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

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

Thermal equation of state of natural tourmaline at high pressure and temperature

Synchrotron-based in situ angle-dispersive X-ray diffraction experiments were conducted on a natural uvite-dominated tourmaline sample by using an external-heating diamond anvil cell at simultaneously high pressures and temperatures up to 18 GPa and 723 K, respectively. The angle-dispersive X-ray diffraction data reveal no indication of a structural phase transition over the P–T range of the current experiment in this study. The pressure–volume–temperature data were fitted by the high-temperature Birch–Murnaghan equation of state. Isothermal bulk modulus of K ₀ = 96.6 (9) GPa, pressure derivative of the bulk modulus of \(K_{0}^{\prime } = 12.5 \;(4)\), thermal expansion coefficient of α ₀ = 4.39 (27) × 10^?5 K^?1 and temperature derivative of the bulk modulus (?K/?T) _P  = ?0.009 (6) GPa K^?1 were obtained. The axial thermoelastic properties were also obtained with K _a0 = 139 (2) GPa, \(K_{a0}^{\prime }\) = 11.5 (7) and α _a0 = 1.00 (11) × 10^?5 K^?1 for the a-axis, and K _c0 = 59 (1) GPa, \(K_{c0}^{\prime }\) = 11.4 (5) and α _c0 = 2.41 (24) × 10^?5 K^?1 for the c-axis. Both of axial compression and thermal expansion exhibit large anisotropic behavior. Thermoelastic parameters of tourmaline in this study were also compared with that of the other two ring silicates of beryl and cordierite.     

Crystallochemical effects of heat treatment on Fe-dominant tourmalines from Dolní Bory (Czech Republic) and Vlachovo (Slovakia)

Heat treatment was performed on selected Fe-dominant tourmalines to establish the nature of any change in optical properties. Two tourmaline samples from Dolní Bory, Czech Republic (TDB) and Vlachovo, Slovakia (TVL) were heated at 450, 700 and 900°C at 0.1 mPa and ambient oxidation conditions for 8 h. EMPA study shows that tourmaline from Vlachovo has schorlitic composition and tourmaline from Dolní Bory is alkali-depleted schorl to foitite. Although the black colour remained unchanged after heating at 450°C, it changed to brown at 700°C and reddish brown at 900°C. No significant changes of chemical composition were observed during heating. X-ray diffraction, infrared and Mössbauer study showed negligible oxidation of tourmaline heated at 450°C, but a significant change in iron valency state and deprotonization at 700°C. The oxidation of Fe is the main cause of tourmaline colour change, and the substitution vector for oxidation of Fe is Fe³⁺OFe _?1 ²⁺ (OH)_?1. The predicted deprotonization of OH was confirmed by infrared spectroscopy, which documented a decrease in OH groups in both samples, mainly at the V site. The oxidation of Fe is mostly significant in the Y site as documented on the compression of the Y-site octahedra and subsequent decrease in the a lattice parameter. This feature is consistent with lattice dimensions in the transition from schorl and foitite dimensions to those consistent with fluor-buergerite. The Z-site octahedra did not compressed and were not affected by heating-induced Fe oxidation, which indicates only negligible content of ^Z Fe²⁺ in original samples. After heating at 900°C, the tourmaline structure collapsed likely due to the thermally induced weakening of bonds in Y and Z octahedra, which results in amorphization of tourmaline. Subsequently, breakdown products including Fe-oxides and mullite replaced alkali-depleted amorphized tourmaline.     

Spectroscopic studies of synthetic and natural ringwoodite, γ-(Mg,Fe)<Subscript>2</Subscript>SiO<Subscript>4</Subscript>

Synthetic ringwoodite γ-(Mg_1?x Fe _x )₂SiO₄ of 0.4 ≤ x ≤ 1.0 compositions and variously colored micro-grains of natural ringwoodite in shock metamorphism veins of thin sections of two S6-type chondrites were studied by means of microprobe analysis, TEM and optical absorption spectroscopy. Three synthetic samples were studied in addition with Mössbauer spectroscopy. The Mössbauer spectra consist of two doublets caused by ^VIFe²⁺ and ^VIFe³⁺, with IS and QS parameters close to those established elsewhere (e.g., O’Neill et al. in Am Mineral 78:456–460, 1993). The Fe³⁺/Fe_total ratio evaluated by curve resolution of the spectra, ranges from 0.04 to 0.1. Optical absorption spectra of all synthetic samples studied are qualitatively very similar as they are directly related to the iron content. They differ mostly in the intensity of the observed absorption features. The spectra consist of a very strong high-energy absorption edge and a series of absorption bands of different width and intensity. The three strongest and broadest absorptions of them are attributed to splitting of electronic spin-allowed ⁵ T _2g → ⁵ E _g transitions of ^VIFe²⁺ and intervalence charge-transfer (IVCT) transition between ferrous and ferric ions in adjacent octahedral sites of the ringwoodite structure. The spin-allowed bands at ca. 8,000 and 11,500 cm^?1 weakly depend on temperature, whilst the Fe²⁺/Fe³⁺ IVCT band at ~16,400 cm^?1 displays very strong temperature dependence: i.e., with increasing temperature it decreases and practically disappears at about 497 K, a behavior typical for bands of this type. With increasing pressure the absorption edge shifts to lower energies while the spin-allowed bands shift to higher energy and strongly decreases in intensity. The IVCT band also strongly weakens and vanishes at about 9 GPa. We assigned this effect to pressure-induced reduction of Fe³⁺ in ringwoodite. By analogy with synthetic samples three broad bands in spectra of natural (meteoritic) blue ringwoodite are assigned to electronic spin-allowed transitions of ^VIFe²⁺ (the bands at ~8,600 and ~12,700 cm^?1) and Fe²⁺/Fe³⁺ IVCT transition (~18,100 cm^?1), respectively. Spectra of colorless ringwoodite of the same composition consist of a single broad band at ca. 12,000 cm^?1. It is assumed that such ringwoodite grains are inverse (Fe, Mg)₂SiO₄-spinels and that the single band is caused by the split spin-allowed ⁵ E → ⁵ T ₂ transition of ^IVFe²⁺. Ringwoodite of intermediate color variations between dark-blue and colorless are assumed to be partly inversed ringwoodite. No glassy material between the grain boundaries in the natural colored ringwoodite aggregates was found in our samples and disprove the cause of the coloration to be due to light scattering effect (Lingemann and Stöffler in Lunar Planet Sci 29(1308), 1998).     

Behavior of 10-Å phase at low temperatures

The thermal evolution of 10-Å phase Mg₃Si₄O₁₀(OH)₂·H₂O, a phyllosilicate which may have an important role in the storage/release of water in subducting slabs, was studied by X-ray single-crystal diffraction in the temperature range 116–293 K. The lattice parameters were measured at several intervals both on cooling and heating. The structural model was refined with intensity data collected at 116 K and compared to the model refined at room temperature. As expected for a layer silicate on cooling in this temperature range, the a and b lattice parameters undergo a small linear decrease, α _a  = 1.7(4) 10^?6 K^?1 and α _b  = 1.9(4) 10^?6 K^?1, where α is the linear thermal expansion coefficient. The greater variation is along the c axis and can be modeled with the second order polynomial c _T  = c ₂₉₃(1 + 6.7(4)10^?5 K^?1ΔT + 9.5(2.5)10^?8 K^?2(ΔT)²) where ΔT = T ? 293 K; the monoclinic angle β slightly increased. The cell volume thermal expansion can be modeled with the polynomial V _T  = V ₂₉₃ (1 + 8.0 10^?5 K^?1 ΔT + 1.4 10^?7 K^?2 (ΔT)²) where ΔT = T ? 293 is in K and V in ų. These variations were similar to those expected for a pressure increase, indicating that T and P effects are approximately inverse. The least-squares refinement with intensity data measured at 116 K shows that the volume of the SiO₄ tetrahedra does not change significantly, whereas the volume of the Mg octahedra slightly decreases. To adjust for the increased misfit between the tetrahedral and octahedral sheets, the tetrahedral rotation angle α changes from 0.58° to 1.38°, increasing the ditrigonalization of the silicate sheet. This deformation has implications on the H-bonds between the water molecule and the basal oxygen atoms. Furthermore, the highly anisotropic thermal ellipsoid of the H₂O oxygen indicates positional disorder, similar to the disorder observed at room temperature. The low-temperature results support the hypothesis that the disorder is static. It can be modeled with a splitting of the interlayer oxygen site with a statistical distribution of the H₂O molecules into two positions, 0.6 Å apart. The resulting shortest O_bas–O_W distances are 2.97 Å, with a significant shortening with respect to the value at room temperature. The low-temperature behavior of the H-bond system is consistent with that hypothesized at high pressure on the basis of the Raman spectra evolution with P.     

Droninoite,Ni<Subscript>3</Subscript>Fe<Superscript>3+</Superscript>Cl(OH)<Subscript>8</Subscript> · 2H<Subscript>2</Subscript>O,a new hydrotalcite-group mineral species from the weathered Dronino meteorite

A new mineral, droninoite, was found in a fragment of a weathered Dronino iron meteorite (which fell near the village of Dronino, Kasimov district, Ryazan oblast, Russia) as dark green to brown fine-grained (the size of single grains is not larger than 1 μm) segregations up to 0.15 × 1 × 1 mm in size associated with taenite, violarite, troilite, chromite, goethite, lepidocrocite, nickelbischofite, and amorphous Fe³⁺ hydroxides. The mineral was named after its type locality. Aggregates of droninoite are earthy and soft; the Mohs hardness is 1–1.5. The calculated density is 2.857 g/cm³. Under a microscope, droninoite is dark gray-green and nonpleochroic. The mean (cooperative for fine-grained aggregate) refractive index is 1.72(1). The IR spectrum indicates the absence of S O ₄ ^2? and C O ₃ ^2? anions. Chemical composition (electron microprobe, partition of total iron into Fe²⁺ and Fe³⁺ made on the basis of the ratio (Ni + Fe²⁺): Fe³⁺ = 3: 1; water is calculated from the difference) is as follows, wt %: 36.45 NiO, 12.15 FeO, 17.55 Fe₂O₃, 23.78 H₂O, 13.01 Cl, ?O=Cl₂ ?2.94, total is 100.00. The empirical formula (Z = 6) is Ni_2.16Fe _0.75 ²⁺ Fe _0.97 ³⁺ Cl_1.62(OH)_7.10 · 2.28H₂O. The simplified formula is Ni₃Fe³⁺Cl(OH)₈ · 2H₂O. Droninoite is trigonal, space group R \(\bar 3\) m, R3m, or R32; a = 6.206(2), c = 46.184(18) Å; V = 1540.4(8) ų. The strong reflections in the X-ray powder diffraction pattern [d, Å (I, %) (hkl)] are 7.76(100)(006), 3.88(40)(0.0.12), 2.64(25)(202, 024), 2.32(20)(0.2.10), 1.965(0.2.16). The holotype specimen is deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow, registration number 3676/1.     

Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.     

Crystal Chemistry of Pyroaurite from the Kovdor Pluton,Kola Peninsula,Russia, and the Långban Fe–Mn deposit,Värmland,Sweden

Pyroaurite [Mg₆Fe₂³⁺ (OH)₁₆][(CO₃)(H₂O)] from the Kovdor Pluton on the Kola Peninsula, Russia, and the Långban deposit in Filipstad, Värmland, Sweden were studied with single crystal and powder X-ray diffraction, an electron microprobe, and Raman spectroscopy. Both samples are rhombohedral, space group R3?m, a = 3.126(3), c = 23.52(2) Å (Kovdor), and a = 3.1007(9), c = 23.34(1) (Långban). The powder XRD revealed only the 3R polytype. The ratio of di- and trivalent cations M²⁺: M³⁺ was determined as ~3.1–3.2 (Kovdor) and ~3.0 (Långban). The Raman spectroscopy of the Kovdor sample verified hydroxyl groups and/or water molecules in the mineral (absorption bands in the region of 3600–3500 cm^–1) and carbonate groups (absorption bands in the region of 1346–1058 cm^–1). Based on the data obtained, the studied samples should be identified as pyroaurite-3R (hydrotalcite group).     

Electron paramagnetic resonance studies on clinochlore from Longitudinal Valley area,northeastern Taiwan

A natural sample of clinochlore from the Longitudinal Valley area of northeastern Taiwan has been characterized by using the powder X-ray diffraction (XRD), differential thermal analysis and electron paramagnetic resonance (EPR) spectroscopic techniques. The lattice parameters of the monoclinic (IIb) clinochlore with the composition (Mg_2.988 Al_1.196 Fe_1.6845 Mn_0.026)_5.8945 (Si_2.559 Al_1.441)₄ O₁₀ (OH)₈ have been calculated from the powder XRD data and are found to be a = 5.347 Å, b = 9.223 Å, c = 14.250 Å, β = 97.2° and Z = 2. The thermal behaviour of the sample showed the typical behaviour of clinochlore with a hydroxyl content of 12.5 wt%. The EPR spectrum at room temperature exhibits two resonance signals centred at g ≈ 2.0 and g ≈ 8.0. The signal at g ≈ 2.0 shows a six-line hyperfine structure which is a characteristic of Mn²⁺ ions in octahedral symmetry. The resonance signal at g ≈ 8.0 is a characteristic of Fe³⁺ ions. The EPR spectra have also been recorded at different temperatures (123–295 K). The population of spin levels (N) has been calculated for g ≈ 2.0 and g ≈ 8.0 resonance signals. It is observed that N increases with decreasing temperature. From EPR spectra, the spin-Hamiltonian parameters have been evaluated. The zero-field splitting parameter (D) is found to be temperature dependent. The peak-to-peak width of the g ≈ 8.0 resonance signal is found to increase with decrease in temperature.     

Fluid production rate during the regional metamorphism of a pelitic schist

Phase equilibria modeling of the pressure–temperature (P–T) path of regional metamorphism and associated fluid expulsion, combined with constraints on the timescale of garnet growth by Sm–Nd geochronology, elucidates the fluid production rate and fluid flux during Barrovian metamorphism of pelitic rocks from Townshend Dam, VT, USA. This modeling builds on a published companion study that utilized Sm–Nd geochronology of concentric growth zones in multiple garnet grains, to constrain the duration of garnet growth in a large sample of schist at Townshend Dam to 3.8?±?2.2 million years (Gatewood et al., Chem Geol 401:151–168, 2015). P–T pseudosections combined with observed mineral compositions constrain garnet growth conditions, and were utilized to construct P–T path-dependent thermodynamic forward models. These models determine that garnet growth was initiated at ~?0.6 GPa and ~?525 °C, with a roughly linear loading and heating P–T trajectory to >?0.8 GPa and ~?610 °C. Loading and heating rates of 2.4 km·Myear^?1 (with a range of 1.6 to 5.8 km·million year^?1) and 23 °C·million year^?1 (with a range of 14 to 54 °C·million year^?1), respectively, are consistent with model estimates and chronologic constraints for tectono-metamorphic rates during orogenesis. Phase equilibria modeling also constrains the amount of water release during garnet growth to be ~?0.7 wt% (or >?2 vol%), largely resulting from the complete consumption of chlorite. Coupling this estimate with calculated garnet growth durations provides a fluid production rate of 5.2 kg·m^?3·million year^?1 (with a range of 3.2 to 12.2 kg·m^?3·million year^?1) and when integrated over the overlying crustal column, a regional-scale fluid flux of 0.07–0.37 kg·m^?2·million year^?1. This range of values is consistent with those derived by numerical models and theory for regional-scale, pervasive fluid flow. This study signifies the first derivation of a fluid production rate and fluid flux in regional metamorphism using a direct chronology of water-producing (garnet-forming) reactions and can provide a framework for future studies on elucidating the nature and timescales of fluid release.     

Single-crystal X-ray diffraction and spectroscopic studies on humboldtine and lindbergite: weak Jahn–Teller effect of Fe<Superscript>2+</Superscript> ion

The single-crystal of humboldtine [Fe²⁺(C₂O₄) · 2H₂O] was first synthesized and the crystal structure has been refined. Single-crystal X-ray diffraction data were collected using an imaging-plate diffractometer system and graphite-monochromatized MoKα radiation. The crystal structure of humboldtine was refined to an agreement index (R1) of 3.22% calculated for 595 unique observed reflections. The mineral crystallizes in the monoclinic system, space group C2/c, with unit cell dimensions of a = 12.011 (11), b = 5.557 (5), c = 9.920 (9) Å, β = 128.53 (3)?, V = 518.0 (8) Å³, and Z = 4. In this crystal structure, the alternation of oxalate anions [(C₂O₄)^2?] and Fe²⁺ ions forms one-dimensional chain structure parallel to [010]; water molecules (H₂O)⁰ create hydrogen bonds to link the chains, where (H₂O)⁰ is essentially part of the crystal structure. The water molecules with the two lone electron pairs (LEPs) on their oxygen atom are tied obliquely to the chains, because the one lone electron pair is considered to participate in the chemical bonds with Fe²⁺ ions. Humboldtine including hydrogen bonds is isotypic with lindbergite [Mn²⁺(C₂O₄) · 2H₂O]. The donor–acceptor separations of the hydrogen bonds in humboldtine are slightly shorter than those in lindbergite, which suggests that the hydrogen bonds in the former are stronger than those in the latter. The infrared and Raman spectra of single-crystals of humboldtine and lindbergite confirmed the differences in hydrogen-bond geometry. In addition, Fe²⁺–O stretching band of humboldtine was split and broadened in the observed Raman spectrum, owing to the Jahn–Teller effect of Fe²⁺ ion. These interpretations were also discussed in terms of bond-valence theory.     

Crystal chemistry of natural and synthetic lead oxyhalides. Part I. Crystal structure of Pb<Subscript>13</Subscript>O<Subscript>10</Subscript>Cl<Subscript>6</Subscript>

Crystals of lead oxychloride Pb₁₃O₁₀Cl₆ have been synthesized on the basis of high-temperature solid-state reactions. The Pb₁₃O₁₀Cl₆ structure was studied using X-ray single-crystal diffraction analysis. The compound is monoclinic, and the space group is C2/c; the unit-cell dimensions are a = 16.1699(14), b = 7.0086(6), c = 23.578(2) Å, β = 97.75°, and V = 2647.6(4) ų. The structure has been solved by direct methods and refined to R ₁ = 0.0505 for 2671 observed unique reflections. The structure is a 3D framework consisting of OPb₄ tetrahedrons. Chlorine atoms are located in the framework channels. The structure contains seven symmetrically independent Pb atoms, which are coordinated by 2 to 4 O^2? and 2 to 4 Cl^? anions. The synthesized compound is compared with other natural and synthetic lead oxyhalides.     

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)°].     

CO<Subscript>2</Subscript> content of andesitic melts at graphite-saturated upper mantle conditions with implications for redox state of oceanic basalt source regions and remobilization of reduced carbon from subducted eclogite

We have performed experiments to determine the effects of pressure, temperature and oxygen fugacity on the CO₂ contents in nominally anhydrous andesitic melts at graphite saturation. The andesite composition was specifically chosen to match a low-degree partial melt composition that is generated from MORB-like eclogite in the convective, oceanic upper mantle. Experiments were performed at 1–3 GPa, 1375–1550?°C, and fO₂ of FMQ ?3.2 to FMQ ?2.3 and the resulting experimental glasses were analyzed for CO₂ and H₂O contents using FTIR and SIMS. Experimental results were used to develop a thermodynamic model to predict CO₂ content of nominally anhydrous andesitic melts at graphite saturation. Fitting of experimental data returned thermodynamic parameters for dissolution of CO₂ as molecular CO₂: ln(K ⁰) = ?21.79?±?0.04, ΔV ⁰?=?32.91?±?0.65 cm³mol^?1, ΔH ⁰?=?107?±?21 kJ mol^?1, and dissolution of CO₂ as CO₃ ^2?: ln(K ⁰ ) = ?21.38?±?0.08, ΔV ⁰?=?30.66?±?1.33 cm³ mol^?1, ΔH ⁰?=?42?±?37 kJ mol^?1, where K ⁰ is the equilibrium constant at some reference pressure and temperature, ΔV ⁰ is the volume change of reaction, and ΔH ⁰ is the enthalpy change of reaction. The thermodynamic model was used along with trace element partition coefficients to calculate the CO₂ contents and CO₂/Nb ratios resulting from the mixing of a depleted MORB and the partial melt of a graphite-saturated eclogite. Comparison with natural MORB and OIB data suggests that the CO₂ contents and CO₂/Nb ratios of CO₂-enriched oceanic basalts cannot be produced by mixing with partial melts of graphite-saturated eclogite. Instead, they must be produced by melting of a source containing carbonate. This result places a lower bound on the oxygen fugacity for the source region of these CO₂-enriched basalts, and suggests that fO₂ measurements made on cratonic xenoliths may not be applicable to the convecting upper mantle. CO₂-depleted basalts, on the other hand, are consistent with mixing between depleted MORB and partial melts of a graphite-saturated eclogite. Furthermore, calculations suggest that eclogite can remain saturated in graphite in the convecting upper mantle, acting as a reservoir for C.     

Chromium solubility in anhydrous Phase B

The crystal structure and chemical composition of a crystal of (Mg_14?x Cr _x )(Si_5?x Cr _x )O₂₄ (x ≈ 0.30) anhydrous Phase B (Anh-B) synthesized in the model system MgCr₂O₄–Mg₂SiO₄ at 12 GPa and 1600 °C have been investigated. The compound was found to be orthorhombic, space group Pmcb, with lattice parameters a = 5.900(1), b = 14.218(2), c = 10.029(2) Å, V = 841.3(2) Å³ and Z = 2. The structure was refined to R ₁ = 0.065 using 1492 independent reflections. Chromium was found to substitute for both Mg at the M3 site (with a mean bond distance of 2.145 Å) and Si at the octahedral Si1 site (mean bond distance: 1.856 Å), according to the reaction Mg²⁺ + Si⁴⁺ = 2Cr³⁺. Such substitutions cause a reduction in the volume of the M3 site and an increase in the volume of the Si-dominant octahedron with respect to the values typically observed for pure Anh-B and Fe²⁺-bearing Anh-B. Taking into account that Cr³⁺ is not expected to be Jahn–Teller active, it appears that both the Cr³⁺–for–Mg and Cr³⁺–for–Si substitutions in the Anh-B structure decrease the distortion of the octahedra. Electron microprobe analysis gave the Mg_13.66(8)Si_4.70(6)Cr_0.62(4)O₂₄ stoichiometry for the studied phase. The successful synthesis of this phase provides new information for the possible mineral assemblages occurring in the Earth’s deep upper mantle and shed new light on the so-called X discontinuity that has been observed at 275–345 km depth in several subcontinental and subduction zone environments.     

Numerical analysis under seismic loads of soils improvement with floating stone columns

Geotechnical Engineering has developed many methods for soil improvement so far. One of these methods is the stone column method. The structure of a stone column generally refers to partial change of suitable subsurface ground through a vertical column, poor stone layers which are completely pressed. In general terms, to improve bearing capacity of problematic soft and loose soil is implemented for the resolution of many problems such as consolidation and grounding problems, to ensure filling and splitting slope stability and liquefaction that results from a dynamic load such as earthquake. In this study, stone columns method is preferred as an improvement method, and especially load transfer mechanisms and bearing capacity of floating stone column are focused. The soil model, 32 m in width and 8 m in depth, used in this study is made through Plaxis 2D finite element program. The clay having 5° internal friction angle with different cohesion coefficients (c 10, c 15, c 20 kN/m²) are used in models. In addition, stone columns used for soil improvement are modeled at different internal friction angles (? 35°, ? 40°, ? 45°) and in different s/D ranges (s/D 2, s/D 3), stone column depths (B, 2B, 3B) and diameters (D 600 mm, D 800 mm, D 1000 mm). In the study, maximum acceleration (a _max = 1.785 m/s²) was used in order to determine the seismic coefficient used. In these soil models, as maximum acceleration, maximum east–west directional acceleration value of Van Muradiye earthquake that took place in October 23, 2011 was used. As a result, it was determined that the stone column increased the bearing capacity of the soil. In addition, it is observed that the bearing capacity of soft clay soil which has been improved through stone column with both static and earthquake load effect increases as a result of increase in the diameter and depth of the stone column and decreases as a result of the increase in the ranges of stone column. In the conducted study, the bearing capacity of the soil models, which were improved with stone column without earthquake force effect, was calculated as 1.01–3.5 times more on the average, compared to the bearing capacity of the soil models without stone column. On the other hand, the bearing capacity of the soil models with stone columns, which are under the effect of earthquake force, was calculated as 1.02–3.7 times more compared to the bearing capacity of the soil models without stone column.     

High-pressure displacive phase transition of a natural Mg-rich pigeonite

A high-pressure single-crystal X-ray diffraction study has been carried out on a P2₁/c natural Mg-rich pigeonite sample with composition ca. Wo₆En₇₆Fs₁₈ using a diamond anvil-cell. The unit-cell parameters were determined at 14 different pressures to 7.14 GPa. The sudden disappearance of the b-type reflections (h + k = odd) and a strong discontinuity (about 2.8%) in the unit-cell volume indicated a first-order P2₁/c–C2/c phase transition between 4.66 and 4.88 GPa. The P(V) data of the P2₁/c phase were fitted to 4.66 GPa by a third-order Birch–Murnaghan equation of state (BM3 EoS), whereas the limited number of experimental data collected within the C2/c phase between 4.88 and 7.14 GPa were fitted using the same equation of state but with K′ constrained to the value obtained for the P2₁/c fitting. The equation of state coefficients are V ₀ = 424.66(6) ų, K _T0 = 104(2) GPa and K′ = 8(1) for the P2₁/c phase, and V ₀ = 423.6(1) ų, K _T0 = 112.4(8) GPa, and K′ fixed to 8(1) for the C2/c phase. The axial moduli for a, b, and c for the P2₁/c phase were obtained using also a BM3-EoS, while for the C2/c phase only a linear calculation could be performed, and therefore the same approach was applied for comparison also to the P2₁/c phase. In general the C2/c phase exhibits axial compressibilities (β _c > β _a >> β _b) lower than those of the P2₁/c phase (β _b > β _c ≈ β _a; similar to those found in previous studies in clinopyroxenes and orthopyroxenes). The lower compressibility of the C2/c phase compared with that of the P2₁/c could be ascribed to the greater stiffness along the b direction. A previously published relationship between P _c and M2 average cation radius (i.r.) has been updated using all the literature data on P2₁/c clinopyroxene containing large cations at M2 site and our new data. The following weighted regression was obtained: P _c (GPa) = 26(4) ? 28(5) ×  i.r (Å), R ² = 0.97. This improved equation can be used to predict the critical pressure of natural P2₁/c clinopyroxene samples just knowing the composition at M2 site.     

The Influence of Benthic Macrofauna on the Erodibility of Intertidal Sediments with Varying mud Content in Three New Zealand Estuaries

Fine sediment inputs can alter estuarine ecosystem structure and function. However, natural variations in the processes that regulate sediment transport make it difficult to predict their fate. In this study, sediments were sampled at different times (2011–2012) from 45 points across intertidal sandflat transects in three New Zealand estuaries (Whitford, Whangamata, and Kawhia) encompassing a wide range in mud (≤63 μm) content (0–56 %) and macrofaunal community structure. Using a core-based erosion measurement device (EROMES), we calculated three distinct measures of sediment erosion potential: erosion threshold (? _c ; N m^?2), erosion rate (ER; g m^?2 s^?1), and change in erosion rate with increasing bed shear stress (m _e ; g N^?1 s^?1). Collectively, these measures characterized surface (? _c and ER) and sub-surface (m _e ) erosion. Benthic macrofauna were grouped by functional traits (size and motility) and data pooled across estuaries to determine relationships between abiotic (mud content, mean grain size) and biotic (benthic macrofauna, microbial biomass) variables and erosion measures. Results indicated that small bioturbating macrofauna (predominantly freely motile species <5 mm in size) destabilized surface sediments, explaining 23 % of the variation in ? _c (p ≤ 0.01) and 59 % of the variation in ER (p ≤ 0.01). Alternatively, mud content and mean grain size cumulatively explained 61 % of the variation in m _e (p ≤ 0.01), where increasing mud and grain size stabilized sub-surface sediments. These results highlight that the importance of biotic and abiotic predictors vary with erosion stage and that functional group classifications are a useful way to determine the impact of benthic macrofauna on sediment erodibility across communities with different species composition.     

Stability at high-pressure,elastic behaviour and pressure-induced structural evolution of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

The elastic and structural behaviour of the synthetic zeolite CsAlSi₅O₁₂ (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V ₀ = 1,155(4) ų, K _T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a ³, b ³, c ³) for the volume. The refined axial-EoS parameters are: a ₀ = 16.701(44) Å, K _T0a = 14(2) GPa (β_a = 0.024(3) GPa^?1), K′ _a = 6.2(8) for the a-axis; b ₀ = 13.778(20) Å, K _T0b = 21(3) GPa (β_b = 0.016(2) GPa^?1), K′ _b = 10(2) for the b-axis; c ₀ = 5.018(7) Å, K _T0c = 33(3) GPa (β_c = 0.010(1) GPa^?1), K′ _c = 3.2(8) for the c-axis (K _T0a:K _T0b:K _T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi₅O_12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi₅O₁₂ allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.