Degradation of Isoprene in the Presence of Sulphoxy Radical Anions

Autoxidation of S(IV) initiated by manganese sulphate or potassium peroxydisulphate in alkaline aqueous solutions was significantly slowed down by dissolved isoprene, which decayed in the process. The laboratory experiments were carried out in a batch, perfectly mixed reactor, which had no gas space. The concentration–time profiles of oxygen were measured with a Clark-type electrode. The profiles of sulphite species and of isoprene were evaluated from the UV spectra of solutions. The kinetic analysis indicated that isoprene reacted directly with sulphate radical anions produced during the S(IV) autoxidation. A relative second-order rate constant of (2.12 ± 0.37) × 10⁹ M^–1 s^–1 was determined for this reaction at 25 °C, pH (8.0–8.5) and ionic strength of (1.7–4.9) × 10^–3 M (the reference rate constant of the reaction of sulphate radical anions with sulphite ions equalled 3.4 × 10⁸ M^–1 s^–1). A tentative mechanism of isoprene oxidation during S(IV) autoxidation, which included formation of isoprene – SO^– ₄ adduct, was based on the analogy to the gas-phase reactions of isoprene and to the liquid-phase reactions of sulphate radical anions with other compounds. Atmospheric significance of the aqueous-phase reaction of isoprene with sulphate radicals was discussed. Approximate analysis showed the reaction is a potential sink for isoprene in the aqueous phase and in the gas–liquid systems of high liquid water content (LWC > 10^–5 m³ m^–3). The aqueous-phase oxidation of isoprene can produce secondary pollutants, and influence transformation and the long-range transport of SO₂ in the atmosphere.     

Nonlinear Stability of the Lagrangian Libration Points in the Chermnykh Problem

In this paper we consider the problem of motion of an infinitesimal point mass in the gravity field of an uniformly rotating dumb-bell. The aim of our study is to investigate Liapunov stability of Lagrangian libration points of this problem. We analyze the stability of libration points in the whole range of parameters ω, μ of the problem. In particular, we consider all resonance cases when the order of resonance is not greater than five. This revised version was published online in August 2006 with corrections to the Cover Date.     

A Lower Palaeozoic shallow water sequence in the eastern European Variscides (SW Poland): provenance and depositional history

The Gackowa Formation of inferred Cambrian —Ordovician age is part of the metamorphosed pre-Variscan basement of the southern Kaczawa Mountains of the Sudetes region, south-west Poland. Previously variously interpreted as lavas, tuffs and sandstones, it is shown to consist of about 200 m of originally well-sorted siliclastic sedimentary rocks within a sequence of predominantly mafic volcanic rocks. Four facies have been distinguished based on relict sedimentary structures and textures and these suggest that deposition took place on a storm-dominated shelf, mostly above the wave base. The petrography, detrital zircon morphologies and geochemistry suggest affinity with, and derivation in large part from, acid volcanic rocks at a comparable stratigraphic position in a separate tectonostratigraphic unit to the south. The Gackowa Formation and its acid volcanic source rocks have a clear continental geochemical signature, in contrast with the mantle-derived basic/bimodal volcanic rocks below and above; it is suggested that the parent acid magma originated by crustal melting during the ascent of these mantle-derived magmas. A continental crust setting is inferred for the deposition of the Gackowa Formation sandstones, thus suggesting a continental setting for the associated within-plate basalts. The entire volcanic/sedimentary succession resembles elements of the Lower Palaeozoic of Germany, and all may have formed in an initial rift setting during Late Precambrian to Ordovician times.     

Multi-resolution clustering analysis and 3-D visualization of multitudinous synthetic earthquakes

We use modern and novel techniques to study the problems associated with detection and analysis of multitudinous seismic events, which form the background for isolated great earthquakes. This new approach involves multivariate analysis of low and large magnitude events recorded in space over a couple of centuries in time. We propose here the deployment of the clustering scheme both for extracting small local structures and large-scale trends in synthetic data obtained from four numerically simulated models with: uniform properties (U), a Parkfield-type asperity (A), fractal brittle properties (F), and multi-size-heterogeneity fault zone (M). The mutual nearest neighbor (mnn) clustering scheme allows for extraction of multi-resolutional seismic anomalies in both the spatio-temporal and multi-dimensional feature space. We demonstrate that the large earthquakes are correlated with a certain pathway of smaller events. Visualization of the anomalies by using a recently introduced visualization package Amira reveals clearly the spatio-temporal relationships between clusters of small, medium and large earthquakes, indicating significant stress relaxation across the entire fault region. We demonstrate that this mnn scheme can extract distinct clusters of the smallest events, which precede and follow a singularly large magnitude earthquake. These clusters form larger spatio-temporal structures comprising a series of large earthquakes. The link between the large and medium magnitude events is not so clearly understood. Short-ranged correlations are dominated by strong spatio-temporal anomalies, thus reflecting the global seismic properties of the entire fault zone.Electronic Supplementary Material Supplementary material is available for this article if you access the article at . A link in the frame on the left on that page takes you directly to the supplementary material.     

M split(q) estimation: estimation of parameters in a multi split functional model of geodetic observations

The method presented here assumes that a single observation can be identified with one of q functional models that compete with one another. The estimation method is based on the assumption that a theoretical quantity, called elementary split potential, can be assigned to each observation. Such quantity is referred to the theory of probability as well as to the theory of information. Parameters of the competitive functional models are estimated by maximizing the split potential globally over for the whole observation set. Additionally, such M _split(q) estimates minimize the amount of information that could be provided by other estimates computed for the same observation set. The method is a certain kind of extension of the maximum likelihood method and if one considers the generalizations presented in the paper it can also be regarded as the development of M-estimation. Special attention is paid to the squared M _split(q) estimation where the objective function is a squared one. If q = 1, then the squared M _split(q) estimation is equivalent to the least squares method. The last part of the paper presents some numerical examples illustrating the properties of the squared M _split(q) estimation as well as pointing at possible applications in geodesy and surveying.     

The extended Lissajous–Levi-Civita transformation

Action-angle variables for the Levi-Civita regularized planar Kepler problem were introduced independently first by Chenciner and then by Deprit and Williams. The latter used explicitly the so-called Lissajous variables. When applied to the transformed Keplerian Hamiltonian, the Lissajous transformation encounters the difficulty of being defined in terms of the constant frequency parameter, whereas the Kepler problem transformed into a harmonic oscillator involves the frequency as a function of an energy-related canonical variable. A simple canonical transformation is proposed as a remedy for this inconvenience. The problem is circumvented by adding to the physical time a correcting term, which occurs to be a generalized Kepler’s equation. Unlike previous versions, the transformation is symplectic in the extended phase space and allows the treatment of time-dependent perturbations. The relation of the extended Lissajous–Levi-Civita variables to the classical Delaunay angles and actions is given, and it turns out to be a straightforward generalization of the results published by Deprit and Williams.     

Hydrological modelling of the Vistula and Odra river basins using SWAT

This paper presents a large-scale application of the SWAT model for water balance and natural streamflow simulation in the entire basins of the Vistula and the Odra, covering most of the territory of Poland. A tailored calibration approach was designed to achieve satisfactory goodness-of-fit across a range of catchment sizes. Model calibration and evaluation driven by high-resolution climate data showed overall good behaviour for 80 benchmark catchments divided into eight clusters, and spatial evaluation for 30 gauges showed that the designed regionalization scheme performed well (median KGE of 0.76). Basin-averaged estimates of blue and green water flow and green water storage estimated using the calibrated model were 185, 517 and 206 mm, respectively. This study provides a basis for future work, such as assessing climate change impacts on hydrology, assessing flow alterations, and water quality simulation. The model output is publicly available through an online research data archive (doi:10.4121/uuid:b8ab4f5f-f692-4c93-a910-2947aea28f42).

EDITOR A. Castellarin

ASSOCIATE EDITOR G. Thirel