Parametrization of orographical effects in the planetary boundary layer     

D. Yordanov  N. Godev 《Boundary-Layer Meteorology》1973,5(3):309-320

Studies of the influence of orography on the dynamics of atmospheric processes usually assume the following relation as a boundary condition at the surface of the Earth, or at the top of the planetary layer: $$w = u\frac{{\delta z_0 }}{{\delta x}} + v\frac{{\delta z_0 }}{{\delta y}}$$ where u, v and w are the components of wind velocity along the x, y and z axes, respectively, and z ₀ = z₀(x, y) is the equation of the Earth's orography. We see that w, and consequently the influence of orography on the dynamics of atmospheric processes, depend on the wind (u, v) and on the slope of the obstacle (δz ₀/δx, δz₀/δy). In the present work, it is shown that the above relation for w is insufficient to describe the influence of orography on the dynamics of the atmosphere. It is also shown that the relation is a particular case of the expression: $$\begin{gathered} w_h = \left| {v_g } \right|\left[ {a_1 (Ro,s)\frac{{\delta z_0 }}{{\delta x}} + a_2 (Ro,s)\frac{{\delta z_0 }}{{\delta y}}} \right] + \hfill \\ + \frac{{\left| {v_g } \right|^2 }}{f}\left[ {b_1 (Ro,s)\frac{{\delta ^2 z_0 }}{{\delta x^2 }} + b_2 (Ro,s)\frac{{\delta ^2 z_0 }}{{\delta y^2 }} + b_3 (Ro,s)\frac{{\delta ^2 z_0 }}{{\delta x\delta y}}} \right] \hfill \\ \end{gathered} $$ where ¦vv _g¦ is the strength of the geostrophic wind, a ₁, a₂, b₁, b₂, b₃ are functions of Rossby number Ro and of the external stability parameter s. The above relation is obtained with the help of similarity theory, with a parametrization of the planetary boundary layer. Finally, the authors show that a close connection exists between the effects described by the above expression and cyclo- and anticyclogenesis.  相似文献   

Surface influence upon vertical profiles in the nocturnal boundary layer     

J. R. Garratt 《Boundary-Layer Meteorology》1983,26(1):69-80

Near-surface wind profiles in the nocturnal boundary layer, depth h, above relatively flat, tree-covered terrain are described in the context of the analysis of Garratt (1980) for the unstable atmospheric boundary layer. The observations at two sites imply a surface-based transition layer, of depth z _*, within which the observed non-dimensional profiles Φ _M ⁰ are a modified form of the inertial sub-layer relation \(\Phi _M \left( {{z \mathord{\left/ {\vphantom {z L}} \right. \kern-0em} L}} \right) = \left( {{{1 + 5_Z } \mathord{\left/ {\vphantom {{1 + 5_Z } L}} \right. \kern-0em} L}} \right)\) according to $$\Phi _M^{\text{0}} \simeq \left( {{{1 + 5z} \mathord{\left/ {\vphantom {{1 + 5z} L}} \right. \kern-\nulldelimiterspace} L}} \right)\exp \left[ { - 0.7\left( {{{1 - z} \mathord{\left/ {\vphantom {{1 - z} z}} \right. \kern-\nulldelimiterspace} z}_ * } \right)} \right]$$ , where z is height above the zero-plane displacement and L is the Monin-Obukhov length. At both sites the depth z _* is significantly smaller than the appropriate neutral value (z _*N ) found from the previous analysis, as might be expected in the presence of a buoyant sink for turbulent kinetic energy.  相似文献   

The observed relation between the Kolmogorov and von Karman constants in the surface boundary layer     

Paul Frenzen 《Boundary-Layer Meteorology》1973,3(3):348-358

In steady, neutrally-stratified flow over uniform terrain, the Kolmogorov constant for the one-dimensional spectrum in the inertial subrange (α ₁) and the von Karman constant of the logarithmic profile (k) are shown to be related by $$\alpha _1 k^{{4 \mathord{\left/ {\vphantom {4 3}} \right. \kern-\nulldelimiterspace} 3}} = \left[ {\frac{{\sum \phi }}{{0.555}}} \right]\left[ {\frac{{nz}}{{\bar U_z }}} \right]^{{2 \mathord{\left/ {\vphantom {2 3}} \right. \kern-\nulldelimiterspace} 3}} \left[ {\frac{{\ln z_2 /z_1 }}{{\bar U_2 - \bar U_1 }}} \right]^2 \simeq 0.136,$$ , where the numerical value results from field measurements recorded in near-ideal conditions. This experimentally-observed Kolmogorov-von Karman ‘K-von K’ product is close to the value designated by a one-dimensional equivalent of the theoretical relation previously given by Roth (1970). More-over, it is in remarkably close agreement with new values of both constants independently proposed in recent years.  相似文献   

Absolute OH quantum yields in the laser photolysis of nitrate,nitrite and dissolved H2O2 at 308 and 351 nm in the temperature range 278–353 K     

R. Zellner  M. Exner  H. Herrmann 《Journal of Atmospheric Chemistry》1990,10(4):411-425

Absolute quantum yields for the formation of OH radicals in the laser photolysis of aqueous solutions of NO₃ ^-, NO₂ ^- and H₂O₂ at 308 and 351 nm and as a function of pH and temperature have been measured. A scavenging technique involving the reaction between OH and SCN^- ions and the time resolved detection by visible absorption of the (SCN)₂ ^- radical ion was used to determine the absolute OH yields. The following results were obtained:

1. NO ₃ ^- -photolysis:% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGceaqabeaacaaIWa% GaaGioaGGaaiab-bcaGiaab6gacaqGTbGaaeOoaiab-bcaGiabfA6a% gnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5a% GaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWFGaaicqWFWaam% cqWFUaGlcqWFWaamcqWFXaqmcqWF3aWncqWFGaaicqGHXcqScqWFGa% aicqWFWaamcqWFUaGlcqWFWaamcqWFWaamcqWFZaWmcqWFGaaicaqG% MbGaae4BaiaabkhacaqGGaGaaeinaiaabccacqGHKjYOcaqGGaGaam% iCaiaabIeacaqGGaGaeyizImQaaeiiaiaabMdaaeaacqWFGaaicqWF% GaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicq% WFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqqHMoGr% daWgaaWcbaGae83Nd8Kae83LdGeabeaakiaacIcacaWGubGaaiykai% abg2da9iabfA6agnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiik% aiaaikdacaaI5aGaaGioaiab-bcaGiab-P5aljaacMcacqWFGaaica% qGLbGaaeiEaiaabchacaqGGaWaamWaaeaacaqGOaGaaeymaiaabIda% caqGWaGaaeimaiaabccacqGHXcqScaaI0aGaaGioaiaaicdacaqGPa% GaaeikamaalaaabaGaaeymaaqaaiaabkdacaqG5aGaaeioaaaacaqG% GaGaeyOeI0IaaeiiamaalaaabaGaaeymaaqaaiaadsfaaaGaaeykaa% Gaay5waiaaw2faaiaac6caaaaa!9673!\[\begin{gathered}08 {\text{nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = 0.017 \pm 0.003 {\text{for 4 }} \leqslant {\text{ }}p{\text{H }} \leqslant {\text{ 9}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(1800 }} \pm 480{\text{)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right]. \hfill \\\end{gathered}\] Selected experiments at 351 nm indicate that these results are essentially unchanged.
2. NO ₂ ^- -photolysis:% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGceaqabeaacaaIWa% GaaGioaGGaaiab-bcaGiaab6gacaqGTbGaaeOoaiab-bcaGiabfA6a% gnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5a% GaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWFGaaicqWFOaak% cqWFWaamcqWFUaGlcqWFWaamcqWFXaqmcqWF3aWncqWFGaaicqGHXc% qScqWFGaaicqWFWaamcqWFUaGlcqWFWaamcqWFWaamcqWFXaqmcqWF% PaqkcqWFGaaicaqGMbGaae4BaiaabkhacaqGGaGaaeinaiaabccacq% GHKjYOcaqGGaGaamiCaiaabIeacaqGGaGaeyizImQaaeiiaiaabMda% caqGSaaabaGae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8% hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIa% e8hiaaIae8hiaaIaeuOPdy0aaSbaaSqaaiab-95apjab-D5aibqaba% GccaGGOaGaamivaiaacMcacqGH9aqpcqqHMoGrdaWgaaWcbaGae83N% d8Kae83LdGeabeaakiaacIcacaaIYaGaaGyoaiaaiIdacqWFGaaicq% WFAoWscaGGPaGae8hiaaIaaeyzaiaabIhacaqGWbGaaeiiamaadmaa% baGaaeikaiaabgdacaqG1aGaaeOnaiaabcdacaqGGaGaeyySaeRaae% iiaiaabodacaqG2aGaaeimaiaabMcacaqGOaWaaSaaaeaacaqGXaaa% baGaaeOmaiaabMdacaqG4aaaaiaabccacqGHsislcaqGGaWaaSaaae% aacaqGXaaabaGaamivaaaacaqGPaaacaGLBbGaayzxaaGaaiilaaqa% aiaaiodacaaI1aGaaGymaiaabccacaqGUbGaaeyBaiaabQdacqWFGa% aicqqHMoGrdaWgaaWcbaGae83Nd8Kae83LdGeabeaakiaacIcacaaI% YaGaaGyoaiaaiIdacqWFGaaicqWFAoWscaGGPaGaeyypa0Jae8hiaa% Iae8hkaGIae8hmaaJae8Nla4Iae8hmaaJae8hnaqJae8NnayJae8hi% aaIaeyySaeRae8hiaaIae8hmaaJae8Nla4Iae8hmaaJae8hmaaJae8% xoaKJae8xkaKIae8hiaaIaaeOzaiaab+gacaqGYbGaaeiiaiaabsda% caqGGaGaeyizImQaaeiiaiaadchacaqGibGaaeiiaiaab2dacaqGGa% GaaeioaiaabYcaaeaacqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWF% GaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicq% WFGaaicqWFGaaicqWFGaaicqqHMoGrdaWgaaWcbaGae83Nd8Kae83L% dGeabeaakiaacIcacaWGubGaaiykaiabg2da9iabfA6agnaaBaaale% aacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5aGaaGioaiab% -bcaGiab-P5aljaacMcacqWFGaaicaqGLbGaaeiEaiaabchacaqGGa% WaamWaaeaacaqGOaGaaeymaiaabIdacaqGWaGaaeimaiaabccacqGH% XcqScaqGGaGaaeinaiaabcdacaqGWaGaaeykaiaabIcadaWcaaqaai% aabgdaaeaacaqGYaGaaeyoaiaabIdaaaGaaeiiaiabgkHiTiaabcca% daWcaaqaaiaabgdaaeaacaWGubaaaiaabMcaaiaawUfacaGLDbaaca% GGUaaaaaa!FC61!\[\begin{gathered}08 {\text{nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.017 \pm 0.001) {\text{for 4 }} \leqslant {\text{ }}p{\text{H }} \leqslant {\text{ 9,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(1560 }} \pm {\text{ 360)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right], \hfill \\351{\text{ nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.046 \pm 0.009) {\text{for 4 }} \leqslant {\text{ }}p{\text{H = 8,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(1800 }} \pm {\text{ 400)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right]. \hfill \\\end{gathered}\]
3. H₂O₂-photolysis:% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGceaqabeaacaaIWa% GaaGioaGGaaiab-bcaGiaab6gacaqGTbGaaeOoaiab-bcaGiabfA6a% gnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5a% GaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWFGaaicqWFOaak% cqWFWaamcqWFUaGlcqWF5aqocqWF4aaocqWFGaaicqGHXcqScqWFGa% aicqWFWaamcqWFUaGlcqWFWaamcqWFZaWmcqWFPaqkcqWFGaaicaqG% MbGaae4BaiaabkhacaqGGaGaamiCaiaabIeacaqGGaGaeyizImQaae% iiaiaabEdacaqGSaaabaGae8hiaaIae8hiaaIae8hiaaIae8hiaaIa% e8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaa% Iae8hiaaIae8hiaaIae8hiaaIaeuOPdy0aaSbaaSqaaiab-95apjab% -D5aibqabaGccaGGOaGaamivaiaacMcacqGH9aqpcqqHMoGrdaWgaa% WcbaGae83Nd8Kae83LdGeabeaakiaacIcacaaIYaGaaGyoaiaaiIda% cqWFGaaicqWFAoWscaGGPaGae8hiaaIaaeyzaiaabIhacaqGWbGaae% iiamaadmaabaGaaeikaiaabAdacaqG2aGaaeimaiaabccacqGHXcqS% caqGGaGaaeymaiaabMdacaqGWaGaaeykaiaabIcadaWcaaqaaiaabg% daaeaacaqGYaGaaeyoaiaabIdaaaGaaeiiaiabgkHiTiaabccadaWc% aaqaaiaabgdaaeaacaWGubaaaiaabMcaaiaawUfacaGLDbaacaGGSa% aabaGaaG4maiaaiwdacaaIXaGaaeiiaiaab6gacaqGTbGaaeOoaiab% -bcaGiabfA6agnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikai% aaikdacaaI5aGaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWF% GaaicqWFOaakcqWFWaamcqWFUaGlcqWF5aqocqWF2aGncqWFGaaicq% GHXcqScqWFGaaicqWFWaamcqWFUaGlcqWFWaamcqWF0aancqWFPaqk% cqWFGaaicaqGMbGaae4BaiaabkhacaqGGaGaaeinaiaabccacqGHKj% YOcaqGGaGaamiCaiaabIeacaqGGaGaaeypaiaabccacaqG3aGaaeil% aaqaaiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGi% ab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bca% Giab-bcaGiabfA6agnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaai% ikaiaadsfacaGGPaGaeyypa0JaeuOPdy0aaSbaaSqaaiab-95apjab% -D5aibqabaGccaGGOaGaaGOmaiaaiMdacaaI4aGae8hiaaIae8NMdS% Kaaiykaiab-bcaGiaabwgacaqG4bGaaeiCaiaabccadaWadaqaaiaa% bIcacaqG1aGaaeioaiaabcdacaqGGaGaeyySaeRaaeiiaiaabgdaca% qG2aGaaeimaiaabMcacaqGOaWaaSaaaeaacaqGXaaabaGaaeOmaiaa% bMdacaqG4aaaaiaabccacqGHsislcaqGGaWaaSaaaeaacaqGXaaaba% GaamivaaaacaqGPaaacaGLBbGaayzxaaGaaiOlaaaaaa!F3D0!\[\begin{gathered}08 {\text{nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.98 \pm 0.03) {\text{for }}p{\text{H }} \leqslant {\text{ 7,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(660 }} \pm {\text{ 190)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right], \hfill \\351{\text{ nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.96 \pm 0.04) {\text{for 4 }} \leqslant {\text{ }}p{\text{H = 7,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(580 }} \pm {\text{ 160)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right]. \hfill \\\end{gathered}\] Together with the absorption coefficients and an assumed actinic flux within atmospheric droplets of twice the clear air value, the partial photolytic lifetimes (τ_OH) of these molecules at 298 K are estimated as 10.5 d, 5.4 h and 30.3 h for NO₃ ^-, NO₂ ^- and H₂O₂, respectively. These lifetimes will increase by a factor of two (NO₃ ^-, NO₂ ^-) and by 15% (H₂O₂) at T=278 K. Using average ambient concentrations in tropospheric aqueous droplets, the photolytic OH source strengths from these species are calculated to be 2.8×10^-11, 1.3×10^-11 and 1.4×10^-11 mol 1^-1 s^-1 for NO₃ ^-, NO₂ ^- and H₂O₂ respectively.

  相似文献   

The source area influencing a measurement in the Planetary Boundary Layer: The “footprint” and the “distribution of contact distance”     

J. D. Wilson  G. E. Swaters 《Boundary-Layer Meteorology》1991,55(1-2):25-46

This paper considers the ground area which affects the properties of fluid parcels observed at a given spot in the Planetary Boundary Layer (PBL). We examine two source-area functions; the footprint, giving the source area for a measurement of vertical flux: and the distribution of contact distance, the distance since a particle observed aloft last made contact with the surface. We explain why the distribution of contact distance extends vastly farther upwind than the footprint, and suggest for the extent of the footprint the inequalities: % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr% 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOabaeqabaGaamyvam% aalaaabaGaamiAaaqaaiabeo8aZnaaBaaaleaacaWGxbaabeaakiaa% cIcacaWGObGaaiykaaaacqGH8aapcaWG4bGaeyipaWJaamyvaKazaa% iadaGabaqaamaaDaaajqwaacqaaiaadIgacaGGVaGabmOEayaacaGa% aiilaiaabccacaGGVbGaaiiDaiaacIgacaGGLbGaaiOCaiaacEhaca% GGPbGaai4CaiaacwgaaeaacaWGubWaaSbaaKazcaiabaGaamitaaqa% baqcKfaGaiaacIcacaWGObGaaiykaiaabYcacaqGGaGaaeiAaiaabc% cacaGGHbGaaiOyaiaac+gacaGG2bGaaiyzaiaabccacaGGZbGaaiyD% aiaackhacaGGMbGaaiyyaiaacogacaGGLbGaeyOeI0IaaiiBaiaacg% gacaGG5bGaaiyzaiaackhaaaaajqgaacGaay5EaaaakeaaaeaacaGG% 8bGaamyEaiaacYhacqGH8aapcqaHdpWCdaWgaaWcbaGaamODaaqaba% GccaGGOaGaamiAaiaacMcadaWcaaqaaiaadIhaaeaacaWGvbaaaaaa% aa!7877!\[\begin{array}{l} U\frac{h}{{\sigma _W (h)}} < x < U\left\{ {_{h/\dot z,{\rm{ }}otherwise}^{T_L (h){\rm{, h }}above{\rm{ }}surface - layer} } \right. \\ \\ |y| < \sigma _v (h)\frac{x}{U} \\ \end{array}\] where U is the mean streamwise (x) velocity, h is the observation height, _L is the Lagrangian timescale, _v and _w are the standard deviations of the cross-stream horizontal (y) and vertical (z) velocity fluctuations, and is the Lagrangian Similarity prediction for the rate of rise of the centre of gravity of a puff released at ground.Simple analytical solutions for the contact-time and the footprint are derived, by treating the PBL as consisting of two sub-layers. The contact-time solutions agree very well with the predictions of a Lagrangian stochastic model, which we adopt in the absence of measurements as our best estimate of reality, but the footprint solution offers no improvement over the above inequality.  相似文献   

Kinetics of the reactions of Cl atoms with 2-buten-1-ol, 2-methyl-2-propen-1-ol, and 3-methyl-2-buten-1-ol as a function of temperature     

Diana Rodriguez  Ana Rodriguez  Amparo Soto  Alfonso Aranda  Yolanda Diaz-de-Mera  Alberto Notario 《Journal of Atmospheric Chemistry》2008,59(3):187-197

The reactions of three structurally similar unsaturated alcohols, 2-buten-1-ol (crotyl alcohol), 2-methyl-2-propen-1-ol (MPO221) and 3-methyl-2-buten-1-ol (MBO321) with Cl atoms, have been investigated for the first time, using a 400 l Teflon reaction chamber coupled with gas chromatograph-coupled with flame-ionization detection (GC-FID). The experiments were performed at atmospheric pressure and at temperatures between 255 and 298 K, in air or nitrogen as the bath gas. The obtained kinetic data were used to derive the Arrhenius expressions , , (in units of cm³ molecule⁻¹ s⁻¹). Finally, atmospheric lifetimes of those unsaturated alcohols with respect to OH, NO₃, O₃ and Cl have been calculated.  相似文献   

Kinetics of ammonia and ammonium ion inhibition of the atmospheric oxidation of aqueous sulfur dioxide by oxygen     

Punit Kumar Mudgal  Anil Kumar Sharma  C. D. Mishra  S. P. Bansal  K. S. Gupta 《Journal of Atmospheric Chemistry》2008,61(1):31-55

This is the first study, which shows both NH₃ and NH₄⁺ to inhibit the autoxidation of aqueous SO₂ in the pH range 7.0–8.5. The rate of the autoxidation, R _aut , in both buffered and unbuffered media at a fixed pH is in conformity with the rate law: where R ₀ is rate in the absence of the inhibitors, B is a pH dependent empirical constant and [Inh]_T is the analytical concentration of NH₃ or NH₄⁺. Both ammonia and ammonium ions appear to inhibit the autoxidation either by scavenging SO₄⁻ radicals or by forming less-reactive /unreactive Co(II)-NH₃ complexes or both. The atmospheric relevance of the inhibition by ammonia and ammonium ions is discussed.  相似文献   

Role of atmospheric ammonia in the formation of inorganic secondary particulate matter: A study at Kanpur,India   总被引：1，自引：0，他引：1  

Mukesh Sharma  Shyam Kishore  S. N. Tripathi  S. N. Behera 《Journal of Atmospheric Chemistry》2007,57(1):1-17

Levels of fine Particulate Matter (PM_fine), SO₂ and NO_x are interlinked through atmospheric reactions to a large extent. NO_x, NH₃, SO₂, temperature and humidity are the important atmospheric constituents/conditions governing formation of fine particulate sulfates and nitrates. To understand the formation of inorganic secondary particles (nitrates and sulfates) in the atmosphere, a study was undertaken in Kanpur, India. Specifically, the study was designed to measure the atmospheric levels of covering winter and summer seasons and day and night samplings to capture the diurnal variations. Results showed are found to be significantly high in winter season compared to the summer season. In winter, the molar ratio of to was found to be greater than 2:1. This higher molar ratio suggests that in addition to (NH₄)₂SO₄, NH₄NO₃ will be formed because of excess quantity of present. In summer, the molar ratio was less than 2:1 indicating deficit of to produce NH₄NO₃. The nitrogen conversion ratio (NO₂ to NO₃) was found to be nearly 50% in the study area that suggested quick conversion of NO₂ into nitric acid. As an overall conclusion, this study finds that NH₃ plays a vital role in the formation of fine inorganic secondary particles particularly so in winter months and there is a need to identify and assess sources of ammonia emissions in India.  相似文献   

Validity of the log-linear profile relationship over a rough terrain during stable conditions     

S. Sethuraman  R. M. Brown 《Boundary-Layer Meteorology》1976,10(4):489-501

The applicability of the log-linear profile relationship over rough terrain to a height of 126 m is investigated. Simultaneous hourly averaged mean wind and temperature profiles measured at the Brookhaven meteorological tower during stable conditions are used in the analysis. The tower was surrounded by fairly homogeneous vegetation to a height of about 8 m. The results indicate that the log-linear profile relationship is valid at least for a height of 126 m for stabilities with Richardson numbers less than the critical value of 0.25. The mean value of in is found to be about 5.2 for these stabilities. The log-linear profile relation is found to be applicable for profiles observed beyond the critical stability; but the height of validity seems to decrease to about 100 m and the mean value of is about 1.6.Research performed under the auspices of the United States Energy Research and Development Administration (Contract E(30-1)-16).  相似文献   

Chemical characterization of wet precipitation events and deposition of pollutants in coal mining region,India     

Abhay Kumar Singh  G. C. Mondal 《Journal of Atmospheric Chemistry》2008,59(1):1-23

The present study investigated the chemical composition of wet atmospheric precipitation in India’s richest coal mining belt. Total 418 samples were collected on event basis at six sites from July to October in 2003 and May to October in 2004 and analysed for pH, EC, F⁻, Cl⁻, , , Ca²⁺, Mg²⁺, Na⁺, K⁺ and . The average pH value (5.7) of the rainwater of the investigated area is alkaline in nature. However, the temporal pH variation showed the alkaline nature during the early phase of monsoonal rainfall but it trends towards acidic during the late and high rainfall periods. The rainwater chemistry of the region showed high contribution of Ca²⁺ (47%) and (21%) in cations and (55%) and Cl⁻ (23%) in anionic abundance. The high non seas salt fraction (nss) of Ca²⁺ (99%) and Mg²⁺ (96%) suggests crustal source of the ions, while the high nss (96%) and high ratio signifying the impact of anthropogenic sources and the source of the acidity. The ratio of varies from 0.03 to 3.23 with the average value of 0.84 suggesting that Ca²⁺ and play a major role in neutralization processes. The assessment of the wet ionic deposition rates shows no any specific trend, however Ca²⁺ deposition rate was highest followed by and _.  相似文献   

Velocity Adjustment and Passive Scalar Diffusion in and Above an Urban Canopy in Response to Various Approach Flows     

Isao Kanda  Yukio Yamao 《Boundary-Layer Meteorology》2011,141(3):415-441

We used wind-tunnel experiments to investigate velocity-field adjustment and scalar diffusion behaviour in and above urban canopies located downwind of various roughness elements. Staggered arrays of rectangular blocks of various heights H and plan area ratios λ_p were used to model the urban canopies. The velocity field in the roughness sublayer (height \({z \lesssim 2H}\)) reached equilibrium at distances proportional to \({\sqrt{L_{\rm c}H}}\) where L _c is the canopy-drag length scale determined as a function of λ_p and the block side length L. A distance of about \({20\sqrt{L_{\rm c}H}}\) was required for adjustment at z = H/2 (in the canopy), and a distance of about \({10\sqrt{L_{\rm c}H}}\) was required at z = 2H (near the top of the roughness sublayer). Diffusion experiments from a ground emission source revealed that differences in upwind roughness conditions had negligible effects on the plume growth near the source (up to a few multiples of L from the source) if the source was located at a fetch F larger than about \({10\sqrt{L_{\rm c}H}}\) from the upwind edge of the canopy. However, at locations farther downwind (more than several multiples of L from the source), upwind conditions had considerable effects on the plume growth. For a representative urban canopy, it was shown that a much larger fetch than required for velocity-field adjustment in the roughness sublayer was necessary to eliminate the effects of upwind conditions on plume widths at 24L downwind from the source.  相似文献   

The NO2-O3 system at sub-ppm concentrations: Influence of temperature and relative humidity     

P. W. C. Verhees  E. H. Adema 《Journal of Atmospheric Chemistry》1985,2(4):387-403

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   

The turbulent heat flux from arctic leads   总被引：2，自引：0，他引：2  

E. L. Andreas  C. A. Paulson  R. M. William  R. W. Lindsay  J. A. Businger 《Boundary-Layer Meteorology》1979,17(1):57-91

The turbulent transfer of heat from Arctic leads in winter is one of the largest terms in the Arctic heat budget. Results from the AIDJEX Lead Experiment (ALEX) suggest that the sensible component of this turbulent heat flux can be predicted from bulk quantities. Both the exponential relation N = 0.14R _x ^0.72 and the linear relation N = 1.6 × 10^–3 R _x+ 1400 fit our data well. In these, N is the Nusselt number formed with the integrated surface heat flux, and R _x is the Reynolds number based on fetch across the lead. Because of the similarity between heat and moisture transfer, these equations also predict the latent heat flux. Over leads in winter, the sensible heat flux is two to four times larger than the latent heat flux.The internal boundary layer (IBL) that develops when cold air encounters the relatively warm lead is most evident in the modified downwind temperature profiles. The height of this boundary layer, , depends on the fetch, x, on the surface roughness of the lead, z ₀ and on both downwind and upwind stability. A tentative, empirical model for boundary layer growth is % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4baFfea0dXde9vqpa0lb9% cq0dXdb9IqFHe9FjuP0-iq0dXdbba9pe0lb9hs0dXda91qaq-xfr-x% fj-hmeGabaqaciGacaGaaeqabaWaaeaaeaaakeaadaWcaaqaaiabes% 7aKbqaaiaadQhadaWgaaWcbaGaaGimaaqabaaaaOGaeyypa0JaeqOS% di2aaeWaaeaacqGHsisldaWcaaqaaiaadQhadaWgaaWcbaGaaGimaa% qabaaakeaacaWGmbaaaaGaayjkaiaawMcaamaaCaaaleqabaGaaGim% aiaac6cacaaI4aaaaOWaaeWaaeaadaWcaaqaaiaadIhaaeaacaWG6b% WaaSbaaSqaaiaaicdaaeqaaaaaaOGaayjkaiaawMcaamaaCaaaleqa% baGaaGimaiaac6cacaaI0aaaaaaa!472D!\[\frac{\delta }{{z_0 }} = \beta \left( { - \frac{{z_0 }}{L}} \right)^{0.8} \left( {\frac{x}{{z_0 }}} \right)^{0.4} \] where L is the Obukhov length based on the values of the momentum and sensible heat fluxes at the surface of the lead, and is a constant reflecting upwind stability.Velocity profiles over leads are also affected by the surface nonhomogeneity. Besides being warmer than the upwind ice, the surface of the lead is usually somewhat rougher. The velocity profiles therefore tend to decelerate near the surface, accelerate in the mid-region of the IBL because of the intense mixing driven by the upward heat flux, and rejoin the upwind profiles above the boundary layer. The profiles thus have distinctly different shapes for stable and unstable upwind conditions.  相似文献   

Chemistry of Precipitation Events and Inter-Relationship with Ambient Aerosols over a Semi-Arid Region in Western India     

N. Rastogi  M. M. Sarin 《Journal of Atmospheric Chemistry》2007,56(2):149-163

The precipitation events (n = 91), collected for 3 years (2000–2002) during the period of SW-monsoon (Jun–Aug) from an urban site (Ahmedabad, 23.0°N, 72.6°E) of a semi-arid region in western India, are found to exhibit characteristic differences in terms of their solute contents. The low solute (<700 μeq L⁻¹) events are either marked by heavy precipitation amount or successive events collected during an extended rain spell; whereas light precipitation events occurring after antecedent dry period are characterized by high solutes (>700 μeq L⁻¹). The ionic composition of low solute events show large variability due to varying contribution of anthropogenic species (: 1%–74%; : 1%–25%; and : 8%–68%) to the respective ion balance. In high solute events, ionic abundances are dominated by mineral dust (Ca²⁺ and ) and sea-salts (Na⁺ and Cl⁻). These differences are also reflected in the pH of low solute events (range: 5.2–7.4, VWM: 6.4) and high solute events (range: 6.6–8.2, VWM: 7.3). The comparison of Ca²⁺/Na⁺ and nss- ratios (on equivalent basis) in rain and aerosols suggests that the ionic composition of high solute events is influenced by below-cloud scavenging; whereas evidence for in-cloud scavenging is significantly reflected in low solute events. The annual wet-deposition fluxes of and are 330 and 480 mg m⁻² y⁻¹, respectively, in contrast to their corresponding dry-deposition fluxes (14 and 160 mg m⁻² y⁻¹); whereas wet and dry removal of Ca²⁺, Mg²⁺ and are comparable.  相似文献   

The acid catalyzed nitration of methanol: formation of methyl nitrate via aerosol chemistry     

Laura T. Iraci  Brent G. Riffel  Carly B. Robinson  Rebecca R. Michelsen  Rachel M. Stephenson 《Journal of Atmospheric Chemistry》2007,58(3):253-266

The aqueous phase acid-catalyzed reaction of methanol (CH₃OH) with nitric acid (HNO₃) to yield methyl nitrate (CH₃ONO₂) under atmospheric conditions has been investigated using gas-phase infrared spectroscopy. Reactions were conducted in aqueous sulfuric acid solutions (50.5–63.6 wt.%) with [CH₃OH] = 0.00005–0.005 M and [HNO₃] = 0.02–0.21 M, at 278.2–328.6 K. Methyl nitrate production rates increased linearly with CH₃OH and HNO₃ concentrations and exponentially with sulfuric acid weight percent within the regime studied. Rates increased linearly with nitronium ion concentration, indicating that the reaction involves as the nitrating agent under these conditions. At 298 K, the rate of methyl nitrate production can be calculated from k _obs [CH₃OH][HNO₃], where k _obs  = 2.337 × 10⁻¹³(exp(0.3198*wt.% H₂SO₄)) when the solubility of CH₃ONO₂ in acidic solution is approximated by H* for pure water. The temperature dependence of the rate coefficient is related to solution composition, with activation energies of 59 and 49 kJ/mol at 51.1 and 63.6 wt.% H₂SO₄, respectively, when k is calculated from rate. The temperature dependence has also been parameterized for application to the atmosphere, but the small quantities of present in aerosol particles will result in methyl nitrate production rates too small to be of significance under most atmospheric conditions. An erratum to this article can be found at  相似文献   

The gas-phase reaction of ClONO2 with hydrogen chloride     

Roger Atkinson  Sara M. Aschmann  Ernesto C. Tuazon  Mark A. Goodman  Arthur M. Winer 《Journal of Atmospheric Chemistry》1987,5(1):83-90

The gas-phase reaction of ClONO₂ with HCl was investigated using two large-volume environmental chambers with analysis by in situ long pathlength Fourier transform infrared absorption spectroscopy. In these chambers the reaction was observed to proceed, at least in part, by heterogenous routes, and an upper limit to the rate constant for the homogeneous gas-phase reaction of geneous routes, and an upper limit to the rate constant for the homogeneous gas-phase reaction of $$k\left( {{\text{ClONO}}_{\text{2}} + {\text{HCl}}} \right) < 1.5 \times 10^{ - 19} {\text{ cm}}^{\text{3}} {\text{ molecule}}^{{\text{ - 1}}} {\text{ s}}^{{\text{ - 1}}}$$ Was derived at 298±2K. Assuming that this room-temperature upper limit to the rate constant is applicable to stratospheric temperatures, this homogeneous gas-phase reaction can be estimated to be of negligible importance as a ClONO₂ loss process in the stratosphere.  相似文献   

Aircraft Observations of Air-mass Modification Over the Sea of Okhotsk during Sea-ice Growth     

Jun?InoueEmail author  Masayuki?Kawashima  Yasushi?Fujiyoshi  Masaaki?Wakatsuchi 《Boundary-Layer Meteorology》2005,117(1):111-129

In order to quantitatively investigate the role of leads and sea-ice in air-mass modification, aircraft observations were conducted over the partially ice-covered Sea of Okhotsk. We investigated two cold-air outbreak events with different sea-ice concentrations. In both cases, the difference between the temperatures of surface air and the sea surface (ΔT) dropped rapidly with the accumulated fetch-width of leads up to about 35-40 km, and then decreased very slowly. The surface sensible heat flux originating from open water was about 300 W m⁻² within a few kilometres from the coast and decreased with increasing accumulated fetch-width. The sensible heat flux was about 100 W m⁻² on average. These results indicate that the downwind air-mass modification depends mainly on the total (accumulated) extent of open water. The total buoyancy flux calculated by the joint frequency distribution method correlated very well with ice concentration. Such a relationship was not clear in the case of the moisture flux . The ratio between rising thermals and cold downdrafts differed significantly between upwind and downwind regions; that is, the buoyancy flux was dominated by in the developing stage of the boundary layer, while also became important after the development of the boundary layer.  相似文献   

Alkyl nitrate formation from the reaction of a series of branched RO2 radicals with NO as a function of temperature and pressure     

Roger Atkinson  Sara M. Aschmann  Arthur M. Winer 《Journal of Atmospheric Chemistry》1987,5(1):91-102

Alkyl nitrate yields from the NO _x photooxidations of neopentane, 2-methylbutane and 3-methylpentane have been determined over the temperature and pressure ranges 281–323 K and 54–740 torr, respectively. The formation of the alkyl nitrates is attributed to the reaction pathway (1b) $${\text{RO}}_{\text{2}} + {\text{NO}}^{{\text{ }}\underrightarrow {\text{M}}} {\text{ RONO}}_{\text{2}}$$ and rate constant ratios k _1b/(k _1a+k _1b) are estimated, where (1a) is the reaction pathway (1a) $${\text{RO}}_{\text{2}} + {\text{NO}} \to {\text{RONO}}_{\text{2}} .$$ A method for estimating this rate constant ratio for primary, secondary and tertiary alkyl peroxy radicals is presented.  相似文献   

Aqueous Oxidation of Sulfur(IV) Catalyzed by Manganese(II): A Generalized Simple Kinetic Model     

Boštjan Podkrajšek  Gorazd Berčič  Janja Turšič  Irena Grgić 《Journal of Atmospheric Chemistry》2004,47(3):287-303

The reaction kinetics of S(IV) autoxidation catalyzed by Mn(II) in the pH range 3–5 typical for atmospheric liquid water, was investigated. For reactions with pH maintained constant during the reaction course, the predictions obtained by a simple integral approach cover kinetic results only for concentrations of HSO ₃ ⁻ up to 0.2 mM at pH 4.5. Thus, a generalized simple kinetic model, which can be used for predicting the reaction kinetics in wider concentration, pH and temperature ranges, was derived. This model is based on the assumption that the reaction rate is proportional to the concentration of a transient manganese-sulfito complex formed in the initial step of a radical chain mechanism. In the proposed power law rate equation the concentration of complex is calculated from the stability constant K and concentrations of reactants at a specific reaction time. This rate equation adequately predicts the reaction kinetics in the pH range 3–5, in the concentration ranges 0.1 ≤ [HSO ₃ ⁻ ] ≤ 0.4 mM and 2 ≤ [Mn(II)] ≤ 14.6 μM. For the temperature range 15–35 °C, the estimated value for activation energy is 92.0 ± 0.1 kJ mol⁻¹ and the Gibbs free energy of formation of the manganese-sulfito complex is −20.4 ± 0.3 kJ mol⁻¹. Furthermore, the kinetics for catalytic reactions with pH maintained constant during the reaction course as well as with initial pH adjusted only at the start of the reaction, is described satisfactorily by the present model.  相似文献   

A comparison of several diffuse solar radiation models for Greece     

B. D. Katsoulis 《Theoretical and Applied Climatology》1991,44(3-4):181-186

Summary This paper attempts to test the applicability of existing correlation models to the estimation of diffuse radiation with respect to measured values at a station. There are two types of model: The first type depends on the fraction of monthly average daily diffuse radiation to total solar radiation, , as a function of the clearness index, . The second type expresses the fraction or as a function of the sunshine fraction Therefore, it presents statistically based correlations between global radiation and its diffuse component on a horizontal surface and suggests two equations to determine the ratio of diffuse radiation to total radiation received on a horizontal surface. The results of these correlation equations are compared with other accepted equations.With 3 Figures  相似文献