Phosphate oxygen isotopes constrain Mesoproterozoic marine temperatures and the paucity of phosphorite

Phosphorus (P) is an essential element for life, and the oceanic P cycle is closely coupled with the global carbon and oxygen cycles via the role of P as a limiting nutrient. Since P has only one stable isotope, tracking the P cycle through geological history is challenging. However, phosphate oxygen isotopes (δO) represent a valuable tool for deciphering various P-related reactions, such as intracellular P turnover and enzymatic P regeneration, and have been successfully applied to modern soils and marine sediments. The marine P cycle prior to the Neoproterozoic Era remains controversial due to the scarcity of phosphorite and large uncertainties in estimating seawater phosphate levels. Here, we present δO of carbonate fluorapatite (CFA) from the Mesoproterozoic Gaoyuzhuang and Xiamaling Formations in North China. Despite considerable uncertainties, the derived authigenic δO values are markedly lower than those from modern sites with similar depth and latitude, which imply a warmer climate during the Mesoproterozoic Era compared to the present day. Based on thermodynamic calculations of saturation state with respect to CFA, we suggest that the elevated temperatures could have hindered P authigenesis, partially accounting for the general absence of phosphorite in contemporaneous successions.