Biogeochemical processes involving dissolved CO2 and CH4 at Albano, Averno, and Monticchio meromictic volcanic lakes (Central-Southern Italy)

This paper focuses on the chemical and isotopic features of dissolved gases (CH4 and CO2) from four meromictic lakes hosted in volcanic systems of Central–Southern Italy: Lake Albano (Alban Hills), Lake Averno (Phlegrean Fields), and Monticchio Grande and Piccolo lakes (Mt. Vulture). Deep waters in these lakes are characterized by the presence of a significant reservoir of extraatmospheric dissolved gases mainly consisting of CH4 and CO2. The δ13C-CH4 and δD-CH4 values of dissolved gas samples from the maximum depths of the investigated lakes (from −66.8 to −55.6‰ V-PDB and from −279 to −195‰ V-SMOW, respectively) suggest that CH4 is mainly produced by microbial activity. The δ13C-CO2 values of Lake Grande, Lake Piccolo, and Lake Albano (ranging from −5.8 to −0.4‰ V-PDB) indicate a significant CO2 contribution from sublacustrine vents originating from (1) mantle degassing and (2) thermometamorphic reactions involving limestone, i.e., the same CO2 source feeding the regional thermal and cold CO2-rich fluid emissions. In contrast, the relatively low δ13C-CO2 values (from −13.4 to −8.2‰ V-PDB) of Lake Averno indicate a prevalent organic CO2. Chemical and isotopic compositions of dissolved CO2 and CH4 at different depths are mainly depending on (1) CO2 inputs from external sources (hydrothermal and/or anthropogenic); (2) CO2–CH4 isotopic exchange; and (3) methanogenic and methanotrophic activity. In the epilimnion, vertical water mixing, free oxygen availability, and photosynthesis cause the dramatic decrease of both CO2 and CH4 concentrations. In the hypolimnion, where the δ13C-CO2 values progressively increase with depth and the δ13C-CH4 values show an opposite trend, biogenic CO2 production from CH4 using different electron donor species, such as sulfate, tend to counteract the methanogenesis process whose efficiency achieves its climax at the water–bottom sediment interface. Theoretical values, calculated on the basis of δ13C-CO2 values, and measured δ13CTDIC values are not consistent, indicating that CO2 and the main carbon-bearing ion species (HCO3−) are not in isotopic equilibrium, likely due to the fast kinetics of biochemical processes involving both CO2 and CH4. This study demonstrates that the vertical patterns of the CO2/CH4 ratio and of δ13C-CO2 and δ13C-CH4 are to be regarded as promising tools to detect perturbations, related to different causes, such as changes in the CO2 input from sublacustrine springs, that may affect aerobic and anaerobic layers of meromictic volcanic lakes.