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1.
High temperature infrared spectra of hydrous microcrystalline quartz   总被引：1，自引：0，他引：1  
A series of in-situ high temperature infrared (IR) measurements of water in an agate sample and in a milky quartz has been conducted in order to understand the nature of water in silica at high temperatures (50–700?°C) and the dehydration behavior. IR absorption bands of water molecules trapped in the milky quartz showed a systematic decrease in intensities and a shift from 3425?cm?1 at 50?°C toward 3590?cm?1 at 700?°C without any loss of water. This indicates a change in IR absorption coefficients corresponding to different polymeric states of water at different temperatures. The broad 3430?cm?1 band in the agate sample also showed a systematic decrease in IR intensity and a band shift toward higher frequency with increasing temperature (～700?°C). This indicates that the agate sample also contains fluid inclusion-like water. For this agate sample, a dehydration of loosely hydrogen-bonded molecular water occurred at lower temperatures (<200?°C). At higher temperatures (>400?°C), sharp bands around 3660 and 3725?cm?1 (3740?cm?1 at 50?°C) due to surface silanols, appeared. This indicates dehydration of H2O molecules that are hydrogen bonded to surface silanols. SiOH species in the agate are divided into three groups, namely SiOH group located at structural defects, surface silanols hydrogen bonded to each other and free surface silanols. Former two dehydrate below 700?°C and the dehydration rate of the SiOH at structural defects is faster than the other. IR spectra show that SiOH species decrease continuously even after the dehydration of most of H2O molecules. All these results provide realistic bases for the change in physicochemical states of different OH species in silica at high temperatures.  相似文献   

2.
Hydrous species and the amount of water (OH? ions and crystal hydrate H2O) in structures of nominally anhydrous rock-forming minerals (olivine, ortho- and clinopyroxenes) were studied with Fourier spectroscopy in peridotite nodules (19 samples) from Cenozoic alkali basalts of the Baikal-Mongolia region (Dariganga Plateau, Taryat Depression, and Vitim Plateau). Single-crystal samples oriented relative to the crystallographic axes of minerals were examined with an FTIR spectrometer equipped with an IR microscope at the points of platelets free from fluid inclusions. FTIR spectra were measured in regions of stretching vibrations of OH? and H2O (3800–3000 cm?1) and deformation vibrations of H2O (1850–1450 cm?1). The water content in mineral structures was determined from integral intensities. To estimate the conditions of entrapment and loss of structural water in minerals, their chemical composition, including Fe2+ and Fe3+ contents, was determined with an electron microprobe analysis and Mössbauer spectroscopy. The bulk chemical composition of some nodules was determined with XRF and ICP MS. The total water content (OH? + H2O) varies from 150 to 1140 ppm in olivines, from 45 to 870 ppm in clinopyroxenes, and from 40 to 1100 ppm in orthopyroxenes. Both water species in the mineral structures are retained down to a depth of 150–160 km in wide temperature and pressure ranges (1100–1500 °C, 32–47 kbar) at the oxygen fugacity of ?1.4 to ?0.1 log units relative to that of the quartz-fayalite-magnetite buffer.  相似文献   

3.
Fluid inclusions and clusters of water molecules at nanometer-to submicron-scale in size have been investigated using transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR) in jadeite, quartz and symplectite aegirine–augite, albite, taramite and magnetite corona minerals from ultrahigh-pressure (UHP) jadeite–quartzite at Shuanghe, the Dabie Mountains, China. Fluid inclusions from 0.003 μm to 0.78 μm in size occur in jadeite and quartz crystals, and a small number of fluid inclusions from 0.001 μm to 0.25 μm have also been detected in symplectite-forming minerals. Most of the fluid inclusions have round or negative crystal morphology and contain aqueous fluids, but some contain CO2-rich fluids. They are usually connected to dislocations undetectable at an optical scale. The dislocations represent favorable paths for fluid leakage, accounting for non-decrepitation of most fluid inclusions when external pressure decreased at later stages, although there was partial decrepitation of some fluid inclusions unconnected to defect microstructures resulting from internal overpressure. Non-decrepitation and partial decrepitation of fluid inclusions resulted in changes of original composition and/or density. It is clear that identification of hidden re-equilibration features has significant implications for the petrological interpretation of post-peak metamorphic processes. Micro-FTIR results show that all jadeite and quartz samples contain structural water occurring as hydroxyl ions (OH−) and free water (H2O) in the form of clusters of water molecules. The H2O transformed from OH− during exhumation and could have triggered and enhanced early retrograde metamorphism of the host rocks and facilitated plastic deformation of jadeite and quartz grains by dislocation movement, and thus the H2O released during decompression might represent early-stage retrograde metamorphic fluid. The nominally anhydrous mineral (NAM) jadeite is able to transport aqueous fluids in concentrations of at least several hundred ppm water along a subduction zone to mantle depths in the form of clusters of water molecules and hydroxyl ions within crystals.  相似文献   

4.
The solubility and incorporation mechanisms of water in synthetic, water-saturated jadeite and Na-rich clinopyroxenes have been experimentally investigated. Infrared spectra for water-saturated jadeite synthesised from 2.0 to 10 GPa show two prominent sharp peaks at 3,373 and 3,613 cm–1 together with several weaker features in the OH-stretching region, indicating that there are at least 5 distinct modes of hydrogen incorporation in the structure. Water solubility in pure jadeite reaches a maximum of about 450 ppm by weight at 2 GPa and slowly decreases with increasing pressure to about 100 ppm at 10 GPa. Solubility can be described by the function cOH=A fH2O0.5 exp (–PVSolid/RT), where cOH is water solubility in ppm H2O by weight, A is 7.144 ppm/bar0.5, fH2O is water fugacity, and VSolid=8.019 cm3/mol is the volume change of the clinopyroxene upon incorporation of OH. Jadeite provides a good model for understanding hydrogen incorporation mechanisms in more complex omphacite compositions. Assignment of absorption bands in IR spectra verifies the importance of cation vacancies on the M2 site in providing mechanisms for hydrogen incorporation. However, results also suggest that substitution of lower valency cations onto the M1 site may also be important. Solid solution of jadeite with diopside and in particular, with Ca-Eskola component leads to a drastic increase of water solubility, and the bulk composition has a more important effect on the capacity of omphacite to store water than pressure and temperature. Omphacite is expected to be the major carrier of water in a subducted eclogite after the breakdown of hydrous minerals.Editorial responsibility: W. Schreyer  相似文献   

5.
The present study illustrates the interest of using the elastic recoil detection analysis (ERDA) method to characterize any geological sample matrix with respect to hydrogen. ERDA is combined with Rutherford back scattering (RBS) and particle induced X-ray emission (PIXE), allowing the simultaneous characterization of the matrix with respect to major and trace elements (Z > 15). Analyses are performed by mapping of a 4 × 16 μm2 incident beam of 4He+ on large areas (50 × 200 μm2). The method is almost not destructive and requires no calibration with respect to well known hydrous samples. Hydrous and nominally anhydrous phases in contact with each other in the same sample may both be characterized. The depth of the analyses is limited to several μm beneath the surface, allowing tiny samples to be investigated, provided their sizes are larger than the incident beam. Our setup has been improved in order to allow H determination on a micrometric scale with a 5-15% relative uncertainty and a detection limit of 94 wt ppm H2O. We present multi-elemental mappings on a large panel of samples: (1) natural and analogue synthetic glasses from Stromboli volcano (0.44-4.59 wt% H2O), natural rhyolitic glasses (1466-1616 wt ppm H2O); (2) magmatic rhyolitic melt inclusions from Guadeloupe Island (4.37-5.47 wt% H2O) and their quartz host crystal (2020 ± 230 wt ppm H2O); (3) nominally anhydrous natural (82-260 wt ppm H2O) and experimentally hydrated (240-790 wt ppm H2O) olivines; natural clinopyroxenes (159-716 wt ppm H2O); natural orthopyroxenes (201-452 wt ppm H2O); a natural garnet (90 wt ppm H2O). Results show that ERDA is a strong and accurate reference method that can be used to characterize geological sample from various matrix compositions from high to low water contents. It can be used to calibrate other methods of microanalysis such as Fourier Transform Infrared Spectroscopy (FTIR) or secondary ion mass spectrometry (SIMS).  相似文献   

6.
Aubrites are achondritic meteorites (enstatite pyroxenites) that were formed in highly reduced magmatic environments on a differentiated parent body sharing a common oxygen isotope reservoir with enstatite chondrites (EC), Earth and Moon, and could be considered as a geochemical model of the early proto-Earth. Some pyroxenes of the Pesyanoe aubrite have high abundance of gaseous inclusions, captured during the crystallization of the rocks. Investigation of the inclusions by IR spectroscopy reveals presence of OH− groups and C–H bonds. The former are assigned to protonated point defects in enstatite lattice and the latter to compounds occupying void walls. Molecular water and CO2 were not observed. Volatile components released from the samples of the Pesyanoe enstatite by stepwise crushing and heating are composed of CO2, H2O and a non-condensable phase. Hydrogen isotopic composition of volatiles extracted in form of molecular water in Px-separates varies in the range δD = −61 – −84‰ with mean value of δD = −73 ± 16‰ VSMOW and is within the ranges of ECs and Earth’s mantle. The total abundance of H2 in the pyroxene of Pesyanoe were estimated as at least 0.047 ppm that is too low in comparison with that of enstatite chondrites (≥30 ppm H2) and could indicate nearly complete degassing of the Pesyanoe primitive precursor material during the Pesyanoe parent body accretion or a mantle degassing in igneous differentiation process. In a last case a primitive precursor could have D/H ratio different from that of enstatite chondrites.  相似文献   

7.
The concentration of the Al and Ti paramagnetic impurity centers in pre-ore and ore-stage quartz at the Peschanka porphyry copper–molybdenum–gold deposit in the Western Chukchi Peninsula, Russia were determined using electron paramagnetic resonance spectroscopy (EPR). The [AlO 4 - /h+]0 concentration in pre-ore and ore-stage quartz varies from 29 to 124 and from 13 to 101 at. ppm, respectively. The contents of the [TiO 4 - /Li+]0 and [TiO 4 - /H+]0 centers reach 20 and 6.3 at. ppm, respectively. Pre-ore quartz associated with the formation of biotite–potassium feldspar–quartz alteration and ore-stage quartz associated with the formation of quartz–sericite rocks followed by the ore deposition differ considerably in the Ti center content, especially the [TiO 4 - /H+]0 center. The [TiO 4 - /H+]0 concentration is much higher in the pre-ore quartz (>2 at. ppm) than that in the ore-stage quartz related to copper mineralization (<2 at. ppm). The [TiO 4 - /Li+]0 concentration also decreases from pre-ore to ore-stage quartz. Taking the data we obtained into account, the formation temperature of pre-ore and ore-stage quartz estimated from a titaniumin-quartz geothermometer is 590–470°C (weighted average 520°C) and 510–310°C (weighted average 430°C), respectively. The obtained temperature range of 590 to 310°C is similar to that determined from homogenization of fluid inclusions in quartz.  相似文献   

8.
Garnets in UHP eclogites from Bixiling in Dabieshan were investigated by Fourier transform infrared spectroscopy (FTIR). The results indicate that all garnets contain structural water that occurs as hydroxyl (OH−) and non-structural molecular water (H2O) possibly in the form of sub-microscopic fluid inclusions. The structural hydroxyl contents range from 92 to 1735 ppm (H2O wt.) and most are between 200 and 1000 ppm. Therefore, garnet in eclogite can recycle surface water into the mantle. Various water contents were observed among different samples of the same outcrop (∼150 m) and in different domains of the same sample (∼1 cm). This variability in structural H2O contents suggests that the mobility of fluids during UHP metamorphism was very limited, and that both subduction and exhumation processes of UHP rocks occurred in a short time interval.  相似文献   

9.
In order to gain insight into the correlations between 29Si, 17O and 1H NMR properties (chemical shift and quadrupolar coupling parameters) and local structures in silicates, ab initio self-consistent field Hartree-Fock molecular orbital calculations have been carried out on silicate clusters of various polymerizations and intertetrahedral (Si-O-Si) angles. These include Si(OH)4 monomers (isolated as well as interacting), Si2O(OH)6 dimers (C2 symmetry) with the Si-O-Si angle fixed at 5° intervals from 120° to 180°, Si3O2(OH)8 linear trimers (C2 symmetry) with varying Si-O-Si angles, Si3O3(OH)6 three-membered rings (D3 and C1 symmetries), Si4O4(OH)8 four-membered ring (C4 symmetry) and Si8O12(OH)8 octamer (D4 symmetry). The calculated 29Si, 17O and 1H isotropic chemical shifts (δi Si, δi O and δi H) for these clusters are all close to experimental NMR data for similar local structures in crystalline silicates. The calculated 17O quadrupolar coupling constants (QCC) of the bridging oxygens (Si-O-Si) are also in good agreement with experimental data. The calculated 17O QCC of silanols (Si-O-H) are much larger than those of the bridging oxygens, but unfortunately there are no experimental data for similar groups in well-characterized crystalline phases for comparison. There is a good correlation between δi Si and the mean Si-O-Si angle for both Q 1 and Q 2, where Q n denotes Si with n other tetrahedral Si next-nearest neighbors. Both the δ i O and the 17O electric field gradient asymmetry parameter, η of the bridging oxygens have been found to depend strongly on the O site symmetry, in addition to the Si-O-Si angle. On the other hand, the 17O QCC seems to be influenced little by structural parameters other than the Si-O-Si angle, and is thus expected to be the most reliable 17O NMR parameter that can be used to decipher Si-O-Si angle distribution information. Both the 17O QCC and the 2H QCC of silanols decrease with decreasing length of hydrogen bond to a second O atom (Si-O-H···O), and the δ i H increase with the same parameter. Received: 18 July 1997 / Revised, accepted: 23 February 1998  相似文献   

10.
Dissolution of water in magmas significantly affects phase relations and physical properties. To shed new light on the this issue, we have applied 1H and 29Si nuclear magnetic resonance (NMR) spectroscopic techniques to hydrous silicate glasses (quenched melts) in the CaO-MgO-SiO2 (CMS), Na2O-SiO2, Na2O-CaO-SiO2 and Li2O-SiO2 systems. We have also carried out ab initio molecular orbital calculations on representative clusters to gain insight into the experimental results.The most prominent result is the identification of a major peak at ∼1.1 to 1.7 ppm in the 1H MAS NMR spectra for all the hydrous CMS glasses. On the basis of experimental NMR data for crystalline phases and ab initio calculation results, this peak can be unambiguously attributed to (Ca,Mg)OH groups. Such OH groups, like free oxygens, are only linked to metal cations, but not part of the silicate network, and are thus referred to as free hydroxyls in the paper. This represents the first direct evidence for a substantial proportion (∼13∼29%) of the dissolved water as free hydroxyl groups in quenched hydrous silicate melts. We have found that free hydroxyls are favored by (1) more depolymerized melts and (2) network-modifying cations of higher field strength (Z/R2: Z: charge, R: cation-oxygen bond length) in the order Mg > Ca > Na. Their formation is expected to cause an increase in the melt polymerization, contrary to the effect of SiOH formation. The 29Si MAS NMR results are consistent with such an interpretation. This water dissolution mechanism could be particularly important for ultramafic and mafic magmas.The 1H MAS NMR spectra for glasses of all the studied compositions contain peaks in the 4 to 17 ppm region, attributable to SiOH of a range of strength of hydrogen bonding and molecular H2O. The relative population of SiOH with strong hydrogen bonding grows with decreasing field strength of the network-modifying cations. Ab initio calculations confirmed that this trend largely reflects hydrogen bonding with nonbridging oxygens.  相似文献   

11.
Impurity inhomogeneities and other structural defects have been studied by means of transmission electron microscopy (TEM), X-ray microanalysis and electron paramagnetic resonance (EPR) in untreated and heat-treated quartz samples of three genetic types: hydrothermal, pegmatitic and magmatic. The impurities present are Al, Na and H2O, which occupy tetrahedral (Al3+) or interstitial (Na+, H2O) positions in the quartz lattice. Impurities form imperfections of various degrees of segregation: from point defects to micropores with a gas-liquid content. Their size, form, density and distribution in the lattice depend on the formation conditions of the quartz, the presence of dislocations and plane defects serving as sinks for the impurity atoms, and the heat treatment regime. Experimental data indicate that gas-liquid inclusions of dimensions up to some microns are the result of impurity segregation during postcrystallizational cooling. Crystalline quartz amorphizes upon electron irradiation. A model of structural water explaining experimentally observed features of this phenomenon is proposed whereby the water molecule, represented as a dipole, enters microregions of the silica lattice with a high impurity content and there forms a bond between ‘defective’ [SiO3]2? and [AlO4]5? tetrahedra. On irradiation, the Si---O donor-acceptor bonds trap nonelastically scattered electrons and are ruptured as a result. The water released by this lattice discontinuity forms microbubbles that diffuse along sinks into the larger micropores thus further increasing their volume.  相似文献   

12.
Sodic amphiboles in high pressure and ultra-high pressure (UHP) metamorphic rocks are complex solid solutions in the system Na2O–MgO–Al2O3–SiO2–H2O (NMASH) whose compositions vary with pressure and temperature. We conducted piston-cylinder experiments at 20–30?kbar and 700–800?°C to investigate the stability and compositional variations of sodic amphiboles, based on the reaction glaucophane=2jadeite+talc, by using the starting assemblage of natural glaucophane, talc and quartz, with synthetic jadeite. A close approach to equilibrium was achieved by performing compositional reversals, by evaluating compositional changes with time, and by suppressing the formation of Na-phyllosilicates. STEM observations show that the abundance of wide-chain structures in the synthetic amphiboles is low. An important feature of sodic amphibole in the NMASH system is that the assemblage jadeite–talc?±?quartz does not fix its composition at glaucophane. This is because other amphibole species such as cummingtonite (Cm), nyböite (Nyb), Al–Na-cummingtonite (Al–Na-Cm) and sodium anthophyllite (Na-Anth) are also buffered via the model reactions: 3cummingtonite?+?4quartz?+?4H2O=7talc, nyböite?+?3quartz=3jadeite?+?talc, 3Al–Na-cummingtonite + 11quartz + 2H2O=6jadeite + 5talc, and 3 sodium anthophyllite?+?13quartz?+?4H2O=3 jadeite + 7talc. We observed that at all pressures and temperatures investigated, the compositions of newly grown amphiboles deviate significantly from stoichiometric glaucophane due to varying substitutions of AlIV for Si, Mg on the M(4) site, and Na on the A-site. The deviation can be described chiefly by two compositional vectors: [NaAAlIV]<=>[□ASi] (edenite) toward nyböite, and [Na(M4)AlVI]<=>[Mg(M4)MgVI] toward cummingtonite. The extent of nyböite and cummingtonite substitution increases with temperature and decreases with pressure in the experiments. Similar compositional variations occur in sodic amphiboles from UHP rocks. The experimentally calibrated compositional changes therefore may prove useful for thermobarometric applications.  相似文献   

13.
Infrared and Raman spectra of the basic copper salts malachite, Cu2(OH)2CO3, and brochantite, Cu4(OH)6SO4, as well as of deuterated and 13C substituted samples are presented and discussed in terms of group theory and the hydrogen bonds present. The main results are that (i) the hydrogen donor strengths of the OH? ions are strongly increased due to the very great synergetic effect of the copper ions, (ii) the acceptor strengths of the H-bond acceptor groups (SO4 2-, CO3 2-, and OH? ions) are significantly modified by the linkage and coordination of the acceptor atoms — this complicates true assignment of the OH bands observed to the two and six different OH? ions present in malachite and brochantite, respectively -, and (iii) the Cu — O stretching modes at 430–590 cm?1 and 420–520 cm?1 for malachite and brochantite, respectively, exhibit strong, partially covalent Cu — O bonding.  相似文献   

14.
Pegmatite quartz from different occurrences in Norway and Namibia was investigated by a combination of ICP-MS, Electron Spin Resonance (ESR), Capillary Ion Analysis (CIA) and Gas Chromatography (GC) to quantify trace elements in very low concentrations and to determine their position in the quartz structure.The studied quartz samples show similar geochemical characteristics with low contents of most trace elements. Remarkable are the elevated concentrations of Al (36-636 ppm), Ti (1.6-25.2 ppm), Ge (1.0-7.1 ppm), Na (5.2 to >50 ppm), K (1.6 to >100 ppm) and Li (2.1-165.6 ppm). These elements are preferentially incorporated into the quartz lattice on substitutional (Al, Ti, Ge) and interstitial (Li, Na, K) positions. Li+ was found to be the main charge compensating ion for Al, Ge and Ti, whereas some ppm of Na and K may also be hosted by fluid inclusions. Ti may be incorporated as substitutional ion for Si or bound on mineral microinclusions (rutile). The results of the ESR measurements show that there may be a redistribution of alkali ions during irradiation. The diamagnetic [AlO4/M+]0 center transforms into the paramagnetic [AlO4]0 center, whilst the compensating ions diffuse away and may be captured by the diamagnetic precursor centers of [GeO4]0 and [TiO4]0 to form paramagnetic centers ([TiO4/Li+]0, [GeO4/Li+]0).In general, fluid inclusions in pegmatite quartz can be classified as H2O-CO2-NaCl type inclusions with water as the predominant volatile. Among the main elements hosted by fluid inclusions in quartz are Na, K, NH4, Ca, Mg and the anionic complexes Cl−, NO3−, HCO3− and SO42−. Gas analysis of trapped fluids shows volatile components in the following order of abundance: H2O > CO2 > N2(+) ≥ CH4 > COS > C2 and C3 hydrocarbons. Additionally, traces of Co, Ni, Zn, Pb, and Cu were detected by CIA in fluid inclusions of some samples. There are indications that the REE and Rb are also bound in fluid inclusions, however, the concentrations of these elements are too low to be measured by CIA. Assuming that the REE preferentially occur in fluid inclusions, the typical chondrite normalized REE distribution patterns with tetrad effects and a distinct negative Eu anomaly would reflect the composition of the mineralizing fluid.For a number of elements, especially those with extremely low concentrations, the “type” of incorporation in quartz could not directly be determined. We conclude that these ions either are too large to substitute for the small Si4+ ion or they are not soluble in the mineralizing fluids to be hosted by fluid inclusions. Some of these elements, which are concentrated in the specific mineralization of certain pegmatites, are not present in elevated concentrations in the paragenetic pegmatite quartz itself. This was observed, for instance, for Be, Cs and Rb in the Li (Be-Cs-Rb) pegmatites of Rubicon or for Nb and Ta for Nb-Ta bearing pegmatites from Norway. It may be concluded that the concentrations of these trace elements in quartz do not reflect the mineralization and that these elements thus, cannot be used as petrogenetic indicator.  相似文献   

15.
Summary Results of a multidisciplinary study on quartz concentrates (mineralogically separated) and etched concentrates (stoichiometric quartz) from three locations at Allchar (Macedonia) are presented. The investigation of quality and composition of these quartz samples is of great interest because the same material has been previously used as monitor for 26Al Acceleration Mass-Spectrometry (AMS) erosion rate estimates. Two genetically different types of quartz are distinguished in the studied samples which petrologically can be described as hydrothermally altered dacites or quartz latites; i.e. volcanic (QV) and hydrothermal (QH) quartz with relative proportions of QH:QV around 3:2. QH is genetically related to the Allchar Sb–As–Tl–S mineralization having very high Sb (85–785 ppm), As (7.6–78 ppm) and (Tl 3.3–4.0 ppm) contents. This type of quartz is also characterized by very high Li (129–138 ppm), Al (2424–2520 ppm) and Ti (153–219 ppm) concentrations. QV appears to be much less enriched in trace elements having Al and K contents ranging from 0 to 280 ppm and from 50 to 85 ppm, respectively. 26Al AMS measurements were done on the samples containing two genetically different types of quartz but this had no effects on the interpretation and erosion rate determinations. However, the extremely high Al concentrations in the analyzed quartz have generally negative effects, mainly by decreasing 26Al/27Al ratios and thus causing an increase of the detection limit. The disagreement between the results of 26Al AMS analyses and quantitative geomorphologic data for one location is probably caused by different geographical position with respect to the direction of cosmic rays.  相似文献   

16.
Four nearly pure MgAl2O4 spinels, of both natural and synthetic occurrence, have been studied by means of X-ray single crystal diffraction and FTIR spectroscopy in order to detect their potential OH content. Absorption bands that can be assigned to OH incorporated in the spinel structure were only observed in spectra of a non-stoichiometric synthetic sample. The absorption intensity of two bands occurring at 3350 and 3548 cm−1 indicate an OH content of 90 ppm H2O. Based on correlations of OH vibrational frequencies and O-H?O distances, the observed absorption bands correspond to O-H?O distances of 2.77 and 2.99 Å, respectively, which is close to the values obtained by the structure refinements for VIO-Ounsh (2.825 Å) and IVO-O (3.001 Å). This indicates that one probable local position for hydrogen incorporation is the oxygens coordinating a vacant tetrahedral site. The present spectra demonstrate that the detection limit for OH in Fe-free spinels is in the range 10-20 ppm H2O. However, at appreciable Fe2+ levels, the detection of OH bands becomes hampered due to overlap with strong absorption bands caused by electronic d-d transitions in Fe2+ in the tetrahedral position.  相似文献   

17.
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   

18.
Tabular steeply dipping cassiterite‐bearing lodes in the Mount Wells region are hosted by lower greenschist fades metasediment of the Pine Creek Geosyncline within the contact aureole of late orogenic granitoids. The latter are predominantly I‐type, but S‐type phases are developed near the sediment‐granitoid contact.

Quartz, cassiterite, pyrite, arsenopyrite, chalcopyrite and pyrrhotite are the main minerals. Two types of lodes are present: (i) Sn‐quartz lodes containing 5–10 vol% sulphide minerals; and (ii) Sn‐sulphide lodes containing ～ 70 vol% sulphide minerals. At the surface, the former appear as normal quartz veins and the latter as hematite‐quartz breccia resulting from the collapse of original sulphide‐rich lodes as a consequence of volume reduction due to oxidation and leaching.

Two stages of quartz veining are recognized in both types of lodes. Cassiterite is present in stage I while stage II is composed of barren quartz with minor pyrite. Late stage III carbonate veinlets are present in Sn‐sulphide lodes. The lode‐wallrock contact is sharp with weak alteration effects confined to the fringe of the lodes. The alteration minerals include sericite, quartz, tourmaline, chlorite, pyrite and minor K‐feldspar.

Four types of fluid inclusions are present in vein quartz and cassiterite: Type A (CO2 ± H2O ± CH4); Type B (H2O+～ 20% vapour); Type C (H2O+ < 15% vapour) and Type D (H2O+ < 15% vapour + NaCl). Early ‘primary’ inclusions represented by Types A and B are present in stage I only and have a well‐defined temperature mode at ～300°C and a salinity range of 1–20 wt% eq NaCl. Types C and D inclusions are ‘secondary’ in stage I and primary in stage II and have a temperature mode at 120–160°C and salinities from about 1 to more than 26 wt% eq NaCl. Variable H2O‐CO2 ratios of Type A inclusions and homogenization in CO2 or H2O phase at near identical temperature indicate entrapment at the H2O‐CO2 solvus and define a pressure of ～ 100 MPa. The melting sequence of frozen inclusions suggests that the ore fluids were mainly H2O‐CO2‐CH4‐Na‐Ca‐Cl brines. This is also confirmed by Raman Laser Spectrometry.

Oxygen and sulphur isotope data are consistent with a magmatic origin of the ore fluids. The δD values are up to 20%0 higher than those expected for magmatic fluids and probably resulted from interaction of the latter with the carbonaceous strata. This interpretation is supported by δ13C data on the fluid inclusion CO2.

Fluid inclusions, stable isotope and mineralogical data are used to approximate the physico‐chemical parameters of the ore fluids which are as follows: T 300°C, m Cl～2, fO2 ～ 10‐35, mSS ～ 0.01, Sn ～ 1 ppm, Cu ～ 1 ppm and pH ～ 5.5.

It is suggested that fluids of granitic parentage interacted with the enclosing sediment and picked up CO2, CH4 and possibly Ca. The granitic phases became reduced due to this interaction and developed S‐type characteristics. Tin was probably partitioned into the CH4‐bearing reduced fluids. At some stage the fluid overpressure exceeded the lithostatic lode enforcing failure of the carapace and the intruded rocks by hydraulic fracturing causing CH4 and CO2 loss resulting in the precipitation of the ore minerals.  相似文献   

19.
Compositional re-equilibration of fluid inclusions in quartz   总被引：3，自引：0，他引：3  
Compositional modifications to salt-water fluid inclusions in quartz were observed following exposure to disequilibrium conditions in a series of laboratory experiments in which samples containing inclusions of known composition were annealed at 3 kbar and 600≤T≤825°C in the presence of fluids having different compositions for time intervals ranging from a few days to one month. Changes in inclusion compositions following re-equilibration were monitored using salt crystal dissolution temperatures and/or IR (infra red) spectroscopy. The behaviors of both synthetic and natural fluid inclusions were studied. The synthetic samples were re-equilibrated under P int=P conf conditions to minimize stress in the crystal surrounding the inclusions, and were subjected to both f H2O int f H2O conf and f H2O int f H2O conf . After re-equilibration for four days at T≥600°C, most inclusions displayed significant compositional changes Without decrepitation. Salinity variations as large as ≈ 25 wt% were inferred for brine inclusions exposed to f H2O int ≠f H2O conf for 16 days at 825°C. The majority of our observations are consistent with the net diffusion of water toward the reservior having the lowest μH2O; i.e., synthetic NaCl−H2O fluid inclusions exhibited increased Tm(NaCl)s (implying lower relative H2O contents) when re-equilibrated in the presence of fluids having lower μH2O, whereas, similar (and, in some cases, the same) inclusions exhibited decreased Tm(NaCl)s (implying higher H2O contents) after exposure to fluids having higher μH2O. The behavior of natural salt-water fluid inclusions during re-equilibration was generally consistent with corresponding observations on synthetic samples verifying that compositional changes are not restricted to synthetic inclusions. Our results clearly show that there was chemical communication between fluids trapped as inclusions in quartz and the external fluid reservoir. Additionally, it is evident that although applied stress can significantly enhance the re-equilibration rate, strain in the crystal host around the inclusions resulting from large pressure differentials between the internal and confining fluids is not a necessary prerequisite for compositional change. Finally, because significant compositional changes can be induced in brine inclusions in quartz during shortterm exposure to non-equilibrium conditions at 600≤T≤825°C in the laboratory, it is likely that similar changes may result at much lower temperatures during exposure of natural rocks to non-equilibrium conditions over geologic time.  相似文献   

20.
High-resolution core level and valence band (VB) X-ray photoelectron spectra (XPS) of olivine [(Mg0.87Fe0.13)2SiO4], bronzite [(Mg0.8Fe0.2)2Si2O6] and diopside [Ca(Mg0.8Fe0.2)Si2O6] were collected before and after leaching in pH ∼2 solutions with the Kratos magnetic confinement charge compensation system which minimizes differential charge broadening. The leached samples yield Si 2p, Mg 2p, Ca 2p and O 1s XPS spectral linewidths and lineshapes similar to those collected from the respective pristine samples prior to leaching. As with previous XPS studies on crushed samples, our broadscan XPS spectra show evidence for initial, preferential leaching of cations (i.e., Ca2+ and Mg2+) from the near-surface of these minerals. The O 1s spectra of leached olivine and pyroxenes show an additional peak due to OH−, which arises from H+ exchange with near-surface cations (Ca2+ and Mg2+) via electrophilic attack of H+ on the M-O-Si moiety to produce the H2Mg(M1)SiO4(surf) complex at olivine surfaces, and two complexes, H2Mg(M1)Si2O6(surf) and H4Si2O6(surf) at diopside and enstatite surfaces. The olivine and pyroxene surface complexes H2Mg(M1)SiO4(surf) and H2Mg(M1)Si2O6(surf) have been proposed previously, but the second pyroxene surface complex H4Si2O6(surf) has not. Two electrophilic reactions occur in both olivine and pyroxene. For olivine, the more rapid attacks the M2-O-Si moiety producing H2Mg(M1)SiO4(surf); while the second attacks the M1-O-Si moiety ultimately producing H4SiO4 which is released to solution. For pyroxenes, the first electrophilic reaction produces H2Mg(M1)Si2O6(surf), while the second produces.H4Si2O6(surf). These two reactions are followed by a nucleophilic attack of H2O (or H3O+) on Si of H4Si2O6(surf). This reaction is responsible for rupture of the brigding oxygen bond of the Si-O-Si moiety and release of H4SiO4 to solution. The intensity of the OH− peak for the leached pyroxenes is about double the OH− intensity for the leached olivine, consistent with the equivalent of about a monolayer of the above surface complexes being formed in all three minerals.Valence band XPS spectra and density functional calculations demonstrate the remarkable insensitivity of the valence band to leaching of Ca2+ and Mg2+ from the surface layers. This insensitivity is due to a dearth of Ca and Mg valence electron density in the valence band: the Ca-O and Mg-O bonds are highly ionic, with metal-derived s orbital electrons taking on strong O 2p character. The valence band spectrum of leached olivine shows an additional very weak peak at about 13.5 eV, which is assigned to Si 3s valence orbitals in the surface complex H2Mg(M1)SiO4, as indicated by high quality density functional calculations on an olivine where Mg2+ in M2 is replaced by 2H+. The intensity of this new peak is consistent with formation of the equivalent of a monolayer of the surface complex.  相似文献   

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