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1.
2.
Alexej N. Platonov Klaus Langer Stanislav S. Matsyuk 《Physics and Chemistry of Minerals》2008,35(6):331-337
In the course of a thorough study of the influences of the second coordination sphere on the crystal field parameters of the
3d
N
-ions and the character of 3d
N
–O bonds in oxygen based minerals, 19 natural Cr3+-bearing (Mg,Ca)-garnets from upper mantle rocks were analysed and studied by electronic absorption spectroscopy, EAS. The
garnets had compositions with populations of the [8]
X-sites by 0.881 ± 0.053 (Ca + Mg) and changing Ca-fractions in the range 0.020 ≤ w
Ca[8] ≤ 0.745, while the [6]
Y-site fraction was constant with x
Cr3+
[6] = 0.335 ± 0.023. The garnets had colours from deeply violet-red for low Ca-contents (up to x
Ca = 0.28), grey with 0.28 ≤ x
Ca ≤ 0.4 and green with 0.4 ≤ x
Ca. The crystal field parameter of octahedral Cr3+ 10Dq decreases strongly on increasing Ca-fraction from 17,850 cm−1 at x
Ca[8] = 0.020 to 16,580 cm−1 at x
Ca[8] = 0.745. The data could be fit with two model which do statistically not differ: (1) two linear functions with a discontinuity
close to x
Ca[8] ≈ 0.3,
(2) one continuous second order function,
The behaviour of the crystal field parameter 10Dq and band widths on changing Ca-contents favour the first model, which is
interpreted tentatively by different influences of Ca in the structure above and below x
Ca[8] ≈ 0.3. The covalency of the Cr–O bond as reflected in the behaviour of the nephelauxetic ratio
decreases on increasing Ca-contents. 相似文献
3.
The diffusion of water in a peralkaline and a peraluminous rhyolitic melt was investigated at temperatures of 714–1,493 K
and pressures of 100 and 500 MPa. At temperatures below 923 K dehydration experiments were performed on glasses containing
about 2 wt% H2O
t
in cold seal pressure vessels. At high temperatures diffusion couples of water-poor (<0.5 wt% H2O
t
) and water-rich (~2 wt% H2O
t
) melts were run in an internally heated gas pressure vessel. Argon was the pressure medium in both cases. Concentration profiles
of hydrous species (OH groups and H2O molecules) were measured along the diffusion direction using near-infrared (NIR) microspectroscopy. The bulk water diffusivity
() was derived from profiles of total water () using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between and Both methods consistently indicate that is proportional to in this range of water contents for both bulk compositions, in agreement with previous work on metaluminous rhyolite. The
water diffusivity in the peraluminous melts agrees very well with data for metaluminous rhyolites implying that an excess
of Al2O3 with respect to alkalis does not affect water diffusion. On the other hand, water diffusion is faster by roughly a factor
of two in the peralkaline melt compared to the metaluminous melt. The following expression for the water diffusivity in the
peralkaline rhyolite as a function of temperature and pressure was obtained by least-squares fitting:
where is the water diffusivity at 1 wt% H2O
t
in m2/s, T is the temperature in K and P is the pressure in MPa. The above equation reproduces the experimental data (14 runs in total) with a standard fit error
of 0.15 log units. It can be employed to model degassing of peralkaline melts at water contents up to 2 wt%. 相似文献
4.
Analysis of existing data and models on point defects in pure (Fe,Mg)-olivine (Phys Chem Miner 10:27–37,1983; Phys Chem Miner 29:680–694, 2002) shows that it is necessary to consider thermodynamic non-ideality of mixing to adequately describe the concentration of
point defects over the range of measurement. In spite of different sources of uncertainties, the concentrations of vacancies
in octahedral sites in (Fe,Mg)-olivine are on the order of 10−4 per atomic formula unit at 1,000–1,200 °C according to both the studies. We provide the first explicit plots of vacancy concentrations
in olivine as a function of temperature and oxygen fugacity according to the two models. It is found that in contrast to absolute
concentrations at ∼1,100 °C and dependence on fO2, there is considerable uncertainty in our knowledge of temperature dependence of vacancy concentrations. This needs to be
considered in discussing the transport properties such as diffusion coefficients. Moreover, these defect models in pure (Fe,Mg)-olivine
need to be extended by considering aliovalent impurities such as Al, Cr to describe the behavior of natural olivine. We have
developed such a formulation, and used it to analyze the considerable database of diffusion coefficients in olivine from Dohmen
et al. (Phys Chem Miner this volume, 2007) (Part - I) and older data in the literature. The analysis documents unequivocally for the first time a change of diffusion
mechanism in a silicate mineral—from the transition metal extrinsic (TaMED) to the purely extrinsic (PED) domain, at fO2 below 10−10 Pa, and consequently, temperatures below 900 °C. The change of diffusion mechanism manifests itself in a change in fO2 dependence of diffusivity and a slight change in activation energy of diffusion—the activation energy increases at lower temperatures. These are consistent with the predictions of Chakraborty (J Geophys Res 102(B6):12317–12331, 1997). Defect formation enthalpies in the TaMED regime (distinct from intrinsic defect formation) lie between −66 and + 15 kJ/mol
and migration energies of octahedral cations in olivine are most likely ∼ 260 kJ/mol, consistent with previous inferences
(Phys Chem 207:147–162, 1998). Plots are shown for diffusion at various constant fO2 as well as along fO2 buffers, to highlight the difference in behavior between the two. Considering all the diffusion data and constraints from
the point defect models, (Fe–Mg) diffusion in olivine along [001] is best described by the Master equations: (1) At oxygen
fugacities greater than 10−10 Pa:
where T is in Kelvin, P and fO2 is in Pascals, X
Fe is the mole fraction of the fayalite component and R is the gas constant in J/mol/K. (2) At oxygen fugacities less than 10−10 Pa:
These equations reproduce all of the 113 experimental data points within half an order of magnitude. (3) Alternately, a global
equation averaging out the change of mechanism may be used, with somewhat larger errors in reproducing the measured diffusion
data. It underestimates data at higher temperatures, and overestimates them at lower temperatures on the average. Note that
fO2 is not explicitly considered here, leading to additional sources of error:
To obtain diffusion coefficients along [100] and [010], log 6 needs to be subtracted from each of the above equations.
An erratum to this article can be found at 相似文献
5.
The chemical potential of oxygen (µO2) in equilibrium with magnesiowüstite solid solution (Mg, Fe)O and metallic Fe has been determined by gas-mixing experiments at 1,473 K supplemented by solid-cell EMF experiments at lower temperatures. The results give:
where IW refers to the Fe-"FeO" equilibrium. The previous work of Srecec et al. (1987) and Wiser and Wood (1991) agree well with this equation, as does that of Hahn and Muan (1962) when their reported compositions are corrected to a new calibration curve for lattice parameter vs. composition. The amount of Fe3+ in the magnesiowüstite solid solution in equilibrium with Fe metal was determined by Mössbauer spectroscopy on selected samples. These data were combined with literature data from gravimetric studies and fitted to a semi-empirical equation:
These results were then used to reassess the activity-composition relations in (Mg, Fe)2SiO4 olivine solid solutions at 1,400 K, from the partitioning of Mg and Fe2+ between olivine and magnesiowüstite in equilibrium with metallic Fe experimentally determined by Wiser and Wood (1991). The olivine solid solution is constrained to be nearly symmetric with
, with a probable uncertainty of less than ±0.5 kJ/mol (one standard deviation). The results also provide a useful constraint on the free energy of formation of Mg2SiO4.Editorial responsibility: B. Collins 相似文献
6.
7.
The electrical conductivity of upper-mantle rocks: water content in the upper mantle 总被引：1，自引：0，他引：1
The electrical conductivity of upper-mantle rocks—dunite, pyroxenite, and lherzolite—was measured at ∼2–3 GPa and ∼1,273–1,573 K
using impedance spectra within a frequency range of 0.1–106 Hz. The oxygen fugacity was controlled by a Mo–MoO2 solid buffer. The results indicate that the electrical conductivity of lherzolite and pyroxenite are approximately half and
one order of magnitude higher than that of dunite, respectively. A preliminary model involving water and iron content effects
on the electrical conductivity was derived and is summarized by the relation:
The results also indicate that pyroxenes dominate the bulk conductivity of upper mantle in hydrous conditions and suggest
the maximum water content in oceanic upper mantle is as high as ∼0.09 wt%. 相似文献
8.
Gold contents of sulfide minerals in granitoids from southwestern New Brunswick,Canada 总被引：4，自引：0，他引：4
The abundance of gold and selected trace elements in magmatic sulfide and rock-forming minerals from Silurian–Devonian granitoids in southwestern New Brunswick were quantitatively analyzed by laser-ablation inductively coupled plasma mass-spectrometry. Gold is mainly hosted in sulfide minerals (i.e., chalcopyrite, pyrrhotite, and pyrite), in some cases perhaps as submicron inclusions (nanonuggets). Gold is below detection (<0.02 ppm) in major rock-forming minerals (i.e., plagioclase, K-feldspar, biotite, hornblende, and muscovite) and oxides (i.e., magnetite, and ilmenite). Gold distribution coefficients between sulfide and granitoid melt are calculated empirically as: . This result suggests that gold behavior in the granitoid systems is controlled by the conditions of sulfur saturation during magmatic evolution; the threshold of physiochemical conditions for sulfur saturation in the melts is a key factor affecting gold activity. Gold behaves incompatibly prior to the formation of sulfide liquids or minerals, but it becomes compatible at their appearance. Gold would be enriched in sulfur-undersaturated granitoid magmas during fractionation, partitioning into evolved magmatic fluids and favoring the formation of intrusion-related gold deposits. However, gold becomes depleted in residual melts if these melts become sulfur-saturated during differentiation, leading to gold precipitation in the early sulfide phases of a granitoid suite. Late-stage Cl-bearing magmatic–hydrothermal fluids with low pH and relatively high oxidation state derived from either progressively cooling magmas at depth or convective circulation of meteoric water buffered by reduced carbon-bearing sediments, may scavenge gold from early sulfide minerals. If a significant amount of gold produced in this manner is concentrated in a suitable geological environment (e.g., shear zones or fracture systems), intrusion-related gold deposits may also be generated. Exploration for intrusion-related gold systems should focus on the areas around evolved phases of granitoid suites that remained sulfur-undersaturated. For sulfur-saturated granitoid suites, the less differentiated phase and associated structures are the most prospective targets.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users. 相似文献
9.
The Chemical Speciation of Fe(III) in Freshwaters 总被引：1，自引：0，他引：1
Dialysis and chemical speciation modelling have been used to calculate activities of Fe3+ for a range of UK surface waters of varying chemistry (pH 4.3–8.0; dissolved organic carbon 1.7–40.3 mg l−1) at 283 K. The resulting activities were regressed against pH to give the empirical model: . Predicted Fe3+ activities are consistent with a solid–solution equilibrium with hydrous ferric oxide, consistent with some previous studies
on Fe(III) solubility in the laboratory. However, as has also sometimes been observed in the laboratory, the slope of the
solubility equation is lower than the theoretical value of 3. The empirical model was used to predict concentrations of Fe
in dialysates and ultrafiltrates of globally distributed surface and soil/groundwaters. The predictions were improved greatly
by the incorporation of a temperature correction for , consistent with the temperature dependence of previously reported hydrous ferric oxide solubility. The empirical model,
incorporating temperature effects, may be used to make generic predictions of the ratio of free and complexed Fe(III) to dissolved
organic matter in freshwaters. Comparison of such ratios with observed Fe:dissolved organic matter ratios allows an assessment
to be made of the amounts of Fe present as Fe(II) or colloidal Fe(III), where no separate measurements have been made.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
10.
TitaniQ: a titanium-in-quartz geothermometer 总被引：21，自引：10，他引：11
Titanium is one of many trace elements to substitute for silicon in the mineral quartz. Here, we describe the temperature dependence of that substitution, in the form of a new geothermometer. To calibrate the “TitaniQ” thermometer, we synthesized quartz in the presence of rutile and either aqueous fluid or hydrous silicate melt, at temperatures ranging from 600 to 1,000°C, at 1.0 GPa. The Ti contents of quartz (in ppm by weight) from 13 experiments increase exponentially with reciprocal T as described by:
Application of this thermometer is straightforward, typically requiring analysis of only one phase (quartz). This can be accomplished either by EPMA for crystallization temperatures above 600°C, or by SIMS for temperatures down to at least 400°. Resulting temperature estimates are very precise (usually better than ±5°C), potentially allowing detailed characterization of thermal histories within individual quartz grains. Although calibrated for quartz crystallized in the presence of rutile, the thermometer can also be applied to rutile-absent systems if TiO2 activity is constrained. 相似文献
11.
A thermobarometer for sphene (titanite) 总被引：9，自引：0，他引：9
Leslie A. Hayden E. Bruce Watson David A. Wark 《Contributions to Mineralogy and Petrology》2008,155(4):529-540
Sphene and zircon are common accessory minerals in metamorphic and igneous rocks of very different composition from many different
geological environments. Their essential structural constituents, Ti and Zr, are capable of replacing each other to some degree.
In this paper we detail the results of high pressure–temperature experiments as well as analyses of natural sphene crystals
that establish a systematic relationship between temperature, pressure and Zr concentration in sphene. Calibrations of the
temperature and pressure relationships are presented as a thermobarometer. Synthetic sphene crystals were crystallized in
the presence of zircon, quartz and rutile at 1–2.4 GPa and 800–1,000°C from hydrothermal solutions. Crystals were analyzed
for Zr by electron microprobe (EMP). The experimental results define a log-linear relationship between equilibrium Zr content
(ppm by weight), pressure (GPa) and reciprocal absolute temperature:
The incorporation of Zr into sphene was found to be rather sensitive to pressure effects and also to the effects of kinetic
disequilibrium and growth entrapment that result in sector zoning. The Zr content of sphene is relatively insensitive to the
presence of both REEs and F-Al substitutions in sphene. To supplement and test the experimental data, sphenes from seven rocks
of well-constrained origin were analyzed for Zr by both EMP and ion microprobe (IMP). The sphene thermobarometer records crystallization
temperatures that are consistent with independent thermometry. When applied to natural sphene of unknown origin or growth
conditions, this thermobarometer has the potential to estimate temperatures with an approximate uncertainty of ±20°C over
the temperature range of interest (600–1,000°C). The Zr-in-sphene thermobarometer can also be used in conjunction with the
Zr-in-rutile thermobarometer to estimate both pressure and temperature of crystallization.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.
相似文献
| Leslie A. HaydenEmail: |
12.
We report the results of experiments designed to separate the effects of temperature and pressure from liquid composition on the partitioning of Ni between olivine and liquid, \(D_{\text{Ni}}^{\text{ol/liq}}\). Experiments were performed from 1300 to 1600 °C and 1 atm to 3.0 GPa, using mid-ocean ridge basalt (MORB) glass surrounded by powdered olivine in graphite–Pt double capsules at high pressure and powdered MORB in crucibles fabricated from single crystals of San Carlos olivine at one atmosphere. In these experiments, pressure and temperature were varied in such a way that we produced a series of liquids, each with an approximately constant composition (~12, ~15, and ~21 wt% MgO). Previously, we used a similar approach to show that \(D_{\text{Ni}}^{\text{ol/liq}}\) for a liquid with ~18 wt% MgO is a strong function of temperature. Combining the new data presented here with our previous results allows us to separate the effects of temperature from composition. We fit our data based on a Ni–Mg exchange reaction, which yields \(\ln \left( {D_{\text{Ni}}^{\text{molar}} } \right) = \frac{{ -\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } }}{RT} + \frac{{\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } }}{R} - \ln \left( {\frac{{X_{\text{MgO}}^{\text{liq}} }}{{X_{{{\text{MgSi}}_{ 0. 5} {\text{O}}_{ 2} }}^{\text{ol}} }}} \right).\) Each subset of constant composition experiments displays roughly the same temperature dependence of \(D_{\text{Ni}}^{\text{ol/liq}}\) (i.e.,\(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\)) as previously reported for liquids with ~18 wt% MgO. Fitting new data presented here (15 experiments) in conjunction with our 13 previously published experiments (those with ~18 wt% MgO in the silicate liquid) to the above expression gives \(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = 3641 ± 396 (K) and \(\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = ? 1.597 ± 0.229. Adding data from the literature yields \(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = 4505 ± 196 (K) and \(\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = ? 2.075 ± 0.120, a set of coefficients that leads to a predictive equation for \(D_{\text{Ni}}^{\text{ol/liq}}\) applicable to a wide range of melt compositions. We use the results of our work to model the melting of peridotite beneath lithosphere of varying thickness and show that: (1) a positive correlation between NiO in magnesian olivine phenocrysts and lithospheric thickness is expected given a temperature-dependent \(D_{\text{Ni}}^{\text{ol/liq}} ,\) and (2) the magnitude of the slope for natural samples is consistent with our experimentally determined temperature dependence. Alternative processes to generate the positive correlation between NiO in magnesian olivines and lithospheric thickness, such as the melting of olivine-free pyroxenite, are possible, but they are not required to explain the observed correlation of NiO concentration in initially crystallizing olivine with lithospheric thickness. 相似文献
13.
The onset of hydrous partial melting in the mantle above the transition zone is dictated by the H2O storage capacity of peridotite, which is defined as the maximum concentration that the solid assemblage can store at P and T without stabilizing a hydrous fluid or melt. H2O storage capacities of minerals in simple systems do not adequately constrain the peridotite water storage capacity because
simpler systems do not account for enhanced hydrous melt stability and reduced H2O activity facilitated by the additional components of multiply saturated peridotite. In this study, we determine peridotite-saturated
olivine and pyroxene water storage capacities at 10–13 GPa and 1,350–1,450°C by employing layered experiments, in which the
bottom ~2/3 of the capsule consists of hydrated KLB-1 oxide analog peridotite and the top ~1/3 of the capsule is a nearly
monomineralic layer of hydrated Mg# 89.6 olivine. This method facilitates the growth of ~200-μm olivine crystals, as well
as accessory low-Ca pyroxenes up to ~50 μm in diameter. The presence of small amounts of hydrous melt ensures that crystalline
phases have maximal H2O contents possible, while in equilibrium with the full peridotite assemblage (melt + ol + pyx + gt). At 12 GPa, olivine and
pyroxene water storage capacities decrease from ~1,000 to 650 ppm, and ~1,400 to 1,100 ppm, respectively, as temperature increases
from 1,350 to 1,450°C. Combining our results with those from a companion study at 5–8 GPa (Ardia et al., in prep.) at 1,450°C,
the olivine water storage capacity increases linearly with increasing pressure and is defined by the relation
C\textH2 \textO\textolivine ( \textppm ) = 57.6( ±16 ) ×P( \textGPa ) - 169( ±18 ). C_{{{\text{H}}_{2} {\text{O}}}}^{\text{olivine}} \left( {\text{ppm}} \right) = 57.6\left( { \pm 16} \right) \times P\left( {\text{GPa}} \right) - 169\left( { \pm 18} \right). Adjustment of this trend for small increases in temperature along the mantle geotherm, combined with experimental determinations
of
D\textH2 \textO\textpyx/olivine D_{{{\text{H}}_{2} {\text{O}}}}^{\text{pyx/olivine}} from this study and estimates of
D\textH2 \textO\textgt/\textolivine D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{gt}}/{\text{olivine}}}} , allows for estimation of peridotite H2O storage capacity, which is 440 ± 200 ppm at 400 km. This suggests that MORB source upper mantle, which contains 50–200 ppm
bulk H2O, is not wet enough to incite a global melt layer above the 410-km discontinuity. However, OIB source mantle and residues
of subducted slabs, which contain 300–1,000 ppm bulk H2O, can exceed the peridotite H2O storage capacity and incite localized hydrous partial melting in the deep upper mantle. Experimentally determined values
of
D\textH2 \textO\textpyx/\textolivine D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{pyx}}/{\text{olivine}}}} at 10–13 GPa have a narrow range of 1.35 ± 0.13, meaning that olivine is probably the most important host of H2O in the deep upper mantle. The increase in hydration of olivine with depth in the upper mantle may have significant influence
on viscosity and other transport properties. 相似文献
14.
The activity of silica in kimberlites,revisited 总被引：1，自引：1，他引：0
Robert W. Luth 《Contributions to Mineralogy and Petrology》2009,158(2):283-294
The activity of silica in a silicate liquid in equilibrium with olivine and orthopyroxene decreases with increasing pressure. In contrast, the activity of silica in
an unbuffered silicate liquid changes little with pressure. Although the implications of these pressure dependencies have
been considered by previous authors in terms of inferring pressures of origin of magmas, less consideration has been given
to the implications of these dependencies on the evolution of the magma en route to the surface, or to the mantle through
which the magma passes. In this paper, a combination of Schreinemakers’ analysis in isothermal section and calculated reactions in space is used to (a) rationalize the absence of orthopyroxene xenocrysts in kimberlites and the relative abundance of olivine
“megacrysts” therein, (b) propose another reason for the paucity of xenocrystic mantle-derived carbonates in kimberlites,
(c) explain why clinopyroxene is much less reactive in the kimberlite melt than is orthopyroxene, and (d) explore the implications
of the relative stabilities of olivine, orthopyroxene, and clinopyroxene in kimberlitic magma for the mantle through which
the magma transits.
相似文献
| Robert W. LuthEmail: |
15.
Lena V. S. Monteiro Roberto P. Xavier Emerson R. de Carvalho Murray W. Hitzman Craig A. Johnson Carlos Roberto de Souza Filho Ignácio Torresi 《Mineralium Deposita》2008,43(2):129-159
The Sossego iron oxide–copper–gold deposit (245 Mt @ 1.1% Cu, 0.28 g/t Au) in the Carajás Mineral Province of Brazil consists
of two major groups of orebodies (Pista–Sequeirinho–Baiano and Sossego–Curral) with distinct alteration assemblages that are
separated from each other by a major high angle fault. The deposit is located along a regional WNW–ESE-striking shear zone
that defines the contact between metavolcano–sedimentary units of the ∼2.76 Ga Itacaiúnas Supergroup and tonalitic to trondhjemitic
gneisses and migmatites of the ∼2.8 Ga Xingu Complex. The deposit is hosted by granite, granophyric granite, gabbro, and felsic
metavolcanic rocks. The Pista–Sequeirinho–Baiano orebodies have undergone regional sodic (albite–hematite) alteration and
later sodic–calcic (actinolite-rich) alteration associated with the formation of massive magnetite–(apatite) bodies. Both
these alteration assemblages display ductile to ductile–brittle fabrics. They are cut by spatially restricted zones of potassic
(biotite and potassium feldspar) alteration that grades outward to chlorite-rich assemblages. The Sossego–Curral orebodies
contain weakly developed early albitic alteration and very poorly developed subsequent calcic–sodic alteration. These orebodies
contain well-developed potassic alteration assemblages that were formed during brittle deformation that resulted in the formation
of breccia bodies. Breccia matrix commonly displays coarse mineral infill suggestive of growth into open space. Sulfides in
both groups of deposits were precipitated first with potassic alteration and more importantly with a later assemblage of calcite–quartz–epidote–chlorite.
In the Sequeirinho orebodies, sulfides range from undeformed to deformed; sulfides in the Sossego–Curral orebodies are undeformed.
Very late, weakly mineralized hydrolytic alteration is present in the Sossego/Currral orebodies. The sulfide assemblage is
dominated by chalcopyrite with subsidiary siegenite, and millerite. Pyrrhotite and pyrite are minor constituents of ore in
the Sequerinho orebodies while pyrite is relatively abundant in the Sossego–Curral bodies. Oxygen isotope partitioning between
mineral pairs constrains temperatures in the deposit spatially and through time. In the Sequeirinho orebody, the early sodic–calcic
alteration stage was characterized by temperatures exceeding 500°C and values for the alteration fluid of 6.9 ± 0.9‰. Temperature declines outward and upward from the zone of most intense alteration.
Paragenetically later copper–gold mineralization displays markedly lower temperatures (<300°C) and was characterized by the
introduction of 18O-depleted hydrothermal fluids −1.8 ± 3.4‰. The calculated δDH2O and values suggest that the fluids that formed the early calcic–sodic alteration assemblage were of formational/metamorphic or
magmatic origin. The decrease of values through time may reflect influx of surficially derived waters during later alteration and mineralization events. Influx
of such fluids could be related to episodic fluid overpressure, resulting in dilution and cooling of the metalliferous fluid,
causing deposition of metals transported as metal chloride complexes. 相似文献
16.
We report new experimental data of Cu diffusivity in granite porphyry melts with 0.01 and 3.9 wt% H2O at 0.15–1.0 GPa and 973–1523 K. A diffusion couple method was used for the nominally anhydrous granitic melt, whereas a Cu diffusion-in method using Pt95Cu5 as the source of Cu was applied to the hydrous granitic melt. The diffusion couple experiments also generate Cu diffusion-out profiles due to Cu loss to Pt capsule walls. Cu diffusivities were extracted from error function fits of the Cu concentration profiles measured by LA-ICP-MS. At 1 GPa, we obtain \({D_{{\text{Cu, dry, 1 GPa}}}}=\exp \left[ {( - {\text{13.89}} \pm {\text{0.42}}) - \frac{{{\text{12878}} \pm {\text{540}}}}{T}} \right],\) and \({D_{{\text{Cu, 3}}{\text{.9 wt\% }}{{\text{H}}_{\text{2}}}{\text{O}},{\text{ 1 GPa}}}}=\exp \left[ {( - 16.31 \pm 1.30) - \frac{{{\text{8148}} \pm {\text{1670}}}}{T}} \right],\) where D is Cu diffusivity in m2/s and T is temperature in K. The above expressions are in good agreement with a recent study on Cu diffusion in rhyolitic melt using the approach of Cu2S dissolution. The observed pressure effect over 0.15–1.0 GPa can be described by an activation volume of 5.9 cm3/mol for Cu diffusion. Comparison of Cu diffusivity to alkali diffusivity and its variation with melt composition implies fourfold-coordinated Cu+ in silicate melts. Our experimental results indicate that in the formation of porphyry Cu deposits, the diffusive transport of magmatic Cu to sulfide liquids or fluid bubbles is highly efficient. The obtained Cu diffusivity data can also be used to assess whether equilibrium Cu partitioning can be reached within certain experimental durations. 相似文献
17.
The diffusion of Ni and Co was measured at atmospheric pressure in synthetic monocrystalline forsterite (Mg2SiO4) from 1,200 to 1,500 °C at the oxygen fugacity of air, along [100], with the activities of SiO2 and MgO defined by either forsterite + periclase (fo + per buffer) or forsterite + protoenstatite (fo + en buffer). Diffusion profiles were measured by three methods: laser-ablation inductively-coupled-plasma mass-spectrometry, nano-scale secondary ion mass spectrometry and electron microprobe, with good agreement between the methods. For both Ni and Co, the diffusion rates in protoenstatite-buffered experiments are an order of magnitude faster than in the periclase-buffered experiments at a given temperature. The diffusion coefficients D M (M = Ni or Co) for the combined data set can be fitted to the equation:with Ea(Ni) = ? 284.3 kJ mol?1 and Ea(Co) = ? 275.9 kJ mol?1, with an uncertainty of ±10.2 kJ mol?1. This equation fits the data (24 experiments) to ±0.1 in log D M. The dependence of diffusion on \(a_{{{\text{SiO}}_{2} }}\) is in agreement with a point-defect model in which Mg-site vacancies are charge-balanced by Si interstitials. Comparative experiments with San Carlos olivine of composition Mg1.8Fe0.2SiO4 at 1,300 °C give a slightly small dependence on \(a_{{{\text{SiO}}_{2} }}\), with D \(\propto\) (\(a_{{{\text{SiO}}_{2} }}^{0.5}\)), presumably because the Mg-site vacancies increase with incorporation of Fe3+ in the Fe-bearing olivines. However, the dependence on fO2 is small, with D \(\propto\) (fO2)0.12±0.12. These results show the necessity of constraining the chemical potentials of all the stoichiometric components of a phase when designing diffusion experiments. Similarly, the chemical potentials of the major-element components must be taken into account when applying experimental data to natural minerals to constrain the rates of geological processes. For example, the diffusion of divalent elements in olivine from low SiO2 magmas, such as kimberlites or carbonatites, will be an order of magnitude slower than in olivine from high SiO2 magmas, such as tholeiitic basalts, at equal temperatures and fO2.
相似文献
$$\log \,D_{\text{M}} \,\left( {{\text{in}}\,{\text{m}}^{2} \,{\text{s}}^{ - 1} } \right) = - 6.77( \pm 0.33) + \Delta E_{\text{a}} (M)/RT + 2/3\log a_{{SiO_{2} }}$$
18.
We present here a numerical modelling study of dislocations in perovskite CaTiO3. The dislocation core structures and properties are calculated through the Peierls–Nabarro model using the generalized stacking
fault (GSF) results as a starting model. The GSF are determined from first-principles calculations using the VASP code. The
dislocation properties such as collinear, planar core spreading and Peierls stresses are determined for the following slip
systems: [100](010), [100](001), [010](100), [010](001), [001](100), [001](010),
and All dislocations exhibit lattice friction, but glide appears to be easier for [100](010) and [010](100).
[001](010) and [001](100) exhibit collinear dissociation. Comparing Peierls stresses among tausonite (SrTiO3), perovskite (CaTiO3) and MgSiO3 perovskite demonstrates the strong influence of orthorhombic distortions on lattice friction. However, and despite some quantitative
differences, CaTiO3 appears to be a satisfactory analogue material for MgSiO3 perovskite as far as dislocation glide is concerned. 相似文献
19.
Interaction of freshly precipitated silica gel with aqueous solutions was studied at laboratory batch experiments under ambient
and near neutral pH-conditions. The overall process showed excellent reversibility: gel growth could be considered as an opposite
process to dissolution and a linear rate law could be applied to experimental data. Depending on the used rate law form, the
resulting rate constants were sensitive to errors in parameters/variables such as gel surface area, equilibrium constants,
Si-fluxes, and reaction quotients. The application of an Integrated Exponential Model appeared to be the best approach for
dissolution data evaluation. It yielded the rate constants k
dissol ∼ (4.50 ± 0.68) × 10−12 and k
growth ∼ (2.58 ± 0.39) × 10−9 mol m−2 s−1 for zero ionic strength. In contrast, a Differential Model gave best results for growth data modeling. It yielded the rate
constants k
dissol ∼ (1.14 ± 0.44) × 10−11 and k
growth ∼ (6.08 ± 2.37) × 10−9 mol m−2 s−1 for higher ionic strength (I ∼ 0.04 to 0.11 mol L−1). The found silica gel solubility at zero ionic strength was somewhat lower than the generally accepted value. Based on the
and standard Gibbs free energy of silica gel formation was calculated as and −850,318 ± 20 J mol−1, respectively. Activation energies for silica gel dissolution and growth were determined as and respectively. An universal value for growth of any silica polymorph, is not consistent with the value for silica gel growth, which questions the hypothesis about one unique activated complex
controlling the silica polymorph growth. 相似文献
20.
Quantitative characterization of plastic deformation of zircon and geological implications 总被引：1，自引：1，他引：0
Steven M. Reddy Nicholas E. Timms Wolfgang Pantleon Patrick Trimby 《Contributions to Mineralogy and Petrology》2007,153(6):625-645
The deformation-related microstructure of an Indian Ocean zircon hosted in a gabbro deformed at amphibolite grade has been
quantified by electron backscatter diffraction. Orientation mapping reveals progressive variations in intragrain crystallographic
orientations that accommodate 20° of misorientation in the zircon crystal. These variations are manifested by discrete low-angle
(<4°) boundaries that separate domains recording no resolvable orientation variation. The progressive nature of orientation
change is documented by crystallographic pole figures which show systematic small circle distributions, and disorientation
axes associated with 0.5–4° disorientation angles, which lie parallel to rational low index crystallographic axes. In the
most distorted part of the grain (area A), this is the [100] crystal direction. A quaternion analysis of orientation correlations confirms the [100] rotation axis
inferred by stereographic inspection, and reveals subtle orientation variations related to the local boundary structure. Microstructural
characteristics and orientation data are consistent with the low-angle boundaries having a tilt boundary geometry with dislocation
line [100]. This tilt boundary is most likely to have formed by accumulation of edge dislocations associated with a 〈001〉{100}
slip system. Analysis of the energy associated with these dislocations suggest they are energetically more favorable than
TEM verified 〈010〉{100} slip. Analysis of minor boundaries in area A indicates deformation by either (001) edge, or [100](100) and [001](100) screw dislocations. In other parts of the grain, cross slip on (111), and (112) planes seems likely. These data provide the first detailed microstructural analysis of naturally deformed zircon
and indicate ductile crystal-plastic deformation of zircon by the formation and migration of dislocations into low-angle boundaries.
Minimum estimates of dislocation density in the low-angle boundaries are of the order of ∼3.1010 cm−2. This value is sufficiently high to have a marked effect on the geochemical behavior of zircon, via enhanced bulk diffusion
and increased dissolution rates. Therefore, crystal plasticity in zircon may have significant implications for the interpretation
of radiometric ages, isotopic discordance and trace element mobility during high-grade metamorphism and melting of the crust. 相似文献