Synchrotron-based P K-edge XANES spectroscopy reveals the transition of phosphorus cycling in the early Cambrian ocean

Abstract

Phosphorus, as a long-term limiting nutrient, is essential for the rapid animal diversification in the early Cambrian ocean. However, the widespread occurrence of phosphorites during this period indicates anomalous phosphorus cycling mechanisms that remain inadequately explored. To investigate the interplay between marine redox conditions and phosphorus cycling, we used geochemical proxies and synchrotron-based P K-edge X-ray Absorption Near Edge Structure (XANES) spectroscopy to analyze the Cambrian Terreneuvian Yurtus Formation (Fortunian to Stage 2) from the Tarim Block. Redox-sensitive elements, iron speciation and nitrogen isotopes reveal an expansion of the surface oxygenated waters, despite persistent ferruginous bottom waters. Moreover, a shift of phosphorus speciation was observed in bedded cherts via P K-edge XANES, suggesting a transition of phosphorus cycling. Specifically, the samples exhibit low total phosphorus contents with a high rate of carbonate-fluorapatite authigenesis in the lower Yurtus Formation. This is followed by an increase in the proportion of terrestrial-derived fluorapatite and iron-bound phosphorus, corresponding to the expansion of surface oxygenated waters. Our findings reveal a significant shift in dominant phosphorus speciation in the early Cambrian marine sediments, which is intricately linked to the coupled phosphorus‑iron‑carbon‑oxygen cycles in the Cambrian ocean.