Measurement of Intergranular Diffusion in a Silicate System: Iron in Forsterite

Nature ◽  
1959 ◽  
Vol 184 (4688) ◽  
pp. BA54-BA56 ◽  
Author(s):  
JOHN J. NAUGHTON ◽  
YASUO FUJIKAWA
Keyword(s):  
Silicate System ◽  
Intergranular Diffusion

scholarly journals F/OH ratio in a rare fluorine-poor blue topaz from Padre Paraíso (Minas Gerais, Brazil) to unravel topaz’s ambient of formation

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
N. Precisvalle ◽  
A. Martucci ◽  
L. Gigli ◽  
J. R. Plaisier ◽  
T. C. Hansen ◽  
...  
Keyword(s):  
Supercritical Fluids ◽  
Fluorine Content ◽  
Minas Gerais ◽  
Hydroxyl Groups ◽  
Exchange Reactions ◽  
Silicate System ◽  
Mullite Phase ◽  
Anomalous Water

AbstractTopaz [Al2SiO4(F,OH)2] is one of the main fluorine-bearing silicates occurring in environments where variably acidic (F)/aqueous (OH) fluids saturate the silicate system. In this work we fully characterized blue topaz from Padre Paraíso (Minas Gerais, Brazil) by means of in situ synchrotron X-Ray and neutron powder diffraction measurements (temperature range 298–1273 K) combined with EDS microanalyses. Understanding the role of OH/F substitution in topaz is important in order to determine the hydrophilicity and the exchange reactions of fluorine by hydroxyl groups, and ultimately to characterize the environmental redox conditions (H2O/F) required for mineral formation. The fluorine content estimated from neutron diffraction data is ~ 1.03 a.f.u (10.34 wt%), in agreement with the chemical data (on average 10.0 wt%). The XOH [OH/(OH + F)] (0.484) is close to the maximum XOH value (0.5), and represents the OH- richest topaz composition so far analysed in the Minas Gerais district. Topaz crystallinity and fluorine content sharply decrease at 1170 K, while mullite phase starts growing. On the basis of this behaviour, we suggest that this temperature may represent the potential initial topaz’s crystallization temperature from supercritical fluids in a pegmatite system. The log(fH2O/fHF)fluid (1.27 (0.06)) is coherent with the fluorine activity calculated for hydrothermal fluids (pegmatitic stage) in equilibrium with the forming mineral (log(fH2O/fHF)fluid = 1.2–6.5) and clearly different from pure magmatic (granitic) residual melts [log(fH2O/fHF)fluid < 1]. The modelled H2O saturated fluids with the F content not exceeding 1 wt% may represent an anomalous water-dominant / fluorine-poor pegmatite lens of the Padre Paraíso Pegmatite Field.

scholarly journals Serpentine–Hisingerite Solid Solution in Altered Ferroan Peridotite and Olivine Gabbro

Minerals ◽  
2019 ◽  
Vol 9 (1) ◽  
pp. 47 ◽  
Author(s):  
Benjamin Tutolo ◽  
Bernard Evans ◽  
Scott Kuehner
Keyword(s):  
Iron Formation ◽  
Olivine Gabbro ◽  
Banded Iron Formation ◽  
Silicate System ◽  
Duluth Complex ◽  
Sheet Silicate ◽  
Structure Modulation ◽  
Compositional Variability ◽  
Common Observation ◽  
End Members

We present microanalyses of secondary phyllosilicates in altered ferroan metaperidotite, containing approximately equal amounts of end-members serpentine ((Mg,Fe2+)3Si2O5(OH)4) and hisingerite (□Fe3+2Si2O5(OH)4·nH2O). These analyses suggest that all intermediate compositions can exist stably, a proposal that was heretofore impossible because phyllosilicate with the compositions reported here have not been previously observed. In samples from the Duluth Complex (Minnesota, USA) containing igneous olivine Fa36–44, a continuous range in phyllosilicate compositions is associated with hydrothermal Mg extraction from the system and consequent relative enrichments in Fe2+, Fe3+ (hisingerite), Si, and Mn. Altered ferroan–olivine-bearing samples from the Laramie Complex (Wyoming, USA) show a compositional variability of secondary FeMg–phyllosilicate (e.g., Mg–hisingerite) that is discontinuous and likely the result of differing igneous olivine compositions and local equilibration during alteration. Together, these examples demonstrate that the products of serpentinization of ferroan peridotite include phyllosilicate with iron contents proportionally larger than the reactant olivine, in contrast to the common observation of Mg-enriched serpentine in “traditional” alpine and seafloor serpentinites. To augment and contextualize our analyses, we additionally compiled greenalite and hisingerite analyses from the literature. These data show that greenalite in metamorphosed banded iron formation contains progressively more octahedral-site vacancies (larger apfu of Si) in higher XFe samples, a consequence of both increased hisingerite substitution and structure modulation (sheet inversions). Some high-Si greenalite remains ferroan and seems to be a structural analogue of the highly modulated sheet silicate caryopilite. Using a thermodynamic model of hydrothermal alteration in the Fe–silicate system, we show that the formation of secondary hydrothermal olivine and serpentine–hisingerite solid solutions after primary olivine may be attributed to appropriate values of thermodynamic parameters such as elevated a S i O 2 ( a q ) and decreased a H 2 ( a q ) at low temperatures (~200 °C). Importantly, recent observations of Martian rocks have indicated that they are evolved magmatically like the ferroan peridotites analyzed here, which, in turn, suggests that the processes and phyllosilicate assemblages recorded here are more directly relevant to those occurring on Mars than are traditional terrestrial serpentinites.

The Prs2O3 /Si(001) Interface: a Mixed Si-Pr Oxide

2003 ◽  
Vol 765 ◽  
Author(s):  
Dieter Schmeißer ◽  
Jarek Dabrowski ◽  
Hans-Joachim Müssig
Keyword(s):  
Depth Profiling ◽  
Dielectric Materials ◽  
Interface Properties ◽  
Silicide Formation ◽  
Silicate System ◽  
No Formation ◽  
Interface Characteristics ◽  
Reactive Interface ◽  
Non Destructive ◽  
Natural Way

AbstractWe studied the Pr2O3/Si(001) interface by a non-destructive depth profiling using synchrotron radiation and photo-electron spectroscopy (SR-PES) at the undulator beam line U49/2-PGM2 and ab initio calculations. Our results provide evidence that a chemical reactive interface exists consisting of a mixed Si-Pr oxide such as (Pr2O3)(SiO)x(SiO2)y. There is no formation of neither an interfacial SiO2 nor interfacial silicide: all Si-Pr bonds are oxidized and all SiO4 units dissolve in the Pr oxide. Under ultrahigh vacuum conditions, silicide formation is observed only when the film is heated above 800°C in vacuum. Interfacial silicates like (Pr2O3)(SiO)x(SiO2)y are promising high-k dielectric materials, e.g., because they represent incremental modification of SiO2 films by Pr ions, so that the interface characteristics can be similar to Si-SiO2 interface properties. The Pr silicate system formed in a natural way at the interface between Si(001) and Pr2O3 offers an increased flexibility towards integration of Pr2O3 into future CMOS technologies.

scholarly journals Test of Anderson-Stuart model in sodium silicate glasses and the general Arrhenian conductivity rule in wide composition range

Cerâmica ◽  
2006 ◽  
Vol 52 (321) ◽  
pp. 22-30 ◽  
Author(s):  
M. L. F. Nascimento ◽  
E. Nascimento ◽  
W. M. Pontuschka ◽  
M. Matsuoka ◽  
S. Watanabe
Keyword(s):  
Activation Energy ◽  
Ionic Conductivity ◽  
Sodium Silicate ◽  
Composition Range ◽  
Absolute Temperature ◽  
Alkali Concentration ◽  
Relative Dielectric Permittivity ◽  
Silicate System ◽  
Wide Composition Range ◽  
Sigma E

We collected and analyzed literature data on ionic conductivity sigma and activation energy E A in the binary sodium silicate system in a wide composition range. The Anderson and Stuart model has been considered to describe the decreasing tendency of activation energy E A with alkali concentration in this system. In this analysis were considered experimental parameters, such as shear modulus G and relative dielectric permittivity epsilon. A general conductivity rule is found in 194 of 205 glasses, when one plots log sigma vs. E A/kB T, where kB is the Boltzmann constant and T is the absolute temperature. This fact means that the arrhenian relation has universal uniqueness of form sigma = sigma (E A,T) in wide Na2O composition range. The results also show that there is strong correlation by more than 19 orders of magnitude on conductivity with E A/kBT. An explanation for this behavior links ionic conductivity and microscopic structure. The problem of phase separation in this system is also considered.

Feedback mechanisms in mineral replacement networks: an experimental investigation of the ultramafic model system

2021 ◽  
Author(s):  
Ingvild Aarrestad ◽  
Oliver Plümper ◽  
Desiree Roerdink ◽  
Andreas Beinlich
Keyword(s):  
Reaction Rate ◽  
Energy Transport ◽  
Kinetic Modelling ◽  
Indirect Evidence ◽  
Reaction Network ◽  
Reaction Networks ◽  
Silicate System ◽  
Rock Interaction ◽  
Feedback Mechanisms ◽  
Salinity Effect

&lt;p&gt;The overall rates of multi-component reaction networks are known to be controlled by feedback mechanisms. Feedback mechanisms represent loop systems where the output of the system is conveyed back as input and the system is either accelerated or regulated (positive and negative feedback respectively). In other words, feedback mechanisms control the rate of a reaction network without external influences. Feedback mechanisms are well-studied in a variety of reaction networks (e.g. bio-chemical, atmospheric); however, in fluid-rock interaction systems they are not researched as such. Still, indirect evidence, theoretical considerations and direct observations attest to their existence [e.g. 1, 2, 3]. It remains unknown how mass and energy transport between distinct reaction sites affect the overall reaction rate and outcome through feedback mechanisms. We propose that feedback mechanisms are a missing critical ingredient to understand reaction progress and timescales of fluid-rock interactions. We apply the serpentinization of ultramafic silicates as a relatively simple reaction network to investigate feedback mechanisms during fluid-rock interactions. Recent studies show that theoretical timescale-predictions appear inconsistent with natural observations [e.g. 4, 5]. The ultramafic silicate system is ideal for investigating feedback mechanisms as it is relevant to natural processes, is reactive on timescales that can be explored in the laboratory, and natural peridotite typically consists of less than four phases. Our preliminary observations indicate a feedback between pyroxene dissolution and olivine serpentinization. Olivine serpentinization appears to proceed faster in the presence of pyroxene. Furthermore, the bulk system reaction rate increases with increasing fluid salinity, which is opposite to the salinity effect on the monomineralic olivine system. Dunite (&gt;90% olivine) is rare, which is why it is crucial to explore the more common pyroxene-bearing systems. The salinity effect is important to investigate due to the inevitable increase in fluid salinity from the boiling-induced phase separation and OH-uptake in the formation of serpentine. Here we present preliminary textural and chemical observations, which will subsequently be used for kinetic modelling of feedback.&lt;/p&gt;&lt;p&gt;[1] Ortoleva P., Merino, E., Moore, C. &amp; Chadam, J. (1987). American Journal of Science &lt;strong&gt;287&lt;/strong&gt;, 997-1007.&lt;/p&gt;&lt;p&gt;[2] Centrella, S., Austrheim, H., &amp; Putnis, A. (2015). Lithos &lt;strong&gt;236&amp;#8211;237&lt;/strong&gt;, 245&amp;#8211;255.&lt;/p&gt;&lt;p&gt;[3] Nakatani, T. &amp; Nakamura, M. (2016). Geochemistry, Geophysics, Geosystems &lt;strong&gt;17&lt;/strong&gt;, 3393-3419.&lt;/p&gt;&lt;p&gt;[4] Ingebritsen, S. E. &amp; Manning, C. E. (2010). Geofluids &lt;strong&gt;10&lt;/strong&gt;, 193-205.&lt;/p&gt;&lt;p&gt;[5] Beinlich, A., John, T., Vrijmoed, J.C., Tominaga, M., Magna, T. &amp; Podladchikov, Y.Y. (2020).&amp;#160;Nature Geoscience&amp;#160;&lt;strong&gt;13&lt;/strong&gt;,&amp;#160;307&amp;#8211;311.&lt;/p&gt;

Perovskite, loparite and Ba-Fe hollandite from the Schryburt Lake carbonatite complex, northwestern Ontario, Canada

1994 ◽  
Vol 58 (390) ◽  
pp. 49-57 ◽  
Author(s):  
R. Garth Platt
Keyword(s):  
Fluid Phase ◽  
Ultramafic Rocks ◽  
Subsequent Reaction ◽  
Carbonatite Complex ◽  
Silicate System ◽  
Northwestern Ontario ◽  
Intimate Association ◽  
Free Mica ◽  
Host Rocks ◽  
Light Rare Earth Elements

AbstractWithin a suite of felsic-free, mica-rich alkaline ultramafic rocks of the Schryburt Lake carbonatite complex of northwestern Ontario, loparite and Ba-Fe hollandite occur in intimate association with perovskite. The host rocks have variable modal proportions of Mg-olivine, phlogopite, magnetite, ilmenite, apatite and carbonate (generally calcite) with minor Mg-salite. Thus, they correspond to ultramafic lamprophyres (i.e. aillikites), in the sense of Rock (1990) or the lamprophyric facies of the melilitite clan, in the sense of Mitchell (1993).Perovskite is the principal titanate phase, forming both euhedral and anhedral grains, the latter showing evidence of marginal resorption. It exhibits complex zonal patterns due principally to variations in the light rare earth elements, Na and Nb. In the nomenclature suggested, they may be termed perovskite and cerian perovskite. Loparite forms as small euhedral overgrowths on corroded perovskite cores. Chemically they are essentially solid solutions of loparite, lueshite and perovskite. Consequently, they may be termed calcian-loparite, calcian niobian loparite, niobian calcian loparite, loparite and niobian loparite. Titanates of the hollandite group are rare accessory minerals whose composition closely approach that of the septatitanate BaFe2+Ti7O16.The complex zoning of the perovskite grains has been attributed to the periodic introduction of carbonatite-derived fluids enriched in REE, Na and Nb into the silicate system during perovskite crystallization. Subsequent reaction of the early perovskite with F-bearing fluids leads to a localized environment enriched in Ti, Na, Nb and REE derived from both the fluid phase and the unstable perovskite. Loparite subsequently crystallizes from these micro-chemical environments.

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