Recognizing microbial manganese reduction in lacustrine carbonate and its linkage to terrestrial biogeochemical processes

Carbonate authigenesis, the in situ precipitation of carbonate minerals within the sediment porewaters, is a key pathway for carbonate deposition and plays a crucial role in global biogeochemical cycles. Heterotrophic microorganisms are essential in regulating authigenic carbonate formation, primarily through the consumption of organic matter. Although bacterial manganese reduction is known to influence the formation of rhodochrosite and dolomite, its role in limestone deposition is unclear. Here, we present a systematic investigation of mixed calcareous siliciclastic rocks from a Paleogene freshwater lake to identify the formation of authigenic carbonate, decode the role of microbial Mn reduction, and understand the microbial response to ancient lacustrine environmental changes. The positive correlation between carbonate fraction in bulk samples (Carb%) and Mn content in carbonate minerals (Mn_carb) suggests that carbonate precipitation is stimulated by Mn²⁺ enrichment. The dissimilarity between Mn_carb and Fe_carb, along with the synergic variations of Mn_carb and diagenetic indicators, support an authigenic rather than a hydrogenetic origin for the carbonates. Using a one-dimensional diffusion–advection-reaction model, we quantify the impact of Mn reduction on promoting carbonate precipitation. Furthermore, correlations between P_carb and other values–positive with the chemical index alteration (CIA), negative with Mn_carb, and none with TOC–suggest that nitrogen availability, regulated by continental weathering, is likely the primary factor limiting both the primary productivity and the bacterial reduction intensity at the study site. Overall, this study uncovers the role of microbial Mn reduction in stimulating authigenic carbonate precipitation, and reveals the modulation mechanism of Mn-reducing microorganisms in an ancient lake. These findings shed new light on the authigenic limestone formation mechanisms and provide a new perspective on interpreting the authigenic impacts on carbonate chemistry.