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1.
Garnet-clinopyroxene geothermometry has been applied to numerous rock types from the blueschist and eclogite terrain of the Sesia zone in the Western Alps. Discrepancies in apparent temperatures of up to 600° C have been found suggesting substantial deviation from ideal behaviour of the garnet-clinopyroxene equilibria in certain assemblages. Assemblages containing jadeitic pyroxenes rather than omphacitic or diopsidic pyroxenes yield very low K D (2.0) values and correspondingly high apparent temperatures (> 1,000° C). The garnets coexisting with high-Na pyroxenes have compositions similar to those coexisting with omphacitic pyroxenes. Departure from ideal behaviour of these garnets is likely to be minor and is accomodated in the formulation of the geothermometer. Numerous examples of coexisting garnet-clinopyroxene pairs indicate that there is no obvious relationship of K D with jadeite content in pyroxenes with jadeite content less than 70%, but at higher values, K D varies inversely with the jadeite content. The dependence of K D upon the jadeite content in the high-Na pyroxenes is believed to be due to the preference of M2 sites for Fe2+ in the enstatite-jadeite substitution (Fe2+MgNa–1Al–1). This substitution is usually very limited and has no demonstrable effect upon X Fe Cpx when the M1 (Fe2++Mg) content of the pyroxenes is high as in omphacitic and diopsidic pyroxenes. However, when the M1 (Fe2++Mg) content is low, as in jadeitic pyroxenes, the non-ideality of the enstatite type exchange has a marked effect on X Fe Cpx and consequently on garnet-clinopyroxene calculations.  相似文献   

2.
The separate distributions for MgSiO3 and FeSiO3 in coexisting pyroxenes from the Skaergaard and Bushveld intrusions and charnockites, which were introduced in an earlier communication, indicate directly that significant amounts of both Fe2+ and Mg were present in the M(2) site of the Ca-rich pyroxene at the temperature of final intercrystalline equilibration. The calculated Fe2+ M(2) site occupancy in the Ca-rich pyroxene increases markedly with decrease in total MgSiO3 content but the corresponding Mg site occupancy appears largely independent of MgSiO3. The mean value of the distribution constant for intracrystalline exchange in the Ca-rich pyroxene decreases, away from unity, with decreasing temperature of equilibration. Occupancy of Mg and Fe2+ in the M (2) site of the Ca-rich pyroxene effectively compensates for the expected variation in K D with composition resulting from intracrystalline partition in Ca-poor pyroxene, and this largely accounts for the difference in K D between igneous and metamorphic pyroxenes. The variation of the augite limb of the pyroxene solvus within the pyroxene quadrilateral is developed as a possible geothermometer.  相似文献   

3.
We experimentally determined F and Cl partition coefficients together with that of 19 trace elements (including REE, U-Th, HFSE and LILE) between basaltic melt and lherzolite minerals: olivine, orthopyroxene, clinopyroxene, plagioclase and garnet. Under conditions from 8 to 25 kbars and from 1,265 to 1,430°C, compatibilities of F and Cl are globally ordered as D Cpx/melt > D Opx/melt > D Grt/melt > D Ol/melt > D Plag/melt, and D F mineral/melt is larger than D Clmineral/melt. Four other major results were brought to light. (1) Chlorine partition coefficients positively correlate with the jadeite component in orthopyroxene, and increase of the CaTs component promotes Cl incorporation in clinopyroxene. (2) Variations of fluorine partition coefficients correlate strongly with melt viscosity. (3) F and Cl partition coefficients correlate with the Young’s modulus (E 0) of pyroxene octahedral sites (M sites) and with Raman vibrational modes of pyroxenes. This demonstrates a fundamental interaction between the M site of pyroxenes and the incorporation of F and Cl. (4) We also determined the parameters of the lattice-strain model applied to 3+ cation trace elements for the two M sites in orthopyroxene and clinopyroxene: D 0M1, D 0M2, r 0M1, r 0M2, E 0M1 and E 0M2.  相似文献   

4.
Kinetic rates of Fe2+-Mg disordering in three orthopyroxenes (mean value of XFe = Fe2+/(Fe2++Mg) = 0.175,0.482,0.770 respectively) have been determined employing heating experiments and single crystal X-ray structural refinements. Disordering rate constants \((\vec K)\) (550800° C) for two pyroxenes are given by: ln \((\vec K)\) = 27.107(±5.177)?32062(±783)T?1(XFe = 0.175) ln \((\vec K)\) = 16.142(±0.057)?18227(±423)T?1(XFe = 0.770) The distribution coefficients KD (representing a steady state of disordering FeM2 + MgM1 ? FeM1 + MgM2) are given by: ln KD = 5.016(±0.223)-7033(±1473) T?1(XFe = 0.175) ln KD = 1.988(±0.122)-3809(±913)T?1(XFe = 0.770) These distribution coefficients provide the constraint of the disordering reaction on the value of the equilibrium constant for Fe2+-Mg order-disorder. Until the low temperature dependence of KD is well constrained, the calculation of cooling rates of pyroxenes and host rocks cannot be done reliably.  相似文献   

5.
This paper reports experiments carried out at 1-atm under conditions of controlled oxygen fugacity, using natural andesites and andesite mixed with augite+synthetic pigeonite or augite+orthopyroxene. The experimental results are used (1) to investigate the controls of Mg# (Mg/[Mg+Fe2+]) and temperature on low-Ca pyroxene stability (pigeonite vs orthopyroxene), (2) to quantify the effects of variations in bulk composition on the position of multiple saturation boundaries in mineral component projection schemes and (3) to develop a thermodynamic model for silica activity for melts saturated with olivine and pyroxene. Over the Mg# range of 0.80–0.30 the minimum temperature of pigeonite stability in natural compositions is equivalent to the Lindsley (1983) boundary determined for pure Ca-Mg-Fe pigeonites. For the low variance, 5-phase assemblage oliv-aug-low-Ca pyroxene-plag-liquid, expressions involving liquid (Na2O+K2O)/(Na2O+K2O+CaO),Mg# and TiO2 content predict temperature and the movement of multiple saturation boundaries in pseudoternary projections in response to changing melt composition. The equilibrium for the low pressure melting of low-Ca pyroxene to olivine+liquid is formulated as a geothermometer and monitor of silica activity. Equilibrium constants estimated from thermochemical data and activities calculated for experimentally produced olivine and pyroxenes are used to develop a model for silica activity in liquid.  相似文献   

6.
The Fe-Mg-Ca-distribution was investigated in synthesis experiments and with the mineral assemblage orthopyroxene+clinopyroxene+quartz. The phase compositions were identified by X-ray diffraction and, where possible, by electron microprobe. The attainment of equilibrium in the run products was signalled by the compositions from control runs (different solutions) becoming closely similar, by recycling runs, by the attainment of equilibrium from different directions (depending on the composition of starting phases), and by special kinetic experiments.The study produced the following results: (1) the Ca content of the clinopyroxenes decreases with increasing Fe (mol%) from 48.4 at X Cpx Fe =5 to 39.8 at X Cpx Fe =45 (800° C); from 47.6 at X Cpx Fe = 10 to 41.7 at X Cpx Fe =45 (750° C); increasing temperature expands the stability field of the less calcic clinopyroxenes. (2) The Ca content of orthopyroxenes increases slightly with Fe content from 1.8 at X Opx Fe =20.5 to 3.2 at X Opx Fe =75; the temperature effect on the Ca content under the T, P conditions of the experiment was not large. (3) Fe and Mg distribution between the coexisting ortho-and clinopyroxenes is largely temperature-dependent, particularly in the compositional range X Opx Fe =15–75 mol%; as T increases, Fe redistributes from the rhombic to monoclinic mineral.Preliminary estimates of rock formation temperatures using the obtained data show that most of the known two-pyroxene geothermometers overstate the actual values by 50–150° C.  相似文献   

7.
The model for the thermodynamic properties of multicomponent pyroxenes (Part I) is calibrated for ortho- and clinopyroxenes in the quadrilateral subsystem defined by the end-member components Mg2Si2O6, CaMgSi2O6, CaFeSi2O6, and Fe2Si2O6. This calibration accounts for: (1) Fe-Mg partitioning relations between orthopyroxenes and augites, and between pigeonites and augites, (2) miscibility gap features along the constituent binary joins CaMgSi2O6-Mg2Si2O6 and CaFeSi2O6-Fe2Si2O6, (3) calorimetric data for CaMgSi2O6-Mg2Si2O6 pyroxenes, and (4) the P-T-X systematics of both the reaction pigeonite=orthopyroxene+augite, and miscibility gap featurs, over the temperature and pressure ranges 800–1500°C and 0–30 kbar. The calibration is achieved with the simplifying assumption that all regular-solution-type parameters are constants independent of temperature. It is predicated on the assumptions that: (1) the Ca-Mg substitution is more nonideal in Pbca pyroxenes than in C2/c pyroxenes, and (2) entropies of about 3 and 6.5 J/K-mol are associated with the change of Ca from 6- to 8-fold coordination in the M2 site in magnesian and iron C2/c pyroxenes, respectively. The model predicts that Fe2+-Mg2+ M1-M2 site preferences in C2/c pyroxenes are highly dependent on Ca and Mg contents, with Fe2+ more strongly preferring M2 sites both in Ca-rich C2/c pyroxenes with a given Fe/(Fe+Mg) ratio, and in magnesian C2/c pyroxenes with intermediate Ca/(Ca+Fe+Mg) ratios.The proposed model is internally consistent with our previous analyses of the solution properties of spinels, rhombohedral oxides, and Fe-Mg olivines and orthpyroxenes. Results of our calibration extend an existing database to include estimates for the thermodynamic properties of the C2/c and Pbca pyroxene end-members clinoenstatite, clinoferrosilite, hedenbergite, orthodiopside, and orthohedenbergite. Phase relations within the quadrilateral and its constitutent subsystems are calculated for temperatures and pressures over the range 800–1700°C and 0–50 kbar and compare favorably with experimental constraints.  相似文献   

8.
The equilibrium intracrystalline distribution coefficient, k D *, of Fe* (i.e. Fe2+ + Mn) and Mg between the M1 and M2 sites of three natural nearly binary Fe2+-Mg orthopyroxene crystals (Fs14, Fs15 and Fs49) were determined by annealing experiments at several temperatures between 550 and 1000 °C and single crystal X-ray structure refinements. In addition, the X-ray data of an orthopyroxene crystal (Fs23), which were collected earlier by Molin et al. (1991) between 700 and 1000 °C, were re-refined. The data were processed through two different refinement programs (SHELXL-93 and RFINE90) using both unit and individual weights and also both ionic and atomic scattering factors. The calculated site occupancies were found to agree within their estimated standard errors. However, the use of ionic scattering factors led to significantly better goodness of fit and agreement index, and smaller standard deviations of the site occupancies than those obtained from the use of atomic scattering factors. Furthermore, the weighted refinements yielded significantly smaller standard deviations of the site occupancies than the unweighted refinements even when the same set of reflections was used in the two procedures. The site occupancy data from this study were combined with selected published data to develop expressions of k D * as a function of temperature and composition. Calculation of the excess configurational entropy, ΔS XS, suggests that orthopyroxene should be treated as a two parameter symmetric solution instead of as a “simple mixture”. The calculated ΔS XS values and the excess Gibbs free energy of mixing suggested by available cation exchange data lead to a slightly negative enthalpy of mixing in the orthopyroxene solid solution. Received: 25 August 1998 / Accepted: 10 March 1999  相似文献   

9.
Ferric iron in mantle-derived garnets   总被引：4，自引：0，他引：4  
The oxidation state of a mantle assemblage may be defined by heterogeneous reactions between oxygen and iron-bearing minerals. In spinel lherzolites, the presence of Fe3+ in spinel allows use of the assemblage olivine-orthopyroxene-spinel to define f O 2 at fixed T and P. As a first step towards establishing an analogous reaction for garnet lherzolites, garnets from mantle-derived xenoliths from South Africa and the USSR have been analyzed with 57Fe Mössbauer spectroscopy at 298 and 77K to determine Fe3+/Fe2+ and the coordination state of iron. Garnets from South African alkremites (pyrope+Mg-spinel) and eclogites, as well as garnet-spinel and low-temperature garnet lherzolites from both South Afica and the USSR, have Fe3+/Fe<0.07. In contrast, garnets from high-temperature garnet lherzolites from within the Kaapvaal craton of South Africa have Fe3+/Fe>0.10. Ferric iron is octahedrally coordinated, and ferrous iron is present in the dodecahedral site in all samples. The occurrence of significant Fe3+ in these garnets necessitates caution in the use of geothermometers and geobarometers that are applied to mantle samples. For example, the presence of 12% of the Fe as Fe3+ in garnets can increase temperatures calculated from existing Fe/Mg geothermometers by>200°C. The concomitant increase in pressures calculated from geobarometers that use the Al content in orthopyroxene coexisting with garnet are 10–15 kbar. Results of calculations based on heterogeneous equilibria between garnet, olivine, and pyroxene are consistent with the derivation of the peridotite samples from source regions that are relatively oxidized, between the f O 2 of the FMQ (quartz-fayalite-magnetite) buffer and that of the WM buffer. No samples yield values of f O 2 as reduced as IW (iron-wüstite buffer).  相似文献   

10.
In order to explore possible quantitative relations between crystal field stabilization energy, CFSE, and partitioning behaviour of the 3d 6-configured Fe2+ ion, a suite of 29 paragenetic rock-forming minerals from 12 high-grade metamorphic rock samples of the Ukrainian shield, including the parageneses garnet/orthopyroxene/clinopyroxene (2x), orthopyroxene/clinopyroxene, garnet/clinopyroxene, garnet/orthopyroxene/biotite, garnet/biotite, garnet/cordierite, garnet/cordierite/biotite, garnet/orthopyroxene/clinopyroxene/Ca-amphibole, Ca-amphibole/biotite (retrograde), was studied by electron microprobe analysis to obtain the respective K D Fe2+ (Ph1/Ph2) values and by polarized single crystal electronic absorption spectroscopy to evaluate the respective CFSEFe2+ values. Other than in the case of Cr3+, a clear quantitative relation between K D (Ph1/Ph2) and the ΔCFSE(Ph1/Ph2) was only observed when geometrical factors, mainly the volume of crystallographic sites and ionic radii of ions competing in the partitioning process, are similar in the respective two paragenetic phases to within 15–20%. In such cases, the ΔCFSEFe2+ contribution to K D (Ph1/Ph2) amounts to 0.1 to 0.2 log K D per 100 cm−1ΔCFSE. The conclusion is that ΔCFSEFe2+ plays only a secondary role after geometrical factors, in the partitioning behaviour of Fe2+. The reason for this is seen in the facts that, compared to the 3d  3-configured Cr3+ ion, CFSE of the 3d 6-configured Fe2+ amounts only to 20–25%, and that the former ion enters only octahedral sites with similar geometrical properties in the paragenetic mineral phases. Received: 17 November 1998 / Accepted: 28 June 1999  相似文献   

11.
Existing data on the temperature and composition dependence of the Fe2+-Mg2+ distribution between Fe-Mg olivine and orthopyroxene, the intra-crystalline distribution of Fe2+ and Mg2+ between M1 and M2 sites in orthopyroxene, and macroscopic activity-composition relations in olivine and orthopyroxene are shown to be inconsistent with generally accepted thermodynamic formulations which assume that the non-configurational Gibbs energy of orthopyroxene is independent of the degree of long-range ordering of Fe2+ and Mg+ between M1 and M2 sites. These data are interpreted in terms of the constraints they provide on the size of Bragg-Williams type energy, entropy, and volume terms for olivine and orthopyroxene. The apparent equilibrium constant for Fe-Mg exchange between olivine and orthopyroxene is shown to be a potentially useful ‘geothermometer’ for olivine-orthopyroxene assemblages with olivines with mole fraction of Fe2SiO4 component less than 0.2 or greater than 0.6. A provisional calibration of this ‘geothermometer’ is presented.  相似文献   

12.
A new determination, using high temperature drop-solution calorimetry, of the enthalpy of transformation of MgSiO3 pyroxene to ilmenite gives H 298 = 59.03 ±4.26 kJ/mol. The heat capacity of the ilmenite and orthopyroxene phases has been measured by differential scanning calorimetry at 170–700 K; Cp of MgSiO3 ilmenite is 4–10 percent less than that of MgSiO3 pyroxene throughout the range studied. The heat capacity differences are consistent with lattice vibrational models proposed by McMillan and Ross (1987) and suggest an entropy change of -18 ± 3 J-K-1 ·mol-1, approximately independent of temperature, for the pyroxene-ilmenite transition. The unit cell parameters of MgSiO3 ilmenite were measured at 298–876 K and yield an average volume thermal expansion coefficient of 2.44 × 10-5 K-1. The thermochemical data are used to calculate phase relations involving pyroxene, -Mg2SiO4 plus stishovite, Mg2SiO4 spinel plus stishovite, and ilmenite in good agreement with the results of high pressure studies.  相似文献   

13.
Although the Beaver Bay ferrogabbro is a small-scale layered intrusion, Ca-rich pyroxenes show a strong iron enrichment during fractionation, ranging from augite (Mg38Fe24 Ca38) to ferrohedengergite (Mg10Fe48Ca42). Ca-poor pyroxenes from intermediate pigeonite (Mg39Fe50Ca11) to ferriferous pigeonite (Mg27Fe65Ca8) occur as intercumulus minerals. The pyroxenes from the non-layered Beaver River gabbro are included in the overall pyroxene fractionation trend of the Beaver Bay gabbro complex. The pyroxene trend of the Beaver Bay gabbro complex is similar to those of the Skaergaard and Bushveld; however, there is a slight difference in that the Ca-rich pyroxenes of Beaver Bay (having Mg content over 30%) are slightly richer in Ca than either the Skaergaard or Bushveld augites.  相似文献   

14.
A detailed crystal chemical study of coexisting olivine, orthopyroxene, clinopyroxene and spinel from selected Victorian (Australia) lherzolite suites was carried out by means of single crystal x-ray diffraction and electron probe microanalysis to obtain actual site occupancies. The aim of this study was primarily to characterise the intracrystalline configurations and related cation ordering on sites in major mantle constituents. The results demonstrate that cation ordering on sites is subject to distinctive crystallographic controls which depend on the petrological evolution of the suite. Mg-Fe2+ ordering in M1–M2 pyroxene sites depends on variations of the smaller cations, mainly Alvi, Ti4+, Fe3+, and related configurations of M 1. Pressuresensitive Alvi is crucial to Fe2+, the more ordered clinopyroxene showing high Alvi configurations which tend to exclude the larger bivalent cations and yield small polyhedral volumes for M 1, M 2, T sites and the unit cell. Conversely, the coexisting orthopyroxene, characterised by lower Alvi configuration and higher M 1 and unit cell volumes, is relatively more disordered. Olivine is consistent with the coexisting clinopyroxene, the more disordered crystals coexisting with more disordered clinopyroxene, while Al-Mg order in the coexisting spinel shows the reverse relationship. Estimated temperatures of apparent equilibration based on current geothermometers are not considered realistic. Assumptions of ideal cation mixing on sites in pyroxene and spinel are not supported.  相似文献   

15.
Summary Microprobe analyses and X-ray crystal structure refinement of terrestrial and lunar olivines are compared, in order to investigate the influence of temperature and composition on Mg-Fe2+ distribution between M1 and M2 sites.Quenching and heating experiments show that, for the same composition, a temperature increase causes an increase in the (Fe2+/Mg)M1/(Fe2+/Mg)M2 ratio (KD. Such experiments also demonstrate that the intracrystalline Mg-Fe2+ ordering in Ml and M2 sites is very fast and the calculated KD values therefore depend on cooling rate (C.R.), i.e., high KD values = high CR.. On the other hand, for the same cooling rate and temperature, Fe-rich olivine has a KD value higher than that of Mg-rich olivine, since Fe2+ is preferentially ordered in M1 site. Oxygen fugacity variations (QFI and QFM buffers) do not appreciably influence KD.The closure temperature of Mg-Fe2+ ordering between M1-M2 sites of olivine is probably lower than that estimated for orthopyroxene (c. 550–600°C; Saxena et al., 1989), owing to a lesser degree of non-equivalence between MI and M2 sites. The highest temperature that can be detected by KD values of natural olivines is 700–800 °C.
Einfluß von Temperatur und Zusammensetzung auf die Mg-Fe2+ Verteilung in Olivin
Zusammenfassung Mikrosondenuntersucbungen und Strukturverfeinerungen an terrestrischen und lunaren Olivinen werden verglichen, um den Einfluß von Temperatur und Zusammensetzung auf die Mg-Fe2+ Verteilung in der MI und M2 Position zu untersuchen. Experimentelle Untersuchungen belegen, daß bei gleichbleibender chemischer Zusamensetzung, eine Temperaturzunahme eine Zunahme im KD Verhältnis (Fe2+ /Mg)M1/(Fe2+/M9)M2 bedingt. Diese Experimente zeigen weiters, daß die Ordnung der Mg-Fe2+ Kationen im Gitter in den M 1 und M2 Positionen sehr rasch erfolgt und die berechnete KD Werte daher von der Abkühlungsrate (C.R.) abhängen; z. B. hohe KD-Werte = hohe C. R.Andererseits hat bei gleicher Abkühlungsrate und Temperatur Fe-reicher Olivin einen höheren KD Wert als Mg-reicher Olivin, da Fe2+ bevorzugt in die M1 Position eingebaut wird. änderungen in der Sauerstoff-Fugazität (QFI und QFM Buffer) beeinflussen die KD Werte unwesentlich.Die Schließungstemperaturen für die Mg-Fe2+ Ordnung zwischen der M1 und M2 Position in Olivin sind wahrscheinlich niedriger als die von Orthopyroxen (ca. 550–600°C;Saxena et al., 1989); dies wird mit einem niedrigeren Grad an non-equivalence von Ml und M2 erklärt. Die höchsten Temperaturen, die an Hand der KD-Werte an natürlichen Olivinen bestimmt wurden liegen bei 700–800°C.

With 2 Figures  相似文献   

16.
Anorthosites, mangerites and charnockites from metamorphosed anorthosite massifs (the Adirondacks and elsewhere) commonly contain coarsely exsolved pyroxenes with substantial amounts of exsolved orthopyroxene (in clinopyroxene) and clinopyroxene (in orthopyroxene). Electron microprobe reintegration of such pyroxenes yields compositions which indicate that pigeonite and subcalcic augite coexisted before metamorphic reequilibration. Equilibration temperatures of 1100 °±100 °C for anorthosite and 1000 °C±100 °C for mangerites and charnockites are inferred from the solvus of Ross and Huebner (1975). These temperatures constrain minimum magmatic thermal conditions and suggest that the magmas were relatively dry. Exsolution lamellae of coarse pyroxenes and small equant coexisting pyroxenes (with little or no exsolution) yield temperatures of 750 °C, consistent with equilibration during granulite facies metamorphism. Relict igneous textures and compositions persisted through the metamorphic event due to dry P(H2O) P(solid) metamorphic conditions. The reintegrated pyroxene compositions provide a window through the metamorphism and yield constraints on the pre-metamorphic igneous events.Contribution No. 340 from the Mineralogical Laboratory, Department of Geology and Mineralogy, The University of Michigan, Ann Arbor, Michigan, 48109, U.S.A.  相似文献   

17.
Unusually iron-rich pyroxene and olivine occur in rocks associatedwith the Nain anorthosite massif, Labrador. Adamellite and granodioritecontain orthopyroxene (inverted from pigeonite) as iron-richas Ca6Fe82Mg12; comparison with experimental data suggests aminimum pressure of crystallization of 5 kb. Some of these iron-richpyroxene crystals have broken down, apparently upon decreasingpressure, to yield intergrowths of less iron-rich orthopyroxene(near Ca7Fe72Mg21), ferroaugite, fayalite (near Fo9), and quartz.Other rocks, monzonites, contain pyroxenes with calcium-poorcores and ferroaugite rims, as well as crystals composed ofbroad lamellae of ferroaugite and orthopyroxene in sub-equalproportions. Analysis of one such crystal with unusually thinand closely spaced lamellae yielded a bulk composition of Ca24Fe58Mg18.Such pyroxenes probably crystallized near or above the crestof the augite-pigeonite two-phase region, probably above 925°C. This high temperature suggests that the monzonites crystallizedfrom relatively dry magmas. If they represent a residual fractionderived from the same magma as the anorthosite, then that magmamust have been nearly anhydrous. Pigeonite rather than orthopyroxene was the primary magmaticCa-poor pyroxene in most of the Nain rocks studied here. Nucleationrates apparently were low under subsolidus conditions, and low-Capigeonite (Ca2Fe78Mg20) is present in grains where orthopyroxenedid not nucleate as pigeonite cooled and exsolved ferroaugite.Iron-rich orthopyroxene (Ca2Fe79M19) crystallized instead ofpigeonite in a Greenland quartz syenite that contains more abundanthydrous phases.  相似文献   

18.
An understanding of the irregular coordination polyhedra exhibited by the M2 cations in clinopyroxenes is of prime importance in connection with the behaviour of solid solutions and polymorphism in pyroxenes.As shown by unfolding the silica chains in pigeonite, cations with octahedral stereochemistry like Mg++and Fe++ cause kinking of the silica chains, whereas larger cations like Ca++and Na+have an opposite namely straightening effect. This is a probable factor causing immiscibility in the Mg++-Ca++ solid solutions in pyroxenes. In pyroxene structures with kinked silica chains the arrangement of oxygen atoms approaches close packing; consequently different stacking sequences will be energetically possible leading to polymorphism in pyroxenes.When Pauling's electrostatic valence rule is applied to clinopyroxenes, the charge balance will be exceedingly improved if effective coordination number of M2 cation is assigned and if the distortions of M 2 coordination polyhedron is considered.  相似文献   

19.
The synthesis and the chemical, structural, magnetic, and Mössbauer spectral characterization of three synthetic alluaudites, Na2Mn2Fe(PO4)3, NaMn Fe2(PO4)3 and Na2MnFeIIFeIII(PO4)3, and a natural sample with the nominal composition of NaMn Fe2(PO4)3, collected in the Buranga pegmatite, Rwanda, are reported. All four compounds have the expected alluaudite monoclinic C2/c structure with the general formula [A(2)A(2)][A(1)A(1)A(1)2]M(1)M(2)2(PO4)3 in which manganese(II) is on the M(1) site and manganese(II), iron(III) and, in some cases, iron(II) on the M(2) site. The X-ray structure of Na2Mn2Fe(PO4)3 also indicates a partially disordered distribution of NaI and MnII on the M(1) and A(1) crystallographic sites. All four compounds are paramagnetic above 40 K and antiferromagnetically ordered below. Above 40 K the effective magnetic moments of NaMnFe2(PO4)3 and Na2MnFeIIFeIII(PO4)3 are those expected of high-spin manganese(II) and iron(III) with the 6A1g electronic ground state and high-spin iron(II) with the 5T2g electronic ground state. In contrast, the effective magnetic moment of Na2Mn2Fe(PO4)3 is lower than expected as a result of enhanced antiferromagnetic exchange coupling by the manganese(II) on the M(2) site. The Mössbauer spectra of all four compounds have been measured from 4.2 to 295 K and have been found to be magnetically ordered below 40 K for Na2Mn2Fe(PO4)3 and 35 K for the remaining compounds. The Mössbauer spectra of Na2Mn2Fe(PO4)3 exhibit the two expected iron(III) quadrupole doublets and/or magnetic sextets expected for a random distribution of manganese(II) and iron(III) ions on the M(2) site. Further, the Mössbauer spectra of Na2MnFeIIFeIII(PO4)3 exhibit the two iron(II) and two iron(III) quadrupole doublets and/or magnetic sextets expected for a random distribution of iron(II) and iron(III) on the M(2) site. Surprisingly, the synthetic and natural samples of NaMnFe2(PO4)3 have 19 and 10% of iron(II) on the M(2) site; apparently the presence of some iron(II) stabilizes the alluaudite structure through the reduction of iron(III)–iron(III) repulsion. The temperature dependence of the iron(II) quadrupole splitting yields a 440 to 600 cm–1 low-symmetry component to the octahedral crystal field splitting at the M(2) site. The iron(II) and iron(III) hyperfine fields observed at 4.2 K are consistent with the presence of antiferromagnetic ordering at low temperatures in all four compounds.  相似文献   

20.
Summary Chemical compositions of orthopyroxene and clinopyroxene from the Jinchuan ultramafic intrusion have been obtained by electron microprobe analysis. The Mg number (MgO/(MgO + FeO)) for both pyroxenes falls within narrow ranges, 82–87 for clinopyroxene and 81–85.5 for orthopyroxene, suggesting limited magma differentiation in regard to the present igneous body. The Al2O3 content ranges from 2.44 wt.% to 4.43 wt.% and increases with decreasing Mg of the pyroxenes, i.e., with the more evolved magma. This is attributed to the relatively greater effects of Al2O3, TiO2, Cr2O3 and Fe2O3 than that of SiO2 on pyroxene crystallization.Negative linear relationships between Ti4+ and Si4+, and Al3+ and Si4+ characterize the pyroxenes. In clinopyroxene, regression of Si4+ versus Al3+ results in a straight line with a slope of –1.012, indicating that the decrease of Si4+ in the crystal structure is matched by an increase only in tetrahedral Al3+; octahedral Al3+ has remained relatively constant. The negative linear relationship between Ti4+ and Si4+ in clinopyroxene reflects either a greater tendency of Ti4+ to occupy octahedral sites than Al3+, or that replacement of Al3+ for Si4+ demands a more efficient charge balance. The scatter in plots of Ti4+ versus Si4+ for orthopyroxene indicates that charge balance is not as critical as structure symmetry.The crystallization temperature of pyroxene is calculated to be 1108–1229°C usingWood andBanno's (1973) two pyroxene thermometer, and is within 40°C of that calculated fromWells's (1977) thermometer. The distribution coefficient (Kd) for Mg2+ and Fe2+ between clinopyroxene and orthopyroxene is estimated to be 0.86, which is higher than that of the other intrusions and lower than that of mantle nodules, but still falls within their Kd-1/T trend. This suggests that the Kd value of pyroxene is controlled mainly by temperature.
Mineralchemie der Pyroxene der Jinchuan-Intrusion, China
Zusammenfassung Die chemische Zusammensetzung von Orthopyroxenen und Klinopyroxenen aus der ultramafischen Jinchuan Intrusion wurden mit der Mikrosonde bestimmt. Die Mg-Zahl (MgO/(MgO + FeO)) beider Pyroxene liegt innerhalb enger Grenzen, 82–87 für Klinopyroxen und 81–85.5 für Orthopyroxen. Dies weist auf beschränkte magmatische Differentiation der Intrusion hin. Der Al2O3-Gehalt liegt zwischen 2.44 Gew.%. und 4.43 Gew.%. und nimmt mit der abnehmenden Mg-Zahl der Pyroxene ab, d.h. mit dem mehr entwickelten Magma. Dies wird damit erklärt, daß Al2O3, TiO2, Cr2O3 und Fe2O3 einen größeren Einfluß auf die Kristallisation der Pyroxene ausüben als SiO2.Die Pyroxene werden durch negative lineare Beziehungen zwischen Ti4+ und Si4+, sowie Al3+ und Si4+ charakterisiert. In Klinopyroxenen resultiert die Regression von Si4+ gegen Al3+ in einer geraden Linie mit einer Neigung von –1.012. Dies weist darauf hin, daß die Abnahme der Si4+ Gehalte in die Kristallstruktur durch Zunahme von ausschliesslich tetraedrischem Al3+ kompensiert wird; oktaedrisches Al3+ ist relativ konstant geblieben. Die negative lineare Beziehung zwischen Ti4+ und Si4+ in Klinopyroxenen geht entweder auf eine stärkere Tendenz des Ti4O2, oktaedrische Plätze zu besetzen zurück, oder darauf daß ein Ersatz von Al3+ für Si4+ einen effizienteren Ladungsausgleich verlangt. Die unregelmäßige Verteilung der Plots von Ti4+ gegen Si4+ in Orthopyroxenen läßt erkennen, daß Ladungsausgleich hier nicht so kritisch ist wie die Symmetrie der Struktur.Die Kristallisationstemperatur der Pyroxene wurde mit dem Zwei Pyroxenthermometer nachWood undBanno (1973) mit 1108–1229°C bestimmt. Diese Werte liegen innerhalb von 40°C des vonWells (1977) berechneten. Der Verteilungskoeffizient (Kd) für Mg2+ und Fe2+ zwischen Klinopyroxen und Orthopyroxen wird auf 0.86 berechnet; das ist höher als der aus anderen Intrusionen und niedriger als der von Mantelxenolithen, fällt aber immer noch innerhalb des Kd-1/T Trends derselben. Dies legt den Gedanken nahe, daß der Kd Wert der Pyroxene hauptsächlich durch Temperatur bestimmt wird.

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