Distinctive crystal chemistry and site configuration of the clinopyroxene from alkali basaltic rocks

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 Al^iv to balance the effect of increasing (Fe³⁺+Ti⁴⁺+Al^vi+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.     

<Superscript>57</Superscript>Fe Mössbauer measurements and electronic structure calculations on natural lawsonites

Three natural lawsonites from Syke Rock, Mendocino Co., Reed Ranch, Marin Co., and Blake Gardens, Sonoma Co., all from the Coast Range Region in California, were studied by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe analysis, and X-ray powder diffraction. The samples contain about 0.6, 1.0, and 1.4 wt% of total iron oxide, respectively. ⁵⁷Fe Mössbauer spectra are consistent with the assumption that high-spin Fe³⁺ substitutes for Al in the octahedrally coordinated site. The Mössbauer spectrum of lawsonite from Syke Rock exhibits a second doublet with ⁵⁷Fe hyperfine parameters typical for octahedrally coordinated high-spin Fe²⁺. Electronic structure calculations in the local spin density approximation yield quadrupole splittings for Fe³⁺ in quantitative agreement with experiment indicating, however, that substitution of Al by Fe³⁺ must be accompanied by local distortion around the octahedral site. Model calculations also reproduce the room temperature hyperfine parameters of ferrous high-spin iron assuming the substitution of Ca by Fe²⁺. However, it cannot be excluded that Fe²⁺ may occupy a more asymmetric site within the microstructural cavity occupied by Ca and a H₂O molecule.     

Crystal chemistry, structure analyses and phase transition experiment on an omphacite from eclogitic metagabbro from Syros island, Greece

Summary Pyroxene samples, from the Greek island of Syros, taken from a blueschist-eclogite facies Mg-rich metagabbro, were investigated by chemical and XRD analyses and M?ssbauer spectroscopy. Single-crystal XRD and microprobe analysis showed that the natural sample is a typical omphacite of intermediate composition in the Ca–Na pyroxene solid solutions. The space group P2/n was confirmed and the cations Mg, Al and Ca, Na were found to be ordered in the M1 and M2 positions, respectively. M?ssbauer spectroscopy showed that there is both ferrous and ferric iron in the structure, with the ratio 1.38:1. The M2 sites are fully occupied by Ca and Na, thus the iron (Fe²⁺ and Fe³⁺) can substitute only for Mg and Al in the M1 sites. Partial disorder was attained by annealing the sample at 850 °C, 20 kbar for 7 days, as confirmed by decrease of intensity of reflections affected by the C-type extinction.     

Thermodynamics of multicomponent pyroxenes: I. Formulation of a general model

A model is proposed for the thermodynamic properties of multicomponent pyroxenes in the composition space defined by the end-member component CaMgSi₂O₆ and the exchange components Fe(Mg)_-1, TiAl₂(MgSi₂)_-1, Fe³⁺(Al)_-1, Fe³⁺Al(MgSi)_-1, and Mg(Ca)_-1. It is formulated for the simplifying assumptions that: (1) a molecular mixing type approximation describes changes in the molar configurational entropy associated with the coupled exchange substitutions TiAl₂MgSi₂, Fe³⁺AlMgSi, and Al₂MgSi (and their ferroan equivalents), and (2) Fe²⁺ and Mg²⁺, and Al³⁺ and Fe³⁺ display long-range non-convergent ordering between M2 and octahedral M1 sites, and octahedral M1 and tetrahedral sites, respectively. The molar vibrational Gibbs energy is described by a Taylor expansion of second degree in seven linearly independent composition and ordering variables, which is extended to third degree to account for asymmetry in the mixing of Ca and Mg, and Ca and Fe on the M2 site, and is further modified for the assumption that the standard state properties of Ca end-member components of clinopyroxenes are linearly dependent on the coordination number of Ca²⁺ on the M2 site. The model is shown to be consistent with miscibility gap feaures of pyroxenes in the system CaMgSi₂O₆–CaTiAl₂O₆–CaAl₂SiO₆. In subsequent papers, the model is calibrated for the simplifying assumptions that: (1) all regular-solution-type parameters are constants independent of temperature, (2) Pbca and C2/c end-members have identical heat capacities and coefficients of thermal expansion and compressibility, and (3) the heat capacities and coefficients of thermal expansion and compressibility are zero for all reciprocal reactions relating Pbca and pigeonite or high-calcium pyroxene C2/c endmember components.     

Crystal-chemistry and cation ordering in the system diopside-jadeite: A detailed study by crystal structure refinement

The Nybö eclogite pod in Norway is characterized by a great variety of clinopyroxene compositions with Jd contents ranging from less than 5% up to nearly 80%, whilst Ac+Hd contents remain almost constant (mostly within 10±5%).Unconstrained X-ray structure refinement has been carried out on 16 pyroxene crystals (8 with C2/c and 8 with P2/n space group) from the Nybö eclogite, and also on one omphacite crystal (from Lago Mucrone in the Sesia-Lanzo Zone, Western Alps) which displays the highest degree of cation ordering yet described. The final discrepancy factors range from 0.014 to 0.029. The population of the sites has been determined on the basis of bond length considerations and of the results of the site occupancy refinement. Six of these crystals were subsequently analysed by electron microprobe.The tetrahedral sites are occupied by Si with negligible amounts of Al. Al, Mg, Fe³⁺ and Fe²⁺ occur at the octahedral sites; in the ordered P2/n crystals Al and Fe³⁺ are concentrated at the M11 site, whilst Mg and Fe²⁺ are concentrated and the M1 site. The eight-coordinated sites contain Ca and Na with negligible amounts of Fe and/or Mg. Ordering of Ca and Na takes place in the P2/n samples in such a way that in the most ordered crystal the M2 site contains almost exactly 0.75 Na+0.25 Ca and the M21 site 0.25 Na+0.75 Ca.Some geometrical features of the tetrahedra as well as of the octahedra (e.g. tetrahedral quadratic elongation and TILT angle) are not a simple linear function of composition, even when no change in space group occurs. The crystals evidently do not behave like a binary system of the two components, Di and Jd, but behave rather as if the composition Di_0.50 Jd_0.50 was a distinct end member.The boundaries between disordered and ordered phases in the Nybö pyroxenes fall at about 0.35 and 0.65 Jd/(Di+ Jd), in close agreement with the previous TEM investigations.The degree of order varies with composition following a bell-shaped curve: different coaxial bell-shaped curves can be drawn for crystals which have similar compositions but come from different metamorphic environments. The order vs composition diagrams may be useful for the interpretation of the P-T-t histories of the host rocks.     

Compositions and phase relations of calcic amphiboles in epidote- and clinopyroxene-bearing rocks of the amphibolite and lower granulite facies,central Massachusetts,USA

Calcic amphiboles coexisting with epidotegroup minerals (zoisite, clinozoisite, epidote) and/or clinopyroxene±plagioclase±quartz±garnet occur in amphibolites and calc-silicate rocks that underwent amphibolite to lower granulite-facies metamorphism in the Acadian metamorphic high of central Massachusetts, USA. Across the region, peak metamorphic conditions range from about 580° C and 6.2 kbar to 730° C and 6.3 kbar. The coexistence of most Ca-amphiboles with Fe³⁺-rich epidote-group minerals suggests the presence of Fe³⁺ in most of these amphiboles. An empirical Fe³⁺ estimation for the microprobe analyses is based on two constraints: the Na?Ca content of the M4 sites of Ca-saturated, gravimetrically analyzed hornblendes gives the relation: Ca(M4) ^c =-1.479 Na(M4) ^c +2 (c=corrected). The second constraint is the stoichiometric equation Ca(M4)+Na(M4)+FM=15, where FM is the sum of all cations exclusive of Ca, Na, and K. Solving the two equations simultaneously gives: 20.185=0.479 Ca(M4)+1.479 ΣFM. Starting with the uncorrected values of Ca(M4) ^u and ΣFM(M4) ^u (u = uncorrected) of the all ferrous formula, the normalization factor NF for calculating the corrected cations of the ferric formulas is: 20.185/(0.478 Ca(M4) ^u +1.479 ΣFM ^u ). From the deficient oxygen the Fe³⁺ content which is equal to 2(23-ΣOX) can be calculated. Determinations of Fe³⁺ contents of four hornblende separates by Mössbauer spectroscopy are in agreement with the calculated values. The Ca-amphiboles show systematic changes in composition with increasing grade of metamorphism within the amphibolite and lower granulite-facies zones: increasing edenite and tschermakite substitution, increasing Ti content, and increasing Fe²⁺/(Fe²⁺+Mg) ratio. In addition, the coexisting clinopyroxenes are also characterized by an increase in Fe²⁺/(Fe²⁺+Mg) ratio. In quartz-free rocks with coexisting Ca-amphibole and plagioclase there is an increase in the ratio X _Ab/X _Ed, where X _Ab=Na/(Na+Ca) in plagioclase and X _Ed=Na in the amphibole A-site. These chemical changes in mineral composition together with the disappearance of epidote at the transition to granulite-facies metamorphic conditions are attributed to the continuous reaction: albite+epidote+Fe-Mg hornblende→Fe?Mg clinopyroxene+anorthite+(NaAlSi_-1)^Hbl+H₂O.     

Mg,Fe2+ site occupancies in coexisting pyroxenes

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.     

Crystal-chemistry of high-pressure clinopyroxene from spinel lherzolite nodules Mts. Leura and Noorat Suites,Victoria, Australia

Summary The clinopyroxene suites from lherzolite nodules from Mts. Leura and Noorat (Victoria, Australia) have been investigated by X-ray diffraction and electron probe microanalyses (Dal Negro et al., 1984; Cundari et al., 1986).The evolution of the host nodule is shown by general depletion of AlIv, AVI, Ti⁴⁺, Fe²⁺ and enrichment of Si, Mgm,, Fe³⁺, Cr³⁺, Ca, while Na depletion occurs only in the clinopyroxenes from Mt. Noorat. Different mechanisms of cation substitution are thus involved in the two clinopyroxene suites, suggesting different total pressures of equilibration in the stability field of spinel.Modifications involving the M1 octahedron are mainly ascribed to variable amounts of trivalent cations, the volume of the M 1 site increasing with decreasing content of trivalent cations in each suite. The differences in M 1 site configuration between the Mt. Leura and Mt. Noorat clinopyroxene suites are ascribed to the different amounts of A1v1 and FeM,.The volume of the T tetrahedral site is generally related to A1Iv in each suite. An increase in T site volume from Mt. Leura to Mt. Noorat clinopyroxenes was found however, due to lengthening of the T-O_brg bond lengths, for similar AIIv contents. The volume of the M2 site, generally related to Ca content, was generally higher in the Noorat clinopyroxenes for similar Ca (and Ca + Na) contents, due to the longer M₂-O₃C₁ bond length, strongly related to Na content. Cell volume is linearly correlated to M 1 volume in each suite, but is definitely higher in the Noorat clinopyroxenes for similar M 1 volume. All the structural data show that the total pressure of equilibration in the Noorat clinopyroxenes was lower than that in the Leura clinopyroxenes, as suggested by chemical data.

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Die Kristallchemie von hochdruck-klinopyroxenen aus spinell-lherzolithknollen von Mt. Leura und Mt. Noorat, Victoria, Australien

Zusammenfassung Die Klinopyroxenparagenesen aus Lherzolitheinschlüssen von Mt. Leura und Mt. Noorat (Victoria, Australien) wurden mittels Röntgendiffraktometrie und Elektronenmikrosonde untersucht (Dal Negro et al., 1984; Cundari et al., 1986). Die Lherzolitheinschlüsse zeigen generell eine Abnahme von Al^IV, Al^VI, Ti⁴⁺, Fe _MI ²⁺ und eine Zunahme von Si, Mgm,, Fe³⁺, Cr³⁺ und Ca. Eine Abnahme von Na tritt nur in Klinopyroxenen von Mt. Noorat auf. Verschiedene Substitutions-Mechanismen der Kationen weisen auf verschiedene Equilibrationsdrucke im Stabilitätsbereich der Spinelle hin und sind daher in den beiden Klinopyroxenserien zu berücksichtigen. Modifikationen in der oktaedrischen M1-Position wurden vor allem dem wechselnden Anteil an dreiwertigen Kationen zugeschrieben, wobei in jeder der beiden Serien das Volumen der Ml-Position mit abnehmenden Gehalten dreiwertiger Kationen zunimmt. Die unterschiedliche Konfiguration der M1-Position der Klinopyroxene von Mt. Leura und Mt. Noorat wird mit unterschiedlichen Gehalten an Al^VI und Fe _MI ²⁺ , in Zusammenhang gebracht.Das Volumen der tetraedrischen T-Position ist normalerweise mit den Gehalten an All^IV in jeder Serie verknüpft. Ein Vergleich der Klinopyroxene von Mt. Leura und Mt. Noorat zeigte jedoch, daß bei gleichen Gehalten an Al^VI das Volumen der tetraedrischen Position infolge einer Aufwertung der T-O_brg.-Bindungen zunimmt. Das Volumen der M2-Position, üblicherweise mit dem Ca-Gehalt korreliert, ist in den Klinopyroxenen von Mt. Noorat bei ähnlichen Ca (und Ca f Na) Gehalten infolge größerer M2--O₃C₁-Abstände größer. Sie stehen also mit den Na-Gehalten in Verbindung.Das Volumen der Elementarzelle korreliert mit dem der M1-Position in jeder Serie; es ist aber in den Klinopyroxenen von Mt. Noorat deutlich höher. Die Ergebnisse der Strukturuntersuchungen zeigen-wie auch die chemischen Daten-, daß die genannten Equilibrationsdrucke für die Klinopyroxene von Mt. Noorat niedriger waren als für die von Mt. Leura.

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With 2 Figures     

Temperature dependence of the 57Fe Mössbauer parameters in riebeckite

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.     

Distribution of cations at two tetrahedral sites in Ca2MgSi2O7-Ca2Fe3+AlSiO7 series synthetic melilite and its relation to incommensurate structure

Synthetic melilites on the join Ca₂MgSi₂O₇ (åkermanite: Ak)-Ca₂Fe³⁺AlSiO₇ (ferrialuminium gehlenite: FAGeh) were studied using X-ray powder diffraction and ⁵⁷Fe Mössbauer spectroscopic methods to determine the distribution of Fe³⁺ between two different tetrahedral sites (T1 and T2), and the relationship between ionic substitution and incommensurate (IC) structure. Melilites were synthesized from starting materials with compositions of Ak₁₀₀, Ak₈₀FAGeh₂₀, Ak₇₀FAGeh₃₀ and Ak₅₀FAGeh₅₀ by sintering at 1,170–1,350 °C and 1 atm. The average chemical compositions and end-member components, Ak, FAGeh and Geh (Ca₂Al₂SiO₇), of the synthetic melilites were Ca_2.015Mg_1.023Si_1.981O₇ (Ak₁₀₀), Ca_2.017Mg_0.788Fe _0.187 ³⁺ Al_0.221Si_1.791O₇ (Ak₇₈FAGeh₁₉Geh₃), Ca_1.995Mg_0.695Fe _0.258 ³⁺ Al_0.318Si_1.723O₇ (Ak₆₉FAGeh₂₅Geh₆) and Ca_1.982Mg_0.495Fe _0.449 ³⁺ Al_0.519Si_1.535O₇ (Ak₄₉FAGeh₄₄Geh₇), respectively. Rietveld refinements using X-ray powder diffraction data measured using CuK _α -radiation at room temperature converged successfully with goodness-of-fits of 1.15–1.26. The refined Fe occupancies at the T1 and T2 sites and the Mg and Si contents determined by electron microprobe analysis gave the site populations of [0.788Mg + 0.082Fe³⁺ + 0.130Al]_T1[0.104Fe³⁺ + 0.104Al + 1.792Si]_T2 for Ak₇₈FAGeh₁₉Geh₃, [0.695Mg + 0.127Fe³⁺ + 0.178Al]_T1[0.132Fe³⁺ + 0.144Al + 1.724Si]_T2 for Ak₆₉FAGeh₂₅Geh₆ and [0.495Mg + 0.202Fe³⁺ + 0.303Al]_T1[0.248Fe³⁺ + 0.216Al + 1.536Si]_T2 for Ak₄₉FAGeh₄₄Geh₇ (apfu: atoms per formula unit), respectively. The results indicate that Fe³⁺ is distributed at both the T1 and the T2 sites. The mean T1–O distance decreases with the substitution of Fe³⁺ + Al³⁺ for Mg²⁺ at the T1 site, whereas the mean T2–O distance increases with substitution of Fe³⁺ + Al³⁺ for Si⁴⁺ at the T2 site, causing decrease in the a dimension and increase in the c dimension. However, in spite of the successful Rietveld refinements for the X-ray powder diffraction data measured using CuK _α-radiation at room temperature, each Bragg reflection measured using CuK _α1-radiation at room temperature showed weak shoulders, which were not observed in those measured at 200 °C. The Mössbauer spectra of the melilites measured at room temperature consist of two doublets assigned to Fe³⁺ at the T1 site and two or three doublets to Fe³⁺ at the T2 site, implying the existence of multiple T1 and T2 sites with different site distortions. These facts can be interpreted in terms of the IC structure in all synthetic melilites at room temperature, respectively. The results of Mössbauer analysis indicate that the IC structure in melilite is caused by not only known multiple T1 site, but also multiple T2 site at room temperature.     

莱河矿的超结构和低温穆斯堡尔谱的对比研究

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。     

巨晶普通辉石的M1位分裂

巨晶普通辉石的Ｍ１位分裂李一良，支霞臣，李玉芝，李铁，张裕恒（中国科学技术大学，合肥２３００２６）关键词巨晶辉石，Ｍ１位分裂，面积约束法，近邻边效应，Ｔ位铁单斜辉石的穆斯堡尔谱学研究历时已久。但由于其晶体结构和成份的复杂性、化学不均一性及出溶现象等［...     

Controlled time–temperature oxidation reaction in a synthetic Mg-hercynite

The oxidation of a synthetic hercynite with composition Fe²⁺ _0.699Mg_0.301Al_1.941Fe³⁺ _0.059O₄ was investigated by X-ray single-crystal diffraction. Heating runs at 500°C up to 212 h did not produce detectable oxidation, but only a small variation in oxygen coordinate u, consistent with very limited reordering of Mg and Al in tetrahedral (T) and octahedral (M) sites, respectively. Oxidation began after the first run at 600°C, producing progressive decreases in u, cell parameter a and the mean atomic number in T site. After 1,842 h at 600°C, the transformation was close to equilibrium, with about 70% of ferrous iron transformed into ferric. This produced about 0.17 vacancies per formula unit, and caused a great increase in the displacement parameters of oxygen and M sites. Vacancies were strongly ordered in M sites, and the oxygen displacement parameter becames anisotropic, unlike stoichiometric spinels—because some of the oxygen coordination polyhedra have a vacancy instead of a cation in one vertex. The behaviour of displacement parameters in this case supports the calculated point defect distribution.     

Biotite and garnet compositional variation and mineral equilibria in Grenville gneisses of the Otter Lake area, Quebec

Garnet-biotite gneisses, some of which contain sillimanite or hornblende, are widespread within the Otter Lake terrain, a portion of the Grenville Province of the Canadian Shield. The metamorphic grade is upper amphibolite to, locally, lower granulite facies. The atomic ratio Fe²⁺/(Fe²⁺+ Fe³⁺) in biotite ranges from 0.79 to 0.89 (ferrous iron determinations in 10 highly pure separates), with a mean of 0.86. Mg and Fe²⁺ atoms occupy 67–78% of the octahedral sites, the remainder are occupied by Fe³⁺, Ti, and Al, and some are vacant. Mg/(Mg + Fe²⁺), denoted X, in the analysed samples ranges from 0.32 to 0.65. Garnet contains 1–24% grossular, 1–12% spessartine and X ranges from 0.07 to 0.34. Compositional variation in biotite and garnet is examined in relation to three mineral equilibria: (I) biotite + sillimanite + quartz = garnet + K-feldspar + H₂O; (II) pyrope + annite = almandine + phlogopite; (III) anorthite = grossular + sillimanite + quartz. Measurements of X (biotite) and X (garnet) are used to construct an illustrative model for equilibrium (I) which relates the observed variation in X to a temperature range of 70°C or a range in H₂O activity of 0.6; the latter interpretation is preferred. In sillimanite-free gneisses, the distribution of Mg and Fe²⁺ between garnet (low in Ca and Mn) and biotite is adequately described by a distribution coefficient (KD) of 4.1 (equilibrium II). The observed increase in the distribution coefficient with increasing Ca in garnet is ln K_D= 1.3 + 2.5 × 10^?2 [Ca] where [Ca] = 100 Ca/(Mg + Fe²⁺+ Mn + Ca). The distribution coefficient is apparently unaffected by the presence of up to 12% spessartine in garnet. In several specimens of garnet-sillimanite-plagioclase gneiss, the Ca contents of garnet and of plagioclase increase in unison, as required by equilibrium (III). The mean pressure calculated from these data (n= 17) is 5.9 kbar, and the 95% confidence limits are ±0.5 kbar.     

Mössbauer spectra and magnetic features of ilvaites

Ilvaite samples from six different localities in Japan are found to be members of a solid-solution series varying from Ca(Fe²⁺,Fe³⁺)₂Fe²⁺(OH)O Si₂O₇ to approaximately Ca(Fe²⁺,Fe³⁺)₂Fe _0.5 ²⁺ Mn _0.5 ²⁺ (OH)O Si₂O₇, and have been studied by Mössbauer spectrometry and magnetic measurements. The variation in intensity of Mössbauer doublets confirms that Mn substitutes for Fe²⁺ in the M(B) cation site. An temperatures decreasing from 300 K to 4K, an abrupt change in the reciprocal mass magnetic susceptibility, 1/x _g, occurs about 120 K; 1/x _g depends linearly upon temperature above 120 K. This change, which is characterized by an unusual mode of decrease in 1/x _g, has been interpreted based on Mössbauer spectra at 80 K: the spectra of Fe²⁺ and Fe³⁺ in the M(A) site show Zeeman splitting, whereas those of Fe²⁺ in the M(B) site do not show the effect. This Mössbauer evidence suggests that magnetic spins of Fe in M(A) are in an ordered state, very likely of antiparallel coupling, whereas those of Fe in M(B) are randomly oriented, showing that below 120 K ilvaite has two different magnetic states for Fe ions. As there is a line of evidence that the spins of Fe in M(B) would take an ordered state at extremely low temperatures, ilvaite magnetism may be regarded as basically antiferromagnetic. The magnetic spins of Fe in M(A) and M(B) undergo magnetic transitions at different specific temperatures, thus giving as a whole unusual features of magnetism.     

Ferric iron in mantle-derived garnets

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).     

Effects of strong network modifiers on Fe<Superscript>3+</Superscript>/Fe<Superscript>2+</Superscript> in silicate melts: an experimental study

The effect of CaO, Na₂O, and K₂O on ferric/ferrous ratio in model multicomponent silicate melts was investigated in the temperature range 1450–1550?°C at 1-atm total pressure in air. It is demonstrated that the addition of these network modifier cations results in an increase of Fe³⁺/Fe²⁺ ratio. The influence of network modifier cations on the ferric/ferrous ratio increases in the order Ca?<?Na?<?K. Some old controversial conceptions concerning the effect of potassium on Fe³⁺/Fe²⁺ ratio in simple model liquids are critically evaluated. An empirical equation is proposed to predict the ferric/ferrous ratio in SiO₂–TiO₂–Al₂O₃–FeO–Fe₂O₃–MgO–CaO–Na₂O–K₂O–P₂O₅ melts at air conditions.     

A Mössbauer and X-ray diffraction study of annites synthesized at different oxygen fugacities and crystal chemical implications

A refined set of Mössbauer parameters (isomer shifts, quadrupole splittings, Fe²⁺/Fe³⁺ ratios) and lattice parameters were obtained from annites synthesized hydrothermally at pressures between 3 and 5 kbars, temperatures ranging from 250 to 780° C and oxygen fugacities controlled by solid state buffers (NNO, QMF, IM, IQF). Mössbauer spectra showed Fe²⁺ and Fe³⁺ on both the M1 and the M2 site. A linear relationship between Fe³⁺ content and oxygen fugacity was observed. Towards low Fe³⁺ values this linear relationship ends at ≈10% of total iron showing that the Fe³⁺ content cannot be reduced further even if more reducing conditions are used. This indicates that in annite at least 10% Fe²⁺ are substituted by Fe³⁺ in order to match the larger octahedral layer to the smaller tetrahedral layer. IR spectra indicate that formation of octahedral vacancies plays an important role for charge balance through the substitution 3 Fe²⁺ → 2 Fe³⁺ + ?_(oct).     

多硅白云母中Fe2+的高压有序效应

21个多硅白云母来自4个低温高压变质带。用电子探针、X射线粉末衍射及穆斯堡尔谱测定其化学成分、b0值及Fe²⁺占位。建立Fe²⁺(M1)/Fe²⁺(M2)对b0值相关图,发现Fe²⁺在八面体晶位有序化并解释其有序机理。     

Pressure effect on the electronic structure of iron in (Mg,Fe)(Si,Al)O3 perovskite: a combined synchrotron Mössbauer and X-ray emission spectroscopy study up to 100 GPa

We investigated the valence state and spin state of iron in an Al-bearing ferromagnesian silicate perovskite sample with the composition (Mg_0.88Fe_0.09)(Si_0.94Al_0.10)O₃ between 1 bar and 100 GPa and at 300 K, using diamond cells and synchrotron Mössbauer spectroscopy techniques. At pressures below 12 GPa, our Mössbauer spectra can be sufficiently fitted by a “two-doublet” model, which assumes one ferrous Fe²⁺-like site and one ferric Fe³⁺-like site with distinct hyperfine parameters. The simplest interpretation that is consistent with both the Mössbauer data and previous X-ray emission data on the same sample is that the Fe²⁺-like site is high-spin Fe²⁺, and the Fe³⁺-like site is high-spin Fe³⁺. At 12 GPa and higher pressures, a “three-doublet” model is necessary and sufficient to fit the Mössbauer spectra. This model assumes two Fe²⁺-like sites and one Fe³⁺-like site distinguished by their hyperfine parameters. Between 12 and 20 GPa, the fraction of the Fe³⁺-like site, Fe³⁺/∑Fe, changes abruptly from about 50 to 70%, possibly due to a spin crossover in six-coordinate Fe²⁺. At pressures above 20 GPa, the fractions of all three sites remain unchanged to the highest pressure, indicating a fixed valence state of iron within this pressure range. From 20 to 100 GPa, the isomer shift between the Fe³⁺-like and Fe²⁺-like sites increases slightly, while the values and widths of the quadruple splitting of all three sites remain essentially constant. In conjunction with the previous X-ray emission data, the Mössbauer data suggest that Fe²⁺ alone, or concurrently with Fe³⁺, undergoes pressure-induced spin crossover between 20 and 100 GPa.