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1.
We performed in situ infrared spectroscopic measurements of OH bands in a forsterite single crystal between ?194 and 200 °C. The crystal was synthesized at 2 GPa from a cooling experiment performed between 1,400 and 1,275 °C at a rate of 1 °C per hour under high silica-activity conditions. Twenty-four individual bands were identified at low temperature. Three different groups can be distinguished: (1) Most of the OH bands between 3,300 and 3,650 cm?1 display a small frequency lowering (<4 cm?1) and a moderate broadening (<10 cm?1) as temperature is increased from ?194 to 200 °C. The behaviour of these bands is compatible with weakly H-bonded OH groups associated with hydrogen substitution into silicon tetrahedra; (2) In the same frequency range, two bands at 3,617 and 3,566 cm?1 display a significantly anharmonic behaviour with stronger frequency lowering (42 and 27 cm?1 respectively) and broadening (~30 cm?1) with increasing temperature. It is tentatively proposed that the defects responsible for these OH bands correspond to H atoms in interstitial position; (3) In the frequency region between 3,300 and 3,000 cm?1, three broad bands are identified at 3,151, 3,178 and 3,217 cm?1, at ?194 °C. They exhibit significant frequency increase (~20 cm?1) and broadening (~70 cm?1) with increasing temperature, indicating moderate H bonding. These bands are compatible with (2H)Mg defects. A survey of published spectra of forsterite samples synthesized above 5 GPa shows that about 75 % of the incorporated hydrogen belongs to type (1) OH bands associated with Si substitution and 25 % to the broad band at 3,566 cm?1 (type (2); 3,550 cm?1 at room temperature). The contribution of OH bands of type (3), associated to (2H)Mg defects, is negligible. Therefore, solubility of hydrogen in forsterite (and natural olivine compositions) cannot be described by a single solubility law, but by the combination of at least two laws, with different activation volumes and water fugacity exponents.  相似文献   

2.
The present analysis adjusts previous estimates of global ocean CaCO3 production rates substantially upward, to 133 × 1012 mol yr?1 plankton production and 42 × 1012 mol yr?1 shelf benthos production. The plankton adjustment is consistent with recent satellite-based estimates; the benthos adjustment includes primarily an upward adjustment of CaCO3 production on so-called carbonate-poor sedimentary shelves and secondarily pays greater attention to high CaCO3 mass (calcimass) and turnover of shelf communities on temperate and polar shelves. Estimated CaCO3 sediment accumulation rates remain about the same as they have been for some years: ~20 × 1012 mol yr?1 on shelves and 11 × 1012 mol yr?1 in the deep ocean. The differences between production and accumulation of calcareous materials call for dissolution of ~22 × 1012 mol yr?1 (~50 %) of shelf benthonic carbonate production and 122 × 1012 mol yr?1 (>90 %) of planktonic production. Most CaCO3 production, whether planktonic or benthonic, is assumed to take place in water depths of <100 m, while most dissolution is assumed to occur below this depth. The molar ratio of CO2 release to CaCO3 precipitation (CO2↑/CaCO3↓) is <1.0 and varies with depth. This ratio, Ψ, is presently about 0.66 in surface seawater and 0.85 in ocean waters deeper than about 1000 m. The net flux of CO2 associated with CaCO3 reactions in the global ocean in late preindustrial time is estimated to be an apparent influx from the atmosphere to the ocean, of +7 × 1012 mol C yr?1, at a time scale of 102–103 years. The CaCO3-mediated influx of CO2 is approximately offset by CO2 release from organic C oxidation in the water column. Continuing ocean acidification will have effects on CaCO3 and organic C metabolic responses to the oceanic inorganic C cycle, although those responses remain poorly quantified.  相似文献   

3.
Cathodoluminescence (CL) spectra of unirradiated, He+ ion-implanted and electron-irradiated plagioclase minerals contain the following emission bands: (1) below 300 nm due to Pb2+, (2) at ~320 and ~350 nm to Ce3+, (3) at 380–420 nm to Eu2+, Ti4+ and/or Al–O?–Al/Ti defects, (4) at 560–580 nm to Mn2+ and (5) at 720–760 nm to Fe3+. During the implantation of He+ ion, much of their energy may be dissipated by partial destruction and strain of the feldspar framework, resulting in quenching of CL. Deconvolution of CL spectra acquired from albite and oligoclase reveals an emission component at 1.86 eV (666 nm) assigned to a radiation-induced defect center associated with Na+ atoms. As its intensity increases with radiation dose, this emission component has potential for geodosimetry and geochronometry. Electron irradiation causes Na+ migration in plagioclase, and then a considerable reduction in intensity of emissions assigned to impurity centers, which is responsible for an alteration in the energy state or a decrease in luminescence efficiency following the change of activation energy. Emission intensity at 1.86 eV positively correlates with electron irradiation time for unimplanted and He+ ion-implanted albite and oligoclase, but negatively for the implanted albite above 1.07 × 10?4 C/cm2. It implies that radiation halo produced by α-particles should not be measured using CL spectroscopy to estimate β radiation dose on albite in the high radiation level.  相似文献   

4.
Cylinders of synthetic periclase single crystals were annealed at 0.15–0.5 GPa and 900–1200 °C under water-saturated conditions for 45 min to 72 h. Infrared spectra measured on the quenched products show bands at 3,297 and 3,312 cm?1 indicating V OH ? centers (OH-defect stretching vibrations in a half-compensated cation vacancy) in the MgO structure as a result of proton diffusion into the crystal. For completely equilibrated specimens, the OH-defect concentration, expressed as H2O equivalent, was calculated to 3.5 wt ppm H2O at 1,200 °C and 0.5 GPa based on the calibration method of Libowitzky and Rossmann (Am Min 82:1111–1115, 1997). This value was confirmed via Raman spectroscopy, which shows OH-defect-related bands at identical wavenumbers and yields an H2O equivalent concentration of about 9 wt ppm using the quantification scheme of Thomas et al. (Am Min 93:1550–1557, 2008), revised by Mrosko et al. (Am Mineral 96:1748–1759, 2011). Results of both independent methods give an overall OH-defect concentration range of 3.5–9 (+4.5/?2.6) ppm H2O. Proton diffusion follows an Arrhenius law with an activation energy E a = 280 ± 64 kJ mol?1 and the logarithm of the pre-exponential factor logDo (m2 s?1) = ?2.4 ± 1.9. IR spectra taken close to the rims of MgO crystals that were exposed to water-saturated conditions at 1,200 °C and 0.5 GPa for 24 h show an additional band at 3,697 cm?1, which is related to brucite precipitates. This may be explained by diffusion of molecular water into the periclase, and its reaction with the host crystal during quenching. Diffusion of molecular water may be described by logDH2O (m2 s?1) = ?14.1 ± 0.4 (2σ) at 1,200 °C and 0.5 GPa, which is ~ 2 orders of magnitude slower than proton diffusion at identical P-T conditions.  相似文献   

5.
We present new partition coefficients for various trace elements including Cl between olivine, pyroxenes, amphibole and coexisting chlorine-bearing aqueous fluid in a series of high-pressure experiments at 2 GPa between 900 and 1,300 °C in natural and synthetic systems. Diamond aggregates were added to the experimental capsule set-up in order to separate the fluid from the solid residue and enable in situ analysis of the quenched solute by LA–ICP–MS. The chlorine and fluorine contents in mantle minerals were measured by electron microprobe, and the nature of OH defects was investigated by infrared spectroscopy. Furthermore, a fluorine-rich olivine from one selected sample was investigated by TEM. Results reveal average Cl concentrations in olivine and pyroxenes around 20 ppm and up to 900 ppm F in olivine, making olivine an important repository of halogens in the mantle. Chlorine is always incompatible with Cl partition coefficients D Cl olivine/fluid varying between 10?5 and 10?3, whereas D Cl orthopyroxene/fluid and D Cl clinopyroxene/fluid are ~10?4 and D Cl amphibole/fluid is ~5 × 10?3. Furthermore, partitioning results for incompatible trace element show that compatibilities of trace elements are generally ordered as D amph/fluid ≈ D cpx/fluid > D opx/fluid > D ol/fluid but that D mineral/fluid for Li and P is very similar for all observed silicate phases. Infrared spectra of olivine synthesized in a F-free Ti-bearing system show absorption bands at 3,525 and ~3,570 cm?1. In F ± TiO2-bearing systems, additional absorption bands appear at ~3,535, ~3,595, 3,640 and 3,670 cm?1. Absorption bands at ~3,530 and ~3,570 cm?1, previously assigned to humite-like point defects, profit from low synthesis temperatures and the presence of F. The presence of planar defects could not be proved by TEM investigations, but dislocations in the olivine lattice were observed and are suggested to be an important site for halogen incorporation in olivine.  相似文献   

6.
A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe2+ at M1 as well as at M2, and in a first approach assigned Fe3+ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε i,tot = 65,000 ± 3,000 lmolH2O ?1 cm?2. Using this new ε i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H2O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe3+ (<0.1 Fe3+ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al3+ at the tetrahedral site (OH bands around 3,525 cm?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe3+-rich sample (0.2 Fe3+ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm?1 plus shoulder at 3,450 cm?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe3+ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe2+ and combined with increase in Fe3+. That dehydration is correlated with oxidation of Fe2+ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH? content and giving no indication of Fe2+-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe2+ at M2 and low-water concentrations, i.e., at a ratio of Fe2+ M2/H > 10 dehydration occurs by iron oxidation of Fe2+ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe2+ at M2 but high-water concentrations, i.e., ratio of Fe2+ M2/H < 5.0 dehydration occurs through oxidation of Fe2+ at M1.  相似文献   

7.
ABSTRACT

Polycrystalline microdiamonds are rare in ultrahigh-pressure (UHP) rocks worldwide. Among samples collected at Erzgebirge, Germany, we found abundant polycrystalline microdiamonds as inclusions in zircons from a quartzofeldspathic rock. To illuminate their origin and forming age, we investigated morphologies and Raman spectra of 52 microdiamond inclusions, and dated the zircon host. The zircons have low Th/U values (0.03–0.07) and a concordia U/Pb age of 335.8 ± 1.9 Ma. Polycrystalline diamond (10–40 µm) consists of many fine-grained crystals (1.5–3 µm) with different orientations; discrete single diamonds (2–20 µm) are rare. All measured Raman spectra show an intense diamond band at 1332–1328 cm?1 and have a negative correlation with full width at half maximum (FWHM) of 5.8–11.3 cm?1. These data combined with previously reported diamond band data (1331–1337 cm?1) are compatible with those of diamond inclusions in various host minerals from other UHP terranes, but are different from those of ureilite diamonds. The Erzgebirge microdiamonds in zircon do not display visible disordered sp3-carbon, but show downshifting of the Raman band from the ideal value (1332 cm?1), and have a broader diamond band (FWHM >3 cm?1) than those of well-ordered diamonds. These features may reflect imperfect ordering due to rapid nucleation/crystallization during UHP metamorphism and rapid exhumation of the UHP terrane. Graphite inclusions in zircon show a typical G-band at 1587 cm?1. Our study together with previously reported C-isotopic compositions (δ13C, ?17 to ?27‰) of diamond and occurrences of fluid/melt inclusions in diamond and garnet indicates that Erzgebirge microdiamonds are metamorphic, have an organic carbon source, and crystallized from aqueous fluids. Limited long-range ordering suggested by the Raman spectra is a function of the P–T time of crystallization and subsequent thermal annealing on decompression. Combined with regional geology, our work further constrains the tectonic evolution of the Erzgebirge terrane.  相似文献   

8.
This study measures the reaction rate of dolomite and aragonite (calcite) into Mg-calcite at 800, 850, and 900°C and 1.6 GPa. The dry synthetic dolomite-aragonite aggregate transformed very rapidly into dolomite-calcite polycrystalline aggregate while Mg-calcites formed at a relatively slow rate, becoming progressively richer in Mg with run time. We modeled the reaction progress semi-empirically by the first-order rate law. The temperature dependence of the overall transport rate of MgCO3 into calcite can be described by the kinetic parameters (E?=?231.7 kJ/mol and A o ?=?22.69 h?1). Extrapolation using the Arrhenius equation to the conditions during exhumation of UHPM rocks indicates that the reaction of dolomite with aragonite into Mg-saturated calcite can be completed as the P-T path enters the Mg-calcite stability field in a geologically short time period (<1 Ky). On the other hand, the extrapolation of the rate to prograde metamorphic conditions reveals that the Mg-calcite formed from dolomitic marble in the absence of metamorphic fluid may not reach Mg-saturation until temperatures corresponding to high-grade metamorphism (e.g., >340°C and >10 My). SEM-EDS analysis of individual calcite grains shows compositional gradients of Mg in the calcite grains. The Mg-Ca inter-diffusion coefficient at 850°C is around 1.68?×?10?14 m2/sec if diffusion is the major control of the reaction. The calculated closure temperatures for Ca-Mg inter-diffusion as a function of cooling rate and grain size reveal that Ca/Mg resetting in calcite in a dry polycrystalline carbonate aggregate (with grain size around 1 mm) may not occur at temperatures below 480°C at a geological cooling rate around 10°C/My, unless other processes, such as short-circuit interdiffusion along grain boundaries and dislocations, are involved.  相似文献   

9.
A luminol chemiluminescence (CL) detection/flow injection analysis technique coupled with ion chromatography (IC) has been employed for the determination of low levels of Cu(II) and Co(II) in drinking water samples. The detection system was the CL of luminol/perborate or luminol/percarbonate in alkaline medium catalyzed by these transition metals. Oxalic acid in a solution of KOH and N(CH3)4OH was used as an eluent in the IC to improve the column selectivity (Dionex CS5A). Concentration and pH of the eluent affected simultaneously the CL intensity and the retention times (t R). Under the elution conditions used here, the retention times of both metal ions were much greater when the concentration of oxalic acid was decreased. Thus, R t(Cu) = 2.15 min and t R(Co) = 4.50 min were measured at 80 mM oxalic acid concentration, while t R raised to 4.12 and 18 min for Cu(II) and Co(II), respectively, using a 10-mM concentration, but on the other hand, the CL signals showed substantially higher values when the concentration of oxalic acid was lesser in the eluent. An optimum oxalic acid concentration of 20 mM and an eluent pH = 4.7 were selected in order to have reproducible signals with a total analysis time of 10 min. The optimum flow rate for the mobile phase was 1.5 mL min?1. The concentration and pH of the postcolumn reagents also affected the CL signal, obtaining optimum concentrations of 5 mM for both oxidants (perborate or percarbonate) and luminol, this last dissolved in a 0.1-M borate buffer at pH 12. The optimum flow rate for the postcolumn reagents was 1 mL min?1. Linear calibrations for both transition metal ions were established, with calculated detection limits of 0.15 ng mL?1 for Co(II) and 0.20 μg mL?1 for Cu(II). Others ions commonly present in natural waters showed little or no interference. The method was successfully applied to water samples spiked with Cu(II) and Co(II), obtaining recoveries in the range of 85–128%, depending on the metal concentrations.  相似文献   

10.
The effect of ion beam irradiations on the elastic properties of hydrous cordierite was investigated by means of Raman and X-ray diffraction experiments. Oriented single crystals were exposed to swift heavy ions (Au, Bi) of various specific energies (10.0–11.1 MeV/u and 80 MeV/u), applying fluences up to 5 × 1013 ions/cm2. The determination of unit-cell constants yields a volume strain of 3.4 × 10?3 up to the maximum fluence, which corresponds to a compression of non-irradiated cordierite at ~480 ± 10 MPa. The unit-cell contraction is anisotropic (e 1 = 1.4 ± 0.1 × 10?3, e 2 = 1.5 ± 0.1 × 10?3, and e 3 = 7 ± 1 × 10?4) with the c-axis to shrink only half as much as the axes within the ab-plane. The lattice elasticity for irradiated cordierite (? = 1 × 1012 ions/cm2) was determined from single-crystal XRD measurements in the diamond anvil cell. The fitted third-order Birch–Murnaghan equation-of-state parameters of irradiated cordierite (V 0 = 1548.41 ± 0.16 Å3, K 0 = 117.1 ± 1.1 GPa, ?K/?P = ?0.6 ± 0.3) reveal a 10–11 % higher compressibility compared to non-irradiated cordierite. While the higher compressibility is attributed to the previously reported irradiation-induced loss of extra-framework H2O, the anomalous elasticity as expressed by elastic softening (β a ?1 , β b ?1 , β c ?1  = 397 ± 9, 395 ± 28, 308 ± 11 GPa, ?(β ?1)/?P = ?4.5 ± 2.7, ?6.6 ± 8.4, ?5.4 ± 3.0) appears to be related to the framework stability and to be independent of the water content in the channels and thus of the ion beam exposure.  相似文献   

11.
We have undertaken a study of the common green or orange-brown spots at the surface of rough diamond specimens, which are caused by alpha particles emanating from radioactive sources outside the diamond. Richly coloured haloes represent elevated levels of structural damage, indicated by strong broadening of the main Raman band of diamond, intense strain birefringence, and up-doming of spots due to their extensive volume expansion. Green radio-colouration was analogously generated through the irradiation of diamond with 8.8 MeV helium ions. The generation of readily visible radio-colouration was observed after irradiating diamond with ≥1015 He ions per cm2. The accumulation of such a high number of alpha particles requires irradiation of the diamond from a radioactive source over long periods of time, presumably hundreds of millions of years in many cases. In the samples irradiated with He ions, amorphisation was observed in volume areas where the defect density exceeded 5 × 10?3 Å?3 (or 0.03 dpa; displacements per target atom). In contrast, graphitisation as a direct result of the ion irradiation was not observed. The green colouration transformed to brown at moderate annealing temperatures (here 450 °C). The colour transformation is associated with only partial recovery of the radiation damage. The colour change is mainly due to the destruction of the GR1 centre, explained by trapping of vacancies at A defects to form the H3 centre. An activation energy of ~2.4 ± 0.2 eV was determined for the GR1 reduction. The H3 centre, in turn, causes intense yellowish-green photoluminescence under ultraviolet illumination. Radio-colouration and associated H3 photoluminescence are due to point defects created by the ions irradiated, whereas lattice ionisation is of minor importance. This is concluded from the depth distribution of the colouration and the photoluminescence intensity (which corresponds to the defect density but not the ionisation distribution pattern). The effect of the implanted He ions themselves on the colour and photoluminescence seems to be negligible, as radio-colouration and H3 emission were analogously produced through irradiation of diamond with C ions. The photoluminescence emission becomes observable at extremely low defect densities on the order of 10?6 Å?3 (or 0.000006 dpa) and is suppressed at moderate defect densities of ~5 × 10?4 Å?3 (or ~0.003 dpa). Intensely brown-coloured diamond hence does not show the H3 emission anymore. Anneals up to 1,600 °C has reduced considerably irradiation damage and radio-colouration, but the structural reconstitution of the diamond (and its de-colouration) was still incomplete.  相似文献   

12.
Interdiffusion coefficients of Al + Al vs. Mg + Si in the gehlenite–åkermanite system of melilite were determined by coupled annealing of synthesized end-member single crystals. The observed diffusion coefficients for a couple-annealed sample vary for about 2 orders of magnitude, showing strong dependence on the gehlenite–åkermanite composition: diffusion coefficient observed at 1350 °C, for example, is 3 × 10?13 cm2 s?1 at 5 mol% åkermanite composition (Ak5), increases to 2 × 10?11 cm2 s?1 at Ak80, and then decreases to 1 × 10?12 cm2 s?1 at Ak95. The diffusion coefficient–temperature relation indicates high activation energy of diffusion of about 420 kJ mol?1 for gehlenite-rich melilite. The observed diffusion coefficient–composition relation may be explained by a combination of (1) the diffusion coefficient–melting temperature relation (Flynn's rule) and (2) the feasibility of local charge compensation, which can possibly be maintained more easily in the intermediate chemical composition. The high activation energy value for gehlenitic melilite appears to correspond to the complex diffusion mechanism. The observed highly variable diffusion coefficients suggest that gehlenite–åkermanite zoning in the melilite crystals in Ca, Al-rich inclusions in the carbonaceous meteorites may provide a sensitive indicator for the thermal history of the inclusions.  相似文献   

13.
Sized aggregates of glasses (47–84 wt% SiO2) were fused from igneous-derived cohesive fault rock and igneous rock, and step-heated from ~400 to >1,200 °C to obtain their 39Ar diffusion properties (average E=33,400 cal mol?1; D o=4.63×10?3 cm2 s?1). At T<~1,000 °C, glasses containing <~69 wt% SiO2 and abundant network-forming cations (Ca, Fe, Mg) reveal moderate to strong non-linear increases in D and E, reflecting structural modifications as the solid transitions to melt. Extrapolation of these Arrhenius properties down to typical geologic T-t conditions could result in a 1.5 log10 unit underestimation in the diffusion rate of Ar in similar materials. Numerical simulations based upon the diffusion results caution that some common geologic glasses will likely yield 40Ar/39Ar cooling ages rather than formation ages. However, if cooling rates are sufficiently high, ambient temperatures are sufficiently low (e.g., <65–175 °C), and coarse particles (e.g., radius (r) >~1 mm) are analyzed, glasses with compositions similar to ours may preserve their formation ages.  相似文献   

14.
Recent (past 100 years) sedimentary processes in the highly dynamic Gulf of Batabano (Cuba, Caribbean Sea) were investigated through the analyses of environmental radionuclides (e.g., 210Pb, 226Ra, 137Cs, 239,240Pu, and 14C) in nine sediment cores. We evaluated the mean mass accumulation rates (MARs) and the surface mixed layers (SMLs) in each sediment core. Based on these results, three sedimentary environments were identified in the study region. In the central zone, the sediments were mainly composed of carbonate transported from the southern area and showed elevated mass accumulation rates (MAR, 0.11–0.23 g cm?2 year?1) and relatively deep surface mixed layers (SML, 14–16 cm). The southwestern zone was characterized by lower MAR (0.05–0.08 g cm?2 year?1) and thinner SML (7–8 cm). In both areas, the long sediment mixing times in the SMLs (of 45–61 years) smoothed out the sedimentary records. The coastline sedimentary environments were characterized by higher MAR (0.30–0.57 g cm?2 year?1) and the sedimentary records displayed clear signatures of extreme climatic events such as the intensive rains in 1999 reported for La Coloma and the hurricanes Lili and Isodore in 2002. Our study shows that the application of the 210Pb sediment dating method in dynamic costal zones is a challenging task but still may provide important information regarding sedimentation and mixing processes in the ecosystem.  相似文献   

15.
Polarized optical absorption spectra of natural olivine, Fa10Fo90, were measured before and after annealing/quenching experiments performed at 650, 800, 1,000 and 1,200°C under controlled oxygen fugacity. It was found that the annealing induces weak but definite changes in the olivine spectra. The intensity of the spin-allowed Z > X-polarized band at 9,560 cm?1 and shoulder at ～8,300 cm?1 attributed to Fe2+(M2), continuously decreases with annealing temperature, whereas a weaker band at ～11,600 cm?1 assigned to electronic spin-allowed transitions of Fe2+(M1), increases. This evidently shows that annealing treatments cause a redistribution of Fe2+ from M2 to M1. The fractionation increases with increasing temperature. This observation is in good correspondence with many diffraction structural studies of natural and synthetic olivines, as well as with recent Raman and Mössbauer investigations by Kolesov and Geiger (Mitt Österr Mineral Ges 149:48, 2004) and Morozov et al. (Eur J Mineral 17:495–500, 2005) evidencing a weak tendency of Fe to order into the M1 site with increasing temperature. However, this deduction is incompatible with the results of the in situ neutron power diffraction study of synthetic FeMgSiO4 by Redfern et al. (Phys Chem Minerals 27:630–637, 2000). Polarization properties of the UV absorption edge, attributed to ligand-to-metal charge-transfer transitions in Fe3+, changes from Y > X ? Z in natural samples to a weak Y ≥ X ≥ Z-pleochroism in annealed ones. This may be due to redistribution of a small content of Fe3+ among M1 and M2 structural sites.  相似文献   

16.
4He accumulated in fluids is a well established geochemical tracer used to study crustal fluid dynamics. Direct fluid samples are not always collectable; therefore, a method to extract rare gases from matrix fluids of whole rocks by diffusion has been adapted. Helium was measured on matrix fluids extracted from sandstones and mudstones recovered during the San Andreas Fault Observatory at Depth (SAFOD) drilling in California, USA. Samples were typically collected as subcores or from drillcore fragments. Helium concentration and isotope ratios were measured 4?C6 times on each sample, and indicate a bulk 4He diffusion coefficient of 3.5?±?1.3?×?10?C8 cm2?s?C1 at 21°C, compared to previously published diffusion coefficients of 1.2?×?10?C18 cm2?s?C1 (21°C) to 3.0?×?10?C15 cm2?s?C1 (150°C) in the sands and clays. Correcting the diffusion coefficient of 4Hewater for matrix porosity (??3%) and tortuosity (??6?C13) produces effective diffusion coefficients of 1?×?10?C8 cm2?s?C1 (21°C) and 1?×?10?C7 (120°C), effectively isolating pore fluid 4He from the 4He contained in the rock matrix. Model calculations indicate that <6% of helium initially dissolved in pore fluids was lost during the sampling process. Complete and quantitative extraction of the pore fluids provide minimum in situ porosity values for sandstones 2.8?±?0.4% (SD, n?=?4) and mudstones 3.1?±?0.8% (SD, n?=?4).  相似文献   

17.
MgSiO3 akimotoite is stable relative to majorite-garnet under low-temperature geotherms within steeply or rapidly subducting slabs. Two compositions of Mg–akimotoite were synthesized under similar conditions: Z674 (containing about 550 ppm wt H2O) was synthesized at 22 GPa and 1,500 °C and SH1101 (nominally anhydrous) was synthesized at 22 GPa and 1,250 °C. Crystal structures of both samples differ significantly from previous studies to give slightly smaller Si sites and larger Mg sites. The bulk thermal expansion coefficients of Z674 are (153–839 K) of a 1 = 20(3) × 10?9 K?2 and a 0 = 17(2) × 10?6 K?1, with an average of α 0 = 27.1(6) × 10?6 K?1. Compressibility at ambient temperature of Z674 was measured up to 34.6 GPa at Sector 13 (GSECARS) at Advanced Photon Source Argonne National Laboratory. The second-order Birch–Murnaghan equation of state (BM2 EoS) fitting yields: V 0 = 263.7(2) Å3, K T0 = 217(3) GPa (K′ fixed at 4). The anisotropies of axial thermal expansivities and compressibilities are similar: α a  = 8.2(3) and α c  = 10.68(9) (10?6 K?1); β a  = 11.4(3) and β c  = 15.9(3) (10?4 GPa). Hydration increases both the bulk thermal expansivity and compressibility, but decreases the anisotropy of structural expansion and compression. Complementary Raman and Fourier transform infrared (FTIR) spectroscopy shows multiple structural hydration sites. Low-temperature and high-pressure FTIR spectroscopy (15–300 K and 0–28 GPa) confirms that the multiple sites are structurally unique, with zero-pressure intrinsic anharmonic mode parameters between ?1.02 × 10?5 and +1.7 × 10?5 K?1, indicating both weak hydrogen bonds (O–H···O) and strong OH bonding due to long O···O distances.  相似文献   

18.
Growth rates of monomineralic, polycrystalline åkermanite (Ca2MgSi2O7) rims produced by solid-state reactions between monticellite (CaMgSiO4) and wollastonite (CaSiO3) single crystals were determined at 0.5 GPa dry argon pressure, 1,000–1,200°C and 5 min to 60 h, using an internally heated pressure vessel. Inert Pt-markers, initially placed at the monticellite–wollastonite interface, indicate symmetrical growth into both directions. This and mass balance considerations demonstrate that rim growth is controlled by transport of MgO. At 1,200°C and run durations between 5 min and 60 h, rim growth follows a parabolic rate law with rim widths ranging from 0.4 to 16.3 μm indicating diffusion-controlled rim growth. The effective bulk diffusion coefficient \( D_{\text{eff,MgO}}^{\text{Ak}} \) is calculated to 10?15.8±0.1 m2 s?1. Between 1,000°C and 1,200°C, the effective bulk diffusion coefficient follows an Arrhenius law with E a = 204 ± 18 kJ/mol and D 0 = 10?8.6±1.6 m2 s?1. Åkermanite grains display a palisade texture with elongation perpendicular to the reaction interface. At 1,200°C, average grain widths measured normal to elongation, increase with the square root of time and range from 0.4 to 5.4 μm leading to a successive decrease in the grain boundary area fraction, which, however, does not affect \( D_{\text{eff,MgO}}^{\text{Ak}} \) to a detectible extent. This implies that grain boundary diffusion only accounts for a minor fraction of the overall chemical mass transfer, and rim growth is essentially controlled by volume diffusion. This is corroborated by the agreement between our estimates of the effective MgO bulk diffusion coefficient and experimentally determined volume diffusion data for Mg and O in åkermanite from the literature. There is sharp contrast to the MgO–SiO2 binary system, where grain boundary diffusion controls rim growth.  相似文献   

19.
It is well established that the fractionation of Li–F granitic magmas at depth leads to the accumulation of flux elements such as F and Li, and metal cations such as Ta and Nb in residual melts. However, it remains to be determined whether magmatic fractionation is sufficient to concentrate Nb and Ta into economically significant quantities, and what role hydrothermal–metasomatic processes play in the formation of such ore deposits. In the literature, reliable data about the solubility of Ta and Nb in hydrothermal solutions is missing or incomplete. This study provides a quantitative experimental estimation of the possible contribution from hydrothermal processes in Ta enrichment in cupolas of albitized and greisenized Li–F granite. Experimental studies of Ta2O5 and columbite–tantalite (Mn,Fe)(Nb,Ta)2O6 solubility were carried out in fluoride solutions consisting of HF, NaF, KF, and LiF. At low fluoride concentrations (0.01 and 0.1 m), Ta2O5 solubility at 550°C and 100 MPa under Co–CoO oxidizing conditions is low (near 10?5–10?4 m) in all fluoride solutions (HF, NaF, KF, LiF). At high fluoride concentrations (1 and 2 m) the highest Ta2O5 concentrations (10?1 m) were detected in HF solutions. In KF, NaF, and LiF solutions, the Ta2O5 solubility is also high (10?3–10?2 m). The dependence of columbite–tantalite (Nb2O5-59 wt. %, Ta2O5-18 wt. %) solubility as a function of solution composition, T, and P has also been investigated. Tantalum and Nb concentrations have the highest values in HF solutions at reduced conditions (up to 10?3 to 10?2 m Ta in 1 m HF). In 1 m NaF solutions, the concentrations of Nb and Ta are, respectively, 2.5 and 3 orders of magnitude less than those in the 1 m HF solutions. Solubility of Ta and Nb in KF solutions has intermediate values. It is established that in NaF and KF solutions the dependence of solubility on pressure is distinctly negative. The Nb and Ta contents increase with increasing concentrations of HF and KF in solution, however, they do not change with increasing NaF concentration. In NaHCO3, Na2CO3, and HCl solutions columbite–tantalite solubility is low. Even in 1 m chloride solutions the content is within the limits of 10?5 m for Nb and 10?6 to 10?8 m for Ta. We conclude that hydrothermal transport of Ta and Nb is possible only in concentrated fluoride solutions.  相似文献   

20.
In situ X-ray diffraction measurements of KAlSi3O8-hollandite (K-hollandite) were performed at pressures of 15–27 GPa and temperatures of 300–1,800 K using a Kawai-type apparatus. Unit-cell volumes obtained at various pressure and temperature conditions in a series of measurements were fitted to the high-temperature Birch-Murnaghan equation of state and a complete set of thermoelastic parameters was obtained with an assumed K′300,0=4. The determined parameters are V 300,0=237.6(2) Å3, K 300,0=183(3) GPa, (?K T,0/?T) P =?0.033(2) GPa K?1, a 0=3.32(5)×10?5 K?1, and b 0=1.09(1)×10?8 K?2, where a 0 and b 0 are coefficients describing the zero-pressure thermal expansion: α T,0 = a 0 + b 0 T. We observed broadening and splitting of diffraction peaks of K-hollandite at pressures of 20–23 GPa and temperatures of 300–1,000 K. We attribute this to the phase transitions from hollandite to hollandite II that is an unquenchable high-pressure phase recently found. We determined the phase boundary to be P (GPa)=16.6 + 0.007 T (K). Using the equation of state parameters of K-hollandite determined in the present study, we calculated a density profile of a hypothetical continental crust (HCC), which consists only of K-hollandite, majorite garnet, and stishovite with 1:1:1 ratio in volume. Density of HCC is higher than the surrounding mantle by about 0.2 g cm?3 in the mantle transition zone while this relation is reversed below 660-km depth and HCC becomes less dense than the surrounding mantle by about 0.15 g cm?3 in the uppermost lower mantle. Thus the 660-km seismic discontinuity can be a barrier to prevent the transportation of subducted continental crust materials to the lower mantle and the subducted continental crust may reside at the bottom of the mantle transition zone.  相似文献   

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