Automated mechanism generation. Part 1: mechanism development and rate constant estimation for VOC chemistry in the atmosphere

A framework for automated mechanism generation for modeling atmospheric chemistry at the mechanistic level was developed. In part 1, categorization of reactions into reaction families and determination of rate coefficients using a hierarchical approach that uses experimental data and kinetic correlations are described. The main focus was to develop kinetic correlations for estimating rate coefficients that are not available experimentally, and the main correlation used was the Evans–Polanyi relationship that relates the activation energy to the heat of reaction. A hierarchical scheme for calculating heats of reaction and other thermodynamic properties was developed. The rate constants calculated using the proposed correlations are in most cases within an order of magnitude of available experimental values, and 82% are within a factor of five.     

Spatial prediction model and its application to chemistry of atmospheric precipitation in Jordan

This study is concerned with the spatial variability of some wet atmospheric precipitation parameters such as; pH, conductivity (EC). The study also depicts the spatial variability of some ions (cations and anions) of atmospheric precipitation in Jordan such as, Ca²⁺, Mg²⁺, Na⁺ and K⁺, HCO₃⁻, Cl⁻, NO₃⁻ and SO₄²⁻. The basis of the work is to establish a relationship through the cumulative semivariogram technique between the distance ratios and the spatial dependence structure of the chemical composition of atmospheric precipitation. All semivariogram models are constructed in this study in order to understand the behavior of the spatial distribution. The spatial distributions of rainwater parameters show differences from station to station which is expressed in terms of angle, where the larger the angle the weaker the correlation. The semivariogram (SV) models are constructed to show the variation of the rainfall chemistry in Jordan. The SV models show weak correlation between mountain and leeside mountain stations, i.e. mountain and desert stations. On the other hand, good correlations are observed when transferring from south to north of the country. The larger is the found angle, the weaker is the correlation. For most of the SV model the correlation is found to be very weak between desert and mountainous locality. The Standard Regional Dependence Factor (SRDF) is used for prediction of the distribution of rain fall parameters. It shows the relative error between observed and predicted values of rainwater parameters. The overall regional relative error between the observed and estimated concentrations remains less than 15%.     

Application of Linear Thermodynamics to the Atmospheric System. Part Ⅰ: Linear Phenomenological Relations and Thermodynamic Property of the Atmospheric System

从一般的热力学原理或其它自然原理对唯象关系所强加的限制，能够演绎出大气系统的一系列热力学性质。利用非平衡态线性热力学导出了湍流K闭合理论中湍流交换系数同唯象系数的关系，从理论上证明大气系统热量湍流输送同水泡之间存在交叉耦合，还导出了湍流强度同速度和位温梯度的关系，从而证明速度和位温空间分布的非均匀性是湍流之源。并证明湍流强度定理，不可压缩气体和各向同性湍流大气中，湍流强度正比于速度与位温梯度的标积。进而证明大气涡旋定理，位温的切变将导致涡旋运动或各种环流运动，速度涡度等于速度同位温相对梯度的矢积。展现了线性热力学在大气系统的应用前景。     

Application of Linear Thermodynamics to the Atmospheric System.Part Ⅱ: Exemplification of Linear Phenomenological Relations in the Atmospheric System

将边界层相似性理论同线性热力学理论结合，间接地以观测实验事实证明大气边界层内线性唯象关系是成立的，而且线性湍流输送系数同相应的线性唯象系数成正比关系。但实验事实表明，大涡对流的混合层线性唯象系数成正比关系。但实验事实表明，大涡对流的混合层线性唯象关系是不成立的，混合层内湍流输送过程是一种强的非线性过程。所以，对流边界层是一种远离平衡态非线性区的热力学状态。地转风和热成风是一种大气系统特有的动力过程和热力过程和交叉耦合现象，这是大气系统交叉耦合现象的一个实际例证。     

The atmospheric chemistry of dimethylsulfoxide (DMSO) kinetics and mechanism of the OH+DMSO reaction

We have employed a pulsed laser photolysis-pulsed laser induced fluorescence technique to study the kinetics and mechanism of the reaction of OH with dimethylsulfoxide and its deuterated analogue. A rate coefficient of (1.0±0.3)×10^-10 cm³ molecule^-1 s^-1 was obtained ar room temperature. The rate coefficient was independent of pressure over the range 25–700 Torr, showed no dependence on the nature of the buffer gas and showed no kinetic isotope effect. A limited study of the temperature dependence indicated that the reaction displays a negative activation energy. The gas phase ultraviolet absorption spectrum was obtained at room temperature and showed a strong absorption feature in the far ultraviolet. The absolute absorption cross-section at 205 nm, the absorption peak, is (1.0±0.3)×10^-17 cm², where the large uncertainty results from experimental difficulties associated with the low vapor pressure and stickiness of DMSO.     

Snowdrift suspension and atmospheric turbulence. Part I: Theoretical background and model description

Snowdrift is one of the manymanifestations of two-phase flow, in which theinteraction between suspended particles and theambient fluid brings about some interesting features.Specifically, the drag required to keep particles insuspension against the downward gravitational pullrequires expenditure of turbulent kinetic energy(TKE). Other effects include the increased density of theair-snow mixture and the stable thermal stratificationcaused by the snowdrift sublimation-induced cooling.An atmospheric surface-layer model that includes snowdriftsuspension is described that includes the effects ofupward diffusion, gravitational settling andsublimation of snow particles in 48 size classes, theeffects of snowdrift sublimation on the heat andmoisture budget of the surface layer and the dampingof turbulence in the presence of suspended particles. Thewell-known E- closure model is applied toevaluate the eddy exchange coefficient, with a newterm representing buoyancy reduction induced by thestably stratified suspended particle profile includedin the prognostic equation for TKE.     

Present-day concepts of atmospheric frontogenesis. Part 1. Theoretical ideas

Presented is a review of quantitative characteristics of atmospheric frontogenesis that describe it as the process of variations of the vector of the horizontal temperature gradient (both in value and in direction) in an individual particle. The frontogenesis that strives for recovering the thermal wind balance disturbed in the case of inhomogeneous advection, generates vertical circulation which is both thermally direct (warm air ascends relative to cold air) and thermally opposite (upward motions in the cold air). Given are the expressions for computing frontogenesis using the data on temperature, pressure, and wind. Used is the resolution of the frontogenetic vector function into components along the isoline of potential temperature both on and across the constant-pressure surface. The first component describes the change in the temperature gradient vector due to the rotation of isotherms (rotational frontogenesis), and the second component, the variations of the absolute value of the gradient (scalar frontogenesis). Quantitative characteristics of frontogenesis are efficient diagnostic parameters both for understanding weather processes and weather forecast specification and for the verification and enhancement of numerical models.     

Towards an operational aqueous phase chemistry mechanism for regional chemistry-transport models: CAPRAM-RED and its application to the COSMO-MUSCAT model

Mechanism reductions of the detailed aqueous phase chemistry mechanism CAPRAM 3.0i are performed. Manual methods and automatic techniques are both applied in order to provide a less computationally intensive mechanism which is operational in regional chemistry transport models (CTMs). The finally reduced mechanism contains less than 200 reactions (4 times smaller than the detailed CAPRAM 3.0i) and describes the main characteristics of inorganic and organic aqueous phase processes occurring in tropospheric warm clouds. Most of the chemical reduction potential is realized in the CAPRAM 3.0i organic chemistry. The number of aqueous phase species decreases from 380 in the full mechanism to 130 in the final reduced version. The calculated percentage deviations between the full and reduced mechanism are on average below 5% for the most important organic and inorganic target compounds such as oxidants, inorganic and organic acids, carbonyls and alcohols. Comparisons of the required CPU times between the full and reduced mechanisms show reductions of approximately 40%. 2-D test simulations with the CTM MUSCAT were performed using prescribed meteorological conditions in order to examine the applicability of the reduced mechanism at regional scale. Simulations with the reduced CAPRAM 3.0i mechanism and a much less complex mechanism with only limited inorganic chemistry (INORG) were compared to evaluate the effects of more detailed chemistry. The model results show large differences in the level of oxidants and the inorganic and organic mass processing. Prospectively, the reduced mechanism represents the basis for studying aerosol cloud processing effects at regional scale with future CTMs and will allow more adequate interpretation of field data.     

Automated in-situ monitoring of atmospheric non-methane hydrocarbon concentrations and gradients

A fully automated system measuring C2–C6 hydrocarbon concentrations and vertical gradients was installed at Harvard Forest in Petersham, Massachusetts, using a gas chromatograph with dual flame ionization detectors and cryogenic sample preconcentration. Measurements were made simultaneously at two heights above the forest canopy at forty five minute intervals, continuously from July 1992 to the present. Data for concentration gradients were combined with CO₂ flux measured by eddy correlation to determine the rates of production of biogenic hydrocarbons by the forest.     

Atmospheric radiative equilibria. Part II: bimodal solutions for atmospheric optical properties

 A simple theoretical model of atmospheric radiative equilibrium is solved analytically to help understand the energetics of maintaining Earth's tropical and subtropical climate. The model climate is constrained by energy balance between shortwave (SW) and longwave (LW) radiative fluxes. Given a complete set of SW and LW optical properties in each atmospheric layer, the model yields a unique equilibrium-temperature profile. In contrast, if the atmospheric temperature profile and SW properties are prescribed, the model yields essentially two distinct LW transmissivity profiles. This bimodality is due to a nonlinear competition between the ascending and descending energy fluxes, as well as to their local conversion to sensible heat in the atmosphere. Idealized slab models that are often used to describe the greenhouse effect are shown to be a special case of our model when this nonlinearity is suppressed. In this special case, only one solution for LW transmissivity is possible. Our model's bimodality in LW transmissivity for given SW fluxes and temperature profile may help explain certain features of Earth's climate: at low latitudes the temperature profiles are fairly homogeneous, while the humidity profiles exhibit a bimodal distribution; one mode is associated with regions of moist-and-ascending, the other with dry-and-subsiding air. The model's analytical results show good agreement with the European Centre for Medium-Range Weather Forecasts' reanalysis data. Sensitivity analysis of the temperature profile with respect to LW transmissivity changes leads to an assessment of the low-latitude climate's sensitivity to the “runaway greenhouse” effect. Received: 7 December 1999 / Accepted: 19 February 2001     

On the generation and maintenance of atmospheric disturbances

Blocking is one of the intensive atmospheric disturbances which can maintain for a long time. In this paprer we investigate the general conditions favorable for the generation and maintenance of the intensive disturbances. First, the evolutional process of disturbances superimposed on a jet-like zonal flow is studied by using the wave-packet representation and the WKBJ method. Second, the mechanism for generation and maintenance of disturbances is investigated by using the nonlinear equations and the general physical laws. Finally, some numerical experiments are given for illustration, showing the rapid absorption of disturbances by the jet-like zonal flow in one case and the maintenance of disturbances for a long time in the other case.     

An application of equivalent modons to atmospheric blocking

Certain consistent features are demonstrated between a particular strong, vortex pair atmospheric blocking pattern over the eastern North Atlantic Ocean and Europe during January 1963 and an equivalent modon solution of the inviscid equivalent barotropic equation. Modons are uniformly translating, shape preserving, non-linear analytic solutions. The equivalent barotropic model for the atmosphere is derived as a lowest-order truncation of an expansion and projection of the quasigeostrophic equations with the empirical orthogonal pressure modes of the troposphere. The horizontal and vertical structure of the blocking pattern, as well as its intensity, are consistent with the modon dispersion relation. On the other hand, there remain some uncertainties about whether the pressure profile of the mean zonal wind is consistent with modon requirements and whether a stationary theoretical solution adequately reflects the essential dynamics of a fluctuating and regenerative blocking pattern.     

Application of regularised optimal fingerprinting to attribution. Part II: application to global near-surface temperature

Attribution of global near-surface temperature changes is revisited using simulations from the coupled model intercomparison project 5 and methodological improvements from the regularised optimal fingerprinting approach. The analysis of global mean temperature shows that changes can be robustly detected and attributed to anthropogenic influence. However, the differences between results from individual models and observations are found to be larger than the simulated internal variability in several cases. Discrimination between greenhouse gases and other anthropogenic forcings, based on the global mean only, is more difficult due to collinearity of temporal response patterns. Using spatio-temporal data provides less robust conclusions with respect to detection and attribution, as the results tend to deteriorate as the spatial resolution increases. More importantly, some inconsistencies between individual models and observations are found in this case. Such behaviour is not observed in a perfect model framework, where pseudo-observations and the expected response patterns are provided by the same model. However, using response patterns from a model other than the one used for pseudo-observations may lead to the same behaviour as real observations. Our results suggest that additional sources of uncertainty, such as modeling uncertainty or observational uncertainty, should not be neglected in detection and attribution.     

MODES系统对贵州月气温、降水预测初步评估

基于CMPAS多源融合降水和ERA5再分析产品,评估ECMWF全球高分辨率确定性预报产品对2020年梅雨期(6月10日—7月20日)极端强降水过程的预报性能。同时,基于面向对象的诊断评估方法(MODE),揭示ECMWF模式对强降水落区的质心经纬度、面积、长度、宽度、轴角等空间特征的预报性能。结果表明,ECMWF模式对于梅雨期的日降水量预报,在雨带的空间位置上,模式预报偏北、偏西的偏差较多;在落区形态上,模式预报的雨带面积偏大,轴角倾斜度更大。观测中江淮流域区域平均降水的日变化主峰值出现在清晨至上午,ECMWF预报能够再现降水日变化特征。针对模式对主雨带南北落区质心位置预报偏差的评估表明,模式预报主雨带位置偏北的频次呈现出双峰分布的日变化特征,峰值出现在夜间和午后。雨带位置预报偏南的频次为单峰分布,峰值在上午。低空急流的日变化特征明显,且峰值时刻超前降水峰值时刻3 h,而ECMWF预报急流峰值时刻则较观测早3 h。ECMWF预报降水落区位置偏差与预报低层南风分量的强弱偏差相关,当对流层低层南风分量偏强时,雨带位置预报易偏北;南风分量较弱时雨带位置预报易偏南。针对ECMWF预报位置偏北和偏差较小的两次典型强降水事件的对比分析,结果表明在小时尺度上急流与降水的日变化一致,ECMWF预报降水落区的偏北与前3 h内强度更强的急流有关。

     

An isentropic vertical coordinate model: Design and application to atmospheric frontogenesis studies

Summary The isentropic vertical coordinate model developed at UCLA is briefly reviewed. The review includes an outline of the approach used to overcome technical difficulties in handling model layers with small mass.The model's performance is demonstrated by simulating the evolution of a middle-latitude baroclinic disturbance. During the evolution of the disturbance, sharp frontal zones are generated in the upper and middle troposphere with realistic tropopause folding. The extent to which different dynamical processes contribute to frontogenesis is analyzed.While the model successfully simulates frontogenesis in the upper and middle troposphere, it has a difficulty in simulating surface fronts. The difficulty arises due to the lack of degrees of freedom in surface temperatures since an isentropic vertical coordinate model requires a large number ofvertical layers to obtain a highhorizontal resolution at the lower boundary. This suggests the potential of a hybrid vertical coordinate, which approaches at upper levels and at lower levels.With 12 Figures     

大气平衡态的动力特征 II:大气的振荡机制和稳定平衡态的吸引机制

本文研究强迫耗散系统的时间积分特征。从各态出发的积分最终都跌入吸引盆。由于能量和角动量的约束,大气向稳定平衡态的跌入成为非随机的、确定的物理过程。由于山脉矩和摩擦矩的相互调整,大气向高能级跌入时伴有次临界的、周期为2—3天的高频次振荡;向低能级跌入时伴有跨临界的、周期为1—2周的低频主振荡。振荡的频率受地形的影响明显。研究还指出,所谓“突变”,实质上是由于大气的能级出现季节性变化,大气状态从一个吸引域转移到另一个吸引域,角动量平衡重新调整的伴随现象。     

Is the recent build-up of atmospheric CO2 over Europe reproduced by models. Part 2: an overview with the atmospheric mesoscale transport model CHIMERE

In this issue, Ramonet et al. revealed a positive trend in European, atmospheric CO₂ concentrations relative to a marine, North Atlantic reference baseline, for the years 2001–2006. The observed build up mainly occurred during the cold season where it reaches a 0.8 ppm yr⁻¹ at low-altitude stations to a 0.3 ppm yr⁻¹ at mid-altitude stations. We explore the cause of this build-up using the mesoscale model CHIMERE. We first model the observed trends, using interannually varying fluxes and transport, then suppress the interannual variability in fluxes or aspects of transport to elucidate the cause. The run with no interannual variability in fluxes still matches observed trends suggesting that transport is the major cause. Separate runs varying either boundary layer height or winds show that changes in boundary layer height explain the trends at low-altitude stations within the continents while changes in wind regimes drive changes elsewhere.     

Changes in atmospheric chemistry and the greenhouse effect: A Southern Hemisphere perspective

In the past decades there has been an explosive increase in studies of the chemistry of the atmosphere. These studies have shown that the chemical composition of the global atmosphere is far from constant. There is a clearly discernible chemical weather and climate and the latter is changing.Global atmospheric chemistry is at a relatively embryonic stage and much of the effort thus far has been directed towards the establishment of an observational basis upon which a sound theoretical understanding of chemical weather and climate can be built. Without this framework we will remain unable to rationally assess the consequences of, or even distinguish between, natural and man-made perturbations to the chemistry of the atmosphere or to understand the instabilities that already exist.Parallel with this development is the major upsurge of interest in the warming of the planet now expected with high probability as a result of the increase of the atmospheric levels of the so-called greenhouse gases. Such changes; although not the only environmental changes expected, are likely to have far-reaching effects on society and the natural environment. Serious decisions are ahead as we strive to adapt to and avoid climatically induced change.     

Effects of tropical deforestation on global and regional atmospheric chemistry

A major portion of tropospheric photochemistry occurs in the tropics. Deforestation, colonization, and development of tropical rain forest areas could provoke significant changes in emissions of radiatively and photochemically active trace gases. A brief review of studies on trace-gas emissions in pristine and disturbed tropical habitats is followed by an effort to model regional tropospheric chemistry under undisturbed and polluted conditions. Model results suggest that changing emissions could stimulate photochemistry leading to enhanced ozone production and greater mineral acidity in rainfall in colonized agricultural regions. Model results agree with measurements made during the NASA ABLE missions. Under agricultural/pastoral development scenarios, tropical rain forest regions could export greater levels of N₂O, CH₄, CO, and photochemical precursors of NO _y and O₃ to the global atmosphere with implications for climatic warming.     

Soil occupation and atmospheric variations over Sobradinho Lake area. Part one: an observational analysis

Summary Sobradinho Lake lies in the S?o Francisco River Basin, in one of the most arid regions in Northeastern Brazil, within a land stretch categorized as the Lower-middle S?o Francisco, situated at about 40 km away from the municipality of Petrolina (09°23′S–40°30′W) in the state of Pernambuco. The dam, in its full capacity, consists of a lake of approximately 4,214 km²; 280 km in length, the width of which varies from 5 to 50 km. The dam storage capacity is that of 34.1 billion m³ of water. Being situated in a semi-arid region, the dam brought about significant development to local irrigated agriculture. The caatinga ecosystem has, for that matter, undergone considerable changes. Statistical analysis techniques applied to data collected before and after the filling of the lake, made it possible both to make an assessment of the impact of the dam construction on the region meteorology and to diagnose the variability of such an impact on environmental conditions. Results showed that the dam has brought about considerable changes to regional meteorology. The alterations were observed to be more significant as regards atmospheric humidity and wind speed.