Variation in calcite dissolution rates:: A fundamental problem?

A comparison of published calcite dissolution rates measured far from equilibrium at a pH of ∼ 6 and above shows well over an order of magnitude in variation. Recently published AFM step velocities extend this range further still. In an effort to understand the source of this variation, and to provide additional constraint from a new analytical approach, we have measured dissolution rates by vertical scanning interferometry. In areas of the calcite cleavage surface dominated by etch pits, our measured dissolution rate is 10^−10.95 mol/cm²/s (PCO₂ 10^−3.41 atm, pH 8.82), 5 to ∼100 times slower than published rates derived from bulk powder experiments, although similar to rates derived from AFM step velocities. On cleavage surfaces free of local etch pit development, dissolution is limited by a slow, “global” rate (10^−11.68 mol/cm²/s). Although these differences confirm the importance of etch pit (defect) distribution as a controlling mechanism in calcite dissolution, they also suggest that “bulk” calcite dissolution rates observed in powder experiments may derive substantial enhancement from grain boundaries having high step and kink density. We also observed significant rate inhibition by introduction of dissolved manganese. At 2.0 μM Mn, the rate diminished to 10^−12.4 mol/cm²/s, and the well formed rhombic etch pits that characterized dissolution in pure solution were absent. These results are in good agreement with the pattern of manganese inhibition in published AFM step velocities, assuming a step density on smooth terraces of ∼9 μm⁻¹.     

Organization of oscillatory zoning in zircon: analysis, scaling, geochemistry, and model of a zircon from Kipawa, Quebec, Canada

The character of oscillatory zoning within a zircon crystal from the syenite Kipawa Complex, Quebec, varies with scale of observation. Analysis of an scanning electron microscopy (SEM) back-scatter gray-scale traverse at a resolution of one pixel = 2.43 μm revealed 145 zones over 5130 μm, whereas a detailed high-resolution (one pixel = 0.195 μm) section near the crystal rim revealed 225 zones over 795 μm. In order to mathematically characterize the zoning pattern, wavelet, Fourier, and nonlinear analysis techniques were used on profiles of the SEM gray-scale data, and a series constructed was from the zone widths. Results demonstrate that the zircon oscillatory zoning preserves nonlinear and periodic components. Secondary ion mass spectrometry, electron microprobe, and SEM analyses of trace elements show the SEM back-scatter bright zones are enriched in U, Th, and rare earth elements (REE) in comparison to the darker zones. REE patterns are sharply heavy REE enriched and have negative Eu anomalies and prominent positive Ce anomalies. We model the oscillatory zoning, including a measure of its chemical variation, by use of a periodically forced nonlinear system. Results of this data-driven model are quantitatively similar to the natural data. We envisage that the small-scale oscillatory zoning was the result of a nonlinear feedback process wherein the crystal growth modified the adjacent melt, which in turn affected the crystal composition. The large-scale harmonic zones likely reflect changes in the bulk geochemistry of the system from which the zircon grew.     

An Empirical Comparison of Kriging Methods for Nonlinear Spatial Point Prediction

Spatial prediction is a problem common to many disciplines. A simple application is the mapping of an attribute recorded at a set of points. Frequently a nonlinear functional of the observed variable is of interest, and this calls for nonlinear approaches to prediction. Nonlinear kriging methods, developed in recent years, endeavour to do so and additionally provide estimates of the distribution of the target quantity conditional on the observations. There are few empirical studies that validate the various forms of nonlinear kriging. This study compares linear and nonlinear kriging methods with respect to precision and their success in modelling prediction uncertainty. The methods were applied to a data set giving measurements of the topsoil concentrations of cobalt and copper at more than 3000 locations in the Border Region of Scotland. The data stem from a survey undertaken to identify places where these trace elements are deficient for livestock. The comparison was carried out by dividing the data set into calibration and validation sets. No clear differences between the precision of ordinary, lognormal, disjunctive, indicator, and model-based kriging were found, neither for linear nor for nonlinear target quantities. Linear kriging, supplemented with the assumption of normally distributed prediction errors, failed to model the conditional distribution of the marginally skewed data, whereas the nonlinear methods modelled the conditional distributions almost equally well. In our study the plug-in methods did not fare any worse than model-based kriging, which takes parameter uncertainty into account.     

Partitioning Between Chlorine Reservoir Species Deduced from Observations in the Arctic Winter Stratosphere

Simultaneous observations of several chlorine source gases, as well asHCl and ClO, have been performed in the Arctic stratosphere on 1 and 9February 1994, using balloon-borne instrumentation as a contribution toSESAME (Second European Stratospheric Arctic and Mid latitude Experiment).The observed mixing ratios of HCl and N₂O show a clearanticorrelation. No severe loss of HCl was observed inside the vortex duringour measurement. These measurements showed that during this period at 20 kmand above, HCl was either in excess, or at least as abundant, asClONO₂ and comprised between 50 and 70% of theavailable chlorine, Cl_y. On 1 February, measurements were madeinside the polar vortex. The air mass sampled on this day showed a clearsignature of diabatic descent, and also enhanced levels of ClO with amaximum of 230 pptv at 22.5 km. A 10 day backward trajectory analysis showedthat these air masses had passed a large region of low temperatures a fewhours prior to the measurement. Temperatures along the back trajectory atthe 475 K and 550 K levels (20.1 and 23.7 km respectively) were cold enoughfor heterogeneous chlorine activation to occur, in agreement with theobserved elevated ClO mixing ratios.     

APPLICATION OF BED EVOLUTION MODELS OVER LOOSE AND RIGID AREAS

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Studying the City Plume of Berlin on 20 July 1998 with Three Different Modelling Approaches

In this paper we try to identify and describe the specifics of the Berlin city plume characterised by a zone of enhanced photochemical activity downwind of the urban area, where the major emissions of ozone precursors (NO_x and VOC) take place. Two Eulerian CTM systems (EURAD and REM3/CALGRID) and one Euler–Lagrangian model (LaMM5) are applied to thearea of Berlin/Brandenburg to investigate the processes involved in the evolution of the Berlin plume inherent to the models. The study focuses on 20 July 1998,the first special observation period (SOP) during BERLIOZ. The examination includes (1) the role of turbulence and transport and the role of mass flux to the surface during the evolution of the plume, (2) the import situation of the ground based measurement sites, (3)the terms of the ozone budget equation and their contribution to precursor distribution and ozone formation, (4) the substructures of the plume defined by its chemical regimes. Main results show that the complex meteorological conditions during this SOP with considerable turbulent transports demand an Euler–Lagrangian approach to determine the source receptor relationshipsfor the ground based measurement sites. These relations reveal that only a minor part (5%) of the air approaching Pabstthum and the more downwind (north-western) stations origins from Berlin and that the mutual transport between all sites was limited. The latter result afflicts the joint interpretation of data from different stations because the presumption to measure the same air mass is violated in many cases for this SOP. The CTM results reveal that the local net production of ozone within the plume was controlled by transport ad chemical processes both owning the same importance but tending to counteract each other. At this SOP far distance sources of ozone precursors originating from the Bohemian basin did not interfere the Berlin city plume although they generally have the potential to do so.     

The Svalbard Eocene‐Oligocene (?) Central Basin succession: Sedimentation patterns and controls

A synthesis has been undertaken based on regionally compiled data from the post early Eocene foreland basin succession of Svalbard. The aim has been to generate an updated depositional model and link this to controlling factors. The more than kilometer thick progradational succession includes the offshore shales of the Gilsonryggen Member of the Frysjaodden Formation, the shallow marine sandstones of the Battfjellet Formation and the predominantly heterolithic Aspelintoppen Formation, together recording the progressive eastwards infill of the foredeep flanking the West Spitsbergen fold‐and‐thrust belt. Here we present a summary of the paleo‐environmental depositional systems across the basin, their facies and regional distribution and link these together in an updated depositional model. The basin‐margin system prograded with an ascending shelf‐edge trajectory in the order of 1°. The basin fill was bipartite, with offset stacked shelf and shelf‐edge deltas, slope clinothems and basin floor fans in the western and deepest part and a simpler architecture of stacked shelf‐deltas in the shallower eastern part. We suggest a foredeep setting governed by flexural loading, likely influenced by buckling, and potentially developing into a wedge top basin in the mature stage of basin filling. High‐subsidence rates probably counteracted eustatic falls with the result that relative sea‐level falls were uncommon. Distance to the source terrain was small and sedimentation rates was temporarily high. Time‐equivalent deposits can be found outbound of Stappen High in the Vestbakken Volcanic Province and the Sørvestsnaget Basin 300 km further south on the Barents Shelf margin. We cannot see any direct evidence of coupling between these more southerly systems and the studied one; southerly diversion of the sediment‐routing, if any, may have taken place beyond the limit of the preserved deposits.     

Cartographic Design Matters – A Comparison of Thematic Polygon Design

The number of web services providing cartographic data is increasing. A main challenge is to enable a user to combine these services, not only from a technical perspective, but also from a cartographic one. One common use case for these services is to create mashups based on thematic polygons on top of background maps. In this study we compare four cartographic designs of thematic polygons: only boundaries, transparencies, hatches and icons. The aim of the comparison is to investigate whether the designs are good for identifying the extent of the polygons and if the design disturbs the reading of the background map. The comparison is based on an eye-tracking study, where 24 participants performed polygon identification tasks as well as background search tasks. The study revealed that hatches were more efficient than the other designs for polygon identification. Hatches had significantly shorter total fixation times as well as scanpath lengths, possibly since the participants were able to identify the extent of the polygon solely based on the interior (i.e. the hatches), while for the other designs the participants were extensively reliant on the boundaries. However, the results also indicate that the hatches design disturbs the reading of the background map more than the other designs; hatches also appear visually unpleasant for many users. Since each design had its strengths and weaknesses, we recommend producers of services for thematic data to provide several designs so users can select an appropriate design for their own use cases.     

Detecting vehicle traffic patterns in urban environments using taxi trajectory intersection points

Abstract

Detecting and describing movement of vehicles in established transportation infrastructures is an important task. It helps to predict periodical traffic patterns for optimizing traffic regulations and extending the functions of established transportation infrastructures. The detection of traffic patterns consists not only of analyses of arrangement patterns of multiple vehicle trajectories, but also of the inspection of the embedded geographical context. In this paper, we introduce a method for intersecting vehicle trajectories and extracting their intersection points for selected rush hours in urban environments. Those vehicle trajectory intersection points (TIP) are frequently visited locations within urban road networks and are subsequently formed into density-connected clusters, which are then represented as polygons. For representing temporal variations of the created polygons, we enrich these with vehicle trajectories of other times of the day and additional road network information. In a case study, we test our approach on massive taxi Floating Car Data (FCD) from Shanghai and road network data from the OpenStreetMap (OSM) project. The first test results show strong correlations with periodical traffic events in Shanghai. Based on these results, we reason out the usefulness of polygons representing frequently visited locations for analyses in urban planning and traffic engineering.