Redox control on nitrogen isotope fractionation during planetary core formation

The present-day nitrogen isotopic compositions of Earth's surficial (¹⁵N-enriched) and deep reservoirs (¹⁵N-depleted) differ significantly. This distribution can neither be explained by modern mantle degassing nor recycling via subduction zones. As the effect of planetary differentiation on the behavior of N isotopes is poorly understood, we experimentally determined N-isotopic fractionations during metal-silicate partitioning (analogous to planetary core formation) over a large range of oxygen fugacities (ΔIW -3.1 < logfO₂ < ΔIW -0.5, where ΔIW is the logarithmic difference between experimental oxygen fugacity [fO₂] conditions and that imposed by the coexistence of iron and wüstite) at 1 GPa and 1,400 °C. We developed an in situ analytical method to measure the N-elemental and -isotopic compositions of experimental run products composed of Fe-C-N metal alloys and basaltic melts. Our results show substantial N-isotopic fractionations between metal alloys and silicate glasses, i.e., from -257 ± 22‰ to -49 ± 1‰ over 3 log units of fO₂ These large fractionations under reduced conditions can be explained by the large difference between N bonding in metal alloys (Fe-N) and in silicate glasses (as molecular N₂ and NH complexes). We show that the δ¹⁵N value of the silicate mantle could have increased by ∼20‰ during core formation due to N segregation into the core.