Thermally activated electron delocalization in deerite

The ⁵⁷Fe Mössbauer spectra of deerites of different chemical composition, taken at several temperatures, show that Fe²⁺ and Fe³⁺ occupy all the six-coordinated lattice sites with a preference of Fe³⁺ probably for the M(1) to M(3) positions, and a preference of Fe²⁺ probably for the M(4) to M(6) and the M(7) to M(9) sites. The room and high temperature spectra reveal absorption patterns due to thermally activated Fe²⁺ → Fe³⁺ electron delocalization. The extent of electron delocalization is dependent on the chemical composition, e.g., the amount of ions (Mg, Mn, Al) substituting for Fe.     

Crystal chemistry of Fe-containing sphalerites

 Cell dimensions and solvus properties of Fe-containing sphalerites, depending on temperature and sulfur fugacity, were investigated using equilibrated powdered materials synthesized from elements and binary sulfides under vacuum. The Fe solvus in sphalerite, determined by optical microscopy and microprobe analysis, are directly correlated with increasing temperature and decreasing sulfur fugacity controlled by solid-state buffers. The increase of lattice parameters with Fe correlates with an increase of FeS independent of sulfur fugacity up to 10 mol% FeS within ZnS. Above about 10 mol% the lattice parameters are strongly depending on the sulfur fugacity controlled Fe³⁺/Fe²⁺ ratios. The Fe³⁺/Fe²⁺ ratios determined by Moessbauer spectroscopy and involving metal vacancies depend on the sulfur fugacity. The critical Fe²⁺ content determined by experimental simulations as well as the minimal Fe³⁺/ Fe²⁺ ratios agree with the required minimal Fe content for CuFeS₂-DIS in sphalerite. The critical Fe²⁺ content also agrees with the change of Moessbauer signal from a singlet to a doublet for Fe²⁺ containing sphalerite. Pyrrhotite exsolutions in sphalerite caused by higher sulfur fugacity show orientationally intergrown with the sphalerite matrix. Density data calculated from lattice parameters and composition are compared with experimental density measurements. Received: 25 April 2001 / Accepted: 14 February 2003     

On local structural changes in lizardite-1T: {Si4+/Al3+}, {Si4+/Fe3+}, [Mg2+/Al3+], [Mg2+/Fe3+] substitutions

Geometrical changes induced by cation substitutions {Si⁴⁺/Al³⁺}[Mg²⁺/Al³⁺], {2Si⁴⁺/2Al³⁺} [2Mg²⁺/2Al³⁺], {Si⁴⁺/Fe³⁺} [Mg²⁺/Al³⁺] or [Mg²⁺/Fe³⁺], where {} and [] indicate tetrahedral and octahedral sheet in lizardite 1T, are studied by ab-initio quantum chemistry calculations. The majority of the models are based on the chemical compositions reported for various lizardite polytypes with the amount of Al in the tetrahedral sheets reported to vary from 3.5% to 8% in the 1T and 2H ₁, up to ~30% in the 2H ₂ polytype. Si⁴⁺ by Fe³⁺ substitution in the tetrahedral sheet with an Al³⁺ (Fe³⁺) in the role of a charge compensating cation in the octahedral sheet is also examined. The cation substitutions result in the geometrical changes in the tetrahedral sheets, while the octahedral sheets remain almost untouched. Substituted tetrahedra are tilted and their basal oxygens pushed down from the plane of basal oxygens. Ditrigonal deformation of tetrahedral sheets depends on the substituting cation and the degree of substitution.     

A temperature-dependent single-crystal Raman spectroscopic study of fayalite: evidence for phonon-magnetic excitation coupling

The polarized single-crystal Raman spectrum of synthetic fayalite, Fe₂SiO₄, was recorded between 5 and 773 K in order to investigate its lattice dynamic behavior. A broad absorption envelope is observed at wavenumbers between 800 and 960 cm^–1 and it contains two intense bands at 816 and 840 cm^–1 at 293 K in the (cc) spectrum. The integral area of the envelope decreases upon cooling from 293 K and reaches a minimum around 55 K. It then increases again with a further decrease in temperature down to 5 K. It is proposed that the envelope in the (cc) spectra consists of seven different modes, some of which are symmetry-forbidden, that arise from combination scattering of nonsymmetric internal SiO₄-stretching modes of B_ig symmetry (i = 1, 2, 3) and low-energy excitations. The individual modes can be observed under different polarizations and agree in number and wavenumber with those obtained by fitting the broad envelope with Lorentzians. An analysis of the Raman spectrum as a function of temperature, using the known magnetic properties of fayalite, allows the assignment of the low-energy excitations to short-range magnetic interactions. Modulation of the Fe²⁺(1)–Fe²⁺(2) exchange energy leads to phonon-magnetic excitation coupling and the main role in the Fe²⁺(1)–Fe²⁺(2) magnetic interaction occurs via superexchange through the oxygens. The magnetic excitations are not magnons in the usual sense, that is as quasiparticles having a long wavelength in an ordered system. The degree of observed broadening of the SiO₄-stretching modes is consonant with a Fe²⁺(1)–Fe²⁺(2) exchange energy of 4.7 cm^–1 presented by Schmidt et al. (1992). At temperatures above 300 K the line width of the mode at 840 cm^–1 decreases slightly, whereas those of low energy lattice modes increase. This suggests that a decrease in mode broadening due to weakened magnetic interactions compensates any thermally related broadening. Complete Fe²⁺ spin disorder may not be reached until at least 530 K. Results from this study show that estimates of third-law entropies for silicates using simple crystal-chemical considerations that do not account for magnetic properties cannot give accurate values for many transition-metal-containing phases.     

Thermodynamic and magnetic properties of surface Fe<Superscript>3+</Superscript> species on quartz: effects of gamma-ray irradiation and implications for aerosol–radiation interactions

Samples of a natural amethyst, pulverized in air, and irradiated for gamma-ray doses from 0.14 to 70 kGy, have been investigated by powder electron paramagnetic resonance (EPR) spectroscopy from 90 to 294 K. The powder EPR spectra show that the surface Fe³⁺ species on the gamma-ray-irradiated quartz differ from its counterpart without irradiation in both the effective g value and the observed line shape, suggesting marked radiation effects. This suggestion is supported by quantitatively determined thermodynamic properties, magnetic susceptibility, relaxation times, and geometrical radius. In particular, the surface Fe³⁺ species on gamma-ray-irradiated quartz has larger Gibbs and activation energies than its non-irradiated counterpart, suggesting radiation-induced chemical reactions. The shorter phase-memory time (T _m) but longer spin–lattice relaxation time (T ₁) of the surface Fe³⁺ species on the gamma-ray-irradiated quartz than that without irradiation indicate stronger dipolar interactions in the former. Moreover, the calculated geometrical radius of the surface Fe³⁺ species on the gamma-ray-irradiated quartz is three orders of magnitude larger than that of its counterpart on the as-is sample. These results provide new insights into radiation-induced aerosol nucleation, with relevance to atmospheric cloud formation and global climate changes.     

The Mössbauer spectrum of 57Fe in titanium-bearing andradites

Mössbauer spectra of ⁵⁷Fe in 2 schorlomite garnets reveal 5 distinct quadrupole-split doublets: dodecahedral Fe²⁺, octahedral Fe²⁺ and Fe³⁺, and tetrahedral Fe²⁺ and Fe³⁺. The isomer shifts and nuclear quadrupole splittings of the 5 doublets were studied between 15 and 500 K. The site occupancies for iron were determined. Reference of the chemical analyses to a basis of 12 oxygens and the Mössbauer data show that in the 2 schorlomites titanium is exclusively quadruvalent within the experimental error. The isomer shift of tetrahedral Fe²⁺ between 15 and 295 K seems to be rather small. The shift is interpreted in terms of localized chemical bonding. Above 295 K the shift cannot be evaluated because of overlapping peaks. If electronic transfer processes (e.g. “electron hopping”) between cations are present their relaxation times must be longer than ～10^?7 s.     

Hydrous olivine (Mg1? y? Fe2+y)2? x ?v x ? SiO4H2 x – a new DHMS phase of variable composition observed as nanometer-sized precipitations in mantle olivine

 An olivine grain from a peridotite nodule 9206 (Udachnaya kimberlite, Siberia) was investigated by TEM methods including AEM, HRTEM, SAED and EELS techniques. A previous study of the 9206 olivine sample revealed OH absorption bands in the IR spectrum and abundant nanometer-sized OH-bearing inclusions, of hexagonal-like or lamellar shape. Inclusions, which are several hundred nm in size, consist of 10 ? phase, talc and serpentine (chrysotile and lizardite). The lamellar (LI) and hexagon-like small inclusions of several ten nm in size (SI) are the topic of the present paper. AEM investigations of the inclusions reveal Mg, Fe and Si as cations only. The Mg/Si and Fe/Si atomic ratios are lower in the inclusions than in the host olivine. The Si concentration in the olivine host and both lamellar inclusions and small inclusions is the same. A pre-peak at 528eV was observed in EEL spectra of LI and SI, which is attributed to OH⁻ or Fe³⁺. From these data it is concluded that there is a OH⁻- or Fe³⁺-bearing cation-deficient olivine-like phase present. HRTEM lattice fringe images of LI and SI exhibit modulated band-like contrasts, which are superimposed onto the olivine lattice. Diffraction patterns (Fourier-transforms) of the HREM images as well as SAED patterns show that the band-like contrasts in HRTEM images of the inclusions are caused by periodic modulations of the olivine lattice. Three kinds of superperiodicity in the olivine structure such as 2a, 3a and 3c, were observed in SAED patterns. The corresponding olivine supercells labelled here as Hy-2a, Hy-3a and Hy-3c were derived. The M1-vacancies located in the (100) and (001) octahedral layers of the olivine lattice are suggested to form ordered arrays of planar defects (PD), which cause the band-like contrasts in HRTEM patterns as well as the superperiodicity in the SAED patterns. The vacancy concentrations as well as the chemical composition of Hy-2a, Hy-3a and Hy-3c olivine supercells were calculated using crystal chemical approaches, assuming either {(OH)^< _O−V^" _Me−(OH)^< _O}^↔, or {F e ^< _Fe −H _Me ^′}^↔ or {2F e ^< _Fe −V _Me ^"}^↔ point defect associates. The calculated theoretical compositions Mg_1.615Fe⁺² _0.135v_0.25SiO₄H_0.5 (Hy-2a) and Mg_1.54Fe²⁺ _0.12v_0.33SiO₄H_0.66 (Hy-3a and Hy-3c) are in a good agreement with the AEM data on inclusions. Hy-2a, Hy-3a and Hy-3c are considered to be a hydrous olivine with the extended chemical formula (Mg_1-yFe²⁺ _y)_2−xv_xSiO₄H_2x. The crystal structure of hydrous olivine is proposed to be a modular olivine structure with Mg-vacant modules. The crystal chemical formula of hydrous olivines in terms of a modular structure can be written as [MgSiO₄H₂] · 3[Mg_1.82Fe_0.18SiO₄] for Hy-2a, [MgSiO₄H₂] · 2[Mg_1.82Fe_0.18SiO₄] for Hy-3a and Hy-3c. Hydrous olivine is suggested to be exsolved from the olivine 9206, which has been initially saturated by OH-bearing point defects. The olivine 9206 hydration as well as the following exsolution of hydrous olivine inclusions is suggested to occur at high pressure-high temperature conditions of the upper mantle. Received: 15 January 2001 / Accepted: 2 July 2001     

Mössbauer and molecular orbital study of chlorites

The different Fe²⁺ lattice sites in iron-rich chlorites have been characterized by Mössbauer spectroscopy and molecular orbital calculations in local density approximation. The Mössbauer measurements were recorded at 77?K within a small velocity range (±3.5?mm?s^?1) to provide high energy resolution. Additionally, measurements were recorded in a wider velocity range (±10.5?mm?s^?1) at temperatures of 140, 200, and 250?K in an applied field (7?T) parallel to the γ-beam. The zero-field spectra were analyzed with discrete Lorentzian-shaped quadrupole doublets to account for the Fe²⁺ sites M1, M2, and M3 and with a quadrupole distribution for Fe³⁺ sites. Such a procedure is justified by the results obtained from MO calculations, which reveal that different anion (OH^?) distributions in the first coordination sphere of M1, M2, and M3 positions have more influence on the Fe²⁺ quadrupole splitting than cationic disorder. The spectra recorded in applied field were analyzed in the spin-Hamiltonian approximation, yielding a negative sign for the electric field gradient (efg) of Fe²⁺ in the M1, M2, and M3 positions. The results of the MO calculations are in quantitative agreement with experiment and reveal that differences in the quadrupole splittings (ΔE _Q ), their temperature dependence and in the isomer shifts (δ) of Fe²⁺ in M1, M2, and M3 positions can theoretically by justified. Therefore, the combined Mössbauer and MO investigation shows that the three Fe²⁺ lattice sites in the chlorites investigated here can be discriminated according to their ΔE _Q -δ parameter pairs. With the calculated average iron-oxygen bond strength, the MO study provides an explanation for the observed trend that the population of the three lattice sites by Fe²⁺ increases according to the relation M1?相似文献   

高放处置罐铁释放诱发膨润土矿物相变研究进展

作为高放废物处置罐候选金属材料,低碳钢在处置库服役期间,其腐蚀产物侵入缓冲屏障,导致缓冲材料矿物相变与性能变异,威胁多重屏障体系的长期安全稳定。本文详细综述了国内外处置库深部还原环境所处的弱碱性化学场与中低温度场的变化趋势,认为处置库深部化学-温度还原条件可导致处置罐Fe腐蚀释放Fe~(2+)。在处置库长期运行过程中,蒙脱石与Fe~(2+)接触发生矿物相变,一方面Fe~(2+)置换蒙脱石八面体晶格中的Al~(3+)和Mg~(2+),还原Fe~(3+)或直接占据空位,生成次生矿物;另一方面Fe~(2+)交换蒙脱石层间的Na~+、K~+和Ca~(2+),转化为铁基蒙脱石。矿物相变可诱发缓冲屏障性能变异甚至退化。基于"抗矿物转化"理念,提出了下一阶段缓冲材料矿物相变研究方向,为地下实验室碳素钢选型、缓冲屏障验证试验设计以及屏障体系安全评价提供科学依据。     

Evaluation of ferrous and ferric Mössbauer fractions. Part II

Mössbauer fractions f are reported for various ferrous- and/or ferric-containing oxides, hydroxides, silicates, and phosphates to extend the list previously reported by De Grave and Van Alboom (1991). The f fractions were evaluated from the experimental temperature dependencies of their center shifts, assuming the Debye model for the lattice vibrations. For most Fe²⁺ sites the characteristic Mössbauer or lattice temperatures Θ_M are in the range 300–400 K, while those for Fe³⁺ sites are close to or exceed 500 K, implying significantly higher f fractions for Fe³⁺ than for Fe²⁺, in particular at room temperature. A correlation between Θ_M and the coordination type, or, for a given valence state and coordination type, between Θ_M and the mineral type is, however, not obvious.     

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.     

Phase transitions in ilvaite,a mixed-valence iron silicate I. A 57Fe Mössbauer study of magnetic order and spin frustration

Ilvaite, Ca(Fe²⁺,Fe³⁺)Fe²⁺Si₂O₈(OH) shows two magnetic phase transitions, which have been studied by Mössbauer spectroscopy within the temperature range 120–4 K. The continued charge localization between Fe²⁺ and Fe³⁺ ions in octahedral A-sites causes the Fe²⁺-Fe³⁺ interaction to be ferromagnetic, although the overall magnetic order is antiferromagnetic. The thermal evolution of the hyperfine fields at the Fe²⁺ (A) and Fe³⁺ (A) sites indicates B _hf: 328 and 523 kOe respectively at 0 K and T _N1= 116K. The corresponding values for Fe²⁺ (B) site are: B _hf 186 kOe and T _N2=36K. An additional hyperfine field exists at the Fe²⁺(B) site within the temperature range 116–36K due to short-range order induced by the spin ordering in A sites. The considerable difference between the two magnetic transition temperatures is due to spin frustration, because the Fe²⁺ (B) site occurs on a corner common between two triangles with respect to two sets of Fe²⁺ (A) and Fe³⁺ (A) sites with opposite spin directions.     

Disproportionation of Fe<Superscript>2+</Superscript> in Al-free silicate perovskite in the laser heated diamond anvil cell as recorded by electron probe microanalysis of oxygen

Experimental evidence is reported for Fe²⁺ disproportionation in Al-free perovskite (Pv), when submitted to large temperature gradients (i.e., under off-equilibrium conditions) in a laser heated diamond anvil cell (LHDAC). To enable this effect, the experimental procedure was designed to produce large radial and axial temperature gradients. In the Pv and ferropericlase (Fp) assemblage synthesized after dissociation of natural olivine, the three chemical states of iron (i.e., Fe⁰, Fe²⁺ and Fe³⁺) could be evidenced by electron probe microanalysis (EPMA), through variations of oxygen contents attached to the Fe cations. Despite inherent difficulties for determination of O-contents and Fe³⁺/ΣFe ratios using EPMA, we recorded significant changes in iron oxidation state across the laser-heated strip. These changes are correlated with variations in composition for the major elements (Fe, Mg, and Si), which evidences that the Pv/Fp assemblage experienced large segregation under the strong temperature gradients. Grains of metallic iron were detected in parts of the laser-heated strip coexisting with a Pv phase with Fe/(Mg + Fe) = 6 at% and most of its iron as Fe³⁺. This Fe²⁺-disproportionation reaction involves insertion of Fe³⁺-defects in the Pv lattice. This Fe³⁺-bearing Pv phase is presumably unstable and decomposes into a mineral assemblage including magnesioferrite, which is detected at the border of the laser-heated strip.     

Crystal Structure and Chemical Composition of Ludwigite from Vranovac Ore Deposit (Boranja Mountain,Serbia)

The crystal structure of ludwigite from Vranovac ore deposit (Boranja Mt., Serbia) was refined using the X-ray powder diffraction (XRPD) Rietveld method in the space group Pbam to a final RB=7.45% and RF=5.26%. It has the unit cell dimensions of: a=9.2515(2) ?; b=12.3109(2) ?; c=3.03712(7) ?; and V=345.91(1) ?3. The calculated distances and angles are mostly in good agreement with the Mg2+-Fe2+ substitutions across the M(1) and M(3) sites, as well as with the Fe3+-Al3+ replacement in the M(4) site. However, the mean observed M(2)-O distance is considerably shorter than prescribed, due to a slight increase of the Fe3+ content in the M(2) site. Such replacement was compensated by slight increase of the Fe2+ content in the M(4) site, resulting in the (Mg1.48Fe2+0.46Fe3+0.05Mn0.02)2.01(Fe3+0.94Fe2+0.04Al0.02)1.00B1.00O5 composition. The formation temperature was estimated to be about 500–600°C. The influences of the various chemical compositions to the crystallographic parameters, M-O distances, M(3) and M(4) sites shift, distortion parameters and estimated valences, were also studied and compared with other reference samples.     

Schmelzgleichgewichte zur Klärung des Augitproblems

In synthetic melts was investigated the substitution of Na⁺, Al³⁺ and Fe³⁺ in the crystal lattice of several CaSIO₃-MgSiO₃-Fe²⁺SiO₃-pyroxenes by means of microanalytical-, X-ray- and optical methods. A considerable mutual influence of these ions could be observed. Optical and X-ray methods are not sufficient for the determination of smaller components in mixed crystals. By combining them with the chemical analysis the partly known system diopside-jadeite could be set right. Further more some other systems seem to contain mixed crystals instead of the pure compounds as was suggested formerly. The methods used in determing the maximum solubility to the present date proved to be insufficient. As a better way the extrapolation of solidus curves is proposed. The influence of larger quantities of Fe³⁺ in Si⁴⁺-position upon the diopside lattice was investigated as well as the problem of the immiscibility gap between pigeonites and augites. Rhombic enstatite was for the first time synthetically prepared from a melt.      

Mössbauer spectroscopic and x-ray powder diffraction studies of synthetic micas on the join annite KFe3AlSi3O10(OH)2-phlogopite KMg3AlSi3O10(OH)2

Micas of the composition K(Fe_3–x Mg _x )AlSi₃ O₁₀(OH)₂ (x=0.6, 1.2, 1.8, 2.4 and 3.0, corresponding to ann₈₀phl₂₀, ann₆₀phl₄₀, ann₄₀phl₆₀, ann₂₀phl₈₀ and ann₀phl₁₀₀) were synthesized hydrothermally under controlled oxygen fugacity conditions. Lattice parameters a ₀ and b ₀ show a distinct linear decrease with increasing Mg content. With increasing ferric iron content a deviation from this linear trend is observed especially within iron rich samples. The tetrahedral rotation angle increases smoothly from 0° in annite to 9.1° in phlogopite. Mössbauer spectra show Fe²⁺ and Fe³⁺ on the octahedral M1 and M2 sites and partially also Fe³⁺ on the tetrahedral site. There is a smooth increase of the quadrupole splitting on both the M1 and the M2 site going from annite to phlogopite, probably due to changes in the lattice contribution to the electric field gradient, assuming a positive correlation between quadrupole splitting and distortion. Fe³⁺ contents, as determined by Mössbauer spectroscopy, versus oxygen fugacity shows that, depending on the composition of the micas, minimum amounts of Fe³⁺ are present. For ann₈₀phl₂₀ this minimum amount of Fe³⁺ is about 8% decreasing to about 1–2% Fe³⁺ for ann₂₀phl₈₀.The molar volume of each solid solution member has been estimated from the determined relations of the molar volume versus % Fe³⁺ contents, extrapolated back to 0% Fe³⁺. Plotting these volumes as a function of X_phl shows that negative excess volume occur in the annitephlogopite join, with the maximum deviation from ideality around X _phl=0.3. Margules volume parameters have been constrained as: Wv, AnnPhl=0.018±0.016 J/(bar.mol) and Wv, PhlAnn=-0.391±0.025 J(bar.mol) (three site basis).     

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).     

P–T–X controls on phase stability and composition in LTMP metabasite rocks – a thermodynamic evaluation

The stability of pumpellyite + actinolite or riebeckite + epidote + hematite (with chlorite, albite, titanite, quartz and H₂O in excess) mineral assemblages in LTMP metabasite rocks is strongly dependent on bulk composition. By using a thermodynamic approach (THERMOCALC), the importance of CaO and Fe₂O₃ bulk contents on the stability of these phases is illustrated using P–T and P–X phase diagrams. This approach allowed P–T conditions of ～4.0 kbar and ～260 °C to be calculated for the growth of pumpellyite + actinolite or riebeckite + epidote + hematite assemblages in rocks containing variable bulk CaO and Fe₂O₃ contents. These rocks form part of an accretionary wedge that developed along the east Australian margin during the Carboniferous–Triassic New England Orogen. P–T and P–X diagrams show that sodic amphibole, epidote and hematite will grow at these conditions in Fe₂O₃‐saturated (6.16 wt%) metabasic rocks, whereas actinolite and pumpellyite will be stable in CaO‐rich (10.30 wt%) rocks. With intermediate Fe₂O₃ (～3.50 wt%) and CaO (～8.30 wt%) contents, sodic amphibole, actinolite and epidote can coexist at these P–T conditions. For Fe₂O₃‐saturated rocks, compositional isopleths for sodic amphibole (Al³⁺ and Fe³⁺ on the M2 site), epidote (Fe³⁺/Fe³⁺ + Al³⁺) and chlorite (Fe²⁺/Fe²⁺ + Mg) were calculated to evaluate the efficiency of these cation exchanges as thermobarometers in LTMP metabasic rocks. Based on these calculations, it is shown that Al³⁺ in sodic amphibole and epidote is an excellent barometer in chlorite, albite, hematite, quartz and titanite buffered assemblages. The effectiveness of these barometers decreases with the breakdown of albite. In higher‐P stability fields where albite is absent, Fe²⁺‐Mg ratios in chlorite may be dependent on pressure. The Fe³⁺/Al and Fe²⁺/Mg ratios in epidote and chlorite are reliable thermometers in actinolite, epidote, chlorite, albite, quartz, hematite and titanite buffered assemblages.     

A clinopyroxene geobarometer for basaltic systems based on crystal-structure modeling

 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⋅Al_T−26.826⋅Fe²⁺ _M1−3.764⋅Fe³⁺ +53.989⋅Al_M1+3.948⋅Ti+14.651⋅Cr −700.431⋅Ca−666.629⋅Na−682.848⋅Mg_M2−691.138⋅Fe²⁺ _M2−688.384⋅Mn−6.267⋅(Mg_M2)²−4.144⋅(Fe²⁺ _M2 where: (Fe²⁺ _M1⋅Mg_M2)/(Fe²⁺ _M2⋅Mg_M1)=e^**(0.238⋅R³⁺+0.289⋅CNM−2.315), CNM=Ca+Na+Mn, and R³⁺=Al_M1+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     

Pristine and reacted surfaces of pyrrhotite and arsenopyrite as studied by X-ray absorption near-edge structure spectroscopy

Fe L-, S L-, and O K-edge X-ray absorption spectra of natural monoclinic and hexagonal pyrrhotites, Fe_1-xS, and arsenopyrite, FeAsS, have been measured and compared with the spectra of minerals oxidized in air and treated in aqueous acidic solutions, as well as with the previous XPS studies. The Fe L-edge X-ray absorption near-edge structure (XANES) of vacuum-cleaved pyrrhotites showed the presence of, aside from high-spin Fe²⁺, small quantity of Fe³⁺, which was higher for a monoclinic mineral. The spectra of the essentially metal-depleted surfaces produced by the non-oxidative and oxidative acidic leaching of pyrrhotites exhibit substantially enhanced contributions of Fe³⁺ and a form of high-spin Fe²⁺ with the energy of the 3d orbitals increased by 0.3–0.8 eV; low-spin Fe²⁺ was not confidently distinguished, owing probably to its rapid oxidation. The changes in the S L-edge spectra reflect the emergence of Fe³⁺ and reduced density of S s–Fe 4s antibonding states. The Fe L-edge XANES of arsenopyrite shows almost unsplit e_g band of singlet Fe²⁺ along with minor contributions attributable to high-spin Fe²⁺ and Fe³⁺. Iron retains the low-spin state in the sulphur-excessive layer formed by the oxidative leaching in 0.4 M ferric chloride and ferric sulphate acidic solutions. The S L-edge XANES of arsenopyrite leached in the ferric chloride, but not ferric sulphate, solution has considerably decreased pre-edge maxima, indicating the lesser admixture of S s states to Fe 3d orbitals in the reacted surface layer. The ferric nitrate treatment produces Fe³⁺ species and sulphur in oxidation state between +2 and +4.