Y/Ho ratios in marine sediments unveil Neoproterozoic ocean acidification

Understanding Precambrian seawater pH is critical for unraveling Earth's early marine environments and biospheric evolution. Yet, quantitative constraints remain elusive due to the lack of robust proxies. Here, we demonstrate that yttrium/holmium (Y/Ho) fractionation during adsorption onto marine sediments serves as a novel and reliable pH proxy. Experimental results reveal that Y/Ho fractionation in ferruginous sediments follows a pH-dependent power-law relationship, while in argillaceous sediments, it is jointly controlled by pH and salinity at low salinities (<29‰) but stabilizes (Kd_Y/Ho ≈ 0.4) at higher salinities (≥29‰). Temperature exerts a negligible influence, ensuring broad applicability across geological timescales. Leveraging these relationships, we develop a quantitative method to reconstruct paleo-seawater pH using Y/Ho ratios from coexisting ferruginous and argillaceous sediments. Validation against modern and Phanerozoic records confirms the proxy's accuracy (e.g., pH 8.21 ± 0.22 for modern Pacific sediments). Application to Neoproterozoic meta-pelites and iron formations reveals prolonged oceanic acidification (pH 5.9-6.4), deviating from previous model-based neutral-to-alkaline estimates. This acidic state, likely sustained by CO₂ outgassing from carbonatite-alkaline volcanism during Rodinia's breakup, challenges conventional views of Precambrian ocean chemistry. Our findings provide a transformative tool for probing early Earth's environmental dynamics and highlight the interplay between tectonics, magmatism, and marine pH evolution.