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Unlocking Earth's Redox History Through Pyrite Isotopes

**Introduction**

Understanding how Earth’s surface evolved from a no-, or low-oxygen (anoxic) to an oxygen-rich (oxygenated) is one of the great challenges of geoscience. Sedimentary pyrite (FeS₂), commonly known as “fool’s gold,” serves as a crucial archive of these redox transitions. Its iron (Fe) and sulfur (S) isotopic compositions have been used for decades to reconstruct past ocean chemistry and the oxidation state of our planet. However, diagenetic overprints—the chemical changes occurring after sediment deposition—complicate the interpretation of these isotopic records. In our recent study, we tackled this challenge by investigating microscale Fe and S isotope variations in pyrite from the oxic margin of the Black Sea.

**The Science Behind the Study**

Historically, the Black Sea have been used as a unique natural laboratory for studying pyrite formation, because its waters transition from oxic to anoxic conditions at depth. Our study focused on sediment cores from the oxic Romanian shelf, where pyrite formation occurs under contrasting redox conditions. Using a cutting-edge secondary ion mass spectrometer (SIMS), we measured microscale variations in Fe and S isotopes within and among individual pyrite grains. This approach provided unprecedented insights into the pathways of pyrite formation and how they reflect local environmental conditions.

We found that pyrite formed in two distinct stages:

\- Early pyrite: Characterized by low relative abundances of the heavy isotopes of Fe and S, reflecting microbial iron reduction and sulfate reduction in the shallow sediment.

\- Late-stage pyrite: Formed under more sulfur-rich conditions in the zone where seawater sulfate reacts with methane produced deeper within the sediment (the sulfate-methane transition zone or SMTZ), with higher relative abundances of the heavy Fe and S isotopes indicating accumulation of sulfide in the sediment porewater.

 **Why It Matters**

Traditionally, bulk isotopic measurements have been used to infer the ocean chemistry from ancient periods of Earth’s history from which only sedimentary rocks survived. However, our study reveals that pyrite can form through multiple pathways even in a single sedimentary environment, each with distinct isotopic signatures. This finding suggests that past reconstructions based on bulk pyrite data may oversimplify the complexity of early diagenesis, and blurr our view of past conditions on Earth’s surface. By using microscale isotopic analyses, we can refine our interpretations of ancient redox conditions and local environmental parameters and improve our understanding of Earth's biogeochemical evolution.

 **The Journey Behind the Research**

Science is not just about data—it’s also about the process. Collecting sediment cores from the Black Sea required careful planning and collaboration among researchers from multiple institutions. Extracting and preparing pyrite grains for SIMS analysis was meticulous work, but the excitement of seeing the beauty of pyrite made it all worthwhile. Acquiring high-resolution isotopic data for individual pyrite grains was an extremely time-consuming process, often requiring long nights and little sleep—a small sacrifice in the pursuit of good science.

One of the biggest surprises was the discovery that pyrite morphologies changed with depth in the core, strongly correlating with shifts in Fe and S isotope compositions. This reinforced our hypothesis that pyrite grain textures can be used as a proxy for the diagenetic history, opening new doors for sedimentary geochemistry research.

 **Future Directions**

Our study highlights the power of combining microscale isotope analyses with petrographic observations to reconstruct early diagenetic processes. The next steps involve applying this approach to ancient rock formations, allowing us to better distinguish primary environmental signals from diagenetic overprints. By improving our ability to read the isotopic history recorded in pyrite, we move closer to unraveling the complexities of Earth’s oxygenation history.

 **Final Thoughts**

Scientific discovery often lies in the details. By zooming in on individual pyrite grains, we uncovered a previously hidden story of diagenetic alteration and redox cycling in marine sediments. This study serves as a reminder that revisiting established proxies with new techniques can lead to transformative insights into Earth’s past.

We invite the scientific community to explore these findings further, test our interpretations, and refine our collective understanding of how life and the environment co-evolved on our planet.

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