Aqueous Oxidation of Sulfur(IV) Catalyzed by Manganese(II): A Generalized Simple Kinetic Model

The reaction kinetics of S(IV) autoxidation catalyzed by Mn(II) in the pH range 3–5 typical for atmospheric liquid water, was investigated. For reactions with pH maintained constant during the reaction course, the predictions obtained by a simple integral approach cover kinetic results only for concentrations of HSO ₃ ⁻ up to 0.2 mM at pH 4.5. Thus, a generalized simple kinetic model, which can be used for predicting the reaction kinetics in wider concentration, pH and temperature ranges, was derived. This model is based on the assumption that the reaction rate is proportional to the concentration of a transient manganese-sulfito complex formed in the initial step of a radical chain mechanism. In the proposed power law rate equation

Modeling compositional compressible two-phase flow in porous media by the concept of the global pressure

We derive a new formulation for the compositional compressible two-phase flow in porous media. We consider a liquid–gas system with two components: water and hydrogen. The formulation considers gravity, capillary effects, and diffusivity of each component. The main feature of this formulation is the introduction of the global pressure variable that partially decouples the system equations. To formulate the final system, and in order to avoid primary unknowns changing between one-phase and two-phase zones, a second persistent variable is introduced: the total hydrogen mass density. The derived system is written in terms of the global pressure and the total hydrogen mass density. The system is capable of modeling the flows in both one and two-phase zones with no changes of the primary unknowns. The mathematical structure is well defined: the system consists of two nonlinear parabolic equations, the global pressure equation, and the total hydrogen mass density equation. The derived formulation is fully equivalent to the original one. Numerical simulations show ability of this new formulation to model efficiently the phase appearance and disappearance.     

Dependence of accumulated precipitation on cloud drop size distribution

Convective precipitation is the main cause of extreme rainfall events in small areas. Its primary characteristics are both large spatial and temporal variability. For this reason, the monitoring of accumulated precipitation fields (liquid and solid components) at the surface is difficult to carry out through the use of rain gauge networks or remote-sensing observations. Alternatively, numerical models seem to be the most powerful tool in simulating convective precipitation for various analyses and predictions. Due to a lack of comparisons between modelled and observed precipitation characteristics over a long period of time, we focus our research on comparisons between observations and three model samples of accumulated convective precipitation over a particular study area. We use a numerical cloud model with two model schemes involving the unified Khrgian–Mazin size distribution of cloud drops and a model scheme involving a monodisperse cloud droplet spectrum and the Marshall–Palmer size distribution for raindrops, respectively. For comparison, we have selected a study area with a sounding site. Our analysis shows that the model version with the Khrgian–Mazin size distribution exhibits a better agreement with the observed mean, median and range of extreme values of accumulated convective precipitation. Model simulations with the Khrgian–Mazin size distribution most closely match observations, with a correlation coefficient of 0.91. Use of the Marshall–Palmer size distribution, on the other hand, systemically underestimates the observed precipitation and has the lowest correlation coefficient among the methods, 0.83. Such an investigation is crucial to improve predictions of accumulated convective precipitation for various climatological and hydrological analyses and predictions.     

Improved bora wind simulation using a nested Eta Model

Summary In connection with a number of recent publications on anomalous (excessive) absorption of shortwave radiation (SWR) by clouds, the data of aircraft observations of spectral and total SWR vertical profiles in the troposphere obtained within the CAENEX, GAAREX and FGGE programmes have been discussed. These data demonstrated persuasively the existence of substantial SWR absorption by clouds in the visible wavelength region. In this context, the results of simulation numerical medelling of the SWR transfer in clouds have been considered. These show a significant enhancement of the SWR absorption by clouds due to an increase of the mean free path of photons under an impact of multiple scattering in clouds. Another important consideration may be the impact of SWR-absorbing pollutants in clouds, especially soot aerosols.With 4 Figures     

Dynamics of inelastic base‐isolated structures subjected to analytical pulse ground motions

Structural design code provisions worldwide prescribe relatively small seismic force reduction factors for seismically base‐isolated structures, making their response to design‐level earthquake excitation essentially elastic. This paper uses the method of dimensional analysis to prove that; in most cases, this is not a conservative design approach but a necessity that emerges from the dynamics of base‐isolated structures. It is shown that allowing typical base‐isolated structures to yield results in large displacement ductility demands for the structure. This phenomenon is caused by the change in the nature of the ground motion excitation as it is transmitted to the structure through the seismic base isolation system as well as by the change in the distribution of displacements between the structure and the isolation bearings caused by yielding of the isolated structure. Copyright © 2013 John Wiley & Sons, Ltd.     

Transgressive overlap of a turbiditic sequence—priabonian of Ovče Pole,Macedonia

Flysch sequences develop normally from pelagic sediments, over a pre-flysch transitional unit, or from a well-developed transgressive base. A different situation has been observed in the western portion of the Upper Eocene flysch basin of Ov?e Pole, Macedonia, where deep-water turbidites appear almost directly over the eroded basement, transgressively overlapping the preexisting submarine relief. These relationships are explained as results of successive phases of subsidence in the basin. The outcrop area, situated between Titov Veles and Gradsko, represented a surface without deposition in the early depositional stages. Later subsidence introduced a turbiditic deposition into the domain without a break in sedimentation. Such cases may occur also in other flysch basins where lateral migration of the main depositional trough took place during the sedimentation.     

Investigations of karstic springs of the Biokovo Mt from the Dinaric karst of Croatia

Ten gravity springs from the slopes of the Biokovo Mt, Adriatic coast of Croatia were investigated. Three of them are included in the regional water supply system. The aim of this study was to investigate hydrogeological and geochemical characteristics of watershed, presenting one of the most typical karstic areas in the world.Hydrogeological investigations were performed during two seasons with dye tracing, using Na-fluoresceine which was poured into two pits, observing springs at distances of 1.82–8.8 km. Apparent velocities were 0.21–0.51 cm s^?1. Dye tracing was first time partially effective and second time ineffective, what could be due to immanent ore mineralization, which presents a natural barrier and was discovered by geochemical and mineralogical methods.Concentrations of 17 dissolved and total trace elements were determined first time in groundwater samples. Their concentrations were extremely low, more than 3 orders of magnitude less than allowed by the Croatian directives for the first category of groundwater and drinking water. The mass fractions of 60 elements were determined in 3 representative spring sediments. Highest concentrations of some metals in sediments (mg kg^?1) are: lead 5440, chromium 118, manganese 935, zinc 116 and barium 238. Origin of some elements and mineralogy is discussed.     

A contribution to the statistical analysis of Zagreb earthquakes in the period 1869–1968

Summary Statistical information on the number of earthquakes felt in Zagreb, Yugoslavia, during the 100 year period 1869–1968 is given and their distribution in time is shown. The largest earthquake in each year is analysed, first by the distribution-free method and then by means of the theory of extremes afterJenkinson. By the latter method we conclude that there is an upper limit to the possible intensity of earthquakes in Zagreb. The results are compared with the data for Californial although the seismicity of Zagreb area is rather high, that of California is considerably higher.