Geochemical evolution of groundwater in sequences of sedimentary rocks

Abstract

A geochemical mass-transfer model (WATEGM-SE) is used to illustrate the effect of several major processes on the chemical evolution of groundwater flowing through hypothetical sequences of sedimentary rocks. Using chemical reactions prevalent in these rock types, the simulations demonstrate the influence of the initial soil P CO 2 , temperature, pressure and the sequence of encounter of the mineral phases along the flow path of the groundwater. The evolution of groundwater in different sequences of limestone and dolostone is simulated with a range of initial P CO 2 -values typical of natural soils. Temperatures of 10° and 25°C are used. The simulations indicate that appreciable differences in the chemical composition of the groundwater and the spring-discharge water will occur, depending on whether a limestone or dolostone unit is first encountered. The cases of more complex stratigraphy are represented by three hypothetical sequences in which each stratum has only one reactive mineral phase. The reactions used in these simulations include calcite dissolution and precipitation, gypsum dissolution and precipitation, cation exchange, and the weathering of albite to kaolinite. Sulfate reduction occurs in the last stratum in each of these sequences. The strata in the three sequences are indentical except for the order in which they are encountered by the groundwater. Considerably different hydrochemistries are calculated for each of these sequences even within the same types of rock units. The effect of increasing total pressure is demonstrated with a water initially saturated with both gypsum and calcite under a pressure of 1 bar. The system is then closed and the pressure is increased to 1 kbar while the temperature remains constant at 25°C. The results indicate that pressure has a significant effect above 50 bar or 500 m hydrostatic head. It is commonly expected that groundwater in sedimentary rocks will exhibit trends in chemistry that are the result of the length of the flow path and the groundwater velocity. The simulated sequences obtained in this study demonstrate that the order in which the various sedimentary strata are encountered by the groundwater and the partial pressure of the CO 2 in the soil zone are important factors. For groundwater systems that are near equilibrium with the host rock, these factors may control the chemical evolution of the water.