A Comparison of Two Canopy Radiative Models in Land Surface Processes

This paper compares the predictions by two radiative transfer models-the two-stream approximation model and the generalized layered model （developed by the authors） in land surface processes -for different canopies under direct or diffuse radiation conditions. The comparison indicates that there are significant differences between the two models, especially in the near infrared （NIR） band. Results of canopy reflectance from the two-stream model are larger than those from the generalized model. However, results of canopy absorptance from the two-stream model are larger in some cases and smaller in others compared to those from the generalized model, depending on the cases involved. In the visible （VIS） band, canopy reflectance is smaller and canopy absorptance larger from the two-stream model compared to the generalized model when the Leaf Area Index （LAI） is low and soil reflectance is high. In cases of canopies with vertical leaf angles, the differences of reflectance and absorptance in the VIS and NIR bands between the two models are especially large. Two commonly occurring cases, with which the two-stream model cannot deal accurately, are also investigated. One is for a canopy with different adaxial and abaxial leaf optical properties; and the other is for incident sky diffuse radiation with a non-uniform distribution. Comparison of the generalized model within the same canopy for both uniform and non-uniform incident diffuse radiation inputs shows smaller differences in general. However, there is a measurable difference between these radiation inputs for a canopy with high leaf angle. This indicates that the application of the two-stream model to a canopy with different adaxial and abaxial leaf optical properties will introduce non-negligible errors.     

A Comparison of Two Canopy Radiative Models in Land Surface Processes

This paper compares the predictions by two radiative transfer models-the two-stream approximation model and the generalized layered model (developed by the authors) in land surface processes-for different canopies under direct or diffuse radiation conditions. The comparison indicates that there are significant differences between the two models, especially in the near infrared (NIR) band. Results of canopy reflectance from the two-stream model are larger than those from the generalized model. However, results of canopy absorptance from the two-stream model are larger in some cases and smaller in others compared to those from the generalized model, depending on the cases involved. In the visible (VIS) band, canopy reflectance is smaller and canopy absorptance larger from the two-stream model compared to the generalized model when the Leaf Area Index (LAI) is low and soil reflectance is high. In cases of canopies with vertical leaf angles, the differences of reflectance and absorptance in the VIS and NIR bands between the two models are especially large.Two commonly occurring cases, with which the two-stream model cannot deal accurately, are also investigated. One is for a canopy with different adaxial and abaxial leaf optical properties; and the other is for incident sky diffuse radiation with a non-uniform distribution. Comparison of the generalized model within the same canopy for both uniform and non-uniform incident diffuse radiation inputs shows smaller differences in general. However, there is a measurable difference between these radiation inputs for a canopy with high leaf angle. This indicates that the application of the two-stream model to a canopy with different adaxial and abaxial leaf optical properties will introduce non-negligible errors.     

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     

Scaling fluctuation analysis and statistical hypothesis testing of anthropogenic warming

Although current global warming may have a large anthropogenic component, its quantification relies primarily on complex General Circulation Models (GCM’s) assumptions and codes; it is desirable to complement this with empirically based methodologies. Previous attempts to use the recent climate record have concentrated on “fingerprinting” or otherwise comparing the record with GCM outputs. By using CO₂ radiative forcings as a linear surrogate for all anthropogenic effects we estimate the total anthropogenic warming and (effective) climate sensitivity finding: ΔT _anth  = 0.87 ± 0.11 K, $\uplambda_{{2{\text{x}}{\text{CO}}_{2} ,{\text{eff}}}} = 3.08 \pm 0.58\,{\text{K}}$ . These are close the IPPC AR5 values ΔT _anth  = 0.85 ± 0.20 K and $\uplambda_{{2{\text{x}}{\text{CO}}_{2} }} = 1.5\!-\!4.5\,{\text{K}}$ (equilibrium) climate sensitivity and are independent of GCM models, radiative transfer calculations and emission histories. We statistically formulate the hypothesis of warming through natural variability by using centennial scale probabilities of natural fluctuations estimated using scaling, fluctuation analysis on multiproxy data. We take into account two nonclassical statistical features—long range statistical dependencies and “fat tailed” probability distributions (both of which greatly amplify the probability of extremes). Even in the most unfavourable cases, we may reject the natural variability hypothesis at confidence levels >99 %.     

Four-stream Radiative Transfer Parameterization Scheme in a Land Surface Process Model

Accurate estimates of albedos are required in climate modeling. Accurate and simple schemes for radiative transfer within canopy are required for these estimates, but severe limitations exist. This paper developed a four-stream solar radiative transfer model and coupled it with a land surface process model. The radiative model uses a four-stream approximation method as in the atmosphere to obtain analytic solutions of the basic equation of canopy radiative transfer. As an analytical model, the four-stream radiative transfer model can be easily applied efficiently to improve the parameterization of land surface radiation in climate models. Our four-stream solar radiative transfer model is based on a two-stream short wave radiative transfer model. It can simulate short wave solar radiative transfer within canopy according to the relevant theory in the atmosphere. Each parameter of the basic radiative transfer equation of canopy has special geometry and optical characters of leaves or canopy. The upward or downward radiative fluxes are related to the diffuse phase function, the G-function, leaf reflectivity and transmission, leaf area index, and the solar angle of the incident beam. The four-stream simulation is compared with that of the two-stream model. The four-stream model is proved successful through its consistent modeling of canopy albedo at any solar incident angle. In order to compare and find differences between the results predicted by the four- and two-stream models, a number of numerical experiments are performed through examining the effects of different leaf area indices, leaf angle distributions, optical properties of leaves, and ground surface conditions on the canopy albedo. Parallel experiments show that the canopy albedos predicted by the two models differ significantly when the leaf angle distribution is spherical and vertical. The results also show that the difference is particularly great for different incident solar beams. One additional experiment is carried out to evaluate the simulations of the BATS land surface model coupled with the two- and four-stream radiative transfer models. Station observations in 1998 are used for comparison. The results indicate that the simulation of BATS coupled with the four-stream model is the best because the surface absorbed solar radiation from the four-stream model is the closest to the observation.     

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.     

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.     

Vertical Distribution of Radiation and Energy Balance Partitioning Within and Above a Lodgepole Pine Stand Recovering from a Recent Insect Attack

The current outbreak of mountain pine beetle (MPB) that started in the late 1990s in British Columbia, Canada, is the largest ever recorded in the north American native habitat of the beetle. The killing of trees is expected to change the vertical distribution of net radiation ( $Q^*$ Q ? ) and the partitioning of latent ( $Q_\mathrm{E}$ Q E ) and sensible ( $Q_\mathrm{H}$ Q H ) heat fluxes in the different layers of an attacked forest canopy. During an intensive observation period in the summer of 2010, eddy-covariance flux and radiation measurements were made at seven heights from ground level up to 1.34 times the canopy height in an MPB-attacked open-canopy forest stand $(\hbox {leaf area index} = 0.55~\mathrm{{m}}^{2}\ \mathrm{{m}}^{-2})$ ( leaf area index = 0.55 m 2 m - 2 ) in the interior of British Columbia, Canada. The lodgepole pine dominated stand with a rich secondary structure (trees and understorey not killed by the beetle) was first attacked by the MPB in 2003 and received no management. In this study, the vertical distribution of the energy balance components and their sources and sinks were analyzed and energy balance closure (EBC) was determined for various levels within the canopy. The low stand density resulted in approximately 60 % of the shortwave irradiance and 50 % of the daily total $Q^*$ Q ? reaching the ground. Flux divergence calculations indicated relatively strong sources of latent heat at the ground and where the secondary structure was located. Only very weak sources of latent heat were found in the upper part of the canopy, which was mainly occupied by dead lodgepole pine trees. $Q_\mathrm{H}$ Q H was the dominant term throughout the canopy, and the Bowen ratio ( $Q_\mathrm{H}/Q_\mathrm{E}$ Q H / Q E ) increased with height in the canopy. Soil heat flux ( $Q_\mathrm{G}$ Q G ) accounted for approximately 4 % of $Q^*$ Q ? . Sensible heat storage in the air ( $\Delta Q_\mathrm{S,H}$ Δ Q S , H ) was the largest of the energy balance storage components in the upper canopy during daytime, while in the lower canopy sensible heat storage in the boles ( $\Delta Q_\mathrm{S,B}$ Δ Q S , B ) and biochemical energy storage ( $\Delta Q_\mathrm{S,C}$ Δ Q S , C ) were the largest terms. $\Delta Q_\mathrm{S,H}$ Δ Q S , H was almost constant from the bottom to above the canopy. $\Delta Q_\mathrm{S,C}$ Δ Q S , C , $\Delta Q_\mathrm{S,B}$ Δ Q S , B and latent heat storage in the air ( $\Delta Q_\mathrm{S,E}$ Δ Q S , E ) varied more than $\Delta Q_\mathrm{S,H}$ Δ Q S , H throughout the canopy. During daytime, energy balance closure was high in and above the upper canopy, and in the lowest canopy level. However, where the secondary structure was most abundant, ${\textit{EBC}} \le 66\,\%$ EBC ≤ 66 % . During nighttime, the storage terms together with $Q_\mathrm{G}$ Q G made up the largest part of the energy balance, while $Q_\mathrm{H}$ Q H and $Q_\mathrm{E}$ Q E were relatively small. These radiation and energy balance measurements in an insect-attacked forest highlight the role of secondary structure in the recovery of attacked stands.     

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.     

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 _.     

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:

E − ε − 〈θ 2〉 turbulence closure model for an atmospheric boundary layer including the urban canopy

A modified three-parameter model of turbulence for a thermally stratified atmospheric boundary layer (ABL) is presented. The model is based on tensor-invariant parameterizations for the pressure–strain and pressure–temperature correlations that are more complete than the parameterizations used in the Mellor–Yamada model of level 3.0. The turbulent momentum and heat fluxes are calculated with explicit algebraic models obtained with the aid of symbol algebra from the transport equations for momentum and heat fluxes in the approximation of weakly equilibrium turbulence. The turbulent transport of heat and momentum fluxes is assumed to be negligibly small in this approximation. The three-parameter $E - \varepsilon - {\left\langle {\theta ^{2} } \right\rangle }$ model of thermally stratified turbulence is employed to obtain closed-form algebraic expressions for the fluxes. A computational test of a 24-h ABL evolution is implemented for an idealized two-dimensional region. Comparison of the computed results with the available observational data and other numerical models shows that the proposed model is able to reproduce both the most important structural features of the turbulence in an urban canopy layer near the urbanized ABL surface and the effect of urban roughness on a global structure of the fields of wind and temperature over a city. The results of the computational test for the new model indicate that the motion of air in the urban canopy layer is strongly influenced by mechanical factors (buildings) and thermal stratification.     

A generalized layered radiative transfer model in the vegetation canopy

In this paper, a generalized layered model for radiation transfer in canopy with high vertical resolution is developed. Differing from the two-stream approximate radiation transfer model commonly used in the land surface models, the generalized model takes into account the effect of complicated canopy morphology and inhomogeneous optical properties of leaves on radiation transfer within the canopy. In the model, the total leaf area index （LAI） of the canopy is divided into many layers. At a given layer, the influences of diffuse radiation angle distributions and leaf angle distributions on radiation transfer within the canopy are considered. The derivation of equations serving the model are described in detail, and these can deal with various diffuse radiation transfers in quite broad categories of canopy with quite inhomogeneons vertical structures and uneven leaves with substantially different optical properties of adaxial and abaxial faces of the leaves. The model is used to simulate the radiation transfer for canopies with horizontal leaves to validate the generalized model. Results from the model are compared with those from the two-stream scheme, and differences between these two models are discussed.     

Assessing the distribution of solar irradiation in Mbarara, Uganda

Summary Existing literature lacks information on formulation and performance assessment of diffuse solar radiation models in the Eastern African region yet this region has a high potential for the utilization of solar energy. The objective of this paper is to assess the performance of seventeen diffuse solar irradiation empirical correlations, at Kampala, Uganda. The best performing correlations were determined using the ranking method. The normalized absolute mean bias error and root mean square error were computed and utilized in the ranking process. The results indicated that the correlations relating diffuse transmittance with relative sunshine duration are more reliable for diffuse solar radiation predictions at least in the Uganda environment. These models are expressed in terms of first, second and third order polynomials of the relative sunshine duration and are particularly recommended for their simplicity and worldwide applicability.     

An Approach to Minimizing Artifacts Caused by Cross-Sensitivity in the Determination of Air–Sea \text{ CO }_{2} Flux Using the Eddy-Covariance Technique

The air–sea $\text{ CO }_{2}$ flux was measured from a research vessel in the North Yellow Sea in October 2007 using an open-path eddy-covariance technique. In 11 out of 64 samples, the normalized spectra of scalars ( $\text{ CO }_{2}$ , water vapour, and temperature) showed similarities. However, in the remaining samples, the normalized $\text{ CO }_{2}$ spectra were observed to be greater than those of water vapour and temperature at low frequencies. In this paper, the noise due to cross-sensitivity was identified through a combination of intercomparisons among the normalized spectra of three scalars and additional analyses. Upon examination, the cross-sensitivity noise appeared to be mainly present at frequencies ${<}0.8\,\text{ Hz }$ . Our analysis also suggested that the high-frequency fluctuations of $\text{ CO }_{2}$ concentration (frequency ${>}0.8\,\text{ Hz }$ ) was probably less affected by the cross-sensitivity. To circumvent the cross-sensitivity issue, the cospectrum in the high-frequency range 0.8–1.5 Hz, instead of the whole range, was used to estimate the $\text{ CO }_{2}$ flux by taking the contribution of the high frequency to the $\text{ CO }_{2}$ flux to be the same as the contribution to the water vapour flux. The estimated air–sea $\text{ CO }_{2}$ flux in the North Yellow Sea was $-0.039\,\pm \,0.048\,\text{ mg } \text{ m }^{-2}\,\text{ s }^{-1},$ a value comparable to the estimates using the inertial dissipation method and Edson’s method (Edson et al., J Geophys Res 116:C00F10, 2011).     

一个简单的陆面过程模式

本模式为针对大气环流模式所发展的一个简单的陆面过程模式，它包含:（1）地表温度计算，（2）冠层叶面贮水量和土壤湿度计算，（3）陆面与大气之间的水分和能量交换。对于表面温度和含水量的计算，采用的是联立求解计算方案，即耦合计算。植被冠层叶面的辐射特性和冠层形态对冠层中的辐射交换的影响得到有效和尽可能简单的模拟。另外，植被的气孔阻抗、表面与大气之间的水热交换通量和土壤中的水热输导作了较为细致的描写。利用此模式开展了对两个不同覆盖类型的陆面过程的模拟，模拟和观测的表面通量、温度和湿度较为相近。     

Global radiation within corn

Global and net solar radiation profiles were measured by traversing sensors at four heights in a square-sown plot and a row plot of field corn on four relatively cloudless days in August 1972. The fluxes and their vertical distributions are discussed. A numerical model of the short-wave radiation fluxes in a canopy is presented. Using leaf area index and fixed leaf radiative properties, calculated values of radiation are within 10% of measurements in most instances. The performance under predominantly beam or diffuse radiation is similar and model values of crop albedo compare well with values calculated from radiation measurements above the crops.     

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.     

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.

     

Dense canopy albedo as a function of illumination direction: Dependence on structure and leaf transmittance

Summary The dependence of the albedo on illumination direction is analyzed by constructing a canopy model in which the individual leaves are planar, Lambertian reflectors. Leaf transmission is treated separately, and is assumed to be proportional to the cosine of the zenith angle of the leaf normal. Effects of shading and obscuration are formulated assuming random distribution of the leaves with respect to the viewing and illumination directions. Variants of the model with different azimuthal leaf distributions are created and discussed as explicit expressions of the viewing/illumination geometry and the canopy characteristics.The canopy spectral single-scattering albedo factors, which are the conditional probabilities of a photon escaping from the canopy after a first reflection or a first transmission, are obtained by numerical integration over a hemisphere of the bidirectional reflectance and transmittance factors. Our analysis identifies the ratio of the projection of leaf area on the vertical plane perpendicular to the principal plane to that on a horizontal plane as the parameter that controls the dependence of the albedo on the solar zenith angle. The albedo factor due to the leaf transmittance generally increases with the zenith angle of illuminating beam more sharply than that due to the leaf reflectance.Model variants with various azimuthal distributions are compared with measured albedo of soybeans. Second and higher order scatterings are accounted for in a simplified way. The degree to which a model variant fits the measured albedo and its change with the solar zenith angle depends both on the leaf inclination angleand the azimuthal distribution of the leaf area.With 6 Figures