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

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.     

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     

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.     

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).     

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.     

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.     

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.     

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 _.     

Asymmetric effects of soil moisture on mean daily maximum and minimum temperatures over eastern China

This study statistically investigates the effects of soil moisture on mean daily maximum ( $T_{\rm{max} }$ ) and minimum temperatures ( $T_{\rm{min} }$ ) over eastern China in spring (from March to May), summer (from June to August) and fall (from September to November), using the Global Land Data Assimilation System (GLDAS) soil moisture and observational temperatures. The results show that soil moisture exerts asymmetric effects on $T_{\rm{max} }$ and $T_{\rm{min} }$ , thereby has substantial effects on the diurnal temperature range (DTR) in the three seasons. The soil moisture feedbacks on $T_{\rm{max} }$ , $T_{\rm{min} }$ , and DTR are found to evidently vary with season. In spring and summer, soil moisture exerts stronger negative forcing on $T_{\rm{max} }$ than $T_{\rm{min} }$ , and thus has negative effects on the DTR over many areas of northern China. In fall, soil moisture has much stronger positive effects on $T_{\rm{min} }$ than $T_{\rm{max} }$ , and thus has significant negative effects on the DTR over Northeast China and some areas of the climatic and ecological transition zone of northern China. The uncertainties in the employed data and method should be noted. Therefore, the results need to be further investigated by other data sets and methods in the future.     

Experimental Investigation of Turbulent Momentum Transfer in a Neutral Boundary Layer over a Rough Surface

The turbulent characteristics of the neutral boundary layer developing over rough surfaces are not well predicted with operational weather-forecasting models. The problem is attributed to inadequate mixing-length models, to the anisotropy of the flow and to a lack of controlled experimental data against which to validate numerical studies. Therefore, in order to address directly the modelling difficulties for the development of a neutral boundary layer over rough surfaces, and to investigate the turbulent momentum transfer of such a layer, a set of hydraulic flume experiments were carried out. In the experiments, the mean and turbulent quantities were measured by a particle image velocimetry (PIV) technique. The measured velocity variances and fluxes \({(\overline{{u_{i}^{\prime}}{u_{j}^{\prime}}})}\) in longitudinal vertical planes allowed the vertical and longitudinal gradients (?/?z and ?/?x) of the mean and turbulent quantities (fluxes, variances and third-order moments) to be evaluated and the terms of the evolution equations for ?e/?t, \({\partial \overline{u^{\prime 2}}/\partial t}\), \({\partial \overline{w^{\prime 2}}/\partial t}\) and \({\partial \overline{{u^{\prime}}{w^{\prime}}}/\partial t}\) to be quantified, where e is the turbulent kinetic energy. The results show that the pressure-correlation terms allow the turbulent energy to be transferred equitably from \({\overline{{u^{\prime}}^{2}}}\) to \({\overline{{w^{\prime}}^{2}}}\). It appears that the repartition between the constitutive terms of the budget of e, \({\overline{{u^{\prime}}^{2}}}\), \({\overline{{w^{\prime}}^{2}}}\) and \({\overline{{u^{\prime}}{w^{\prime}}}}\) is not significantly affected by the development of the rough neutral boundary layer. For the whole evolution, the transfers of energy are governed by the same terms that are also very similar to the smooth-wall case. The PIV measurements also allowed the spatial integral scales to be computed directly and to be compared with the dissipative and mixing length scales, which were also computed from the data.     

Determination of the onset dates of the rainy season in central Amazon with equatorially antisymmetric outgoing longwave radiation

The present work provides a new methodology to determine onset dates of the rainy season (ONR) in central Amazon (CAM) using the antisymmetric in relation to the equator outgoing longwave radiation (OLR) (AOLR) data, for the 1979–2006 period. Spatial averages of the AOLR ( $\overline {AOLR} $ ) over the CAM for the ONR periods are obtained. These periods correspond to 25 pentads centered on the mean pentad for the ONR. The sign changes from positive to negative of the $\overline {AOLR} $ for the ONR periods indicate the transition from dry to wet season. Composites of several variables are done for pentads before and after the ONR dates. These composites show physically consistent features. The potential of the $\overline {AOLR} $ time series as an index for monitoring tasks is analyzed. The results here show that the $\overline {AOLR} $ for the ONR period captures the transition from dry to wet conditions in the CAM area during 2006. The advantages of this method are discussed. The new simple method proposed here seems to be efficient in determining the ONR in the CAM.     

Variability of the Structure Parameters of Temperature and Humidity Observed in the Atmospheric Surface Layer Under Unstable Conditions

The structure parameters of temperature and humidity are important in scintillometry as they determine the structure parameter of the refractive index of air, the primary atmospheric variable obtained with scintillometers. In this study, we investigate the variability of the logarithm of the Monin-Obukhov-scaled structure parameters (denoted as $\log ({\widetilde{C_{s}^2}_{\mathrm {}}})$ ) of temperature and humidity. We use observations from eddy-covariance systems operated at three heights (2.5, 50, and 90 m) within the atmospheric surface layer under unstable conditions. The variability of $\log ({\widetilde{C_{s}^2}_{\mathrm {}}})$ depends on instability and on the size of the averaging window over which $\log ({\widetilde{C_{s}^2}_{\mathrm {}}})$ is calculated. If instability increases, differences in $\log ({\widetilde{C_{s}^2}_{\mathrm {}}})$ between upward motions (large $C_{s}^2$ ) and downward motions (small $C_{s}^2$ ) increase. The differences are, however, not sufficiently large to result in a bimodal probability density function. If the averaging window size increases, the variances of $\log ({\widetilde{C_{s}^2}_{\mathrm {}}})$ decrease. A linear regression of the variances of $\log ({\widetilde{C_{s}^2}_{\mathrm {}}})$ versus the averaging window size for various stability classes shows an increase of both the offset and slope (in absolute sense) with increasing instability. For temperature, data from the three heights show comparable results. For humidity, in contrast, the offset and slope are larger at 50 and 90 m than at 2.5 m. In the end we discuss how these findings could be used to assess whether observed differences in $C_{s}^2$ along a scintillometer path or aircraft flight leg are just within the range of local variability in $C_{s}^2$ or could be attributed to surface heterogeneity. This is important for the interpretation of data measured above a heterogeneous surface.     

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.     

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.     

Impacts of Mixing Processes in Nocturnal Atmospheric Boundary Layer on Urban Ozone Concentrations

A number of open questions remain regarding the role of low-level jets (LLJs) and nocturnal mixing processes in the buildup of tropospheric ozone. The prevalence of southerly winds and LLJs in the U.S. Southern Great Plains during summer makes this region an ideal site for investigating the structure of the nocturnal boundary layer and its impacts on urban air quality. Ozone $(\mathrm{O}_{3})$ and nitrogen oxide concentrations measured at regulatory monitoring sites in the Oklahoma City (OKC) area and simulations with the Weather Research and Forecasting with Chemistry (WRF/Chem) model were analyzed to show how the nocturnal LLJ moderates boundary-layer mixing processes and air quality. Datasets collected during the Joint Urban 2003 campaign, which took place in July 2003 in OKC, provided detailed information about nocturnal boundary-layer structure and dynamics. In general, ${\mathrm{O}_{3}}$ time series show the expected behavior that urban ${\mathrm{O}_{3}}$ concentrations decrease at night due to nitrogen oxide titration reactions, but elevated ${\mathrm{O}_{3}}$ concentrations and secondary ${\mathrm{O}_{3}}$ peaks are also seen quite frequently after sunset. LLJs developed on most nights during the study period and were associated with strong vertical wind shear, which affected the boundary-layer stability and structure. Near-surface ${\mathrm{O}_{3}}$ concentrations are higher during less stable nights when active mixing persists throughout the night. The WRF/Chem model results agree well with the observations and further demonstrate the role of LLJs in moderating nocturnal mixing processes and air quality. The highest nocturnal ${\mathrm{O}_{3}}$ concentrations are linked to a strong LLJ that promotes both nocturnal long-range transport and persistent downward mixing of ${\mathrm{O}_{3}}$ from the residual layer to the surface.     

Subarea characteristics of the long-range correlations and the index χ for daily temperature records over China

Daily temperature records including daily minimum, maximum, and average temperature from 190 meteorological stations over China during 1951–2000 are analyzed from two perspectives: (a) long-term persistence in direction of time varies, and (b) standard deviation in direction of amplitude varies. By employing the detrended fluctuation analysis (DFA), we find all the temperature records are long-term correlated, while the exponent α obtained from DFA varies from different districts of China due to different climate conditions, such as the southwest monsoon, subtropical high, northeast cold vortex, and the Tibetan plateau, etc. After we take the standard deviation into account, a new index χ?=?α?×?σ, which has been proposed recently, can be obtained. By further rescaling it as $ \chi = \overline \chi - {{1} \left/ {5} \right.} \times {\sigma_{{\overline \chi }}} $ , we find an obvious change of χ for these three kinds of time series, from which the whole China can be divided into two groups, which are comparatively consistent with dry/wet distributions in the south–north areas over China.     

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.     

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.     

Turbulent Schmidt Numbers Above a Wheat Crop

Measurements of vertical fluxes and concentration differences above a spring wheat crop (height $h=0.9$ – $0.95$  m, row spacing 0.25 m, displacement height $d=0.5$ – $0.6$  m) were analyzed to determine the Schmidt numbers for water vapour ( $S^\mathrm{v}$ ) and carbon dioxide ( $S^\mathrm{c}$ ) based on concentration differences between intakes 2.55 and 3.54 m above the ground. During nearly-neutral stratification $S^\mathrm{v}(0) = 0.68 \pm 0.1$ while $S^\mathrm{c} = 0.78 \pm 0.2$ , implying that the roughness sublayer extended above $2.5 h$ .