Redox control on nitrogen isotope fractionation during planetary core formation

The present-day nitrogen isotopic compositions of Earth’s surficial ((15)N-enriched) and deep reservoirs ((15)N-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 < logfO(2) < ΔIW −0.5, where ΔIW is the logarithmic difference between experimental oxygen fugacity [fO(2)] 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 fO(2). 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 N(2) and NH complexes). We show that the δ(15)N value of the silicate mantle could have increased by ∼20‰ during core formation due to N segregation into the core.