Geochemistry of biotites from granitic rocks,Northern Portugal

The biotites from a series of rocks ranging in composition from tonalite to granite have been analysed for both major and trace elements.The relations between chemical composition and paragenesis of the biotites are studied. Most biotites co-exist with potassium feldspar and ilmenite. Variations in composition can be correlated with the occurrence of amphibole, primary muscovite and aluminosilicates in the rocks.Variation diagrams of the trace element contents and element ratios of biotite are compared to those of the host rocks. Fractionation of elements can be defined more accurately as the influence of other mineral phases is eliminated.Variations in the proportions of the octahedrally co-ordinated Al, Ti and Fe³⁺ are correlated with the conditions of crystallization and comparisons made with biotites from other suites of calc-alkali rocks.In the light of the experimental data available, the petrographic observations and the chemical data it is apparent that biotites crystallized from systems in which fO₂ was buffered, its values remaining close to that of the buffer FMQ. From the same data, a temperature of 800°C for fO₂ = 10^?14to 10^?15 bars is deduced as prevalent during the crystallization of the tonalites while for the granites, at a temperature of crystallization of 680°C, fO₂ = 10^?16to 10^?18 bars.A calc-alkali trend of fractionation is therefore apparent with decreasing fO₂ while fH₂O₂ remains relatively high.     

Coexisting hornblendes and biotites from Precambrian gneisses of the south coast of Western Australia

The compositions of coexisting hornblendes and biotites from amphibolite and granulite facies gneisses from the south coast of Western Australia were controlled by host rock composition, paragenesis, metamophic grade, pressure, and oxygen fugacity. The Mg/(Mg + Fe²⁺) and Mn/Fe²⁺ ratios in both minerals and possibly the Al^vi contents of the hornblendes are related to host rock compositions. Metamorphic grade appears to influence, perhaps only indirectly, the Ti, Mn, and Fe³⁺ contents of both minerals and possibly the hornblende Ca content. The higher Ti and lower Mn contents of the granulite facies hornblendes and biotites are attributed to their coexistence with pyroxenes, whereas their lower Fe³⁺/(Fe²⁺ + Fe³⁺) ratios are probably due to lower oxygen fugacity in the granulite facies environment. Grade-related colour variations in both minerals were controlled by their Ti/Fe²⁺ and Fe³⁺/(Fe²⁺ + Fe³⁺ ratios. The relatively low Al^vi contents of the hornblendes suggest low- to moderate-pressure metamorphism.Variations in element distribution coefficients are related to variations in mineral compositions rather than metamorphic grade. Thus K_{D(Al^iv ?Si)} is related to the Al^iv andedenite alkali contents of the hornblendes, K_{D(Fe²⁺ ?Mg)} to the distributions of Al^iv ?Si and Al^vi + Ti + Fe³⁺, K_D(Mn) to the Mn contents of both minerals, and K_D(Al^vi) to the Al^vi contents of the biotites.     

Geochemistry of actinolitic hornblendes from tonalitic rocks,Northern Portugal

Chemical analyses are given for actinolitic hornblendes of tonalitic rocks from the Hercynian belt of Northern Portugal. The distribution of elements between amphibole and co-existing biotite is studied. The composition of the amphiboles is analysed in the light of experimental data on amphiboles and the physical conditions of crystallization inferred from the study of the biotite and rock series. The data on the biotites lead to the definition of a temperature of 800°C for the crystallization of actinolitic hornblendes with Mg/(Mg + Fe) ratios of 0·72-0·61 at pressures of about 3 Kb and fO₂ defined by FMQ.     

湘南宝山矿床花岗闪长斑岩中黑云母的矿物学特征及其指示意义

湖南宝山矿床处于坪宝矿带的北端,是湘南地区最大的铜多金属矿床。为了进一步探讨矿区内花岗质岩石的形成条件及成矿潜力,文章在详细的野外地质和岩相学观察的基础上,对与成矿密切相关的花岗闪长斑岩中的黑云母进行了详细的矿物化学分析。电子探针分析结果表明:宝山花岗闪长斑岩中的黑云母为铁质黑云母和镁质黑云母,其中,Ti介于0.18~0.30,且Mg/(Mg+Fe2+)值介于0.42~0.58,属于典型的岩浆成因黑云母;黑云母的氧化系数为0.16~0.26,w(Mg O)为8.17%~11.72%,平均9.3%,MF值范围为0.38~0.50,指示其岩体属于壳幔混源型的I型花岗岩;岩体中以黑云母的全铝含量计算的结晶压力为97~174 MPa,相应的结晶深度为3.67~6.57 km,平均深度为5.12 km。其log f(O2)变化范围为-14.5~-12.8,表明黑云母是在较高氧逸度条件下结晶形成的,有利于铜矿的形成。     

Chemical Mineralogy of Hornblendes and Biotites from the Charnockitic Rocks of Kondapalli, India

Complete chemical analyses, structural formulae and trace elementdata are presented for 9 hornblendes and 12 biotites from thecharnockitic and associated rock types of Kondapalli (AndhraPradesh, India), some 200 miles north of the type area nearMadras. The chemical characteristics of the hornblendes are:very high [Al]⁴, nearly constant Ca, very high and nearly constanttotal alkalis (Na₂O > K₂O in the hornblendes of ultrabasiccharnockites and Na₂O < K₂O in those of basic charnockites),very high F and Cl, low total water, and Ni in amount greaterthan Co. The biotites are characterized by high Ti and F, lowMn, total absence of Ca, exceptionally high amounts of Cl, lowtotal water, and have Ni > Co; the biotites from differentgroups of host rocks have different Al and Fe³+ contents. Thevariations in composition of these minerals are interpretedas due to the change in bulk rock chemistry and mineralogy andnot to the change in temperatures of crystallization. The element distributional relationships in hornblende-biotite,hornblende-orthopyroxene, hornblende-clinopyroxene, biotite-orthopyroxene,and biotite-clinopyroxene pairs from the Kondapalli charnockitesare evaluated, with particular attention to the partition ofFe²+, Mg, Mn, Ti, Cr, Ni, Co, and V, and comparisons are madewith similar data available for corresponding mineral pairs.Highly consistent and uniform distribution coefficients forFe²+ and Mg (and a small range of distribution coefficientsfor many of the trace elements) are obtained for most of thedifferent sets of mineral pairs from Kondapalli, suggestingthat equilibrium distribution of the elements between the phaseshad been attained.     

Mössbauer effect study of anapaite, Ca2Fe2+(PO4)2 · 4H2O, and of its oxidation products

Mössbauer spectra (MS) of anapaite (Ca₂ Fe²⁺(PO₄)₂?·?4H₂O) and of a sample after being immersed in a 4% H₂O₂ solution at room temperature (RT) over 12 days (hereafter an4ox) were collected at temperatures in the range 4.2 to 420?K and 11 to 300?K respectively. All MS consist of symmetrical doublets, hence magnetic ordering was not observed. The temperature dependencies of the Fe²⁺ centre shifts of anapaite and an4ox were analysed with the Debye model for the lattice vibrations. The characteristic Mössbauer temperatures were found as 370?K?±?25?K and 340?K?±?25?K, and the intrinsic isomer shifts as 1.427?±?0.005?mm/s and 1.418?±?0.005?mm/s respectively. From the external-field (60?kOe) MS recorded at 4.2 and 189?K for the non-treated sample, the principal component V _zz of the electric field gradient (EFG) is determined to be positive and the asymmetry parameter η?≈?0.2 and 0.4 respectively. The temperature variations of the quadrupole splittings, ΔE _Q(T), cannot be interpreted on the basis of the thermal population of the ⁵ D electronic levels resulting from the tetragonal compression of the O₆ co-ordination. The low-temperature linear behaviour of ΔE _Q(T) is attributed to a strong orbit-lattice coupling. A field of 60 kOe applied to anapaite at 4.2?K produces magnetic hyperfine splitting with effective hyperfine fields of ?136, ?254 and ?171?kOe along the principal axes Ox, Oy and Oz of the EFG tensor respectively. Additional oxidation treatments in solutions with various H₂O₂ concentrations up to 20% and subsequent Mössbauer experiments at room temperature, have revealed that the anapaite structure is not sensitive to oxidation since eventually only a small amount of Fe²⁺ (～6.5%) is converted into Fe³⁺.     

Influence of oxygen fugacity and temperature on the redox state of iron in natural silicic aluminosilicate melts

The influence of oxygen fugacity (fO₂) and temperature on the valence and structural state of iron was experimentally studied in glasses quenched from natural aluminosilicate melts of granite and pantellerite compositions exposed to various T-fO₂ conditions (1100–1420°C and 10^?12–10^?0.68 bar) at a total pressure of 1 atm. The quenched glasses were investigated by Mössbauer spectroscopy. It was shown that the effect of oxygen fugacity on the redox state of iron at 1320–1420°C can be described by the equation log(Fe³⁺/Fe²⁺) = k log(fO₂) + q, where k and q are constants depending on melt composition and temperature. The Fe³⁺/Fe²⁺ ratio decreases with decreasing fO₂ (T = const) and increasing temperature (fO₂ = const). The structural state of Fe³⁺ depends on the degree of iron oxidation. With increasing Fe³⁺/Fe²⁺ ≥ 1, the dominant coordination of Fe³⁺ changes from octahedral to tetrahedral. Ferrous iron ions occur in octahedral (and/or five-coordinated) sites independent of Fe³⁺/Fe²⁺.     

Oxydation expérimentale de Fe-tourmalines et corrélation avec une déprotonation des groupes hydroxyleAnnealing in oxidising conditions of Fe-tourmalines and correlated deprotonation of OH groups

Annealing at 400?T?600 °C (40?P?60 MPa and HM buffer-controlled f(O₂)) of tourmalines synthesised at the same T and P with NNO buffer induces an oxidation of Fe²⁺ into Fe³⁺ in some Y sites only (Mössbauer Spectroscopy data). Annealing in the same conditions of natural tourmalines is consistent with these results. FTIR spectroscopy shows that oxidation of Fe²⁺ into Fe³⁺ is charge-balanced by deprotonation of the external OH₍₃₎ groups. To cite this article: Y. Fuchs et al., C. R. Geoscience 334 (2002) 245–249.     

The Fe/ΣFe ratios of MORB glasses and their implications for mantle melting

The Fe³⁺/ΣFe ratio of 104 MORB glasses from the Pacific, the Atlantic, the Indian, and the Red Sea spreading centers have been determined using wet chemical Fe²⁺ analyses and electron microprobe FeO_total measurements. The data provide a new estimate for the MORB oxygen fugacity (fO₂) of 0.41 ± 0.43 (1sigma, N = 100) log units below the fayalite-magnetite-quartz buffer (FMQ), equivalent to a Fe³⁺/ΣFe = 0.12 ± 0.02 (1sigma, N = 104). This new fO₂ estimate is 0.8 log units more oxidized than the average fO₂ proposed by Christie et al. (1986) (FMQ-1.20 ± 0.44; Fe³⁺/ΣFe = 0.07 ± 0.01; N = 87). This slight difference may be related in part to the 3.5% underestimation of the Fe²⁺ concentration determined by Christie et al. (1986) compared with this study. MORB oxygen fugacity does not display any significant difference between the three main oceanic domains, or between enriched and depleted MORB. Yet, the iron red-ox state ratio shows a broad increase during fractional crystallization. Detailed study of magmatic suites highlights the lack of systematic Fe³⁺/ΣFe ratio fractionation during differentiation. Despite the large variations of inferred partial melting degrees (from 5 to 20%), the present data set does not provide any evidence of Fe³⁺/ΣFe relationships with partial melting proxies such as Na_8.0.Based on the Fe³⁺ systematics during partial melting, it is suggested that the oxidation state of MORB reflects a “buffered mantle melting process” resulting in the apparent compatible behavior of Fe³⁺ during partial melting, and in the relatively constant Fe³⁺/ΣFe ratio irrespective of the extent of melting. This result implies that partial melting processes may be open relative to oxygen. We propose a model where the Fe³⁺/ΣFe ratio in the melt is buffered during partial melting. The MORB Fe₂O₃ systematics can be accounted for by using a fO₂ of FMQ-1 that is equivalent to the average fO₂ reported for abyssal peridotites.     

SCF-Xα-SW MO Study of Fe-O and Fe-OH chemical bonds; applications to the mössbauer spectra and magnetochemistry of hydroxyl-bearing Fe3+ oxides and silicates

Results of SCF-Xα-SW molecular orbital calculations on (FeO₄(OH)₂)^7? and (FeO₆)^9? clusters are used to investigate the differences between Fe-O and Fe-OH bonding in hydroxyl-bearing iron oxides and silicates. The Fe³⁺-OH^? bond is more ionic, and has a smaller spinpolarization, then the Fe³⁺-O^2? bond. The smaller spinpolarizability of OH^? ligands explains why superexchange interactions between hydroxo-bridged Fe³⁺ cations are much weaker than those between oxo-bridged Fe³⁺ cations. Replacement of oxygens in the Fe³⁺ coordination environment by OH^? ligands appears to promote the covalency between Fe³⁺ centers and O^2? oxygens. The increased covalency lowers the effective spin of the Fe atom. This, in turn, explains the decreased magnetic hyperfine fields at the Fe nucleus in FeOOH polymorphs relative to those found in Fe³⁺ oxides.     

Heat of formation of petalite, LiAlSi4O10

The enthalpy of formation of petalite, LiAlSi₄O₁₀, has been measured using high-temperature solution calorimetry. The measurements were carried out in a Calvet-type twin micro calorimeter at 728?°C. A 2PbO?·?B₂O₃ melt was used as a solvent. Tabulated heats of formation of the components and tabulated heat capacities of the reactants and the product (Robie and Hemingway 1995) were used to calculate the standard heat of formation of petalite from the measured heats of solution. The calculations yielded a mean value of Δ _f H ^pet _298.15=?4872±5.4 kJ mol^?1. This value may be compared to the heat of formation of Δ _f H ^pet _298.15= ?4886.5±6.3 kJ mol^?1 determined by the HF solution calorimetry by Bennington et?al. (1980). Faßhauer et?al. (1998) combined thermodynamic data with phase-equilibrium results to obtain best-fit thermodynamic results using the Bayes method, in order to derive an internally consistent dataset for phases in the NaAlSiO₄– LiAlSiO₄–Al₂O₃–SiO₂–H₂O system. They determined ?4865.6?±?0.8?kJ?mol^?1 as the enthalpy of formation of petalite, a value that is appreciably closer to the enthalpy found in this work.     

Spectroscopic active IVFe3+–VIFe3+ clusters in spinel–magnesioferrite solid solution crystals: a potential monitor for ordering in oxide spinels

Optical absorption spectra (OAS) of synthetic single crystals of the solid solution spinel sensu stricto (s.s.)–magnesioferrite, Mg(Fe³⁺Al_1???y)₂O₄ (0?y?≤ 0.3), have been measured between 12 500 and 28 500?cm^?1. Chemical composition and Fe³⁺ site distribution have been measured by electron microprobe and Mössbauer spectroscopy, respectively. Ferric iron is ordered to the tetrahedral site for samples with small magnesioferrite component, and this ordering is shown to increase with magnesioferrite component. The optical absorption spectra show a strong increase in band intensities with Fe³⁺→Al substitution. Prominent and relatively sharp absorption bands are observed at 25 300 and 21 300?cm^?1, while less intense bands occur at 22 350, 18 900, 17 900 and 15 100?cm^?1. On the basis of band energies, band intensities and the compositional effect on band intensity, as well as structural considerations, we assign the observed bands to electronic transitions in ^IVFe³⁺–^VIFe³⁺clusters. A linear relationship (R ²= 0.99) between the α_net value of the absorption band at 21 300?cm^?1 and [^IVFe³⁺]?·?[^VIFe³⁺] concentration product has been defined: α_net=2.2?+?15.8 [^IVFe³⁺]?·?[^VIFe³⁺]. Some of the samples have been heat-treated between 700 and 1000?°C to investigate the relation between Fe³⁺ ordering and absorption spectra. Increase of cation disorder with temperature is observed, which corresponds to a 4% reduction in the number of active clusters. Due to the high spatial resolution (??～?10?μm), the OAS technique may be used as a microprobe for determination of Fe³⁺ concentration or site partitioning. Potential applications of the technique include analysis of small crystals and of samples showing zonation with respect to total Fe³⁺ and/or ordering.     

Crystallographic,Mössbauer and electrokinetic study of synthetic lipscombite

The transformation of vivianite and the direct synthesis starting from pure chemicals lead to the formation of lipscombite {Fe _x ²⁺ Fe _3?x ³⁺ [(OH)_3?x/(PO₄)₂]} with varying Fe²⁺/Fe³⁺ molar ratios. The influence of this ratio on the Mössbauer spectra, solubility, electrokinetic potential and infrared spectra has been studied. By means of Mössbauer spectroscopy, the distribution of the Fe²⁺ and Fe³⁺ ions between the octahedral sites I and II has been investigated. The unit cell dimensions have been determined from Guinier-Hägg X-ray diffraction patterns. The crystal system is tetragonal for synthetic lipscombite with a=5.3020±0.0005 Å and c=12.8800±0.0005 Å. Lipscombite has been found to show a negative and time-dependent zeta-potential which, moreover, is influenced by the pH of the suspension and the Fe²⁺/Fe³⁺ molar ratio. An explanation of the time-dependence of the zeta-potential on variations of solubility is proposed. Infrared absorption spectrum only is characterized by two absorption bands: v _OH(3,500 cm^?1) and v _P?O(1,100-960 cm^?1). The density at 25° C is determined in toluene as 3.36±0.01 g·cm^?3.     

Activity-composition relationship in Tschermak's substituted Fe biotites at 700°C, 2 kbar

The reaction-displacement technique was applied to the end-member reaction annite = sanidine + magnetite + H₂ in order to determine the activity of the annite component (a _Ann) in iron biotites with variable degrees of the Tschermak's substitution (^[6]Fe + ^[4]Si = ^[6]Al + ^[4]Al). Based on the simplified relation a _Ann = f _{H 2}/foH₂ (foH₂ = hydrogen fugacity of the end-member reaction at P, T), two types of experiments were performed at 700°C / 2 kbar: Type I used Fe-Al biotites of known starting composition together with sanidine + magnetite + H₂O. This assemblage was exposed to various f _{H 2} conditions (f _{H 2} < foH₂) produced in the pressure vessel either by using different ratios of water/oil as pressure medium (f _{H 2} in this case was measured by the hydrogen sensor technique), or by the Ni′NiO buffer. The composition of the Fe-Al biotites changed through incorporation or release of the annite component in response to the externally imposed f _{H 2}. By using opposite biotite starting compositions, the equilibrium composition as a function of f _H2 was bracketed. For type II, f _{H 2} in equilibrium with a specific combination of fine-grained Fe-Al biotite (+ sanidine + magnetite + H₂O) was measured internally by application of the hydrogen sensor technique. Both type I and type II experiments yield consistent results demonstrating that a fine-grained assemblage of Fe-Al biotite (+ sanidine + magnetite + H₂O) is able to act as a sliding-scale buffer. The final chemical composition of the Fe-Al biotite after the experiments was determined by electron microprobe and Mössbauer spectroscopy. The ^[4]Al and ^[6]Al in the biotites are coupled according to the Tschermak's substitution. In the tetrahedral sheet 0.1 Al-atoms per formula unit are present in excess to the amount required to balance ^[6]Al, and all Fe-Al biotites contain 8–10% Fe³⁺. Therefore, they are not members of the pure annite - siderophyllite join, but have an almost constant amount (15 Mol%) of two additional Fe³⁺-bearing components (ferri-siderophyllite and a vacancy end-member). The volume - composition relationship obtained does not indicate excess molar volumes of mixing for the annite (Ann) - siderophyllite (Sid) binary. The data are consistent with a molar volume of annite of 15.46 ± 0.02 Jbar^–1 and of 15.06 ± 0.02 Jbar^–1 for siderophyllite. The experimentally determined activity - composition relation shows that biotites on the join annite - siderophyllite deviate negatively from ideality. A symmetric interaction parameter W_AnnSid is sufficient to represent the data within error. This was constrained as: W _AnnSid = –29 ± 4 kJmol^–1. This is in contradiction to empirical interaction parameters derived from natural assemblages for this binary that predict positive deviation from ideality. Reasons for this discrepancy are discussed.     

A reassignment of the optical absorption bands in biotites

The electronic absorption spectra of three biotites with largely differing Fe²⁺/Fe³⁺ ratios were studied before and after thermal dehydration and oxidation of divalent iron. Three absorption bands near 17,100, 20,500 and 24,100 cm^?1 and an absorption edge at slightly higher energies are assigned to trivalent iron present in clusters of strongly interacting ions. The presence of additional broad absorption bands due to intervalence transfer between Fe²⁺ and Fe³⁺ or Ti⁴⁺ in this region cannot be excluded for biotites with high Fe²⁺ concentrations. Three bands at lower energies show a satisfactory correlation with concentration of divalent iron and decrease in the same proportions with oxidation. We therefore assign them to split components of the spin-allowed ligand field transition of Fe²⁺ at the M ₁ and M ₂ sites. This contradicts the assignment of one of these bands to an intervalence charge transfer between Fe²⁺ and Fe³⁺ by previous authors. It is shown that there is no indisputable evidence against our assignment.     

Redox state of deep off-craton lithospheric mantle: new data from garnet and spinel peridotites from Vitim, southern Siberia

Oxygen fugacity (fO₂) affects melting, metasomatism, speciation of C–O–H fluids and carbon-rich phases in the upper mantle. fO₂ of deep off-craton mantle is poorly known because garnet-peridotite xenoliths are rare in alkali basalts. We examine the redox and thermal state of the lithospheric mantle between the Siberian and North China cratons using new Fe³⁺/ΣFe ratios in garnet and spinel obtained by M?ssbauer spectroscopy, major element data and P–T estimates for 22 peridotite xenoliths as well as published data for 15 xenoliths from Vitim, Russia. Shallow spinel-facies mantle is more oxidized than deep garnet peridotites (average, ?0.1 vs. ?2.5 ΔlogfO₂(FMQ)). For intermediate garnet–spinel peridotites, fO₂ estimates from spinel-based oxybarometers are 1.5–3.2 ΔlogfO₂(FMQ) lower than those from garnet-based oxybarometers. These rocks may be out of phase and chemical inter-mineral equilibrium because the spinel–garnet reaction and concomitant changes in mineral chemistry do not keep up with P–T changes (e.g., lithospheric heating by recent volcanism) due to slow diffusion of trivalent cations and because gar-, gar-spl and spl-facies rocks may coexist on centimeter–meter scale. The spinel-based fO₂ estimates may not be correct while garnet-based fO₂ values provide conditions before the heating. The T (780–1,100?°C) and fO₂ ranges of the Vitim xenoliths overlap those of coarse garnet and spinel cratonic peridotites. However, because of a higher geothermal gradient, the deepest Vitim garnet peridotites are more reduced (by 0.5–2.0 ΔlogfO₂(FMQ)) than cratonic garnet peridotites at similar depths, and the “water maximum” conditions (>80?% H₂O) in the off-craton mantle exist in a more shallow and narrow depth range (60–85?km) than in cratonic roots (100–170?km). The base of the off-craton lithospheric mantle (≥90?km) at 2.5?GPa and 1,150?°C has fO₂ of ?3.0 ?logfO₂(FMQ), with dominant CH₄ and H₂O and minor H₂ in the fluid. Melting near the base of off-craton mantle lithosphere may be induced by increasing water share in migrating fluids due to oxidation of methane.     

Thermodynamic analysis of the system Fe2O3-FeTiO3

The cluster variation method, in the single prism approximation, is used to model phase relations in the system, Fe₂O₃-FeTiO₃. Ordering in FeTiO₃ is analyzed, and it is shown that the stabilization of FeTiO₃ (relative to mechanical mixing of Fe₂O₃ and Ti₂O₃) includes: (1) a contribution from the redox reaction, Fe³⁺+Ti³⁺→Fe²⁺+Ti⁴⁺ (ΔH _redox～?70kJ mole^?1); and (2) a contribution from ordering (ΔH _OD～?8kJ mole^?1). A theoretical phase diagram is presented and compared with available experimental data. Semiquantitative agreement between theory and experiment (on the location of phase boundaries) is achieved; but, owing to the paucity of experimental data on coexisting phases, these results may be fortuitous.     

The oxidation state of Ti in hornblende and biotite determined by electron energy-loss spectroscopy,with inferences regarding the Ti substitution

Structural formulae of many Ti-rich hornblendes and biotites exhibit cation deficiencies that increase with Ti content. These deficiencies may be caused by the presence of trivalent instead of tetravalent Ti, of oxygen replacing hydroxyl, or of vacancies on octahedral cation sites. In order to determine the oxidation state of their Ti, electron energy-loss spectra of natural, Ti-rich hornblende and biotites are compared with spectra of natural and synthetic Ti-bearing oxides and silicates. Spectra of Ti₂O₃ and TiO₂ demonstrate that the Ti L _2,3 edge for Ti³⁺ is shifted by ca. 2 eV to lower energy relative to the edge for Ti⁴⁺. Oxidation states of Ti determined by energy-loss spectroscopy for several minerals agree with data from other techniques: tetravalent for Ti-omphacite, perovskite, ilmenite and titanite; trivalent for NaTi³⁺Si₂O₆ pyroxene and fassaite from the Allende meteorite. The energy-loss spectra of the hornblende and biotite show that their Ti is tetravalent and cannot be the cause of the cation deficiencies. The relations between Ti contents and the number of deficiencies differ for hornblende and biotite. Hornblende shows a 2:1 relation between Ti content and deficiencies, suggesting Ti is coupled to an oxygen that is replacing hydroxyl (Ti-oxyhornblende substitution). Biotite shows a 1:1 relation, consistent with coupling of Ti to a vacant octahedral cation site (Ti-vacancy substitution) or to a variable combination of such vacancies and two oxygens replacing hydroxyls (Ti-oxybiotite substitution).     

A thermochemical study of monohydrocalcite

The thermodynamic properties of monohydrocalcite, CaCO₃ · H₂O, have been obtained using a well-characterized natural specimen. Equilibration of the solid with water at 25°C under 0.97 atm CO₂ led to an activity product [Ca²⁺][CO₃^2?] = 10^?7.60±0.03 and a free energy of formation ΔG_f^o = ?325,430 ± 270 calmol^?. The enthalpy of solution of monohydrocalcite in 0.1 N HCl at 25°C led to a standard enthalpy of formation ΔH_f^o = ?358,100 ± 280 cal mol^?1. Estimates of the variation of ΔG_f with temperature and pressure showed monohydrocalcite to be metastable with respect to calcite and aragonite.     

Biotites and associated minerals as markers of magmatic fractionation and deuteric equilibration in granites

Analyses of 80 biotite, alkali feldspar, oligoclase, hornblende, Fe-Ti oxide separates from the coarse-grained granites of a late-hercynian epizonal diapir, the Ploumanac'h complex, Brittany, show that these minerals display a regular concentric cryptic layering related to fractional crystallization. The Ca, Mg, Ba, Sr, Cr, V content of minerals decreases as the Na, Fe, and Rb content increases. Biotites become more dioctahedral towards the outer residual syenogranite, with a correlative K deficiency. Trioctahedral biotites from the inner accumulative monzogranite are secondarily oxidized with a gain of Fe³⁺ and a loss of OH. This alteration id due to the percolation of exsolved fluids rich in H₂O and containing a small amount of CO₂, F, S, Cl. During this autometamorphic stage, trace elements like Rb, Sr are completely redistributed on the scale of hand specimens, with a restricted range of partition coefficients between biotite, perthite and oligoclase. This equilibration occurred at a temperature about 550 ° C and a fluid pressure about 1,000 bars, with f _H2_O probably less than 500 bars. A later stage of fluid circulation along fractures brings up a slight Li metasomatism. Biotites are a sensitive marker of both magmatic and postmagmatic stages of subsolvus or ‘wet’ plutonites.