Unité Mixte de Recherche Centre National de la Recherche Scientifique 7590, Institut de Minéralogie et de Physique des Milieux Condensés, Université Pierre et Marie Curie,75005 Paris, France.
Proc Natl Acad Sci U S A. 2011 Mar 29;108(13):5184-7. doi: 10.1073/pnas.1016934108. Epub 2011 Mar 14.
The global geochemical carbon cycle involves exchanges between the Earth's interior and the surface. Carbon is recycled into the mantle via subduction mainly as carbonates and is released to the atmosphere via volcanism mostly as CO(2). The stability of carbonates versus decarbonation and melting is therefore of great interest for understanding the global carbon cycle. For all these reasons, the thermodynamic properties and phase diagrams of these minerals are needed up to core mantle boundary conditions. However, the nature of C-bearing minerals at these conditions remains unclear. Here we show the existence of a new Mg-Fe carbon-bearing compound at depths greater than 1,800 km. Its structure, based on three-membered rings of corner-sharing (CO(4))(4-) tetrahedra, is in close agreement with predictions by first principles quantum calculations [Oganov AR, et al. (2008) Novel high-pressure structures of MgCO(3), CaCO(3) and CO(2) and their role in Earth's lower mantle. Earth Planet Sci Lett 273:38-47]. This high-pressure polymorph of carbonates concentrates a large amount of Fe((III)) as a result of intracrystalline reaction between Fe((II)) and (CO(3))(2-) groups schematically written as 4FeO + CO(2) → 2Fe(2)O(3) + C. This results in an assemblage of the new high-pressure phase, magnetite and nanodiamonds.
全球地球化学碳循环涉及地球内部与地表之间的交换。碳主要以碳酸盐的形式通过俯冲循环到地幔中,并主要以 CO(2)的形式通过火山作用释放到大气中。因此,碳酸盐相对于脱碳和熔融的稳定性对于理解全球碳循环至关重要。出于所有这些原因,需要了解这些矿物在直至地核-地幔边界条件下的热力学性质和相图。然而,在这些条件下含碳矿物的性质仍不清楚。在这里,我们表明在深度大于 1800 公里处存在一种新的含镁-铁的碳化合物。其结构基于共享顶角的三个成员环(CO(4))(4-)四面体,与第一性原理量子计算的预测非常吻合[Oganov AR 等人(2008 年)新型高压结构的 MgCO(3)、CaCO(3)和 CO(2)及其在地球下地幔中的作用。地球行星科学快报 273:38-47]。由于 Fe((II))和(CO(3))(2-)基团之间的晶内反应,这种碳酸盐的高压多晶型物集中了大量的 Fe((III)),反应式可简写为 4FeO + CO(2) → 2Fe(2)O(3) + C。这导致了新的高压相、磁铁矿和纳米金刚石的组合。