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Carbon-bearing iron phases and the carbon isotope composition of the deep Earth

Significance Due to its bonding environments, carbon can make up numerous compounds with many other elements. However, the abundance and dynamics of carbon in the deep Earth remains uncertain due to its complex behavior during the primary accretion and differentiation of the Earth in its early history. The naturally occurring stable isotopes of carbon serve as a useful tracer to study the carbon cycle, both on the surface and in the deep Earth. Here, a new model is presented for understanding a first-order carbon cycle within the Earth, including the sources of the building blocks and core formation processes. Low carbon isotope compositions of carbonaceous materials from ancient rocks have to be used with a caution as biosignatures. The carbon budget and dynamics of the Earth’s interior, including the core, are currently very poorly understood. Diamond-bearing, mantle-derived rocks show a very well defined peak at δ13C ≈ −5 ± 3‰ with a very broad distribution to lower values (∼−40‰). The processes that have produced the wide δ13C distributions to the observed low δ13C values in the deep Earth have been extensively debated, but few viable models have been proposed. Here, we present a model for understanding carbon isotope distributions within the deep Earth, involving Fe−C phases (Fe carbides and C dissolved in Fe−Ni metal). Our theoretical calculations show that Fe and Si carbides can be significantly depleted in 13C relative to other C-bearing materials even at mantle temperatures. Thus, the redox freezing and melting cycles of lithosphere via subduction upwelling in the deep Earth that involve the Fe−C phases can readily produce diamond with the observed low δ13C values. The sharp contrast in the δ13C distributions of peridotitic and eclogitic diamonds may reflect differences in their carbon cycles, controlled by the evolution of geodynamical processes around 2.5–3 Ga. Our model also predicts that the core contains C with low δ13C values and that an average δ13C value of the bulk Earth could be much lower than ∼−5‰, consistent with those of chondrites and other planetary body. The heterogeneous and depleted δ13C values of the deep Earth have implications, not only for its accretion−differentiation history but also for carbon isotope biosignatures for early life on the Earth.