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1.
Exposure of the ca. 6 Ma Taitao ophiolite, Chile, located 50 km south of the Chile Triple Junction, allows detailed chemical and isotopic study of rocks that were recently extracted from the depleted mantle source of mid-ocean ridge basalts (DMM). Ultramafic and mafic rocks are examined for isotopic (Os, Sr, Nd, and O), and major and trace element compositions, including the highly siderophile elements (HSE). Taitao peridotites have compositions indicative of variable extents of partial melting and melt extraction. Low δ18O values for most whole rock samples suggest some open-system, high-temperature water–rock interaction, most likely during serpentinization, but relict olivine grains have δ18O values consistent with primary mantle values. Most of the peridotites analyzed for Nd–Sr isotopes have compositions consistent with estimates for the modern DMM, although several samples are characterized by 87Sr/86Sr and 143Nd/144Nd indicative of crustal contamination, most likely via interactions with seawater. The peridotites have initial 187Os/188Os ratios that range widely from 0.1168 to 0.1288 (γOs = −8.0 to +1.1), averaging 0.1239 (γOs = −2.4), which is comparable to the average for modern abyssal peridotites. A negative correlation between the Mg# of relict olivine grains and Os isotopic compositions of whole rock peridotites suggests that the Os isotopic compositions reflect primary mantle Re/Os fractionation produced by variable extents of partial melting at approximately 1.6 Ga. Recent re-melting at or near the spatially associated Chile Ridge further modified these rocks, and Re, and minor Pt and Pd were subsequently added back into some rocks by late-stage melt–rock or fluid–rock interactions.In contrast to the peridotites, approximately half of the mafic rocks examined have whole rock δ18O values within the range of mantle compositions, and their Nd and Sr isotopic compositions are all generally within the range of modern DMM. These rocks have initial 187Os/188Os ratios, calculated for 6 Ma, that range from 0.126 (γOs = −1) to as high as 0.561 (γOs = +342). The Os isotopic systematics of each of these rocks may reflect derivation from mixed lithologies that include the peridotites, but may also include pyroxenites with considerably more radiogenic Os than the peridotites. This observation supports the view that suprachondritic Os present in MORB derives from mixed mantle source lithologies, accounting for some of the worldwide dichotomy in 187Os/188Os between MORB and abyssal peridotites.The collective results of this study suggest that this >500 km3 block of the mantle underwent at least two stages of melting. The first stage occurred at 1.6 Ga, after which the block remained isolated and unmixed within the DMM. A final stage of melting recently occurred at or near the Chile Ridge, resulting in the production of at least some of the mafic rocks. Convective stirring of this mantle domain during a >1 Ga period was remarkably inefficient, at least with regard to Os isotopes.  相似文献   

2.
An integrated study of the sedimentology, micropalaeontology, mineralogy and geochemistry of glauconites in the Oligocene Maniyara Fort Formation (western Kutch, India), has been undertaken. Authigenic glauconites, mostly of evolved type, formed within a back‐barrier lagoonal environment. Foraminifera help constrain the biostratigraphy and along with sedimentological evidence, provide information on the depositional conditions. Glauconite in the Maniyara Fort Formation occurs either as infillings within intra‐particle pores of larger foraminifers, or as an altered form of faecal pellets. X‐ray diffraction studies reveal the less mature nature of glauconite infillings compared to the glauconite pellets. Electron microprobe investigation confirms a relative enrichment of K2O and total Fe2O3 in the latter. Both varieties of glauconite formed by initial authigenic precipitation of K‐poor glauconite and subsequently matured by addition of potassium in the interlayer sites and fixation of total iron in the octahedral sites; calcium, magnesium and aluminum were released from the glauconite structure concomitantly. Alkaline conditions during the entire process of glauconite formation did not allow dissolution of foraminiferal tests. Mineralogical and chemical characteristics of the Maniyara Fort Formation glauconites are more similar to deep marine glauconites than those reported from other shallow or marginal marine settings. A low negative cerium anomaly, as well as abundant pyrite, suggests formation of glauconite in sub‐oxic micro‐environments, created by decay of organic matter associated with foraminiferal chambers and faecal pellets. Sub‐oxic condition apparently prevailed relatively longer within the Maniyara Fort Formation lagoons. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

3.
Thermal transformations in biotites depending on increasing postshock temperatures were studied.A decrease of the unit cell volume, caused by oxidation of octahedral Fe2+ to Fe3+ at temperature rangings of about 400–500° C was observed.In the same temperature range (500° C) the biotite lattice becomes thermodynamically unstable. Intersheet and octahedral layers are decomposed, whereas individual SiO4-tetrahedra are more resistant to thermal vibrations. The decomposition of the biotite leads to the formation of new minerals and amorphous phases. By X-ray analysesmagnetite, hercynite, pyroxene, feldspar, and quartz were identified.Thermal transformations of biotite induced by shock waves are characterized by states of distinct disequilibrium.  相似文献   

4.
The zoned pluton from Castelo Branco consists of Variscan peraluminous S-type granitic rocks. A muscovite>biotite granite in the pluton's core is surrounded successively by biotite>muscovite granodiorite, porphyritic biotite>muscovite granodiorite grading to biotite=muscovite granite, and finally by muscovite>biotite granite. ID-TIMS U–Pb ages for zircon and monazite indicate that all phases of the pluton formed at 310 ± 1 Ma. Whole-rock analyses show slight variation in 87Sr/86Sr310 Ma between 0.708 and 0.712, Nd310 Ma values between − 1 and − 4 and δ18O values between 12.2 and 13.6. These geological, mineralogical, geochemical and isotopic data indicate a crustal origin of the suite, probably from partial melting of heterogeneous Early Paleozoic pelitic country rock. In detail there is evidence for derivation from different sources, but also fractional crystallization linking some of internal plutonic phases. Least-squares analysis of major elements and modelling of trace elements indicate that the porphyritic granodiorite and biotite=muscovite granite were derived from the granodiorite magma by fractional crystallization of plagioclase, quartz, biotite and ilmenite. By contrast variation diagrams of major and trace elements in biotite and muscovite, the behaviours of Ba in microcline and whole-rock δ18O, the REE patterns of rocks and isotopic data indicate that both muscovite-dominant granites were probably originated by two distinct pulses of granite magma.  相似文献   

5.
The volume of fluid and amount of heat involved in a portion of a metamorphic event around three synmetamorphic granitic stocks has been quantitatively estimated using mineral composition and modal data from carbonate rocks. Values of volumetric fluid-rock ratios range, with respect to a reference zoisite isograd, from 0.001 to 0.434. Amounts of heat involved range from –25 to 134 cal/cm3 rock. Contours of constant fluid-rock ratio and of constant amount of heat are generally concentric about the granitic stocks indicating that the stocks are foci of high heat and fluid fluxes during metamorphism. In addition, contours of fluid-rock ratios and amount of heat outline NE-SW-trending channelways of high fluid and heat fluxes that alternate with regions of lower fluid and heat fluxes. The NE-SW-trending vertical bedding and schistosity in the area — of premetamorphic origin — probably constrained fluid and heat transfer to occur preferentially in NE-SW directions. Large values of heat involved in metamorphism are strongly correlated with large fluid-rock ratios, suggesting that fluids are an important carrier of heat during metamorphism. Configurations of mapped isograds in the area mimic the patterns of contours of constant fluid-rock ratio and of heat content, indicating that configurations of isograds may contain useful information about regional patterns of heat and fluid transfer during metamorphism.Notation T Last temperature recorded by metacarbonate rocks (°C) - P Lithostatic pressure (bars) - Pi Partial pressure of component i (bars) - of last fluid in equilibrium with carbonate rocks during metamorphism - R 1.987 cal/bar-degree - K s Activity constant for an assemblage of solid mineral phases - In Natural logarithm - c v Volumetric heat capacity (cal/cm3-degree) - Q Heat added to or subtracted from a rock during metamorphism in the zoisite zone (kcal/100 cm3 rock; cal/cm3 rock) - Q{ibrxn} Heat added to or subtracted from a rock due to mineral reactions during metamorphism in the zoisite zone (kcal/100 cm3 rock; cal/cm3 rock) - Std. Dev. Standard Deviation - Average of fluid in equilibrium with carbonate rocks during their metamorphism in the zoisite zone - of fluid in equilibrium with carbonate rocks at the zoisite isograd - T Temperature at the zoisite isograd (°C) - X i,j Mole fraction of component i in phase j - H i Molar enthalpy of reaction i at 0 bars pressure - ¯V i Change of molar volume due to reaction ii - i Measure of progress of reaction i - V Change in rock volume due to fluid-rock reactions - iV Initial rock volume before metamorphism within the zoisite zone - ¯V s,i Change in molar volume of solid minerals due to reaction i Component notation an CaAl2Si2O8 Phase notation Pl Plagioclase - Am Amphibole - Cc Calcite - Qz Quartz - Di Diopside - Zo Zoisite - Ga Garnet - Bi Biotite - Kf Microcline - Mu Muscovite  相似文献   

6.
Clay minerals in the diagenetic/very low-grade metamorphic–sedimentary series from southeastern Anatolia in Turkey were analyzed to determine their mineralogical and chemical compositions. In the Amanos region, the lowermost unit is composed of metaclastics with primary clastic textures, as well as slaty cleavages and chlorite-mica stacks including volcanic rock intercalations. The Lower Cambrian is composed of mainly very low-grade metamorphic clastic rocks, while the Ordovician units have siliciclastic and carbonate rocks. In the Hazro region, the Late Silurian–Lower Triassic units are represented by highly diagenetic carbonate and clastic rocks. All of the rock units include illite. In addition, chlorite, mixed-layered illite–chlorite and chlorite–vermiculite are present in the Amanos region, while calcite, dolomite, kaolinite, mixed-layered illite–smectite (I–S) and glauconite occur in the Hazro region. The illites are characterized by the dominance of 2M1 polytype in the Amanos samples; and 1Md + 2M1 in the Hazro samples. The I–S, glauconite and kaolin have R1 and R3, 1M and kaolinite polytypes, respectively. The illites have greater tetrahedral and lower octahedral substitutions than the I–S. Total trace element contents, elemental substitutions and chondrite-normalized trace element and REE values decrease toward illite–I–S–kaolinite. There are obvious fractionations for some major – trace and rare earth elements with respect to each other and clear enrichment with respect to the chondrite, with strong anomalies of positive for Gd and negative for P, K and Eu in the clay minerals. The textural, morphological and geochemical data indicate that kaolinite and I–S in the Hazro area occur in supergene conditions with due to a full neoformation mechanism, whereas illites in the Amanos region represent the hypogene origin. In brief, the K2O contents, ratios of Eu/Eu* and LaN/LuN and δ18O and δD values of I–S and illite exhibit notable relationships with increasing diagenetic/metamorphic grade.  相似文献   

7.
The mineralogy and chemistry of some analcime-rich igneous rocks — analcimites from the potassic Highwood province, Montana, and an analcime tinguaite from the Dunedin Volcanic Complex, New Zealand — have been investigated to obtain some indication of the KNa substitution in natural analcimes. The analcimes have potash-poor compositions, the K2O revealed by the rock analyses being represented in the mode mainly by Or-rich feldspar (hyalophane or sanidine). These data and the evidence afforded by other analcime compositions confirm earlier conclusions based on experimental studies (Peters, Luth and Tuttle, 1966), namely that analcime solid solutions may contain up to approximately 2% K2O. Some aspects of analcime-rich igneous assemblages are also discussed.  相似文献   

8.
This paper describes the distribution of Fe and Ni between the octahedral and tetrahedral sites in pentlandite (Fe,Ni)9S8. The dependence of the distribution on pressure and temperature and the activation energy of the cation exchange reaction were determined through annealing experiments. Synthetic crystals were annealed at 433–723 K and pressures up to 4 GPa, and natural crystals were annealed at 423, 448 and 473 K in evacuated silica capillary tubes for various durations. The cation distributions in the synthetic crystals were determined with an X-ray powder method employing the anomalous dispersion effect of CuK. and FeK radiations, while those of natural crystals were calculated from the cell dimensions. The values of U, S and V for the Fe/Ni exchange reaction are –6818 J mol–1, 20.52 J K–1 mol–1, and 6.99 × 10–6 m3 mol–1, respectively. The dependence of the Fe/Ni distribution on pressure (Pa) and temperature (Kelvin) was determined as lnK = 2.47+8.20 × 102 T –1+8.41 x 10–7 T –1 P, where K = (Fe/Ni)octahedral /(Fe/Ni)tetrahedral. The activation energy of the cation exchange reaction was 185 kJ mol–1.  相似文献   

9.
In the eastern, external part of the Grenvillian Belt in SW Sweden, five formations of granitic rocks were found in the basement of the Dalslandian Supracrustal Group. The granitic rocks have been strongly recrystallized but have preserved most of their granitic texture in the process. Most magmatic crystals have been pseudomorphed by metamorphic minerals: quartz, albite, chlorite, biotite, white mica, epidote, titanite, hematite, pyrite and carbonate. Two of the formations have subsequently been affected by a cataclastic deformation and at present consist of mylogneisses. 18O whole-rock values for the granitic rocks vary from +3.0 to +11.1. Quartz-apatite, quartz-zircon and quartz-titanite pairs show 18O/16O fractionations corresponding to equilibrium temperatures of 550–700° C, which are believed to reflect in the main continued closed-system isotopic exchange at high temperatures following solidification. In contrast highly positive 18O/16O fractionations for quartz-K-feldspar, quartz-biotite, quartz-chlorite and quartz-sericite pairs in some granitic samples indicate that these rocks have exchanged oxygen with heated, meteoric, H2O dominated fluids. Other granitic samples, however, show virtually undisturbed magmatic 18O/16O fractionation values for the same mineral pairs, even though these rocks are equally altered.It is concluded that all granitic rock units recrystallized under greenschist facies conditions during the infiltration of fluids under the influence of hydrothermal convection systems set up by the intrusion of the granitic plutons. The fluids probably had a range of 18O values from ca. -14 to ca. +10, indicating the mixing of distinct fluid reservoirs, one of meteoric origin and the others of magmatic and/or metamorphic origin. The temperature of alteration is estimated at 450–500° C.Estimation of pre-alteration 18O whole rock values for the five granitic units suggests that three units should be assigned a dominantly S-type origin, where as the other two units may partly or wholly have an I-type origin.  相似文献   

10.
Manganiferous quartz-mica schists (4 m in stratigraphic thickness) overlie epidote amphibolite in the Chiroro River area, Hidaka Mountains, Hokkaido. The schist layers have a considerable range of A/F ratios and bulk oxidation ratios which vary from 21.5 to 100. Manganese contents are from 4 to 30 times higher than that of the average shale with 0.09% MnO. The schists are essentially quartz-white mica-biotite-Mn garnet-tourmaline-±epidote-magnetite assemblages. A highly oxidized layer (5–8 cm thick) 95 cm above the epidote amphibolite contact is characterized by viridine-piemontite-spessartine-Mn white mica-Mn tourmaline-Ti-Mn haematite indicative of both high initial manganese content and very high f O2 conditions of recrystallization.Viridine contains up to 17 mol% Mn3+SiO5 and coexists with piemontite with between 13.6 and 15.4 wt% Mn2O3. Mn-poor-Fe-rich (Ps32) epidote occurs in the less oxidized schist enclosing the viridine-piemontite bearing seam. Garnets vary widely in composition with end member variations (mol%) of Spess22.9–80.5; And0.2–11.7; Alm1.1–57.1; Pyr2.0–12.2; Gross7.0–49.0. The more manganiferous garnets occur in rocks with higher oxidation ratios while almandiferous varieties occur in schists with low oxidation ratios. Biotite ranges from green to red-brown varieties (increasing Ti and Fe) with Mg/ (Mg+Fe) ratios varying from 56 to 48. Ten to fifteen percent octahedral R2+ is replaced by Al indicating a trend towards eastonite-siderophyllite. The white micas deviate only slightly from dioctahedral stoichiometry but have up to 25% of octahedral sites occupied by Fe, Mg and to a lesser extent Mn and Ti as R2+ Si4+2Al3+ and in highly oxidized rocks as (Fe,Mn)3+Al3+. The white mica in the highly oxidized viridine-piemontite schist is pale pinkishorange, exhibits reverse pleochroism, and has between 0.30 and 0.43 wt% Mn2O3.There is a close comparison, both in terms of stratigraphic thickness and Fe-Mn variation, between the Chiroro schist sequence and many oceanic cores so that the bulk chemistry and mineralogy of the pelitic schists is largely an extension of the original Eh-pH conditions of hemipelagic sedimentation and post-depositional adjustments during diagenesis. The thin viridine-piemontite bearing schist is correlated with an oxidized, Fe-Mn rich layer commonly found in present day oceanic cores. The viridine presumably formed by reaction of original ferro-manganese microgranules and clay minerals. Halmrolytic alteration of the underlying metabasalt resulted in leaching of Mn and Fe (in particular) into the overlying sediments and the formation of concentrations of haematite — manganese oxide — Mn garnet along the schist-epidote amphibolite contact.Estimation of the P-T conditions of metamorphism from the phase relations and compositions in the epidote amphibolite associated with the manganiferous schist gives T °C = 530560 and a minimum P fluid > 3 kb which corresponds to the epidote amphibolite facies of Barrovian-type terrains.This paper is dedicated to Professor Kenzo Yagi on the occasion of his retirement from the Chair of Mineralogy, Department of Geology and Mineralogy, Hokkaido University, Sapporo, Japan  相似文献   

11.
The behaviour of synthetic Mg-ferrite (MgFe2O4) has been investigated at high pressure (in situ high-pressure synchrotron radiation powder diffraction at ESRF) and at high temperature (in situ high-temperature X-ray powder diffraction) conditions. The elastic properties determined by the third-order Birch–Murnaghan equation of state result in K0=181.5(± 1.3) GPa, K=6.32(± 0.14) and K= –0.0638 GPa–1. The symmetry-independent coordinate of oxygen does not show significant sensitivity to pressure, and the structure shrinking is mainly attributable to the shortening of the cell edge (homogeneous strain). The lattice parameter thermal expansion is described by a0+a1*(T–298)+a2/(T–298)2, where a0=9.1(1) 10–6 K–1, a1=4.9(2) 10–9 K–2 and a2= 5.1(5) 10–2 K. The high-temperature cation-ordering reaction which MgFe-spinel undergoes has been interpreted by the ONeill model, whose parameters are = 22.2(± 1.8) kJ mol–1 and =–17.6(± 1.2) kJ mol–1. The elastic and thermal properties measured have then been used to model the phase diagram of MgFe2O4, which shows that the high-pressure transition from spinel to orthorombic CaMn2O4-like structure at T < 1700 K is preceded by a decomposition into MgO and Fe2O3.  相似文献   

12.
The paper presents mineralogical, crystallochemical, and Rb–Sr age data on globular layer silicates of the glauconitic series from lower horizons of the Upper Riphean Kil'din Group, Srednii Peninsula. Chloritization significantly changed the globular Al-glauconite in sandstones of the Päräjarvinskaya Formation. However, it almost did not affect glauconite globules in sandstones of the Palvinskaya Formation and altered only clayey component of the rock. Mössbauer spectroscopy showed that Al-glauconite in the Palvinskaya Formation was affected by secondary transformations, which caused the Fe2+ oxidation in octahedral sheets and loss of radiogenic 87Sr. The transformations were presumably related to exhumation of rocks of the Päräjarvinskaya and Palvinskaya formations to the circulation level of the oxygen-rich meteoric waters. Thus, Rb–Sr datings obtained for Al-glauconites of the Palvinskaya (781–786 Ma) and Päräjarvinskaya(744–751 Ma) formations correspond to the tectonic uplift of Kil'din rocks and have no stratigraphic significance.  相似文献   

13.
The unit-cell and atomic parameters of perdeuterated brushite have been extracted from Rietveld analysis of neutron powder diffraction data within the temperature range 4.2 to 470 K. The thermal expansion of brushite is anisotropic, with the largest expansion along the b axis due principally to the effect of the O(1)···D(4) and O(3)···D(2) hydrogen bonds. Expansion along the c axis, influenced by the Ow1···D(5) interwater hydrogen bond, is also large. The high temperature limits for the expansion coefficients for the unit-cell edges a, b and c are 9.7(5) × 10–6, 3.82(9) × 10–5 and 5.54(5) × 10–5 K–1, respectively, and for the cell volume it is 9.7(1) × 10–5 K–1. The angle displays oscillatory variation, and empirical data analysis results in = 1.28(3) × 10–6sin(0.0105 T) K–1, within this temperature range. The evolution of the thermal expansion tensor of brushite has been calculated between 50 T 400 K. At 300 K the magnitudes of the principal axes are 11 = 50(6) × 10–6 K–1, 22 = 26.7(7) × 10–6 K–1 and 33 = 7.0(5) × 10–6 K–1. The intermediate axis, 22, is parallel to b, and using IRE convention for the tensor orthonormal basis, the axes 11 and 33 have directions equal to (–0.228, 0, –0.974) and (–0.974, 0, 0.228) respectively. Under the conditions of these experiments, the onset of dehydration occurred at temperatures above 400 K. Bond valence analysis combined with assessments of the thermal evolution of the bonding within brushite suggests that dehydration is precipitated through instabilities in the chemical environment of the second water molecule.  相似文献   

14.
In-situ synchrotron X-ray diffraction experiments were conducted using the SPEED-1500 multi-anvil press of SPring-8 on stishovite SiO2 and pressure-volume-temperature data were collected at up to 22.5 GPa and 1,073 K, which corresponds to the pressure conditions of the base of the mantle transition zone. The analysis of room-temperature data yielded V0=46.56(1) Å3, KT 0=296(5) GPa and K T =4.2(4), and these properties were consistent with the subsequent thermal equation of state (EOS) analyses. A fit of the present data to high-temperature Birch-Murnaghan EOS yielded (KT /T) P =–0.046(5) GPa K–1 and = a + bT with values of a =1.26(11)×10–5 K–1 and b =1.29(17)×10–8 K–2. A fit to the thermal pressure EOS gives 0=1.62(9)×10–5 K–1, ( K T / T) V =–0.027(4) GPa K–1 and (2P /T 2) V =27(5)×10–7 GPa K–2. The lattice dynamical approach by Mie-Grüneisen-Debye EOS yielded 0=1.33(6), q =6.1(8) and 0=1160(120) K. The strong volume dependence of the thermal pressure of stishovite was revealed by the analysis of present data, which was not detectable by the previous high-temperature data at lower pressures, and this yields ( K T / T) V 0 and q 1. The analyses for the fictive volume for a and c axes show that relative stiffness of c axis to a axis is similar both on compression and thermal expansion. Present EOS enables the accurate estimate of density of SiO2 in the deep mantle conditions.  相似文献   

15.
Petrochemical and Rb-Sr, K-Ar and Sm-Nd isotopic data presented for the Mitterteich granite provide information on whole rock and mineral compositional characteristics, intrusion and cooling history, and protolith nature and put further constraints on the Variscan magmatic evolution in north-east Bavaria.The compositional characteristics classify the Mitterteich granite as a peraluminous (monzo-)granite (SiO2 67.3–73.5 wt.% ). Values for K2O/Na2O (> 1.2 and Al2O3/(CaO + N2O + K2O) (>1.1) are in the range of S-type granites. The rare earth elements show fractionated chondrite-normalized patterns (La N /Yb N =24–19) with negative Eu anomalies (Eu N /Eu N *=0.35–0.19). The micas have restricted ranges of major element composition, but reveal notable variations in trace element concentrations. Different biotite fractions of single specimens show a trend to lower concentrations of compatible elements in the finer fraction which can be explained as a result of asynchronous growth during the fractionation process. The PT conditions of crystallization of the magma based on muscovite and biotite is 600–640°C at 3 kbar. Regression of the whole rock samples gives an isochron corresponding to a 87Rb-87Sr age of 310 ± 7 Ma, initial 87Sr/86Sr of 0.7104±0.0010 (2 errors) and MSWD =0.03. Muscovite and biotite yield concordant K-Ar ages between 310 and 308 Ma, indicating a fast cooling rate of the granite intrusion. Nd T310values average –4.2±1.0. Nd model ages of 1.4 Ga suggest a source region of mid-Proterozoic age.The Rb-Sr isochron age and initial Sr ratio of the Mitterteich granite are indistinguishable from those of the adjacent Falkenberg granite, establishing a genetic link. However, the K-Ar mica ages suggest that the Mitterteich granite must have undergone a faster uplift or cooling history than Falkenberg. Confronted with the geochronological record of granite emplacement in north-east Bavaria, the new results substantiate the view of three key periods of magmatic activity around 330–325, 315–305 and 290 Ma.  相似文献   

16.
Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO4 solutions. Single-crystal XRD refinement with R1=0.0232 for the unique observed reflections (|Fo| > 4F) and wR2=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, Vo=160.11(4) cm3, and fractional positions for all atoms except the H in the H3O groups. The chemical composition of this sample is described by the formula (H3O)0.91Fe2.91(SO4)2[(OH)5.64(H2O)0.18]. The enthalpy of formation (Hof) is –3694.5 ± 4.6 kJ mol–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H2O, and -MgSO4. The entropy at standard temperature and pressure (So) is 438.9±0.7 J mol–1 K–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (Cp) data between 273 and 400 K were fitted to a Maier-Kelley polynomial Cp(T in K)=280.6 + 0.6149T–3199700T–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol–1. Speciation and activity calculations for Fe(III)–SO4 solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the Cp data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in Cp, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H3O)Fe3(SO4)2(OH)6 was estimated: Gof= –3226.4 ± 4.6 kJ mol–1, Hof=–3770.2 ± 4.6 kJ mol–1, So=448.2 ± 0.7 J mol–1 K–1, Cp (T in K)=287.2 + 0.6281T–3286000T–2 (between 273 and 400 K).  相似文献   

17.
A 4 km2 exposure of shallowly-emplaced leucogranite on the Atlantic coast at Cabo de Santo Agostinho, 30 km south of Recife, Brazil has been extensively studied chemically and isotopically. Twenty-three major-element analyses indicate that the Cabo granite ranges from peralkaline to peraluminous; Na2O+K2O is very high (7.4 to 10.4 wt.%), with CaO low (0.3%) and MgO vanishing (<0.06%). Microprobe analyses confirm the presence of arfvedsonite (biotite absent), and nearly total absence of plagioclase. The rocks are moderately to highly enriched in LREE (La 45 to 350 times chondritic), with extremely pronounced negative Eu anomalies (Eu/Eu*=0.02 to 0.07). Whole-rock 18O is consistent at +8.5±0.3%.oSMOW A Rb-Sr isochron age of isotopically slightly disturbed samples is 104.8±1.8 Ma, with initial87Sr/86Sr=0.7084±0.0011. Sr is depleted (2–20 ppm) but Ba is 200–750 ppm.Crystallization path calculations and petrographic observations suggest that magma formed at a pressure close to 6 kbar but rose to a crustal level equivalent to roughly 1 kbar. Quartz, the liquidus phase at moderate H2O concentrations and pressures above 2 kbar, was resorbed during decompression as the magma moved upwards. Ultimately, quartz and alkali feldspar coprecipitated. Feldspar was not retained in the source rock nor removed early from the fractionating magma. Therefore the strong negative Eu anomaly and low Sr abundance are characteristics inherited from the source. A high H2O concentration necessary for a large degree of melting was lacking, hence the Cabo magma composition must reflect a small degree of partial melting of a rather quartz-rich rock such as a feldspathic arenite.In a pre-drift reconstruction of Gondwanaland, the Cabo granite fits on the southernmost and youngest end of the trend of the Niger-Nigerian igneous centers with which it has close affinity. The Cabo granite occupies the western end of the trace of the ancestral Ascension mantle plume which presumably served as the heat source.  相似文献   

18.
Gneisses in the Guri area of the Venezuelan Guayana Shield contain mineral assemblages with cordierite, garnet, sillimanite, hypersthene, biotite and Fe-Ti oxide intergrowths.Analysis of mineral assemblages and compositional relationships in the light of experimental data indicate metamorphic conditions of 725–800° C, 5–6 kb P T , <P T for the highest grade rocks and 650–700° C, 5–7 kb P T , approximating P T for the lowest grade rocks. Oxygen fugacities in different lithologies ranged between those of the MH and QFM buffers.The distribution coefficient K D (Mg-Fe) (gar-bio), decreases by 0.006 per atom percent increase in (Mn/Mn+Mg+Fe)gar, falls in the range of K D typical of the sillimanite-K feldspar zone and granulite facies, and is systematically lower in lower grade rocks-all in accord with observation in other localities. K D (Mg-Fe) (cord-bio) ranges from 3.0 in the highest grade rocks to 10.0 in the lowest grade rocks, appears independent of FeO/MgO of cordierite or biotite, and varies systematically with grade. In contrast with conclusions based on observation in other localities, data from the Guri area suggest -KD(cord-bio) may be a sensitive index of grade.A number of mineralogic and geologic observations are difficultly reconciled with existing experimental data.  相似文献   

19.
Six diverse intrusive igneous types are exposed as discrete outcrops within an area of 900 km2 in the southern Snake Range, White Pine County, Nevada. The previously recognized variety among these igneous types is reflected in the wide range of 18O values (–1.1 to 13.4 permil) found in these rocks. This range of 18O values probably results from differences in source material and post-crystallization history of the different intrusive types.The Jurassic intrusive of the Snake Creek-Williams Canyon area represents the chemical equivalent of a large part of a differentiation sequence, with the entire range of composition (63–76 percent SiO2) exposed over a horizontal distance of about five km. The rather regular increase of 18O values from the most mafic to the most felsic parts of this pluton, together with 18O values determined for constituent minerals recovered from five of the samples, supports a fractional crystallization model. The high 18O values found (10.2–12.2 permil) indicate that the magma likely was derived from or assimilated sedimentary materials.Nine samples of the Cretaceous two-mica granite of the Pole Canyon-Can Young Canyon area have 18O values in the range 10.6–12.1 permil. These high 18O values, an initial87Sr/86Sr ratio of 0.7165, and the presence of muscovite along with an accessory mineral suite limited to monazite, apatite, zircon, and an allanite-like mineral, characterize this intrusive mass as an S-type granite. It probably formed through anatexis of late Precambrian pelitic rocks.The granitoid rock exposed in the Young Canyon-Kious Basin area is Tertiary (32 m.y.). Most of this intrusive has been cataclastically deformed as a result of late (18 m.y.) movement on the overlying Snake Range decollement. The undeformed portion of this intrusive has 18O values of 8.7–10.0 permil. However, the deformed portion of this intrusive has 18O values as low as –1.1 permil, apparently resulting from isotopic exchange between this rock and ground water at the time of cataclasis.Although the igneous types exposed in the southern Snake Range differ petrologically and range in age from Jurassic to Tertiary, most have relatively high 18O values compared with other granitoid rocks of the Basin-Range Province.  相似文献   

20.
The univariant reaction governing the upper stability of heulandite (CaAl2Si7O18·6H2O), heulandite=laumontite+3 quartz+2H2O (1), has been bracketed through reversal experiments at: 155±6° C, 1000 bar; 175±6° C, 1500 bar; and 180±8° C, 2000 bar. Reversals were established by determining the growth of one assemblage at the expense of the other, using both XRD and SEM studies. The standard molal entropy of heulandite is estimated to be 783.7±16 J mol–1 K–1 from the experimental brackets. Predicted standard molal Gibbs free energy and enthalpy of formation of heulandite are –9722.3±6.3 kJ mol–1 and –10524.3±9.6 kJ mol–1, respectively. The reaction (1), together with the reaction, stilbite=laumontite+3 quartz+3 H2O, defines an invariant point at which a third reaction, stilbite=heulandite+ H2O, meets. By combining the present experimental data with past work, this invariant point is located at approximately 600 bar and 140° C. Heulandite, which is stable between the stability fields of stilbite and laumontite, can occur only at pressures higher than that of the invariant point, for = P total.These results are consistent with natural parageneses in low-grade metamorphic rocks recrystallized in equilibrium with an aqueous phase in which is very close to unity.  相似文献   

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