Electronic environments of ferrous iron in rhyolitic and basaltic glasses at high pressure

The physical properties of silicate melts within Earth's mantle affect the chemical and thermal evolution of its interior. Chemistry and coordination environments affect such properties. We have measured the hyperfine parameters of iron-bearing rhyolitic and basaltic glasses up to ~120 GPa and ~100 GPa, respectively, in a neon pressure medium using time domain synchrotron Mössbauer spectroscopy. The spectra for rhyolitic and basaltic glasses are well explained by three high-spin Fe^(2+)-like sites with distinct quadrupole splittings. Absence of detectable ferric iron was confirmed with optical absorption spectroscopy. The sites with relatively high and intermediate quadrupole splittings are likely a result of fivefold and sixfold coordination environments of ferrous iron that transition to higher coordination with increasing pressure. The ferrous site with a relatively low quadrupole splitting and isomer shift at low pressures may be related to a fourfold or a second fivefold ferrous iron site, which transitions to higher coordination in basaltic glass, but likely remains in low coordination in rhyolitic glass. These results indicate that iron experiences changes in its coordination environment with increasing pressure without undergoing a high-spin to low-spin transition. We compare our results to the hyperfine parameters of silicate glasses of different compositions. With the assumption that coordination environments in silicate glasses may serve as a good indicator for those in a melt, this study suggests that ferrous iron in chemically complex silicate melts likely exists in a high-spin state throughout most of Earth's mantle

A Synchrotron Mössbauer Spectroscopy Study of a Hydrated Iron-Sulfate at High Pressures

Szomolnokite is a monohydrated ferrous iron sulfate mineral, FeSO₄·H₂O, where the ferrous iron atoms are in octahedral coordination with four corners shared with SO4 and two with H₂O groups. While somewhat rare on Earth, szomolnokite has been detected on the surface of Mars along with several other hydrated sulfates and is suggested to occur near the surface of Venus. Previous measurements have characterized the local environment of the iron atoms in szomolnokite using Mössbauer spectroscopy at a range of temperatures and 1 bar. Our study represents a step towards understanding the electronic environment of iron in szomolnokite under compression at 300 K. Using a hydrostatic helium pressure-transmitting medium, we explored the pressure dependence of iron’s site-specific behavior in a synthetic szomolnokite powdered sample up to 95 GPa with time-domain synchrotron Mössbauer spectroscopy. At 1 bar, the Mössbauer spectrum is well described by two Fe²⁺-like sites and no ferric iron, consistent with select conventional Mössbauer spectra evaluations. At pressures below 19 GPa, steep gradients in the hyperfine parameters are most likely due to a structural phase transition. At 19 GPa, a fourth site is required to explain the time spectrum with increasing fractions of a low quadrupole splitting site, which could indicate the onset of another transition. Above 19 GPa we present three different models, including those with a high- to low-spin transition, that provide reasonable scenarios of electronic environment changes of the iron in szomolnokite with pressure. We summarize the complex range of Fe²⁺ spin transition characteristics at high-pressures by comparing szomolnokite with previous studies on ferrous-iron bearing phases

Electronic environments of ferrous iron in rhyolitic and basaltic glasses at high pressure

The physical properties of silicate melts within Earth's mantle affect the chemical and thermal evolution of its interior. Chemistry and coordination environments affect such properties. We have measured the hyperfine parameters of iron-bearing rhyolitic and basaltic glasses up to ~120 GPa and ~100 GPa, respectively, in a neon pressure medium using time domain synchrotron Mössbauer spectroscopy. The spectra for rhyolitic and basaltic glasses are well explained by three high-spin Fe^(2+)-like sites with distinct quadrupole splittings. Absence of detectable ferric iron was confirmed with optical absorption spectroscopy. The sites with relatively high and intermediate quadrupole splittings are likely a result of fivefold and sixfold coordination environments of ferrous iron that transition to higher coordination with increasing pressure. The ferrous site with a relatively low quadrupole splitting and isomer shift at low pressures may be related to a fourfold or a second fivefold ferrous iron site, which transitions to higher coordination in basaltic glass, but likely remains in low coordination in rhyolitic glass. These results indicate that iron experiences changes in its coordination environment with increasing pressure without undergoing a high-spin to low-spin transition. We compare our results to the hyperfine parameters of silicate glasses of different compositions. With the assumption that coordination environments in silicate glasses may serve as a good indicator for those in a melt, this study suggests that ferrous iron in chemically complex silicate melts likely exists in a high-spin state throughout most of Earth's mantle

Earth's volatile depletion trend is consistent with a high-energy Moon-forming impact

International audienceThe abundance of volatile elements in the silicate Earth relative to primitive chondrites provides an important constraint on the thermochemical evolution of the planet. However, an overabundance of indium relative to elements with similar nebular condensation temperatures is a source of debate. Here we use ab initio molecular dynamics simulations to explore the vaporization behavior of indium from pyrolite melt at conditions of the early magma ocean just after the Moon-forming impact. We then compare this to the vaporization behavior of other minor elements. When considering the volatility of the elements from the magma ocean in the absence of the solar nebula gas, we find that there is no overabundance of indium. On the contrary, there is a slight deficit in the abundance of indium, which is consistent with its moderately siderophile nature. Thus, we propose that a high-energy Moon-forming impact may have had a more significant contribution to volatile depletion than previously believed

Ab initio study of the structure and stability of CaMg(CO_3)_2 at high pressure

Dolomite is one of the major mineral forms in which carbon is subducted into the Earth’s mantle. End-member CaMg(CO_3)_2 dolomite typically breaks down upon compression into two carbonates at 5–6 GPa in the temperature range of 800–1200 K (Shirasaka et al. 2002). However, high-pressure X-ray diffraction experiments have shown that dense high-pressure polymorphs of dolomite may be favored over single-cation carbonates (Santillán et al. 2003; Mao et al. 2011; Merlini et al. 2012). Here we compare calculated dolomite structures to experimentally observed phases. Using density functional theory interfaced with a genetic algorithm that predicts crystal structures (USPEX), a monoclinic phase with space group C2/c was found to have lower energy at pressures above 15 GPa than all previously reported dolomite structures. It is possible that this phase is not observed experimentally due to a large activation energy of transition from dolomite I, resulting in the observed second-order phase transition to a metastable dolomite II. Due to the complex energy landscape for candidate high-pressure dolomite structures, several structurally unique metastable polymorphs exist. We calculate the equation of state of a set of lowest-energy dolomite polymorphs with space groups P1, P2/c, and C2/c up to 80 GPa. Our results demonstrate a need for calculations and experiments on Fe-Mn bearing high-pressure carbonate phases to extend our understanding of Earth’s deep carbon cycle and test whether high-pressure polymorphs of double-cation carbonates represent the main reservoir for carbon storage within downwelling regions of Earth’s mantle

Ab initio study of the structure and stability of CaMg(CO_3)_2 at high pressure

Dolomite is one of the major mineral forms in which carbon is subducted into the Earth’s mantle. End-member CaMg(CO_3)_2 dolomite typically breaks down upon compression into two carbonates at 5–6 GPa in the temperature range of 800–1200 K (Shirasaka et al. 2002). However, high-pressure X-ray diffraction experiments have shown that dense high-pressure polymorphs of dolomite may be favored over single-cation carbonates (Santillán et al. 2003; Mao et al. 2011; Merlini et al. 2012). Here we compare calculated dolomite structures to experimentally observed phases. Using density functional theory interfaced with a genetic algorithm that predicts crystal structures (USPEX), a monoclinic phase with space group C2/c was found to have lower energy at pressures above 15 GPa than all previously reported dolomite structures. It is possible that this phase is not observed experimentally due to a large activation energy of transition from dolomite I, resulting in the observed second-order phase transition to a metastable dolomite II. Due to the complex energy landscape for candidate high-pressure dolomite structures, several structurally unique metastable polymorphs exist. We calculate the equation of state of a set of lowest-energy dolomite polymorphs with space groups P1, P2/c, and C2/c up to 80 GPa. Our results demonstrate a need for calculations and experiments on Fe-Mn bearing high-pressure carbonate phases to extend our understanding of Earth’s deep carbon cycle and test whether high-pressure polymorphs of double-cation carbonates represent the main reservoir for carbon storage within downwelling regions of Earth’s mantle