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1.
The rate of formation of N2O via the thermochemically favourable reaction of NO3(A2E) with N2, which would represent an additional source of stratospheric N2O and therefore NOx, has been investigated. Mixtures of NO2+O3 in synthetic air were photolysed at 662 nm. No evidence was found for the production of N2O via this pathway, the upper limit for the quantum yield of nitrous oxide formation being % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiiYdd9qrFfea0dXdf9vqai-hEir8Ve% ea0de9qq-hbrpepeea0db9q8as0-LqLs-Jirpepeea0-as0Fb9pgea% 0lrP0xe9Fve9Fve9qapdbaqaaeGacaGaaiaabeqaamaabaabcaGcba% GaeqOXdy2aaSbaaSqaamaaBaaameaadaWgaaqaamaaBaaabaGaamOt% amaaBaaabaGaaGOmaiaad+eaaeqaaaqabaaabeaaaeqaaaWcbeaatu% uDJXwAK1uy0HMmaeHbfv3ySLgzG0uy0HgiuD3BaGqbaOGae8hzIqOa% aGimaiaac6cacaaI2aGaaiyjaaaa!4E60!\[\phi _{_{_{_{N_{2O} } } } } \le 0.6\% \]. However, a dark conversion of NOx to N2O was observed and is attributed tentatively to a heterogeneous reaction on the wall of the reaction vessel. This process, although most likely to be insignificant in the atmosphere, needs to be taken into consideration in laboratory investigations or field studies of N2O emission or deposition.  相似文献   

2.
The kinetics of the reaction of NO2 with O3 have been investigated at 296 K, using UV absorption spectroscopy to monitor decay of NO2 or O3 and infrared laser absorption spectroscopy to monitor formation of the reaction product N2O5. The results both for the rate coefficient at 296 K (k 1=3.5×10-17 cm3 molecule-1 s-1) and the reaction stoichiometry (NO2/O3=1.85±0.09) are in good agreement with previous studies, confirming that the two step mechanism involving formation of symmetrical NO3 as an intermediate is predominant.% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaeOtaiaab+% eadaWgaaWcbaGaaeOmaaqabaGccqGHRaWkcaqGpbWaaSbaaSqaaiaa% bodaaeqaaOWaa4ajaSqaaaqabOGaayPKHaGaaeOtaiaab+eadaWgaa% WcbaGaae4maaqabaGccqGHRaWkcaqGpbWaaSbaaSqaaiaabkdaaeqa% aaaa!41D7!\[{\text{NO}}_{\text{2}} + {\text{O}}_{\text{3}} \xrightarrow{{}}{\text{NO}}_{\text{3}} + {\text{O}}_{\text{2}} \]% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaeOtaiaab+% eadaWgaaWcbaGaae4maaqabaGccqGHRaWkcaqGobGaae4tamaaBaaa% leaacaqGYaaabeaakiabgUcaRiaab2eadaGdKaWcbaaabeGccaGLsg% cacaqGobWaaSbaaSqaaiaabkdaaeqaaOGaae4tamaaBaaaleaacaqG% 1aaabeaakiabgUcaRiaab2eaaaa!4464!\[{\text{NO}}_{\text{3}} + {\text{NO}}_{\text{2}} + {\text{M}}\xrightarrow{{}}{\text{N}}_{\text{2}} {\text{O}}_{\text{5}} + {\text{M}}\]A possible minor role for the unsymmetrical ONOO species is suggested to account for the lower-than-expected stoichiometry factor. The importance of this reaction in the oxidation of atmospheric NO2 is discussed.  相似文献   

3.
The stoichiometry and kinetics of the reaction of NO2 with O3 at sub-ppm concentration level have been investigated as a function of temperature and relative humidity. The experiments were performed in a continuous flow reactor using chemiluminescent and wet chemical methods of analysis.The rate constant found can be described by the Arrhenius expression: % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaiikaiaaik% dacaGGUaGaaGyoaiaaiEdacqGHXcqScaaIWaGaaiOlaiaaigdacaaI% 0aGaaiykaiabgEna0kaaigdacaaIWaWaaWbaaSqabeaacqGHsislca% aIXaGaaG4maaaakiaabwgacaqG4bGaaeiCaiaacIcadaWcgaqaaiaa% cIcacqGHsislcaaIYaGaaGOnaiaaikdacaaIWaGaeyySaeRaaGyoai% aaicdacaGGPaaabaGaamivaiaacMcacaqGGaGaae4yaiaab2gadaah% aaWcbeqaaiaabodaaaGccaqGGaWaaSGbaeaacaqGTbGaae4BaiaabY% gacaqGLbGaae4yaiaabwhacaqGSbGaaeyzamaaCaaaleqabaGaaeyl% aiaabgdaaaaakeaacaqGZbWaaWbaaSqabeaacaqGTaGaaeymaaaaaa% aaaaaa!62A3!\[(2.97 \pm 0.14) \times 10^{ - 13} {\text{exp}}({{( - 2620 \pm 90)} \mathord{\left/ {\vphantom {{( - 2620 \pm 90)} {T){\text{ cm}}^{\text{3}} {\text{ }}{{{\text{molecule}}^{{\text{ - 1}}} } \mathord{\left/ {\vphantom {{{\text{molecule}}^{{\text{ - 1}}} } {{\text{s}}^{{\text{ - 1}}} }}} \right. \kern-\nulldelimiterspace} {{\text{s}}^{{\text{ - 1}}} }}}}} \right. \kern-\nulldelimiterspace} {T){\text{ cm}}^{\text{3}} {\text{ }}{{{\text{molecule}}^{{\text{ - 1}}} } \mathord{\left/ {\vphantom {{{\text{molecule}}^{{\text{ - 1}}} } {{\text{s}}^{{\text{ - 1}}} }}} \right. \kern-\nulldelimiterspace} {{\text{s}}^{{\text{ - 1}}} }}}}\] and are independent of the relative humidity. As commonly encountered in previous studies a lower-than-two reaction stoichiometry is observed.Heterogeneous reactions occurring at the reactor wall seem to be essential in the reaction mechanism. The NO3 wall conversion to NO2 and the N2O5 wall scavenging in the presence of H2O are suggested to account for the observed stoichiometric factors.  相似文献   

4.
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   

5.
Formation of methoxy (CH3O) radicals in the reaction (1) CH3O2+NOCH3O+NO2 at 298 K has been observed directly using time resolved LIF. The branching ratio % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdyMaae% 4qaiaabIeadaWgaaWcbaGaae4maaqabaGccaqGpbGaaeiiaiaabIca% ieqacaWF9aGaa8hiaiaa-nbicaWFGaGaeuiLdqKaai4waiaaboeaca% qGibWaaSbaaSqaaiaabodaaeqaaOGaae4taiaac2facaWFVaGaeuiL% dqKaai4waiaaboeacaqGibWaaSbaaSqaaiaabodaaeqaaOGaae4tam% aaBaaaleaacaqGYaaabeaakiaac2facaqGPaaaaa!4E31!\[\phi {\rm{CH}}_{\rm{3}} {\rm{O (}} = -- \Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}]/\Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}_{\rm{2}} ]{\rm{)}}\] has been determined by quantitative cw-UV-laser absorption at 257 nm of CH3O2 and CH3ONO, the product of the consecutive methoxy trapping reaction (2) % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaae4qaiaabI% eadaWgaaWcbaGaae4maaqabaGccaqGpbacbeGaa83kaiaa-bcaieaa% caGFobGaa43taiaa+bcacaGFOaGaa83kaiaa+1eacaGFPaGaa4hiai% abgkziUkaabccacaqGdbGaaeisamaaBaaaleaacaqGZaaabeaakiaa% b+eacaqGGaGaaeOtaiaab+eacaqGGaGaa4hkaiaa-TcacaGFnbGaa4% xkaiaa+5cacaGFGaGaa4hiaiabeA8aMnaaBaaajqwaacqaaiaaboea% caqGibWaaSbaaKazcaiabaGaae4maaqabaqcKfaGaiaab+eaaSqaba% aaaa!55AC!\[{\rm{CH}}_{\rm{3}} {\rm{O}} + NO ( + M) \to {\rm{ CH}}_{\rm{3}} {\rm{O NO }}( + M). \phi _{{\rm{CH}}_{\rm{3}} {\rm{O}}} \] is found to be (1.0±0.2). The rate constant k 1 is (7±2) 10-12 cm3/molecule · s in good agreement with previous results.  相似文献   

6.
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   

7.
The growth of monodisperse particles (0.07 to 0.5 µm) exposed to SO2 (0–860 ppb), H2O2 (0–150 ppb) and sometimes NH3 (0–550 ppb) in purified air at 22 °C at relative humidities ranging from 25 to 75% were measured using the Tandem Differential Mobility Analyzer technique. The experiments were performed in a flow reactor with aqueous (NH4)2SO4 and Na2SO4 droplets. For (NH4)2SO4 droplets the fractional diameter growth was independent of size above 0.3 µm but decreased with decreasing size below that. When NH3 was added the fractional growth increased with decreasing size. Measurements were compared with predictions of a model that accounts for solubility of the reactive gases, the liquid phase oxidation of SO2 by H2O2, and ionic equilibria. Agreement between measured and predicted droplet growth is reasonable when the ionic strength effects are included. Theory and experiments suggest that NH3 evaporation is responsible for the decrease in relative growth rates for small aqueous ammonium sulfate particles. The observed droplet growth rates are too slow to explain observed growth rates of secondary atmospheric sulfate particles.  相似文献   

8.
We investigated the partitioning of trace substances during the phase transition from supercooled to mixed-phase cloud induced by artificial seeding. Simultaneous determination of the concentrations of H2O2, NH3 and black carbon (BC) in both condensed and interstitial phases with high time resolution showed that the three species undergo different behaviour in the presence of a mixture of ice crystals and supercooled droplets. Both H2O2 and NH3 are efficiently scavenged by growing ice crystals, whereas BC stayed predominantly in the interstitial phase. In addition, the scavenging of H2O2 is driven by co-condensation with water vapour onto ice crystals while NH3 uptake into the ice phase is more efficient than co-condensation alone. The high solubility of NH4+ in the ice could explain this result. Finally, it appears that the H2O2–SO2 reaction is very slow in the ice phase with respect to the liquid phase. Our results are directly applicable for clouds undergoing limited riming.  相似文献   

9.
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10.
In view of the uncertainty of the origin of the secular increase of N2O, we studied heterogeneous processes that contribute to formation of N2O in an environment that comes as close as possible to exhaust conditions containing NO and SO2, among other constituents. The N2O formation was followed using electron capture gas chromatography (ECD-GC). The other reactants and intermediates (SO2, NO, NO2 and HONO) were monitored using gas phase UV-VIS absorption spectroscopy. Experiments were conducted at 298 and 368 K as well as at dry and high humidity (approaching 100% rh) conditions. There is a significant heterogeneous rate of N 2 O formation at conditions that mimic an exhaust plume from combustion processes.The simultaneous presence of NO, SO2, O2 in the gas phase and condensed phase water, either in the bulk liquid or adsorbed state has been confirmed to be necessary for the production of significant levels of N2O. The stoichiometry of the overall reaction is: 2 NO+SO2+H2O N2O+H2SO4. The maximum rate of N2O formation occurred at the beginning of the reaction and scales with the surface area of the condensed phase and is independent of its volume. A significant rate of N2O formation at 368 K at 100% rh was also observed in the absence of a bulk substrate. The diffusion of both gas and liquid phase reactants is not rate limiting as the reaction kenetics is dominated by the rate ofN2O formation under the experimental conditions used in this work. The simultaneous presence of high humidity (90–100% rh at 368 K) and bulk condensed phase results in the maximum rate and final yield of N2O approaching 60% and 100% conversion after one hour in the presence of amorphous carbon and fly-ash, respectively.Work performed in partial fulfillment of the requirements of Dr ès Sciences at EPFL.  相似文献   

11.
The latitudinal variation of the photolysis frequency of ozone to O(1D) atoms, J(O1D), was measured using a filter radiometer during the cruise ANT VII/1 of the research vessel Polarstern in September/October 1988. The J(O1D) noon values exhibited a maximum of 3.6×10-5 s-1 (2 sr) at the equator and decreased strongly towards higher latitudes. J(O1D) reached highest values for clean marine background air with low aerosol load and almost cloudless sky. The J(O1D) data, measured under these conditions and a temperature of 295 K, can be expressed by: % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamOsaiaacI% cacaqGpbWaaWbaaSqabeaaiiaacqWF8baFaaGccaqGebGaaeykaiaa% bccacqWF9aqpcaqGGaGaaeyzaiaabIhacaqGWbGaaeiiaiaabUhacq% GHsislcaaI4aGaaiOlaiaaicdacaaIYaGaeyOeI0IaaGioaiaac6ca% caaI4aGaaiiEaiaaigdacaaIWaWaaWbaaSqabeaacqGHsislcaaIZa% aaaOGaaeiiaiaabIhacaqGGaGaam4uaiabgUcaRiaaiodacaGGUaGa% aGinaiaacIhacaaIXaGaaGimamaaCaaaleqabaGaeyOeI0IaaGOnaa% aakiaadofadaahaaWcbeqaaiaaikdaaaGccaGG9bGaaeikaiaaboha% daahaaWcbeqaaiabgkHiTiaaigdaaaGccaGGPaaaaa!5EE9!\[J({\text{O}}^| {\text{D) }} = {\text{ exp \{ }} - 8.02 - 8.8x10^{ - 3} {\text{ x }}S + 3.4x10^{ - 6} S^2 \} {\text{(s}}^{ - 1} )\] where S represents the product of the overhead ozone column (DU) and the secant of the solar zenith angle. The meridional profile of the primary OH radical production rate P(OH) was calculated from the J(O1D) measurements and simultaneously recorded O3 and H2O mixing ratios. While the latitudinal distribution of J(O1D) and water vapour was nearly symmetric to the equator, high tropospheric ozone levels up to 40 ppb were observed in the Southern Hemisphere, SH, resulting in higher P(OH) in the SH.  相似文献   

12.
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   

13.
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14.
We present here experimental determinations of mass accommodation coefficients using a low pressure tube reactor in which monodispersed droplets, generated by a vibrating orifice, are brought into contact with known amounts of trace gases. The uptake of the gases and the accommodation coefficient are determined by chemical analysis of the aqueous phase.We report in this article measurements of exp=(6.0±0.8)×10–2 at 298 K and with a total pressure of 38 Torr for SO2, (5.0±1.0)×10–2 at 297 K and total pressure of 52 Torr for HNO3, (1.5±0.6)×10–3 at 298 K and total pressure of 50 Torr for NO2, (2.4±1.0)×10–2 at 290 K and total pressure of 70 Torr for NH3.These values are corrected for mass transport limitations in the gas phase leading to =(1.3±0.1)×10–1 (298 K) for SO2, (1.1±0.1)×10–1 (298 K) for HNO3, (9.7±0.9)×10–2 (290 K) for NH3, (1.5±0.8)×10–3 (298 K) for NO2 but this last value should not be considered as the true value of for NO2 because of possible chemical interferences.Results are discussed in terms of experimental conditions which determine the presence of limitations on the mass transport rates of gaseous species into an aqueous phase, which permits the correction of the experimental values.  相似文献   

15.
A balloon-borne continuous actinometer has been developed which measures stratospheric N2O photolysis coefficients, % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamOAamaaBa% aaleaacaGGobWaaSbaaWqaaiaaikdaaeqaaSGaci4taiabg2da9iab% gkHiTiGacsgaciGGSbGaaiOBaiaacIcaciGGobWaaSbaaWqaaiaaik% daaeqaaSGaci4taiGacMcacaGGVaGaciizaiaadshaaeqaaaaa!44F2!\[j_{N_2 \operatorname{O} = - \operatorname{d} \ln (\operatorname{N} _2 \operatorname{O} )/\operatorname{d} t} \], with a time resolution of approximately 100 s, and a lower detection limit approaching 10-10 s-1. The instrument performed successfully, or was at least partially successful, on five stratospheric balloon flights between October 1982 and September 1986. The experimental profiles are compared with model calculations of % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamOAamaaBa% aaleaacaGGobWaaSbaaWqaaiaaikdaaeqaaSGaci4taaqabaaaaa!39A3!\[j_{N_2 \operatorname{O} } \]. The model takes full account of the sphericity of the atmosphere and of the specific flight conditions, but neglects scattering, which should have a negligible effect on % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamOAamaaBa% aaleaacaGGobWaaSbaaWqaaiaaikdaaeqaaSGaci4taaqabaaaaa!39A3!\[j_{N_2 \operatorname{O} } \]. The quantitative results, particularly the altitude and solar zenith angle dependences under extreme conditions, support the low absorption cross-sections of oxygen in the Herzberg continuum as recommended by WMO in 1986 and are inconsistent with Ackerman's tabulations of 1971. It is shown that the altitude dependence of Brewer and Wilson's historical irradiance measurements in the stratospheric window region is well reproduced by our model, but should be multiplied by a factor of 1.75.  相似文献   

16.
Products and mechanisms of the reaction between the nitrate radical (NO3) and three of the most abundant reduced organic sulphur compounds in the atmosphere (CH3SCH3, CH3SH and CH3SSCH3), have been studied in a 480 L reaction chamber using in situ FT-IR and ion chromatography as analytical techniques. In the three reactions, methanesulphonic acid was found to be the most abundant sulphur containing product. In addition the stable products SO2, H2SO4, CH2O, and CH3ONO2 were identified and quantified and thionitric acid-S-methyl ester (CH3SNO2) was observed in the i.r. spectrum from all of the three reactions. Deuterated dimethylsulphide (CD3SCD3) showed an isotope effect on the reaction Deuterated dimethylsulphide (CD3SCD3) showed an isotope effect on the reaction rate constant (kH/kD) of 3.8±0.6, indicating that hydrogen abstraction is the first step in the NO3+CH3SCH3 reaction, probably after the formation of an inital adduct.Based on the products and intermediates identified, reaction mechanisms are proposed for the three reactions.  相似文献   

17.
对临安大气本底站2003-2004年冬、夏季二氧化氮(NO2)、二氧化硫(SO2)、臭氧(O3)进行了分析.结果表明:冬季NO2和SO2平均体积分数分别为19.48×10-9和35.74 x10-9,而夏季的平均体积分数分别为4.81×10-9和8.12×10-9,冬季高于夏季;O3在夏季的平均体积分数为33.55×10-9,略高于冬季的25.44×10-9;夜间NO2和SO2体积分数比白天高,并且NO2呈明显的单峰单谷型分布,O3也呈单峰型但峰值出现在白天.NO2、SO2体积分数存在着明显的“假日效应”,假日比非假日低,周五高于假日和非假日;但O3体积分数没有明显的假日效应.降水对SO2有明显的清除作用,但对NO2的清除作用不明显.与风向对比发现,夏季高体积分数的NO2、SO2都受到NW、WNW风的影响,冬季则分别受NE和SW、SSW风的影响;而O3受风向的影响较复杂,与局地光化学反应有关.  相似文献   

18.
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   

19.
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   

20.
An analytic solution for a steady, horizontally homogeneous boundary layer with rotation, % MathType!MTEF!2!1!+- % feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l % b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr % 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiaadAgaaaa!38AA! \[ f \] , and surface friction velocity, û*, subjected to surface buoyancy characterized by Obukhov length L, is proposed as follows. Nondimensional variables are % MathType!MTEF!2!1!+- % feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l % b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr % 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiabeA7a6jabg2 % da9iaadAgacaWG6bGaai4laiabeE7aOnaaBaaaleaacqGHxiIkaeqa % aOGaamyDamaaBaaaleaacqGHxiIkaeqaaOGaaiilaiqadwhagaqcai % abg2da9iabeE7aOnaaBaaaleaacqGHxiIkaeqaaOGabmyvayaajaGa % ai4laiqadwhagaqcamaaBaaaleaacqGHxiIkaeqaaOGaaiilaiqads % fagaqcaiabg2da9iqbes8a0zaajaGaai4laiaadwhadaWgaaWcbaGa % ey4fIOcabeaakiqadwhagaqcamaaBaaaleaacqGHxiIkcaGGSaaabe % aaaaa!5587! \[ \zeta = fz/\eta _ * u_ * ,\hat u = \eta _ * \hat U/\hat u_ * ,\hat T = \hat \tau /u_ * \hat u_{ * ,} \] , where carets denote complex (vector) quantities; Û is the mean velocity; % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr% 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiqbes8a0zaaja% aaaa!3994!\[\hat \tau \]is the kinematic turbulent stress; and % MathType!MTEF!2!1!+- % feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l % b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr % 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiabeE7aOnaaBa % aaleaacqGHxiIkaeqaaOGaeyypa0JaaiikaiaaigdacqGHRaWkcqaH % +oaEdaWgaaWcbaGaamOtaaqabaGccaWG1bWaaSbaaSqaaiabgEHiQa % qabaGccaGGVaGaamOuamaaBaaaleaacaWGJbaabeaakiaadAgacaWG % mbGaaiykamaaCaaaleqabaGaeyOeI0IaaGymaiaac+cacaaIYaaaaa % aa!4B1F! \[ \eta _ * = (1 + \xi _N u_ * /R_c fL)^{ - 1/2} \]is a stability parameter. The constant % MathType!MTEF!2!1!+- % feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l % b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr % 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiabe67a4naaBa % aaleaacaWGobaabeaaaaa!3A81! \[\xi _N \] is the ratio of the maximum mixing length(% MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr% 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaamaaBaaaleaaca% WGTbaabeaaaaa!38DD!\[_m \]) to the PBL depth, % MathType!MTEF!2!1!+- % feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l % b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr % 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiaadwhadaWgaa % WcbaGaey4fIOcabeaakiaac+cacaWGMbaaaa!3B7C! \[ u_ * /f \] , for neutrally stable conditions; and % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr% 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiaadkfadaWgaa% WcbaGaam4yaaqabaaaaa!39AA!\[R_c\](the critical flux Richardson number) is the ratio % MathType!MTEF!2!1!+- % feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l % b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr % 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiaadYgadaWgaa % WcbaGaamyBaaqabaGccaGGVaGaamitaaaa!3B5C! \[ l_m /L \] under highly stable conditions. Profiles of stress and velocity in the ocean (<0) are given by % MathType!MTEF!2!1!+- % feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l % b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr % 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaamaaxacabaGabm % yDayaajaGaeyypa0ZaaiqaaqaabeqaaiabgkHiTiaadMgacqaH0oaz % caWGLbWaaWbaaSqabeaacqaH0oazcqaH2oGEaaGccaqGGaGaaeiiai % aabccacaqGGaGaaeiiaiaabccacaqGGaGaaeiiaiaabccacaqGGaGa % aeiiaiaabccacaqGGaGaaeiiaiaabccacaqGGaGaaeiiaiaabccaca % qGGaGaaeiiaiaabccacaqGGaGaaeiiaiaabccacaqGGaGaaeiiaiaa % bccacaqGGaGaaeiiaiaabccacaqGGaGaaeiiaiaabccacaqGGaGaae % iiaiaabccacaqGGaGaaeiiaiaabccacaqGGaGaaeiiaiaabccacaqG % GaGaaeiiaiaabccacaqGGaGaaeiiaiaabccacaqGGaGaaeiiaiaabc % cacaqGGaGaaeiiaiaabccacaqGGaGaaeiiaiaabccacaqGGaGaaeii % aiaabccacaqGGaGaaeiiaiaabccacaqGGaGaaeiiaiaabccacaqGGa % GaaeiiaiaabccacaqGGaGaaeiiaiaabccacaqGGaGaaeiiaiaabcca % caqGGaGaaeiiaiaabccacaqGGaGaeqOTdONaeyizImQaeyOeI0Iaeq % OVdG3aaSbaaSqaaiaad6eaaeqaaaGcbaGaeyOeI0IaamyAaiabes7a % KjaadwgadaahaaWcbeqaaiabes7aKjabe67a4naaBaaameaacaWGob % aabeaaaaGccqGHsisldaWcaaqaaiabeE7aOnaaBaaaleaacaGGQaaa % beaaaOqaaiaadUgaaaWaamWaaeaaciGGSbGaaiOBamaalaaabaWaaq % WaaeaacqaH2oGEaiaawEa7caGLiWoaaeaacqaH+oaEdaWgaaWcbaGa % amOtaaqabaaaaOGaey4kaSIaaiikaiabes7aKjabgkHiTiaadggaca % GGPaGaaiikaiabeA7a6jabgUcaRiabe67a4naaBaaaleaacaWGobaa % beaakiaacMcacqGHsisldaWcaaqaaiaadggaaeaacaaIYaaaaiabes % 7aKjaacIcacqaH2oGEdaahaaWcbeqaaiaaikdaaaGccqGHsislcqaH % +oaEdaqhaaWcbaGaamOtaaqaaiaaikdaaaGccaGGPaaacaGLBbGaay % zxaaGaaeiiaiaabccacaqGGaGaaeiiaiabeA7a6naaBaaaleaacaaI % WaaabeaakiabgwMiZkabeA7a6jabg6da+iabgkHiTiabe67a4naaBa % aaleaacaWGobaabeaaaaGccaGL7baaaSqabKazbaiabaGabmivayaa % jaGaeyypa0JaamyzamaaCaaajqMaacqabeaacaWGPbGaeqiTdqMaeq % OTdOhaaaaaaaa!C5AA! \[ \mathop {\hat u = \left\{ \begin{array}{l} - i\delta e^{\delta \zeta } {\rm{ }}\zeta \le - \xi _N \\ - i\delta e^{\delta \xi _N } - \frac{{\eta _* }}{k}\left[ {\ln \frac{{\left| \zeta \right|}}{{\xi _N }} + (\delta - a)(\zeta + \xi _N ) - \frac{a}{2}\delta \end{array} \right.}\limits^{\hat T = e^{i\delta \zeta } } \] where % MathType!MTEF!2!1!+- % feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l % b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr % 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiabes7aKjabg2 % da9maabmaabaGaamyAaiaac+cacaWGRbGaeqOVdG3aaSbaaSqaaiaa % d6eaaeqaaaGccaGLOaGaayzkaaWaaWbaaSqabeaacaaIXaGaai4lai % aaikdaaaGccaGG7aGaamyyaiabg2da9iabeE7aOnaaBaaaleaacqGH % xiIkaeqaaOGaaiikaiaaigdacaGGVaGaeqOVdG3aaSbaaSqaaiaad6 % eaaeqaaOGaey4kaSIaamyDamaaBaaaleaacqGHxiIkaeqaaOGaai4l % aiaadAgacaWGmbGaamOuamaaBaaaleaacaWGJbaabeaakiaacMcaca % GGOaGaaGymaiabgkHiTiabeE7aOnaaBaaaleaacqGHxiIkaeqaaOGa % aiykaiaacUdaaaa!5CB6! \[ \delta = \left( {i/k\xi _N } \right)^{1/2} ;a = \eta _ * (1/\xi _N + u_ * /fLR_c )(1 - \eta _ * ); \] and 0 is the nondimensional surface roughness. The constants are% MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr% 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiaadkfadaWgaa% WcbaGaam4yaaqabaaaaa!39AA!\[R_c \]= 0.2 and% MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr% 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiabe67a4naaBa% aaleaacaWGobaabeaaaaa!3A81!\[\xi _N \]= 0.052. The solutions for the atmosphere are similar except û is the nondimensional velocity The model produces satisfactory predictions of geostrophic drag and near-surface current (wind) profiles under stable stratification.  相似文献   

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