An application of least-squares inverse analysis in kinetic interpretations of hydrous pyrolysis experiments

A least-squares inverse method is applied to the estimation of optimum kinetic parameters with statistical error bounds from concentration data obtained in isothermal hydrous pyrolysis experiments. The inverse method requires the specification of a data-parameter relationship (e.g., classical kinetic theory), the prior covariance matrices of data and parameter errors, as well as the prior central estimates of data and parameters. The reaction scheme considered is the common case of kerogen breakdown by Gaussian-weighted independent parallel first-order reactions and bitumen cracking by a single first-order reaction. The nonlinearity of the problem is reduced by a logarithmic transformation, which suggests a parameterization in terms of logarithmic concentrations, activation energies, and logarithmic Arrhenius factors. The linearized variance analysis is valid for the case studied, and the posterior covariance matrix reveals which parameters are constrained by the data. We find that the statistical errors in the average activation energy and the associated Arrhenius factor are strongly correlated. Hence, the parameters which determine the temperature dependence of the reaction rate have not been resolved independently. Furthermore, the kinetic results are very sensitive to the presence of a distribution of activation energies in kerogen breakdown. This distribution is not constrained by the data. As a consequence, neglecting the consideration of distributions of activation energies results in activation parameter values which are much too low. This is the major reason for the commonly encountered discrepancy between kinetic parameter values obtained from hydrous pyrolysis and micropyrolysis experiments, respectively.     

Magma influx and mixing in the Bjerkreim-Sokndal layered intrusion, South Norway: evidence from the boundary between two megacyclic units at Storeknuten

The Bjerkreim-Sokndal layered intrusion belongs to the Proterozoic anorthositic province in the Rogaland area of southern Norway. The northwestern part of the intrusion comprises a ca. 6 km-thick Layered Series made up of megacyclic units (MCU) arranged in a syncline; each megacyclic unit reflects the influx of fresh magma into the chamber. The boundary between megacyclic units III and IV has been studied in detail at Storeknuten on the southern flank of the syncline. The megacyclic units can be subdivided into a series of cumulate stratigraphic zones; the interval from the top of zone IIIe to the base of zone IVd is exposed in the Storeknuten area. Modally layered plagioclase-hypersthene-ilmenite-magnetite-augite-apatite cumulates belonging to zone IIIe are overlain by 30 m of massive plagioclase-rich rocks (commonly containing ilmenite and/or hypersthene) constituting zone IVa. The entry of cumulus olivine defines the base of zone IVb (dominantly plagioclase-olivine-ilmenite cumulates) which is about 100 m thick. Many of the olivines are partly or completely replaced by Ca-poor pyroxene/Fe---Ti oxide symplectites. This massive leucotroctolitic zone is overlain by modally layered, laminated plagioclase-hypersthene-ilmenite cumulates of zone IVc. The successive entry of magnetite, apatite (accompanied by Ca-rich pyroxene) and inverted pigeonite defines zones IVd, e and f respectively. The entry of K-feldspar (accompanied by Fe-rich olivine) defines the base of a jotunitic transition zone which passes upwards into mangerites and quartz mangerites.

There is a compositional regression through zone IVa. The upper part of zone IIIe has Ca-poor pyroxene with about En68, plagioclase with An44–48 and a Sr-isotope ratio of about 0.7062, while the base of zone IVb has olivine with Fo75 together with En78, An53 and 0.7050 respectively. Similar reversals are shown by the minor element compositions of plagioclase and Fe---Ti oxides. Sr-isotope ratios increase systematically up through zone IVb (reaching 0.7058 in zone IVd) while An% and Sr in plagioclase and Ni and Cr in Fe---Ti oxides decrease. Olivine compositions vary unsystematically and are believed to have changed their Fe:Mg ratios as a result of trapped liquid shift.

The magma residing in the chamber when the influx at the base of megacyclic unit IV took place was compositionally zoned, and assimilation of gneissic country rock at the roof had resulted in the Sr-isotope ratio increasing up through the magma column. The new magma had a Sr-isotope ratio of about 0.7050 while the resident magma had a ratio of 0.7062 at the floor, increasing upwards. The new magma mixed with the basal layer(s) of the compositionally zoned resident magma and crystallization of this hybrid magma during influx and mixing produced the compositional regression in zone IVa. When magma influx ceased, olivine-bearing rocks began to crystallize at the base of zone IVb. The leucotroctolites at the base of this zone are the most primitive rocks in the entire intrusion. The systematic increase in Sr-isotope ratios up through zone IVb resulted from progressive mixing between new and resident magma. This mixing either took place during magma influx or by the progressive mixing of overlying resident magma layers during crystallization.

Calculations based on geochemical modelling, the thickness of cumulate stratigraphy repeated and Sr-isotope ratios indicate that the new magma influx had a thickness of 350–500 m in the Storeknuten section and that the leucotroctolites of zone IVb represent about 20–30% crystallization of this influx.     

basin%Ro: A vitrinite reflectance model derived from basin and laboratory data

The combination of vitrinite reflectance, apatite fission track and present‐day borehole temperature data is very useful when performing tectonic and thermal reconstructions in sedimentary basins which, in turn, are essential for assessing risk in hydrocarbon exploration and for testing hypotheses of basin evolution. Releasing the full potential of the combined data set requires that the predictive models are accurate in themselves. Here, we calibrate a new kinetic vitrinite reflectance model ‘basin%R_o’ using borehole data from a number of sedimentary basins and vitrinite reflectance data from laboratory maturation experiments. The entire data set is inverted for the kinetic parameters of the reflectance model under consideration of uncertainty in the temperature histories of the calibration samples. The method is not sensitive to inconsistent calibration data, which are revealed by significant corrections to the temperature histories. The performance of the model is tested on independent well data from the East China Sea and the Nova Scotian Shelf. The widely used easy%R_o‐model overestimates vitrinite reflectance in the interval 0.5–1.7% R_o by up to 0.35%. Delimiting of oil generating intervals by prediction of vitrinite reflectance may lead to significant underestimation of the generative potential, which may call for a revision of some petroleum systems. The overestimation by easy%R_o may have fuelled the idea of pressure retardation of vitrinite reflectance evolution under sedimentary basin conditions, where pressures in fact are too low for this to be important.     

Inferring organic content of sediments by scanning reflectance spectroscopy (380–730 nm): applying a novel methodology in a case study from proglacial lakes in Norway

Reflectance spectroscopy in the visible spectrum (VIS-RS) is a method that has been successfully applied for inferring organic content of sediments. In this study, we test the applicability of VIS-RS to lake sediments in Norway. On the one hand we use conventional, established algorithms for inferring organic content of sediments, on the other hand we test the potential of multivariate calibration techniques to infer organic content. For absolute quantification of organic content, conventional C_org measurements are needed when using conventional algorithms as well as when employing multivariate calibration techniques. Both, conventional algorithms and multivariate calibrations, result in estimates of organic content closely mirroring loss-on-ignition measurements. When using multivariate calibration techniques, a conventional C_org measurement every 5 cm is sufficient to obtain estimates of organic matter that are more accurate than those obtained by means of conventional algorithms. Therefore, the potential of multivariate calibration techniques and VIS-RS to substitute measurements of more time consuming and costly sediment parameters (e.g. clay minerals) should be tested.     

Commuting behaviour and urban form: a longitudinal study of a polycentric urban region in Denmark

This paper is an empirical investigation of the relation between urban form and commuting behaviour in a polycentric urban region. It explores to what extent urban form and location variables help to explain commuting time, distance and mode based on an empirical case, East Jutland, which is a polycentric urban region in Denmark. Data from the National Transport Survey of Denmark were used for this quantitative analysis and two time periods were selected to highlight any potential changes over time. Empirical findings indicate that urban form and location variables help to explain the three selected aspects of commuting. However, urban form variables have greater explanatory power in explaining commuting modes than commuting time and commuting distance. No general trends in commuting were detectable from the data. Finally, the empirical findings revealed specificities of the case study. For instance, two of the important findings are that the distance to the closest urban centre is an important factor which affects the three selected aspects of commuting, while the distance from the residence to the closest large city (i.e. second-ranked city) is associated with a relatively short commuting distance in East Jutland.     

Documentation and evaluation of the CSE NOAA AVHRR data set

A NOAA AVHRR data set covering Senegal and parts of the surrounding countries during the period from 1987 to present is under construction and improvement in an ongoing collaboration between Centre de Suivi Écologique (CSE). Dakar. Senegal, and Institute of Geography, University of Copenhagen (IGUC). This paper details the entire processing chain from raw images to a properly calibrated, geometrically rectified and cloud-masked time-series tracking a number of well-defined variables. Two vital aspects of this time series, the cloud masking procedure and the geometrical rectification, are evaluated in detail. A two-step, multi-criteria cloud masking procedure requiring a manual input does not consistently improve the quality of the data set compared to the simpler, automated procedure. With respect to geometrical rectification an accuracy on the order of I km is obtained. Finally, suggestions for further improving the data set are forwarded