Metal cycling in Mesoproterozoic microbial habitats: Insights from trace elements and stable Cd isotopes in stromatolites

Abstract

Abstract Reconstructing the environmental conditions that supported early life on Earth relies on well-preserved geochemical archives in the rock record. However, many geochemical tracers either lack specificity or they are affected by post-depositional alteration. We present a data set of major and trace element abundances and Cd isotope compositions of dome-shaped and conophyton-type stromatolites of the Late Mesoproterozoic Paranoa Group (Brazil), showing distinct values with unprecedented resolution at the lamina scale. The studied stromatolites consist of dolomite with a high purity and a negligible content of immobile elements (e.g., Two endmember compositions can be distinguished by multiple proxy analysis, reflecting the contrasting depositional environments of the two types of stromatolites: Shale-normalized rare earth elements including yttrium (REYSN) patterns of domal stromatolites show a light REYSN (LREY) enrichment (YbSN/PrSN\u202f In contrast, REYSN patterns of the conophyta are parallel those of modern seawater with an LREYSN depletion relative to HREYSN (YbSN/PrSN\u202f=\u202f2.1 to 3.9), positive GdSN anomalies (1.1 to 1.4) and strong super-chondritic Y/Ho ratios (37.9 to 46.2), suggesting a microbial habitat that was dominated by seawater. Cd isotopes correlate negatively with Cd and U, but positively with Mn and Ce concentrations, reflecting authigenic carbonate formation at different depths within a redox gradient of the ancient microbial mat. e112/110Cddol values increase from −3.52 at the mat surface to +3.46 in the interior of the mat, due to the effect of kinetic fractionation during Cd-uptake, e.g. by adsorption onto organic matter or by precipitation of sulfides, in addition to incorporation into carbonate minerals. Hence, our multi-proxy approach including Cd isotopes bears a high potential to shed light on environmental conditions in ancient microbial habitats and the activity of microbial life on Early Earth.