The influence of isoprene peroxy radical isomerization mechanisms on ozone simulation with the presence of NOx

Isoprene peroxy radical isomerizations (1,5- and 1,6-H shifts) have recently been proposed as important pathways regenerating and recycling HO_x (OH?+?HO₂) in the atmosphere under low-NO_x conditions (Peeters et al. Phys. Chem. Chem. Phys. 28: 5935?C5939 2009; da Silva et al. Environ. Sci. Technol. 44:250?C256 2010). Evaluation and comparison of the isoprene peroxy radical isomerization mechanisms from recent studies have been performed against isoprene-NO_x experiments conducted in the UNC dual outdoor smog chambers. Five different kinetic mechanisms were tested in this study, including the original Master Chemical Mechanism (MCM) v3.1; two modified MCM mechanisms both implementing isoprene peroxy radical isomerization reactions but with different rate coefficients; the Carbon Bond 6 (CB6) mechanism; and the ISO-UNC mechanism. Sensitivity analyses of the unsaturated hydroxyperoxy aldehydes (HPALDs) reaction mechanisms under fast isomerization have also been performed. The results indicate that the fast isomerization mechanism and the mechanisms with high OH yields from HPALDs photolysis both significantly enhance HO_x estimates with increasing isoprene/NO_x ratios. However, O₃ predictions, as well the isoprene decay rates are substantially overestimated. Our results suggest that given the current state of our knowledge, it is difficult to improve both HO_x levels and maintain reasonable O₃ simulations using the Peeters et al. (Peeters et al. Phys. Chem. Chem. Phys. 28: 5935?C5939 2009) mechanism.     

A note on frame transformations with applications to geodetic datums

Rigorous equations in compact symbolic matrix notation are introduced to transform coordinates and velocities between ITRF frames and modern GPS-based geocentric geodetic datums. The theory is general but, after neglecting higher than second-order terms, it is shown that the equations revert to the formulation currently applied in most major continental datums. We discuss several examples: the North American Datum of 1983 (NAD83), the European Terrestrial Reference System of 1989 (ETRS89), the Geodetic Datum of Australia of 1994 (GDA94), and the South American Geocentric Reference System (SIRGAS). Electronic Publication     

Influences of Al,Mg, and K on Calculating Concentrations of Other Formation Elements and Their Corrections in Geochemical Logging

In geochemical logging, the standard capture gamma-ray spectra of Al, Mg, and K have no distinct characteristic energy peaks. This feature easily influences the spectral bands of characteristic peaks of other elements and thus affects the accuracy of calculating their concentrations. To study this influence, we constructed a model formation containing Al, Mg, and K, and employed the Monte Carlo N Particle Transport Code (MCNP) program to simulate their capture spectra. The results indicate that the calculated dry weights of Si are almost free from the influences of Mg, K, and Al. The ones of Ca and Fe are influenced, but only to a minor extent. The dry weight of S is concurrently influenced. Specifically, the K concentration causes S concentration to deviate significantly from its real concentration. By correcting for such influences, we can obtain relatively accurate values. Data processing for a real well validates the finding that Mg, Al, and K in the formation influence the precision of calculation of other elements and also testifies to the effectiveness of the correction method.     

Paleowind velocity and paleocurrents of pluvial Lake Manly,Death Valley,USA

Pluvial lake deposits are found throughout western North America and are frequently used to reconstruct regional paleoclimate. In Death Valley, California, USA, we apply the beach particle technique (BPT) of Adams (2003), Sedimentology, 50, 565–577 and Adams (2004), Sedimentology, 51, 671–673 to Lake Manly deposits at the Beatty Junction Bar Complex (BJBC), Desolation Canyon, and Manly Terraces and calculate paleowind velocities of 14–27 m/s. These wind velocities are within the range of present-day wind velocities recorded in the surrounding area. Sedimentary structures and clast provenance at Desolation Canyon and the Manly Terraces indicate sediment transport from north to south. Lake level, based on the elevation of constructional features, indicates that the hill west of the BJBC was an island and that the BJBC spits formed during simple lake regression. The data are consistent with the hypothesis that the present wind regime (velocity and direction) formed the pluvial Lake Manly features.     

A GIS-Based Tool for Representing Larval Dispersal for Marine Reserve Selection

Increasing efforts to implement marine protected areas (MPAs) as a means of managing marine ecosystems have created a need for evaluating potential spatial management plans. Almost all marine populations are metapopulations, connected reproductively by the dispersal of pelagic larvae. Models of marine population dynamics must account for larval connectivity, but despite recent advances connectivity patterns are still poorly understood. To allow more informed decision making when complete information on dispersal is lacking, we have developed a method based on geographic information systems (GIS) for representing larval dispersal distributions based on bathymetry and typical flows in the coastal ocean. These distributions reflect (1) generally greater flow in directions along, rather than across, lines of constant bathymetry and (2) lesser flow in shallow near-shore waters. We demonstrate how to parameterize this two-dimensional method for depicting larval dispersal based on comparisons to local oceanographic data. We then compare the predictions of the two-dimensional method to those of a simpler one-dimensional alternative in a population model used to evaluate proposed MPAs along the coast of central California. The method produces reasonable larval dispersal patterns and appears to include the effects of bathymetry on population dynamics better than commonly used one-dimensional methods and without requiring the significantly greater investment of developing particle-tracking circulation models. An important advantage of a two-dimensional approach is more realistic portrayal of the dependence of population persistence on the cross-shelf dimension of available habitat.     

Framboidal sulphides precipitated synthetically

Framboidal sulphides of iron, copper, lead, zinc, nickel and arsenic have been precipitated from aqueous solutions by hydrogen sulphide in the absence of any bacterial agency. The formation of framboids is considered to be a normal result of the precipitation of discrete sulphide particles in suspension from reactants in true solution at a concentration between twice and ten times the solubility of the sulphides. The preservation of framboids demands protection from further access to a solvent within a few days of precipitation. The significance of the formation and preservation of framboids in sedimentary and magmatic rocks and in the genesis of stratiform sulphide ores is discussed and the role of organic material in sediments is suggested.

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Zusammenfassung Eisen-, Kupfer-, Blei-, Zink-, Nickel- und Arsensulfid-Himbeeren wurden durch Schwefelwasserstoff-Fällung, unter Ausschluß von Bakterieneinwirkungen, erhalten. Die Bildung der Himbeeren wird als normales Resultat der Fällung begrenzter Sulfid-Einzelteilchen angesehen, wie sie aus 2- bis 10-fach übersättigten echten Lösungen entstehen. Nach der Fällung bleiben die Himbeeren eine Woche erhalten, danach nur, wenn das Lösungsmittel zu ihnen keinen weiteren Zutritt erlangt. Die Bedeutung der Bildung und Erhaltung von Himbeeren in sedimentären und magmatischen Gesteinen, sowie der Entstehungsprozeß von Sulfiderzschichten, wird besprochen und die Annahme diskutiert, daß organischem Material in Sedimenten eine bestimmte Rolle zukommt.

     

The ionic conductivity in high-pressure polymorphs of calcite

Ionic conductivity of polycrystalline calcite containing varying amounts of PO ₄ ^3? ions was measured in the pressure range of 1–6 GPa and at room temperature. Electrical conductivity increased with pressure corresponding to the phase transition of calcite I to calcite II. The conductivity in calcite III decreased exponentially with pressure. Calculated activation volumes of the conductivity varied with PO ₄ ^3? content in the range of 0.94–5.34 cm³/mol. This variation corresponded to the lattice parameter change of calcite I due to PO ₄ ^3? incorporation and indicated the contribution of CO ₃ ^2? -vacancies associated with PO ₄ ^3? ions to the conductivity.     

Middle Eocene‐Oligocene broken‐foreland evolution in the Andean Calchaqui Valley,NW Argentina: insights from stratigraphic,structural and provenance studies

Two end‐member models have been proposed for the Paleogene Andean foreland: a simple W‐E migrating foreland model and a broken‐foreland model. We present new stratigraphic, sedimentological and structural data from the Paleogene Quebrada de los Colorados (QLC) Formation, in the Eastern Cordillera, with which to test these two different models. Basin‐wide unconformities, growthstrata and changes in provenance indicate deposition of the QLC Formation in a tectonically active basin. Both west‐ and east‐vergent structures, rooted in the basement, controlled the deposition and distribution of the QLC Formation from the Middle Eocene to the Early Miocene. The provenance analysis indicates that the main source areas were basement blocks, like the Paleozoic Oire Eruptive Complex, uplifted during Paleogene shortening, and that delimits the eastern boundary of the present‐day intraorogenic Puna plateau. A comparison of the QLC sedimentary basin‐fill pattern with those of adjacent Paleogene basins in the Puna plateau and in the Santa Bárbara System highlights the presence of discrete depozones. These reflect the early compartmentalization of the foreland, rather than a stepwise advance of the deformation front of a thrust belt. The early Tertiary foreland of the southern central Andes is represented by a ca. 250‐km‐wide area comprising several deformation zones (Arizaro, Macón, Copalayo and Calchaquí) in which doubly vergent or asymmetric structures, rooted in the basement, were generated. Hence, classical foreland model is difficult to apply in this Paleogene basin; and our data and interpretation agree with a broken‐foreland model.     

Pile foundation analysis and design using experimental data and 3-D numerical analysis

Capacity based design of pile foundations limits the soil-structure interaction mechanism to group bearing capacity estimation, neglecting, in most cases, the contribution of the raft. On the other hand, a straightforward, nonlinear, 3-D analysis, accounting for soil and structural nonlinearities and the effects arising from pile–soil–pile interaction, would be extremely high CPU-time demanding and will necessitate the use of exceptionally powerful numerical tools. With the aim of investigating the most efficient, precise, and economical design for a bridge foundation, a hybrid method, compatible with the notion of sub-structuring is proposed. It is based on both experimental data and nonlinear 3-D analysis. The first step to achieve these targets is a back-analysis of a static pile load test, fitting values for soil shear strength, deformation modulus, and shear strength mobilization at the soil–pile interface. Subsequently, the response of 2 × 2 and 3 × 3 pile group configurations is numerically established and the distribution of the applied load to the raft and the characteristic piles is discussed. Finally, a design strategy for an optimized design of pile raft foundations subjected to non-uniform vertical loading is proposed.