Application of reactive fluid transport modeling to hydrothermal systems

A one-dimensional multi-component reactive fluid transport algorithm, 1DREACT (Steefel, 1993) was used to investigate different fluid-rock interaction systems. A major short coming of mass transport calculations which include mineral reactions is that solid solutions occurring in many minerals are not treated adequately. Since many thermodynamic models of solid solutions are highly non-linear, this can seriously impact on the stability and efficiency of the solution algorithms used. Phase petrology community saw itself faced with a similar predicament 10 years ago. To improve performance and reliability, phase equilibrium calculations have been using pseudo compounds. The same approach is used here in the first, using the complex plagioclase solid solution as an example. Thermodynamic properties of a varying number of intermediate plagioclase phases were calculated using ideal molecular, Al-avoidance, and non-ideal mixing models. These different mixing models can easily be incorporated into the simulations without modification of the transport code. Simulation results show that as few as nine intermediate compositions are sufficient to characterize the diffusional profile between albite and anorthite. Hence this approach is very efficient, and can be used with little effort. A subsequent chapter reports the results of reactive fluid transport modeling designed to constrain the hydrothermal alteration of Paleoproterozoic sediments of the Southern Lake Superior region. Field observations reveal that quartz-pyrophyllite (or kaolinite) bearing assemblages have been transformed into muscovite-pyrophyllite-diaspore bearing assemblages due to action of fluids migrating along permeable flow channels. Fluid-rock interaction modeling with an initial qtz-prl assemblage and a K-rich fluid simulates the formation of observed mineralogical transformation. The bulk composition of the system evolves from an SiO2-rich one to an Al2O3+K2O-rich one. Simulations show that the fluid flow was up-temperature (e.g. recharge) and that fluid was K-rich. Pseudo compound approach to include solid solutions in reactive transport models was tested in modeling hydrothermal alteration of Icelandic basalts. Solid solutions of chlorites, amphiboles and plagioclase were included as the secondary mineral phases. Saline and fresh water compositions of geothermal fluids were used to investigate the effect of salinity on alteration. Fluid-rock interaction simulations produce the observed mineral transformations. They show that roughly the same alteration minerals are formed due to reactions with both types of fluid which is in agreement with the field observations. A final application is directed towards the remediation of nitrate rich groundwaters. Removal of excess nitrate from groundwater by pyrite oxidation was modeled using the reactive fluid transport algorithm. Model results show that, when a pyrite-bearing, permeable zone is placed in the flow path, nitrate concentration in infiltrating water can be significantly lowered, in agreement with proposals from the literature. This is due to nitrogen reduction. Several simulations investigate the efficiency of systems with different mineral reactive surface areas, reactive barrier zone widths, and flow rates to identify the optimum setup.

Investigations on maar-diatreme volcanoes by inversion of magnetic and gravity data from the Eifel area, Germany

A study of maar-diatreme volcanoes has been perfomed by inversion of gravity and magnetic data. The geophysical inverse problem has been solved by means of the damped nonlinear least-squares method. To ensure stability and convergence of the solution of the inverse problem, a mathematical tool, consisting in data weighting and model scaling, has been worked out. Theoretical gravity and magnetic modeling of maar-diatreme volcanoes has been conducted in order to get information, which is used for a simple rough qualitative and/or quantitative interpretation. The information also serves as a priori information to design models for the inversion and/or to assist the interpretation of inversion results. The results of theoretical modeling have been used to roughly estimate the heights and the dip angles of the walls of eight Eifel maar-diatremes — each taken as a whole. Inversemodeling has been conducted for the Schönfeld Maar (magnetics) and the Hausten-Morswiesen Maar (gravity and magnetics). The geometrical parameters of these maars, as well as the density and magnetic properties of the rocks filling them, have been estimated. For a reliable interpretation of the inversion results, beside the knowledge from theoretical modeling, it was resorted to other tools such like field transformations and spectral analysis for complementary information. Geologic models, based on thesynthesis of the respective interpretation results, are presented for the two maars mentioned above. The results gave more insight into the genesis, physics and posteruptive development of the maar-diatreme volcanoes. A classification of the maar-diatreme volcanoes into three main types has been elaborated. Relatively high magnetic anomalies are indicative of scoria cones embeded within maar-diatremes if they are not caused by a strong remanent component of the magnetization. Smaller (weaker) secondary gravity and magnetic anomalies on the background of the main anomaly of a maar-diatreme — especially in the boundary areas — are indicative for subsidence processes, which probably occurred in the late sedimentation phase of the posteruptive development. Contrary to postulates referring to kimberlite pipes, there exists no generalized systematics between diameter and height nor between geophysical anomaly and the dimensions of the maar-diatreme volcanoes. Although both maar-diatreme volcanoes and kimberlite pipes are products of phreatomagmatism, they probably formed in different thermodynamic and hydrogeological environments. In the case of kimberlite pipes, large amounts of magma and groundwater, certainly supplied by deep and large reservoirs, interacted under high pressure and temperature conditions. This led to a long period phreatomagmatic process and hence to the formation of large structures. Concerning the maar-diatreme and tuff-ring-diatreme volcanoes, the phreatomagmatic process takes place due to an interaction between magma from small and shallow magma chambers (probably segregated magmas) and small amounts of near-surface groundwater under low pressure and temperature conditions. This leads to shorter time eruptions and consequently to structures of smaller size in comparison with kimberlite pipes. Nevertheless, the results show that the diameter to height ratio for 50% of the studied maar-diatremes is around 1, whereby the dip angle of the diatreme walls is similar to that of the kimberlite pipes and lies between 70 and 85°. Note that these numerical characteristics, especially the dip angle, hold for the maars the diatremes of which — estimated by modeling — have the shape of a truncated cone. This indicates that the diatreme can not be completely resolved by inversion.

Numerical analysis of the relation between interactions and structure in a molecular fluid

Coarse graining is a popular technique used in physics to speed up the computer simulation of molecular fluids. An essential part of this technique is a method that solves the inverse problem of determining the interaction potential or its parameters from the given structural data. Due to discrepancies between model and reality, the potential is not unique, such that stability of such method and its convergence to a meaningful solution are issues.rnrnIn this work, we investigate empirically whether coarse graining can be improved by applying the theory of inverse problems from applied mathematics. In particular, we use the singular value analysis to reveal the weak interaction parameters, that have a negligible influence on the structure of the fluid and which cause non-uniqueness of the solution. Further, we apply a regularizing Levenberg-Marquardt method, which is stable against the mentioned discrepancies. Then, we compare it to the existing physical methods - the Iterative Boltzmann Inversion and the Inverse Monte Carlo method, which are fast and well adapted to the problem, but sometimes have convergence problems.rnrnFrom analysis of the Iterative Boltzmann Inversion, we elaborate a meaningful approximation of the structure and use it to derive a modification of the Levenberg-Marquardt method. We engage the latter for reconstruction of the interaction parameters from experimental data for liquid argon and nitrogen. We show that the modified method is stable, convergent and fast. Further, the singular value analysis of the structure and its approximation allows to determine the crucial interaction parameters, that is, to simplify the modeling of interactions. Therefore, our results build a rigorous bridge between the inverse problem from physics and the powerful solution tools from mathematics. rn