Mesoarchean Microbial Cd, Ba, and Ni Cycling: Evidence for Photosynthesis in Pongola Group Stromatolites through Novel Stable Isotopes and High-Resolution Trace Element Maps.

Nontraditional stable isotopes of bioactive metals emerged as novel proxies for reconstructing the biogeochemical cycling of metals, which serve as cofactors in major metabolic pathways. The fractionation of metal isotopes between ambient fluid and microorganisms is ultimately recorded in authigenic minerals, such as carbonates, which makes them potentially more reliable than standard biomarkers in organic matter. Stromatolitic carbonates are geochemical archives that allow for the study of the long-term interplay of the biosphere, atmosphere, and hydrosphere through deep time, with the unique potential to investigate early life environments and the evolution of the metallome. The present study uses stromatolites from the ∼2.95-billion-year-old Pongola Supergroup (S. Africa) as a field laboratory for combined in situ trace metal mapping and layer-specific, novel stable metal isotope compositions to infer early Earth microbial metal cycling via phototrophic and chemo-litho-autotrophic metabolisms. Quantitative in situ trace element maps reveal intrinsic biosedimentary enrichments of nickel (Ni), cadmium (Cd), phosphorus (P), iron (Fe), and manganese (Mn) in stromatolitic laminae. In contrast, barium (Ba) shows a more homogeneous distribution. Authigenic carbonates from pristine stromatolite laminae show distinct δ¹³⁸Ba and δ¹¹²Cd fractionation above detrital background and bulk silicate Earth values, but opposing correlation with trace metal concentrations. Authigenic δ⁶⁰Ni values overlap with Mesoarchean diamictite compositions. Nickel isotopic compositions in authigenic stromatolitic carbonates, potentially a new proxy for methanogenic metal uptake, do not show any proof of the presence of this metabolism in the samples of this study. Meanwhile, Cd isotopic compositions in authigenic carbonates follow typical Rayleigh-type isotope fractionation; that is, the isotopic composition of Cd evolves to heavy values close to modern surface compositions. Correlations of δ¹¹²Cd with the micronutrients copper (Cu), molybdenum (Mo), and P, at positively fractionated carbon (C) isotopes (δ¹³C ∼+2‰), argue for active photosynthesis in the Pongola microbial habitat. We show that Ba isotopes can be used to infer carbonate precipitation rates similar to modern microbial carbonates. Thus, the combination of Cd and Ni isotopes has the unique potential as novel isotope biomarkers for the biochemical sedimentary record of early Earth where traditional lipid biomarkers are not applicable due to the incomplete preservation of organic matter.