Exploring uranium isotopes in shark teeth as a paleo-redox proxy

Abstract

The uranium isotope composition (δ238U) of seawater is a powerful proxy for the extent of marine anoxia. For paleoredox reconstructions, carbonates are the most popular U isotope archive, but they have recently come under increased scrutiny as their δ238U values are subject to diagenetic alteration after deposition. Therefore, there is a need to investigate other archives that may record and preserve the original seawater δ238U signal. In this study, we explore whether shark teeth provide such an archive. Shark teeth enameloid consisting of crystalline fluorapatite is more resistant to post-depositional alteration and less sensitive to isotopic exchange than marine carbonates due to the lower solubility of the crystalline fluorapatite. Since U is readily incorporated into phosphate, shark teeth could incorporate and preserve the original δ238U signature of seawater.To assess whether U isotopes in shark teeth can record seawater signatures, we measured the U isotopes (both δ238U and δ234Usec) in 39 fossil shark teeth from various locations, including Banks Island (Arctic), the Gulf of Mexico (GOM), and Pisco Basin (Peru), and ranging in age from modern to Cretaceous. Our results show that U concentrations are negligible in modern shark teeth (<1 ppb) but elevated in fossil samples (up to several hundred ppm), indicating that U is incorporated into shark teeth postmortem during burial. The δ238U values range from −0.72 to +0.57 ‰, and the δ234U values from −162.1 to +969.7 ‰. The data indicate that (i) diagenetic overprinting of seawater U isotope ratios is common among shark teeth, and (ii) δ238U data are influenced by local depositional environments. Nonetheless, the U isotope variations observed in shark teeth are comparable to those seen in marine carbonates, indicating that the samples with less diagenetic alterations might offer useful insight into the past extent of ocean anoxia.