Aerosol-Cloud-Precipitation Interactions in a Closed-cell and Non-homogenous MBL Stratocumulus Cloud

A closed-cell marine stratocumulus case during the Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA) aircraft field campaign is selected to examine the heterogeneities of cloud and drizzle microphysical properties and the aerosol-cloud-precipitation interactions. The spatial and vertical variabilities of cloud and drizzle microphysics are found in two different sets of flight legs: Leg-1 and Leg-2, which are parallel and perpendicular to the cloud propagation, respectively. The cloud along Leg-2 was close to adiabatic, where cloud-droplet effective radius and liquid water content linearly increase from cloud base to cloud top with less drizzle. The cloud along Leg-1 was sub-adiabatic with lower cloud-droplet number concentration and larger cloud-droplet effective, but higher drizzle droplet number concentration, larger drizzle droplet median diameter and drizzle liquid water content. The heavier drizzle frequency and intensity on Leg-1 were enhanced by the collision-coalescence processes within cloud due to strong turbulence. The sub-cloud precipitation rate on Leg-1 was significantly higher than that along Leg-2. As a result, the sub-cloud accumulation mode aerosols and CCN on Leg-1 were depleted, but the coarse model aerosols increased. This further leads to a counter-intuitive phenomenon that the CCN is less than cloud-droplet number concentration for Leg-1. The average CCN loss rates are ?3.89 \begin{document}$\mathrm{c}{\mathrm{m}}^{-3}\;{\mathrm{h}}^{-1}$\end{document} and ?0.77 \begin{document}$\mathrm{c}{\mathrm{m}}^{-3}\;{\mathrm{h}}^{-1}$\end{document} on Leg-1 and Leg-2, respectively. The cloud and drizzle heterogeneities inside the same stratocumulus can significantly alter the sub-cloud aerosols and CCN budget. Hence it should be treated with caution in the aircraft assessment of aerosol-cloud-precipitation interactions.     

Comparative Analysis of the Generalized Omega Equation and Generalized Vertical Motion Equation

Research on vertical motion in mesoscale systems is an extraordinarily challenging effort. Allowing for fewer assumptions, a new form of generalized vertical motion equation and a generalized Omega equation are derived in the Cartesian coordinate system(nonhydrostatic equilibrium) and the isobaric coordinate system(hydrostatic equilibrium),respectively. The terms on the right-hand side of the equations, which comprise the Q vector, are composed of three factors:dynamic, thermodynamic, and mass. ...     

Atmospheric Disturbance Characteristics in the Lower-middle Stratosphere Inferred from Observations by the Round-Trip Intelligent Sounding System (RTISS) in China

Through multi-order structure function analysis and singularity measurement,the Hurst index and intermittent parameter are obtained to quantitatively describe the characteristics of atmospheric disturbance based on the round-trip intelligent sounding system(RTISS)in the lower-middle stratosphere.According to the third-order structure function,small-scale gravity waves are classified into three states:stable,unstable,and accompanied by turbulence.The evolution of gravity waves is reflected by the variation of the third-order structure function over time,and the generation of turbulence is also observed.The atmospheric disturbance intensity parameter RT is defined in this paper and contains both wave disturbance(H₁)and random intermittency(C₁).RT is considered to reflect the characteristics of atmospheric disturbance more reasonably than either of the above two alone.In addition,by obtaining the horizontal wavenumber spectrum from the flat-floating stage and the vertical wavenumber spectrum from the ascending and descending stages at the height range of18-24 km,we found that when the gravity wave activity is significantly enhanced in the horizontal direction,the amplitude of the vertical wavenumber spectrum below is significantly larger,which shows a significant impact of gravity wave activity on the atmospheric environment below.     

Water-Channel Estimation of Eulerian and Lagrangian Time Scales of the Turbulence in Idealized Two-Dimensional Urban Canopies

Lagrangian and Eulerian statistics are obtained from a water-channel experiment of an idealized two-dimensional urban canopy flow in neutral conditions. The objective is to quantify the Eulerian \((T^{\mathrm{E}})\) and Lagrangian \((T^{\mathrm{L}})\) time scales of the turbulence above the canopy layer as well as to investigate their dependence on the aspect ratio of the canopy, AR, as the latter is the ratio of the width (W) to the height (H) of the canyon. Experiments are also conducted for the case of flat terrain, which can be thought of as equivalent to a classical one-directional shear flow. The values found for the Eulerian time scales on flat terrain are in agreement with previous numerical results found in the literature. It is found that both the streamwise and vertical components of the Lagrangian time scale, \(T_\mathrm{u}^\mathrm{L} \) and \(T_\mathrm{w}^\mathrm{L} \), follow Raupach’s linear law within the constant-flux layer. The same holds true for \(T_\mathrm{w}^\mathrm{L} \) in both the canopies analyzed \((AR= 1\) and \(AR= 2\)) and also for \(T_\mathrm{u}^\mathrm{L} \) when \(AR = 1\). In contrast, for \(AR = 2\), \(T_\mathrm{u}^\mathrm{L} \) follows Raupach’s law only above \(z=2H\). Below that level, \(T_\mathrm{u}^\mathrm{L} \) is nearly constant with height, showing at \(z=H\) a value approximately one order of magnitude greater than that found for \(AR = 1\). It is shown that the assumption usually adopted for flat terrain, that \(\beta =T^{\mathrm{L}}/T^{\mathrm{E}}\) is proportional to the inverse of the turbulence intensity, also holds true even for the canopy flow in the constant-flux layer. In particular, \(\gamma /i_\mathrm{u} \) fits well \(\beta _\mathrm{u} =T_\mathrm{u}^\mathrm{L} /T_\mathrm{u}^\mathrm{E} \) in both the configurations by choosing \(\gamma \) to be 0.35 (here, \(i_\mathrm{u} =\sigma _\mathrm{u} / \bar{u} \), where \(\bar{u} \) and \(\sigma _\mathrm{u} \) are the mean and the root-mean-square of the streamwise velocity component, respectively). On the other hand, \(\beta _\mathrm{w} =T_\mathrm{w}^\mathrm{L} /T_\mathrm{w}^\mathrm{E} \) follows approximately \(\gamma /i_\mathrm{w} =0.65/\left( {\sigma _\mathrm{w} /\bar{u} } \right) \) for \(z > 2H\), irrespective of the AR value. The second main objective is to estimate other parameters of interest in dispersion studies, such as the eddy diffusivity of momentum \((K_\mathrm{{T}})\) and the Kolmogorov constant \((C_0)\). It is found that \(C_0\) depends appreciably on the velocity component both for the flat terrain and canopy flow, even though for the latter case it is insensitive to AR values. In all the three experimental configurations analyzed here, \(K_\mathrm{{T}}\) shows an overall linear growth with height in agreement with the linear trend predicted by Prandtl’s theory.     

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.     

Air–Sea \mathrm{CO}_{2} Gas Transfer Velocity in a Shallow Estuary

The air–sea transfer velocity of $\mathrm{CO}_{2}\, (k_{\mathrm{CO}_{2}})$ was investigated in a shallow estuary in March to July 2012, using eddy-covariance measurements of $\mathrm{CO}_{2}$ fluxes and measured air–sea $\mathrm{CO}_{2}$ partial-pressure differences. A data evaluation method that eliminates data by nine rejection criteria in order to heighten parametrization certainty is proposed. We tested the data evaluation method by comparing two datasets: one derived using quality criteria related solely to the eddy-covariance method, and the other derived using quality criteria based on both eddy-covariance and cospectral peak methods. The best parametrization of transfer velocity normalized to a Schmidt number of 600 $(k_{600})$ was determined to be: $k_{600} = 0.3\,{U_{10}}^{2.5}$ where $U_{10}$ is the wind speed in m $\mathrm{s}^{-1}$ at 10 m; $k_{600}$ is based on $\mathrm{CO}_{2}$ fluxes calculated by the eddy-covariance method and including the cospectral peak method criteria. At low wind speeds, the transfer velocity in the shallow water estuary was lower than in other coastal waters, possibly a symptom of low tidal amplitude leading to low intensity water turbulence. High transfer velocities were recorded above wind speeds of 5 m $\mathrm{s}^{-1}$ , believed to be caused by early-breaking waves and the large fetch (6.5 km) of the estuary. These findings indicate that turbulence in both air and water influences the transfer velocity.     

CAS FGOALS-f3-H Dataset for the High-Resolution Model Intercomparison Project (HighResMIP) Tier 2

Following the High-Resolution Model Intercomparison Project(HighResMIP) Tier 2 protocol under the Coupled Model Intercomparison Project Phase 6(CMIP6), three numerical experiments are conducted with the Chinese Academy of Sciences Flexible Global Ocean-Atmosphere-Land System Model, version f3-H(CAS FGOALS-f3-H), and a 101-year(1950–2050) global high-resolution simulation dataset is presented in this study. The basic configuration of the FGOALSf3-H model and numerical experiments design are brief...     

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.     

Some Statistics of the Temperature Structure Parameter in the Convective Boundary Layer Observed by Sodar

The characteristics of the temporal and height variations of the temperature structure parameter $C_\mathrm{T}^{2}$ in strongly convective situations derived from the sodar echo-signal intensity measurements were analyzed for the first 100 m. It was corroborated that the probability density function (pdf) of the logarithm of $C_\mathrm{T}^{2}$ in the lower convective boundary layer is markedly non-Gaussian, whereas turbulence theory predicts it to be normal. It was also corroborated that the sum of two weighted Gaussians, which characterize the statistics of $C_\mathrm{T}^{2}$ within convective plumes and in their environment and the probability of plume occurrence, well approximates the observed pdfs. It was shown that the height behaviour of the arithmetic mean of $ C_\mathrm{T}^{2}$ (both total and within plumes) follows well a power law $C_\mathrm{T}^{2} (z) \sim z^{-q}$ with the exponent $q$ close to the theoretically predicted value of 4/3. But for the geometrical means of $C_\mathrm{T}^{2}$ (both total and within the plumes), $q$ is close to 1. The difference between arithmetically and geometrically averaged $C_\mathrm{T}^{2}$ profiles was analyzed. The vertical profiles of the standard deviation, skewness and kurtosis of $\hbox {ln}C_\mathrm{T}^{2}$ pdfs were analyzed to show their steady behaviour with height. The standard deviations of the logarithm of $C_\mathrm{T}^{2}$ within the plumes and between them are similar and are 1.5 times less than the total standard deviation. The estimate of the variability index $F_\mathrm{T}$ and its height behaviour were obtained, which can be useful to validate some theoretical and modelling predictions. The vertical profiles of the skewness and kurtosis show the negative asymmetry of pdfs and their flatness, respectively. The spectra of variations in $\hbox {ln}C_\mathrm{T}^{2}$ are shown to be satisfactorily fitted by the power law $f^{-\gamma } $ in the frequency range 0.02 and 0.2 Hz, with the average exponent $\approx $ 1.27  $\pm $  0.22.     

Chemical composition of wet deposition in a Mediterranean site Athens,Greece related to the origin of air masses

The goal of this study is to determine the chemical composition of rain, in the wider region of Athens, Greece for the time period 1st September 2001 to 31st August 2002. Two model automatic rain samplers were installed in the Meteorological Station of Laboratory of Climatology (latitude: 37° 58′ N, longitude: 23° 47′ E) inside the Athens University Campus and in a site at Heraklio Attica, a northern suburb of Athens (latitude: 38° 03′ N, longitude: 23° 45′ E). The concentrations (μeq l⁻¹) of the major cations (H⁺, Na⁺, K⁺, Ca²⁺ and Mg²⁺) and anions (Cl⁻, , και ), as well as pH and conductivity of rain in 39 total samples were determined. The figures of pH range from 6.4 to 8.4 and conductivity from 8 to 207 μS cm⁻¹. The analysis showed that Ca²⁺ ions are abundant within all examined samples, while and present the highest concentrations from the anions. In order to find out the origin of the air masses, the air mass back trajectories were calculated. Five sectors of the origin of air masses were revealed: the North, the South, the Local, the West and the East sector. Multivariate methods included Factor Analysis and Discriminant Analysis were applied to the examined ion concentrations and three main factors were extracted, which discriminated the ions according to their origin. The first group of ions is interpreted as the result of the anthropogenic activity, the second group represents the acidity–alkalinity independently of their source and the third one the marine influence.     

Cross-Validation of Open-Path and Closed-Path Eddy-Covariance Techniques for Observing Methane Fluxes

Methane ( ${\mathrm {CH}}_{4}$ ) fluxes observed with the eddy-covariance technique using an open-path ${\mathrm {CH}}_{4}$ analyzer and a closed-path ${\mathrm {CH}}_{4}$ analyzer in a rice paddy field were evaluated with an emphasis on the flux correction methodology. A comparison of the fluxes obtained by the analyzers revealed that both the open-path and closed-path techniques were reliable, provided that appropriate corrections were applied. For the open-path approach, the influence of fluctuations in air density and the line shape variation in laser absorption spectroscopy (hereafter, spectroscopic effect) was significant, and the relative importance of these corrections would increase when observing small ${\mathrm {CH}}_{4}$ fluxes. A new procedure proposed by Li-Cor Inc. enabled us to accurately adjust for these effects. The high-frequency loss of the open-path ${\mathrm {CH}}_{4}$ analyzer was relatively large (11 % of the uncorrected covariance) at an observation height of 2.5 m above the canopy owing to its longer physical path length, and this correction should be carefully applied before correcting for the influence of fluctuations in air density and the spectroscopic effect. Uncorrected ${\mathrm {CH}}_{4}$ fluxes observed with the closed-path analyzer were substantially underestimated (37 %) due to high-frequency loss because an undersized pump was used in the observation. Both the bandpass and transfer function approaches successfully corrected this flux loss. Careful determination of the bandpass frequency range or the transfer function and the cospectral model is required for the accurate calculation of ${\mathrm {CH}}_{4}$ fluxes with the closed-path technique.     

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.     

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.     

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 _.     

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.     

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.     

Understanding Diurnality and Inter-Seasonality of a Sub-tropical Urban Heat Island

We quantify the spatial and temporal aspects of the urban heat-island (UHI) effect for Kanpur, a major city in the humid sub-tropical monsoon climate of the Gangetic basin. Fixed station measurements are used to investigate the diurnality and inter-seasonality in the urban–rural differences in surface temperature (\({\Delta } T_\mathrm{s}\)) and air temperature (\({\Delta } T_\mathrm{c}\)) separately. The extent of the spatial variations of the nighttime \({\Delta } T_\mathrm{c}\) and \({\Delta } T_\mathrm{s}\) is investigated through mobile campaigns and satellite remote sensing respectively. Nighttime \({\Delta } T_\mathrm{c}\) values dominate during both the pre-monsoon (maximum of 3.6 \(^\circ \hbox {C}\)) and the monsoon (maximum of 2.0 \(^\circ \hbox {C}\)). However, the diurnality in \({\Delta } T_\mathrm{s}\) is different, with higher daytime values during the pre-monsoon, but very little diurnality during the monsoon. The nighttime \({\Delta } T_\mathrm{s}\) value is mainly associated with differences in the urban–rural incoming longwave radiative flux (\(r^{2}=0.33\) during the pre-monsoon; 0.65 during the monsoon), which, in turn, causes a difference in the outgoing longwave radiative flux. This difference may modulate the nighttime \({\Delta } T_\mathrm{c}\) value as suggested by significant correlations (\(r^{2}=0.68\) for the pre-monsoon; 0.50 for the monsoon). The magnitude of \({\Delta } T_\mathrm{c}\) may also be modulated by advection, as it is inversely related with the urban wind speed. A combination of in situ, remotely sensed, and model simulation data were used to show that the inter-seasonality in \({\Delta } T_\mathrm{s}\), and, to a lesser extent, in \({\Delta } T_\mathrm{c}\), may be related to the change in the land use of the rural site between the pre-monsoon and the monsoon periods. Results suggest that the degree of coupling of \({\Delta } T_\mathrm{s}\) and \({\Delta } T_\mathrm{c}\) may be a strong function of land use and land cover.     

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.     

An Investigation on Temperature Variance Scaling in the Atmospheric Surface Layer

We present surface-layer measurements of temperature fluctuation variance from a site characterized by small-scale inhomogeneities. Periods of marked radiative forcing are selected. The data characterized by diabatic conditions and vertical heat flux larger than some threshold (here, chosen to be 0.01 K ms⁻¹) agree quite well with the convective scaling in unstable cases, and with the z-less parameterisation (with a large scatter) in stable cases. For near-neutral cases, the similarity function diverges because of the loss of significance of the temperature scale. Departures from similarity are highlighted in cases with smaller thermal fluxes, because horizontal heterogeneity and unsteadiness become important as production terms.     

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.