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1.
The minerals of the jarosite group, including the jarosite-beudantite-segnitite and jarosite-beaverite-osarizawaite isomorphic series, were studied with M?ssbauer spectroscopy. All the samples were collected from the oxidation zones of the South Urals sulfide deposits. In contrast to the jarosite containing one Fe3+ doublet in the M?ssbauer spectrum, the Pb-bearing members of the jarosite group—beudantite and beaverite—have two doublets in their spectra. Fe3+ is distributed at two sites with similar isomer shifts and different quadrupole splitting. The quantitative ratio of those doublets in the structure is roughly equal. The M?ssbauer spectra of the intermediate jarosite-beudantite and beaverite-osarizawaite members are superpositions of the jarosite and beudantite spectrum types with a prevalent jarosite doublet and larger quadrupole splitting. An admixture of antimony increases the Fe3+ content in the doublet with smaller quadrupole splitting. The unequal Fe3+ distribution in those two sites may be related to the ordering of cations in octahedrons. The appearance of two different Fe3+ sites probably resulted from the local coordinating role of Pb rather than from isomorphic replacement in anion groups.  相似文献   

2.
It is well known that in pyroxene structure,there are two metal sites,M1 and M2.Generally speaking,Ferrous iron in each of these sites would normally be expected to give rise to a doublet,However,anomalies have been found in the relative areas of the peaks in the room temperature spectra of some clinopyroxene(CPX)when the above assignment is followed.According to the calculation of Next Nearest Neighbor configurations of divalent cations in M1,we found that the four configurations of M1 can be divided into two groups.One group is 3Ca configuration that increases with the content of Ca(p.f.u);the other group is made up of three No-3Ca configurations that decrease with the content of Ca.The two groups contribute to the spectrum structure of M1.so in this study we fit two doublets for ferrous iron in M1.Though there were several reports on Fe^3 in tetrahedral site previously,it was not sure that Fe^3 occupies the T site is a universal fact in CPX,despite of the content of Al.We found that the Fe^3 in the T site fitted by Moessbauer spectroscopy is negatively correlated to the Si content in the T site and positively correlated to the Fe^3 in the T site estimated on the supposition that Fe^3 and Al occupy the T site randomly.If it is true.it is important in the modeling of ion exchange geobarometries and geothermomeries.  相似文献   

3.
A natural sample of aegirine, ideally NaFeSi2O6, has been studied by transmission Mössbauer spectroscopy in the range 4.2–480?K. At selected temperatures, a longitudinal external field of 60?kOe was applied to the absorber. The sample was observed to order magnetically at 11±1?K. The paramagnetic Mössbauer spectra (MS) show the presence of ～10% Fe2+ in the M1 sites of the clinopyroxene structure. These MS have been decomposed into four quadrupole doublets: two minor ones for Fe2+ on M1 sites, a dominant one due to Fe3+ on M1 sites, and a second ferric component, with a contribution of ～3% and attributable to the tetrahedral sites. Two possibilities concerning the origin of the two distinct Fe2+ (M1) doublets are discussed. They are respectively based on inter-valence charge transfer and on the existence of distinct Fe2+ orbital configurations at the two M1 sites. Neither of the two models could be firmly excluded. The asymmetry parameter η of the electric field gradient at the Fe3+ (M1) sites is close to 1.0 and the quadrupole splitting within 0.34±0.01?mm/s at all temperatures. The MS at 4.2?K shows an asymmetric hyperfine-field distribution for Fe3+, with a maximum-probability field of 468?kOe. The maximum-probability field for Fe2+ is found to be 220?kOe. The shape of the applied-field MS at 4.2?K implies a static antiferromagnetic ordering and was successfully interpreted by a bidimensional distribution of the magnitude and orientation of the hyperfine field. Finally, the temperature variations of the respective centre shifts and quadrupole splittings could be explained on the basis of existing theoretical models.  相似文献   

4.
莱河矿的超结构和低温穆斯堡尔谱的对比研究   总被引：1，自引：0，他引：1       下载免费PDF全文
沈步明 《地质科学》1995,30(4):374-383
本文进行了莱河矿3C超结构和4.2K穆斯堡尔谱的对比研究。研究表明。莱河矿的非等效位置M2A+M2C,M2B,M1B,M1A和VB能够分别与Kan等(1985)测定的莱河矿穆斯堡尔谱的吸收双峰A,B,C,D和E对应,不仅解决了超结构位置和吸收双峰之间的对应,而且圆满解释了吸收双峰A:B和C:D的强度比为2:1的关系。另外,还利用莱河矿超结构的资料讨论了莱河矿的反铁磁性内部作用。  相似文献   

5.
Natural alexandrite Al2BeO4:Cr from Malyshevo near Terem Tschanka, Sverdlovsk, Ural, Russia, has been characterized by 57Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine oxidation state and location of iron. The sample contains 0.3 wt% of total iron oxide. The 57Fe Mössbauer spectrum can be resolved into three doublets. Two of them with hyperfine parameters typical for octahedrally coordinated high-spin Fe3+ and Fe2+, respectively, are assigned to iron substituting for Al in the octahedral M2-site. The third doublet is attributed to Fe3+ in hematite. Electronic structure calculations in the local spin density approximation are in reasonable agreement with experimental data provided that expansion and/or distortion of the coordination octahedra are presumed upon iron substitution. The calculated hyperfine parameters of Fe3+ are almost identical for the M1 and M2 positions, but the calculated ligand-field splitting is by far too large for high-spin Fe3+ on M1.  相似文献   

6.
A crystal chemical investigation of clinopyroxenes from a suite of nepheline-bearing lavas located in the Nyambeni Range of Kenya has delineated the polyhedral site configurations and related intracrystalline relationships. These are distinct from those determined for the clinopyroxene in an analogous suite of leucite-bearing lavas from the Sabatini volcanoes in the Roman Region of Italy (Dal Negro et al. 1985).The Nyambeni clinopyroxene, varying from salite to hedenbergite, preferentially accepts Na in the M2 site to balance increasing Fe2+ and Si, respectively, whereas the Sabatini clinopyroxene is confined within the salite field and preferentially accepts Aliv to balance the effect of increasing (Fe3++Ti4++Alvi+Cr3+)M1.The Fe2+/Fe3+ and K/Na ratios of the host rocks emerge as significant factors in determining the different polyhedral configurations and evolutions of the clinopyroxene from the two lava suites, respectively. The resulting Mg-Fe2+ order-disorder relationships in M1–M2 are also distinct in the two clinopyroxenes. A high degree of MgFe2+ order in M1–M2 corresponds to the largest configurational, hence energetic, difference between M1 and M2 in the Nyambeni clinopyroxene, whereas the converse applies to the Sabatini clinopyroxene.In view of the significant crystal chemical differences and distinct evolution trends, it is proposed that salites from alkali volcanic rocks may be referred to as Nyambeni-type or Sabatini-type, respectively.  相似文献   

7.
A clinopyroxene suite from lherzolite inclusions associated with the Victorian (Australia) “Newer Volcanics” has been investigated with the aim of understanding the clinopyroxene crystal-chemical response to increasing temperature (e.g. a melting model and/or crystallization processes prevailing at high pressure). The M1 clinopyroxene polyhedron dominates the intracrystalline physical-chemical variations, essentially given by the triple substitution AlVIFe M1 2 Ti4+⇌Cr3+ Fe3+Mg M1 2+ corresponding to an increase in the volume of M1 with increasing Mg/Mg+Fe2+ (mg) for the clinopyroxene. A relative Ca2+ increase in M2 ensures the necessary charge balance. However, Na+ occupancy of M2 persists to the highest mg values, i.e. maximum thermal stability, where the volume of M2 is the largest due to Fe M2 2+ depletion. The variations of M1 and M2 volumes are greater than, and opposite to, the variations in the volume of T (tetrahedron) by factors of ca. 3 and 1.5, respectively. Inclusions with relatively low clinopyroxene content (Mt. Porndon specimens) show distinct intracrystalline variations, essentially reflecting lower AlVI, i.e. higher volume of M1, and implying a lower pressure regime compared to clinopyroxene-rich analogues (Mt. Leura specimens). The intracrystalline relationships of the Mt. Porndon clinopyroxene suggest that the host peridotite inclusions survived larger degree of mantle melting at shallower depths relative to the Leura analogues.  相似文献   

8.
Three chloritoid samples from the Stavelot massif (Belgium) and one sample from the Serpont massif (Belgium) have been characterized by chemical analyses and differential X-ray diffraction. A classification of chloritoid is proposed. Mössbauer spectra at temperatures between 78 and 360 K and in external magnetic fields were obtained for a triclinic and for a monoclinic specimen. The spectra show a superposition of a weak Fe3+ doublet (less than 10%) and an intense Fe2+ doublet. It is found that a decomposition of the ferrous absorption into two distinct quadrupole doublets leads to smaller deviations between experimental and calculated line shapes, especially at low temperatures. This suggests that Fe2+ is present in both cis and trans O2(OH)4 octahedral positions in the trioctahedral layer. However, the structural data derived from the temperature dependence of isomer shifts and quadrupole splittings, are found to be inconsistent with known crystallographic data. It is therefore concluded that Fe2+ is present in only one type of lattice site and that the numerically imposed decomposition into two ferrous doublets is merely an artifact due to thickness saturation effects and to the distributive character of the hyperfine parameters. The negative sign of the electric field gradient further confirms the assignment of the Fe2+ doublet to a cis octahedral configuration. Finally, only minor differences between the Mössbauer results for triclinic and monoclinic chloritoid are observed. The infrared absorption spectra of the four samples are almost identical except in the region around 600 cm?1 at which the monoclinic phase exhibits two absorption bands instead of one band for the triclinic samples. All absorption bands can be well assigned to the different vibrations. Inter-layer hydrogen bonding is evidenced by the occurrence of two v O-H absorption bands. Furthermore, the specific nature of the infrared spectra enables a fast identification of chloritoid samples.  相似文献   

9.
A mid‐ocean ridge basalt (MORB)‐type eclogite from the Moldanubian domain in the Bohemian Massif retains evidence of its prograde path in the form of inclusions of hornblende, plagioclase, clinopyroxene, titanite, ilmenite and rutile preserved in zoned garnet. Prograde zoning involves a flat grossular core followed by a grossular spike and decrease at the rim, whereas Fe/(Fe + Mg) is also flat in the core and then decreases at the rim. In a pseudosection for H2O‐saturated conditions, garnet with such a zoning grows along an isothermal burial path at c. 750 °C from 10 kbar in the assemblage plagioclase‐hornblende‐diopsidic clinopyroxene‐quartz, then in hornblende‐diopsidic clinopyroxene‐quartz, and ends its growth at 17–18 kbar. From this point, there is no pseudosection‐based information on further increase in pressure or temperature. Then, with garnet‐clinopyroxene thermometry, the focus is on the dependence on, and the uncertainties stemming from the unknown Fe3+ content in clinopyroxene. Assuming no Fe3+ in the clinopyroxene gives a serious and unwarranted upward bias to calculated temperatures. A Fe3+‐contributed uncertainty of ±40 °C combined with a calibration and other uncertainties gives a peak temperature of 760 ± 90 °C at 18 kbar, consistent with no further heating following burial to eclogite facies conditions. Further pseudosection modelling suggests that decompression to c. 12 kbar occurred essentially isothermally from the metamorphic peak under H2O‐undersaturated conditions (c. 1.3 mol.% H2O) that allowed the preservation of the majority of garnet with symplectitic as well as relict clinopyroxene. The modelling also shows that a MORB‐type eclogite decompressed to c. 8 kbar ends as an amphibolite if it is H2O saturated, but if it is H2O‐undersaturated it contains assemblages with orthopyroxene. Increasing H2O undersaturation causes an earlier transition to SiO2 undersaturation on decompression, leading to the appearance of spinel‐bearing assemblages. Granulite facies‐looking overprints of eclogites may develop at amphibolite facies conditions.  相似文献   

10.
Published experimental data including garnet and clinopyroxene as run products were used to develop a new formulation of the garnet–clinopyroxene geothermometer based on 333 garnet–clinopyroxene pairs. Only experiments with graphite capsules were selected because of difficulty in estimating the Fe3+ content of clinopyroxene. For the calibration, a published subregular‐solution model was adopted to express the non‐ideality of garnet. The magnitude of the Fe–Mg excess interaction parameter for clinopyroxene (WFeMgCpx), and differences in enthalpy and entropy of the Fe–Mg exchange reaction were regressed from the accumulated experimental data set. As a result, a markedly negative value was obtained for the Fe–Mg excess interaction parameter of clinopyroxene (WFeMgCpx = ? 3843 J mol?1). The pressure correction is simply treated as linear, and the difference in volume of the Fe–Mg exchange reaction was calculated from a published thermodynamic data set and fixed to be ?120.72 (J kbar?1 mol?1). The regressed and obtained thermometer formulation is as follows: where T = temperature, P = pressure (kbar), A = 0.5 Xgrs (Xprp ? Xalm ? Xsps), B = 0.5 Xgrs (Xprp ? Xalm + Xsps), C = 0.5 (Xgrs + Xsps) (Xprp ? Xalm), Xprp = Mg/(Fe2+ + Mn + Mg + Ca)Grt, Xalm = Fe/(Fe2+ + Mn + Mg + Ca)Grt, Xsps = Mn/(Fe2+ + Mn + Mg + Ca)Grt, Xgrs = Ca/(Fe2+ + Mn + Mg + Ca)Grt, XMgCpx = Mg/(Al + Fetotal + Mg)Cpx, XFeCpx = Fe2+/(Al + Fetotal + Mg)Cpx, KD = (Fe2+/Mg)Grt/(Fe2+/Mg)Cpx, Grt = garnet, Cpx = clinopyroxene. A test of this new formulation to the accumulated data gave results that are concordant with the experimental temperatures over the whole range of the experimental temperatures (800–1820 °C), with a standard deviation (1 sigma) of 74 °C. Previous formulations of the thermometer are inconsistent with the accumulated data set; they underestimate temperatures by about 100 °C at >1300 °C and overestimate by 100–200 °C at <1300 °C. In addition, they tend to overestimate temperatures for high‐Ca garnet (Xgrs ≈ 0.30–0.50). This new formulation has been tested against previous formulations of the thermometer by application to natural eclogites. This gave temperatures some 20–100 °C lower than previous formulations.  相似文献   

11.
Mössbauer spectra for two riebeckite minerals were collected at temperatures in the range 4.2 to 500 K. The magnetic-ordering temperatures were found to be 33±1 and 31±1 K respectively. Fitting the paramagnetic spectra with a discrete number of doublets (three or four) did not lead to consistent results. Instead, a superposition of an Fe3+ (M2) doublet and one distributed ferrous component was found to produce adequate fits with reasonable parameter values. For both samples, a minor fraction of ferrous ions was observed to be present at the M4 sites and for one of the samples at the M2 sites as well. The temperature variations of the center shifts were well reproduced using the Debye model of the lattice vibrational spectrum to evaluate the second-order Doppler shift. The characteristic Mössbauer temperatures were calculated to be in the range 340–390 K for Fe2+, and 520 K for Fe3+. The temperature dependences of the various ferrous quadrupole splittings could not be explained in terms of the point-charge model and assuming a temperature-independent energy-level scheme for the 5D term. It is suggested that a gradual change with temperature of the orbital-level splittings takes place. All calculations yielded a positive sign for the principal component of the electric field gradient (EFG). The spectrum recorded at 4.2 K for one of the riebeckites was fitted with a superposition of an Fe3+ and a Fe2+ hyperfine-field distribution, the latter one primarily characterizing the Fe2+ (M1) cations. The following relevant hyperfine data were calculated: H hf=161 kOe, ΔE Q=3.11 mm/s, and V zz<0, all referring to the maximum-propability values. For the second riebeckite at 4.2 K, an additional distributed ferrous component could independently be resolved. The two maximum-probability hyperfine fields were found to be 189 and 98 kOe and the corresponding ΔE Q values 3.10 and 2.67 mm/s. Both components exhibit a negative V zz. The subspectra were attributed to M1 and M3 sites respectively. The Fe3+ hyperfine fields are 548+-2 kOe for both riebeckites. The different values found for the Fe3+ quadrupole shift 2?Q for the two samples is explained by a different angle between the hyperfine field and the EFG's principal axis. The magnetic spectra recorded at 15 K and higher, could not be reproduced adequately with reasonable parameter values.  相似文献   

12.
The Mössbauer spectra of five samples of Fe x O with compositions in the range 1.00>x>0.95 have been recorded at 298 K and 4.2 K. The spectrum of Fe x O at 298 K consists of an asymmetric doublet which was fitted to one Fe2+ singlet, two Fe2+ doublets and 1 Fe3+ singlet. The Mössbauer parameters vary consistently with the increasing density of defects as x decreases. The Mössbauer spectrum of Fe x O at 4.2 K consists of a large number of unresolved lines. The data were fitted to a series of singlets to enable the rough calculation of quantities relating to the mean Fe2+ and Fe3+ environments. The results of the fits to the 298 K spectra are briefly discussed in terms of a physical model for the defect structure of Fe x O.  相似文献   

13.
Natural and synthetic olivines with ferrous and ferric iron have been studied by Mössbauer spectroscopy. Their spectra exhibit three superimposed quadrupole-split doublets corresponding to Fe2+ at M1 and M2 sites and Fe3+ at an unidentified position, which is probably M2. The hyperfine parameters of Fe3+ at temperatures between 300°C and 450°C are: Δ=0.67–1.23 mm/s, δ=0.04–0.23 mm/s relative to metallic iron, and the full width at half height, HW=0.15–0.43 mm/s. The Fe2+ populations of M2 decrease with increasing Fe3+ content. However, Fe2+ prefers M1 in synthetic olivines, even at high temperatures (800°–1,400°C). In kirschsteinite, Fe2+ and Fe3+ are exclusively in M1. Fe2+/Fe3+ ratios estimated from the peak areas are consistent with chemical analyses.  相似文献   

14.
Synthetic Fe3+-melilites containing NaCaFe3+-Si2O7-, Ca2Fe3+AlSiO7- or Sr2Fe3+AlSiO7-components have been studied by 57Fe Mössbauer spectroscopy. The spectrum of åkermanite containing an NaCaFe3+Si2O7-component consists of one doublet identified to belong to Fe3+ in T1 sites. The spectra of åkermanite and gehlenite containing Ca2Fe3+ AlSiO7- or Sr2Fe3+ AlSiO7-component consist of two doublets. The inner and outer doublets are identified to belong to Fe3+ in the less distorted T1 and that in the more distorted T2 sites, respectively. The area ratios of the spectra show that the site occupancy of Fe3+ (T1) in gehlenite is less than that in åkermanite in which the distribution of Fe3+ in T1 and T2 sites is apparently random. The different distributions can be explained in terms of competition between minimizing the deficiency in the electrostatic valence and the preference of Al for T1 sites which the isomer shift measurements show to be more ionic.  相似文献   

15.
The Mössbauer spectra of several blue beryls have been obtained in the temperature range of 4.2–500 K. A common feature observed in all room-temperature spectra is the presence of an asymmetric Fe2+ doublet (ΔE Q ?～?2.7?mm?s?1, δ?～?1.1?mm?s?1), with a very broad low-velocity peak. This asymmetry seems to be related to a relaxation process involving ferrous ions and water molecules in the structural channels, as suggested by Price et?al. (1976). Surprisingly, the spectrum at 500?K also shows a broad, but symmetrical, doublet, with a clear splitting of the lines indicating the presence of at least two Fe2+ components. The room-temperature spectrum obtained after the 500?K run shows the same features as prior to the heating. At 4.2?K the spectrum of a deep blue beryl was well fitted with four symmetrical doublets, one of which could be related to Fe2+ in the structural channels. Ferrous ion was also found to occupy the octahedral and tetrahedral sites, whereas ferric ion is most probably located in the octahedral site. A meaningful fit of the room-temperature spectrum, as well as an explanation for the temperature dependence of the Mössbauer spectra, are discussed. Finally, it is believed that the color in beryl will be dictated by the relative proportions of Fe3+ in the octahedral sites and of Fe2+ in the channels.  相似文献   

16.
The crystallochemical variations of clinopyroxene in response to changes in fO 2 and melt composition have been determined for a basalt-pantellerite suite (Boseti Complex, Main Ethiopian Rift) by crystal structure refinement and microprobe analysis. The pyroxene evolutionary trend has both a “Ca-minimum” and late iron enrichment. During crystallization from basalts to trachytes, clinopyroxene geometry depends mainly on the relationships between T and M2 sites; for example, high SiO2 activity in the magma causes high Si occupancy in T site, which in turn requires low Ca occupancy in M2 site in order to fulfill the local charge balance requirements. In contrast, clinopyroxene crystallized from acid melts is characterized by high Fe2+ (M1) content and therefore by a very large M1 site. Longer 〈M1-O1〉 and M1-O2 bond lengths require shorter T-O1 and T-O2 bond lengths and high Si occupancy in T site. It is concluded that the “Ca-minimum” in the clinopyroxene structure is regarded as the lowest value at which the charge balance requirements are satisfied in a C2/c clinopyroxene structure.  相似文献   

17.
Multiple regression analysis on an extended dataset has been performed to refine the relationship between temperature, pressure, composition and the Fe–Mg distribution between garnet and clinopyroxene. In addition to a significant dependence between the distribution coefficient KD and X GrtCa and X GrtMg#, as shown by the experimental data, the effect of X GrtMn has also been incorporated using data from natural Mn‐rich garnet–clinopyroxene pairs. Multiple regression of data (n=360) covering a large span in pressure, temperature and composition from 27 experimental datasets, combined with 49 natural high‐Mn granulites from Ruby Range, Montana, USA, and Karnataka, India, yields the P–T –compositional relationship (r2=0.98): where KD=(Fe2+/Mg)Grt/(Fe2+/Mg)Cpx, X GrtCa=Ca/(Ca+Mn+Fe2++Mg) in garnet, X GrtMn= Mn/(Ca+Mn+Fe2++Mg) in garnet, and X GrtMg#=Mg/(Mg+Fe2+) in garnet. The Fe2+–Mg equilibrium between garnet and clinopyroxene does not seem to be affected by variations in the sodic content of the co‐existing clinopyroxene in the range X CpxNa=0–0.51. Comparisons between the new and former calibrations of the garnet–clinopyroxene Fe2+–Mg geothermometer clearly demonstrate how the various parameters in each case affect the calculated temperatures. Application of the new expression gives reasonable results for natural garnet–clinopyroxene pairs from various rock types and settings, and should be preferred to previous formulations. Using the new calibration to the self‐consistent dataset of Pattison & Newton (Contributions to Mineralogy and Petrology, 1989, 101, 87–103) suggests a systematic deviation with regard to both temperature and composition between their dataset and the datasets used in the present calibration.  相似文献   

18.
Celadonite from the northwestern Mojave Desert area of California was examined by detailed Mössbauer spectroscopy at temperatures from 10 K to 400 K. In addition to the predominant Fe3+ doublet with isomer shift 0.4 mm s–1 and quadrupole splitting 0.4 mm s–1, another Fe3+ doublet with 0.4, 1.2 mm/s and two Fe2+ doublets with 1.1, 1.7, 2.7 mm s–1 at 300 K were distinguished. The minor Fe3+ component is ascribed to dehydroxylated surface sites. Most of the remaining Fe(90%) is M2 cis-OH octahedral in an ordered M+–M2+ array. However, about 10% is M1 trans-OH Fe2+. Isomer shift vs. T gives Debye temperatures of 570 K for Fe3+ in M2 and 380 K for both Fe2+ sites, indicating greater vibrational freedom for Fe2+. Quadrupole splitting vs. T for Fe2+ gives a valence electronic energy splitting of 760 cm–1 between the ground and first excited state for M2. The M1 sites have a more drastic variation in vs. T which indicates not only a lower first excited state but a rhombic distortion at these sites. A proposed explanation is a neighboring M2 site vacancy. The soil clay formed from this celadonite, which is mostly Fe-rich smectite, was also studied by Mössbauer spectroscopy. About half the Fe2+ has been oxidized in the clay, but the isomer shifts and quadrupole splittings are essentially the same as in the original celadonite. A texture orientation in the clay absorber was detected by measuring the absorber at 55° to the source radiation. This texture effect produces asymmetric doublets in the usual 90° measurement.  相似文献   

19.
 The crystal chemical response of basalt clinopyroxene to increasing pressure was investigated by means of crystal-structure simulation (a procedure that enables modeling of the structural parameters of a clinopyroxene of known chemistry without requiring direct X-ray diffraction analysis) using available experimental chemical data. Pressure proved the main physical variable governing clinopyroxene behavior in a magmatic environment. The general internal consistency of the simulation data permitted construction of an empirical geobarometer based on the relationship of cell volume (Vc) vs M1-site volume (VM1). The straightforward geobarometric formulation in the absence of direct X-ray analysis is: P(kbar)=698.443+4.985⋅AlT−26.826⋅Fe2+ M1−3.764⋅Fe3+ +53.989⋅AlM1+3.948⋅Ti+14.651⋅Cr −700.431⋅Ca−666.629⋅Na−682.848⋅MgM2−691.138⋅Fe2+ M2−688.384⋅Mn−6.267⋅(MgM2)2−4.144⋅(Fe2+ M2 where: (Fe2+ M1⋅MgM2)/(Fe2+ M2⋅MgM1)=e**(0.238⋅R3++0.289⋅CNM−2.315), CNM=Ca+Na+Mn, and R3+=AlM1+Fe3++Ti+Cr, with cations in atoms per formula unit. The geobarometer reproduces experimental pressures within ±2 kbar (=1σ; max. dev. ≤5 kbar; N=29) in the range 0–24 kbar and is applicable to near-liquidus C2/c clinopyroxenes crystallized from basaltic melts in the absence of garnet (excepting high-Al2O3 basalts). It is therefore suitable for many natural clinopyroxenes occurring as mega- or phenocrysts or forming well-preserved cumulate pyroxenites. If the above restrictions are not wholly satisfied, the Vc vs VM1 plot can also be used qualitatively to deduce the relative pressure conditions of clinopyroxenes forming from similar batches of magma. The structural simulation of experimental data also provided insight into the influence of minor chemical changes of the parental magma on the crystal chemistry of clinopyroxene at high pressure. Within the considered compositional space at given P-T, a CaO and a SiO2 in the melt have opposite effects on M2- and T-site cation populations. As a result, under similar physical conditions, clinopyroxenes from higher-CaO or more undersaturated basalts have higher VM2, VT and Vc and lower VM1. For basalts with normal contents of Al2O3 (<18 wt %), variations of major elements in the melt do not reduce the accuracy of the geobarometer. Received: 3 April 1994 / Accepted: 23 December 1995  相似文献   

20.
Natural sinhalites, MgAlBO4, from the Ratnapura District, Sri Lanka, and from Bodnar Quarry near Hamburg, Sussex Co., New Jersey, USA, have been characterized by 57Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine the oxidation state and site occupancy of iron in the sinhalite structure. The samples contain about 3.35 and 1.46 wt% of total iron oxide, respectively. The structure refinement is successful and reproduces the total iron content provided that the substitution of Mg2+ by Fe2+ on the M2 position only is assumed. The 57Fe Mössbauer spectra at 77, 293, 573 and 773 K can be resolved into two doublets with hyperfine parameters common for octahedrally coordinated high-spin Fe2+. There is no evidence for iron in the tetrahedral site. Electronic structure calculations in local spin density approximation yield hyperfine parameters for Fe2+ on the M2-site at 0, 293, 573 and 773 K in quantitative agreement with experiments. Calculated spectroscopic properties for Fe2+ on the M1-site are at variance with the experimental data and, thus, indicate that substitution of Al3+ by Fe2+, if occurring at all, must be accompanied by considerable local expansion and distortion of the M1-octahedron.  相似文献   

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