Raman analyses of single crystals of ikaite, CaCO3-6H(2)O, synthesized in a diamond-anvil cell at ambient temperature yield spectra from 0.14 to 4.08 GPa; the most intense peaks are at 228 and 1081 cm(-1) corresponding to E-g (external) and A(1g) (internal) modes of vibrations in CO32 ions, respectively. These are in good agreement with Raman spectra previously published for ikaite in powder form at ambient temperature and pressure. Visual observations of a sample consisting initially of a mixture of calcite + water in a hydrothermal diamond-anvil cell yielded a P-T phase diagram up to 2 GPa and 120 degrees C; the boundary for the reaction ikaite <-> aragonite + water has a positive slope and is curved convexly toward the aragonite + water field similar to typical melt curves. This curvature can be explained in terms of the Clapeyron equation for a boundary between a solid phase and a more compressible liquid phase or largely liquid phase assemblage.

Electrical resistivity measurements of polycrystalline iron have been performed at 5, 7, and 15 GPa and in the temperature range 293-2200 K by employing a four-wired method. The kinks in electrical resistivity associated with solid iron phase transitions and the solid to liquid transition were clearly observed upon increasing temperature. Geometry corrections due to volume variations with pressure and temperature were applied to the entire data set. High pressure and temperature thermal conductivity were calculated by fitting resistivity data through the Wiedemann-Franz law. The temperature dependences of electrical resistivity and thermal conductivity for alpha, gamma, and epsilon solid iron have been determined at high-pressure conditions. Our study provides the first experimental constraint on the heat flux conducted at Mercury's outmost core, estimated to be 0.29-0.36 TW, assuming an adiabatic core. Extrapolations of our data to Martian outer core conditions yield a series of heat transport parameters (e. g., electrical resistivity, thermal conductivity, and heat flux), which are in reasonable comparison with various geophysical estimates. Citation: Deng, L., C. Seagle, Y. Fei, and A. Shahar (2013), High pressure and temperature electrical resistivity of iron and implications for planetary cores, Geophys. Res. Lett., 40, 33-37, doi: 10.1029/2012GL054347.

High-pressure melting experiments in the Fe-S-C ternary and Fe-S-Si-C quaternary systems have been conducted in the range of 3.5-20 GPa and 920-1700 degrees C in the multi-anvil press. The mutual solubility, melting relations, and crystallization sequences were systematically investigated with changes of pressure, temperature and bulk composition. Five starting materials of Fe(84.69 wt%)-C(4.35 wt%)-S(7.85 wt%), Fe(84.87 wt%)-C(2.08 wt%)-S(11.41 wt%), Fe(86.36 wt%)-C(0.96 wt%)S( 10.31 wt%), Fe(85.71 wt%)-C(0.33 wt%)-S(11.86 wt%) and Fe(82.95 wt%)-C(0.66 wt%)-S(13.7 wt%)-Si(2.89 wt%) were employed. For Fe(84.69 wt%)-C(4.35 wt%)-S(7.85 wt%), the first crystallized phase is Fe3C at 5 GPa and Fe7C3 at 10-20 GPa. For Fe(84.87 wt%)-C(2.08 wt%)-S(11.41 wt%), Fe3C is the stable carbide at subsolidus temperature at 5-15 GPa. For Fe(86.36 wt%)-C(0.96 wt%)-S(10.31 wt%) and Fe(85.71 wt%)-C(0.33 wt%)-S(11.86 wt%), the first crystallized phase is metallic Fe instead of iron carbide at 5-10 GPa. The cotectic curves in Fe-S-C ternary system indicate only a small amount of C is needed to form an iron carbide solid inner core with the presence of S. Experiments on Fe(82.95 wt%)-C(0.66 wt%)-S( 13.7 wt%)-Si(2.89 wt%) showed that a small amount of C does not significantly change the closure pressure of miscibility gap compared with that in Fe-S-Si system. It is observed that S preferentially partitions into molten iron while a significant amount of Si enters the solid phase with temperature decrease. Meanwhile, the C concentration in the liquid and solid iron metal changes little with temperature variations. If S, C and Si partitioning behavior between molten iron and solid iron metal with temperature remains the same under Earth's present core pressure conditions, the solid inner core should be iron dominated with dissolved Si. On the other hand, the liquid outer core will be S rich and Si poor. Moderate carbon will be evenly present in both solid and liquid cores. Based on our melting data in a multi-component system, no layered liquid core should exist in the Earth, Mars and Mercury. (C) 2013 Published by Elsevier Ltd.

A series of high pressure and temperature experiments were conducted to better constrain the Fe isotope fractionation during core-mantle differentiation in planetesimal and planetary bodies. Synthetic mixtures of oxides and metal having varying amounts of sulfur, approximating terrestrial and Martian compositions, were melted at 1-2 GPa and 1650 degrees C. Iron isotopic equilibrium between the resulting metal and glass run products was verified for all experiments using the three-isotope technique. Purified Fe from metal and glass was analyzed by multiple-collector ICP-MS in high resolution mode. Iron alloy and silicate glass show a well-resolved Delta Fe-57(metal-silicate) of +0.12 +/- 0.04 parts per thousand in a sulfur-free system. Isotope fractionation increases with sulfur content to +0.43 +/- 0.03 parts per thousand at 18 wt.% sulfur in the metal. These results cannot be easily interpreted within the context of known Fe isotope ratios in most natural samples of planetary and asteroidal mantles and therefore suggest more complex processes affected the Fe isotope fractionation therein. However, to reconcile Martian meteorite iron isotopic signatures with geophysical models using this new experimental data requires a smaller amount of sulfur in the Martian core than previous estimates, with an upper limit of similar to 8 wt.%. (C) 2014 Elsevier Ltd. All rights reserved.

We present a new approach to model planetary accretion and continuous core formation, and discuss the implications if Earth accreted under conditions initially more oxidized than the modem day mantle. The modified model uses the same partitioning data that were previously used to model accretion under reducing conditions, however, changing the partitioning between accreting metal and silicate mantle means that reducing conditions fail to meet expected core/mantle values. Instead, the model requires conditions more oxidized than the modern day mantle to converge and to yield expected elemental core/mantle distribution values for moderately siderophile elements. The initial oxygen fugacity required to provide the crucial level of oxidation is approximately Delta IW similar to -1.2 to -1.7 and thus is in the range of carbonaceous and ordinary chondrites. The range of peak pressures for metal silicate partitioning is 60-6 GPa and oxygen fugacity must decrease to meet modem FeO mantle contents as accretion continues. Core formation under oxidizing conditions bears some interesting consequences for the terrestrial Si budget. Although the presented partitioning model can produce a Si content in the core of 5.2 wt%, oxidizing accretion may limit this to a maximum of similar to 3.0 to 2.2 wt%, depending on the initial f(O2) in BSE, which places bulk earth Mg/Si ratio between 0.98-1.0. In addition, under oxidizing conditions, Si starts partitioning late during accretion, e.g., when model earth reached >60% of total mass. As a consequence, the high P-T regime reduces the accompanied isotope fractionation considerably, to 0.07 parts per thousand for 5.2 wt% Si in the core. The isotope fractionation is considerably less, when a maximum of 3.0 wt% in the core is applied. Under oxidizing conditions it becomes difficult to ascertain that the Si isotope composition of BSE is due to core-formation only. Bulk Earth's Si isotope composition is then not chondritic and may have been inherited from Earth's precursor material.

Through Earth history, atmospheric oxygen has increased from initial values near zero to its present day level of about 21 % by volume; concomitantly, changes in ocean redox conditions have fundamentally altered global biogeochemical cycles. While there is a reasonable understanding of where oxygen history begins and ends, the quantitative timetable of oxygenation that links the endpoints has proven contentious. Equilibrium between marine surface environments and the overlying atmosphere suggests that carbonate-based redox proxies could refine palaeoredox records in time and space. Here we explore the use of Zn/Fe ratios to infer the evolution of atmospheric O-2 through time, based on marine carbonate rocks that are well characterised in terms of depositional age, environmental setting, and diagenetic history. While Fe and Zn in the shallow ocean are mainly sourced from hydrothermal inputs, their redox sensitivities differ significantly, so that geological intervals with higher O-2 would be characterised by stepped increases in Zn/Fe as preserved in shallow marine carbonates. Therefore, Zn/Fe analyses of ancient carbonates allow us to constrain past atmospheric pO(2) levels, providing a secular record of atmospheric O-2 over the past 3.5 billion years. In particular, we corroborate an earlier proposal that for much of the Proterozoic Eon, O-2 levels were as low as 0.1-1 % of present atmospheric level. We conclude that Zn/Fe in shallow marine carbonate rocks has potential to provide a quantitative tracer for the longterm redox evolution of the oceans and the rise of atmospheric O-2.

The Earth's mantle displays a subchondritic S-34/S-32 ratio. Sulfur is a moderately siderophile element (i.e. iron-loving), and its partitioning into the Earth's core may have left such a distinctive isotope composition on the terrestrial mantle. In order to constrain the sulfur isotope fractionation occurring during core-mantle differentiation, high-pressure and temperature experiments were conducted with synthetic mixtures of metal and silicate melts. With the purpose to identify the mechanism(s) responsible for the S isotope fractionations, we performed our experiments in different capsules - namely, graphite and boron nitride capsules - and thus at different fO(2), with varying major element chemistry of the silicate and metal fractions.

Our current understanding of Earth's core formation is limited by the fact that this profound event is far removed from us physically and temporally. The composition of the iron metal in the core was a result of the conditions of its formation, which has important implications for our planet's geochemical evolution and physical history. We present experimental and theoretical evidence for the effect of pressure on iron isotopic composition, which we found to vary according to the alloy tested (FeO, FeHx, or Fe3C versus pure Fe). These results suggest that hydrogen or carbon is not the major light-element component in the core. The pressure dependence of iron isotopic composition provides an independent constraint on Earth's core composition.