440C stainless steel is presented. The study used a standard ball on disk (BoD) tribometer in dry nitrogen and a vacuum spiral orbit tribometer (SOT). Stainless steel surfaces were passivated with one of four techniques: high and low temperature chromic acid bath, a tricresyl phosphate (TCP) soak, or UV/Ozone treated for 15 min. After passivation, each BoD disk had a 400A film of Krytox 16256 (PFPE) applied to it. The lifetimes of these films were quantified by measuring the number of sliding cycles before an increase in friction occurred. The lubricated lifetime of the 440C couple was not altered as a result of the various passivation techniques. The resulting surface chemistry of each passivation technique was examined using X-ray photoelectron spectroscopy (XPS). The SOT was used to examine the effects of the TCP treatment on the lubricated lifetime of another PFPE, Brayco 815Z, under rolling conditions. None of the passivation techniques were found to dramatically increase the oxide film thickness or lubricated lifetimes.

  13. 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.

  14. 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.

  15. Potential sources of nitrous acid (HONO) and their impacts on ozone: A WRF-Chem study in a polluted subtropical region

    NASA Astrophysics Data System (ADS)

    Zhang, Li; Wang, Tao; Zhang, Qiang; Zheng, Junyu; Xu, Zheng; Lv, Mengyao

    2016-04-01

    Current chemical transport models commonly undersimulate the atmospheric concentration of nitrous acid (HONO), which plays an important role in atmospheric chemistry, due to the lack or inappropriate representations of some sources in the models. In the present study, we parameterized up-to-date HONO sources into a state-of-the-art three-dimensional chemical transport model (Weather Research and Forecasting model coupled with Chemistry: WRF-Chem). These sources included (1) heterogeneous reactions on ground surfaces with the photoenhanced effect on HONO production, (2) photoenhanced reactions on aerosol surfaces, (3) direct vehicle and vessel emissions, (4) potential conversion of NO2 at the ocean surface, and (5) emissions from soil bacteria. The revised WRF-Chem was applied to explore the sources of the high HONO concentrations (0.45-2.71 ppb) observed at a suburban site located within complex land types (with artificial land covers, ocean, and forests) in Hong Kong. With the addition of these sources, the revised model substantially reproduced the observed HONO levels. The heterogeneous conversions of NO2 on ground surfaces dominated HONO sources contributing about 42% to the observed HONO mixing ratios, with emissions from soil bacterial contributing around 29%, followed by the oceanic source (~9%), photochemical formation via NO and OH (~6%), conversion on aerosol surfaces (~3%), and traffic emissions (~2%). The results suggest that HONO sources in suburban areas could be more complex and diverse than those in urban or rural areas and that the bacterial and/or ocean processes need to be considered in HONO production in forested and/or coastal areas. Sensitivity tests showed that the simulated HONO was sensitive to the uptake coefficient of NO2 on the surfaces. Incorporation of the aforementioned HONO sources significantly improved the simulations of ozone, resulting in increases of ground-level ozone concentrations by 6-12% over urban areas in Hong Kong and

  16. Ozone Production in the Southern San Joaquin Valley: A NOx Perspective

    NASA Astrophysics Data System (ADS)

    Pusede, S. E.; Wooldridge, P. J.; Browne, E. C.; Rollins, A. W.; Min, K.; Cohen, R. C.; Baier, B. C.; Beaver, M. R.; Boyle, E.; Brune, W. H.; Digangi, J. P.; Gentner, D. R.; Goldstein, A. H.; Keutsch, F.; Ren, X.; Sanders, J.; St Clair, J. M.; Thomas, J.; Weber, R.; Wennberg, P. O.; Zhang, L.

    2010-12-01

    We present measurements of NO2, total alkyl nitrates (ΣANs), and HNO3 by thermal dissociation-laser induced fluorescence (TD-LIF) and NO by chemiluminescence made as part of CalNex-2010 at the San Joaquin Valley supersite in Bakersfield, California (May 15-June 28). We discuss these nitrogen oxide observations in the context of co-located OH, HO2, HONO, H2CO, H2O2, VOC, and O3 measurements, examining the instantaneous ozone production rate (PO3) as a function of NO concentration and HOx production rate. Furthermore, using the slope of the Ox/ΣANs correlation, we report the lowest ever observed urban ΣANs branching ratio (1.5-2%). We test our understanding of this chemistry with a photochemical model, evaluating the implications of suppressed alkyl nitrate formation on O3 production.

  17. More rapid polar ozone depletion through the reaction of HOCl with HCl on polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Prather, Michael J.

    1992-01-01

    The direct reaction of HOCl with HCl is shown here to play a critical part in polar ozone loss. Observations of high levels of OClO and ClO in the springtime Antarctic stratosphere confirm that most of the available chlorine is in the form of ClO(x). But current photochemical models have difficulty converting HCl to ClO(x) rapidly enough in early spring to account fully for the observations. Here, a chemical model is used to show that the direct reaction of HOCl with HCl provides the missing mechanism. As alternative sources of nitrogen-containing oxidants have been converted in the late autumn to inactive HNO3 by known reactions on the sulfate layer aerosols, the reaction of HOCl with HCl on polar stratospheric clouds becomes the most important pathway for releasing that stratospheric chlorine which goes into polar night as HCl.

  18. Degradation of Amino Acids and Structure in Model Proteins and Bacteriophage MS2 by Chlorine, Bromine, and Ozone.

    PubMed

    Choe, Jong Kwon; Richards, David H; Wilson, Corey J; Mitch, William A

    2015-11-17

    Proteins are important targets of chemical disinfectants. To improve the understanding of disinfectant-protein reactions, this study characterized the disinfectant:protein molar ratios at which 50% degradation of oxidizable amino acids (i.e., Met, Tyr, Trp, His, Lys) and structure were observed during HOCl, HOBr, and O3 treatment of three well-characterized model proteins and bacteriophage MS2. A critical question is the extent to which the targeting of amino acids is driven by their disinfectant rate constants rather than their geometrical arrangement. Across the model proteins and bacteriophage MS2 (coat protein), differing widely in structure, methionine was preferentially targeted, forming predominantly methionine sulfoxide. This targeting concurs with its high disinfectant rate constants and supports its hypothesized role as a sacrificial antioxidant. Despite higher HOCl and HOBr rate constants with histidine and lysine than for tyrosine, tyrosine generally was degraded in preference to histidine, and to a lesser extent, lysine. These results concur with the prevalence of geometrical motifs featuring histidines or lysines near tyrosines, facilitating histidine and lysine regeneration upon Cl[+1] transfer from their chloramines to tyrosines. Lysine nitrile formation occurred at or above oxidant doses where 3,5-dihalotyrosine products began to degrade. For O3, which lacks a similar oxidant transfer pathway, histidine, tyrosine, and lysine degradation followed their relative O3 rate constants. Except for its low reactivity with lysine, the O3 doses required to degrade amino acids were as low as or lower than for HOCl or HOBr, indicating its oxidative efficiency. Loss of structure did not correlate with loss of particular amino acids, suggesting the need to characterize the oxidation of specific geometric motifs to understand structural degradation.

  19. Quantifying wet scavenging processes in aircraft observations of nitric acid and cloud condensation nuclei

    NASA Astrophysics Data System (ADS)

    Garrett, T. J.; Avey, L.; Palmer, P. I.; Stohl, A.; Neuman, J. A.; Brock, C. A.; Ryerson, T. B.; Holloway, J. S.

    2006-12-01

    Wet scavenging is an important sink term for many atmospheric constituents. However, production of precipitation in clouds is poorly understood, and pollutant removal through wet scavenging is difficult to separate from removal through dry scavenging, atmospheric mixing, or chemical transformations. Here we use airborne data from the International Consortium for Atmospheric Research on Transport and Transformation project to show that measured ratios of soluble and insoluble trace gases provide a useful indicator for quantifying wet scavenging. Specifically, nitric acid (HNO3), produced as a by-product of combustion, is highly soluble and removed efficiently from clouds by rain. Regional carbon monoxide (CO), which is also an indicator of anthropogenic activity, is insoluble and has a lifetime against oxidation of about a month. We find that relative concentrations of HNO3 to regional CO observed in clear air are negatively correlated with precipitation production rates in nearby cloudy air (r2 = 0.85). Also, we show that relative concentrations of HNO3 and CO can be used to quantify cloud condensation nucleus (CCN) scavenging by precipitating clouds. This is because CCN and HNO3 molecules are both fully soluble in cloud water and hence can be treated as analogous species insofar as wet scavenging is concerned. While approximate, the practical advantage of this approach to scavenging studies is that it requires only measurement in clear air and no a priori knowledge of the cloud or aerosol properties involved.

  20. 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

  1. Nitric acid adsorption on ice at environmental temperatures

    NASA Astrophysics Data System (ADS)

    Laird, Susan Kay

    1998-12-01

    Nitric acid has become an important pollutant in areas which depend on snowpack melt for their water supply. The adsorption of HNO3 on the ice surface was investigated at [-]20oC using artificial snow packed into glass columns and exposed to nitric acid vapor in a flow system. It was observed that, given sufficient acid vapor, HNO3 would adsorb in multilayers on the ice, with the bulk of the acid remaining near the input face. With time, molecules from this high-concentration would slowly diffuse down the column, mainly along the ice surface. The surface diffusion coefficient, D, was calculated from both the average linear migration distance, /langle x/rangle, and Fick's First Law to be 3.5×10-7 cm2/sec. The vapor pressure was calculated from Fick's First Law to be 2.3([/pm]0.3)×10-7 torr. Desorption was found to be of zero order and the energy of desorption at [-]20oC was calculated from an Arrhenius-type equation to be 88.8([/pm]0.1) kJ/mol. This means that the HNO3 will tend to stay on the ice surface in a snowpack.

  2. Differences in leaf characteristics between ozone-sensitive and ozone-tolerant hybrid aspen (Populus tremula x Populus tremuloides) clones.

    PubMed

    Häikiö, Elina; Freiwald, Vera; Julkunen-Tiitto, Riitta; Beuker, Egbert; Holopainen, Toini; Oksanen, Elina

    2009-01-01

    The authors analyzed a suite of leaf characteristics that might help to explain the difference between ozone-sensitive and ozone-tolerant hybrid aspen (Populus tremula L. x Populus tremuloides Michx.) clones. An open-field experiment comprising ambient ozone and 1.5x ambient ozone concentration (about 35 ppb) and two soil nitrogen regimes (60 and 140 kg N ha(-1) year(-1)) was conducted over two growing seasons on potted plants of eight hybrid aspen clones. Four of the clones had previously been determined to be ozone sensitive based on impaired growth in response to elevated ozone concentration. Photosynthetic rate, chlorophyll fluorescence, and concentrations of chlorophyll, protein and carbohydrates were analyzed three times during the second growing season, and foliar phenolic concentrations were measured at the end of the second growing season. Nitrogen amendment counteracted the effects of ozone, but had no effect on growth-related ozone sensitivity of the clones. Ozone-sensitive clones had higher photosynthetic capacity and higher concentrations of Rubisco and phenolics than ozone-tolerant clones, but the effects of ozone were similar in the sensitive and tolerant groups. Nitrogen addition had no effect on phenolic concentration, but elevated ozone concentration increased the concentrations of chlorogenic acid and (+)-catechin. This study suggests that condensed tannins and catechin, but not salicylates or flavonol glycosides, play a role in the ozone tolerance of hybrid aspen.

  3. 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.

  4. 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

  5. Ozone Hole Over Antarctica

    NASA Technical Reports Server (NTRS)

    2002-01-01

    These images from the Total Ozone Mapping Spectrometer (TOMS) show the progressive depletion of ozone over Antarctica from 1979 to 1999. This 'ozone hole' has extended to cover an area as large as 10.5 million square miles in September 1998. The previous record of 10.0 million square miles was set in 1996. The Antarctic ozone hole develops each year between late August and early October. Regions with higher levels of ozone are shown in red. NASA and NOAA instruments have been measuring Antarctic ozone levels since the early 1970s. Large regions of depleted ozone began to develop over Antarctica in the early 1980s. Ozone holes of substantial size and depth are likely to continue to form during the next few years, scientists hope to see a reduction in ozone loss as levels of ozone-destroying CFCs (chlorofluorocarbons) are gradually reduced. Credit: Images by Greg Shirah, NASA Goddard Space Flight Center Scientific Visualization Studio

  6. Ozone Sensitivity in Hybrid Poplar Is Correlated with a Lack of Defense-Gene Activation1

    PubMed Central

    Riehl Koch, Jennifer; Scherzer, Amy J.; Eshita, Steven M.; Davis, Keith R.

    1998-01-01

    Ozone is a major gaseous pollutant thought to contribute to forest decline. Although the physiological and morphological responses of forest trees to ozone have been well characterized, little is known about the molecular basis for these responses. Our studies compared the response to ozone of ozone-sensitive and ozone-tolerant clones of hybrid poplar (Populus maximowizii × Populus trichocarpa) at the physiological and molecular levels. Gas-exchange analyses demonstrated clear differences between the ozone-sensitive clone 388 and the ozone-tolerant clone 245. Although ozone induced a decrease in photosynthetic rate and stomatal conductance in both clones, the magnitude of the decrease in stomatal conductance was significantly greater in the ozone-tolerant clone. RNA-blot analysis established that ozone-induced mRNA levels for phenylalanine ammonia-lyase, O-methyltransferase, a pathogenesis-related protein, and a wound-inducible gene were significantly higher in the ozone-tolerant than in the ozone-sensitive plants. Wound- and pathogen-induced levels of these mRNAs were also higher in the ozone-tolerant compared with the ozone-sensitive plants. The different physiological and molecular responses to ozone exposure exhibited by clones 245 and 388 suggest that ozone tolerance involves the activation of salicylic-acid- and jasmonic-acid-mediated signaling pathways, which may be important in triggering defense responses against oxidative stress. PMID:9847098

  7. A new numerical model of the middle atmosphere. 2: Ozone and related species

    SciTech Connect

    Garcia, R.R.; Solomon, S. |

    1994-06-01

    A new two-dimensional model with detailed photochemistry is presented. The model includes descriptions of planetary wave and gravity wave propagation and dissipation to characterize the wave forcing and associated mixing in the stratosphere and mesosphere. Such a representation allows for explicit calculation of the regions of strong mixing in the middle atmosphere required for accurate simulation of trace gas transport. The new model also includes a detailed description of photochemical processes in the stratosphere and mesosphere. The downward transport of H2, H2O, and NO(y) from the mesosphere to the stratosphere is examined, and it is shown that mesospheric processes can influence the distributions of these chemical species in polar regions. For HNO3 we also find that small concentrations of liquid aerosols above 30 km could play a major role in determining the abundance in polar winter at high latitudes. The model is also used to examine the chemical budget of ozone in the midlatitude stratosphere and to set constraints on the effectiveness of bromine relative to chlorine for ozone loss and the role of the HO2 + BrO reaction. Recent laboratory data used in this modeling study suggest that this process greatly enhances the effectiveness of bromine for ozone destruction, making bromine-catalyzed chemistry second only to HO(x)-catalyzed ozone destruction in the contemporary stratosphere at midlatitudes below about 18 km. The calculated vertical distribution of ozone in the lower stratosphere agrees well with observations, as does the total column ozone during most seasons and latitudes, with the important exception of southern hemisphere winter and spring.

  8. A Three-Tier Diagnostic Test to Assess Pre-Service Teachers' Misconceptions about Global Warming, Greenhouse Effect, Ozone Layer Depletion, and Acid Rain

    NASA Astrophysics Data System (ADS)

    Ozge Arslan, Harika; Cigdemoglu, Ceyhan; Moseley, Christine

    2012-07-01

    This study describes the development and validation of a three-tier multiple-choice diagnostic test, the atmosphere-related environmental problems diagnostic test (AREPDiT), to reveal common misconceptions of global warming (GW), greenhouse effect (GE), ozone layer depletion (OLD), and acid rain (AR). The development of a two-tier diagnostic test procedure as described by Treagust constitutes the framework for this study. To differentiate a lack of knowledge from a misconception, a certainty response index is added as a third tier to each item. Based on propositional knowledge statements, related literature, and the identified misconceptions gathered initially from 157 pre-service teachers, the AREPDiT was constructed and administered to 256 pre-service teachers. The Cronbach alpha reliability coefficient of the pre-service teachers' scores was estimated to be 0.74. Content and face validations were established by senior experts. A moderate positive correlation between the participants' both-tiers scores and their certainty scores indicated evidence for construct validity. Therefore, the AREPDiT is a reliable and valid instrument not only to identify pre-service teachers' misconceptions about GW, GE, OLD, and AR but also to differentiate these misconceptions from lack of knowledge. The results also reveal that a majority of the respondents demonstrated limited understandings about atmosphere-related environmental problems and held six common misconceptions. Future studies could test the AREPDiT as a tool for assessing the misconceptions held by pre-service teachers from different programs as well as in-service teachers and high school students.

  9. The Antarctic ozone hole

    NASA Technical Reports Server (NTRS)

    Molina, Mario J.

    1988-01-01

    Observations of Antarctic ozone levels and the discovery of a hole in the Antarctic region are examined. The effects of chlorofluorocarbons (CFCs) on the level of stratospheric ozone are analyzed. Three cycles explaining the cause of ozone depletion in the poles are proposed. A comparison of field data and proposed depletion cycles reveals that the chemical origin of the ozone hole is due to CFCs. The potential global effects of the Antarctic ozone hole are discussed.

  10. 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

  11. 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.

  12. 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.

  13. 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

  14. Early stage composition of SOA produced by α-pinene/ozone reaction: α-Acyloxyhydroperoxy aldehydes and acidic dimers

    NASA Astrophysics Data System (ADS)

    Witkowski, Bartłomiej; Gierczak, Tomasz

    2014-10-01

    Composition of the freshly formed secondary organic aerosol (SOA) generated by ozonolysis of cyclohexene, cyclohexene-d10 (model precursors) and α-pinene was studied using liquid chromatography coupled to electrospray ionization tandem mass spectrometry (LC-ESI/MS2). SOA was generated in the flow-tube reactor under the following conditions: 22 ± 2 °C, 1 atm and reaction time was approx. 30 s. In an attempt to resolve the current ambiguities, regarding the structure of α-pinene SOA nucleating agents, analytical methods for analysis of α-acyloxyhydroperoxy aldehydes and oligomers containing carboxylic group were developed to study the potential nucleating agents. Negatively charged m/z 351, 341, 337, 357 and 367 ions corresponding to the acidic oligomers were detected in freshly formed α-pinene SOA. For the first time, structures and formation mechanism for compounds detected as m/z 337 and 351 ions were proposed. Based on the model precursor analysis (cyclohexene and cyclohexene-d10) it was concluded that these compounds were most likely formed via aldol reaction of the lower molecular weight aerosol components. α-Acyloxyhydroperoxy aldehydes were studied in the SOA samples using previously developed, novel method, based on the prediction of fragmentation spectrum for the compounds of interest. It was concluded that α-acyloxyhydroperoxy aldehydes were not formed in significant quantities. Based on the obtained results, possible SOA formation and growth mechanism is discussed.

  15. 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

  16. Effect of byproducts from the ozonation of pyrene: biphenyl-2,2',6,6'-tetracarbaldehyde and biphenyl-2,2',6,6'-tetracarboxylic acid on gap junction intercellular communication and neutrophil function.

    PubMed

    Luster-Teasley, Stephanie L; Ganey, Patricia E; DiOrio, Mary; Ward, Joseph S; Maleczka, Robert E; Trosko, James E; Masten, Susan J

    2005-03-01

    In this study, biphenyl-2,2',6,6'-tetracarbaldehyde, an initial byproduct formed from the ozonation of pyrene, and biphenyl-2,2',6,6'-tetracarboxylic acid, a subsequent pyrene ozonation byproduct, were evaluated using two toxicology assays to compare the toxicity of ozonation byproducts with that of the parent compound. The first assay measured the potential for the compounds to block gap junctional intercellular communication (GJIC) using the scrape loading/dye transfer technique in normal WB-344 rat liver epithelial cells. The second assay evaluated the ability of the compounds to affect neutrophil function by measuring the production of superoxide in a human cell line (HL-60). Pyrene significantly blocked intercellular communication (f = 0.2-0.5) at 40 microM and complete inhibition of communication (f < 0.2) occurred at 50 microM. Gap junctional intercellular communication in cells exposed to biphenyl-2,2',6,6'-tetracarbaldehyde reached f < 0.5 at a concentration of 15 microM. At concentrations greater than 20 microM, biphenyl-2,2',6,6'-tetracarbaldehyde was cytotoxic and the inhibition of GJIC was caused by cell death. Biphenyl-2,2',6,6'-tetracarboxylic acid was neither cytotoxic nor inhibitory to GJIC at the concentrations tested (10-500 microM). Exposure to biphenyl-2,2',6,6'-tetracarbaldehyde resulted in a concentration-dependent decrease in phorbol 12-myristate 13-acetate-stimulated O2- production. Neither exposure to pyrene nor biphenyl-2,2',6,6'-tetracarboxylic acid caused a significant toxic effect on neutrophil function.

  17. Antarctic Ozone Hole, 2000

    NASA Technical Reports Server (NTRS)

    2002-01-01

    Each spring the ozone layer over Antarctica nearly disappears, forming a 'hole' over the entire continent. The hole is created by the interaction of some man-made chemicals-freon, for example-with Antarctica's unique weather patterns and extremely cold temperatures. Ozone in the stratosphere absorbs ultraviolet radiation from the sun, thereby protecting living things. Since the ozone hole was discovered many of the chemicals that destroy ozone have been banned, but they will remain in the atmosphere for decades. In 2000, the ozone hole grew quicker than usual and exceptionally large. By the first week in September the hole was the largest ever-11.4 million square miles. The top image shows the average total column ozone values over Antarctica for September 2000. (Total column ozone is the amount of ozone from the ground to the top of the atmosphere. A relatively typical measurement of 300 Dobson Units is equivalent to a layer of ozone 0.12 inches thick on the Earth's surface. Levels below 220 Dobson Units are considered to be significant ozone depletion.) The record-breaking hole is likely the result of lower than average ozone levels during the Antarctic fall and winter, and exceptionally cold temperatures. In October, however (bottom image), the hole shrank dramatically, much more quickly than usual. By the end of October, the hole was only one-third of it's previous size. In a typical year, the ozone hole does not collapse until the end of November. NASA scientists were surprised by this early shrinking and speculate it is related to the region's weather. Global ozone levels are measured by the Total Ozone Mapping Spectrometer (TOMS). For more information about ozone, read the Earth Observatory's ozone fact sheet, view global ozone data and see these ozone images. Images by Greg Shirah, NASA GSFC Scientific Visualization Studio.

  18. The cascade mechanism to explain ozone toxicity: the role of lipid ozonation products.

    PubMed

    Pryor, W A; Squadrito, G L; Friedman, M

    1995-12-01

    Ozone is so reactive that it can be predicted to be entirely consumed as it passes through the first layer of tissue it contacts at the lung/air interface. This layer includes the lung lining fluid (tracheobronchial surface fluid and alveolar and small airway lining fluid) and, where the lung lining fluid is thin or absent, the membranes of the epithelial cells that line the airways. Therefore, the biochemical changes that follow the inhalation of ozone must be relayed into deeper tissue strat by a cascade of ozonation products. Lipid ozonation products (LOP) are suggested to be the most likely species to act as signal transduction molecules. This is because unsaturated fatty acids are present in the lipids in both the lung lining fluid and in pulmonary cell bilayers, and ozone reacts with unsaturated fatty acids to produce ozone-specific products. Further, lipid ozonation products are finite in number, have structures that are predictable from the Criegee ozonation mechanism, and are small, diffusible, stable (or metastable) molecules. Preliminary data show that individual LOP cause the activation of specific lipases, which trigger the release of endogenous mediators of inflammation.

  19. 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.

  20. Efficacy of Slightly Acidic Electrolyzed Water and UV-Ozonated Water Combination for Inactivating Escherichia Coli O157:H7 on Romaine and Iceberg Lettuce during Spray Washing Process.

    PubMed

    Pang, Yu-Hsin; Hung, Yen-Con

    2016-07-01

    Spray washing is a common sanitizing method for the fresh produce industry. The purpose of this research was to investigate the antimicrobial effect of spraying slightly acidic electrolyzed water (SAEW) and a combination of ozonated water with ultraviolet (UV) in reducing Escherichia coli O157:H7 on romaine and iceberg lettuces. Both romaine and iceberg lettuces were spot inoculated with 100 μL of a 3 strain mixture of E. coli O157:H7 to achieve an inoculum of 6 log CFU/g on lettuce. A strong antimicrobial effect was observed for the UV-ozonated water combination, which reduced the population of E. coli by 5 log CFU/g of E. coli O157:H7 on both lettuces. SAEW achieved about 5 log CFU/g reductions in the bacterial counts on romaine lettuce. However, less than 2.5 log CFU/g in the population of E. coli O157:H7 was reduced on iceberg lettuce. The difference may be due to bacteria aggregation near and within stomata for iceberg lettuce but not for romaine lettuce. The UV light treatment may stimulate the opening of the stomata for the UV-ozonated water treatment and hence achieve better bacterial inactivation than the SAEW treatment for iceberg lettuce. Our results demonstrated that the combined treatment of SAEW and UV-ozonated water in the spray washing process could more effectively reduce E. coli O157:H7 on lettuce, which in turn may help reduce incidences of E. coli O157:H7 outbreaks. PMID:27305593

  1. Oxidant and acid aerosol exposure in healthy subjects and subjects with asthma. Part 1. Effects of oxidants, combined with sulfuric or nitric acid, on the pulmonary function of adolescents with asthma. Part 2. Effects of sequential sulfuric acid and ozone exposures on the pulmonary function of healthy subjects and subjects with asthma. Research report, February 1989-April 1994

    SciTech Connect

    Koenig, J.Q.; Covert, D.S.; Pierson, W.E.; Hanley, Q.S.; Rebolledo, V.

    1994-11-01

    The study investigated the pulmonary effects of acid summer haze in a controlled laboratory setting. Of 28 adolescent subjects with allergic asthma, exercise-induced bronchospasm, and a positive response to a standardized methacholine challenge enrolled in the study, 22 completed the study. For two consecutive days each subject inhaled each of four test atmospheres by mouthpiece. The order of exposure to the four test atmospheres was assigned via a random protocol; air, oxidants (0.12 parts per million (ppm) ozone plus 0.30 ppm nitrogen dioxide), oxidants plus sulfuric acid at 70 micro/m3 of air, or oxidants plus 0.05 ppm nitric acid. Exposure to each of the different atmospheres was separated by at least one week. A postexposure methacholine challenge was performed on Day 3.

  2. Reactive nitrogen oxides and ozone above a taiga woodland

    NASA Technical Reports Server (NTRS)

    Bakwin, Peter S.; Jacob, Daniel J.; Wofsy, Steven C.; Munger, J. William; Daube, Bruce C.; Bradshaw, John D.; Sandholm, Scott T.; Talbot, Robert W.; Singh, Hanwant B.; Gregory, Gerald L.

    1994-01-01

    Measurements of reactive nitrogen oxides (NO(x) and NO(y)) and ozone (O3) were made in the planetary boundary layer (PBL) above a taiga woodland in northern Quebec, Canada, during June-August, 1990, as part of NASA Artic Boundary Layer Expedition (ABLE) 3B. Levels of nitrogen oxides and O3 were strongly modulated by the synoptic scale meteorology that brought air from various source regions to the site. Industrial pollution from the Great Lakes region of the U.S. and Canada appears to be a major source for periodic elevation of NO(x), and NO(y) and O3. We find that NO/NO2 ratios at this site at midday were approximately 50% those expected from a simple photochemical steady state between NO(x) and O3, in contrast to our earlier results from the ABLE 3A tundra site. The difference between the taiga and tundra sites is likely due to much larger emissions of biogenic hydrocarbons (particularly isoprene) from the taiga vegetation. Hydrocarbon photooxidation leads to relatively rapid production of peroxy radicals, which convert NO to NO2, at the taiga site. Ratios of NO(x) to NO(y) were typically 2-3 times higher in the PBL during ABLE 3B than during ABLE 3A. This is probably the result of high PAN levels and suppressed formation of HNO3 from NO2 due to high levels of biogenic hydrocarbons at the ABLE 3B site.

  3. Reactive nitrogen oxides and ozone above a taiga woodland

    NASA Astrophysics Data System (ADS)

    Bakwin, Peter S.; Jacob, Daniel J.; Wofsy, Steven C.; Munger, J. William; Daube, Bruce C.; Bradshaw, John D.; Sandholm, Scott T.; Talbot, Robert W.; Singh, Hanwant B.; Gregory, Gerald L.; Blake, Donald R.

    1994-01-01

    Measurements of reactive nitrogen oxides (NOx and NOy) and ozone (O3) were made in the planetary boundary layer (PBL) above a taiga woodland in northern Quebec, Canada, during June-August, 1990, as part of NASA Artie Boundary Layer Expedition (ABLE) 3B. Levels of nitrogen oxides and O3 were strongly modulated by the synoptic scale meteorology that brought air from various source regions to the site. Industrial pollution from the Great Lakes region of the U.S. and Canada appears to be a major source for periodic elevation of NOx, NOy and O3. We find that NO/NO2 ratios at this site at midday were approximately 50% those expected from a simple photochemical steady state between NOx and O3, in contrast to our earlier results from the ABLE 3A tundra site. The difference between the taiga and tundra sites is likely due to much larger emissions of biogenic hydrocarbons (particularly isoprene) from the taiga vegetation. Hydrocarbon photooxidation leads to relatively rapid production of peroxy radicals, which convert NO to NO2, at the taiga site. Ratios of NOx to NOy were typically 2-3 times higher in the PBL during ABLE 3B than during ABLE 3 A. This is probably the result of high PAN levels and suppressed formation of HNO3 from NO2 due to high levels of biogenic hydrocarbons at the ABLE 3B site.

  4. Photochemical ozone budget during the BIBLE A and B campaigns

    NASA Astrophysics Data System (ADS)

    Ko, Malcolm; Hu, Wenjie; Rodríguez, José M.; Kondo, Yutaka; Koike, Makoto; Kita, Kazuyuki; Kawakami, Shuji; Blake, Donald; Liu, Shaw; Ogawa, Toshihiro

    2003-02-01

    Using the measured concentrations of NO, O3, H2O, CO, CH4, and NMHCs along the flight tracks, a photochemical box model is used to calculate the concentrations of the Ox radicals, the HOx radicals, and the nitrogen species at the sampling points. The calculations make use of the measurements from radiometers to scale clear sky photolysis rates to account for cloud cover and ground albedo at the sampling time/point. The concentrations of the nitrogen species in each of the sampled air parcels are computed assuming they are in instantaneous equilibrium with the measured NO and O3. The diurnally varying species concentrations are next calculated using the box model and used to estimate the diurnally averaged production and removal rates of ozone for the sampled air parcels. Clear sky photolysis rates are used in the diurnal calculations. The campaign also provided measured concentration of NOy. The observed NO/NOy ratio is usually larger than the model calculated equilibrium value. There are several possible explanations. It could be a result of recent injection of NO into the air parcel, recent removal of HNO3 from the parcel, recent rapid transport of an air parcel from another location, or a combination of all processes. Our analyses suggest that the local production rate of O3 can be used as another indicator of recent NO injection. However, more direct studies using air trajectory analyses and other collaborative evidences are needed to ascertain the roles played by individual process.

  5. Photochemical ozone budget during the BIBLE A and B campaigns

    NASA Astrophysics Data System (ADS)

    Ko, Malcolm; Hu, Wenjie; RodríGuez, José M.; Kondo, Yutaka; Koike, Makoto; Kita, Kazuyuki; Kawakami, Shuji; Blake, Donald; Liu, Shaw; Ogawa, Toshihiro

    2002-02-01

    Using the measured concentrations of NO, O3, H2O, CO, CH4, and NMHCs along the flight tracks, a photochemical box model is used to calculate the concentrations of the Ox radicals, the HOx radicals, and the nitrogen species at the sampling points. The calculations make use of the measurements from radiometers to scale clear sky photolysis rates to account for cloud cover and ground albedo at the sampling time/point. The concentrations of the nitrogen species in each of the sampled air parcels are computed assuming they are in instantaneous equilibrium with the measured NO and O3. The diurnally varying species concentrations are next calculated using the box model and used to estimate the diurnally averaged production and removal rates of ozone for the sampled air parcels. Clear sky photolysis rates are used in the diurnal calculations. The campaign also provided measured concentration of NOy. The observed NO/NOy ratio is usually larger than the model calculated equilibrium value. There are several possible explanations. It could be a result of recent injection of NO into the air parcel, recent removal of HNO3 from the parcel, recent rapid transport of an air parcel from another location, or a combination of all processes. Our analyses suggest that the local production rate of O3 can be used as another indicator of recent NO injection. However, more direct studies using air trajectory analyses and other collaborative evidences are needed to ascertain the roles played by individual process.

  6. Field method comparison for the characterization of acid aerosols and gases

    NASA Astrophysics Data System (ADS)

    Suh, Helen H.; Allen, George A.; Aurian-Blájeni, Benedict; Koutrakis, Petros; Burton, Robert M.

    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. As part of these studies, acid aerosol and gas concentrations (NH 3, HNO 3, HNO 2, SO 2, H +, NH 4+, NO 3, SO 42-) were measured using five systems: the Harvard/EPA Annular Denuder Systems (HEADS), the Personal Annular Denuder System (PADS), the Continuous Sulfate/Thermal Speciation system (CSTS), the Micro-Orifice Impactor (MOI), and the Harvard Marple Impactor (HI). Concentrations were measured over 3, 12, and 24 h periods, with resultant acid aerosol and gas measurements compared for each system. Results from these studies show excellent agreement among the particulate measurement systems. The sulfate (SO 42-), aerosol strong acidity (H +), and ammonium (NH 4+) concentrations measured by all systems were highly correlated. In addition, 3 and 12 h particulate measurements were comparable for HEADS, MO1, and PADS samplers. Although significantly different, mean relative differences between HEADS measurements and those obtained using the HI and CSTS (SO 42- only) systems were small. For the gases nitric acid (HNO 3) and sulfur dioxide (SO 2), the performance of the HEADS sampler was found to be independent of sample duration, as the 3 and 12 h HEADS measurements were comparable. The PADS sampler, however, was found to measure concentrations of both HNO 3 and SO 2 poorly. PADS measurements, of HNO 3 in particular, were significantly lower than corresponding HEADS measurements. These lower values probably resulted from their deposition on the inlet surfaces of the PADS sampler. The performance of the measurement systems for ammonia (NH 3), nitrous acid (HONO), and nitrate (NO 3-) could not be determined, since their outdoor levels generally were near or below the limit of detection (LOD).

  7. Identification of heptanal and nonanal in bronchoalveolar lavage from rats exposed to low levels of ozone

    SciTech Connect

    Cueto, R.; Squadrito, G.L.; Bermudez, E.; Pryor, W.A. )

    1992-10-15

    Heptanal and nonanal are identified from in vitro studies as potential biomarkers of exposure to ozone, the former resulting from ozonation of palmitoleic acid and the latter from oleic acid. An analytical method is developed based on derivatization using O-pentafluorobenzylhydroxylamine HCl and gas chromatography. These molecules also are present in the lung lavage of Sprague-Dawley rats exposed to 1.3 ppm ozone for 10 hr. These results suggest aldehydes may be useful dosimeters for ozone and indicate that unsaturated fatty acids in the lung lining fluid layer undergo ozonation in vivo.

  8. Identification of heptanal and nonanal in bronchoalveolar lavage from rats exposed to low levels of ozone.

    PubMed

    Cueto, R; Squadrito, G L; Bermudez, E; Pryor, W A

    1992-10-15

    Heptanal and nonanal are identified from in vitro studies as potential biomarkers of exposure to ozone, the former resulting from ozonation of palmitoleic acid and the latter from oleic acid. An analytical method is developed based on derivatization using O-pentafluorobenzylhydroxylamine HCl and gas chromatography. These molecules also are present in the lung lavage of Sprague-Dawley rats exposed to 1.3 ppm ozone for 10 hr. These results suggest aldehydes may be useful dosimeters for ozone and indicate that unsaturated fatty acids in the lung lining fluid layer undergo ozonation in vivo.

  9. Lignin transformations and reactivity upon ozonation in aqueous media

    NASA Astrophysics Data System (ADS)

    Khudoshin, A. G.; Mitrofanova, A. N.; Lunin, V. V.

    2012-03-01

    The reaction of ozone with lignin in aqueous acidic solutions is investigated. The Danckwerst model is used to describe the kinetics of gas/liquid processes occurring in a bubble reactor. The efficient ozonation rate of a soluble lignin analog, sodium lignosulfate, is determined. The main lines of the reaction between ozone and lignin are revealed on the basis of kinetic analysis results and IR and UV spectroscopy data.

  10. Ozone Trend Detectability

    NASA Technical Reports Server (NTRS)

    Campbell, J. W. (Editor)

    1981-01-01

    The detection of anthropogenic disturbances in the Earth's ozone layer was studied. Two topics were addressed: (1) the level at which a trend in total ozoning is detected by existing data sources; and (2) empirical evidence in the prediction of the depletion in total ozone. Error sources are identified. The predictability of climatological series, whether empirical models can be trusted, and how errors in the Dobson total ozone data impact trend detectability, are discussed.

  11. Ozone Layer Observations

    NASA Technical Reports Server (NTRS)

    McPeters, Richard; Bhartia, P. K. (Technical Monitor)

    2002-01-01

    The US National Aeronautics and Space Administration (NASA) has been monitoring the ozone layer from space using optical remote sensing techniques since 1970. With concern over catalytic destruction of ozone (mid-1970s) and the development of the Antarctic ozone hole (mid-1980s), long term ozone monitoring has become the primary focus of NASA's series of ozone measuring instruments. A series of TOMS (Total Ozone Mapping Spectrometer) and SBUV (Solar Backscatter Ultraviolet) instruments has produced a nearly continuous record of global ozone from 1979 to the present. These instruments infer ozone by measuring sunlight backscattered from the atmosphere in the ultraviolet through differential absorption. These measurements have documented a 15 Dobson Unit drop in global average ozone since 1980, and the declines in ozone in the antarctic each October have been far more dramatic. Instruments that measure the ozone vertical distribution, the SBUV and SAGE (Stratospheric Aerosol and Gas Experiment) instruments for example, show that the largest changes are occurring in the lower stratosphere and upper troposphere. The goal of ozone measurement in the next decades will be to document the predicted recovery of the ozone layer as CFC (chlorofluorocarbon) levels decline. This will require a continuation of global measurements of total column ozone on a global basis, but using data from successor instruments to TOMS. Hyperspectral instruments capable of measuring in the UV will be needed for this purpose. Establishing the relative roles of chemistry and dynamics will require instruments to measure ozone in the troposphere and in the stratosphere with good vertical resolution. Instruments that can measure other chemicals important to ozone formation and destruction will also be needed.

  12. Ozone Antimicrobial Efficacy

    EPA Science Inventory

    Ozone is a potent germicide that has been used extensively for water purification. In Europe, 90 percent of the municipal water systems are treated with ozone, and in France, ozone has been used to treat drinking water since 1903. However, there is limited information on the bioc...

  13. Ozone drinking water treatment handbook

    SciTech Connect

    Rice, R.G.

    1990-01-01

    This book explains how ozone can be used to provide primary disinfection, while minimizing halogenated by-products. This is of use to those who design pilot plant studies in full scale ozone plants-and those who employ ozone and regulatory personnel. Detailed section on components of an ozonization system outlines feed gas preparation (air and oxygen), ozone generation, ozone contacting, ozone off gas destruction, monitoring and control of ozonation systems, engineering aspects of ozone, cost factors in ozone technology, case histories (European and U.S.).

  14. Ozone production in four major cities of China: sensitivity to ozone precursors and heterogeneous processes

    NASA Astrophysics Data System (ADS)

    Xue, L. K.; Wang, T.; Gao, J.; Ding, A. J.; Zhou, X. H.; Blake, D. R.; Wang, X. F.; Saunders, S. M.; Fan, S. J.; Zuo, H. C.; Zhang, Q. Z.; Wang, W. X.

    2013-10-01

    Despite a large volume of research over a number of years, our understandings of the key precursors that control tropospheric ozone production and the impacts of heterogeneous processes remain incomplete. In this study, we analyze measurements of ozone and its precursors made at rural/suburban sites downwind of four large Chinese cities - Beijing, Shanghai, Guangzhou and Lanzhou. At each site the same measurement techniques were utilized and a photochemical box model based on the Master Chemical Mechanism (v3.2) was applied, to minimize uncertainties in comparison of the results due to differences in methodology. All four cities suffered from severe ozone pollution. At the rural site of Beijing, export of the well-processed urban plumes contributed to the extremely high ozone levels (up to an hourly value of 286 ppbv), while the pollution observed at the suburban sites of Shanghai, Guangzhou and Lanzhou was characterized by intense in-situ ozone production. The major anthropogenic hydrocarbons were alkenes and aromatics in Beijing and Shanghai, aromatics in Guangzhou, and alkenes in Lanzhou. The ozone production was found to be in a VOCs-limited regime in both Shanghai and Guangzhou, and a mixed regime in Lanzhou. In Shanghai, the ozone formation was most sensitive to aromatics and alkenes, while in Guangzhou aromatics were the predominant ozone precursors. In Lanzhou, either controlling NOx or reducing emissions of olefins from the petrochemical industry would mitigate the local ozone production. The potential impacts of several heterogeneous processes on the ozone formation were assessed. The hydrolysis of dinitrogen pentoxide (N2O5), uptake of the hydroperoxyl radical (HO2) on particles, and surface reactions of NO2 forming nitrous acid (HONO) present considerable sources of uncertainty in the current studies of ozone chemistry. Further efforts are urgently required to better understand these processes and refine atmospheric models.

  15. Quantitative evaluation of ozone and selected climate parameters in a set of EMAC simulations

    NASA Astrophysics Data System (ADS)

    Righi, M.; Eyring, V.; Gottschaldt, K.-D.; Klinger, C.; Frank, F.; Jöckel, P.; Cionni, I.

    2015-03-01

    the temperature in the tropical tropopause layer. Ozone and ozone precursor concentrations, on the other hand, are very similar in the different model setups, if similar boundary conditions are used. Different boundary conditions however lead to relevant differences in the four simulations. Biases which are common to all simulations are the underestimation of the ozone hole and the overestimation of tropospheric column ozone, the latter being significantly reduced when lower lightning emissions of nitrogen oxides are used. To further investigate possible other reasons for such bias, two sensitivity simulations with an updated scavenging routine and the addition of a newly proposed HNO3-forming channel of the HO2+NO reaction were performed. The update in the scavenging routine resulted in a slightly better representation of ozone compared to the reference simulation. The introduction of the new HNO3-forming channel significantly reduces the overestimation of tropospheric ozone. Therefore, including the new reaction rate could potentially be important for a realistic simulation of tropospheric ozone, although laboratory experiments and other model studies need to confirm this hypothesis and some modifications to the rate, which has a strong dependence on water vapor, might also still be needed.

  16. Photoenhanced degradation of veratraldehyde upon the heterogeneous ozone reactions.

    PubMed

    Net, Sopheak; Gligorovski, Sasho; Pietri, Sylvia; Wortham, Henri

    2010-07-21

    Light-induced heterogeneous reactions between gas-phase ozone and veratraldehyde adsorbed on silica particles were performed. At an ozone mixing ratio of 250 ppb, the loss of veratraldehyde largely increased from 1.81 x 10(-6) s(-1) in the dark to 2.54 x 10(-5) s(-1) upon exposure to simulated sunlight (lambda > 300 nm). The observed rates of degradation exhibited linear dependence with the ozone in the dark ozonolysis experiments which change in the non-linear Langmuir-Hinshelwood dependence in the experiments with simultaneous ozone and light exposure of the coated particles. When the coated silica particles were exposed only to simulated sunlight in absence of ozone the loss of veratraldehyde was about three times higher i.e. 5.97 x 10(-6) s(-1) in comparison to the ozonolysis experiment under dark conditions at 250 ppb ozone mixing ratio, 1.81 x 10(-6) s(-1).These results clearly show that the most important loss of veratraldehyde occurs under simultaneous ozone and light exposure of the coated silica particles. The main identified product in the heterogeneous reactions between gaseous ozone and adsorbed veratraldehyde under dark conditions and in presence of light was veratric acid.Carbon yields of veratric acid were calculated and the obtained results indicated that at low ozone mixing ratio (250 ppb) the carbon yield obtained under dark conditions is 70% whereas the carbon yield obtained in the experiments with simultaneous ozone and light exposure of the coated particles is 40%. In both cases the carbon yield of veratric acid exponentially decayed leading to the plateau ( approximately 35% of carbon yield) at an ozone mixing ratio of 6 ppm. Two reaction products i.e. 3-hydroxy-4-methoxybenzoic acid and 4-hydroxy-3-methoxybenzoic acid were identified (confirmed with the standards) only in the experiments performed under simultaneous ozonolysis and light irradiation of the particles.

  17. Ozonation of sunflower oils: impact of experimental conditions on the composition and the antibacterial activity of ozonized oils.

    PubMed

    Moureu, Sophie; Violleau, Frédéric; Ali Haimoud-Lekhal, Djamila; Calmon, Anne

    2015-02-01

    Ozone can react with vegetable oils to produce ozonized oils which have antimicrobial properties and can be used in dermatology. The aim of this study was to evaluate the influence of ozonation conditions and of the initial fatty acid composition on iodine index (II), peroxide index (IP), acidity value (AV) of ozonized sunflower oils. The antibacterial activity of these products against the three bacterial strains that are more often involved in mastitis (Staphylococcus aureus, Escherichia coli and Streptococcus uberis) was also evaluated. In that purpose, two different sunflower oils have been studied: a "classical" oil (55% linoleic acid, 35% oleic acid) and a "high oleic" oil (90% oleic acid). Both were ozonized with or without water during different times (from 1 to 7 h). Results show that the addition of water has a direct impact on the increase in IP (up to 2600 meq of active oxygen/kg of oil with water and 430 without) and AV but does not influence the kinetic of the decrease in II. Minimal inhibitory concentrations were ranging from 1.25 to 40 mg/mL and the antibacterial activity of oils ozonized with water was better than the one of oils ozonized alone. These results are an open door to new applications of ozonized oils.

  18. 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.

  19. Biochemical Plant Responses to Ozone 1

    PubMed Central

    Langebartels, Christian; Kerner, Kristina; Leonardi, Silvio; Schraudner, Martina; Trost, Monika; Heller, Werner; Sandermann, Heinrich

    1991-01-01

    Polyamine metabolism was examined in tobacco (Nicotiana tabacum L.) exposed to a single ozone treatment (5 or 7 hours) and then postcultivated in pollutant-free air. The levels of free and conjugated putrescine were rapidly increased in the ozone-tolerant cultivar Bel B and remained high for 3 days. This accumulation was preceded by a transient rise of l-arginine decar-boxylase (ADC, EC 4.1.1.19) activity. The ozone-sensitive cultivar Bel W3 showed a rapid production of ethylene and high levels of 1-aminocyclopropane-1-carboxylic acid after 1 to 2 hours of exposure. Induction of putrescine levels and ADC activity was weak in this cultivar and was observed when necrotic lesions developed. Leaf injury occurred in both lines when the molar ratio of putrescine to 1-aminocyclopropane-1-carboxylic acid or ethylene fell short of a certain threshold value. Monocaffeoyl-putrescine, an effective scavenger for oxyradicals, was detected in the apo-plastic fluid of the leaves of cv Bel B and increased upon exposure to ozone. This extracellular localization could allow scavenging of ozone-derived oxyradicals at the first site of their generation. Induction of either polyamine or ethylene pathways may represent a control mechanism for inhibition or promotion of lesion formation and thereby contribute to the disposition of plants for ozone tolerance. PMID:16668067

  20. The Ozone-Iodine-Chlorate Clock Reaction

    PubMed Central

    Sant'Anna, Rafaela T. P.; Monteiro, Emily V.; Pereira, Juliano R. T.; Faria, Roberto B.

    2013-01-01

    This work presents a new clock reaction based on ozone, iodine, and chlorate that differs from the known chlorate-iodine clock reaction because it does not require UV light. The induction period for this new clock reaction depends inversely on the initial concentrations of ozone, chlorate, and perchloric acid but is independent of the initial iodine concentration. The proposed mechanism considers the reaction of ozone and iodide to form HOI, which is a key species for producing non-linear autocatalytic behavior. The novelty of this system lies in the presence of ozone, whose participation has never been observed in complex systems such as clock or oscillating reactions. Thus, the autocatalysis demonstrated in this new clock reaction should open the possibility for a new family of oscillating reactions. PMID:24386257

  1. The ozone-iodine-chlorate clock reaction.

    PubMed

    Sant'Anna, Rafaela T P; Monteiro, Emily V; Pereira, Juliano R T; Faria, Roberto B

    2013-01-01

    This work presents a new clock reaction based on ozone, iodine, and chlorate that differs from the known chlorate-iodine clock reaction because it does not require UV light. The induction period for this new clock reaction depends inversely on the initial concentrations of ozone, chlorate, and perchloric acid but is independent of the initial iodine concentration. The proposed mechanism considers the reaction of ozone and iodide to form HOI, which is a key species for producing non-linear autocatalytic behavior. The novelty of this system lies in the presence of ozone, whose participation has never been observed in complex systems such as clock or oscillating reactions. Thus, the autocatalysis demonstrated in this new clock reaction should open the possibility for a new family of oscillating reactions. PMID:24386257

  2. The ozone-iodine-chlorate clock reaction.

    PubMed

    Sant'Anna, Rafaela T P; Monteiro, Emily V; Pereira, Juliano R T; Faria, Roberto B

    2013-01-01

    This work presents a new clock reaction based on ozone, iodine, and chlorate that differs from the known chlorate-iodine clock reaction because it does not require UV light. The induction period for this new clock reaction depends inversely on the initial concentrations of ozone, chlorate, and perchloric acid but is independent of the initial iodine concentration. The proposed mechanism considers the reaction of ozone and iodide to form HOI, which is a key species for producing non-linear autocatalytic behavior. The novelty of this system lies in the presence of ozone, whose participation has never been observed in complex systems such as clock or oscillating reactions. Thus, the autocatalysis demonstrated in this new clock reaction should open the possibility for a new family of oscillating reactions.

  3. Photochemical modeling of the Antarctic stratosphere: Observational constraints from the airborne Antarctic ozone experiment and implications for ozone behavior

    NASA Technical Reports Server (NTRS)

    Rodriguez, Jose M.; Sze, Nien-Dak; Ko, Malcolm K. W.

    1988-01-01

    The rapid decrease in O3 column densities observed during Antarctic spring has been attributed to several chemical mechanisms involving nitrogen, bromine, or chlorine species, to dynamical mechanisms, or to a combination of the above. Chlorine-related theories, in particular, predict greatly elevated concentrations of ClO and OClO and suppressed abundances of NO2 below 22 km. The heterogeneous reactions and phase transitions proposed by these theories could also impact the concentrations of HCl, ClNO3 and HNO3 in this region. Observations of the above species have been carried out from the ground by the National Ozone Expedition (NOZE-I, 1986, and NOZE-II, 1987), and from aircrafts by the Airborne Antarctic Ozone Experiment (AAOE) during the austral spring of 1987. Observations of aerosol concentrations, size distribution and backscattering ratio from AAOE, and of aerosol extinction coefficients from the SAM-II satellite can also be used to deduce the altitude and temporal behavior of surfaces which catalyze heterogeneous mechanisms. All these observations provide important constraints on the photochemical processes suggested for the spring Antarctic stratosphere. Results are presented for the concentrations and time development of key trace gases in the Antarctic stratosphere, utilizing the AER photochemical model. This model includes complete gas-phase photochemistry, as well as heterogeneous reactions. Heterogeneous chemistry is parameterized in terms of surface concentrations of aerosols, collision frequencies between gas molecules and aerosol surfaces, concentrations of HCl/H2O in the frozen particles, and probability of reaction per collision (gamma). Values of gamma are taken from the latest laboratory measurements. The heterogeneous chemistry and phase transitions are assumed to occur between 12 and 22 km. The behavior of trace species at higher altitudes is calculated by the AER 2-D model without heterogeneous chemistry. Calculations are performed for

  4. Heterogeneous conversion of calcite aerosol by nitric acid.

    PubMed

    Preszler Prince, A; Grassian, V H; Kleiber, P; Young, M A

    2007-02-01

    The reaction of nitric acid with calcite aerosol at varying relative humidities has been studied under suspended particle conditions in an atmospheric reaction chamber using infrared absorption spectroscopy. The reactant concentration in the chamber, as well as the appearance of gas phase products and surface adsorbed species, was spectroscopically monitored before and after mixing with CaCO(3) (calcite) particles. The interaction with HNO(3) was found to lead to gas phase CO(2) evolution and increased water uptake due to heterogeneous conversion of the carbonate to particulate nitrate. The reaction was enhanced as the relative humidity of the system was increased, especially at relative humidities above the reported deliquescence point of particulate Ca(NO(3))(2). The measured reaction extent demonstrates that the total calcite particulate mass is available for reaction with HNO(3) and the conversion process is not limited to the particle surface. The spectroscopy of the surface formed nitrate suggests a highly concentrated solution environment with a significant degree of ion pairing. The implications of the HNO(3) loss and the formation of the particulate nitrate product for atmospheric chemistry are discussed. PMID:17242744

  5. Ozone-induced changes in natural organic matter (NOM) structure

    USGS Publications Warehouse

    Westerhoff, P.; Debroux, J.; Aiken, G.; Amy, G.

    1999-01-01

    Hydrophobic organic acids (combined humic and fulvic acids), obtained from an Antarctic Lake with predominantly microbially derived organic carbon sources and two US fiver systems with terrestrial organic carbon sources, were ozonated. Several analyses, including 13C-NMR, UV absorbance, fluorescence, hydrophobic/transphilic classification, and potentiometric titrations, were performed before and after ozonation. Ozonation reduced aromatic carbon content, selectively reducing phenolic carbon content. Ozonation of the samples resulted in increased aliphatic, carboxyl, plus acetal and ketal anomeric carbon content and shifted towards less hydrophobic compounds.Hydrophobic organic acids (combined humic and fulvic acids), obtained from an Antarctic Lake with predominantly microbially derived organic carbon sources and two US river systems with terrestrial organic carbon sources, were ozonated. Several analyses, including 13C-NMR, UV absorbance, fluorescence, hydrophobic/transphilic classification, and potentiometric titrations, were performed before and after ozonation. Ozonation reduced aromatic carbon content, selectively reducing phenolic carbon content. Ozonation of the samples resulted in increased aliphatic, carboxyl, plus acetal and ketal anomeric carbon content and shifted towards less hydrophobic compounds.

  6. Ozone and the stratosphere

    NASA Technical Reports Server (NTRS)

    Shimazaki, Tatsuo

    1987-01-01

    It is shown that the stratospheric ozone is effective in absorbing almost all radiation below 300 nm at heights below 300 km. The distribution of global ozone in the troposphere and the lower stratosphere, and the latitudinal variations of the total ozone column over four seasons are considered. The theory of the ozone layer production is discussed together with catalytic reactions for ozone loss and the mechanisms of ozone transport. Special attention is given to the anthropogenic perturbations, such as SST exhaust gases and freon gas from aerosol cans and refrigerators, that may cause an extensive destruction of the stratospheric ozone layer and thus have a profound impact on the world climate and on life.

  7. INHALATION OF OZONE AND DIESEL EXHAUST PARTICLES (DEP) INDUCES ACUTE AND REVERSIBLE CARDIAC GENE EXPRESSION CHANGES

    EPA Science Inventory

    We have recently shown that episodic but not acute exposure to ozone or DEP induces vascular effects that are associated with the loss of cardiac mitochondrial phospholipid fatty acids (DEP 2.0 mg/m3 > ozone, 0.4 ppm). In this study we determined ozone and DEP-induced cardiac gen...

  8. Advanced treatment of biotreated textile industry wastewater with ozone, virgin/ozonated granular activated carbon and their combination.

    PubMed

    Arslan-Alaton, Idil; Seremet, Ozden

    2004-01-01

    Biotreated textile wastewater (CODo = 248 mg L(-1); TOCo = 58 mg L(-1); A620 = 0.007 cm(-1); A525 = 0.181 cm(-1); A436 = 0.198 cm(-1)) was subjected to advanced treatment with ozonation, granular activated carbon (GAC) adsorption in serial and simultaneous applications. Experiments were conducted to investigate the effects of applied ozone dose, ozone absorption rate, specific ozone absorption efficiency, GAC dose, and reaction pH on the treatment performance of the selected tertiary treatment scheme. In separate experiments, the impact of virgin GAC ozonation on its adsorptive capacity for biotreated and biotreated + ozonated textile effluent was also investigated. Ozonation appeared to be more effective for decolorization (kd = 0.15 min(-1) at pH = 3), whereas GAC adsorption yielded higher COD removal rates (54% at pH = 3). It was also found that GAC addition (4 g/L) at pH = 7 and 9 enhanced the COD abatement rate of the ozonation process significantly and that the sequential application of ozonation (at pH = 3-11, 675 mg L(-1) O3) followed by GAC adsorption (at pH = 3-7, 10 g L(-1) GAC) resulted in the highest treatment performances both in terms of color and COD reduction. Simultaneous application of GAC and ozone at acidic and alkaline pH seriously inhibited COD abatement rates as a consequence of competitive adsorption and partial oxidation of textile components and GAC. It could also be established that ozone absorption efficiency decreased after color removal was complete. Ozonation of biotreated textile wastewater with 113 mg L(-1) ozone resulted in an appreciable enhancement of GAC adsorptive capacity in terms of residual color removal. Ozonation of GAC at relatively low doses (= 10.8 mg/g GAC) did not improve its overall adsorption capacity.

  9. Modeling ozone plumes observed downwind of New York City over the North Atlantic Ocean during the ICARTT field campaign

    NASA Astrophysics Data System (ADS)

    Lee, S.-H.; Kim, S.-W.; Trainer, M.; Frost, G. J.; McKeen, S. A.; Cooper, O. R.; Flocke, F.; Holloway, J. S.; Neuman, J. A.; Ryerson, T.; Senff, C. J.; Swanson, A. L.; Thompson, A. M.

    2011-07-01

    Transport and chemical transformation of well-defined New York City (NYC) urban plumes over the North Atlantic Ocean were studied using aircraft measurements collected on 20-21 July 2004 during the ICARTT (International Consortium for Atmospheric Research on Transport and Transformation) field campaign and WRF-Chem (Weather Research and Forecasting-Chemistry) model simulations. The strong NYC urban plumes were characterized by carbon monoxide (CO) mixing ratios of 350-400 parts per billion by volume (ppbv) and ozone (O3) levels of about 100 ppbv near New York City on 20 July in the WP-3D in-situ and DC-3 lidar aircraft measurements. On 21 July, the two aircraft captured strong urban plumes with about 350 ppbv CO and over 150 ppbv O3 (~160 ppbv maximum) about 600 km downwind of NYC over the North Atlantic Ocean. The measured urban plumes extended vertically up to about 2 km near New York City, but shrank to 1-1.5 km over the stable marine boundary layer (MBL) over the North Atlantic Ocean. The WRF-Chem model reproduced ozone formation processes, chemical characteristics, and meteorology of the measured urban plumes near New York City (20 July) and in the far downwind region over the North Atlantic Ocean (21 July). The quasi-Lagrangian analysis of transport and chemical transformation of the simulated NYC urban plumes using WRF-Chem results showed that the pollutants can be efficiently transported in (isentropic) layers in the lower atmosphere (<2-3 km) over the North Atlantic Ocean while maintaining a dynamic vertical decoupling by cessation of turbulence in the stable MBL. The O3 mixing ratio in the NYC urban plumes remained at 80-90 ppbv during nocturnal transport over the stable MBL, then grew to over 100 ppbv by daytime oxidation of nitrogen oxides (NOx = NO + NO2) with mixing ratios on the order of 1 ppbv. Efficient transport of reactive nitrogen species (NOy), specifically nitric acid (HNO3), was confirmed through the comparison of the CO/NOy ratio in

  10. Modeling ozone plumes observed downwind of New York City over the North Atlantic Ocean during the ICARTT field campaign

    NASA Astrophysics Data System (ADS)

    Lee, S.-H.; Kim, S.-W.; Trainer, M.; Frost, G. J.; McKeen, S. A.; Cooper, O. R.; Flocke, F.; Holloway, J. S.; Neuman, J. A.; Ryerson, T.; Senff, C. J.; Swanson, A. L.; Thompson, A. M.

    2011-05-01

    Transport and chemical transformation of well-defined New York City (NYC) urban plumes over the North Atlantic Ocean were studied using aircraft measurements collected on 20-21 July 2004 during the ICARTT (International Consortium for Atmospheric Research on Transport and Transformation) field campaign and WRF-Chem (Weather Research and Forecasting-Chemistry) model simulations. The strong NYC urban plumes were characterized by carbon monoxide (CO) mixing ratios of 350-400 parts per billion by volume (ppbv) and ozone (O3) levels of about 100 ppbv near New York City on 20 July in the WP-3D in-situ and DC-3 lidar aircraft measurements. On 21 July, the two aircraft captured strong urban plumes with about 350 ppbv CO and over 150 ppbv O3 (~160 ppbv maximum) about 600 km downwind of NYC over the North Atlantic Ocean. The measured urban plumes extended vertically up to about 2 km near New York City, but shrank to 1-1.5 km over the stable marine boundary layer (MBL) over the North Atlantic Ocean. The WRF-Chem model reproduced ozone formation processes, chemical characteristics, and meteorology of the measured urban plumes near New York City (20 July) and in the far downwind region over the North Atlantic Ocean (21 July). The quasi-Lagrangian analysis of transport and chemical transformation of the simulated NYC urban plumes using WRF-Chem results showed that the pollutants can be efficiently transported in (isentropic) layers in the lower atmosphere (<2-3 km) over the North Atlantic Ocean while maintaining a dynamic vertical decoupling by cessation of turbulence in the stable MBL. The O3 mixing ratio in the NYC urban plumes remained at 80-90 ppbv during nocturnal transport over the stable MBL, then grew to over 100 ppbv by daytime oxidation of nitrogen oxides (NOx = NO + NO2) with mixing ratios on the order of 1 ppbv. Efficient transport of reactive nitrogen species (NOy), specifically nitric acid (HNO3), was confirmed through the comparison of the CO/NOy ratio in

  11. 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

  12. Origin and Variability of Upper Tropospheric Nitrogen Oxides and Ozone at Northern Mid-Latitudes

    NASA Technical Reports Server (NTRS)

    Grewe, V.; Brunner, D.; Dameris, M.; Grenfell, J. L.; Hein, R.; Shindell, D.; Staehelin, J.

    1999-01-01

    Measurements of NO(x) and ozone performed during the NOXAR project are compared with results from the coupled chemistry-climate models ECHAM4.L39(DLR)/CHEM and GISS-model. The measurements are based on flights between Europe and the East coast of America and between Europe and the Far East in the latitude range 40 deg N to 65 deg N. The comparison concentrates on tropopause altitudes and reveals strong longitudinal variations of seasonal mean NO,, of 200 pptv. Either model reproduced strong variations 3 km below but not at the tropopause, indicating a strong missing NO(x) or NO(y) sink over remote areas, e.g. NO(x) to HNO3 conversion by OH from additional OH sources or HNO3 wash-out. Vertical profiles show maximum NO(x) values 2-3 km below the tropopause with a strong seasonal cycle. ECHAM4.L39(DLR)/CHEM reproduces a maximum, although located at the tropopause with a less pronounced seasonal cycle, whereas the GISS model reproduces the seasonal cycle but not the profile's shape due to its coarser vertical resolution. A comparison of NO(x) frequency distributions reveals that both models are capable of reproducing the observed variability, except that ECHAM4.L39(DLR)/CHEM shows no very high NO(x) mixing ratios. Ozone mean values, vertical profiles and frequency distributions are much better reproduced in either model, indicating that the NO(x) frequency distribution, namely the most frequent NO(x) mixing ratio, is more important for the tropospheric photochemical ozone production than its mean value. Both models show that among all sources, NO(x) from lightning contributes most to the seasonal cycle of NO(x) at tropopause altitudes. The impact of lightning in the upper troposphere on NO(x) does not vary strongly with altitude, whereas the impact of surface emissions decreases with altitude. However, the models show significant differences in lightning induced NO(x) concentrations, especially in winter, which may be related to the different treatment of the lower

  13. Quantitative evaluation of ozone and selected climate parameters in a set of EMAC simulations

    NASA Astrophysics Data System (ADS)

    Righi, M.; Eyring, V.; Gottschaldt, K.-D.; Klinger, C.; Frank, F.; Jöckel, P.; Cionni, I.

    2014-10-01

    the temperature in the tropical tropopause layer. Ozone and ozone precursor concentrations on the other hand are very similar in the different model setups, if similar boundary conditions are used. Different boundary conditions however lead to relevant differences in the four simulations. SSTs and SICs, which are prescribed in all simulations, play a key role in the representation of the ozone hole, which is significantly underestimated in some experiments. A bias that is present in all simulations is an overestimation of tropospheric column ozone, which is significantly reduced when lower lightning emissions of nitrogen oxides are used. To further investigate possible other reasons for such bias, two sensitivity simulations with an updated scavenging routine and the addition of a newly proposed HNO3-forming channel of the HO2+ NO reaction were performed. The update in the scavenging routine resulted in a slightly better representation of ozone compared to the reference simulation. The introduction of the new HNO3-forming channel significantly reduces this bias. Therefore, including the new reaction rate could potentially be important for a realistic simulation of tropospheric ozone, although laboratory experiments and other models studies need to confirm this hypothesis and some modifications to the rate, which has a strong dependence on water vapour, might also still be needed.

  14. Homogeneous and heterogeneous reactions of phenanthrene with ozone

    NASA Astrophysics Data System (ADS)

    Zhang, Yang; Yang, Bo; Meng, Junwang; Gao, Shaokai; Dong, Xinyu; Shu, Jinian

    2010-02-01

    The reactions of gas-phase phenanthrene and suspended phenanthrene particles with ozone were conducted in a 200l chamber. The secondary organic aerosol formation was observed in the reaction of gas-phase phenanthrene with ozone and simultaneously the size distribution of the secondary organic aerosol was monitored with a scanning mobility particle sizer during the formation process. The particulate ozonation products from both reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer. 2,2'-Diformylbiphenyl was identified as the dominant product in both homogeneous and heterogeneous reactions of phenanthrene with ozone. GC/MS analysis of ozonation products of phenanthrene in glacial acetic acid was carried out for assigning time-of-flight mass spectra of reaction products formed in the homogeneous and heterogeneous reactions of phenanthrene with ozone.

  15. Ozone-initiated chemistry in an occupied simulated aircraft cabin.

    PubMed

    Weschler, Charles J; Wisthaler, Armin; Cowlin, Shannon; Tamás, Gyöngyi; Strøm-Tejsen, Peter; Hodgson, Alfred T; Destaillats, Hugo; Herrington, Jason; Zhang, Junfeng; Nazaroff, William W

    2007-09-01

    We have used multiple analytical methods to characterize the gas-phase products formed when ozone was added to cabin air during simulated 4-hour flights that were conducted in a reconstructed section of a B-767 aircraft containing human occupants. Two separate groups of 16 females were each exposed to four conditions: low air exchange (4.4 (h-1)), <2 ppb ozone; low air exchange, 61-64 ppb ozone; high air exchange (8.8 h(-1)), <2 ppb ozone; and high air exchange, 73-77 ppb ozone. The addition of ozone to the cabin air increased the levels of identified byproducts from approximately 70 to 130 ppb at the lower air exchange rate and from approximately 30 to 70 ppb at the higher air exchange rate. Most of the increase was attributable to acetone, nonanal, decanal, 4-oxopentanal (4-OPA), 6-methyl-5-hepten-2-one (6-MHO), formic acid, and acetic acid, with 0.25-0.30 mol of quantified product volatilized per mol of ozone consumed. Several of these compounds reached levels above their reported odor thresholds. Most byproducts were derived from surface reactions with occupants and their clothing, consistent with the inference that occupants were responsible for the removal of >55% of the ozone in the cabin. The observations made in this study have implications for other indoor settings. Whenever human beings and ozone are simultaneously present, one anticipates production of acetone, nonanal, decanal, 6-MHO, geranyl acetone, and 4-OPA.

  16. Fluorescence spectroscopic characterization of DOM fractions isolated from a filtered river water after ozonation and catalytic ozonation.

    PubMed

    Zhang, Tao; Lu, Jinfeng; Ma, Jun; Qiang, Zhimin

    2008-03-01

    Fluorescence spectra were applied to investigate the structural changes of four dominant dissolved natural organic matter (DOM) fractions of a filtered river water before and after ozonation and catalytic ozonation. The ozonation and catalytic ozonation with synthetic goethite (FeOOH) and cerium dioxide (CeO(2)) were carried out under normal conditions, i.e. pH 7, reaction time of 10 min, and ozone/DOC ratio of about 1. The fluorescence spectra were recorded at both excitation-emission matrix (EEM) and synchronous scanning modes. EEM results reveal that ozonation of these DOM fractions causes a significant decrease of the aromaticity of humic-like structures and an increase of electron withdrawing groups, e.g., carboxylic groups. The catalysts can further improve the destruction of the humic-like structures in catalytic ozonation. Synchronous spectra reveal that ozonation of hydrophobic acid and hydrophilic acid (HIA) yields a significant amount of by-products with low aromaticity and low molecular weight. Catalytic ozonation enhances substantially the formation of these by-products from HIA and improves the destruction of highly polycyclic aromatic structures for all examined DOM fractions. PMID:18190948

  17. 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.

  18. [Ozone exposure and asthma].

    PubMed

    Kleis, S; Louis, R; Bartsch, P

    2003-03-01

    Ozone is a pollutant the production of which depends on weather conditions and car engine combustion. Numerous epidemiological studies have indicated that high ozone levels correlated with morbidity in asthma. Experimental studies have shown that exposure of healthy subjects and asthmatics to ozone levels comparable to those measured in ambient air during hot summer days can generate respiratory symptoms, neutrophilic airways inflammation and lung function impairment. Lung function changes following ozone exposure are more pronounced in asthmatics and are dependent on the duration and intensity of exposure, a previous exposure and the nutritional status of the subjects. The airway epithelial cell layer is likely to play a pivotal role in initiating the inflammatory process following ozone exposure. Control of ambient air ozone levels must be a target for public health authorities.

  19. Biological effects of ozone

    SciTech Connect

    Lippmann, M. )

    1989-09-01

    Tropospheric ozone, a classic anthropogenic air pollutant, is going to remain a troublesome byproduct of contemporary civilization for many decades. We have known for some time that the hydrocarbons and nitrogen oxides from motor vehicles, together with actinic radiation, account for local and regional photochemistry leading to prolonged afternoon ozone peaks. We also now know that agricultural burning and intensive animal husbandry elevate regional and mesoscale concentrations of ozone and its precursors, and that remote background levels of ozone have been rising steadily throughout this century. The changes we will have to make in emission controls to appreciably reduce current tropospheric ozone levels will have profound effects on our transportation systems, consumer products, and lifestyles. As a society, we will have to make difficult choices about the levels of ozone-associated health, welfare, and natural system damage we will tolerate, or conversely, how much we are willing to pay for controls which can minimize the damage.

  20. Ozone therapy in periodontics

    PubMed Central

    Gupta, G; Mansi, B

    2012-01-01

    Gingival and Periodontal diseases represent a major concern both in dentistry and medicine. The majority of the contributing factors and causes in the etiology of these diseases are reduced or treated with ozone in all its application forms (gas, water, oil). The beneficial biological effects of ozone, its anti-microbial activity, oxidation of bio-molecules precursors and microbial toxins implicated in periodontal diseases and its healing and tissue regeneration properties, make the use of ozone well indicated in all stages of gingival and periodontal diseases. The primary objective of this article is to provide a general review about the clinical applications of ozone in periodontics. The secondary objective is to summarize the available in vitro and in vivo studies in Periodontics in which ozone has been used. This objective would be of importance to future researchers in terms of what has been tried and what the potentials are for the clinical application of ozone in Periodontics. PMID:22574088

  1. Formation of stratospheric nitric acid by a hydrated ion cluster reaction: Implications for the effect of energetic particle precipitation on the middle atmosphere

    NASA Astrophysics Data System (ADS)

    Kvissel, O.-K.; Orsolini, Y. J.; Stordal, F.; Isaksen, I. S. A.; Santee, M. L.

    2012-08-01

    In order to improve our understanding of the effects of energetic particle precipitation on the middle atmosphere and in particular upon the nitrogen family and ozone, we have modeled the chemical and dynamical middle atmosphere response to the introduction of a chemical pathway that produces HNO3 by conversion of N2O5 upon hydrated water clusters H+·(H2O)n. We have used an ensemble of simulations with the National Center for Atmospheric Research (NCAR) Whole-Atmosphere Community Climate Model (WACCM) chemistry-climate model. The chemical pathway alters the internal partitioning of the NOy family during winter months in both hemispheres, and ultimately triggers statistically significant changes in the climatological distributions of constituents including: i) a cold season production and loss of HNO3 and N2O5, respectively, and ii) a cold season decrease and increase in NOx/NOy-ratio and O3, respectively, in the polar regions of both hemispheres. We see an improved seasonal evolution of modeled HNO3 compared to satellite observations from Microwave Limb Sounder (MLS), albeit not enough HNO3 is produced at high altitudes. Through O3changes, both temperature and dynamics are affected, allowing for complex chemical-dynamical feedbacks beyond the cold season when the pathway is active. Hence, we also find a NOxpolar increase in spring-to-summer in the southern hemisphere, and in spring in the northern hemisphere. The springtime NOxincrease arises from anomalously strong poleward transport associated with a weaker polar vortex. We argue that the weakening of zonal-mean polar winds down to the lower stratosphere, which is statistically significant at the 0.90 level in spring months in the southern hemisphere, is caused by strengthened planetary waves induced by the middle and sub-polar latitude zonal asymmetries in O3and short-wave heating.

  2. [Effect of acid-base two steps surface modification on the adsorption of Cr(VI) onto activated carbon].

    PubMed

    Liu, Shou-xin; Chen, Xiao-yun; Chen, Xi; Sun, Cheng-lin

    2005-11-01

    Effect of HNO3-NaOH two steps surface modification on the adsorption of Cr(VI) from aqueous solution onto activated carbon was evaluated. Activated carbon was oxidized in HNO3 aqueous solution at first (AC1), then treated in the mixture of NaOH and NaCl solution (AC2). Batch equilibrium and continuous adsorption experiments were conducted to determine the adsorption characteristics. Boehm titration method, element analysis were used to characterize the surface properties. N2/77 K adsorption isotherm method was used to characterize the pore structure. The results reveal that adsorption capacity and adsorption rate increase significantly, which in the following order: AC2>AC1>AC0. Surface modification caused BET surface area decreased and the total number of surface oxygen acid groups increased. First oxidation modification in HNO3 solution produced positive acid groups on the surface of activated carbon. Subsequent 2nd modification replaced H+ of carbon surface groups by Na+, the acidity of AC2 was decreased. The main cause of higher Cr(VI) adsorption capacity and rate for AC2 was the more oxygen surface acid groups, and suitable solution pH provide by surface groups.

  3. The Antarctic ozone hole

    NASA Technical Reports Server (NTRS)

    Stolarski, Richard S.

    1988-01-01

    Processes that may be responsible for the thinning in the ozone layer above the South Pole are described. The chlorine catalytic cycle which destroys ozone is described, as are the major types of reactions that are believed to interfere with this cycle by forming chlorine reservoirs. The suspected contributions of polar stratospheric clouds to these processes are examined. Finally, the possibility that the ozone hole may be due more to a shift in atmospheric dynamics than to chemical destruction is addressed.

  4. Changes in stratospheric ozone.

    PubMed

    Cicerone, R J

    1987-07-01

    The ozone layer in the upper atmosphere is a natural feature of the earth's environment. It performs several important functions, including shielding the earth from damaging solar ultraviolet radiation. Far from being static, ozone concentrations rise and fall under the forces of photochemical production, catalytic chemical destruction, and fluid dynamical transport. Human activities are projected to deplete substantially stratospheric ozone through anthropogenic increases in the global concentrations of key atmospheric chemicals. Human-induced perturbations may be occurring already.

  5. 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.

  6. Adsorption air cleaning from ozone.

    PubMed

    Baltrenas, Pranas; Paliulis, Dainius; Vasarevicius, Saulius; Simaitis, Ramutis

    2003-01-01

    Not much has been written about air cleaning from ozone. The aim of this paper was to demonstrate the possibility of adsorption air cleaning from ozone. The second aim was to investigate the dependence of the efficiency of ozone removal from the air on the height of the adsorber layer and on concentrations of ozone, and to obtain empirical formulas for calculating the efficiency of ozone treatment. Equipment for air cleaning from ozone and nitrogen and sulphur dioxides is suggested.

  7. Ozone photolysis of paracetamol in aqueous solution.

    PubMed

    Neamţu, Mariana; Bobu, Maria; Kettrup, Antonius; Siminiceanu, Ilie

    2013-01-01

    The degradation of a paracetamol (N-acetil-para-aminofenol) aqueous solution (C (0) P = 5 mmol L(-1)) is studied in a bench-scale setup by means of simple ozonation (O3) and ozonation catalyzed with UV light (O3/UV) in order to quantify the influence of UV light on the degradation process. The results have shown that under the adopted experimental conditions (25°C, applied ozone dose = 9.8 mg L(-1) and gas flow rate of 20 L h(-1)) both oxidative systems are capable of removing the substrate with mineralization degrees up to 51% for ozonation and 53% for O3/UV. HPICE chromatography allowed the detection of nitrate ions and maleic and oxalic acids as ultimate carboxylic acids. The experimental data have been interpreted through 5 indicators: the conversion of paracetamol (XP ), the conversion degree of TOC (XTOC ), the apparent rate constant (kap ), the Hatta number (Ha) and the enhancement factor (E). The main advantage of photo-ozonation compared to simple ozonation was a more advanced conversion (79% vs. 92% after 90 min). The paracetamol decay follows a pseudo-first-order reaction with a superior rate constant (higher by 54%) for the UV catalyzed system in comparison with direct ozonation. Mineralization is slightly accelerated (+4%) in the O3/UV system, due to the additional production of hydroxyl radicals induced by the UV light and a higher Hatta number (+24%). Nevertheless, the process was still in the slow reaction kinetic regime (Ha < 0.3), and the enhancement factor was not significantly increased. The results are useful for the design and scale-up of the gas-liquid processes.

  8. Discovery of a Nitric Acid Trihydrate (NAT) PSC Belt Around Antarctica by MIPAS on Envisat

    NASA Astrophysics Data System (ADS)

    Hopfner, M.; Larsen, N.; Spang, R.; Luo, B.; Ma, J.; Svendsen, S. H.; Eckermann, S. D.; Massoli, P.; Cairo, F.; Snels, M.; di Donfrancesco, G.; Knudsen, B.; Biermann, U.; Stiller, G.; von Clarmann, T.; Fischer, H.

    2005-12-01

    Due to a globally changing climate with decreasing stratospheric temperatures, polar stratospheric cloud (PSC) occurrence might intensify in future. This could counteract the recovery of the ozone layer due to a decreasing stratospheric chlorine loading as consequence of the Montreal protocol and its amendments. To improve models of future ozone loss it is necessary to answer still open questions regarding nucleation processes of nitric acid containing solid cloud particles. The mid-infrared limb-emission sounder Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on Envisat is the first instrument able to monitor continuously the development of PSC appearance and composition with full coverage of the polar regions even during polar night. We have analyzed MIPAS observations during the Antarctic winter 2003 with respect to PSC composition. Coincident lidar observations from McMurdo were used for comparison. By application of new refractive index data we could prove that a distinct spectral signature at around 820~cm-1 as observed by MIPAS is due to a composition of β-NAT. This has been the first evidence for the existence of NAT PSCs on a large scale. We could not find any spectroscopic evidence for the presence of nitric acid dihydrate (NAD) from any MIPAS PSC observation. During the initial phase of PSC development over Antarctica the MIPAS measurements reveal the formation of a belt of NAT PSCs in mid-June 2003. By mesoscale microphysical simulations we have shown that this sudden onset of NAT was caused by heterogeneous nucleation on ice in the cooling phases of large-amplitude stratospheric mountain waves over the Antarctic Peninsula and the Ellsworth Mountains. This suggests a more significant role for mountain waves in Antarctic PSC formation than has heretofore been appreciated. MIPAS observations of PSCs in a period of three weeks before this event show no indication for the presence of NAT clouds, but are consistent with supercooled

  9. 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.

  10. Growth, physiological and biochemical response of ponderosa pine pinus ponderosa' to ozone. Final report

    SciTech Connect

    Temple, P.J.; Bytnerowicz, A.

    1993-11-01

    In 1989 and 1990, the effects of multi-year ozone exposures on growth, foliar injury and physiological responses in ponderosa pine were examined. Two-year old seedlings were exposed to four ozone treatments in open-top chambers: clean air (subambient levels of oxidants and particles); ambient ozone; twice-ambient ozone; or ambient air. The study was performed at Shirley Meadow in the southern Sierra Nevada. In both years, ambient ozone levels were representative of other forests in the region. While ozone is the most phytotoxic air pollutant, seedlings also experienced elevated concentrations of nitric acid and ammonia. In 1990, ambient ozone significantly increased injury to previous year needles. Premature senescence and alterations in physiological responses were also noted. Exposure to twice-ambient ozone reduced seedling biomass, increased injury and caused decreases in a variety of physiological responses.

  11. Theoretical analysis of physicochemical processes occurring during water treatment by ozone and ultraviolet radiation.

    PubMed

    Mishchuk, N A; Goncharuk, V V; Vakulenko, V F

    2008-06-22

    The paper presents a kinetic model developed for ozone dissolution in water and taking into account convective and diffusion processes occurring in the vicinity of floating bubbles that contain an ozone-air mixture. It was shown that the gradient of ozone concentration in a convective-diffusion layer and consequently the rate of ozone transfer from bubbles to the solution depended on the rate of ozone decomposition both in its reaction with organic admixtures and in the conditions of exposure to ultraviolet radiation. The obtained kinetic curves of destruction of organic compounds and changes of ozone concentration in water and ozone-air mixture are compared with experimental data for humic acids. The paper also analyzes additional factors affecting the kinetics of ozone dissolution and the rate of resultant reactions.

  12. A new mechanism for the toxicity of ozone.

    PubMed

    Pryor, W A; Squadrito, G L; Friedman, M

    1995-12-01

    Ozone, with its high reactivity, is entirely consumed as it passes through the first layer of tissue it contacts at the lung/air interface. This layer includes the epithelial cell lining fluid (ELF) and, where the ELF is thin or absent, the membranes of the epithelial cells that line the airways. Thus the biochemical changes that follow the inhalation of ozone must be relayed into deeper tissue strata by a cascade of ozonation products. Lipid ozonation products (LOP) are suggested to be the most likely relay molecules of ozone's signal. This is because unsaturated fatty acids are present in relatively high concentrations in both the ELF and in pulmonary cell bilayers, and ozone reacts with unsaturated fatty acids to produce ozone-specific products. Further, LOP are finite in number, have structures that are predictable from the Criegee ozonation mechanism, and are small, diffusible, stable (or meta-stable) molecules, similar to other lipid-derived signal transduction species. Preliminary data show that individual LOP cause the activation of specific lipases, which trigger the release of endogenous mediators of inflammation.

  13. What Causes Aerosol Growth and Ozone Production in Smoke Plumes?

    NASA Astrophysics Data System (ADS)

    Alvarado, M. J.; Prinn, R. G.

    2006-12-01

    The growth of aerosol particles and production of ozone in smoke plumes is the result of a complex interaction between horizontal diffusion, gas-phase oxidation, coagulation, and mass transfer between phases. Models allow us to separate the effects of these processes and predict their impact on the global environment. We present the results of a new model of gas and aerosol chemistry applied to young biomass burning plumes. The model includes heterogeneous chemistry, kinetic mass transfer, coagulation and the formation of secondary organic and inorganic aerosol. Comparison with measurements from SAFARI 2000 (Hobbs et al., 2003, JGR, doi:10.1029/2002JD002352) suggests the baseline model underpredicts ozone formation and the growth of aerosol within the plume. We explore whether the model predictions can be improved by (1) including heterogeneous HONO production, and (2) adding in surrogates for the uncharacterized organic compounds emitted by the biomass burning. Including the heterogeneous reaction NO2 => HONO greatly improves the match for ozone, OH, and aerosol nitrate concentration, but only when the uptake coefficient approaches 10-3, which is over an order of magnitude higher than previously reported values (Stemmler et al., 2006, doi:10.1038/nature04603). Using the reaction NO2 => 0.5 HONO + 0.5 HNO3 with an uptake coefficient of 10-3 (the top of the range recommended by Jacob, 2000, Atm. Env.,34, 2131-2159) provides an even better match for aerosol nitrate, but produces less O3 and OH than the first reaction. Direct measurements of HONO and OH in young biomass plumes would help determine if this chemistry is taking place. We used two surrogates to model the uncharacterized compounds: long chain alkanes and monoterpenes, representing primary and secondary sources of condensable compounds respectively. Complete condensation of the long-chain alkanes can account for nearly all of the observed increase in organic carbon. However, the accommodation coefficient

  14. The Antarctic Ozone Hole.

    ERIC Educational Resources Information Center

    Stolarski, Richard S.

    1988-01-01

    Discusses the Airborne Antarctic Ozone Experiment (1987) and the findings of the British Antarctic Survey (1985). Proposes two theories for the appearance of the hole in the ozone layer over Antarctica which appears each spring; air pollution and natural atmospheric shifts. Illustrates the mechanics of both. Supports worldwide chlorofluorocarbon…

  15. Surface Ozone in Kiev

    NASA Astrophysics Data System (ADS)

    Shavrina, A. V.; Mikulskaya, I. A.; Kiforenko, S. I.; Blum, O. B.; Sheminova, V. A.; Veles, A. A.

    The study of total ozone over Kiev and its concentration changes with height in the troposphere has been made on the base of ground-based observations with the infrared Fourier-spectrometer in the Main Astronomical Observatory of National Academy of Sciences of Ukraine (MAO NASU) as part of ESA-NIVR-KNMI project no 2907 "OMI validation by ground based remote sensing: ozone columns and atmospheric profiles "(2005-2008) [1,2,4]. Ground-level ozone in Kiev for an episode of its high concentrations in August 2000 was also simulated with the model of urban air pollution UAM-V [5,6]. In 2008 the satellite data Aura-OMI on profiles of ozone in the atmosphere OMO3PR became available (http://disc.sci.gsfc.nasa.gov/ Aura/data-holdings/OMI/ omo3pr_v003.shtml). They include ozone content in the lower layer of the atmosphere, beginning from 2005, which can be used to evaluate the ground-level ozone in all cities of Ukraine. The comparison of the data of ozone air pollution in Kiev (ozone - the pollutant of the first class of danger) and medical statistics data of of respiratory system (RS) diseases of the city population was carried out with the package "Statistica". A regression analysis, prognostic regression modelling, and retrospective prognosis of the epidemiological situation with respect to RS pathologies in Kiev in 2000-2006 were performed.

  16. Ozone and temperature trends

    NASA Technical Reports Server (NTRS)

    Stolarski, Richard S.; Fioletov, Vitali; Bishop, Lane; Godin, Sophie; Bojkov, Rumen D.; Kirchhoff, Volker; Chanin, Marie-Lise; Zawodny, Joseph M.; Zerefos, Christos S.; Chu, William

    1991-01-01

    An update of the extensive reviews of the state of knowledge of measured ozone trends published in the Report of the International Ozone Trends Panel is presented. The update contains a review of progress since these reports, including reviewing of the ozone records, in most cases through March 1991. Also included are some new, unpublished reanalyses of these records including a complete reevaluation of 29 stations located in the former Soviet Union. The major new advance in knowledge of the measured ozone trend is the existence of independently calibrated satellite data records from the Total Ozone Mapping Spectrometer (TOMS) and Stratospheric Aerosol and Gas Experiment (SAG) instruments. These confirm many of the findings, originally derived from the Dobson record, concerning northern mid-latitude changes in ozone. We now have results from several instruments, whereas the previously reported changes were dependent on the calibration of a single instrument. This update will compare the ozone records from many different instruments to determine whether or not they provide a consistent picture of the ozone change that has occurred in the atmosphere. The update also briefly considers the problem of stratospheric temperature change. As in previous reports, this problem received significantly less attention, and the report is not nearly as complete. This area needs more attention in the future.

  17. Saving Our Ozone Shield.

    ERIC Educational Resources Information Center

    Lacoste, Beatrice

    1992-01-01

    Discusses the introduction and continued use of chlorofluorocarbons (CFCs) as related to stratospheric ozone depletion. Presents the characteristics of CFCs conducive to the chemical reaction with ozone, the history of CFC use and detection of related environmental problems, health hazards, and alternatives to CFC use. (MCO)

  18. Polar Ozone Workshop. Abstracts

    NASA Technical Reports Server (NTRS)

    Aikin, Arthur C.

    1988-01-01

    Results of the proceedings of the Polar Ozone Workshop held in Snowmass, CO, on May 9 to 13, 1988 are given. Topics covered include ozone depletion, ozonometry, polar meteorology, polar stratospheric clouds, remote sensing of trace gases, atmospheric chemistry and dynamical simulations.

  19. Observing trends in total ozone and extreme ozone events

    NASA Astrophysics Data System (ADS)

    Balcerak, Ernie

    2014-05-01

    The ozone layer in the stratosphere has been recovering since the 1989 Montreal Protocol reduced the use of ozone-destroying chlorofluorocarbons. Fitzka et al. observed trends in total ozone levels and the vertical distribution of ozone at Hoher Sonnblick, a mountain in Austria, from 1994 to 2011.

  20. Polar stratospheric clouds and the ozone hole

    NASA Technical Reports Server (NTRS)

    Hamill, Patrick; Toon, Owen B.

    1991-01-01

    An account is given of physical processes governing the formation of stratospheric particles, in order to dramatize the interactions between polar stratospheric clouds and the Antarctic ozone-destruction mechanism. Attention is given to the successive stages of particle nucleation, condensation/evaporation and sedimentation/coagulation phenomena, and the ways in which polar stratospheric clouds are observed. Considerable evidence exists that polar stratospheric cloud particles are composed of nitric acid. The relatively small Arctic ozone hole depletion is due to the much smaller duration of Arctic stratospheric clouds.

  1. Ozone in equatorial latitudes

    NASA Astrophysics Data System (ADS)

    Martini, L.; Zimmermann, G.; Trinkkeller, B.

    The presence of ozone in the atmosphere protects the biosphere against harmful solar UV radiation. The ozone distribution in the atmosphere is maintained on the basis of a complex system of reactions. The amount of atmospheric ozone might be reduced as a consequence of human activities. Such reduction in the atmospheric ozone could affect climate and biological processes on earth. As a part of plans for a further enhancement of the global surveillance of the atmospheric ozone layer, a series of radiation experiments concerning the quartz-ultraviolet region were conducted as a joint project of the German Democratic Republic and the USSR. The experiments had the objective to measure the radiative flux of the solar UV radiation and to determine absorption and dispersion of the radiation in the upper atmosphere. The investigation included the launching of 12 rockets from a research vessel in the Indian Ocean near the equator and 34 balloon flights.

  2. 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

  3. Photochemistry in biomass burning plumes and implications for tropospheric ozone over the tropical South Atlantic

    NASA Astrophysics Data System (ADS)

    Mauzerall, Denise L.; Logan, Jennifer A.; Jacob, Daniel J.; Anderson, Bruce E.; Blake, Donald R.; Bradshaw, John D.; Heikes, Brian; Sachse, Glenn W.; Singh, Hanwant; Talbot, Bob

    1998-04-01

    Photochemistry occuring in biomass burning plumes over the tropical south Atlantic is analyzed using data collected during the Transport and Atmospheric Chemistry Near the Equator-Atlantic aircraft expedition conducted during the tropical dry season in September 1992 and a photochemical point model. Enhancement ratios (ΔY/ΔX, where Δ indicates the enhancement of a compound in the plume above the local background mixing ratio, Y are individual hydrocarbons, CO, O3, N2O, HNO3, peroxyacetyl nitrate (PAN), CH2O, acetone, H2O2, CH3OOH, HCOOH, CH3COOH or aerosols and X is CO or CO2) are reported as a function of plume age inferred from the progression of Δnon-methane hydrocarbons/ΔCO enhancement ratios. Emission, formation, and loss of species in plumes can be diagnosed from progression of enhancement ratios from fresh to old plumes. O3 is produced in plumes over at least a 1 week period with mean ΔO3/ΔCO = 0.7 in old plumes. However, enhancement ratios in plumes can be influenced by changing background mixing ratios and by photochemical loss of CO. We estimate a downward correction of ˜20% in enhancement ratios in old plumes relative to ΔCO to correct for CO loss. In a case study of a large persistent biomass burning plume at 4-km we found elevated concentrations of PAN in the fresh plume. The degradation of PAN helped maintain NOx mixing ratios in the plume where, over the course of a week, PAN was converted to HNO3. Ozone production in the plume was limited by the availability of NOx, and because of the short lifetime of O3 at 4-km, net ozone production in the plume was negligible. Within the region, the majority of O3 production takes place in air above median CO concentration, indicating that most O3 production occurs in plumes. Scaling up from the mean observed ΔO3/ΔCO in old plumes, we estimate a minimum regional O3 production of 17×1010molecules O3 cm-2 s-1. This O3 production rate is sufficient to fully explain the observed enhancement in

  4. The Hole in the Ozone Layer.

    ERIC Educational Resources Information Center

    Hamers, Jeanne S.; Jacob, Anthony T.

    This document contains information on the hole in the ozone layer. Topics discussed include properties of ozone, ozone in the atmosphere, chlorofluorocarbons, stratospheric ozone depletion, effects of ozone depletion on life, regulation of substances that deplete the ozone layer, alternatives to CFCs and Halons, and the future of the ozone layer.…

  5. Fundamentals of ISCO Using Ozone

    EPA Science Inventory

    In situ chemical oxidation (ISCO) using ozone involves the introduction of ozone gas (O3) into the subsurface to degrade organic contaminants of concern. Ozone is tri-molecular oxygen (O2) that is a gas under atmospheric conditions and is a strong oxidant. Ozone may react with ...

  6. The Two Faces of Ozone.

    ERIC Educational Resources Information Center

    Monastersky, Richard

    1989-01-01

    Provides answers to questions regarding the ozone problem: (1) nature of ozone in the troposphere and stratosphere; (2) possibility of sending the excess ozone at ground level to the stratosphere; (3) possibility of producing pure ozone and carrying it to the stratosphere; and (4) banning chlorofluorocarbons. (YP)

  7. Some consequences of ozone exposure on health.

    PubMed

    Paz, C

    1997-01-01

    The reaction of ozone with polyunsaturated fatty acids from the surfactant factor and pulmonary epithelial cells produces different reaction products which can cross the alveolar-capillary barrier and reach distant structures. Although only a few papers claim extrapulmonary changes in animals exposed to this gas, some neurological deficits, such as complaints of fatigue, lethargy, headache in humans, as well as significant disarrangements in the sleep pattern related to biochemical changes in the brain have been referred to in animals exposed to ozone. In the present review, the molecular configuration and the reaction of ozone at different lung levels are related to impairment at the respiratory and blood systems, in order to elucidate the mechanisms by which this gas or its reaction products, such as free radicals, prostaglandins and others can cross the alveolar-capillary and hemato-encephalic barriers, and to explain those neurological effects.

  8. Application of ozone based treatments of secondary effluents.

    PubMed

    Tripathi, Smriti; Pathak, Vinita; Tripathi, Devendra Mani; Tripathi, B D

    2011-02-01

    The present work was aimed at studying the efficiency of ozone in oxidation processes, coliform inactivation and Disinfection Byproducts (DBPs) formation, associated with the potential of ozone to increase the Biodegradable Dissolved Organic Carbon (BDOC) in secondary effluent with applied ozone doses of 5.0, 10.0 and 15.0 mg/L for contact times of 2, 5 and 10 min. The wastewater used in this work was collected from the Bhagwanpur Sewage Treatment Plant, Varanasi, India. Results of this experiment showed that 10 mg O(3)/L O(3) for 5 min exposure was found most suitable dose for highest degradation of COD, TOC, UV(254), color, turbidity and total nitrogen parameters. The inactivation range of microbial biomass range was found in between 95% and 98%. Experiment revealed the fact that aldehydes and carboxylic acid formation were significantly related with the ozone dose and exposure time and ozone might enhance the treatment efficiency of secondary effluent treatment.

  9. Ozone Depletion Potential of CH3Br. Appendix H

    NASA Technical Reports Server (NTRS)

    Ko, Malcolm K. W.; Sze, Nien Dak; Scott, Courtney; Rodriguez, Jose M.; Weisenstein, Debra K.; Sander, Stanley P.

    1998-01-01

    The ozone depletion potential (ODP) of methyl bromide (CH3Br) can be determined by combining the model-calculated bromine efficiency factor (BEF) for CH3Br and its atmospheric lifetime. This paper examines how changes in several key kinetic data affect BEF. The key reactions highlighted in this study include the reaction of BrO + HO2, the absorption cross section of HOBr, the absorption cross section and the photolysis products of BrONO2, and the heterogeneous conversion of BrONO2 to HOBr and HNO3 on aerosol particles. By combining the calculated BEF with the latest estimate of 0.7 year for the atmospheric lifetime of CH3Br, the likely value of ODP for CH3Br is 0.39. The model-calculated concentration of HBr (approx. 0.3 pptv) in the lower stratosphere is substantially smaller than the reported measured value of about 1 pptv. Recent publications suggested models can reproduce the measured value if one assumes a yield for HBr from the reaction of BrO + OH or from the reaction of BrO + HO2. Although the evaluation concluded any substantial yield of HBr from BrO + HO2 is unlikely, for completeness, we calculate the effects of these assumed yields on BEF for CH3Br. Our calculations show that the effects are minimal: practically no impact for an assumed 1.3% yield of HBr from BrO + OH and 10% smaller for an assumed 0.6% yield from BrO + HO2.

  10. Ozone precursor levels and responses to emissions reductions: Analysis of regional oxidant model results

    NASA Astrophysics Data System (ADS)

    Milford, Jana B.; Gao, Dongfen; Zafirakou, Antigoni; Pierce, Thomas E.

    An analysis of results from the Regional Oxidant Modeling for Northeast Transport (ROMNET) study ( U.S. EPA, 1991, EPA-450/4-91-002a) has investigated the chemical conditions under which air quality was predicted to improve with reductions in ROG and/or NO ξ emissions, or with changes in the composition of ROG emissions. The ROMNET simulations used emissions projected to the year 2005, with meteorological conditions from July 1988. Predicted concentrations of PAN, HNO 3, H 2O 2 and HCHO are shown along with O 3 for the 2005 base case, allowing limited comparisons to be made with field observations and results from other modeling studies. Predicted secondary pollutant concentrations indicate an unusual degree of photochemical activity over much of the model domain, directionally consistent with the extreme nature of the July 1988 episode. Reducing NO ξ emissions was predicted to reduce O 3 in grid cells in which reactive nitrogen (NO y) concentrations were below about 25 ppb, but to be counterproductive for some cells with higher NO y. The New York City area where NO ξ control was predicted to be counterproductive was characterized by very high NO ξ to NO y ratios. Ozone was relatively insensitive to ROG controls in grid cells with NO y concentrations below 5-10 ppb. Comparison of unweighted ROG concentrations with concentrations weighted by HO rate constants (i.e. reactivity) showed that the latter varied less across locations. Predicted spatial gradients of NO y were generally sharper than those of reactivity-weighted ROG, supporting a dominant role for variations in NO y in controlling the sensitivity of ozone to its precursors. Reductions in reactivity-weighted ROG achieved with composition changes were similar to reductions achieved with ROG emissions cuts, explaining the similar response of ozone to these two control strategies.

  11. Reaction products of ozone: a review.

    PubMed Central

    Glaze, W H

    1986-01-01

    The reaction products of ozone that form during the oxidation of compounds found in aqueous media are reviewed. Reaction products of ozone are well documented only for a limited number of substrates, and mechanistic information is quite rare. Decomposition of ozone during its reactions, sometimes induced by matrix impurities or by the by-products of the reactions, will generate highly reactive hydroxyl radicals. Thus, even reactions occurring at pH less than 7 may have radical character. More complete destruction of organic substrates may be enhanced by using catalysts, such as ultraviolet radiation or hydrogen peroxide, to accelerate radical formation. However, complete mineralization is generally not practical economically, so partially oxidized by-products can be expected under typical treatment conditions. Ozone by-products tend to be oxygenated compounds that are usually, but not always, more biodegradable and less toxic than xenobiotic precursors. Of particular interest are hydroperoxide by-products, which may have escaped detection because of their lability, and unsaturated aldehydes. Inorganic by-products tend to be in high oxidation states, which in some cases (e.g., some metallic elements) may lead to enhanced removal by flocculation and sedimentation. In other cases oxidation may lead to formation of reactive species such as hypobromous acid from bromide ion or permanganate from manganous ion. In general, more research is required before a valid assessment of the risks of ozone by-products can be made. PMID:3545802

  12. 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.