LAUSR

Abstract Chemical weathering of sedimentary rocks is of great importance in determining seepage water chemistry, carbon, iron, calcium and sulfur turnover, as well as mineral transformation. In this study, we used the numerical code MIN3P to investigate controls on seepage water chemistry during chemical weathering of marine mudrocks. In particular, we focused on the pyrite- and kerogen-bearing formation, Opalinus Clay (with outcrops in the area of the Swabian and Franconian Alb in Southern Germany), a typical fine-grained sedimentary mudrock that had been deposited during the Middle Jurassic in a shallow marine environment. In the geochemical model we considered four reactive minerals, i.e. , pyrite, kerogen, calcite and siderite (assuming silicate minerals to be stable), and ran model scenarios over a time period of 10 kyrs (since the last ice age). Our numerical results show that chemical weathering of Opalinus Clay is driven by oxygen ingress (which depends on effective gas diffusion, and thus on water saturation). Due to oxidation of pyrite and kerogen seepage water acidifies, which leads to dissolution of carbonate minerals, i.e. , calcite and siderite. As a consequence, porosity and groundwater alkalinity increase, and CO 2 is released into the atmosphere at early decades. Following the consumption of primary reactive minerals, iron oxides precipitate in the oxic zone. We compared our model results with field data of water saturation, porosity, and water chemistry. The overall reasonable fit between model results and field data demonstrates the applicability of the numerical code MIN3P to quantify chemical weathering of pyrite-bearing sedimentary mudrocks and to predict seepage water chemistry that is impacted by geochemical water-rock interactions.