Chemical Mechanism Development: Laboratory Studies and Model Applications

Within the German Tropospheric Research Programme (TFS) numerous kinetic and mechanistic studies on the tropospheric reaction/degradation of the following reactants were carried out: oxygenated VOC, aromatic VOC, biogenic VOC, short-lived intermediates, such as alkoxy and alkylperoxy radicals.At the conception of the projects these selected groups were classes of VOC or intermediates for which the atmospheric oxidation mechanisms were either poorly characterised or totally unknown. The motivation for these studies was the attainment of significant improvements in our understanding of the atmospheric chemical oxidation processes of these compounds, particularly with respect to their involvement in photooxidant formation in the troposphere. In the present paper the types of experimental investigations performed and the results obtained within the various projects are briefly summarised. The major achievements are highlighted and discussed in terms of their contribution to improving our understanding of the chemical processes controlling photosmog formation in the troposphere.     

Evaluation of pre-CHAMP gravity models `GRIM5-S1' and `GRIM5-C1' with satellite crossover altimetry

 The new GFZ/GRGS gravity field models GRIM5-S1 and GRIM5-C1, currently used as initial models for the CHAMP mission, have been compared with other recent models (JGM 3, EGM 96) for radial orbit accuracy (by means of latitude lumped coefficients) in computations on altimetry satellite orbits. The bases for accuracy judgements are multi-year averages of crossover sea height differences from Geosat and ERS 1/2 missions. This radially sensitive data is fully independent of the data used to develop these gravity models. There is good agreement between the observed differences in all of the world's oceans and projections of the same errors from the scaled covariance matrix of their harmonic geopotential coefficients. It was found that the tentative scale factor of five for the formal standard deviations of the harmonic coefficients of the new GRIM fields is justified, i.e. the accuracy estimates, provided together with the GRIM geopotential coefficients, are realistic. Received: 20 February 2001 / Accepted: 24 October 2001     

Radio Emission from Three-dimensional Relativistic Hydrodynamic Jets: Observational Evidence of Jet Stratification

High-resolution, high signal-to-noise ratio, blue-violet spectra of three red giant branch tip stars in M15 have been obtained with the Keck I High-Resolution Echelle Spectrograph. These spectra have been analyzed to determine the abundances of several neutron-capture elements, including the radioactive chronometer element thorium. There are two principal results of this study. First, the abundances of the heavier (Z>/=56) elements for each of the three stars is well matched by a scaled solar system r-process abundance distribution. Second, a weighted mean-observed Th/Eu ratio for the stars implies an age for the neutron-capture material in M15 stars of 14+/-3 Gyr, in reasonable agreement with other recent age estimates for Galactic globular clusters.     

Topex/Poseidon Altimetry and Dynamics of the Ocean-Atmosphere System

The T/P altimeter data 1993 – 1997 (cycles 11 – 194) has been analyzed with emphases on seasonal variations in sea surface topography (SST). The amplitude of the annual variations amounted to (5.9±0.3) mm when inverted barometer (IB) corrections were applied and (2.0±0.4) mm without any IB corrections. The amplitude of the semi-annual variations in SST was small with IB corrections applied: (0.6±0.3) mm. However, when no IB corrections were applied, it was (1.8±0.4) mm, i.e. the semiannual variations are at the same level as the annual variations with no IB corrections. The phase angle offset of the annual term has shifted by about 180° when IB correction was applied. The dynamics of the ocean-atmosphere system is discussed and it is concluded that it could, at least partly, be responsible for the above observed effects.     

A Lost Realm in the Internal Domains of the Betic-Rif Orogen (Spain and Morocco): Evidence from Conglomerates and Consequences for Alpine Geodynamic Evolution

The Malaguide-Ghomaride Complex is capped by Upper Oligocene-Aquitanian clastic deposits postdating early Alpine orogenesis but predating the main tectonic-metamorphic evolution, end of nappe emplacement, unroofing, and exhumation of the metamorphic units of the Betic-Rif Orogen. Two conglomerate intervals within these deposits are characterized by clasts of sedimentary, epimetamorphic, and mafic volcanic rocks derived from Malaguide-Ghomaride units and by clasts of acidic magmatic and orthogneissic rocks of unknown provenance, here studied. Magmatic rocks originated from late-Variscan two-mica cordierite-bearing granitoids and, subordinately, from aplitic dikes. Orthogneisses derive from similar plutonic rocks but are affected by an Alpine metamorphic overprint evolving from greenschist (T=510&j0;-530 degrees C and P=5-6 kbar) to low-temperature amphibolite facies (T>550&j0;C and P<3 kbar). Such a plutonic rock suite is unknown in any Betic-Rif unit or in the basement of the Alboran Sea, and the metamorphic evolution in the orthogneisses is different from (and older than) that of Alpujarride-Sebtide rocks to which they were formerly ascribed. Magmatic and metamorphic rocks very similar to those studied characterize the basements of some Kabylia and Calabria-Peloritani units. Therefore, the source area is a currently lost continental-crust realm of Calabria-Peloritani-Kabylia type, located to the ESE of the Malaguide-Ghomaride Domain and affected by a pre-latest Oligocene Alpine metamorphism. Increasingly active tectonics transformed this realm into rising areas from which erosion fed small subsiding synorogenic basins formed on the Malaguide-Ghomaride Complex. This provenance analysis demonstrates that all these domains constituted a single continental-crust block until Aquitanian-Burdigalian times, before its dispersal around nascent western Mediterranean basins.     

Enforcing smoothness and assessing uncertainty in non-linear one-dimensional prestack seismic inversion

Estimation of elastic properties of rock formations from surface seismic amplitude measurements remains a subject of interest for the exploration and development of hydrocarbon reservoirs. This paper develops a global inversion technique to estimate and appraise 1D distributions of compressional‐wave velocity, shear‐wave velocity and bulk density, from normal‐moveout‐corrected PP prestack surface seismic amplitude measurements. Specific objectives are: (a) to evaluate the efficiency of the minimization algorithm (b) to appraise the impact of various data misfit functions, and (c) to assess the effect of the degree and type of smoothness criterion enforced by the inversion. Numerical experiments show that very fast simulated annealing is the most efficient minimization technique among alternative approaches considered for global inversion. It is also found that an adequate choice of data misfit function is necessary for a reliable and efficient match of noisy and sparse seismic amplitude measurements. Several procedures are considered to enforce smoothness of the estimated 1D distributions of elastic parameters, including predefined quadratic measures of length, flatness and roughness. Based on the general analysis of global inversion techniques, we introduce a new stochastic inversion algorithm that initializes the search for the minimum with constrained random distributions of elastic parameters and enforces predefined autocorrelation functions (semivariograms). This strategy readily lends itself to the assessment of model uncertainty. The new global inversion algorithm is successfully tested on noisy synthetic amplitude data. Moreover, we present a feasibility analysis of the resolution and uncertainty of prestack seismic amplitude data to infer 1D distributions of elastic parameters measured with wireline logs in the deepwater Gulf of Mexico. The new global inversion algorithm is computationally more efficient than the alternative global inversion procedures considered here.     

An audio-magnetotelluric investigation in Terceira Island (Azores)

Ten audio-magnetotelluric soundings have been carried out along a profile crossing the Serra do Cume caldera in the eastern part of the Terceira Island (Azores). The main objectives of this investigation were to detect geoelectrical features related with tectonic structures and to characterize regional hydrological and hydrothermal aspects mainly those related to geothermal fluid dynamics.Three-dimensional numerical investigation showed that the data acquired at periods shorter than 1 s are not significantly affected by ocean effect. The data was analysed using the Smith's decomposition method in order to investigate possible distortions caused by superficial structures and to estimate a global regional strike. The results suggest that in general the soundings were not distorted. A regional N55°W strike was chosen for the two-dimensional data inversion.The low-resistivity zones (10–30 ohm-m) displayed in the central part of the 2-D geoelectrical model have been interpreted as caused by hydrothermal circulation. The low-resistivity anomalies at the ends of the profile might be attributed to alteration zones with interaction of seawater intrusion. High-resistivity (> 300 ohm-m) values have been related with less permeable zones in the SW of Cinco Picos and Guilherme Moniz caldera walls.     

The relation between rigorous and Helmert’s definitions of orthometric heights

Following our earlier definition of the rigorous orthometric height [J Geod 79(1-3):82–92 (2005)] we present the derivation and calculation of the differences between this and the Helmert orthometric height, which is embedded in the vertical datums used in numerous countries. By way of comparison, we also consider Mader and Niethammer’s refinements to the Helmert orthometric height. For a profile across the Canadian Rocky Mountains (maximum height of ~2,800 m), the rigorous correction to Helmert’s height reaches ~13 cm, whereas the Mader and Niethammer corrections only reach ~3 cm. The discrepancy is due mostly to the rigorous correction’s consideration of the geoid-generated gravity disturbance. We also point out that several of the terms derived here are the same as those used in regional gravimetric geoid models, thus simplifying their implementation. This will enable those who currently use Helmert orthometric heights to upgrade them to a more rigorous height system based on the Earth’s gravity field and one that is more compatible with a regional geoid model.     

Seismic quantification of the explosions that destroyed the dome of Volcán de Colima, Mexico, in July–August 2003

In July–August 2003, the andesitic lava dome at Volcán de Colima, México, was destroyed by a sequence of explosions that replaced the 2×10⁶ m³ dome with a crater 200 m across and 30 m deep. The two strongest explosions occurred on July 17 and August 28. The initial low-frequency impulses that they produced, which were recorded on broadband seismic records, allowed an estimation of the counter forces of the initiating process as being equal to 0.3×10¹¹ N and 1×10¹¹ N for the July and August events, respectively. The seismic characteristics follow the Nishimura-Hamaguchi scaling law for volcanic explosions, reflecting self-similarity in the processes initiating explosive events. The results also show that counter forces can discriminate between the sizes of explosive eruptions that are assigned the same magnitude by conventional methods of classification such as the Volcanic Explosivity Index. The increasing use of broadband seismometers may therefore provide the basis for using counter forces to determine the magnitude of explosive eruptions.