Thermochemical study of Mg–Fe chlorites

The thermochemical study of two natural trioctahedral Mg–Fe chlorites—clinochlores was carried out using high-temperature melt solution calorimetry with a Tian–Calvet microcalorimeter. The enthalpies of formation of clinochlores of compositions (Mg_4.9Fe _0.3 ²⁺ Al_0.8)[Si_3.2Al_0.8O₁₀](OH)₈ (–8811 ± 12 kJ/mol) and (Mg_4.3Fe _0.7 ²⁺ Al_1.0)[Si_3.0Al_1.0O₁₀](OH)₈ (–8696 ± 13 kJ/mol) from elements were determined. The values of the standard entropies and the Gibbs energies of formation of the studied natural minerals as well as thermodynamic properties of Mg–Fe chlorites of theoretical composition were estimated.     

A thermodynamic model of Fe–Cr spinels

A new thermodynamic model for multi-component spinel solid solutions has been developed which takes into account thermodynamic consequences of cation mixing in spinel sublattices. It has been applied to the evaluation of thermodynamic functions of cation mixing and thermodynamic properties of Fe₃O₄–FeCr₂O₄ spinels using intracrystalline cation distribution in magnetite, lattice parameters and activity-composition relations of magnetite–chromite solid solutions. According to the model, cation distribution in binary spinels, (Fe_1-x²⁺ Fe_x³⁺)[Fe_x²⁺Fe_2-2y-x³⁺Cr_2y]O₄, and their thermodynamic properties depend strongly on Fe²⁺–Cr³⁺ cation mixing. Mixing of Fe²⁺–Fe³⁺ and Fe³⁺–Cr³⁺ can be accepted as ideal. If Fe²⁺, Fe³⁺ and Cr are denoted as 1, 3 and 4 respectively, the equation of cation distribution is –RT ln(x²/((1–x)(2–2y–x)))= G₁₃^* + (1–2x)W₁₃+y(W₁₄–W₁₃–W₃₄) where G₁₃^* is the difference between the Gibbs energy of inverse and normal magnetite, W_ij is a Margules parameter of cation mixing and G₁₃^*, J/mol =–23,000+13.4 T, W₁₄=36 kJ/mol, W₁₃=W₃₄=0. The positive nonconfigurational Gibbs energy of mixing is the main reason for changing activity–composition relations with temperature. According to the model, the solvus in Fe₃O₄–FeCr₂O₄ spinel has a critical temperature close to 500°C, which is consistent with mineralogical data.     

57Fe Mössbauer spectroscopy of tektites

Tektite glasses are investigated using ⁵⁷Fe Mössbauer spectroscopy. Room temperature spectra analysis is performed using two complementary analytical methods based on two-dimensional distributions of both isomer shift and quadrupole splitting. No a priori correlation between the two hyperfine parameters is considered. The first method, based on a shape independent distribution, provides the justification for the Gaussian distribution shape used in the second method. No ferric iron contribution is evidenced by Mössbauer spectra analysis in these samples, although several criteria are used. Ferrous iron sites are shown to be continuously distributed between four- and five-fold co-ordinated sites.     

Advanced analyses of 57Fe Mössbauer data of alumino-silicate glasses

⁵⁷Fe Mössbauer spectra of iron bearing alumino-silicate glasses are analysed by two complementary methods (SID and x-VBF) especially adapted for the analysis of disordered systems by taking into account distributions of hyperfine Mössbauer parameters. Qualitative and quantitative information about the oxidation state of iron are obtained as well as information about the distribution of local environments of iron. The possibility to separate the signal of ferric iron from that of ferrous iron allows to derive precise redox ratio in favourable cases but also to analyse more sharply the different contributions to Mössbauer spectra. Using two different glass series (feldspar composition, haplo-tonalitic composition), the characteristics of the two methods are described and employed to study the effect of composition, water incorporation and oxidation state on the glass structure. Optical absorption spectroscopy is used to support the interpretation of the Mössbauer spectra in case of the feldspar glasses.     

A Raman spectroscopic study of Fe–Mg olivines

End-member synthetic fayalite and forsterite and a natural solid-solution crystal of composition (Mg_1.80,Fe_0.20)SiO₄ were investigated using Raman spectroscopy. Polarized single-crystal spectra were measured as a function of temperature. In addition, polycrystalline forsterite and fayalite, isotopically enriched in ²⁶Mg and ⁵⁷Fe, respectively, were synthesized and their powder spectra measured. The high-wavenumber modes in olivine consist of internal SiO₄ vibrations that show little variation upon isotopic substitution. This confirms conclusions from previous spectroscopic studies that showed that the internal SiO₄ vibrations have minimal coupling with the lower-wavenumber lattice modes. The lowest wavenumber modes in both forsterite and fayalite shift in energy following isotopic substitution, but with energies less than that which would be associated with pure Mg and Fe translations. The low-wavenumber Raman modes in olivine are best described as lattice modes consisting to a large degree of mixed vibrations of M(2) cation translations and external vibrations of the SiO₄ tetrahedra. The single-crystal spectra of forsterite and Fo₉₀Fa₁₀ were recorded at a number of temperatures from room temperature to about 1200 °C. From these data the microscopic Grüneisen parameters for three different A_g modes for both compositions were calculated, and also the structural state of the solid solution crystal was investigated. Small discontinuities observed in the wavenumber behavior of a low-energy mixed Mg/T(SiO₄) mode between 700 and 1000 °C may be related to minor variations in the Fe–Mg intracrystalline partitioning state in the Fo₉₀Fa₁₀ crystal, but further spectroscopic work is needed to clarify and quantify this issue. The mode wavenumber and intensity behavior of internal SiO₄ vibrations as a function of temperature are discussed in terms of crystal field and dynamic splitting and also ₁ and ₃ coupling. Crystal-field splitting increases only very slightly with temperature, whereas dynamical-field splitting is temperature dependent. The degree of ₁–₃ coupling decreases with increasing temperature.     

Applications of Fe Isotopic Systematics in Ore Deposit Geology

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Effect of chlorine on near-liquidus phase equilibria of an Fe–Mg-rich tholeiitic basalt

The importance of Cl in basalt petrogenesis has been recognized, yet constraints on its effect on liquidus crystallization of basalts are scarce. In order to quantify the role of Cl in basaltic systems, we have experimentally determined near-liquidus phase relations of a synthetic Fe–Mg-rich basalt, doped with 0.0–2.5 wt% dissolved Cl, at 0.7, 1.1, and 1.5 GPa. Results have been parameterized and compared with previous data from literature. The effect of Cl on mineral chemistry and liquidus depression is dependent on the starting basaltic composition. The liquidus depression measured for a SiO₂-rich, Al₂O₃-poor basalt is smaller than that observed for a basaltic melt depleted in silica and enriched in FeO_T and Al₂O₃. The effect of Cl on depression of the olivine–orthopyroxene–liquid multiple saturation pressure does not seem to vary with the starting composition of the basaltic liquid. This suggests that Cl may significantly promote the generation of silica-poor, Fe–Al-rich magmas in the Earth, Mars, and the Moon.     

A 57Fe M?ssbauer spectroscopic study of sogdianite: an example of a symmetric electric field gradient around Fe3+

Sogdianite, a double-ring silicate of composition ( \textZr_{0. 7 6} \textTi_{0. 3 8}^{4 +} \textFe_{0. 7 3}^{3 +} \textAl_0.13 )_{\Upsigma = 2} ( \square _{1. 1 5} \textNa_{0. 8 5} )_{\Upsigma = 2} \textK[\textLi ₃ \textSi _{1 2} \textO ₃₀ ] ( {\text{Zr}}_{0. 7 6} {\text{Ti}}_{0. 3 8}^{4 + } {\text{Fe}}_{0. 7 3}^{3 + } {\text{Al}}_{0.13} )_{\Upsigma = 2} \left( {\square_{ 1. 1 5} {\text{Na}}_{0. 8 5} } \right)_{\Upsigma = 2} {\text{K}}[{\text{Li}}_{ 3} {\text{Si}}_{ 1 2} {\text{O}}_{ 30} ] from Dara-i-Pioz, Tadjikistan, was studied by the combined application of ⁵⁷Fe M?ssbauer spectroscopy and electronic structure calculations. The M?ssbauer spectrum confirms published microprobe and X-ray single-crystal diffraction results that indicate that Fe³⁺ is located at the octahedral A-site and that no Fe²⁺ is present. Both the measured and calculated quadrupole splitting, ΔE _Q, for Fe³⁺ are virtually 0 mm s⁻¹. Such a value is unusually small for a silicate and it is the same as the ΔE _Q value for Fe³⁺ in structurally related sugilite. This result is traced back to the nearly regular octahedral coordination geometry corresponding to a very symmetric electric field gradient around Fe³⁺. A crystal chemical interpretation for the regular octahedral geometry and the resulting low ΔE _Q value for Fe³⁺ in the M?ssbauer spectrum of sogdianite is that structural strain is largely “taken up” by weak Li–O bonds permitting highly distorted LiO₄ tetrahedra. Weak Li–O bonding allows the edge-shared more strongly bonded Fe³⁺O₆ octahedra to remain regular in geometry. This may be a typical property for all double-ring silicates with tetrahedrally coordinated Li.     

Determination of Fe2+/Fe3+ Ratios of Magnetite using Different Methods: A Case Study from the Qimantag Metallogenic Belt

Determination of Fe2+/Fe3+ ratios from metallogenic belts to explore controlling physical and chemical conditions of rock formation is of great significance. In order to explore magnetite Fe2+/Fe3+ ratios of the Qimantag metallogenic belt, part of the Eastern Kunlun orogenic belt in the northeastern margin of the Qinghai–Tibetan plateau, western Central Orogenic Belt of China, and overcome the limitation of the traditional electronic probe, five different measurement methods are proposed and their respective advantages and disadvantages evaluated, with the composition data of the magnetite obtained using electron probe microanalysis (EPMA). The direct oxygen measurement method has a significant impact on the determination results of FeO and Fe2O3, but the accuracy and uniformity of the results are low. The valence method (Flank method) based on the spectral intensity ratio of Lα to Lβ for iron is also unreliable for FeO and Fe2O3 measurements because it is difficult to establish a relationship between Lβ/Lα, the spectral intensity ratio, and the Fe2+/Fe3+ content ratio. In comparison, the charge difference method, the surplus-oxygen method and the M?ssbauer spectrum method are still the most favorable. M?ssbauer spectroscopy, with its isomer movement particularly sensitive to the oxidation state of iron, yields results closer to 0.5, which is relatively reliable. Earlier magnetite deposits are located in intrusions or contact zones and formed by magmatic fluids with high Fe2+/Fe3+ ratios, whereas later magnetite deposits are farther away from intrusions and have low Fe2+/Fe3+ ratios. The transformation mechanism of hematite and magnetite in the Qimantage metallogenic belt is also studied. No large volume changes, such as pore filling and shrinkage fracture, were detected in the metallogenic belt, and the transformation mechanism is more similar to a reoxidation and reduction mechanism.     

The Behavior of Fe—Ni Metal during Thermal Metamorphism of the Jilin Chondrite

Conclusions 1. Under heat influence, the mobility of Fe-Ni metal was relatively high as compared with silicates. During thermal metamorphism of the Jilin meteorite (T ⩽ 800 °C), fine Fe-Ni metal particles in silicate condrules and matrix aggregated into coarse metal grains, which are as large as 5–10 mm in size,in situ or after a short-distance migration and concentration, and some even aggregated into metal nodules as large as 20–30mm in size, but their chemical composition still remains unchanged. 2. High-temperature and high pressure, as well as shock-loading experiments on Jilin meteorite samples provide further evidence that temperature plays an important role in metal /silicate redistribution and differentiation. The variation of temperature exerts great influence on the mode of metal-silicate redistribution. At about 1000 °C or less, metal particles moved and aggregated into rather coarse grains by thermal diffusion, or through the formation of eutectic melts together with FeS. When the temperature reaches about 1300 °C, full melting take place in the meteorite specimens, and at this time metals and metal sulfides play an important role in the immiscibility and gravitational differentiation of metal-silicate melts, thus leading to the rapid separation of metals or metal-sulfides from silicates, followed by the sinking of pure metals and metal-sulfides to the bottom of the experimental products and the formation of silicate melts almostly with no metals and sulfides in the upper parts.     

A crystallographic and m?ssbauer spectroscopy study of Fe

The crystal chemistry of garnet solid solutions on the Fe ₃ ²⁺ Al₂Si₃O₁₂-Fe ₃ ²⁺ Fe ₂ ³⁺ Si₃O₁₂ (almandine-“skiagite”) and Ca₃Fe ₂ ³⁺ Si₃O₁₂-Fe ₃ ²⁺ Fe ₂ ³⁺ Si₃O₁₂ (andradite-“skiagite”) joins have been investigated by single-crystal X-ray structure refinements and M?ssbauer spectroscopy. Together, these two solid solution series encompass the complete range in Fe³⁺/ΣFe from 0.0 to 1.0. All garnets are isotropic and were re0fined in the Ia d space group. Small excess volumes of mixing are observed in andradite-“skiagite” solid solutions (W _v =1.0±0.2 cm³ mol^-1) and along the almandine-“skiagite” join (W _v =-0.77±0.17cm³ mol^-1). The octahedral (Al, Fe³⁺)-O bond lengths show a much greater variation across the almandine-skiagite join compared to the andradite-skiagite garnets. The dodecahedral (X)-O bond lengths show the opposite behaviour. In andradite-“skiagite” solid solutions, the octahedral site passes from being flattened to elongated parallel to the 3 axis of symmetry with increasing “skiagite” content. A perfect octahedron occurs in a composition of ≈35 mol% “skiagite”. The occupancy of the neighboring dodecahedral sites has the greatest effect on octahedral distortion and vice versa. The M?ssbauer hyperfine parameters of Fe²⁺remain constant in both solid solutions. The hyperfine parameters of Fe³⁺ (at room temperature: centre shift=0.32–0.40 mm/sec, quadrupole splitting (QS)≈0.21–0.55 mm/ sec) indicate that all Fe³⁺ is in octahedral coordination. The Fe³⁺ parameters are nearly constant in almandine-“skiagite” solid solutions, but vary significantly across the andradite-“skiagite” join. The structural unit that contributes to the electric field gradient of the octahedral site is different from that of the coordinating oxygen polyhedron, probably involving the neighboring dodeca-hedral sites.     

Impact Factors on Removal of Perchloroethylene with Nano-Ni/Fe Methodology

Chlorinated hydrocarbons are widely detected in groundwater, but conventional removal methodologies are not time-and-cost effective. With the development of iron reducing technology in recent years, research on nano-iron and nano-bimetal has become a hot spot. The paper presents the results of impact factors on perchloroethylene （PCE） removal by nano-Ni/Fe method. The data show that the reaction rate of unexposed nano-Ni/Fe is 4 times higher than exposed one; and temperature is one of the important controlling factors. Reaction rate constant KSA increases by 2-3 times with every 10℃ increment of temperature. Within a specific range, higher Ni/Fe ratio favors dechlorination process. When the Ni/Fe is 8%, the dechlorination process reaches the highest rate. Dissoved oxygen in the solution does not favor the degradation of chlorinated hydrocarbons.     

Sound velocity and elastic properties of Fe–Ni and Fe–Ni–C liquids at high pressure

The sound velocity (V _P) of liquid Fe–10 wt% Ni and Fe–10 wt% Ni–4 wt% C up to 6.6 GPa was studied using the ultrasonic pulse-echo method combined with synchrotron X-ray techniques. The obtained V _P of liquid Fe–Ni is insensitive to temperature, whereas that of liquid Fe–Ni–C tends to decrease with increasing temperature. The V _P values of both liquid Fe–Ni and Fe–Ni–C increase with pressure. Alloying with 10 wt% of Ni slightly reduces the V _P of liquid Fe, whereas alloying with C is likely to increase the V _P. However, a difference in V _P between liquid Fe–Ni and Fe–Ni–C becomes to be smaller at higher temperature. By fitting the measured V _P data with the Murnaghan equation of state, the adiabatic bulk modulus (K _S0) and its pressure derivative (K _S ^′ ) were obtained to be K _S0 = 103 GPa and K _S ^′  = 5.7 for liquid Fe–Ni and K _S0 = 110 GPa and K _S ^′  = 7.6 for liquid Fe–Ni–C. The calculated density of liquid Fe–Ni–C using the obtained elastic parameters was consistent with the density values measured directly using the X-ray computed tomography technique. In the relation between the density (ρ) and sound velocity (V _P) at 5 GPa (the lunar core condition), it was found that the effect of alloying Fe with Ni was that ρ increased mildly and V _P decreased, whereas the effect of C dissolution was to decrease ρ but increase V _P. In contrast, alloying with S significantly reduces both ρ and V _P. Therefore, the effects of light elements (C and S) and Ni on the ρ and V _P of liquid Fe are quite different under the lunar core conditions, providing a clue to constrain the light element in the lunar core by comparing with lunar seismic data.     

Dechlorination of trichloroethylene in solution over supported nano zero valent Fe and Cu/Fe bimetal on exfoliated graphite

Degradation of organic halides by reductive dehalogenation promoted by zerovalent metals is a very active research area. The use of nano-sized particles of zero valent iron （ZVI） or bimetallic combinations of ZVI currently attracts the most attention due to their high surface areas and high reactive activity. The introduction of second catalytic metals, such as Pd, Pt, Cu, or Ni, results in an even higher dehalogenation rate. The supported zero-valent iron materials have higher activity and greater flexibility for environmental remediation applications than other forms of ZVI. Nano ZVI supported on micro-scale exfoliated graphite was prepared by using KBH4 as the reducing agent in the H2O/ethanol solution of Fe^2＋ in the laboratory. Then the ethanol solution of Cu^2＋ was added to the fleshly prepared wet supported nano ZVI. The Fe/Cu bimetallic particles supported on the graphite were obtained because of the reduction and deposition of Cu on the Fe surface. The TEM image showed that iron particles were highly dispersed on the surface of graphite. In this study, supported zero valent Cu/Fe bimetallic nanoparticles were used for the dehalogenation of trichloroethylene （TCE） in batch experiments. The dechlorination rate of supported zero valent Fe/Cu bimetallic nanoparticles was greater than the supported nano ZVI. Supported Cu/Fe bimetal with 4 wt% Cu had the fastest dehalogenation rate than that with different content of Cu. When the nana FeO dosage was 5 g/L in the dehalogention system, 8 mg/L of TCE was completely dechlorinated within 4 hours. Increasing or decreasing the FeO dosage, the dechlorination rate could be worse. When the concentration of Fe^2＋ was 0.05 mol/L during the preparation by KBH4 reduction, the nano Cu/Fe particles exhibited the spheral shape with 50-80 nm in size. When the concentration of Fe^2＋ was higher （0.2 mol/L）, the nano particles were the palpus structure and had the poor dehalogenation effect on the TCE.     

Petrographic and Fe Isotopic Constraints on the Genesis of the Shilu Fe Ore Deposit in Hainan Province, China

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The effect of sulfur content on density of the liquid Fe–S at high pressure

The density of liquid Fe–S was measured at 4 GPa and 1,923 K using a sink/float method with a composite density marker. The density marker consisted of a Pt rod core and an Al₂O₃ tube surrounding. The uncertainty in the density of the composite marker is much smaller than that of the composite sphere, which had been used in previous density measurements. The density of liquid Fe–S decreases nonlinearly with increasing sulfur content at 4 GPa and 1,923 K. This tendency is consistent with the results measured at ambient pressure. The molar volume of FeS calculated from the measured density gradually increases with sulfur content. The excess molar volume from ideal mixing of Fe and S at 4 GPa was negative value. The new method proposed here is applicable to the density measurement of other Fe alloys at high pressure. The tendency of the molar volume and the excess molar volume with sulfur content at ambient pressure is consistent with these at high pressure at least up to 4 GPa. The excess molar volume at high pressure is essential for estimating the amount of light elements in the outer core.     

Experimental determination of activities in Fe−Mg olivine at 1400 K

The exchage equilibrium has been used to measure activity-composition relations along the olivine join FeSi_0.5O₂−MgSi_0.5O₂ at 1400 K and 1 atm pressure. Equilibrium Fe−Mg partitioning between the two phases was determined by reversing the compositions of olivine coexisting with oxide and matallic iron over the composition range Fo₂₃ to Fo₉₂. A detailed study of the thermodynamic properties of the oxide phase has recently been made by Srečec et al. and we have confirmed their results in the composition range of interest. Application of the oxide data to the exchange equilibrium enables the properties of olivine to be determined. Within experimental uncertainly (Fe, Mg)Si_0.5O₂ olivine can, at 1400 K, be treated as a symmetric solution with W _Fe-Mg ^o1 of 3.7±0.8 kJ/mol. The data permit the presence of only very slight asymmetry in the series. The data do not support recent assertions that olivine is highly non-ideal (W≈10 kJ/mol) under these conditions.     

Aluminum coprecipitates with Fe (hydr)oxides: Does isomorphous substitution of Al for Fe in goethite occur?

Iron (hydr)oxides are common in natural environments and typically contain large amounts of impurities, presumably the result of coprecipitation processes. Coprecipitation of Al with Fe (hydr)oxides occurs, for example, during alternating reduction-oxidation cycles that promote dissolution of Fe from Fe-containing phases and its re-precipitation as Fe-Al (hydr)oxides. We used chemical and spectroscopic analyses to study the formation and transformation of Al coprecipitates with Fe (hydr)oxides. In addition, periodic density functional theory (DFT) computations were performed to assess the structural and energetic effects of isolated or clustered Al atoms at 8 and 25 mol% Al substitution in the goethite structure. Coprecipitates were synthesized by raising the pH of dilute homogeneous solutions containing a range of Fe and Al concentrations (100% Fe to 100% Al) to 5. The formation of ferrihydrite in initial suspensions with ?20 mol% Al, and of ferrihydrite and gibbsite in initial suspensions with ?25 mol% Al was confirmed by infrared spectroscopic and synchrotron-based X-ray diffraction analyses. While base titrations showed a buffer region that corresponded to the hydrolysis of Fe in initial solutions with ?25 mol% Al, all of the Al present in these solutions was retained by the solid phases at pH 5, thus indicating Al coprecipitation with the primary Fe hydroxide precipitate. In contrast, two buffer regions were observed in solutions with ?30 mol% Al (at pH ∼2.25 for Fe³⁺ and at pH ∼4 for Al³⁺), suggesting the formation of Fe and Al (hydr)oxides as two separate phases. The Al content of initial coprecipitates influenced the extent of ferrihydrite transformation and of its transformation products as indicated by the presence of goethite, hematite and/or ferrihydrite in aged suspensions. DFT experiments showed that: (i) optimized unit cell parameters for Al-substituted goethites (8 and 25 mol% Al) in clustered arrangement (i.e., the formation of diaspore-like clusters) were in good agreement with available experimental data whereas optimized unit cell parameters for isolated Al atoms were not, and (ii) Al-substituted goethites with Al in diaspore-like clusters resulted in more energetically favored structures. Combined experimental and DFT results are consistent with the coprecipitation of Al with Fe (hydr)oxides and with the formation of diaspore-like clusters, whereas DFT results suggest isomorphous Al for Fe substitution within goethite is unlikely at ?8 mol% Al substitution.     

Multistage growth of Fe–Mg–carpholite and Fe–Mg–chloritoid,from field evidence to thermodynamic modelling

We provide new insights into the prograde evolution of HP/LT metasedimentary rocks on the basis of detailed petrologic examination, element-partitioning analysis, and thermodynamic modelling of well-preserved Fe–Mg–carpholite- and Fe–Mg–chloritoid-bearing rocks from the Afyon Zone (Anatolia). We document continuous and discontinuous compositional (ferromagnesian substitution) zoning of carpholite (overall X _Mg = 0.27–0.73) and chloritoid (overall X _Mg = 0.07–0.30), as well as clear equilibrium and disequilibrium (i.e., reaction-related) textures involving carpholite and chloritoid, which consistently account for the consistent enrichment in Mg of both minerals through time, and the progressive replacement of carpholite by chloritoid. Mg/Fe distribution coefficients calculated between carpholite and chloritoid vary widely within samples (2.2–20.0). Among this range, only values of 7–11 correlate with equilibrium textures, in agreement with data from the literature. Equilibrium phase diagrams for metapelitic compositions are calculated using a newly modified thermodynamic dataset, including most recent data for carpholite, chloritoid, chlorite, and white mica, as well as further refinements for Fe–carpholite, and both chloritoid end-members, as required to reproduce accurately petrologic observations (phase relations, experimental constraints, Mg/Fe partitioning). Modelling reveals that Mg/Fe partitioning between carpholite and chloritoid is greatly sensitive to temperature and calls for a future evaluation of possible use as a thermometer. In addition, calculations show significant effective bulk composition changes during prograde metamorphism due to the fractionation of chloritoid formed at the expense of carpholite. We retrieve P–T conditions for several carpholite and chloritoid growth stages (1) during prograde stages using unfractionated, bulk-rock XRF analyses, and (2) at peak conditions using compositions fractionated for chloritoid. The P–T paths reconstructed for the Kütahya and Afyon areas shed light on contrasting temperature conditions for these areas during prograde and peak stages.