Thermodynamic and kinetic degradation reactions of organic substances in groundwater modelled with PHREEQC

Aim of this diploma thesis is to approach to kinetic modelling of subsurface hydrochemistry with the program code phreeqc. The reaction considered is the degradation of organic mass and its concomitant reactions. Phreeqc is a program for thermodynamical based equilibrium calculations of geo- and hydrochemistry. Although the degradation of organic matter, and the associated reduction reactions due to the oxidation of organic matter, can be modelled with phreeqc, it does not account for kinetically controlled reactions, whose characteristic feature is the dependency of time. This study focuses on the state of the art of environmental modelling, the thermodynamical based calculation of the degradation of organic matter and on two mathematical approaches to model bacterial degradation of a contaminant, the Monod equation and the Michaelis-Menten approach. Sensitivity analyses of the respective models runs were done. As a result one can see, that the redox chemistry of a natural water depends strongly on the abundance of oxygen and nitrate and, as a matter of course, on the abundance of organic matter. Considering bacterial activity within the degradation process, two basic mathematical formulations have been stated. The Monod equation and the Michaelis-Menten formulation were implemented in a BASIC interpreter in PHREEQC. The sensitivity analyses show, that that a accurate determination of the parameters in laboratory or field is essential. The coupling of kinetically controlled reactions and thermodynamical based equilibrium calculations might lead to auspicious hydrochemical modelling capabilities.