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1.
 In order to develop a model for simulating naturally occurring chromian spinel compositions, we have processed published experimental data on chromian spinel-melt equilibrium. Out of 259 co-existing spinel-melt experiments reported in the literature, we have selected 118 compositions on the basis of run time, melt composition and experimental technique. These data cover a range of temperatures 1150–1500° C, oxygen fugacities of −13<log f O2< −0.7, and bulk compositions ranging from basalt and norite, to komatiite. Six major spinel components with Cr3+, Al3+, Ti4+, Mg2+, Fe3+ and Fe2+-bearing end-members were considered for the purpose of describing chromite saturation as a function of melt composition, temperature and oxygen fugacity at 1 atmosphere pressure (0.101 MPa). The empirically calibrated mineral-melt expression based on multiple linear regressions is: K Sp i =A/T(K)+B log f O2+C ln (Fe3+/Fe2+)L+D ln R L +E, where K Sp i is an equilibrium constant and R L is a melt structure-chemical parameter (MSCP). Twenty-eight forms of equilibrium constants were considered, including single distribution coefficients, exchange equilibrium constants, formation constants for AB2O4 components, as well as simple “spinel cation ratios”. For each form of the equilibrium constants, a set of 16 combinations of the MSCPs have been investigated. The MSCP is present in the form of composite ratios [e.g., Si/O, NBO/T,(Al+Si)/Si, or (Na+K)/Al] or as simple cation ratios (e.g., Mg/Fe2+). For the calculation of Fe3+ and Fe2+ species in silicate melts, we used existing equations, whereas the Fe3+/Fe2+ ratio of spinels was calculated from the spinel stoichiometry. The regression parameters that best repoduce the experimental data were for the following constants: (Fe3+/Fe2+) Sp , (Mg/Fe2+) Sp /(Mg/Fe2+) L , (Cr/Al) Sp / (Cr/Al) L , K FeCr2O4, and Ti Sp /Ti L . These expressions have been combined into a single program called SPINMELT, which calculates chromite crystallization temperature and composition at a given f O2 with an average accuracy of ∼10° C and 1–2 mol%. An example of the use of SPINMELT is presented for a magma parental to the Bushveld Complex. Received: 30 May 1995/Accepted: 1 November 1995  相似文献   

2.
Activities of CoO in (Co,Mn)O solid solutions in contact with metallic Co have been determined on ten compositions ranging from 0.12 to 0.84 XCoO in order to calibrate the divariant equilibrium between (Co,Mn)O oxide solutions and Co metal as an oxygen fugacity sensor for application in experimental petrology. Experiments were conducted over the temperature range 900–1300 K at 1 bar, using an electrochemical technique with oxygen-specific calcia-stabilized zirconia (CSZ) electrolytes. Co + CoO or Fe + FeO was used as the reference electrode. Compositions of the (Co,Mn)O solid solutions were measured after each run by electron microprobe, and these were checked for internal consistency by measuring the lattice parameter by X-ray diffraction. Activity–composition relations were fitted to the Redlich–Kister formalism. (Co,Mn)O solid solutions exhibit slight positive deviations from ideality, which are symmetrical (corresponding to a regular solution mixing model) across the entire composition range with A0 G = 3690(±47) Jmol−1. Excess entropies and enthalpies were also derived from the emf data and gave Sex=0.77(±0.08) JK−1 mol−1 and Hex=4558(±90) Jmol−1 respectively. The experimental data from this study have been used to formulate the (Co,Mn)O/Co oxygen fugacity sensor to give an expression: where μO2 CoCoO=−492,186 + 509.322 T − 53.284 T lnT + 0.02518 T2, taken from O'Neill and Pownceby (1993). Received: 10 September 1999 / Accepted: 4 April 2000  相似文献   

3.
 Diffusion rates for sulfur in rhyolite melt have been measured at temperatures of 800–1100° C, water contents of 0–7.3 wt%, and oxygen fugacities from the quartz-fayalite-magnetite buffer to air. Experiments involved dissolution of anhydrite or pyrrhotite into rhyolite melt over time scales of hours to days. Electron microprobe analysis was used to measure sulfur concentration profiles in the quenched glasses. Regression of the diffusion data in dry rhyolite melt gives Dsulfur=0.05·exp{−221±80RT}, which is one to two orders of magnitude slower than diffusion of other common magmatic volatiles such as H2O, CO2 and Cl-. Diffusion of sulfur in melt with 7 wt% dissolved water is 1.5 to 2 orders of magnitude faster than diffusion in the anhydrous melt, depending on temperature. Sulfur is known to dissolve in silicate melts as at least two different species, S2− and S6+, the proportions of which vary with oxygen fugacity; despite this, oxygen fugacity does not appear to affect sulfur diffusivity except under extremely oxidizing conditions. This result suggests that diffusion of sulfur is controlled by one species over a large range in oxygen fugacity. The most likely candidate for the diffusing species is the sulfide ion, S2−. Re-equilibration between S2− and S6+ in oxidized melts must generally be slow compared to S2− diffusion in order to explain the observed results. In a silicic melt undergoing degassing, sulfur will tend to be fractionated from other volatile species which diffuse more rapidly. This is consistent with analyses of tephra from the 1991 eruption of Mount Pinatubo, Philippines, and from other high-silica volcanic eruptions. Received: 26 April 1995 / Accepted: 1 November 1995  相似文献   

4.
Phase relations of three samples of the Laacher See Tephra (LST) have been determined experimentally as a function of temperature (760 to 880 °C), pressure (200, 300 and 400 MPa), water content of the melt and oxygen fugacity (ƒO2). The crystallization experiments were carried out at ƒO2=NNO buffer and at NNO=+ 2.3 log units. The melt water contents varied between 6 and more than 8 wt% H2O, corresponding to water-undersaturated and water saturated conditions respectively. The synthetic products are compared to the natural phases to constrain pre-eruptive conditions in the Laacher See magma chamber. The major phases occurring in the LST have been reproduced. The stability of hauyne is favoured at high ƒO2 (≈NNO + 2.3). The CaO contents in melt and plagioclase synthesized under water-saturated conditions are significantly higher than in the natural phases, implying that most of the differentiation of the phonolites took place under water-undersaturated conditions. However, this does not exclude the presence of a S-, Cl- and CO2-rich fluid phase in the upper parts of the magma chamber. The phase relationships and the TiO2 contents of melts show that the temperature was lower than 760 °C in the upper part of the magma column (probably down to 720 °C in the most differentiated levels) and that temperatures above 840–860 °C prevailed in the lower part. The variation of the X Mg of ferromagnesian minerals observed in both natural and experimental phases reflects the strong variations in ƒO2 in the lower magma chamber just prior to eruption (probably variation of about 2 log units). The most probable explanation for these ƒO2 variations is the injection of an oxidized alkali-rich magma, containing Mg-rich phenocrysts, at the base of a chemically zoned and more reduced magma column prior to eruption. Although the amount of injected magma may not have been very important, it was sufficient to change the ƒO2 conditions locally, explaining the heterogeneous X Mg of ferromagnesian minerals and the formation of hauyne at the base of the chamber. Received: 30 May 2000 / Accepted: 12 August 2000  相似文献   

5.
 Thermodynamic analysis of Fe- and Mg-bearing plagioclase and silicate liquid was carried out based on reported element partitioning data between plagioclase and silicate liquid in reduced conditions, solution properties of ternary feldspar, standard state properties of plagioclase endmembers and solution properties of multicomponent silicate liquid. Derived mixing properties of Fe- and Mg-bearing plagioclase are in harmony with estimated results from synthetic experiments in the systems CaAl2Si2O8-CaFeSi3O8 and CaAl2Si2O8-CaMgSi3O8. Based on the determined solution properties of the plagioclase, a computer program to calculate the element partition relationships between Fe- and Mg-bearing plagioclase and multicomponent silicate liquid was developed. The FeO, MgO and MgO/(MgO + FeO) in plagioclase predicted from known liquid compositions and pressure are in agreement with measurements within 0.2 wt%, 0.1 wt% and 0.1 (mol ratio), respectively. The Fe3+ content in plagioclase crystallized at high oxygen fugacity can be estimated with this program. The Fe3+/total Fe ratio in plagioclase crystallized near the quartz-fayalite-magnetite buffer ranges from 0 to 0.5, which is consistent with previous study on natural plagioclase in submarine basalt. Derived solution properties of the Fe- and Mg-bearing plagioclase are also used to calculate equilibrium composition relationship between olivine and plagioclase. Change of X Fo in olivine coexisting with plagioclase affects MgO and FeO contents in plagioclase greatly. The present model predicts X Fo of coexisting olivine from the chemical composition of plagioclase to ±0.1 accuracy at given pressure and temperature. Received: 27 March 1998 / Accepted: 30 September 1999  相似文献   

6.
Summary The crystal structure of arsentsumebite, ideally, Pb2Cu[(As, S)O4]2(OH), monoclinic, space group P21/m, a = 7.804(8), b = 5.890(6), c = 8.964(8) ?, β = 112.29(6)°, V = 381.2 ?3, Z = 2, dcalc. = 6.481 has been refined to R = 0.053 for 898 unique reflections with I> 2σ(I). Arsentsumebite belongs to the brackebuschite group of lead minerals with the general formula Pb2 Me(XO4)2(Z) where Me = Cu2+, Mn2+, Zn2+, Fe2+, Fe3+; X = S, Cr, V, As, P; Z = OH, H2O. Members of this group include tsumebite, Pb2Cu(SO4)(PO4)(OH), vauquelinite, Pb2Cu(CrO4)(PO4)(OH), brackebuschite, Pb2 (Mn, Fe)(VO4)2(OH), arsenbracke buschite, Pb2(Fe, Zn)(AsO4)2(OH, H2O), fornacite, Pb2Cu(AsO4)(CrO4)(OH), and feinglosite, Pb2(Zn, Fe)[(As, S)O4]2(H2O). Arsentsumebite and all other group members contain M = M–T chains where M = M means edge-sharing between MO6 octahedra and M–T represents corner sharing between octahedra and XO4 tetrahedra. A structural relationship exists to tsumcorite, Pb(Zn, Fe)2(AsO4)2 (OH, H2O)2 and tsumcorite-group minerals Me(1)Me(2)2(XO4)2(OH, H2O)2. Received June 24, 2000; revised version accepted February 8, 2001  相似文献   

7.
The system KAlO2–MgO–SiO2–H2O–CO2 has long been used as a model for the processes of granulite-facies metamorphism and the development of orthopyroxene-bearing mineral assemblages through the breakdown of biotite-bearing assemblages. There has been considerable controversy regarding the role of carbon dioxide in metamorphism and partial melting. We performed new experiments in this system (at pressures of 342 to 1500 MPa with T between 710 and 1045 °C and X Fl H2O between 0.05 and 1.00), accurately locating most of the dehydration and melting equilibria in P-T-X Fl H2O space. The most important primary result is that the univariant reaction Phl + Qtz + Fl = En + Sa + melt must be almost coincident with the fluid-absent reaction (Phl + Qtz = En + Sa + melt) in the CO2-free subsystem. In conjunction with the results of previous measurements of CO2 solubility in silicate melts and phase equilibrium experiments, our theoretical analysis and experiments suggest that CO2 cannot act as a flux for partial melting. Crustal melting in the presence of H2O–CO2 mixed fluids will always occur at temperatures higher than with pure H2O fluid present. Magmas produced by such melting will be granitic (s.l.) in composition, with relatively high SiO2 and low MgO contents, irrespective of the H2O–CO2 ratio in any coexisting fluid phase. We find no evidence that lamprophyric magmas could be generated by partial fusion of quartz-saturated crustal rocks. The granitic melts formed will not contain appreciable dissolved CO2. The channelled passage of hot CO2-rich fluids can cause local dehydration of the rocks through which they pass. In rock-dominated (as opposed to fluid-dominated) systems, minor partial melting can also occur in veins initially filled with CO2-rich fluid, as dehydration and local disequilibrium drive the fluid towards H2O-rich compositions. However, CO2 is unlikely to be a significant agent in promoting regional granulite-grade metamorphism, melting, magma generation, metasomatism or long-range silicate mass transfer in Earth's crust. The most viable model for the development of granulite-facies rocks involves the processes of fluid-absent partial melting and withdrawal of the melt phase to higher crustal levels. Received: 28 November 1996 / Accepted: 25 June 1997  相似文献   

8.
 Calc-silicate granulites from Rayagada, north-central sector of Eastern Ghats granulite belt show a wide range of mineral assemblages and chemical compositions, which can be grouped as Gr. I (grossular- rich garnet-wollastonite-scapolite-calcite-clinopyroxene), Gr. II (andradite-rich garnet-scapolite-calcite-clinopyr- oxene), and Gr. III (scapolite-calcite-clinopyroxene-plagioclase) assemblages. Petrographic features suggest the following several reactions in the CaO–Al2O3–SiO2-vapor system: Mei+4Wo+Cal=3Grs+Qtz +2CO2, Mei+3Wo+2Cal=3Grs+CO2, Mei= 3An+Cal, Wo+CO2=Cal+Qtz, Mei+5Wo =3Grs+2Qtz+CO2, An+Wo=Grs+Qtz, Mei+ 5Cal+3Qtz=3Grs+6CO2, and the following reactions in the CaO–FeO–MgO–Al2O3–SiO2-vapor system: Cpxss+Scp+Wo=Grtss+Qtz+CO2, 4Hd+ 2Cal+O2=2Adr+2Qtz+2CO2, Cpxss+Scp= Grtss+Cal+Qtz. These reactions have been used to estimate peak T-X CO2 condition for these granulites. A maximum temperature of ∼920 °C has been calculated at an estimated pressure of 9 kbar. A T-X CO2 diagram shows an isobaric cooling from ∼920 °C to ∼815 °C. A range of X CO2 (0.50 at 920 °C to 0.25 at 815 °C) has been observed for Gr. I calc-silicate granulites based on the reaction sequences including coronal garnet-forming reactions. This sequence is suggestive of internal fluid buffering rather than external fluid influx and the differences in X CO2 conditions has been thought to be due to local buffering of fluid phases. Group II and Gr. III calc-silicate granulites, on the other hand, exhibit relatively lower temperature conditions. Received: 11 September 1995/Accepted: 20 June 1996  相似文献   

9.
 Enthalpies of drop solution (ΔH drop-sol) of CaGeO3, Ca(Si0.1Ge0.9)O3, Ca(Si0.2Ge0.8)O3, Ca(Si0.3Ge0.7)O3 perovskite solid solutions and CaSiO3 wollastonite were measured by high-temperature calorimetry using molten 2PbO · B2O3 solvent at 974 K. The obtained values were extrapolated linearly to the CaSiO3 end member to give ΔH drop-sol of CaSiO3 perovskite of 0.2 ± 4.4 kJ mol−1. The difference in ΔH drop-sol between CaSiO3, wollastonite, and perovskite gives a transformation enthalpy (wo → pv) of 104.4 ± 4.4 kJ mol−1. The formation enthalpy of CaSiO3 perovskite was determined as 14.8 ± 4.4 kJ mol−1 from lime + quartz or −22.2 ± 4.5 kJ mol−1 from lime + stishovite. A comparison of lattice energies among A2+B4+O3 perovskites suggests that amorphization during decompression may be due to the destabilizing effect on CaSiO3 perovskite from a large nonelectrostatic energy (repulsion energy) at atmospheric pressure. By using the formation enthalpy for CaSiO3 perovskite, phase boundaries between β-Ca2SiO4 + CaSi2O5 and CaSiO3 perovskite were calculated thermodynamically utilizing two different reference points [where ΔG(P,T )=0] as the measured phase boundary. The calculations suggest that the phase equilibrium boundary occurs between 11.5 and 12.5 GPa around 1500 K. Its slope is still not well constrained. Received: 20 September 2000 / Accepted: 17 January 2001  相似文献   

10.
西天山哈拉达拉辉长岩的Fe-Ti富集机制及其构造意义   总被引：4，自引：4，他引：0  
贺鹏丽  黄小龙  李洪颜  李洁  于洋  李武显 《岩石学报》2013,29(10):3457-3472
特克斯哈拉达拉辉长岩体是西南天山出露规模最大的层状基性-超基性侵入杂岩体,其富含Fe-Ti氧化物(含量高达15%)。哈拉达拉辉长岩中的橄榄石具有较低的Fo值(64~75),斜长石主要为中-拉长石,单斜辉石相对低Mg#(0.66~0.87),属于次透辉石或普通辉石,总体上显示出较高的岩浆演化程度。Fe-Ti氧化物以钒钛磁铁矿为主(TiO2=0.8%~20.6%;V2O3=0.10%~0.83%),常与钛铁矿呈矿物对共生或出溶钛铁矿。晚期的云母矿物均围绕他形的Fe-Ti氧化物生长,主要为富MgO的金云母,少量属于黑云母;大部分云母成分富含F、Cl(F+Cl高达3.14%),指示岩浆形成于贫水环境。哈拉达拉辉长岩体的主量元素成分变化很大(Mg#=0.48~0.73),橄榄辉长岩主要受橄榄石和斜长石的结晶分异/堆晶作用影响,而辉长岩的成分变化主要受控于斜长石和Fe-Ti氧化物的堆晶作用。哈拉达拉岩体的Fe-Ti氧化物主要为岩浆正常结晶分异作用的结果,该体系具有较低氧逸度、贫水的特点,其地幔源区的熔融程度较高,可能是塔里木地幔柱在天山造山带这一构造薄弱带的早期岩浆活动。  相似文献   

11.
 The microstructure of hematite-ilmenite exsolution intergrowth of a natural titanohematite crystal from a granulite has been investigated in a transmission electron microscope equipped with an energy filter. Special emphasis is on quantitative compositional mapping at the nanometre scale using electron spectroscopic imaging, as well as mapping the Fe3+ and Fe2+ valence distribution in the intergrowth. Quantitative point analyses by energy-dispersive X-ray analysis have been compared with results from electron energy-loss spectroscopy and element-distribution mapping. The results indicate that the coexisting compositions of the two phases (Ilm88Hem12 and Ilm16Hem84) are independent of the size of the exsolution. The application of quantitative mapping to determining diffusion profiles around precipitates is demonstrated. Received: 30 March 2000 / Accepted: 7 September 2000  相似文献   

12.
Summary Mineral chemistry and petrological data of chromites from chromitite bands in the N–S trending schist belt of Nuggihalli (southern Karnataka, India), belonging to the Dharwar craton of South India, are presented in this paper. Crystal chemical data indicate a komatiitic affinity of the chromitite. P–T calculations of the chromite-hosting peridotites yielded a pressure range of 13 to 28 kbar and temperatures ranging from 775 to 1080 °C; the oxygen fugacity (log fO2) varies from +0.5 to +1.6 above the QFM buffer. The P, T and fO2 data indicate that Nuggihalli chromitites crystallized in an environment akin to the upper mantle. The studied samples also show partial resetting; the lower temperatures ranging from 515 to 680 °C are ascribed to subsequent metamorphism of the area.  相似文献   

13.
The exchange equilibrium
was studied by reversal experiments as a function of temperature (650 ≤ T ≤ 1000 °C), pressure (10 ≤ P ≤ 20 kbar), and chemical composition. Experiments were performed in a piston-cylinder apparatus using starting mixtures consisting of 95% garnet and 5% ilmenite. At the lower temperatures, 3–5% PbO flux was added to the reactants. The PbO was reduced to metallic lead by the graphite of the capsules. The EMP analysis shows that ilmenite is essentially a solid solution of FeTiO3 and MnTiO3 with up to 4.5 mol% Fe2O3 (for Fe-rich compositions). Garnet is compositionally close to (Fe,Mn)3 Al2Si3O12 but apparently contains up to 1.0 wt% TiO2. As garnet was usually analyzed within 5–15 μm distance from ilmenite grains, the Ti measured in garnet appears to be largely an analytical artifact (due to secondary fluorescence). This was confirmed by analyzing profiles across a couple constructed from ilmenite and Ti-free garnet. The more than 100 exchange runs indicate that the distribution coefficient KD [=(X Mn gnt·X Fe ilm)/(X Fe gnt·X Mn ilm)] is essentially independent of P and decreases with T. With a few exceptions at Mn-rich compositions, the present results are consistent with previous studies on the Fe-Mn partitioning between garnet and ilmenite. Contrary to previous studies, however, the narrow experimental brackets obtained during the present calibration constrain that, at constant T, KD is larger for Mn-rich compositions than for Fe-rich ones. This compositional dependence of KD will complicate garnet-ilmenite geothermometry. Mutually consistent activity models for Fe-Mn garnet and ilmenite, based on a thermodynamic analysis of the present results and other phase equilibria studies in the system Fe-MnO-Al2O3-TiO2-SiO2-O2, will be presented in a following contribution (M. Engi and A. Feenstra, in preparation). Received: 12 September 1996 / Accepted: 11 December 1997  相似文献   

14.
 The stability of pargasite in the presence of excess quartz has been determined in the range of 0.5–6.0 kbar and 500–950 °C in the system Na2O– CaO–MgO–Al2O3–SiO2–H2O, using synthetic minerals. The experimental results from this study indicate the presence of two distinct mineral assemblage regions: (1) a high temperature supersolidus region containing tremolitic amphibole+melt+quartz; (b) a low temperature subsolidus region consisting of Al-rich amphibole+plagioclase+enstatite+quartz. Compositional reversals have been determined for the following three equilibria: (a) 2 pargasite+9 quartz=tremolite+4 plagioclase (An50)+1.5 enstatite+H2O, (b) 2 pargasite+10 quartz=tremolite+4 plagioclase (An50)+talc, and (c) pargasite+diopside+5 quartz=tremolite+2 plagioclase (An50). These experiments indicate a continuous change of amphibole composition from pargasite to tremolite with increasing temperature, and an opposite effect with increasing pressure. The third equilibria is used to constrain a site-mixing model for the pargasitic amphiboles, which favor a single-coupled NaA-AlT1 site mixing. The thermochemical data for pargasite estimated from the reversal data of the three equilibrium reactions is estimated as for ΔG 0 f ,Pg=−12022.11±5.2 kJ mole-1, and S 0 Pg=591.7 ±7.9 JK-1 mole-1. Received: 31 July 1995/Accepted: 3 June 1996  相似文献   

15.
Summary The complexation of aluminium(III) and silicon(IV) was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25 °C. The measurements were performed as potentiometric titrations using a hydrogen electrode with OH − ions being generated coulometrically. The total concentrations of Si(IV) and Al(III) respectively [Si tot ] and [Al t ot], and −log[H +] were varied within the limits 0.3 < [Si tot ] < 2.5 mM, 0.5 < [Al tot ] < 2.6 mM, and 2 ≤ -log[H +] ≤ 4.2. Within these ranges of concentration, evidence is given for the formation of an AlSiO(OH) 3 2+ complex with a formation constant log β1,1-1 = −2.75 ± 0.1 defined by the reaction Al 3++Si (OH)4 ↔ AlOSi(OH) 3 2+ +H + An extrapolation of this value to I=0 gives log β1,1-1 = −2.30. The calculated value of log K (Al 3++SiO(OH) 3 − ↔ AlOSi(OH) 3 2+ ) = 6.72 (I=0.6 M) can be compared with corresponding constants for the formation of AlF 2+ and AlOH 2+ , which are equal to 6.16 and 8.20. Obviously, the stability of these Al(III) complexes decreases within the series OH −>SiO(OH) 3 −  > F −  相似文献   

16.
Relationships between mineral/silicate melt partition coefficients and melt structure have been examined by combining Ca and Mn olivine/melt partitioning data with available melt structure information. Compositions were chosen so that melts with olivine on their liquidii range in degree of polymerization, NBO/T, from ∼0.5 to ∼2.5 under near isothermal conditions (1350-1400°C). Olivine/melt Ca-Mn exchange coefficients, Ca(olivine)/CaO(melt)/MnO(olivine)/MnO(melt) (KD Ca-Mnolivine/melt), as a function of melt NBO/T have a parabolic shape with a minimum KD Ca-Mnolivine/melt-value at NBO/T near 1. Notably, published KD Fe2+-Mgolivine/melt versus NBO/T functions are also parabolic with a maximum in KD Fe2+-Mgolivine/melt near 1 (Kushiro and Mysen, 2002).The olivine/melt partitioning data are modeled in terms of structural units (Qn-species) in the melt. The NBO/T-value corresponding to the minimum KD Ca-Mnolivine/melt is near that where the abundance ratio of Qn-species, XQ3/XQ2, has its largest value. Therefore, the activity coefficient ratio in the melt, γCa2+(melt)/γMn2+(melt), attains a minimum where the abundance ratio of XQ3/XQ2 is at maximum. It is inferred from this relationship that Ca2+ in the melts is dominantly bonded to nonbridging oxygen (Ca-NBO) in Q3-species, whereas Mn2+ is bonded to nonbridging oxygen (Mn-NBO) in less polymerized Qn-species such as Q2.  相似文献   

17.
The Archean Shawmere anorthosite lies within the granulite facies portion of the Kapuskasing Structural Zone (KSZ), Ontario, and is crosscut by numerous linear alteration veins containing calcite + quartz ± dolomite ± zoisite ± clinozoisite ± margarite ±paragonite ± chlorite. These veins roughly parallel the trend of the Ivanhoe Lake Cataclastic Zone. Equilibria involving clinozoisite + margarite + quartz ± calcite ± plagioclase show that the vein minerals were stable at T < 600 °C, XCO2 < 0.4 at P ≈ 6 kbar. The stabilities of margarite and paragonite in equilibrium with quartz are also consistent with T < 600 °C and XCO2 < 0.4 at 6 kbar. Additional assemblages consisting of calcite + clinochlore + quartz + talc + margarite indicate T < 500 °C with XCO2 > 0.9. Thus, vein formation, while clearly retrograde, spanned a range of temperatures, and fluid compositions evolved from H2O-rich to CO2-rich. The calcite in the retrograde veins has δ18O values that range from 8.4 to 11.2‰ (average = +9.7 ± 0.9‰) and δ13C values that range from −3.9 to −1.6‰ (average = −3.1 ± 0.6‰). These values indicate that the fluids from which calcite precipitated underwent extensive exchange with the anorthosite and other crustal lithologies. The fluids may have been initially derived either from devolatilization of metamorphic rocks or crystallization of igneous rocks in the adjacent Abitibi subprovince. Vein quartz contains CO2-rich fluid inclusions (final melting T = −57.0 to −58.7 °C) that range in size from 5 to 17 μm. Measured homogenization temperatures (T h) range from −44.0 to 14.5 °C, however for most inclusions (46 of S1), T h = −44.0 to −21.1 °C (ρCO2 ≈ 1.13 to 1.05 g/cm3). At 400 to 600 °C, these densities correspond to pressures of 3.5 to 7 kbar, which is the best estimate of pressures of vein formation. It has been argued that some high density CO2-rich fluid inclusions found in the KSZ were formed during peak metamorphism and thus document the presence of a CO2-rich fluid during peak granulite facies metamorphism (Rudnick et al. 1984). The association of high density CO2-rich fluid inclusions with clearly retrograde veins documents the formation of similar composition and density inclusions after the peak of metamorphism. Thus, the coincidence of entrapment pressures calculated from fluid inclusion density measurements with peak metamorphic pressures alone should not be considered strong evidence for peak metamorphic inclusion entrapment. All fluid inclusion results are consistent with an initially semi-isobaric retrograde P–T path. Received: 2 April 1996 / Accepted: 15 November 1996  相似文献   

18.
 Equilibrium C–O–H fluid speciation calculations predict that graphite will precipitate from initially graphite saturated fluid inclusions during cooling and exhumation of metamorphic rocks. In the case that no mass is gained or lost by the inclusions, the original X O ratio [O/(O+H)] of the fluid phase must be maintained. Given this closed system constraint, the down-temperature progress of graphite precipitation can easily be monitored as a function of the varible X O, and produces some effects that are of significance to fluid inclusion studies: 1. Variation of the H2O : CO2 : CH4 relationship in the graphite-saturated COH fluid, namely increase of X H2 O and decrease of the carbonic fraction; 2. Decrease of fluid density due to precipitation of graphite, which is denser than the residual fluid; 3. Alteration of the CO2 : CH4 ratio of the fluid, depending on the initial O : H ratio of the fluid: for X O>1/3, fluids increase their CO2 : CH4 ratio with decreasing temperature, and vice-versa. This implies that the CO2 : CH4 ratio measured at room T will not represent the trapping value, which is in any case closer to unity. As a consequence of density reduction, isochores extrapolated from densities observed at room temperature do not pass through the pressure-temperature conditions at which the inclusion was trapped, with pressure underestimates of up to 2 kbar. Actual P-T trapping conditions are located along the equilibrium “bulk isochore” (curve of constant-X O, constant-volume) of the fluid. Alteration of the CO2 : CH4 ratio is a mechanism by which a CO2-rich or CH4-rich carbonic phase can be formed from aqueous fluids that are slightly off the neutral X O=1/3 value. Subsequent segregation of this phase from the aqueous counterpart may account for the formation of pure CO2 and CH4 fluids in the upper crust. Received: 15 March 1995 / Accepted: 1 June 1995  相似文献   

19.
 The partitioning of Fe and Mg between the M1 and M2 octahedral sites of olivine has been investigated by in situ time-of-flight neutron powder diffraction. The degree of M-cation order was determined from direct measurements of site occupancies in a synthetic sample of Fo50Fa50 heated to 1250 °C at the Fe-FeO oxygen buffer. Fe shows slight preference for M1 at temperatures below about 600 °C, progressively disordering on heating to this temperature. Above 630 °C, the temperature at which site preferences cross over (T cr), Fe preferentially occupies M2, becoming progressively more ordered into M2 on increasing temperature. The cation-ordering behaviour is discussed in relation to the temperature dependence of the M1 and M2 site geometries, and it is suggested that vibrational entropy, crystal field effects and changes in bond characteristics play a part in the cross-over of partitioning behaviour. The temperature dependence of site ordering is modelled using a Landau expansion of the free energy of ordering of the type ΔG = −hQ + gTQ +  (T − T c)Q 2 +  Q 4, with a/h = 0.00406 K−1, b/h = 2.3, T c = 572 K and g/h = 0.00106 K−1. These results suggest that the high-temperature ordering behaviour across the forsterite-fayalite join will have a bearing on the activity-composition relations of this important rock-forming mineral, and indicate that Fe-Mg olivine solid solutions become less ideal as temperature increases. Received: 12 August 1999 / Accepted: 25 April 2000  相似文献   

20.
The fluid-absent reaction 12 zoisite = 3 lawsonite + 7 grossular + 8 kyanite + 1 coesite was experimentally reversed in the model system CaO-Al2O3-SiO2-H2O (CASH) using a multi-anvil apparatus. The upper pressure stability limit for zoisite was found to extend to 5.0 GPa at 700 °C and to 6.6 GPa at 950 °C. Additional experiments both in the H2O-SiO2-saturated and in the H2O-Al2O3-saturated portions of CASH provide further constraints on high pressure phase relationships of lawsonite, zoisite, grossular, kyanite, coesite, and an aqueous fluid. Consistency of the present experiments with the H2O-saturated breakdown of lawsonite is demonstrated by thermodynamic analysis using linear programming techniques. Two sets of data consistent with databases of Berman (1988) and Holland and Powell (1990) were retrieved combining experimental phase relationships, calorimetric constraints, and recently measured elastic properties of solid phases. The best fits result in G f ,1,298 ∘,zoisite=−6,499,400 J and S 1,298 ∘,zoisite=302 J/K, and G f ,1,298 ∘,lawsonite=−4,514,600 J and S 1,298 ∘,lawsonite=220 J/K for the dataset of Holland and Powell, and G f ,1,298 ∘,zoisite=−6,492,120 J and S 1,298 ∘,zoisite=304 J/K, and G f ,1,298 ∘,lawsonite=−4,513,000 J and S 1,298 ∘,lawsonite= 218 J/K for the dataset of Berman. Examples of the usage of zoisite as a geohygrometer and as a geobarometer in rocks metamorphosed at eclogite facies conditions are worked, profiting from the thermodynamic properties retrieved here. Received: 23 December 1996 / Accepted: 29 August 1997  相似文献   

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