Methodology for construction, calibration and validation of a national hydrological model for Denmark

An integrated groundwater/surface water hydrological model with a 1 km² grid has been constructed for Denmark covering 43,000 km². The model is composed of a relatively simple root zone component for estimating the net precipitation, a comprehensive three-dimensional groundwater component for estimating recharge to and hydraulic heads in different geological layers, and a river component for streamflow routing and calculating stream–aquifer interaction. The model was constructed on the basis of the MIKE SHE code and by utilising comprehensive national databases on geology, soil, topography, river systems, climate and hydrology. The present paper describes the modelling process for the 7330 km² island of Sjælland with emphasis on the problems experienced in combining the classical paradigms of groundwater modelling, such as inverse modelling of steady-state conditions, and catchment modelling, focussing on dynamic conditions and discharge simulation. Three model versions with different assumptions on input data and parameter values were required until the performance of the final, according to pre-defined accuracy criteria, model was evaluated as being satisfactory. The paper highlights the methodological issues related to establishment of performance criteria, parameterisation and assessment of parameter values from field data, calibration and validation test schemes. Most of the parameter values were assessed directly from field data, while about 10 ‘free’ parameters were subject to calibration using a combination of inverse steady-state groundwater modelling and manual trial-and-error dynamic groundwater/surface water modelling. Emphasising the importance of tests against independent data, the validation schemes included combinations of split-sample tests (another period) and proxy-basin tests (another area).     

Stochastic Structural Modeling

A consistent stochastic model for faults and horizons is described. The faults are represented as a parametric invertible deformation operator. The faults may truncate each other. The horizons are modeled as correlated Gaussian fields and are represented in a grid. Petrophysical variables may be modeled in a reservoir before faulting in order to describe the juxtaposition effect of the faulting. It is possible to condition the realization on petrophysics, horizons, and fault plane observations in wells in addition to seismic data. The transmissibility in the fault plane may also be included in the model. Four different methods to integrate the fault and horizon models in a common model is described. The method is illustrated on an example from a real petroleum field with 18 interpreted faults that are handled stochastically.     

Gravity reduction with three-dimensional atmospheric pressure data for precise ground gravity measurements

The redistribution of air masses induces gravity variations (atmospheric pressure effect) up to about 20 μgal. These variations are disturbing signals in gravity records and they must be removed very carefully for detecting weak gravity signals. In the past, different methods have been developed for modelling of the atmospheric pressure effect. These methods use local or two-dimensional (2D) surface atmospheric pressure data and a standard height-dependent air density distribution. The atmospheric pressure effect is consisting of the elastic deformation and attraction term. The deformation term can be well modelled with 2D surface atmospheric pressure data, for instance with the Green's function method. For modelling of the attraction term, three-dimensional (3D) data are required. Results with 2D data are insufficient.From European Centre for Medium-Range Weather Forecasts (ECMWF) 3D atmospheric pressure data are now available. The ECMWF data used here are characterised by a spacing of Δ and Δλ = 0.5°, 60 pressure levels up to a height of 60 km and an interval of 6 h. These data are used for modelling of the atmospheric attraction term. Two attraction models have been developed based on the point mass attraction of air segments and the gravity potential of the air masses. The modelling shows a surface pressure-independent part of gravity variations induced by mass redistribution of the atmosphere in the order of some μgal. This part can only be determined by using 3D atmospheric pressure data. It has been calculated for the Vienna Superconducting Gravimeter site.From this follows that the gravity reduction can be improved by applying the 3D atmospheric attraction model for analysing long-periodic tidal waves including the polar tide. The same improvement is expected for reduction of long-term absolute gravity measurements or comparison of gravity measurements at different seasonal times. By using 3D atmospheric pressure data, the gravity correction can be improved up to some μgal.     

Chemical and isotopic equilibrium between CO2 and CH4 in fumarolic gas discharges: Generation of CH4 in arc magmatic-hydrothermal systems

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH₄) within two subduction-related magmatic-hydrothermal environments.Apparent temperatures derived from carbon isotope partitioning between CH₄ and CO₂ of around 340°C for Nisyros and 470°C for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H₂O-H₂-CO₂-CO-CH₄ geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH₄, CO₂ and H₂O implying that carbon isotope partitioning between CO₂ and CH₄ in both systems is controlled by aquifer temperature.N₂/³He and CH₄/³He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH₄ may have been primarily generated through the reduction of CO₂ by H₂ in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH₄ and subsequent re-equilibration with co-existing CO₂ cannot be ruled out entirely. CO₂/³He ratios and δ¹³C_CO2 values imply that the evolved CO₂ either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH₄ during thermometamorphism.     

A statistical procedure for the analysis of seismotectonically induced hydrochemical signals: A case study from the Eastern Carpathians, Romania

Changes in the stress field of an aquifer system induced by seismotectonic activity may change the mixing ratio of groundwaters with different compositions in a well, leading to hydrochemical signals which in principle could be related to discrete earthquake events. Due to the complexity of the interactions and the multitude of involved factors the identification of such relationships is a difficult task. In this study we present an empiric statistical approach suitable to analyse if there is an interdependency between changes in the chemical composition of monitoring wells and the regional seismotectonic activity of a considered area. To allow a rigorous comparison with hydrochemistry the regional earthquake time series was aggregated into an univariate time series. This was realized by expressing each earthquake in form of a parameter “e”, taking into consideration both energetic (magnitude of a seismic event) and spatial parameters (position of epi/hypocentrum relative to the monitoring site). The earthquake and the hydrochemical time-series were synchronised aggregating the e-parameters into “earthquake activity” functions E, which takes into account the time of sampling relative to the earthquakes which occurred in the considered area. For the definition of the aggregation functions a variety of different “e” parameters were considered. The set of earthquake functions E was grouped by means of factor analysis to select a limited number of significant and representative earthquake functions E to be used further on in the relation analysis with the multivariate hydrochemical data set. From the hydrochemical data a restricted number of hydrochemical factors were extracted. Factor scores allow to represent and analyse the variation of the hydrochemical factors as a function of time. Finally, regression analysis was used to detect those hydrochemical factors which significantly correlate with the aggregated earthquake functions.This methodological approach was tested with a hydrochemical data set collected from a deep well monitored for two years in the seismically active Vrancea region, Romania. Three of the hydrochemical factors were found to correlate significantly with the considered earthquake activities. A screening with different time combinations revealed that correlations are strongest when the cumulative seismicity over several weeks was considered. The case study also showed that the character of the interdependency depends sometimes on the geometrical distribution of the earthquake foci. By using aggregated earthquake information it was possible to detect interrelationships which couldn't have been identified by analysing only relations between single geochemical signals and single earthquake events. Further on, the approach allows to determine the influence of different seismotectonic patterns on the hydrochemical composition of the sampled well. The method is suitable to be used as a decision instrument in assessing if a monitoring site is suitable or not to be included in a monitoring net within a complex earthquake prediction strategy.     

Correlation between hydrogen isotope ratios of lipid biomarkers and sediment maturity

We investigated the influence of thermal maturity on the hydrogen isotope ratios of sedimentary hydrocarbons to prove that the isotope ratio of hydrocarbons mirrors paleoclimate signatures. δD values from n-alkanes and acyclic isoprenoids of two sediment sections (Kupferschiefer [KS], 258 Ma, and Posidonienschiefer [PS], 184 Ma) with different maturation history were investigated. Both covered thermal maturity from 0.48 to 1.3 R_c (vitrinite reflectance and reflectance calculated from MPI1). Sediment burial up to 4500 m caused thermal maturation of organic matter in the KS horizon from the Early Zechstein basin of Poland, whereas contact metamorphic thermal maturation originated in the Early Toarcian PS (Posidonienschiefer) of the North German Vlotho Massif. The δD values of the extracted n-alkanes positively correlate with thermal maturity in the KS (y = 56‰ × MPI1[x] − 160‰ [VSMOW]) and in the PS (y = 104‰ × MPI1[x] − 200‰ [VSMOW]). The δD values of isoprenoids (i.e., pristane, phytane) were even more enriched with increasing maturity (y = 179‰ × MPI1[x] − 341‰ [VSMOW] in the KS; y = 300‰ × MPI1[x] − 415‰ [VSMOW] in PS).These results explain why isotope ratios of n-alkanes and isoprenoids in mature sediments are generally enriched in D and do not have the expected isotopic difference between n-alkanes and isoprenoids of ∼190‰. Moreover, the correlation between sediment maturity parameters and δD values suggests that after correction the δD values of n-alkanes can be used to reconstruct climate and environment in the geological past.