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1.
We use a global atmospheric chemistry transport model to study the possible influence of aqueous phase reactions of peroxynitric acid (HNO4) on the concentrations and budgets of NOx, SOx, O3 and H2O2. Laboratory studies have shown that the aqueous reaction of HNO4aq withHSO–
3aq, and the uni-molecular decomposition of the NO4
– anion to form NO2
– (nitrite) occur on a time scale of about a second. Despite a substantial contribution of the reaction of HSO–
3aq with HNO4aq to the overall in-cloud conversion of SO2 to SO4
2–, a simultaneous decrease of other oxidants (most notably H2O2) more than compensated the increase in SO4
2– production. The strongest influence of heterogeneous HNO4 chemistry was found in the boundary layer, where calculated monthly average ozone concentrations were reduced between 2% to 10% andchanges of H2O2 between –20% to +10%compared to a simulation which ignores this reaction. Furthermore, SO2 was increased by 10% to 20% and SO4
2–depleted by up to 10%. Since the resolution of our global model does not enable a detailed comparison with measurements in polluted regions, it is not possible to verify whether considering heterogeneous HNO4 reactions results in a substantial improvement of atmospheric chemistry transport models. However, the conversion of HNO4 in the aqueous phase seems to be efficient enough to warrant further laboratory investigations and more detailed model studies on this topic. 相似文献
2.
R. N. Colvile T. W. Choularton J. N. Cape B. J. Bandy K. N. Bower R. A. Burgess T. J. Davies G. J. Dollard M. W. Gallagher K. J. Hargreaves B. M. R. Jones S. A. Penkett R. L. Storeton-West 《Journal of Atmospheric Chemistry》1996,24(3):211-239
Four case studies are described, from a three-site field experiment in October/November 1991 using the Great Dun Fell flow-through reactor hill cap cloud in rural Northern England. Measurements of total odd-nitrogen nitrogen oxides (NO
y
) made on either side of the hill, before and after the air flowed through the cloud, showed that 10 to 50% of the NO
y
, called NO
z
, was neither NO nor NO2. This NO
z
failed to exhibit a diurnal variation and was often higher after passage through cloud than before. No evidence of conversion of NO
z
to NO3
- in cloud was found. A simple box model of gas-phase chemistry in air before it reached the cloud, including scavenging of NO3 and N2O5 by aerosol of surface area proportional to the NO2 mixing ratio, shows that NO3 and N2O5 may build up in the boundary layer by night only if stable stratification insulates the air from emissions of NO. This may explain the lack of evidence for N2O5 forming NO3
- in cloud under well-mixed conditions in 1991, in contrast with observations under stably stratified conditions during previous experiments when evidence of N2O5 was found. Inside the cloud, some variations in the calculated total atmospheric loading of HNO2 and the cloud liquid water content were related to each other. Also, indications of conversion of NO
x
to NO
z
were found. To explain these observations, scavenging of NO
x
and HNO2 by cloud droplets and/or aqueous-phase oxidation of NO2
- by nitrate radicals are considered. When cloud acidity was being produced by aqueous-phase oxidation of NO
x
or SO2, NO3
- which had entered the cloud as aerosol particles was liberated as HNO3 vapour. When no aqueous-phase production of acidity was occurring, the reverse, conversion of scavenged HNO3 to particulate NO3
-, was observed. 相似文献
3.
A method for the estimation of the reaction probability of the heterogeneous N2O5+H2O 2HNO3 reaction using the deposition profile in a laminar flow tube, in which the walls are coated with the condensed aqueous phase of interest, is presented. The production of gas phase nitric acid on the surface followed by its absorption complicates the deposition profiles and hence the calculation of the reaction probability. An estimation of the branching ratio for this process enables a more appropriate calculation to be carried out. Reaction probabilities of N2O5 on substances including some normally constituting atmospheric aerosols, NaCl, NH4HSO4, as well as Na2CO3 are estimated and found to depend on relative humidity and characteristics of the coating used. These fell within the range (0.04–2.0)×10–2. 相似文献
4.
F. H. Adema J. R. Ybema P. Heeres H. C. P. Wegh 《Journal of Atmospheric Chemistry》1990,11(3):255-269
In a nighttime system and under relatively dry conditions (about 15 ppm H2O), the reaction mixture of NO2, O3, and NH3 in purified air turns out to result in the formation of nitrous oxide (N2O). The experiments were performed in a continuous stirred flow reactor, in the concentration region of 0.02–2 ppm.N2O is thought to arise through the heterogeneous reaction of gaseous N2O5 and absorbed NH3 at the wall of the reaction vessel % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9sq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9pue9Fve9% Ffc8meGabaqaciGacaGaaeqabaWaaeaaeaaakeaatCvAUfKttLeary% qr1ngBPrgaiuaacqWFOaakcqWFobGtcqWFibasdaWgaaWcbaGae83m% amdabeaakiab-LcaPmaaBaaaleaacqWFHbqyaeqaaOGaey4kaSIaai% ikaiab-5eaonaaBaaaleaacqWFYaGmaeqaaOGae83ta80aaSbaaSqa% aiab-vda1aqabaGccaGGPaWaaSbaaSqaaiaadEgaaeqaaOGaeyOKH4% Qae8Nta40aaSbaaSqaaiab-jdaYaqabaGccqWFpbWtcqGHRaWkcqWF% ibascqWFobGtcqWFpbWtdaWgaaWcbaGae83mamdabeaakiabgUcaRi% ab-HeainaaBaaaleaacqWFYaGmaeqaaOGae83ta8eaaa!59AC!\[(NH_3 )_a + (N_2 O_5 )_g \to N_2 O + HNO_3 + H_2 O\]In principle, there is competition between this reaction and that of adsorbed H2O with N2O5, resulting in the formation of HNO3. At high water concentrations (RH>75%), no formation of N2O was found. Although the rate constant of adsorbed NH3 with gaseous N2O5 is much larger than that of the reaction of adsorbed H2O with gaseous N2O5, the significance of the observed N2O formation for the outside atmosphere is thought to be dependent on the adsorption properties of H2O and NH3 on a surface. A number of NH3 and H2O adsorption measurements on several materials are discussed. 相似文献
5.
The kinetics of the reaction of nitrous acid (HONO) with nitric acid (HNO3), nitrate radicals (NO3) and dinitrogen pentoxide (N2O5) have been studied using Fourier transform infrared spectroscopy. Experiments were performed at 700 torr total pressure using synthetic air or argon as diluents. From the observed decay of HONO in the presence of HNO3 a rate constant of k<7×10-19 cm3 molecule-1 s-1 was derived for the reaction of HONO with HNO3. From the observed decay of HONO in the presence of mixtures of N2O5 and NO2 we have also derived upper limits for the rate constants of the reactions of HONO with NO3 and N2O5 of 2×10-15 and 7×10-19 cm3 molecule-1 s-1, respectively. These results are discussed with respect to previous studies and to the atmospheric chemistry of HONO. 相似文献
6.
Simulations of seasonal variations of sulfur compounds in the remote marine atmosphere 总被引:1,自引:0,他引:1
A photochemical box model is used to simulate seasonal variations in concentrations of sulfur compounds at latitude 40° S. It is assumed that the hydroxyl radical (OH) addition reaction to sulfur in the dimethyl sulfide (DMS) molecule is the predominant pathway for methanesulfonic acid (MSA) production, and that the rate constant increases as the air temperature decreases. Concentration of the nitrate radical (NO3) is a function of the DMS flux, because the reaction of DMS with NO3 is the most important loss mechanism of NO3. While the diurnally averaged concentration of OH in winter is a factor of about 8 smaller than in summer, due to the weak photolysis process, the diurnally averaged concentration of NO3 in winter is a factor of about 4–5 larger than in summer, due to the decrease of DMS flux. Therefore, at middle and high latitudes in winter, atmospheric DMS is mainly oxidized by the reaction with NO3. The calculated ratio of the MSA to SO2 production rates is smaller in winter than in summer, and the MSA to non-sea-salt sulfate (nssSO4
2-) molar ratio varies seasonally. This result agrees with data on the seasonal variation of the MSA/nssSO4
2- molar ratio obtained at middle and high latitudes. The calculations indicate that during winter the reaction of DMS with NO3 is likely to be a more important sink of NOx (NO+NO2) than the reaction of NO2 with OH, and to serve as a significant pathway of the HNO3 production. If dimethyl sulfoxide (DMSO) is produced through the OH addition reaction and is heterogeneously oxidized in aqueous solutions, half of the nssSO4
2- produced in summer may be through the oxidation process of DMSO. It is necessary to further investigate the oxidation products by the reaction of DMS with OH, and the possibility of the reaction of DMS with NO3 during winter. 相似文献
7.
Generally, it is assumed that UV-light, high temperature or reactive molecules like O3 and OH are needed to activate gas reactions in air. In consequence, the catalytic activity on natural materials such as sand and soil on the earth's surface is assumed to be insignificant. We have measured O2-dissociation rates on natural quartz sand at 40˚C and compared these with O2-dissociation rates near 500˚C on materials with well-known catalytic activity. In terms of probabilities for dissociation of impinging O2-molecules the measured rates are in the 10−12–10−4 range. We have also measured dissociation rates of H2 and N2, water-formation from H2 and O2 mixtures, exchange of N between N2, NO
x
and a breakdown of HNO3, NO2 and CH4 on natural quartz sand at 40˚C. The measured rates together with an effective global land area have been used to estimate the impact of thermodynamically driven reactions on the earth's surface on the global atmospheric budgets of H2, NO2 and CH4. The experimental data on natural quartz sand together with data from equilibrium calculations of air suggest that an expected increase in anthropogenic supply of air pollutants, such as NO
x
or other “reactive” nitrogen compounds, hydrogen and methane, will be counter-acted by catalysis on the earth's surface. On the other hand, at Polar Regions and boreal forests where the “reactive” nitrogen concentration is below equilibrium, the same catalytic effect activates formation of bio-available nitrogen compounds from N2, O2 and H2O. 相似文献
8.
9.
Jayanarayanan Kuttippurath Armin Kleinböhl Holger Bremer Harry Küllmann Justus Notholt Björn-Martin Sinnhuber Wuhu Feng Martyn Chipperfield 《Journal of Atmospheric Chemistry》2010,66(1-2):41-64
Airborne measurements of stratospheric ozone and N2O from the SCIAMACHY (Scanning Imaging Absorption Spectrometer) Validation and Utilization Experiment (SCIA-VALUE) are presented. The campaign was conducted in September 2002 and February–March 2003. The Airborne Submillimeter Radiometer (ASUR) observed stratospheric constituents like O3 and N2O, among others, spanning a latitude from 5°S to 80°N during the survey. The tropical ozone source regions show high ozone volume mixing ratios (VMRs) of around 11 ppmv at 33 km altitude, and the altitude of the maximum VMR increases from the tropics to the Arctic. The N2O VMRs show the largest value of 325 ppbv in the lower stratosphere, indicating their tropospheric origin, and they decrease with increasing altitude and latitude due to photolysis. The sub-tropical and polar mixing barriers are well represented in the N2O measurements. The most striking seasonal difference found in the measurements is the large polar descent in February–March. The observed features are interpreted with the help of SLIMCAT and Bremen Chemical Transport Model (CTMB) simulations. The SLIMCAT simulations are in good agreement with the measured O3 and N2O values, where the differences are within 1 ppmv for O3 and 15 ppbv for N2O. However, the CTMB simulations underestimate the tropical middle stratospheric O3 (1–1.5 ppmv) and the tropical lower stratospheric N2O (15–30 ppbv) measurements. A detailed analysis with various measurements and model simulations suggests that the biases in the CTMB simulations are related to its parameterised chemistry schemes. 相似文献
10.
A photochemical box model including a detailed heterogeneous chemistrymodule has been used to analyze in detail the effects of temperature andaerosol surface area on odd oxygen production/depletion in the lowerstratosphere at 30° S. Results show that for background aerosolloading, the hydrolysis of BrONO2 and N2O5are most important atall temperatures studied except when the temperature falls below about205 K, when ClONO2 hydrolysis becomes most important. Thisprocessing leads to removal of active nitrogen to form nitric acid andenhancement of HOx, BrOx, ClOx levels. Detailed O3 budgets asa function of temperature are presented showing how ozone loss andproduction terms vary with changes in stratospheric sulfate aerosol loadingfor the individual families. For (most) aerosol loading levels, thelargest ozone losses occurred at warmer temperatures due to the strongtemperature dependence of the NOx ozone-destroying reactions. Theexception to this occurred for the conditions representative of volcanicloading, which showed a strong increase in ozone destruction due toincreases in destruction from the ClOx and HOx families.The ozoneproduction term k[NO][HO2] did not show a strong dependence oneithertemperature or aerosol loading, due to the offsetting effect of reducedNOxand increased HOx concentrations. 相似文献
11.
C. Camy-Peyret J. -M. Flaud A. Perrin C. P. Rinsland A. Goldman F. J. Murcray 《Journal of Atmospheric Chemistry》1993,16(1):31-40
Stratospheric volume mixing ratio profiles of N2O5, CH4, and N2O have been retrieved from a set of 0.052 cm–1 resolution (FWHM) solar occultation spectra recorded at sunrise during a balloon flight from Aire sur l'Adour, France (44° N latitude) on 12 October 1990. The N2O5 results have been derived from measurements of the integrated absorption by the 1246 cm–1 band. Assuming a total intensity of 4.32×10–17 cm–1/molecule cm–2 independent of temperature, the retrieved N2O5 volume mixing ratios in ppbv (parts per billion by volume, 10–9), interpolated to 2 km height spacings, are 1.64±0.49 at 37.5 km, 1.92±0.56 at 35.5 km, 2.06±0.47 at 33.5 km, 1.95±0.42 at 31.5 km, 1.60±0.33 at 29.5 km, 1.26±0.28 at 27.5 km, and 0.85±0.20 at 25.5 km. Error bars indicate the estimated 1- uncertainty including the error in the total band intensity (±20% has been assumed). The retrieved profiles are compared with previous measurements and photochemical model results.Laboratoire associé aux Universités Pierre et Marie Curie et Paris Sud. 相似文献
12.
A multi-layer deposited ice film was prepared through water vapor deposition on a Ni plate in a vacuum chamber at 90 K, and was used as it was or after annealing at 140 K. NO2 was adsorbed as N2O4 approximately 90 K on the ice film prepared as above, and irradiated by 193 nm excimer laser light. The time-of-flight (TOF) spectra of the desorbed species, i.e., NO2, NO, O2 and O, were measured by a quadrupole mass spectrometer. The photochemical process obeyed an one-photon process. The relative yields of the products and their TOF spectra were dependent on the preparation condition of the ice film and also varied with the continuation of the laser irradiation. From the ice film annealed at 140 K, NO2, NO and O2 were desorbed with an approximate ratio of 1:1:0.01. From the non-annealed film, the relative yield of NO2 was much smaller than that of NO. The TOF spectrum of NO from the non-annealed ice film consisted of distinctly different two components corresponding to the 1700 and 100 K translational temperature, respectively. The fast component was lost when additional ice was deposited on the adsorbed N2O4. NO was supposed to be a predissociation product from the electronically excited NO2 prepared through the photodissociation of N2O4. 相似文献
13.
14.
The photochemical oxidation of SO2 in the presence of NO and C3H6 was studied in a 18.2 liter pyrex reactor. When light intensity, irradiation time and SO2 concentration were constant, SO4
2- concentration, derived from the total volume of aerosol produced, peaked when [C3H6]/[NO] was approximately 6.0. Another increase im SO4
2- formation was reached at very high ratios (>50). The experimental observations are consistent with the two SO2 oxidation mechanisms. At low [C3H6]/[NO] ratios, the processes proceed via the HO–SO2 reaction, while at high ratios the O3–C3H6 adduct is assumed to oxidize SO2 to produce SO4
2- aerosols. 相似文献
15.
Laboratory Study of O(1S) Formation Process in the Photolysis of O3 and its Atmospheric Implications
Tomoki Nakayama Kenshi Takahashi Yutaka Matsumi Hitoshi Fujiwara 《Journal of Atmospheric Chemistry》2006,53(2):107-122
A high-sensitive technique to detect O(1S) atoms using vacuum ultraviolet laser-induced fluorescence (VUV-LIF) spectroscopy has been applied to study the O(1S) production process from the UV photodissociation of O3, N2O, and H2O2. The quantum yields for O(1S) formation from O3 photolysis at 215 and 220 nm are determined to be (1.4 ± 0.4) × 10−4 and (5 ± 3) × 10−5, respectively. Based on thermochemical considerations, the O(1S) formation from O3 photolysis at 215 and 220 nm is attributed to a spin-forbidden process of O(1S)+O2(X3Σg
−). Analysis of the Doppler profile of O(1S) produced from O3 photolysis at 193 nm also indicates that the O(1S) atoms are produced from the spin-forbidden process. In the photolysis of N2O and H2O2 at 193 nm, no discernible signal of O(1S) atoms has been detected. The upper limit values of the quantum yields for O(1S) production from N2O and H2O2 photolysis at 193 nm are estimated to be 8 × 10−5 and 3 × 10−5, respectively. Using the experimental results, the impact of the O(1S) formation from O3 photolysis on the atmospheric OH radical formation through the reaction of O(1S)+H2O has been estimated. The calculated results show that the contribution of the O(1S)+H2O reaction to the OH production rate is ∼2% of that of the O(1D)+H2O reaction at 30 km altitude in mid-latitude. Implications of the present laboratory experimental results for the terrestrial airglow of O(1S) at 557.7 nm have also been discussed. 相似文献
16.
We have used a two dimensional radiative-chemical-transport model of the stratosphere to investigate the sensitivity of trace gas distributions to absorption of oxygen in the wavelength region 175–210 nm. Two different formulations for the Herzberg continuum absorption cross sections are used. The calculated transmission of ultra-violet light in the stratosphere is lower and higher than observed, depending on the choice of absorption cross section. For the higher transmission O3, ClO, and HO2 are found to be significantly increased in the lower stratosphere. Calculated O3 in the upper stratosphere, chlorofluorocarbons, N2O and odd-nitrogen are lower. The photolysis of oxygen is considerably faster at high latitudes implying that the photochemical recovery of depleted polar ozone is faster than currently assumed. 相似文献
17.
A one-dimensional photochemical model was used to explore the role of chlorine atoms in oxidizing methane and other nonmethane hydrocarbons (NMHCs) in the marine troposphere and lower stratosphere. Where appropriate, the model predictions were compared with available measurements. Cl atoms are predicted to be present in the marine troposphere at concentrations of approximately 103 cm-3, mostly as a consequence of the reaction of OH with HCl released from sea spray. Despite this low abundance, our results indicate that 20 to 40% of NMHC oxidation in the troposphere (0–10 km) and 40 to 90% of NMHC oxidation in the lower stratosphere (10–20 km) is caused by Cl atoms. At 15 km, NMHC-Cl reactions account for nearly 80% of the PAN produced.The model was also used to test the longstanding hypothesis that NOCl is an intermediate to HCl formation from sea salt aerosols. It was found that the NOCl concentration required (10 ppt) would be incompatible with field observations of reactive nitrogen and ozone abundance. Chlorine nitrate (ClONO2) and methyl nitrate (CH3ONO2) were shown to be minor components of the total NO
y
abundance. Heterogeneous reactions that might enhance photolysis of halocarbons or convert ClONO2 to HOCl or Cl2 were determined to be relatively unimportant sources of Cl atoms. Specific and reliable measurements of HCl and other reactive chlorine species are needed to better assess their role in tropospheric chemistry. 相似文献
18.
We have investigated the problem of testing photochemical theory using solar occultation data. We show, simply using a diurnal model, that for many steady-state relationships sunrise and sunset are not good times for performing quantitative tests. Departures should be expected between the true profile of a substance and that derived using a steady-state argument. Critical tests of theory can, however, be made by considering what we call the rate ratio of a species. A rate ratio, ø, is defined as the ratio of the rate of production to the rate of loss of the species under consideration. This is a simple way to quantify departures from steady-state. Using ATMOS data rate ratios for NO2, ClONO2. HNO4 and N2O5 have been evaluated. These can then be compared with theoretical (model) predictions of the relevant rate ratio. The tests performed confirm our general understanding of the chemistry controlling these species. To make firm conclusions, the measurement of all the relevant parameters would be required. The usefulness in applying rate ratios to measurements made at occultation times is demonstrated. 相似文献
19.
Paolo Laj Julie M. Palais James E. Gardner Haraldur Sigurdsson 《Journal of Atmospheric Chemistry》1993,16(3):219-230
Using the chemical composition of snow and ice of a central Greenland ice core, we have investigated changes in atmospheric HNO3 chemistry following the large volcanic eruptions of Laki (1783), Tambora (1815) and Katmai (1912). The concentration of several cations and anions, including SO
4
2–
and NO
3
–
, were measured using ion chromatography. We found that following those eruptions, the ratio of the concentration of NO
3
–
deposited during winter to that deposited during summer was significantly higher than during nonvolcanic periods. Although we cannot rule out that this pattern originates from snow pack effects, we propose that increased concentrations of volcanic H2SO4 particles in the stratosphere may have favored condensation and removal of HNO3 from the stratosphere during Arctic winter. In addition, this pattern might have been enhanced by slower formation of HNO3 during summer, caused by direct consumption of OH through oxidation of volcanic SO2. 相似文献
20.
A 1-D model of the formation and seasonal evolution of Polar Stratospheric Clouds (PSCs) is described. The model considers PSCs of types 1 and 2 in the vertical range from 8 to 30 km and utilizes real temperature data. The micro-physical processes included in the model are the heterogeneous nucleation and condensation (or evaporation), while sedimentation, gas diffusion and vertical wind velocity are the processes responsible for transport. Model simulations have been compared with PSC data obtained by lidar at the South Pole: results for the winter 1990 are discussed. The different contribution of type 1 and type 2 PSCs to the measured backscattering coefficient has been evidenced. In the simulations, layers of NAT particles form when low values of the backscattering coefficient are measured; similarly, ice particles form when sharper and rapidly changeable structures with higher values of the backscattering coefficient are observed. Significant results on the condensation and depletion of HNO3 and H2O are presented. Water vapor profiles measured during winter 1990 are reproduced quite well. 相似文献