Molar-Tooth Carbonate: An excellent proxy for reconstructing lithium isotopic composition of Precambrian seawater

Abstract

Shallow water carbonates are extensively utilized as archives for reconstructing past seawater chemistry and understanding global geochemical cycles. However, their reliability is often compromised by diagenetic alteration, obscuring primary environmental signals. Molar-tooth carbonate (MTC) exhibits exceptional resistance to diagenesis compared to other carbonate minerals, making it a promising candidate for reliably reconstructing ancient seawater chemistry. This study investigates the preservation of primary lithium isotopic composition in Neoproterozoic (Tonian) MTC and its host carbonate from the Dalian area, northeastern China (ca. 980 Ma – 920 Ma). We assess the reliability of MTC in reconstructing paleo-seawater δ7Li evolution and provide a reconstruction of Tonian seawater δ7Li.Geochemical filter tests indicate that both MTC and host carbonate remain largely unaltered by meteoric and burial diagenesis. Carbonate δ7Li values exhibit a consistent decrease with stratigraphic height, with MTC displaying a narrower range of variation (4–12‰) compared to its host carbonate (1–15‰). Numerical modeling of early marine carbonate diagenesis suggests minimal impact on MTC δ7Li values, while host carbonates show varying degrees of diagenetic alteration. Based on the consistent Li isotopic offset observed between ‘fluid-buffered’ diagenetic host carbonate and MTC in our data, we deduce a fractionation factor of 4.8 ± 1.2‰ for seawater-MTC Li isotopic exchange.Reconstructed paleoseawater δ7Li values reveal a progressive decrease from 16.9 ± 1.2‰ to 8.8 ± 1.2‰ during the early Tonian period. This change is likely linked to the assembly of the Rodinia supercontinent and emplacement of large igneous province (LIP). Furthermore, mass balance modeling and Monte Carlo simulations suggest that this decline in seawater δ7Li can be attributed to the transition towards more congruent weathering during the early Tonian, facilitated by the assembly of Rodinia and associated large igneous province events.Overall, our findings underscore the potential of MTC as a reliable proxy for elucidating Precambrian seawater Li isotopic composition and understanding associated paleoenvironmental and paleoclimatic changes.