Stable carbon isotope composition and concentrations of CO2 and CH4 in the deep catotelm of a peat bog

Vertical profiles of concentration and C-isotopic composition of dissolved methane and carbon dioxide were observed over 26 months in the catotelm of a deep (6.5 m) peat bog in Switzerland. The dissolved concentrations of these gases increase with depth while CO2 predominates over CH4 (CO2 ca. 5 times CH4). This pattern can be reproduced by a reaction–advection–ebullition model, where CO2 and CH4 are formed in a ratio of 1:1. The less soluble methane is preferentially lost via outgassing (bubbles). The isotopic fractionation between CO2 and CH4 also increases with depth, with αC values ranging from 1.045 to 1.075. The isotopic composition of the gases traces the passage of respiration-derived CO2 (from the near surface) through a shallow zone with methanogenesis of low isotopic fractionation (splitting of fermentation-derived acetate). This solution then moves through the catotelm, where methanogenesis occurs by CO2 reduction (large isotopic fractionation). In the upper part of the catotelm the C-13-depleted respiration-derived CO2 pool buffers the isotopic composition of CO2; the δ13C of CO2 increases only slowly. At the same time strongly depleted CH4 is formed as CO2 reduction consumes the depleted CO2. In the lower part of the catotelm, the respiration-derived CO2 and shallow CH4 become less important and CO2 reduction is the dominant source of CO2 and CH4. Now, the δ13C values of both gases increase until equilibrium is reached with respect to the isotopic composition of the substrate. Thus, the δ13C values of methane reach a minimum at intermediate depth, and the deep methane has δ13C values comparable to shallow methane. A simple mixing model for the isotopic evolution is suggested. Only minor changes of the observed patterns of methanogenesis (in terms of concentration and isotopic composition) occur over the seasons. The most pronounced of these is a slightly higher rate of acetate splitting in spring.