The influence of the Jahn–Teller effect at Fe<Superscript>2+</Superscript> on the structure of chromite at high pressure

The crystal structure of chromite FeCr₂O₄ was investigated to 13.7 GPa and ambient temperature with single-crystal X-ray diffraction techniques. The unit-cell parameter decreases continuously from 8.3832 (5) to 8.2398 (11) Å up to 11.8 GPa. A fit to the Birch–Murnaghan equation of state (EoS) based on the P–V data gives: K ₀ = 209 (13) GPa, K′ = 4.0 (fixed), and V ₀ = 588 (1) ų. The FeO₄ tetrahedra and CrO₆ octahedra are compressed isotropically with pressure with their Fe–O and Cr–O bond distances decreasing from 1.996 (6) to 1.949 (7) Å and from 1.997 (3) to 1.969 (7) Å, respectively. The tetrahedral site occupied by the Fe²⁺ cation is more compressible than the octahedral site occupied by the Cr³⁺ cation. The resulting EoS parameters for the tetrahedral and the octahedral sites are K ₀ = 147 (9) GPa, K′ = 4.0 (fixed), V ₀ = 4.07 (1) ų and K ₀ = 275 (24) GPa, K′ = 4.0 (fixed), V ₀ = 10.42 (2) ų, respectively. A discontinuous volume change is observed between 11.8 and 12.6 GPa. This change indicates a phase transition from a cubic (space group Fd-[`3]{\overline{3}} m) to a tetragonal structure (space group I4₁ /amd). At the phase transition boundary, the two Cr–O bonds parallel to the c-axis shorten from 1.969 (7) to 1.922 (17) Å and the other four Cr–O bonds parallel to the ab plane elongate from 1.969 (7) to 1.987 (9) Å. This anisotropic deformation of the octahedra leads to tetragonal compression of the unit cell along the c-axis. The angular distortion in the octahedron decreases continuously up to 13.7 GPa, whereas the distortion in the tetrahedron rises dramatically after the phase transition. At the pressure of the phase transition, the tetrahedral bond angles along the c-axis direction of the unit cell begin decreasing from 109.5° to 106.6 (7)°, which generates a “stretched” tetrahedral geometry. It is proposed that the Jahn–Teller effect at the tetrahedrally coordinated Fe²⁺ cation becomes active with compression and gives rise to the tetrahedral angular distortion, which in turn induces the cubic-to-tetragonal transition. A qualitative molecular orbital model is proposed to explain the origin and nature of the Jahn–Teller effect observed in this structure and its role in the pressure-induced phase transition.     

Elasticity and equation of state of Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript>

A single crystal X-ray diffraction study on lithium tetraborate Li₂B₄O₇ (diomignite, space group I4₁ cd) has been performed under pressure up to 8.3 GPa. No phase transitions were found in the pressure range investigated, and hence the pressure evolution of the unit-cell volume of the I4₁ cd structure has been described using a third-order Birch–Murnaghan equation of state (BM-EoS) with the following parameters: V ₀  = 923.21(6) ų, K ₀  = 45.6(6) GPa, and K′ = 7.3(3). A linearized BM-EoS was fitted to the axial compressibilities resulting in the following parameters a ₀  = 9.4747(3) Å, K _0a  = 73.3(9) GPa, K′ _a  = 5.1(3) and c ₀  = 10.2838(4) Å, K _0c  = 24.6(3) GPa, K′ _c  = 7.5(2) for the a and c axes, respectively. The elastic anisotropy of Li₂B₄O₇ is very large with the zero-pressure compressibility ratio β _0c /β _0a  = 3.0(1). The large elastic anisotropy is consistent with the crystal structure: A three-dimensional arrangement of relatively rigid tetraborate groups [B₄O₇]²⁻ forms channels occupied by lithium along the polar c–axis, and hence compression along the c axis requires the shrinkage of the lithium channels, whereas compression in the a direction depends mainly on the contraction of the most rigid [B₄O₇]²⁻ units. Finally, the isothermal bulk modulus obtained in this work is in general agreement with that derived from ultrasonic (Adachi et al. in Proceedings-IEEE Ultrasonic Symposium, 228–232, 1985; Shorrocks et al. in Proceedings-IEEE Ultrasonic Symposium, 337–340, 1981) and Brillouin scattering measurements (Takagi et al. in Ferroelectrics, 137:337–342, 1992).     

Infrared spectroscopic characterization of dehydration and accompanying phase transition behaviors in NAT-topology zeolites

Relative humidity ( P_{\textH 2 \textO} P_{{{\text{H}}_{ 2} {\text{O}}}} , partial pressure of water)-dependent dehydration and accompanying phase transitions in NAT-topology zeolites (natrolite, scolecite, and mesolite) were studied under controlled temperature and known P_{\textH 2 \textO} P_{{{\text{H}}_{ 2} {\text{O}}}} conditions by in situ diffuse-reflectance infrared Fourier transform spectroscopy and parallel X-ray powder diffraction. Dehydration was characterized by the disappearance of internal H₂O vibrational modes. The loss of H₂O molecules caused a sequence of structural transitions in which the host framework transformation path was coupled primarily via the thermal motion of guest Na⁺/Ca²⁺ cations and H₂O molecules. The observation of different interactions of H₂O molecules and Na⁺/Ca²⁺ cations with host aluminosilicate frameworks under high- and low- P_{\textH 2 \textO} P_{{{\text{H}}_{ 2} {\text{O}}}} conditions indicated the development of different local strain fields, arising from cation–H₂O interactions in NAT-type channels. These strain fields influence the Si–O/Al–O bond strength and tilting angles within and between tetrahedra as the dehydration temperature is approached. The newly observed infrared bands (at 2,139 cm⁻¹ in natrolite, 2,276 cm⁻¹ in scolecite, and 2,176 and 2,259 cm⁻¹ in mesolite) result from strong cation–H₂O–Al–Si framework interactions in NAT-type channels, and these bands can be used to evaluate the energetic evolution of Na⁺/Ca²⁺ cations before and after phase transitions, especially for scolecite and mesolite. The 2,176 and 2,259 cm⁻¹ absorption bands in mesolite also appear to be related to Na⁺/Ca²⁺ order–disorder that occur when mesolite loses its Ow4 H₂O molecules.     

Behavior of epidote at high pressure and high temperature: a powder diffraction study up to 10 GPa and 1,200 K

The thermo-elastic behavior of a natural epidote [Ca_1.925 Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH)] has been investigated up to 1,200 K (at 0.0001 GPa) and 10 GPa (at 298 K) by means of in situ synchrotron powder diffraction. No phase transition has been observed within the temperature and pressure range investigated. P–V data fitted with a third-order Birch–Murnaghan equation of state (BM-EoS) give V ₀ = 458.8(1)ų, K _T0 = 111(3) GPa, and K′ = 7.6(7). The confidence ellipse from the variance–covariance matrix of K _T0 and K′ from the least-square procedure is strongly elongated with negative slope. The evolution of the “Eulerian finite strain” vs “normalized stress” yields Fe(0) = 114(1) GPa as intercept values, and the slope of the regression line gives K′ = 7.0(4). The evolution of the lattice parameters with pressure is slightly anisotropic. The elastic parameters calculated with a linearized BM-EoS are: a ₀ = 8.8877(7) Å, K _T0(a) = 117(2) GPa, and K′(a) = 3.7(4) for the a-axis; b ₀ = 5.6271(7) Å, K _T0(b) = 126(3) GPa, and K′(b) = 12(1) for the b-axis; and c ₀ = 10.1527(7) Å, K _T0(c) = 90(1) GPa, and K’(c) = 8.1(4) for the c-axis [K _T0(a):K _T0(b):K _T0(c) = 1.30:1.40:1]. The β angle decreases with pressure, β_P(°) = β_P0 −0.0286(9)P +0.00134(9)P ² (P in GPa). The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α₀ + α₁ T ^−1/2. The refined parameters for epidote are: α₀ = 5.1(2) × 10⁻⁵ K⁻¹ and α₁ = −5.1(6) × 10⁻⁴ K^1/2 for the unit-cell volume, α₀(a) = 1.21(7) × 10⁻⁵ K⁻¹ and α₁(a) = −1.2(2) × 10⁻⁴ K^1/2 for the a-axis, α₀(b) = 1.88(7) × 10⁻⁵ K⁻¹ and α₁(b) = −1.7(2) × 10⁻⁴ K^1/2 for the b-axis, and α₀(c) = 2.14(9) × 10⁻⁵ K⁻¹ and α₁(c) = −2.0(2) × 10⁻⁴ K^1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α₀(a): α₀(b): α₀(c) = 1 : 1.55 : 1.77. The β angle increases continuously with T, with β_T(°) = β_T0 + 2.5(1) × 10⁻⁴ T + 1.3(7) × 10⁻⁸ T ². A comparison between the thermo-elastic parameters of epidote and clinozoisite is carried out.     

Solute dynamics of meltwater of Gangotri glacier,Garhwal Himalaya,India

The present study investigates solute dynamics of meltwater of Gangotri glacier system in terms of association of different chemical compounds with the geology of the area. In the meltwater, the presence of cations varied as c(Mg²⁺) > c(Ca²⁺) > c(Na⁺) > c(K⁺), while order of concentration of anions has been c(HCO₃ ⁻) > c(SO₄ ²⁻) > c(Cl⁻) > c(NO₃ ⁻) in years 2003 and 2004. The magnesium and calcium are found as the dominant cations along with bicarbonate and sulphate as dominant anions. The high ratios of c(Ca²⁺ + Mg²⁺)/total cations and c(Ca²⁺ + Mg²⁺)/c(Na⁺ + K⁺) indicate that the meltwater chemistry of the Gangotri glacier system catchment is mostly controlled by carbonate weathering. Attempts are made to develop rating curves for discharge and different cations. Sporadic rise in discharge without corresponding rise in concentration of most of cations is responsible for their loose correlation in a compound valley glacier like Gangotri glacier.     

Trace element partitioning between orthopyroxene and anhydrous silicate melt on the lherzolite solidus from 1.1 to 3.2 GPa and 1,230 to 1,535°C in the model system Na<Subscript>2</Subscript>O–CaO–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>

We determined experimentally the Nernst distribution coefficient between orthopyroxene and anhydrous silicate melt for trace elements i in the system Na₂O–CaO–MgO–Al₂O₃–SiO₂ (NCMAS) along the dry model lherzolite solidus from 1.1 GPa/1,230°C up to 3.2 GPa/1,535°C in a piston cylinder apparatus. Major and trace element composition of melt and orthopyroxene were determined with a combination of electron microprobe and ion probe analyses. We provide partitioning data for trace elements Li, Be, B, K, Sc, Ti, V, Cr, Co, Ni, Rb, Sr, Y, Zr, Nb, Cs, Ba, La, Ce, Sm, Nd, Yb, Lu, Hf, Ta, Pb, U, and Th. The melts were chosen to be boninitic at 1.1 and 2.0 GPa, picritic at 2.3 GPa and komatiitic at 2.7 and 3.2 GPa. Orthopyroxene is Tschermakitic with 8 mol% Mg-Tschermaks MgAl[AlSiO₆] at 1.1 GPa while at higher pressure it has 18–20 mol%. The rare earth elements show a continuous, significant increase in compatibility with decreasing ionic radius from D _La^opx−melt ∼ 0.0008 to D _Lu^opx−melt ∼ 0.15. For the high-field-strength elements compatibility increases from D _Th^opx−melt ∼ 0.001 through D _Nb^opx−melt ∼ 0.0015, D _U^opx−melt ∼ 0.002, D _Ta^opx−melt ∼ 0.005, D _Zr^opx−melt ∼ 0.02 and D _Hf^opx−melt ∼ 0.04 to D _Ti^opx−melt ∼ 0.14. From mathematical and graphical fits we determined best-fit values for D ₀^M1, D ₀^M2, r ₀^M1, r ₀^M2, E ₀^M1, and E ₀^M2 for the two different M sites in orthopyroxene according to the lattice strain model and calculated the intracrystalline distribution between M1 and M2. Our data indicate extreme intracrystalline fractionation for most elements in orthopyroxene; for the divalent cations D _i ^M2−M1 varies by three orders of magnitude between D _Co^M2−M1 = 0.00098–0.00919 and D _Ba^M2−M1 = 2.3–28. Trivalent cations Al and Cr almost exclusively substitute on M1 while the other trivalent cations substitute on M2; D _La^M2−M1 reaches extreme values between 6.5 × 10⁷ and 1.4 × 10¹⁶. Tetravalent cations Ti, Hf, and Zr almost exclusively substitute on M1 while U and Th exclusively substitute on M2. Our new comprehensive data set can be used for polybaric-polythermal melting models along the Earth’s mantle solidus. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthetic lead bromapatite: X-ray structure at ambient pressure and compressibility up to about 20 GPa

Lead bromapatite [Pb₁₀(PO₄)₆Br₂] has been synthesized via solid-state reaction at pressures up to 1.0 GPa, and its structure determined by single-crystal X-ray diffraction at ambient temperature and pressure. The large bromide anion is accommodated in the c-axis channel by lateral displacements of structural elements, particularly of Pb2 cations and PO₄ tetrahedra. The compressibility of bromapatite was also investigated up to about 20.7 GPa at ambient temperature, using a diamond-anvil cell and synchrotron X-ray radiation. The compressibility of lead bromapatite is significantly different from that of lead fluorapatite. The pressure–volume data of lead bromapatite (P < 10 GPa) fitted to the third-order Birch-Murnaghan equation yield an isothermal bulk modulus (K _T ) of 49.8(16) GPa and first pressure derivative (K_T^￠ K_{T}^{\prime } ) of 10.1(10). If K_T^￠ K_{T}^{\prime } is fixed at 4, the derived K _T is 60.8(11) GPa. The relative difference of the bulk moduli of these two lead apatites is thus about 12%, which is about two times the relative difference of the bulk moduli (~5%) of the calcium apatites fluorapatite [Ca₁₀(PO₄)₆F₂]_, chlorapatite [Ca₁₀(PO₄)₆Cl₂] and hydroxylapatite [Ca₁₀(PO₄)₆(OH)₂]. Another interesting feature apparently related to the replacement of F by Br in lead apatite is the switch in the principle axes of the strain ellipsoid: the c-axis is less compressible than the a-axis in lead bromapatite but more compressible in lead fluorapatite.     

(Na,Ca)(Ti3+,Mg)Si2O6-clinopyroxenes at high pressure: influence of cation substitution on elastic behavior and phase transition

A compressional study of (Na,Ca)(Ti³⁺,Mg)Si₂O₆-clinopyroxenes was carried out at high pressures between 10⁻⁴ and 10.2 GPa using in situ single-crystal X-ray diffraction, Raman spectroscopy and optical absorption spectroscopy. Compressional discontinuities accompanied by structural changes, in particular, the appearance of two distinct Ti³⁺–Ti³⁺ distances within the octahedral chains at 4.37 GPa, provide evidence for the occurrence of a phase transition in NaTi³⁺Si₂O₆. Equation-of-state parameters are K ₀ = 115.9(7) GPa with K′ = −0.9(3) and K ₀ = 102.7(8) GPa with K′ = 4.08(5) for the low- and high-pressure range, respectively. The transition involves a C2/c–P [`1] \overline{1} symmetry change, which can be confirmed by the occurrence of new modes in Raman spectra. Since no significant discontinuity in the evolution of the unit-cell volume with pressure has been observed, the transition appears to be second-order in character. The influence of the coupled substitution Na⁺Ti³⁺↔Ca²⁺Mg²⁺ on the static compression behavior and the structural stability has been investigated using a sample of the intermediate composition (Na_0.54Ca_0.46)(Mg_0.46Ti_0.54)Si₂O₆. No evidence for a deviation from continuous compression behavior has been found, neither in lattice parameter nor in structural data and the fit of a third-order Birch–Murnaghan equation-of-state to the pressure–volume data yields a bulk modulus of K ₀ = 109.1(5) GPa and K′ = 5.02(13). Raman and polarized absorption spectra have been compared to NaTiSi₂O₆ and reveal major similarities. The main driving force for the phase transition in NaTi³⁺Si₂O₆ is the localization of the Ti³⁺ d-electron and the accompanying distortion, which is suppressed in the (Na,Ca)(Ti³⁺,Mg)Si₂O₆-clinopyroxene.     

Optical spectroscopic study of synthetic NaScSi<Subscript>2</Subscript>O<Subscript>6</Subscript>–CaNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxenes at normal and high pressures

Six synthetic NaScSi₂O₆–CaNiSi₂O₆ pyroxenes were studied by optical absorption spectroscopy. Five of them of intermediate (Na_1−x , Ca _x )(Sc_1−x , Ni _x )Si₂O₆ compositions show spectra typical of Ni²⁺ in octahedral coordination, more precise Ni²⁺ at the M1 site of the pyroxene structure. The common feature of all spectra is three broad absorption bands with maxima around 8,000, 13,000 and 24,000 cm⁻¹ assigned to ³ A _2g → ³ T _2g, ³ A _2g → ³ T _1g and →³ T _1g (³ P) electronic spin-allowed transitions of ^VINi²⁺. A weak narrow peak at ∼14,400 cm⁻¹ is assigned to the spin-forbidden ³ A _2g → ¹ T _2g (¹ D) transition of Ni²⁺. Under pressure the spin-allowed bands shift to higher energies and change in intensity. The octahedral compression modulus, calculated from the shift of the ³ A _2g → ³ T _2g band in the (Na_0.7Ca_0.3)(Sc_0.7Ni_0.3)Si₂O₆ pyroxene is evaluated as 85±20 GPa. The Racah parameter B of Ni²⁺(M1) is found gradually changing from ∼919 cm⁻¹ at ambient pressure to ∼890 cm⁻¹ at 6.18 GPa. The Ni end-member pyroxene [(Ca_0.93 Ni_0.07)NiSi₂O₆] has a spectrum different from all others. In addition to the above mentioned bands of Ni²⁺(M1) it displays several new relatively intense and broad extra bands, which were attributed to electronic transitions of Ni²⁺ at the M2 site. In difference to CaO₈ polyhedron geometry of an eightfold coordination, Ni²⁺(M2)O₈ polyhedra are assumed to be relatively large distorted octahedra. Due to different distortions and different compressibilities of the M1 and M2 sites the Ni²⁺(M1)- and Ni²⁺(M2)-bands display rather different pressure-induced behaviors, becoming more resolved in the high-pressure spectra than in that measured at atmospheric pressure. The octahedral compression modulus of Ni²⁺(M1) in this end-member pyroxene is evaluated as 150 ± 25 GPa, which is noticeably larger than in Ni_0.3 pyroxene. This is due to a smaller size and, thus, a stiffer character of Ni²⁺(M1)O₆ octahedron in the (Ca_0.93Ni_0.07)NiSi₂O₆ pyroxene compared to (Na_0.7Ca_0.3)(Sc_0.7Ni_0.3)Si₂O₆.

Ocean floor and subduction record in the Zermatt‐Saas rodingites,Valtournanche, Western Alps

Multiscale structural analysis and petrological modelling were used to establish the pressure‐peak mineral assemblages and pressure–temperature (P–T) conditions recorded in the rodingites of the upper Valtournanche portion of the oceanic Zermatt‐Saas Zone (ZSZ; Western Alps, northwestern Italy) during Alpine subduction. Rodingites occur in the form of deformed dykes and boudins within the hosting serpentinites. A field structural analysis showed that rodingites and serpentinites record four ductile deformation stages (D1–D4) during the Alpine cycle, with the first three stages associated with new foliations. The most pervasive fabric is S2 that is marked by mineral assemblages in serpentinite indicating pressure‐peak conditions, involving mostly serpentine, clinopyroxene, olivine, Ti‐clinohumite and chlorite. Three rodingite types can be defined: epidote‐bearing, garnet–chlorite–clinopyroxene‐bearing and vesuvianite‐bearing rodingite. In these, the pressure‐peak assemblages coeval with S2 development involve: (i) epidote_II + clinopyroxene_II + Mg‐chlorite_II + garnet_II ± rutile ± tremolite_I in the epidote‐bearing rodingite; (ii) Mg‐chlorite_II + garnet_II clinopyroxene_II ± vesuvianite_II ± ilmenite in the garnet–chlorite–clinopyroxene‐bearing rodingite; (iii) vesuvianite_II + Mg‐chlorite_II + clinopyroxene_II + garnet_II ± rutile ± epidote in vesuvianite‐bearing rodingite. Despite the pervasive structural reworking of the rodingites during Alpine subduction, the mineral relicts of the pre‐Alpine ocean floor history have been preserved and consist of clinopyroxene porphyroclasts (probable igneous relicts from gabbro dykes) and Cr‐rich garnet and vesuvianite (relicts of ocean floor metasomatism). Petrological modelling using thermocalc in the NCFMASHTO system was used to constrain the P–T conditions of the S2 mineral assemblages. The inferred values of 2.3–2.8 GPa and 580–660 °C are consistent with those obtained for syn‐S2 assemblages in the surrounding serpentinites. Multiscale structural analysis indicates that some ocean floor minerals remained stable under eclogite facies conditions suggesting that minerals such as vesuvianite, which is generally regarded as a low‐P phase, could also be stable in favourable chemical systems under high‐P/ultra‐high‐pressure (HP/UHP) conditions. Finally, the reconstructed P–T–d–t path indicates that the P/T ratio characterizing the D2 stage is consistent with cold subduction as estimated in this part of the Alps. The estimated pressure‐peak values are higher than those previously reported in this part of ZSZ, suggesting that the UHP units are larger and/or more abundant than those previously suggested.     

Synchrotron X-ray analysis of norbergite, Mg2.98Fe0.01Ti0.02Si0.99O4(OH0.31F1.69) structure at high pressure up to 8.2?GPa

The natural norbergite, Mg_2.98Fe_0.01Ti_0.02Si_0.99O₄(OH_0.31F_1.69) is examined by synchrotron X-ray diffraction analysis at pressures up to 8.2 GPa. The measured linear compressibilities of the crystallographic axes are β _a  = 2.18(4) × 10⁻³, β _b  = 2.93(7) × 10⁻³, and β _c  = 2.77(7) × 10⁻³ (GPa⁻¹), respectively and the calculated isothermal bulk modulus of the norbergite is K _T = 113(2) GPa based on the Birch–Murnaghan equation of state assuming a pressure derivative of K′ = 4. The crystal structures of norbergite are refined at room temperature and pressures of 4.7, 6.3, and 8.2 GPa, yielding R values for the structure refinements of 4.6, 5.3, and 5.3%, respectively. The bulk moduli of the polyhedral sites are 293(15) GPa for the tetrahedron, 106(5) GPa for the M2 octahedron, 113(2) GPa for the M3 octahedron, and 113(3) GPa for the total void space. The bulk modulus exhibits a good linear correlation with the filling factor for polyhedral sites in structures of the humite minerals and forsterite, reflecting the Si⁴⁺ + 4O²⁻ ⇔ □ + 4(OH, F)⁻ substitution in the humite minerals. Moreover, two simply linear trends were observed in the relationship between bulk modulus and packing index for natural minerals and dense hydrous magnesium silicate minerals. This relationship would reflect that the differences in compression mechanism were involved with hydrogen bonding in these minerals. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

New thermoelastic parameters of natural <Emphasis Type="Italic">C</Emphasis>2/<Emphasis Type="Italic">c</Emphasis> omphacite

The compressibility at room temperature and the thermal expansion at room pressure of two disordered crystals (space group C2/c) obtained by annealing a natural omphacite sample (space group P2/n) of composition close to Jd₅₆Di₄₄ and Jd₅₅Di₄₅, respectively, have been studied by single-crystal X-ray diffraction. Using a Birch–Murnaghan equation of state truncated at the third order [BM3-EoS], we have obtained the following coefficients: V ₀ = 421.04(7) Å³, K _T0 = 119(2) GPa, K′ = 5.7(6). A parameterized form of the BM3 EoS was used to determine the axial moduli of a, b and c. The anisotropy scheme is β _c  ≤ β _a  ≤ β _b , with an anisotropy ratio 1.05:1.00:1.07. A fitting of the lattice variation as a function of temperature, allowing for linear dependency of the thermal expansion coefficient on the temperature, yielded α_V(1bar,303K) = 2.64(2) × 10⁻⁵ K⁻¹ and an axial thermal expansion anisotropy of α _b  ≫ α _a  > α _c . Comparison of our results with available data on compressibility and thermal expansion shows that while a reasonable ideal behaviour can be proposed for the compressibility of clinopyroxenes in the jadeite–diopside binary join [K _T0 as a function of Jd molar %: K _T0 = 106(1) GPa + 0.28(2) × Jd_(mol%)], the available data have not sufficient quality to extract the behaviour of thermal expansion for the same binary join in terms of composition.     

Excess heat capacity and entropy of mixing along the chlorapatite–fluorapatite binary join

The heat capacity at constant pressure, C _p, of chlorapatite [Ca₅(PO₄)₃Cl – ClAp], and fluorapatite [Ca₅(PO₄)₃F – FAp], as well as of 12 compositions along the chlorapatite–fluorapatite join have been measured using relaxation calorimetry [heat capacity option of the physical properties measurement system (PPMS)] and differential scanning calorimetry (DSC) in the temperature range 5–764 K. The chlor-fluorapatites were synthesized at 1,375–1,220°C from Ca₃(PO₄)₂ using the CaF₂–CaCl₂ flux method. Most of the chlor-fluorapatite compositions could be measured directly as single crystals using the PPMS such that they were attached to the sample platform of the calorimeter by a crystal face. However, the crystals were too small for the crystal face to be polished. In such cases, where the sample coupling was not optimal, an empirical procedure was developed to smoothly connect the PPMS to the DSC heat capacities around ambient T. The heat capacity of the end-members above 298 K can be represented by the polynomials: C _p^ClAp = 613.21 − 2,313.90T ^−0.5 − 1.87964 × 10⁷ T ⁻² + 2.79925 × 10⁹ T ⁻³ and C _p^FAp = 681.24 − 4,621.73 × T ^−0.5 − 6.38134 × 10⁶ T ⁻² + 7.38088 × 10⁸ T ⁻³ (units, J mol⁻¹ K⁻¹). Their standard third-law entropy, derived from the low-temperature heat capacity measurements, is S° = 400.6 ± 1.6 J mol⁻¹ K⁻¹ for chlorapatite and S° = 383.2 ± 1.5 J mol⁻¹ K⁻¹ for fluorapatite. Positive excess heat capacities of mixing, ΔC _p^ex, occur in the chlorapatite–fluorapatite solid solution around 80 K (and to a lesser degree at 200 K) and are asymmetrically distributed over the join reaching a maximum of 1.3 ± 0.3 J mol⁻¹ K⁻¹ for F-rich compositions. They are significant at these conditions exceeding the 2σ-uncertainty of the data. The excess entropy of mixing, ΔS ^ex, at 298 K reaches positive values of 3–4 J mol⁻¹ K⁻¹ in the F-rich portion of the binary, is, however, not significantly different from zero across the join within its 2σ-uncertainty.     

Thermoelasticity and high-<Emphasis Type="Italic">T</Emphasis> behaviour of anthophyllite

The thermoelastic behaviour of anthophyllite has been determined for a natural crystal with crystal-chemical formula ^ANa_0.01 ^B(Mg_1.30Mn_0.57Ca_0.09Na_0.04) ^C(Mg_4.95Fe_0.02Al_0.03) ^T(Si_8.00)O₂₂ ^W(OH)₂ using single-crystal X-ray diffraction to 973 K. The best model for fitting the thermal expansion data is that of Berman (J Petrol 29:445–522, 1988) in which the coefficient of volume thermal expansion varies linearly with T as α _V,T  = a ₁ + 2a ₂ (T − T ₀): α₂₉₈ = a ₁ = 3.40(6) × 10⁻⁵ K⁻¹, a ₂ = 5.1(1.0) × 10⁻⁹ K⁻². The corresponding axial thermal expansion coefficients for this linear model are: α _a ,₂₉₈ = 1.21(2) × 10⁻⁵ K⁻¹, a _2,a  = 5.2(4) × 10⁻⁹ K⁻²; α _b ,₂₉₈ = 9.2(1) × 10⁻⁶ K⁻¹, a _2,b  = 7(2) × 10⁻¹⁰ K⁻². α _c ,₂₉₈ = 1.26(3) × 10⁻⁵ K⁻¹, a _2,c  = 1.3(6) × 10⁻⁹ K⁻². The thermoelastic behaviour of anthophyllite differs from that of most monoclinic (C2/m) amphiboles: (a) the ε ₁ − ε ₂ plane of the unit-strain ellipsoid, which is normal to b in anthophyllite but usually at a high angle to c in monoclinic amphiboles; (b) the strain components are ε ₁ ≫ ε ₂ > ε ₃ in anthophyllite, but ε ₁ ~ ε ₂ ≫ ε ₃ in monoclinic amphiboles. The strain behaviour of anthophyllite is similar to that of synthetic C2/m ^ANa ^B(LiMg) ^CMg₅ ^TSi₈ O₂₂ ^W(OH)₂, suggesting that high contents of small cations at the B-site may be primarily responsible for the much higher thermal expansion ⊥(100). Refined values for site-scattering at M4 decrease from 31.64 epfu at 298 K to 30.81 epfu at 973 K, which couples with similar increases of those of M1 and M2 sites. These changes in site scattering are interpreted in terms of Mn ↔ Mg exchange involving M1,2 ↔ M4, which was first detected at 673 K.     

A modern, guano-related occurrence of foggite, CaAl(PO4)(OH)2 · H2O and churchite-(Y), YPO4 · 2H2O in Cioclovina Cave, Romania

Summary This study reports foggite and churchite-(Y) from two spatially separate locations in the guano-related phosphate deposit from the Cioclovina Cave, Romania. Optical microscope observations, powder X-ray diffraction, electron microprobe analyses, and FTIR were used in the analysis of the two minerals. The chemical composition of foggite was determined to be Ca_0.925(Al_0.91Fe²⁺_0.016)_Σ0.926(P_0.991Si_0.043)_Σ1.034O_3.74(OH)_2.26 · H₂O and churchite-(Y) [(Y_0.830Dy_0.043Er_0.033Gd_0.029Yb_0.022)_Σ0.957Ca_0.009]P_1.023O_4.00 · 2H₂O. Chemical analyses of Cioclovina churchite-(Y) clearly revealed enrichment in lanthanides of even atomic number. The refined unit-cell parameters are for foggite (orthorhombic) a = 9.264(1) ?, b = 21.334(8) ?, c = 5.197(7) ?, and V = 1027.13(8) ?³ (Z = 8); for churchite-(Y) (monoclinic): a = 5.578(8) ?, b = 15.013(6) ?, c = 6.277(8) ?, β = 117.94(4)°, and V = 464.38(5) ?³ (Z = 4). FTIR spectrum of churchite-(Y) exhibits all the bands assigned to the vibrations of PO₄, OH, and water groups. Unlike other documented occurrences of foggite and churchite-(Y), in Cioclovina Cave, the occurrence of these minerals are related to a process that phosphatized subjacent limestone and various cave sediments (sand, clay, and limy mud) to form a complex phosphate assemblage. The minerals are presumably derived from phosphate-rich solutions that reacted with clay earth while moving downward through the sediments. Foggite was formed at the expense of the originally precipitated crandallite. Locally concentrated yttrium, REE, and dissolved phosphate are probably responsible for the precipitation of churchite-(Y). Present address: Department of Geology, University of South Florida, Tampa, FL, USA     

Water geochemical characteristic variations in and around a karst-dominated natural reserve area,southwestern China

This paper reports original data on the physical and chemical parameters of precipitation, river water and groundwater in and around the Longhushan Nature Reserve Area, located in southwestern China karst region, and provides a preliminary characterization of the hydrogeochemical process governing the natural water evolution in this area. The rainfall and river water mainly pertain to the HCO₃ ⁻–Ca²⁺ type and groundwater mainly pertain to the HCO₃ ⁻–Ca²⁺ + Mg²⁺ type. The HCO₃ ⁻ was the predominant anion and Ca²⁺ was the predominant cation in all waters, respectively. The Gibbs Boomerang Envelop model, the 1:1 relationship of Na⁺ plus K⁺ versus Cl⁻ as well as the 1:1 relationship of Ca²⁺ plus Mg²⁺ versus HCO₃ ⁻ all suggested geochemical weathering is the main controlling factor for the geochemical compositions of this natural water. In surface water, the Mg²⁺/Ca²⁺ ratios ranged from 0.32 to 0.42 and the Na⁺/Ca²⁺ varied between 0.04 and 0.05. In the groundwater, the Mg²⁺/Ca²⁺ ratios varied from 0.37 to 0.62 and were below the ideal ratio of 0.8. These ratios showed the presence of a dolomite source. Analysis of trace elements showed that As, B, Pb, Se, Sr, V and Zn elements were abundant in the natural water during summer in this region.     

Correlative and comparative characterization of main ion concentrations in laterite groundwater in semi-arid northern Burkina Faso

About 24 samples from hand-dug wells and boreholes were used to characterize concentrations of the main inorganic ions in a laterite environment under semi-arid climatic conditions in Tikaré, northern Burkina Faso. It was found that the most represented groundwater anion in groundwater was HCO₃ ⁻ with average levels of 49.1 mg/L in the dry season and 33.5 mg/L in the rainy season. The most represented cation was Ca²⁺ with mean concentrations of 13.7 and 9.5 mg/L, respectively. The main processes, which influence the concentrations of these ions, are evaporation (dry season), local enrichment of recharge water in some elements, ion exchange and fixation by clay minerals (in case of K⁺). The best correlations were found between Ca²⁺ and Mg²⁺ (r = 0.95), Cl⁻ and Na⁺ (r = 0.95), HCO₃ ⁻ and Mg²⁺ (r = 0.89), HCO₃ ⁻ and Ca²⁺ (r = 0.89), and between HCO₃ ⁻ and Na⁺ (r = 0.80). In general, the quality of the groundwater from the different wells sampled for this study was good enough to serve as drinking water. However, there were situations where the quality of water was polluted because of anthropogenic contaminants (mainly NO₃ ⁻, K⁺, Cl⁻) from septic tanks and manure pits located in the vicinity of some sampled wells. In addition, application of fertilizers also represents a potential anthropogenic contamination source with regard to SO₄ ²⁻, Ca²⁺, K⁺, Na⁺, and Mg²⁺. Considering the high concentrations of SO₄ ²⁻, Mg²⁺, Na⁺ and Ca²⁺ found in one borehole, the deeper, fractured aquifers were also likely to be enriched in these elements. In contrast, the shallow aquifers are likely to be contaminated with Cl⁻, NO₃ ⁻ and K⁺. Cl⁻ and K⁺ seem to be locally present in recharge water as shown by their relative higher mean concentrations in the rainy season samples.     

Experimental Study of Dissolution Rates of Fluorite in HCl–H2O Solutions

The experiments of the dissolution kinetics of fluorite were performed in aqueous HCl solutions over the temperature range of 25–100 °C using a flow-through experimental apparatus. With a constant input of aqueous HCl solution through the reactor, output concentrations of the dissolved species Ca, F, Cl vary with flow rate, as well as with the surface compositions. Measured output concentrations of dissolved species and the pH can be used to determine a rate law for fluorite dissolution. Fluorite dissolution rates are found to be pH dependent. Usually, dissolution rates of fluorite decreases with increasing dissolved Ca in the output solution at 25 and 100 °C. Dissolution rate can be expressed as

The thermoelastic behavior of clintonite up to 10?GPa and 1,000°C

The thermoelastic behavior of a natural clintonite-1M [with composition: Ca_1.01(Mg_2.29Al_0.59Fe_0.12)_Σ3.00(Si_1.20Al_2.80)_Σ4.00O₁₀(OH)₂] has been investigated up to 10 GPa (at room temperature) and up to 960°C (at room pressure) by means of in situ synchrotron single-crystal and powder diffraction, respectively. No evidence of phase transition has been observed within the pressure and temperature range investigated. P–V data fitted with an isothermal third-order Birch–Murnaghan equation of state (BM-EoS) give V ₀ = 457.1(2) ?³, K _T0 = 76(3)GPa, and K′ = 10.6(15). The evolution of the “Eulerian finite strain” versus “normalized stress” shows a linear positive trend. The linear regression yields Fe(0) = 76(3) GPa as intercept value, and the slope of the regression line leads to a K′ value of 10.6(8). The evolution of the lattice parameters with pressure is significantly anisotropic [β(a) = 1/3K _T0(a) = 0.0023(1) GPa⁻¹; β(b) = 1/3K _T0(b) = 0.0018(1) GPa⁻¹; β(c) = 1/K _T0(c) = 0.0072(3) GPa⁻¹]. The β-angle increases in response to the applied P, with: β_P = β₀ + 0.033(4)P (P in GPa). The structure refinements of clintonite up to 10.1 GPa show that, under hydrostatic pressure, the structure rearranges by compressing mainly isotropically the inter-layer Ca-polyhedron. The bulk modulus of the Ca-polyhedron, described using a second-order BM-EoS, is K _T0(Ca-polyhedron) = 41(2) GPa. The compression of the bond distances between calcium and the basal oxygens of the tetrahedral sheet leads, in turn, to an increase in the ditrigonal distortion of the tetrahedral ring, with ∂α/∂P ≈ 0.1°/GPa within the P-range investigated. The Mg-rich octahedra appear to compress in response to the applied pressure, whereas the tetrahedron appears to behave as a rigid unit. The evolution of axial and volume thermal expansion coefficient α with temperature was described by the polynomial α(T) = α₀ + α₁ T ^−1/2. The refined parameters for clintonite are as follows: α₀ = 2.78(4) 10⁻⁵°C⁻¹ and α₁ = −4.4(6) 10⁻⁵°C^1/2 for the unit-cell volume; α₀(a) = 1.01(2) 10⁻⁵°C⁻¹ and α₁(a) = −1.8(3) 10⁻⁵°C^1/2 for the a-axis; α₀(b) = 1.07(1) 10⁻⁵°C⁻¹ and α₁(b) = −2.3(2) 10⁻⁵°C^1/2 for the b-axis; and α₀(c) = 0.64(2) 10⁻⁵°C⁻¹ and α₁(c) = −7.3(30) 10⁻⁶°C^1/2for the c-axis. The β-angle appears to be almost constant within the given T-range. No structure collapsing in response to the T-induced dehydroxylation was found up to 960°C. The HP- and HT-data of this study show that in clintonite, the most and the less expandable directions do not correspond to the most and the less compressible directions, respectively. A comparison between the thermoelastic parameters of clintonite and those of true micas was carried out.     

A theoretical investigation of the relative stabilities of Fe-free clinozoisite and orthozoisite

 The relative stabilities of orthozoisite, Ca₂Al₃[O|OH|Si₂O₇|SiO₄], space group Pnma, and the monoclinic polymorph, clinozoisite, space group P2₁/m, have been investigated using calculations based on density functional theory. It is found that orthozoisite is more stable than clinozoisite by about 1 kJ mol⁻¹ at zero pressure in the athermal limit. The bulk moduli of the two polymorphs have been calculated to be B_ortho=117.5(1.7) GPa and B_clino=136(4) GPa. Received: 20 March 2000 / Accepted: 26 February 2001