Experimental and computational study of trace element distribution between orthopyroxene and anhydrous silicate melt: substitution mechanisms and the effect of iron

Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 to $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 , D values for highly charged elements vary from $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 through $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 and $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 to $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 , and are all virtually independent of temperature. Cr and Co are the only compatible trace elements at the studied conditions. To elucidate charge-balancing mechanisms for incorporation of REE into Opx and to assess the possible influence of Fe on Opx-melt partitioning, we compare our experimental results with computer simulations. In these simulations, we examine major and minor trace element incorporation into the end-members enstatite (Mg₂Si₂O₆) and ferrosilite (Fe₂Si₂O₆). Calculated solution energies show that R²⁺ cations are more soluble in Opx than R³⁺ cations of similar size, consistent with experimental partitioning data. In addition, simulations show charge balancing of R³⁺ cations by coupled substitution with Li⁺ on the M1 site that is energetically favoured over coupled substitution involving Al–Si exchange on the tetrahedrally coordinated site. We derived best-fit values for ideal ionic radii r ₀, maximum partition coefficients D ₀, and apparent Young’s moduli E for substitutions onto the Opx M1 and M2 sites. Experimental r ₀ values for R³⁺ substitutions are 0.66–0.67 ? for M1 and 0.82–0.87 ? for M2. Simulations for enstatite result in r ₀ = 0.71–0.73 ? for M1 and ~0.79–0.87 ? for M2. Ferrosilite r ₀ values are systematically larger by ~0.05 ? for both M1 and M2. The latter is opposite to experimental literature data, which appear to show a slight decrease in $ r_{0}^{{{\text{M}}2}} $ r_{0}^{{{\text{M}}2}} in the presence of Fe. Additional systematic studies in Fe-bearing systems are required to resolve this inconsistency and to develop predictive Opx-melt partitioning models for use in terrestrial and lunar magmatic differentiation models.     

Dehydration kinetics of antigorite using in situ high-temperature infrared microspectroscopy

The dehydration kinetics of serpentine was investigated using in situ high-temperature infrared microspectroscopy. The analyzed antigorite samples at room temperature show relatively sharp bands at around 3,655–3,660 cm^?1 (band 1), 3,570–3,595 cm^?1 (band 2), and 3,450–3,510 cm^?1 (band 3). Band 1 corresponds to the Mg–OH bond, and bands 2 and 3 correspond to OH associated with the substitution of Al for Si. Isothermal kinetic heating experiments at temperatures ranging from 625 to 700 °C showed a systematic decrease of the OH band absorbance with heating duration. The one-dimensional diffusion was found to provide the best fit to the experimental data, and diffusion coefficients were determined with activation energies of 219 ± 37 kJ mol^?1 for the total water band area, 245 ± 46 kJ mol^?1 for band 1, 243 ± 57 kJ mol^?1 for band 2, and 256 ± 53 kJ mol^?1 for band 3. The results indicate that the dehydration process is controlled by one-dimensional diffusion through the tetrahedral geometry of serpentine. Fluid production rates during antigorite dehydration were calculated from kinetic data and range from 3 × 10^?4 to 3 × 10^?5  $ {\text{m}}_{\text{fluid}}^{ 3} \,{\text{m}}_{\text{rock}}^{ - 3} \,{\text{s}}^{ - 1} $ . The rates are high enough to provoke hydraulic rupture, since the relaxation rates of rocks are much lower than these values. The results suggest that the rapid dehydration of antigorite can trigger an intermediate-depth earthquake associated with a subducting slab.     

Optical absorption and mössbauer spectra of purple and green yoderite,a kyanite-related mineral

Mössbauer and polarized optical absorption spectra of the kyanite-related mineral yoderite were recorded. Mössbauer spectra of the purple (PY) and green yoderite (GY) from Mautia Hill, Tanzania, show that the bulk of the iron is Fe³⁺ in both varieties, with Fe²⁺/(Fe²⁺+Fe³⁺) ratios near 0.05. Combining this result with new microprobe data for PY and with literature data for GY gives the crystallochemical formulae: $$\begin{gathered} ({\text{Mg}}_{{\text{1}}{\text{.95}}} {\text{Fe}}_{{\text{0}}{\text{.02}}}^{{\text{2 + }}} {\text{Mn}}_{{\text{0}}{\text{.01}}}^{{\text{2 + }}} {\text{Fe}}_{{\text{0}}{\text{.34}}}^{{\text{3 + }}} {\text{Mn}}_{{\text{0}}{\text{.07}}}^{{\text{3 + }}} {\text{Ti}}_{{\text{0}}{\text{.01}}} {\text{Al}}_{{\text{3}}{\text{.57}}} )_{5.97}^{[5,6]} \hfill \\ {\text{Al}}_{{\text{2}}{\text{.00}}}^{{\text{[5]}}} [({\text{Si}}_{{\text{3}}{\text{.98}}} {\text{P}}_{{\text{0}}{\text{.03}}} ){\text{O}}_{{\text{18}}{\text{.02}}} ({\text{OH)}}_{{\text{1}}{\text{.98}}} ] \hfill \\ \end{gathered}$$ and PY and $$\begin{gathered} ({\text{Mg}}_{{\text{1}}{\text{.98}}} {\text{Fe}}_{{\text{0}}{\text{.02}}}^{{\text{2 + }}} {\text{Mn}}_{{\text{< 0}}{\text{.001}}}^{{\text{2 + }}} {\text{Fe}}_{{\text{0}}{\text{.45}}}^{{\text{3 + }}} {\text{Ti}}_{{\text{0}}{\text{.01}}} {\text{Al}}_{{\text{3}}{\text{.56}}} )_{6.02}^{[5,6]} \hfill \\ {\text{Al}}_{{\text{2}}{\text{.00}}}^{{\text{[5]}}} [({\text{Si}}_{{\text{3}}{\text{.91}}} {\text{O}}_{{\text{17}}{\text{.73}}} {\text{(OH)}}_{{\text{2}}{\text{.27}}} ] \hfill \\ \end{gathered}$$ for GY. The Mössbauer spectra at room temperature contain one main doublet with isomer shifts and quadrupole splittings of 0.36 (PY), 0.38 (GY) and 1.00 (PY), 0.92 (GY) mm s^?1, respectively. These values correspond to Fe³⁺ in six or five-fold coordination. The doublet components have anomalously large half widths indicating either accomodation of Fe³⁺ in more than one position (e.g., octahedraA1 and five coordinatedA2) or the yet unresolved superstructure. Besides strong absorption in the ultraviolet (UV) starting from about 25,000 cm^?1, the polarized optical absorption spectra are dominated by strong bands around 16,500 and 21,000 cm^?1 (PY) and a medium strong band at around 13,800 cm^?1 (GY). Position and polarization of these bands, in combination with the UV absorption, explain the colour and pleochroism of the two varieties. The bands in question are assigned to homonuclear metal-to-metal charge transfer transitions: Mn²⁺(A1) Mn³⁺(A1′) ? Mn³⁺(A1) Mn²⁺(A1′) and Mn²⁺(A1) Mn³⁺(A2 ? Mn³⁺(A1) Mn²⁺(A2) in PY and Fe²⁺(A1) Fe³⁺(A1′) ? Fe³⁺(A1) Fe²⁺(A1′) in GY. The evidence for homonuclear Mn²⁺ Mn³⁺ charge transfer (CTF) is not quite clear and needs further study. Heteronuclear FeTi CTF does not contribute to the spectra. In PY, additional weak bands were resolved at energies around 17,700, 18,700, 21,000, and 21,900 cm^?1 and assigned to Mn³⁺ in two positions. Weak bands around 10,000 cm^?1 in both varieties are assigned to Fe²⁺ spin-alloweddd-transitions. Very weak and sharp bands, around 15,400, 16,400, 21,300, 22,100, 23,800, and 25,000 cm^?1 are identified in GY and assigned to Fe³⁺ spin-forbiddendd-transitions.     

Crystal chemistry of Fe3+-bearing (Mg,Fe)SiO3 perovskite: a single-crystal X-ray diffraction study

Magnesium silicate perovskite is the predominant phase in the Earth’s lower mantle, and it is well known that incorporation of iron has a strong effect on its crystal structure and physical properties. To constrain the crystal chemistry of (Mg, Fe)SiO₃ perovskite more accurately, we synthesized single crystals of Mg_0.946(17)Fe_0.056(12)Si_0.997(16)O₃ perovskite at 26 GPa and 2,073 K using a multianvil press and investigated its crystal structure, oxidation state and iron-site occupancy using single-crystal X-ray diffraction and energy-domain Synchrotron Mössbauer Source spectroscopy. Single-crystal refinements indicate that all iron (Fe²⁺ and Fe³⁺) substitutes on the A-site only, where \( {\text{Fe}}^{ 3+ } /\Upsigma {\text{Fe}}\sim 20\,\% \) based on Mössbauer spectroscopy. Charge balance likely occurs through a small number of cation vacancies on either the A- or the B-site. The octahedral tilt angle (Φ) calculated for our sample from the refined atomic coordinates is 20.3°, which is 2° higher than the value calculated from the unit-cell parameters (a = 4.7877 Å, b = 4.9480 Å, c = 6.915 Å) which assumes undistorted octahedra. A compilation of all available single-crystal data (atomic coordinates) for (Mg, Fe)(Si, Al)O₃ perovskite from the literature shows a smooth increase of Φ with composition that is independent of the nature of cation substitution (e.g., \( {\text{Mg}}^{ 2+ } - {\text{Fe}}^{ 2+ } \) or \( {\text{Mg}}^{ 2+ } {\text{Si}}^{ 4+ } - {\text{Fe}}^{ 3+ } {\text{Al}}^{ 3+ } \) substitution mechanism), contrary to previous observations based on unit-cell parameter calculations.     

The effect of silica activity on the diffusion of Ni and Co in olivine

The diffusion of Ni and Co was measured at atmospheric pressure in synthetic monocrystalline forsterite (Mg₂SiO₄) from 1,200 to 1,500 °C at the oxygen fugacity of air, along [100], with the activities of SiO₂ and MgO defined by either forsterite + periclase (fo + per buffer) or forsterite + protoenstatite (fo + en buffer). Diffusion profiles were measured by three methods: laser-ablation inductively-coupled-plasma mass-spectrometry, nano-scale secondary ion mass spectrometry and electron microprobe, with good agreement between the methods. For both Ni and Co, the diffusion rates in protoenstatite-buffered experiments are an order of magnitude faster than in the periclase-buffered experiments at a given temperature. The diffusion coefficients D _M (M = Ni or Co) for the combined data set can be fitted to the equation:

$$\log \,D_{\text{M}} \,\left( {{\text{in}}\,{\text{m}}^{2} \,{\text{s}}^{ - 1} } \right) = - 6.77( \pm 0.33) + \Delta E_{\text{a}} (M)/RT + 2/3\log a_{{SiO_{2} }}$$

with E_a(Ni) = ? 284.3 kJ mol^?1 and E_a(Co) = ? 275.9 kJ mol^?1, with an uncertainty of ±10.2 kJ mol^?1. This equation fits the data (24 experiments) to ±0.1 in log D _M. The dependence of diffusion on \(a_{{{\text{SiO}}_{2} }}\) is in agreement with a point-defect model in which Mg-site vacancies are charge-balanced by Si interstitials. Comparative experiments with San Carlos olivine of composition Mg_1.8Fe_0.2SiO₄ at 1,300 °C give a slightly small dependence on \(a_{{{\text{SiO}}_{2} }}\), with D \(\propto\) (\(a_{{{\text{SiO}}_{2} }}^{0.5}\)), presumably because the Mg-site vacancies increase with incorporation of Fe³⁺ in the Fe-bearing olivines. However, the dependence on fO₂ is small, with D \(\propto\) (fO₂)^0.12±0.12. These results show the necessity of constraining the chemical potentials of all the stoichiometric components of a phase when designing diffusion experiments. Similarly, the chemical potentials of the major-element components must be taken into account when applying experimental data to natural minerals to constrain the rates of geological processes. For example, the diffusion of divalent elements in olivine from low SiO₂ magmas, such as kimberlites or carbonatites, will be an order of magnitude slower than in olivine from high SiO₂ magmas, such as tholeiitic basalts, at equal temperatures and fO₂.

     

Magnesiochloritoid: Compressibility and high pressure structure refinement

The response of magnesiochloritoid to pressure has been studied by single crystal X-ray diffraction in a diamond anvil cell, using crystals with composition Mg_1.3Fe_0.7Al₄Si₂O₁₀(OH)₄. The unit cell parameters decrease from a = 9.434 (3), b = 5.452 (2), c = 18.136 (5) Å, β = 101.42° (2) (1 bar pressure) to a = 9.370 (7), b = 5.419 (5), c = 17.88 (1) Å, β = 101.5° (1) (42 kbar pressure), following a slightly anisotropic compression pattern (linear compressibilities parallel to unit cell edges: β _a = 1.85, β _b = 1.74, β_c = 3.05 × 10^?4 kbar^?1) with a bulk modulus of 1480 kbar. Perpendicular to c, the most compressible direction, the crystal structure (space group C2/c) consists of two kinds of alternating octahedral layers connected via isolated SiO₄ tetrahedra. With increasing pressure the slightly wavy layer [Mg_1.3Fe_0.7AlO₂(OH)₄] tends to flatten. Furthermore, the octahedra in this layer, with all cations underbonded, are more compressible than the octahedra in the (A1₃O₈) layer with slightly overbonded aluminum. Comparison between high-pressure and high-temperature data yields the following equations: $$\begin{gathered} a_{P,T} = 9.434{\text{ }}{\AA} - 174 \cdot 10^{ - 5} {\text{ }}{\AA}{\text{kb}}^{{\text{ - 1}}} \cdot P \hfill \\ {\text{ }} + 9 \cdot 10^{ - 5} {\text{ }}{\AA}^\circ C^{ - 1} \cdot (T - 25^\circ C) \hfill \\ b_{P,T} = 5.452{\text{ }}{\AA} - 95 \cdot 10^{ - 5} {\text{ }}{\AA}{\text{kb}}^{{\text{ - 1}}} \cdot P \hfill \\ {\text{ }} + 5 \cdot 65 \cdot 10^{ - 5} {\text{ }}{\AA}^\circ C^{ - 1} \cdot (T - 25^\circ C) \hfill \\ c_{P,T} = 18.136{\text{ }}{\AA} - 549 \cdot 10^{ - 5} {\text{ }}{\AA}{\text{kb}}^{{\text{ - 1}}} \cdot P \hfill \\ {\text{ }} + 16 \cdot 2^{ - 5} {\text{ }}{\AA}^\circ C^{ - 1} \cdot (T - 25^\circ C) \hfill \\ \end{gathered} $$ with P in kbar and T in °C. These equations indicate that the unit cell and bond geometry of magnesiochloritoid at formation conditions do not differ greatly from those at the outcrop conditions, e.g. the calculated unitcell volume is 917.3 ų at P = 16 kbar and T=500 °C, whereas the observed volume at room conditions is 914.4 ų. In addition, they show that the specific gravity increases from formation at depth to outcrop at surface conditions.     

Raman spectra of gypsum under pressure

Raman sprectra of a gypsum crystal were made at pressures between 0.001 and 7 kbar using He gas as the pressure medium. \(\frac{{{\text{d}}v}}{{dP}}\) values for bands in the range 3,600–100 cm^?1 were obtained. Comparison of results with \(\frac{{{\text{d}}v}}{{{\text{d}}T}}\) from the literature for temperatures of 77 and 300° K. shows that the internal modes of the SO₄ units are more sensitive to pressure than to temperature. The effect is small. Coupled H₂O-SO₄ translational modes are greatly affected by both pressure and temperature while coupled Ca-SO₄ mode are less so. It was found that stretching vibrations of water molecules were affected differently under pressure. The band at 3,500 cm^?1 is more greatly displaced by pressure \(\left( {\frac{{{\text{d}}v}}{{{\text{d}}P}} = {\text{2}}{\text{.11cm}}^{{\text{ - 1}}} /{\text{kbar}}} \right)\) than the band at 3,400 cm^?1 \(\left( {\frac{{{\text{d}}v}}{{{\text{d}}P}} \simeq {\text{2}}{\text{.11cm}}^{{\text{ - 1}}} /{\text{kbar}}} \right)\) . Assuming two different hydrogen bond intensities for the water molecules, one can attribute this difference in behavior of stretching modes to and increase in hydrogen bonding of one of the hydrogens which is exterior to the double H₂O planes in the gypsum structure. The great variety of pressure derivatives for the different types of vibrational modes observed indicates that each molecular unit readjusts internally to pressure induced volume changes and the some of the chemical bonds between the units are significantly affected.     

An experimental study of Ti and Zr partitioning among zircon, rutile, and granitic melt

In order to evaluate the effect of trace and minor elements (e.g., P, Y, and the REEs) on the high-temperature solubility of Ti in zircon (zrc), we conducted 31 experiments on a series of synthetic and natural granitic compositions [enriched in TiO₂ and ZrO₂; Al/(Na + K) molar ~1.2] at a pressure of 10 kbar and temperatures of ~1,400 to 1,200 °C. Thirty of the experiments produced zircon-saturated glasses, of which 22 are also saturated in rutile (rt). In seven experiments, quenched glasses coexist with quartz (qtz). SiO₂ contents of the quenched liquids range from 68.5 to 82.3 wt% (volatile free), and water concentrations are 0.4–7.0 wt%. TiO₂ contents of the rutile-saturated quenched melts are positively correlated with run temperature. Glass ZrO₂ concentrations (0.2–1.2 wt%; volatile free) also show a broad positive correlation with run temperature and, at a given T, are strongly correlated with the parameter (Na + K + 2Ca)/(Si·Al) (all in cation fractions). Mole fraction of ZrO₂ in rutile $ \left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) $ in the quartz-saturated runs coupled with other 10-kbar qtz-saturated experimental data from the literature (total temperature range of ~1,400 to 675 °C) yields the following temperature-dependent expression: $ {\text{ln}}\left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) + {\text{ln}}\left( {a_{{{\text{SiO}}_{2} }} } \right) = 2.638(149) - 9969(190)/T({\text{K}}) $ , where silica activity $ a_{{{\text{SiO}}_{2} }} $ in either the coexisting silica polymorph or a silica-undersaturated melt is referenced to α-quartz at the P and T of each experiment and the best-fit coefficients and their uncertainties (values in parentheses) reflect uncertainties in T and $ \mathop X\nolimits_{{{\text{ZrO}}_{2} }}^{\text{rt}} $ . NanoSIMS measurements of Ti in zircon overgrowths in the experiments yield values of ~100 to 800 ppm; Ti concentrations in zircon are positively correlated with temperature. Coupled with values for $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ for each experiment, zircon Ti concentrations (ppm) can be related to temperature over the range of ~1,400 to 1,200 °C by the expression: $ \ln \left( {\text{Ti ppm}} \right)^{\text{zrc}} + \ln \left( {a_{{{\text{SiO}}_{2} }} } \right) - \ln \left( {a_{{{\text{TiO}}_{2} }} } \right) = 13.84\left( {71} \right) - 12590\left( {1124} \right)/T\left( {\text{K}} \right) $ . After accounting for differences in $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ , Ti contents of zircon from experiments run with bulk compositions based on the natural granite overlap with the concentrations measured on zircon from experiments using the synthetic bulk compositions. Coupled with data from the literature, this suggests that at T ≥ 1,100 °C, natural levels of minor and trace elements in “granitic” melts do not appear to influence the solubility of Ti in zircon. Whether this is true at magmatic temperatures of crustal hydrous silica-rich liquids (e.g., 800–700 °C) remains to be demonstrated. Finally, measured $ D_{\text{Ti}}^{{{\text{zrc}}/{\text{melt}}}} $ values (calculated on a weight basis) from the experiments presented here are 0.007–0.01, relatively independent of temperature, and broadly consistent with values determined from natural zircon and silica-rich glass pairs.     

Redox-controlled iron isotope fractionation during magmatic differentiation: an example from the Red Hill intrusion, S. Tasmania

This study presents accurate and precise iron isotopic data for 16 co-magmatic rocks and 6 pyroxene–magnetite pairs from the classic, tholeiitic Red Hill sill in southern Tasmania. The intrusion exhibits a vertical continuum of compositions created by in situ fractional crystallisation of a single injection of magma in a closed igneous system and, as such, constitutes a natural laboratory amenable to determining the causes of Fe isotope fractionation in magmatic rocks. Early fractionation of pyroxenes and plagioclase, under conditions closed to oxygen exchange, gives rise to an iron enrichment trend and an increase in $ f_{{{\text{O}}_{2} }} $ of the melt relative to the Fayalite–Magnetite–Quartz (FMQ) buffer. Enrichment in Fe³⁺/ΣFe_melt is mirrored by δ⁵⁷Fe, where ^VIFe²⁺-bearing pyroxenes partition ⁵⁷Fe-depleted iron, defining an equilibrium pyroxene-melt fractionation factor of $ \Updelta^{57} {\text{Fe}}_{{{\text{px}} - {\text{melt}}}} \le - 0.25\,\permille \times 10^{6} /T^{2} $ . Upon magnetite saturation, the $ f_{{{\text{O}}_{2} }} $ and δ⁵⁷Fe of the melt fall, commensurate with the sequestration of the oxidised, ⁵⁷Fe-enriched iron into magnetite, quantified as $ \Updelta^{57} {\text{Fe}}_{{{\text{mtn}} - {\text{melt}}}} = + 0.20\,\permille \times 10^{6} /T^{2} $ . Pyroxene–magnetite pairs reveal an equilibrium fractionation factor of $ \Updelta^{57} {\text{Fe}}_{{{\text{mtn}} - {\text{px}}}} \approx + 0.30\,\permille $ at 900–1,000?°C. Iron isotopes in differentiated magmas suggest that they may act as an indicator of their oxidation state and tectonic setting.     

Majoritic garnet grains within shock-induced melt veins in amphibolites from the Ries impact crater suggest ultrahigh crystallization pressures between 18 and 9 GPa

Shock-induced melt veins in amphibolites from the Nördlinger Ries often have chemical compositions that are similar to bulk rock (i.e., basaltic), but there are other veins that are confined to chlorite-rich cracks that formed before the impact and these are poor in Ca and Na. Majoritic garnets within the shock veins show a broad chemical variation between three endmembers: (1) \({}^{\text{VIII}}{{\text{M}^{2+}}_3} {}^{\text{VI}}{\text{Al}}_{2} ({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\) (normal garnet, Grt), (2) \({}^{\text{VIII}}{{\text{M}^{2+}}_3} {}^{\text{VI}}[{\text{M}}^{2 + } ({\text{Si,Ti}})]({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\)  (majorite, Maj), and (3) \({}^{\text{VIII}}({{\text {Na} {\text M}^{2+}}_2}) {}^{\text{VI}}[ ({\text{Si,Ti}}){\text {Al}}]({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\) (Na-majorite₅₀Grt₅₀), whereby M²⁺ = Mg²⁺, Fe²⁺, Mn²⁺, Ca²⁺. In particular, we observed a broad variation in ^VI(Si,Ti) which ranges from 0.12 to 0.58 cations per formula unit (cpfu). All these majoritic garnets crystallized during shock pressure release at different ultrahigh pressures. Those with high ^VI(Si,Ti) (0.36–0.58 cpfu) formed at high pressures and temperatures from amphibole-rich melts, while majoritic garnets with lower ^VI(Si,Ti) of 0.12–0.27 cpfu formed at lower pressures and temperatures from chlorite-rich melts. Furthermore, majoritic garnets with intermediate values of ^VI(Si,Ti) (0.24–0.39) crystallized from melts with intermediate contents of Ca and Na. To the best of our knowledge the ‘MORB-type’ Ca–Na-rich majoritic garnets with maximum contents of 2.99 wt% Na₂O and calculated crystallisation pressures of 16–18 GPa are the most extreme representatives ever found in terrestrial shocked materials. At the Ries, the duration of the initial contact and compression stage at the central location of impact is estimated to only ~ 0.1 s. We used a ~ 200-µm-thick shock-induced vein in a moderately shocked amphibolite to model its pressure–temperature–time (P–T–t) path. The graphic model manifests a peak temperature of ~ 2600 °C for the vein, continuum pressure lasting for ~ 0.02 s, a quench duration of ~ 0.02 s and a shock pulse of ~ 0.038 s. The small difference between the continuum pressure and the pressure of majoritic garnet crystallization underlines the usefulness of applying crystallisation pressures of majoritic garnets from metabasites for calculation of dynamic shock pressures of host rocks. Majoritic garnets of chlorite provenance, however, are not suitable for the determination of continuum pressure since they crystallized relatively late during shock release. An extraordinary glass- and majorite-bearing amphibole fragment in a shock-vein of one amphibolite documents the whole unloading path.     

The carbon dioxide solubility in alkali basalts: an experimental study

Experiments were conducted to determine CO₂ solubilities in alkali basalts from Vesuvius, Etna and Stromboli volcanoes. The basaltic melts were equilibrated with nearly pure CO₂ at 1,200°C under oxidizing conditions and at pressures ranging from 269 to 2,060 bars. CO₂ solubility was determined by FTIR measurements. The results show that alkalis have a strong effect on the CO₂ solubility and confirm and refine the relationship between the compositional parameter Π devised by Dixon (Am Mineral 82:368–378, 1997) and the CO₂ solubility. A general thermodynamic model for CO₂ solubility in basaltic melts is defined for pressures up to 2 kbars. Based on the assumption that O²⁻ and CO₃²⁻ mix ideally, we have:

(Ca,Mg)2Si2O6 clinopyroxenes: A solution model based on nonconvergent site-disorder

Experiments at high pressure and temperature indicate that excess Ca may be dissolved in diopside. If the (Ca, Mg)₂Si₂O₆ clinopyroxene solution extends to more Ca-rich compositions than CaMgSi₂O₆, macroscopic regular solution models cannot strictly be applied to this system. A nonconvergent site-disorder model, such as that proposed by Thompson (1969, 1970), may be more appropriate. We have modified Thompson's model to include asymmetric excess parameters and have used a linear least-squares technique to fit the available experimental data for Ca-Mg orthopyroxene-clinopyroxene equilibria and Fe-free pigeonite stability to this model. The model expressions for equilibrium conditions \(\mu _{{\text{Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{opx}}} = \mu _{{\text{Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{cpx}}} \) (reaction A) and \(\mu _{{\text{Ca}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{opx}}} = \mu _{{\text{Ca}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{cpx}}} \) (reaction B) are given by: 1 $$\begin{gathered} \Delta \mu _{\text{A}}^{\text{O}} = {\text{RT 1n}}\left[ {\frac{{(X_{{\text{Mg}}}^{{\text{opx}}} )^2 }}{{X_{{\text{Mg}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} }}} \right] - \frac{1}{2}\{ W_{21} [2(X_{{\text{Ca}}}^{{\text{M2}}} )^3 - (X_{{\text{Ca}}}^{{\text{M2}}} ] \hfill \\ {\text{ + 2W}}_{{\text{22}}} [X_{{\text{Ca}}}^{{\text{M2}}} )^2 - (X_{{\text{Ca}}}^{{\text{M2}}} )^3 + \Delta {\text{G}}_{\text{*}}^{\text{0}} (X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Ca}}}^{{\text{M2}}} )\} \hfill \\ {\text{ + W}}^{{\text{opx}}} (X_{{\text{Wo}}}^{{\text{opx}}} )^2 \hfill \\ \Delta \mu _{\text{B}}^{\text{O}} = {\text{RT 1n}}\left[ {\frac{{(X_{{\text{Ca}}}^{{\text{opx}}} )^2 }}{{X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Ca}}}^{{\text{M2}}} }}} \right] - \frac{1}{2}\{ 2W_{21} [2(X_{{\text{Mg}}}^{{\text{M2}}} )^2 - (X_{{\text{Mg}}}^{{\text{M2}}} )^3 ] \hfill \\ {\text{ + W}}_{{\text{22}}} [2(X_{{\text{Mg}}}^{{\text{M2}}} )^3 - (X_{{\text{Mg}}}^{{\text{M2}}} )^2 + \Delta {\text{G}}_{\text{*}}^{\text{0}} (X_{{\text{Mg}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} )\} \hfill \\ {\text{ + W}}^{{\text{opx}}} (X_{{\text{En}}}^{{\text{opx}}} )^2 \hfill \\ \hfill \\ \end{gathered} $$ where 1 $$\begin{gathered} \Delta \mu _{\text{A}}^{\text{O}} = 2.953 + 0.0602{\text{P}} - 0.00179{\text{T}} \hfill \\ \Delta \mu _{\text{B}}^{\text{O}} = 24.64 + 0.958{\text{P}} - (0.0286){\text{T}} \hfill \\ {\text{W}}_{{\text{21}}} = 47.12 + 0.273{\text{P}} \hfill \\ {\text{W}}_{{\text{22}}} = 66.11 + ( - 0.249){\text{P}} \hfill \\ {\text{W}}^{{\text{opx}}} = 40 \hfill \\ \Delta {\text{G}}_*^0 = 155{\text{ (all values are in kJ/gfw)}}{\text{.}} \hfill \\ \end{gathered} $$ . Site occupancies in clinopyroxene were determined from the internal equilibrium condition 1 $$\begin{gathered} \Delta G_{\text{E}}^{\text{O}} = - {\text{RT 1n}}\left[ {\frac{{X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} }}{{X_{{\text{Ca}}}^{{\text{M2}}} \cdot X_{{\text{Mg}}}^{{\text{M1}}} }}} \right] + \tfrac{1}{2}[(2{\text{W}}_{{\text{21}}} - {\text{W}}_{{\text{22}}} )(2{\text{X}}_{{\text{Ca}}}^{{\text{M2}}} - 1) \hfill \\ {\text{ + }}\Delta G_*^0 (X_{{\text{Ca}}}^{{\text{M1}}} - X_{{\text{Ca}}}^{{\text{M2}}} ) + \tfrac{3}{2}(2{\text{W}}_{{\text{21}}} - {\text{W}}_{{\text{22}}} ) \hfill \\ {\text{ (1}} - 2X_{{\text{Ca}}}^{{\text{M1}}} )(X_{{\text{Ca}}}^{{\text{M1}}} + \tfrac{1}{2})] \hfill \\ \end{gathered} $$ where δG _E ⁰ =153+0.023T+1.2P. The predicted concentrations of Ca on the clinopyroxene Ml site are low enough to be compatible with crystallographic studies. Temperatures calculated from the model for coexisting ortho- and clinopyroxene pairs fit the experimental data to within 10° in most cases; the worst discrepancy is 30°. Phase relations for clinopyroxene, orthopyroxene and pigeonite are successfully described by this model at temperatures up to 1,600° C and pressures from 0.001 to 40 kbar. Predicted enthalpies of solution agree well with the calorimetric measurements of Newton et al. (1979). The nonconvergent site disorder model affords good approximations to both the free energy and enthalpy of clinopyroxenes, and, therefore, the configurational entropy as well. This approach may provide an example for Febearing pyroxenes in which cation site exchange has an even more profound effect on the thermodynamic properties.     

TiO2 exsolution from garnet by open-system precipitation: evidence from crystallographic and shape preferred orientation of rutile inclusions

We investigated rutile needles with a clear shape preferred orientation in garnet from (ultra) high-pressure metapelites from the Kimi Complex of the Greek Rhodope by electron microprobe, electron backscatter diffraction and TEM techniques. A definite though complex crystallographic orientation relationship between the garnet host and rutile was identified in that Rt[001] is either parallel to Grt<111> or describes cones with opening angle 27.6° around Grt<111>. Each Rt[001] small circle representing a cone on the pole figure displays six maxima in the density plots. This evidence together with microchemical observations in TEM, when compared to various possible mechanisms of formation, corroborates a precipitate origin. A review of exchange vectors for Ti substitution in garnet indicates that rutile formation from garnet cannot occur in a closed system. It requires that components are exchanged between the garnet interior and the rock matrix by solid-state diffusion, a process we refer to as “open-system precipitation” (OSP). The kinetically most feasible reaction of this type will dominate the overall process. The perhaps most efficient reaction involves internal oxidation of Fe²⁺ to Fe³⁺ and transfer from the dodecahedral to the octahedral site just vacated by $ {\text{Ti}}^{ 4+ }: 6\,{\text{M}}^{ 2+ }_{ 3} {\text{TiAl}}\left[ {{\text{AlSi}}_{ 2} } \right]{\text{O}}_{ 1 2} + 6\,{\text{M}}^{ 2+ }_{ 2, 5} {\text{TiAlSi}}_{ 3} {\text{O}}_{ 1 2} = 10\,{\text{M}}^{ 2+ }_{ 3.0} {\text{Al}}_{ 1. 8} {\text{Fe}}_{0. 2} {\text{Si}}_{ 3} {\text{O}}_{ 1 2} + {\text{M}}^{2+} + 2 {\text{e}}^{-} + 1 2\,{\text{TiO}}_{ 2} . $ OSP is likely to occur at conditions where the transition of natural systems to open-system behaviour becomes apparent, as in the granulite and high-temperature eclogite facies.     

Thermodynamic mixing properties of Mg(Al,Cr)2O4 spinel crystalline solution at high temperatures and pressures

Three Al-Cr exchange isotherms at 1,250°, 1,050°, and 796° between Mg(Al, Cr)₂O₄ spinel and (Al, Cr)₂O₃ corundum crystalline solutions have been studied experimentally at 25 kbar pressure. Starting from gels of suitable bulk compositions, close approach to equilibrium has been demonstrated in each case by time studies. Using the equation of state for (Al, Cr)₂O₃ crystalline solution (Chatterjee et al. 1982a) and assuming that the Mg(Al, Cr)₂O₄ can be treated in terms of the asymmetric Margules relation, the exchange isotherms were solved for Δ G ^*, and . The best constrained data set from the 1,250° C isotherm clearly shows that the latter two quantities do not overlap within three standard deviations, justifying the choice of asymmetric Margules relation for describing the excess mixing properties of Mg(Al, Cr)₂O₄ spinels. Based on these experiments, the following polybaric-polythermal equation of state can be formulated: , P expressed in bars, T in K, G _m ^ex and W _G,i ^Sp in joules/mol. Temperature-dependence of G _m ^ex is best constrained in the range 796–1,250° C; extrapolation beyond that range would have to be done with caution. Such extrapolation to lower temperature shows tentatively that at 1 bar pressure the critical temperature, T _c, of the spinel solvus is 427° C, with dT_c/dP≈1.3 K/kbar. The critical composition, X _c, is 0.42 , and changes barely with pressure. Substantial error in calculated phase diagrams will result if the significant positive deviation from ideality is ignored for Al-Cr mixing in such spinels.     

The high-pressure stability of chlorite and other hydrates in subduction mélanges: experiments in the system Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O

The solubility of chromium in chlorite as a function of pressure, temperature, and bulk composition was investigated in the system Cr₂O₃–MgO–Al₂O₃–SiO₂–H₂O, and its effect on phase relations evaluated. Three different compositions with X _Cr = Cr/(Cr + Al) = 0.075, 0.25, and 0.5 respectively, were investigated at 1.5–6.5 GPa, 650–900 °C. Cr-chlorite only occurs in the bulk composition with X _Cr = 0.075; otherwise, spinel and garnet are the major aluminous phases. In the experiments, Cr-chlorite coexists with enstatite up to 3.5 GPa, 800–850 °C, and with forsterite, pyrope, and spinel at higher pressure. At P > 5 GPa other hydrates occur: a Cr-bearing phase-HAPY (Mg_2.2Al_1.5Cr_0.1Si_1.1O₆(OH)₂) is stable in assemblage with pyrope, forsterite, and spinel; Mg-sursassite coexists at 6.0 GPa, 650 °C with forsterite and spinel and a new Cr-bearing phase, named 11.5 Å phase (Mg:Al:Si = 6.3:1.2:2.4) after the first diffraction peak observed in high-resolution X-ray diffraction pattern. Cr affects the stability of chlorite by shifting its breakdown reactions toward higher temperature, but Cr solubility at high pressure is reduced compared with the solubility observed in low-pressure occurrences in hydrothermal environments. Chromium partitions generally according to \(X_{\text{Cr}}^{\text{spinel}}\) ? \(X_{\text{Cr}}^{\text{opx}}\) > \(X_{\text{Cr}}^{\text{chlorite}}\) ≥ \(X_{\text{Cr}}^{\text{HAPY}}\) > \(X_{\text{Cr}}^{\text{garnet}}\). At 5 GPa, 750 °C (bulk with X _Cr = 0.075) equilibrium values are \(X_{\text{Cr}}^{\text{spinel}}\) = 0.27, \(X_{\text{Cr}}^{\text{chlorite}}\) = 0.08, \(X_{\text{Cr}}^{\text{garnet}}\) = 0.05; at 5.4 GPa, 720 °C \(X_{\text{Cr}}^{\text{spinel}}\) = 0.33, \(X_{\text{Cr}}^{\text{HAPY}}\) = 0.06, and \(X_{\text{Cr}}^{\text{garnet}}\) = 0.04; and at 3.5 GPa, 850 °C \(X_{\text{Cr}}^{\text{opx}}\) = 0.12 and \(X_{\text{Cr}}^{\text{chlorite}}\) = 0.07. Results on Cr–Al partitioning between spinel and garnet suggest that at low temperature the spinel- to garnet-peridotite transition has a negative slope of 0.5 GPa/100 °C. The formation of phase-HAPY, in assemblage with garnet and spinel, at pressures above chlorite breakdown, provides a viable mechanism to promote H₂O transport in metasomatized ultramafic mélanges of subduction channels.     

Stabilitätsbeziehungen zwischen Chlorit,Cordierit und Almandin bei der Metamorphose

The stability relations between cordierite and almandite in rocks, having a composition of CaO poor argillaceous rocks, were experimentally investigated. The starting material consisted of a mixture of chlorite, muscovite, and quartz. Systems with widely varying Fe²⁺/Fe²⁺+Mg ratios were investigated by using two different chlorites, thuringite or ripidolite, in the starting mixture. Cordierite is formed according to the following reaction: $${\text{Chlorite + muscovite + quartz}} \rightleftharpoons {\text{cordierite + biotite + Al}}_{\text{2}} {\text{SiO}}_{\text{5}} + {\text{H}}_{\text{2}} {\text{O}}$$ . At low pressures this reaction characterizes the facies boundary between the albite-epidotehornfels facies and the hornblende-hornfels facies, at medium pressures the beginning of the cordierite-amphibolite facies. Experiments were carried out reversibly and gave the following equilibrium data: 505±10°C at 500 bars H₂O pressure, 513±10°C at 1000 bars H₂O pressure, 527±10°C at 2000 bars H₂O pressure, and 557±10°C at 4000 bars H₂O pressure. These equilibrium data are valid for the Fe-rich starting material, using thuringite as the chlorite, as well as for the Mg-rich starting mixture with ripidolite. At 6000 bars the equilibrium temperature for the Mg-rich mixture is 587±10°C. In the Fe-rich mixture almandite was formed instead of cordierite at 6000 bars. The following reaction was observed: $${\text{Thuringite + muscovite + quartz}} \rightleftharpoons {\text{almandite + biotite + Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + H}}_{\text{2}} {\text{O}}$$ . Experiments with the Fe-rich mixture, containing Fe²⁺/Fe²⁺+Mg in the ratio 8∶10, yielded three stability fields in a P,T-diagram (Fig.1):

1. Above 600°C/5.25 kb and 700°C/6.5 kb almandite+biotite+Al₂SiO₅ coexist stably, cordierite being unstable.
2. The field, in which almandite, biotite and Al₂SiO₅ are stable together with cordierite, is restricted by two curves, passing through the following points:
   1. 625°C/5.5 kb and 700°C/6.5 kb,
   2. 625°C/5.5 kb and 700°C/4.0 kb.
3. At conditions below curves 1 and 2b, cordierite, biotite, and Al₂SiO₅ are formed, but no garnet.

An appreciable MnO-content in the system lowers the pressures needed for the formation of almandite garnet, but the quantitative influence of the spessartite-component on the formation of almandite could not yet be determined. the Mg-rich system with Fe²⁺/Fe²⁺+Mg=0.4 garnet did not form at pressures up to 7 kb in the temperature range investigated. Experiments at unspecified higher pressures (in a simple squeezer-type apparatus) yielded the reaction: $${\text{Ripidolite + muscovite + quartz}} \rightleftharpoons {\text{almandite + biotite + Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + H}}_{\text{2}} {\text{O}}$$ . Further experiments are needed to determine the equilibrium data. The occurence of garnet in metamorphic rocks is discussed in the light of the experimental results.     

H<Subscript>2</Subscript>O diffusion in peralkaline to peraluminous rhyolitic melts

The diffusion of water in a peralkaline and a peraluminous rhyolitic melt was investigated at temperatures of 714–1,493 K and pressures of 100 and 500 MPa. At temperatures below 923 K dehydration experiments were performed on glasses containing about 2 wt% H₂O _t in cold seal pressure vessels. At high temperatures diffusion couples of water-poor (<0.5 wt% H₂O _t ) and water-rich (~2 wt% H₂O _t ) melts were run in an internally heated gas pressure vessel. Argon was the pressure medium in both cases. Concentration profiles of hydrous species (OH groups and H₂O molecules) were measured along the diffusion direction using near-infrared (NIR) microspectroscopy. The bulk water diffusivity () was derived from profiles of total water () using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between and Both methods consistently indicate that is proportional to in this range of water contents for both bulk compositions, in agreement with previous work on metaluminous rhyolite. The water diffusivity in the peraluminous melts agrees very well with data for metaluminous rhyolites implying that an excess of Al₂O₃ with respect to alkalis does not affect water diffusion. On the other hand, water diffusion is faster by roughly a factor of two in the peralkaline melt compared to the metaluminous melt. The following expression for the water diffusivity in the peralkaline rhyolite as a function of temperature and pressure was obtained by least-squares fitting:

Experimental constraints on hydrogen diffusion in garnet

The incorporation mechanisms and diffusional loss of hydrogen in garnet have been experimentally investigated. A suite of gem-quality hydrous spessartine- and grossular-rich garnets were analysed by Fourier transform infrared spectroscopy (FTIR) and by ion microprobe (SHRIMP-SI) to determine the calibration coefficients for quantification of FTIR data. The excellent agreement between measured absorption and OH/O indicates that the same molar extinction coefficient can be used for spessartine and grossular. The coefficient of 14400 l mol^??1 cm^??2 proposed by Maldener et al. (Phys Chem Miner 30:337–344, 2003) seems the most appropriate for both minerals. A grossular with 6.4% andradite and 1.6% almandine containing 834 ppm H₂O, and an almost pure spessartine with 282 ppm H₂O, were selected for diffusion experiments. 1.5-mm cubes of garnets were heated between 12 h and 10 days at 1 atm under various temperature (750–1050 °C) and oxygen fugacity (\({f_{{{\text{O}}_2}}}\)) conditions, (ΔQFM +?15.2 to ??3.0). Diffusion profiles were acquired from sections through the cubes using FTIR, with a deconvolution algorithm developed to assess peak-specific behaviour. Different families of peaks have been identified based on their diffusive behaviour, representing hydrogen incorporated in different H-bearing defects. A dominant, fast, strongly \({f_{{{\text{O}}_2}}}\)-dependent oxidation-related diffusion mechanism is proposed \(\left( {\{ {{\text{M}}^{2+}}+{{\text{H}}^+}\} +\frac{1}{4}{{\text{O}}_2}={{\text{M}}^{3+}}+\frac{1}{2}{{\text{H}}_2}{\text{O}}} \right)\) (M=Fe, Mn) with a relatively low activation energy (158?±?19 kJ mol^??1). This diffusion mechanism is likely restricted by availability of ferrous iron in grossular. At low oxygen fugacity, this diffusion mechanism is shut off and the diffusivity decreased by more than three orders of magnitude. A second, slower hydrogen diffusion mechanism has been observed in minor bands, where charge balance might be maintained by diffusion of cation vacancies, with much higher activation energy (≈?200–270 kJ mol^??1). Spessartine shows clear differences in peak retentivity suggesting that up to four different H sites might exist. This opens exciting opportunities to use hydrogen diffusion in garnet as speedometer. However, it is essential to constrain the main diffusion mechanisms and the oxygen fugacity in the rocks investigated to obtain timescales for metamorphic or igneous processes.     

H-bonding scheme and cation partitioning in axinite: a single-crystal neutron diffraction and Mössbauer spectroscopic study

The crystal chemistry of a ferroaxinite from Colebrook Hill, Rosebery district, Tasmania, Australia, was investigated by electron microprobe analysis in wavelength-dispersive mode, inductively coupled plasma–atomic emission spectroscopy (ICP–AES), ⁵⁷Fe Mössbauer spectroscopy and single-crystal neutron diffraction at 293 K. The chemical formula obtained on the basis of the ICP–AES data is the following: \( ^{X1,X2} {\text{Ca}}_{4.03} \,^{Y} \left( {{\text{Mn}}_{0.42} {\text{Mg}}_{0.23} {\text{Fe}}^{2 + }_{1.39} } \right)_{\varSigma 2.04} \,^{Z1,Z2} \left( {{\text{Fe}}^{3 + }_{0.15} {\text{Al}}_{3.55} {\text{Ti}}_{0.12} } \right)_{\varSigma 3.82} \,^{T1,T2,T3,T4} \left( {{\text{Ti}}_{0.03} {\text{Si}}_{7.97} } \right)_{\varSigma 8} \,^{T5} {\text{B}}_{1.96} {\text{O}}_{30} \left( {\text{OH}} \right)_{2.18} \). The ⁵⁷Fe Mössbauer spectrum shows unambiguously the occurrence of Fe²⁺ and Fe³⁺ in octahedral coordination only, with Fe²⁺/Fe³⁺ = 9:1. The neutron structure refinement provides a structure model in general agreement with the previous experimental findings: the tetrahedral T1, T2, T3 and T4 sites are fully occupied by Si, whereas the T5 site is fully occupied by B, with no evidence of Si at the T5, or Al or Fe³⁺ at the T1–T5 sites. The structural and chemical data of this study suggest that the amount of B in ferroaxinite is that expected from the ideal stoichiometry: 2 a.p.f.u. (for 32 O). The atomic distribution among the X1, X2, Y, Z1 and Z2 sites obtained by neutron structure refinement is in good agreement with that based on the ICP–AES data. For the first time, an unambiguous localization of the H site is obtained, which forms a hydroxyl group with the oxygen atom at the O16 site as donor. The H-bonding scheme in axinite structure is now fully described: the O16–H distance (corrected for riding motion effect) is 0.991(1) Å and an asymmetric bifurcated bonding configuration occurs, with O5 and O13 as acceptors [i.e. with O16···O5 = 3.096(1) Å, H···O5 = 2.450(1) Å and O16–H···O5 = 123.9(1)°; O16···O13 = 2.777(1) Å, H···O13 = 1.914(1) Å and O16–H···O13 = 146.9(1)°].     

The Hydrolysis of Al(III) in NaCl solutions: A Model for M(II), M(III), and M(IV) Ions

Understanding the identity and stability of the hydrolysis products of metals is required in order to predict their behavior in natural aquatic systems. Despite this need, the hydrolysis constants of many metals are only known over a limited range of temperature and ionic strengths. In this paper, we show that the hydrolysis constants of 31 metals [i.e. Mn(II), Cr(III), U(IV), Pu(IV)] are nearly linearly related to the values for Al(III) over a wide range of temperatures and ionic strengths. These linear correlations allow one to make reasonable estimates for the hydrolysis constants of +2, +3, and +4 metals from 0 to 300°C in dilute solutions and 0 to 100°C to 5 m in NaCl solutions. These correlations in pure water are related to the differences between the free energies of the free ion and complexes being almost equal $$ \Updelta {\text{G}}^\circ \left( {{\text{Al}}^{3 + } } \right) - \Updelta {\text{G}}^\circ \left( {{\text{Al}}\left( {\text{OH}} \right)_{j}^{{\left( {3 - j} \right)}} } \right) \cong \Updelta {\text{G}}^\circ \left( {{\text{M}}^{n + } } \right) - \Updelta {\text{G}}^\circ \left( {{\text{M}}\left( {\text{OH}} \right)_{j}^{{\left( {n - j} \right)}} } \right) $$ The correlation at higher temperatures is a result of a similar relationship between the enthalpies of the free ions and complexes $$ \Updelta {\text{H}}^\circ \left( {{\text{Al}}^{3 + } } \right) - \Updelta {\text{H}}^\circ \left( {{\text{Al}}\left( {\text{OH}} \right)_{j}^{3 - j} } \right) \cong \Updelta {\text{H}}^\circ \left( {{\text{M}}^{n + } } \right) - \Updelta {\text{H}}^\circ \left( {{\text{M}}\left( {\text{OH}} \right)_{j}^{n - j} } \right) $$ The correlations at higher ionic strengths are the result of the ratio of the activity coefficients for Al(III) being almost equal to that of the metal. $$ \gamma \left( {{\text{M}}^{n + } } \right)/\gamma \left( {{\text{M}}\left( {\text{OH}} \right)_{j}^{n - j} } \right) \cong \gamma \left( {{\text{Al}}^{3 + } } \right)/\gamma \left( {{\text{Al}}\left( {\text{OH}} \right)_{j}^{3 - j} } \right) $$ The results of this study should be useful in examining the speciation of metals as a function of pH in natural waters (e.g. hydrothermal fresh waters and NaCl brines).