Strontium isotope composition of the lower proterozoic carbonate concretions: The Zaonega Formation,Southeast Karelia

The middle part of the volcanosedimentary Zaonega Formation of the Ludikovian Suprahorizon (approximately 2.0 Ga) includes large carbonates concretions and lenses in shungite layers. Carbonate lenses and concretions are primarily elongated and flattened, and their thickness varies from tens of centimeters to a few meters. Some lenses retain relicts of lamination. Concretions are composed of calcite or dolomite. They contain abundant organic matter, as well as mica, talc, chlorite, quartz, and pyrite crystals. The calcite concretions contain some dolomite admixture (Mg/Ca = 0.011?0.045) and differ from sedimentary limestones by a low Fe/Mn value (0.3–2.1). The Sr content is as much as 385–505 μg/g in most samples and is low (86 μg/g) only in one sample. The Rb-Sr systematics of carbonate concretions was studied with the stepwise dissolution procedure, which included processing with the ammonium acetate solution (AMA fraction) to partially remove the secondary carbonate material, with dissolution of the residue in acetic acid (ACA fraction). In individual calcite samples, discrepancy between the measured ⁸⁷Sr/⁸⁶Sr values in the AMA and ACA calcite fractions shows a variation range of 0.0008–0.0033. The initial ⁸⁷Sr/⁸⁶Sr ratio in the ACA fractions of the studied samples varies from 0.7053 to 0.7162. The ratio shows a positive correlation with Mg/Ca and the proportion of siliciclastic admixture and negative correlation with the Mn content. The concretions were formed when the sediments subsided, probably, during the transition from a zone with “mild” reductive conditions to zones with active sulfate reduction and methanogenesis. In the sulfate reduction zone, where most pyrite-bearing concretions were formed, the sediment was not geochemically exchaged with the bottom water and was evolved into a closed or semiclosed system. Processes of diagenesis in this zone promoted the release of the radiogenic ⁸⁷Sr from the associated siliciclastic minerals, resulting in growth of the initial ⁸⁷Sr/⁸⁶Sr in concretions up to 0.7108–0.7162. Some calcite concretions, which lacked pyrite (or contained its minimal amount) were likely formed in a thin surficial sediment layer located above the sulfate reduction zone. Therefore, they precipitated Sr in isotope equilibrium with Sr of the bottom water. However, large concretions and carbonate lenses with an insignificant siliciclastic admixture could retain the signature of early diagenesis or even sedimentation. The initial ⁸⁷Sr/⁸⁶Sr ratio in one of such samples with the siliciclastic admixture of 6.2% makes it possible to estimate the maximal value of this ratio (0.7053) in the Ludikovian paleobasin.