A comparison of several diffuse solar radiation models for Greece

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     

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

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).     

Surface influence upon vertical profiles in the nocturnal boundary layer

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.     

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

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.     

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

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.     

Parametrization of orographical effects in the planetary boundary layer

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.     

Numerical simulation of particle trajectories in inhomogeneous turbulence,III: Comparison of predictions with experimental data for the atmospheric surface layer

It is shown that predictions of a numerical trajectory-simulation method agree closely with the Project Prairie Grass observations of the concentrations 100 m downwind of a continuous point source of sulphur dioxide if the height (z) dependence of the Lagrangian length scale Λ _L is chosen as: whereL is the Monin-Obukhov length. The value of 0.5 for Λ _L /z in neutral conditions is consistent with the findings of Reid (1979) for the Porton experiment, and is also shown to be the best choice for simulation of an experiment in which concentration profiles were measured a short distance (< 40 m) downwind of an elevated point source of glass beads (40 μn diameter). $$\begin{gathered} \Lambda _L = 0.5z\left( {1 - 6\frac{z}{L}} \right)^{{1 \mathord{\left/ {\vphantom {1 4}} \right. \kern-\nulldelimiterspace} 4}} L< 0 \hfill \\ \Lambda _L = 0.5z/\left( {1 + 5\frac{z}{L}} \right)L > 0 \hfill \\ \end{gathered} $$      

Role of atmospheric ammonia in the formation of inorganic secondary particulate matter: A study at Kanpur,India

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.     

On the location and orientation of the South Pacific Convergence Zone

Three semi-permanent cloud bands exist in the Southern Hemisphere extending southeastward from the equator, through the tropics, and into the subtropics. The most prominent of these features occurs in the South Pacific and is referred to as the South Pacific Convergence Zone (SPCZ). Similar bands, with less intensity, exist in the South Indian and Atlantic oceans. We attempt to explain the physical mechanisms that promote the diagonal orientation of the SPCZ and the processes that determine the timescales of its variability. It is argued that the slowly varying sea surface temperature patterns produce upper tropospheric wind fields that vary substantially in longitude. Regions where 200?hPa zonal winds decrease with longitude (i.e., negative zonal stretching deformation, or $ {{\partial \overline{U} } \mathord{\left/ {\vphantom {{\partial \overline{U} } {\partial x}}} \right. \kern-0em} {\partial x}} < 0 $ ) reduce the group speed of the eastward propagating synoptic (3?C6?day period) Rossby waves and locally increase the wave energy density. Such a region of wave accumulation occurs in the vicinity of the SPCZ, thus providing a physical basis for the diagonal orientation and earlier observations that the zone acts as a ??graveyard?? of propagating synoptic disturbances. In essence, $ {{\partial \overline{U} } \mathord{\left/ {\vphantom {{\partial \overline{U} } {\partial x}}} \right. \kern-0em} {\partial x}} = 0 $ demarks the boundary of the graveyard while regions where $ {{\partial \overline{U} } \mathord{\left/ {\vphantom {{\partial \overline{U} } {\partial x}}} \right. \kern-0em} {\partial x}} < 0 $ denote the graveyard itself. Composites of the life cycles of synoptic waves confirm this hypothesis. From the graveyard hypothesis comes a more general theory accounting for the SPCZ??s spatial orientation and its longer term variability influenced by the El Ni?o-Southern Oscillation (ENSO), or alternatively, the changing background SST associated with different phases of ENSO.     

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

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 _.     

A verification of an analytical formula for estimating the height of the stable internal boundary layer

A stable thermal internal boundary layer (IBL) develops when warm air is advected from warmer land upstream to a cooler sea downstream. It is shown that the analytical model for estimating the height (h) of this stable IBL as formulated by Garratt (1987) is verified. It is also demonstrated that a simpler equation, % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4baFfea0dXde9vqpa0lb9% cq0dXdb9IqFHe9FjuP0-iq0dXdbba9pe0lb9hs0dXda91qaq-xfr-x% fj-hmeGabaqaciGacaGaaeqabaWaaeaaeaaakeaacaWGObGaeyisIS% RaaGymaiaaiAdacaWGybWaaWbaaSqabeaadaWcgaqaaiaaigdaaeaa% caaIYaaaaaaaaaa!390B!\[h \approx 16X^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} \] (where h is in meters and X, the fetch downwind, is in kilometers), is useful operationally as a first approximation.     

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

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.     

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

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:

On the profiles of wind velocity in the roughness sublayer above a coniferous forest

Wind velocity and temperature measurements from a 200 m tower, locatedin a forest near Karlsruhe were used to investigatethe modified profile function of the wind velocity in theroughness sublayer.To avoid determination of the friction velocity we introduced analternative analysis with the expression instead of From the observed Fm* profiles we evaluated the profile function m*. The wind profiles observed under neutral conditions were well representedby a modified non-dimensional profile function with physically based boundary values at the top and at the bottom of theroughness sublayer.The results of our analysis can be used to take into consideration themomentum exchange between the atmosphere and a forest in mesoscaleatmospheric models in a refined way.     

Minimum friction velocity and heat transfer in the rough surface layer of a convective boundary layer

A simple model is deduced for the surface layer of a convective boundary layer for zero mean wind velocity over homogeneous rough ground. The model assumes large-scale convective circulation driven by surface heat flux with a flow pattern as it would be obtained by conditional ensemble averages. The surface layer is defined here such that in this layer horizontal motions dominate relative to vertical components. The model is derived from momentum and heat balances for the surface layer together with closures based on the Monin-Obukhov theory. The motion in the surface layer is driven by horizontal gradients of hydrostatic pressure. The balances account for turbulent fluxes at the surface and fluxes by convective motions to the mixed layer. The latter are the dominant ones. The model contains effectively two empirical coefficients which are determined such that the model's predictions agree with previous experimental results for the horizontal turbulent velocity fluctuations and the temperature fluctuations. The model quantitatively predicts the decrease of the minimum friction velocity and the increase of the temperature difference between the mixed layer and the ground with increasing values of the boundary layer/roughness height ratio. The heat transfer relationship can be expressed in terms of the common Nusselt and Rayleigh numbers, Nu and Ra, as Nu ~ Ra^{% MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaaSGbaeaaca% aIXaaabaGaaGOmaaaaaaa!3779!\[{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}\]}. Previous results of the form Nu ~ Ra^{% MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaaSGbaeaaca% aIXaaabaGaaG4maaaaaaa!377A!\[{1 \mathord{\left/ {\vphantom {1 3}} \right. \kern-\nulldelimiterspace} 3}\]} are shown to be restricted to Rayleigh-numbers less than a certain value which depends on the boundary layer/roughness height ratio.     

Some aspects of modelling low-level jets

An improved non-stationary two-layer model is presented for the simulation of wind speed maxima in the nocturnal boundary layer. The model is based on the idea of Blackadar (1957), who proposed as forcing mechanism an inertial oscillation of the ageostrophic component of the wind vector in the levels above the top of the nocturnal radiation inversion. First, the time-dependent variation of the nocturnal boundary-layer height is studied by means of prognostic equations; there is a good agreement between observed and calculated height data for three days of the Wangara experiment. Furthermore, a diurnal variation of the drag coefficient is considered in the lower layer by decreasing the coefficient by a factor of 10–20 due to stabilization of this layer during the night. The marked temporal decrease (increase) of the drag coefficient in the first hours after sunset (sunrise) is described by a function . The incorporation of these two effects into the model gives results which are in good agreement with observed wind data for Wangara days 13/14, 30/31, and 33/34.     

The atmospheric tide as a continuous spectrum: Lunar semidiurnal tide in surface pressure

Summary The standard equations for the theory of atmospheric tides are solved here by an integral representation on the continuous spectrum of free oscillations. The model profile of back-ground temperature is that of the U.S. Standard Atmosphere in the lower and middle atmosphere, and in the lower thermosphere, above which an isothermal top extends to arbitrarily great heights. The top is warm enough to bring both the Lamb and the Pekeris modes into the continuous spectrum.Computations are made for semidiurnal lunar tidal pressure at sea level at the equator, and the contributions are partitioned according to vertical as well as horizontal structure. Almost all the response is taken up by the Lamb and Pekeris modes of the slowest westward-propagating gravity wave. At sea level, the Lamb-mode response is direct and is relatively insensitive to details of the temperature profile. The Pekeris mode at sea level has an indirect response-in competition with the Lamb mode-and, as has been known since the time of its discovery, it is quite sensitive to the temperature profile, in particular to stratopause temperature. In the standard atmosphere the Lamb mode contributes about +0.078 mb to tidal surface pressure at the equator and the Pekeris mode about –0.048 mb.The aim of this investigation is to illustrate some consequences of representing the tide in terms of the structures of free oscillations. To simplify that task as much as possible, all modifying influences were omitted, such as background wind and ocean or earth tide. Perhaps the main defect of this paper's implementation of the free-oscillation spectrum is that, in contrast to the conventional expansion in the structures of forced oscillations, it does not include dissipation, either implicity or explicity, and thus does not satisfy causality. Dissipation could be added implicity by means of an impedance condition, for example, which would cause up-going energy flux to exceed downgoing flux at the base of the isothermal top layer. To achieve complete causality, however, the dissipation must be modeled explicity. Nevertheless, since the Lamb and Pekeris modes are strongly trapped in the lower and middle atmosphere, where dissipation is rather weak (except possibly in the surface boundary layer), more realistic modeling is not likely to change the broad features of the present results.Symbols a earth's mean radius; expansion coefficient in (5.3) - b recursion variable in (7.4); proximity to resonance in (9.2) - c sound speed in (2.2); specific heatc _p in (2.2) - f Coriolis parameter 2sin in (2.2) - g standard surface gravity - h equivalent depth - i ; discretization index in (7.3) - j index for horizontal structure - k index for horizontal structure; upward unit vectork in (2.2) - m wave number in longitude - n spherical-harmonic degree; number of grid layers in a model layer - p tidal pressure perturbation; background pressurep ₀ - q heating function (energy per mass per time) - r tidal state vector in (2.1) - s tidal entropy perturbation; background entropys ₀ - t time - u tidal horizontal velocityu - w tidal vertical component of velocity - x excitation vector defined in (2.3); vertical coordinate lnp _*/p ₀ [except in (3.8), where it is lnp /p ₀] - y vertical-structure function in (7.1) - z geopotential height - A constant defined in (6.2) - C spherical-harmonic expansion coefficient in (3.6) - D vertical cross section defined in (5.6) and (5.9) - E eigenstate vector - F vertical-structure function for eigenstate pressure in (3.2) [re-defined with WKB scaling in (7.2)] - G vertical-structure function for eigenstate vertical velocity in (3.2) [re-defined with WKB scaling in (7.2)] - H pressure-scale height - I mode intensity defined in (8.1) - K quadratic form defined in (4.4) - L quadratic form defined in (4.4); horizontal-structure magnification factor defined in (5.11) - M vertical-structure magnification factor defined in (4.6) - P eigenstate pressure in (3.2); tidal pressure in (6.2) - R tidal state vector in (5.1) - S eigenstate entropy in (3.2); spherical surface area, in differential dS - T background molecular-scale (NOAA, 1976) absolute temperatureT ₀ - U eigenstate horizontal velocityU in (3.2); coefficient in (7.3) - V horizontal-structure functionV for eigenstate horizontal velocity in (3.2); recursion variable in (7.3) - W eigenstate vertical velocity in (3.2) - X excitation vector in (5.1) - Y surface spherical harmonic in (3.7) - Z Hough function defined in (3.6) - +dH/dz - (1––)/2 - Kronecker delta; Dirac delta; correction operator in (7.6) - equilibrium tide elevation - (square-root of Hough-function eigenvalue) - ratio of specific gas constant to specific heat for air=2/7 - longitude - - - background density ₀ - eigenstate frequency in (3.1) - proxy for heating functionq =c _P/t - latitude - tide frequency - operator for the limitz - horizontal-structure function for eigenstate pressure in (3.2) - Hough function defined in (6.2) - earth's rotation speed - horizontal gradient operator - ()₀ background variable - ()_* surface value of background variable - () value at base of isothermal top layer - Õ state vector with zerow-component - , energy product defined in (2.4) - | | energy norm - ()^* complex conjugate With 10 Figures     

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

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.

     

The gas-phase reaction of ClONO2 with hydrogen chloride

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.     

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

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.