Viability of pyrite pulled metabolism in the ‘iron-sulfur world’ theory: Quantum chemical assessment

The viability of pyrite-pulled metabolism in the ‘iron-sulfur world’ theory was assessed using a simple model of iron-nickel sulfide (Fe-Ni-S) surface and data obtained from quantum chemical calculations. We have investigated how the individual reactions in the carbon fixation cycle (carboxylic acids formation) on an Fe-Ni-S surface could have operated to produce carboxylic acids from carbon oxide and water. The proposed model cycle reveals how the individual reactions might have functioned and provides the thermodynamics of each step of the proposed pathway. The feasibility of individual reactions, as well the whole cycle was considered. The reaction of acetic acid production from CH₃SH and CO on an Fe-Ni sulfide surface was revealed to be endergonic with a few partial steps having positive Gibbs free energy. On the other hand, the pyrite formation was found to be slightly exergonic. The significance of the catalytic activity of transition metal sulfides in generation of acetic acid was shown. The Gibbs free energy values indicate that the acetic acid synthesis is unfavorable to proceed on the studied Fe-Ni-S model under simulated conditions. The importance of these results in terms of a primordial chemistry on iron-nickel sulfide surfaces is discussed.     

GETEMME—a mission to explore the Martian satellites and the fundamentals of solar system physics

GETEMME (Gravity, Einstein??s Theory, and Exploration of the Martian Moons?? Environment), a mission which is being proposed in ESA??s Cosmic Vision program, shall be launched for Mars on a Soyuz Fregat in 2020. The spacecraft will initially rendezvous with Phobos and Deimos in order to carry out a comprehensive mapping and characterization of the two satellites and to deploy passive Laser retro-reflectors on their surfaces. In the second stage of the mission, the spacecraft will be transferred into a lower 1500-km Mars orbit, to carry out routine Laser range measurements to the reflectors on Phobos and Deimos. Also, asynchronous two-way Laser ranging measurements between the spacecraft and stations of the ILRS (International Laser Ranging Service) on Earth are foreseen. An onboard accelerometer will ensure a high accuracy for the spacecraft orbit determination. The inversion of all range and accelerometer data will allow us to determine or improve dramatically on a host of dynamic parameters of the Martian satellite system. From the complex motion and rotation of Phobos and Deimos we will obtain clues on internal structures and the origins of the satellites. Also, crucial data on the time-varying gravity field of Mars related to climate variation and internal structure will be obtained. Ranging measurements will also be essential to improve on several parameters in fundamental physics, such as the Post-Newtonian parameter ?? as well as time-rate changes of the gravitational constant and the Lense-Thirring effect. Measurements by GETEMME will firmly embed Mars and its satellites into the Solar System reference frame.     

High-grade iron ore at Windarling, Yilgarn Craton: a product of syn-orogenic deformation, hypogene hydrothermal alteration and supergene modification in an Archean BIF-basalt lithostratigraphy

Banded iron formation (BIF)-hosted iron ore deposits in the Windarling Range are located in the lower greenstone succession of the Marda–Diemals greenstone belt, Southern Cross domain, Yilgarn Craton and constitute a total hematite–martite–goethite ore resource of minimum 52 Mt at 60 wt.% Fe (0.07 P). Banded iron formation is interlayered with high-Mg basalts at Windarling and precipitated during episodes of volcanic quiescence. Trace element content and the rare earth element (REE) ratios Y/Ho (42 to 45), Sm/Yb (1.5), together with positive La and Gd anomalies in ‘least-altered’ hematite–magnetite–metachert–BIF indicate the precipitation from Archean seawater that was fertilised by hydrothermal vent fluids with a basaltic HREE-Y signature. Hypogene iron ore in sub-greenschist facies metamorphosed BIF formed during three distinct stages: ore stage 1 was a syn- to post-metamorphic, syn-D₁, Fe–Ca–Mg–Ni–Co–P–REE metasomatism that produced local Ni–REE-rich Fe–dolomite–magnetite alteration in BIF. Hydrothermal alteration was induced by hot fluid flow controlled by brittle–ductile reactivation of BIF-basalt margins and crosscutting D₁ faults. The Ni–Co-rich content of dolomite and a shift in REE ratios in carbonate-altered BIF towards Archean mafic rock signature (Y/Ho to 31 to 40, Sm/Yb to 1 to 2 and Gd/Gd* to 1.2 to 1.4) suggest that high-Mg basalts in the Windarling Range were the primary source of introduced metals. During ore stage 2, a syn-deformational and likely acidic and oxidised fluid flow along BIF-basalt margins and within D₁ faults leached carbonate and precipitated lepidoblastic and anhedral/granoblastic hematite. High-grade magnetite–hematite ore is formed during this stage. Ore stage 3 hydrothermal specular hematite (spcH)–Fe–dolomite–quartz alteration was controlled by a late-orogenic, brittle, compressional/transpressional stage (D₄; the regional-scale shear-zone-related D₃ is not preserved in Windarling). This minor event remobilised iron oxides, carbonate and quartz to form veins and breccia but did not generate significant volumes of iron ore. Ore stage 4 involved Mesozoic(?) to recent supergene oxidation and hydration in a weathering environment reaching down to depths of ～100 to maximum 200 m below surface. Supergene ore formation involved goethite replacement of dolomite and quartz as well as martitisation. Important ‘ground preparation’ for supergene modification and upgrade were mainly the formation of steep D₁ to D₄ structures, steep BIF/basalt margins and particularly the syn-D₁ to syn-D₂ carbonate alteration of BIF that is most susceptible to supergene dissolution. The Windarling deposits are structurally controlled, supergene-modified hydrothermal iron ore systems that share comparable physical, chemical and ore-forming characteristics to other iron ore deposits in the Yilgarn Craton (e.g. Koolyanobbing, Beebyn in the Weld Range, Mt. Gibson). However, the remarkable variety in pre-, syn- and post-deformational ore textures (relative to D₁ and D₂) has not been described elsewhere in the Yilgarn and are similar to the ore deposits in high-strain zones, such as of Brazil (Quadrilátero Ferrífero or Iron Quadrangle) and Nigeria. The overall similarity of alteration stages, i.e. the sequence of hydrothermal carbonate introduction and hypogene leaching, with other greenstone belt-hosted iron ore deposits supports the interpretation that syn-orogenic BIF alteration and upgrade was crucial in the formation of hypogene–supergene iron ore deposits in the Yilgarn Craton and possibly in other Archean/Paleoproterozoic greenstone belt settings worldwide.     

A Long-Term Decrease of the Mid-Size Segmentation Lengths Observed in the He <Emphasis Type="SmallCaps">ii</Emphasis> (30.4 nm) Solar EUV Emission

Power spectra of segmentation-cell length (a dominant length scale of EUV emission in the transition region) from full-disk He?ii extreme ultraviolet (EUV) images observed by the Extreme ultraviolet Imaging Telescope (EIT) onboard the Solar and Heliospheric Observatory (SOHO) and the Atmospheric Imaging Assembly (AIA) onboard the Solar Dynamics Observatory (SDO) during periods of quiet-Sun conditions for a time interval from 1996 to 2015 were analyzed. The spatial power as a function of the spatial frequency from about 0.04 to 0.27 (EIT) or up to 0.48 (AIA) Mm^?1 depends on the distribution of the observed segmentation-cell dimensions – a structure of the solar EUV network. The temporal variations of the spatial power reported by Didkovsky and Gurman (Solar Phys. 289, 153, 2014) were suggested as decreases at the mid-spatial frequencies for the compared spectra when the power curves at the highest spatial frequencies of 0.5 pix^?1 were adjusted to match each other. This approach has been extended in this work to compare spectral ratios at high spatial frequencies expressed in the solar spatial frequency units of Mm^?1. A model of EIT and AIA spatial responses allowed us to directly compare spatial spectral ratios at high spatial frequencies for five years of joint operation of EIT and AIA, from 2010 to 2015. Based on this approach, we represent these ratio changes as a long-term network transformation that may be interpreted as a continuous dissipation of mid-size network structures to the smaller-size structures in the transition region. In contrast to expected cycling of the segmentation-cell dimension structures and associated spatial power in the spectra with the solar cycle, the spectra demonstrate a significant and steady change of the EUV network. The temporal trend across these structural spectra is not critically sensitive to any long-term instrumental changes, e.g. degradation of sensitivity, but to the change of the segmentation-cell dimensions of the EUV network structure.     

Parameterization of iron and manganese cycling in the Black Sea suboxic and anoxic environment

New and published data on the distribution and speciation of manganese and iron in seawater are analyzed to identify and parameterize major biogeochemical processes of their cycling within the suboxic (15.6σ_t16.2) and anoxic layers (σ_t16.2) of the Black Sea. A steady-state transport-reaction model is applied to reveal layering and parameterize kinetics of redox and dissolution/precipitation processes. Previously published data on speciation of these elements in seawater are used to specify the nature of the transformations. Two particulate species of iron (Fe(III) hydroxide and Fe(II) sulfide) are necessary to adequately parameterize the vertical profile of suspended iron, while three particulate species (hydrous Mn(IV) oxide, Mn(II) sulfide, and Mn(II) carbonate) are necessary to describe the profile of suspended manganese. In addition to such processes as mixing and advection, precipitation, sinking, and dissolution of manganese carbonate are found to be essential in maintaining the observed vertical distribution of dissolved Mn(II). These results are used to interpret the observed difference in the form of vertical distribution for dissolved Mn(II) and Fe(II). Redox transformations of iron and manganese are coupled via oxidation of dissolved iron by sinking suspended manganese at σ_t16.2±0.2 kg m⁻³. The particulate manganese, necessary for this reaction, is supplied through oxidation of dissolved Mn(II). The best agreement with observations is achieved when nitrate, rather than oxygen, is set to oxidize dissolved Mn(II) in the lower part of the suboxic layer (15.90σ_t16.2). The results support the idea that, after sulfides of these metals are formed, they sink with particulate organic matter. The sinking rates of the particles and specific rates of individual redox and dissolved-particulate transformations have been estimated by fitting the vertical profile of the net rate.     

Immiscible silicate liquid partition coefficients: implications for crystal-melt element partitioning and basalt petrogenesis

This study investigates partitioning of elements between immiscible aluminosilicate and borosilicate liquids using three synthetic mixtures doped with 32 trace elements. In order to get a good spatial separation of immiscible liquids, we employed a high-temperature centrifuge. Experiments were performed at 1,050–1,150°C, 1 atm, in sealed Fe and Pt containers. Quenched products were analysed by electron microprobe and LA ICP-MS. Nernst partition coefficients (D’s) between the Fe-rich and Si-rich aluminosilicate immiscible liquids are the highest for Zn (3.3) and Fe (2.6) and the lowest for Rb and K (0.4–0.5). The plots of D values against ionic potential Z/r in all the compositions show a convex upward trend, which is typical also for element partitioning between immiscible silicate and salt melts. The results bear upon the speciation and structural position of elements in multicomponent silicate liquids. The ferrobasalt–rhyolite liquid immiscibility is observed in evolved basaltic magmas, and may play an important role in large gabbroic intrusions, such as Skaergaard, and during the generation of unusual lavas, such as ferropicrites.     

峨眉火成岩省内带岩浆硫化物含矿岩体橄榄石的成因意义

岩浆镍-铜-铂族元素(PGE)硫化物矿床是峨眉火成岩省地幔柱活动形成的两个重要的成矿系列之一[1～3].目前已发现的与峨眉火成岩省相关的40余个镍-铜-铂族元素硫化物矿床(或矿点)中,多数分布在内带[3,4].它们可分为:1)富Ni、Cu而贫PGE的Ni-Cu型(如力马河和清水河);2)富Ni,Cu且PGE中等的Ni-Cu-PGE型(如清矿山和黄草坪);3)贫Ni、Cu富PGE的PGE型(如金宝山和杨合武).     

High-pressure and high-temperature Raman spectroscopic study of hydrous wadsleyite (β-Mg2SiO4)

In situ Raman spectra of hydrous wadsleyite (β-Mg₂SiO₄) with ~1.5 wt% H₂O, synthesized at 18 GPa and 1,400°C, have been measured in an externally heated diamond anvil cell up to 15.5 GPa and 673 K. With increasing pressure (at room temperature), the three most intense bands at ~549, 720 and 917 cm⁻¹ shift continuously to higher frequencies, while with increasing temperature at 14.5 GPa, these bands generally shift to lower frequencies. The temperature-induced frequency shifts at 14.5 GPa are significantly different from those at ambient pressure. Moreover, two new bands at ~714 and ~550 cm⁻¹ become progressively significant above 333 and 553 K, respectively, and disappear upon cooling to room temperature. No corresponding Raman modes of these two new bands were reported for wadsleyite at ambient conditions, and they are thus probably related to thermally activated processes (vibration modes) at high-pressure and temperature conditions.