Solubility of platinum and palladium in silicate melts under high water pressure as a function of redox conditions

The solubility of platinum and palladium in a silicate melt of the composition Di ₅₅ An ₃₅ Ab ₁₀ was determined at 1200°C and 2 kbar pressure in the presence of H₂O-H₂ fluid at an oxygen fugacity ranging from the HM to WI buffer equilibria. The influence of sulfur on the solubility of platinum in fluid-bearing silicate melt was investigated at a sulfur fugacity controlled by the Pt-PtS equilibrium at 1200°C and a pressure defined in such a way that the \(f_{H_2 O} \) and \(f_{O_2 } \) values were identical to those of the experiments without sulfur. The experiments were conducted in a high pressure gas vessel with controlled hydrogen content in the fluid. Oxygen fugacity values above the NNO buffer were controlled by solid-phase buffer mixtures using the two-capsule technique. Under more reducing conditions, the contents of H₂O and H₂ were directly controlled by the argon to hydrogen ratio in a special chamber. The hydrogen fugacity varied from 5.2 × 10^?2 bar (HM buffer) to 1230 bar (\(X_{H_2 } \) = 0.5). Pt and Pd contents were measured in quenched glass samples by neutron activation analysis. The results of these investigations showed that the solubility of Pt and Pd increases significantly in the presence of water compared with experiments in dry systems. The content of Pd within the whole range of redox conditions and that of Pt at an oxygen fugacity between the HM to MW buffer reactions are weakly dependent on \(f_{O_2 } \) and controlled mainly by water fugacity. This suggests that, in addition to oxide Pt and Pd species soluble at the ppb level in haplobasaltic melts, much more soluble (ppm level) hydroxide complexes of these metals are formed under fluid-excess conditions. Despite a decrease in water fugacity under reducing conditions, Pt solubility increases sharply near the MW buffer. It was shown by electron paramagnetic resonance spectrometry that, in contrast to dry melts, fluid-saturated silicate melts do not contain a pure metal phase (micronuggets). Therefore, the increase in Pt solubility under reducing conditions can be explained by the formation of Pt hydride complexes or Pt-fluid-silicate clusters. At a sulfur fugacity controlled by the Pt-PtS equilibrium, the solubility of Pt in iron-free silicate melts as a function of redox conditions is almost identical to that obtained in the experiments without sulfur at the same water and oxygen fugacity values. These observations also support Pt dissolution in iron-free silicate melts as hydroxide species.     

Associations of Mn-bearing minerals as indicators of oxygen fugacity during the metamorphism of metalliferous deposits

The paper summarizes experimental and calculation data on the effect of oxygen fugacity on the origin of mineral assemblages in Mn-bearing rocks and demonstrates the possibility of application of these data to the reconstruction of conditions under which metalliferous deposits were metamorphosed. A new variant of the T-log\(f_{O_2 } \) diagram is proposed for the Mn-Si-O system, which differs from previous ones by the location of the lines for the formation (decomposition) of braunite and tephroite. These two minerals are the most universal indicators of oxygen fugacity during the metamorphism of Mn-bearing deposits, because these minerals are widespread in nature and can be formed in diverse environments: braunite at high \(f_{O_2 } \) values in the pore solution, and tephroite at low \(f_{O_2 } \) values. The occurrence of Mn oxides and rhodonite (pyroxmangite) in a rock makes it possible to constrain the oxygen fugacity range. An original T-log\(f_{O_2 } \) diagram is constructed for the Ca-Mn-Si-O system. As follows from this diagram, a Ca admixture expands the stability field of rhodonite toward higher oxygen fugacity values. Johannsenite can be formed in these rocks at even higher \(f_{O_2 } \). The stability of both minerals is constrained in the region of low \(f_{CO_2 } \). The paper reports data on the Fe-Si-O and Mn-Fe-Si-O systems and discusses the possibility of applying the results of experiments in the Mn-Al-Si-O system to the estimation of conditions under which andalusite, spessartine, and galaxite can be formed in Mn-bearing rocks. Data on the mineralogy of numerous Mn deposits metamorphosed under various PTX parameters indicate that the origin of Mn-bearing mineral assemblages depends not so much on the temperature and pressure as on the oxygen fugacity, which is, in turn, controlled primarily by the composition of the pristine sediments (the presence or absence of organic matter in them) and host rocks and depends on the permeability of the rocks to oxygen, the P-T conditions, and the duration of the metamorphic processes.     

Thermal equation of state of CaIrO<Subscript>3</Subscript> post-perovskite

The pressure–volume–temperature (P–V–T) relation of CaIrO₃ post-perovskite (ppv) was measured at pressures and temperatures up to 8.6 GPa and 1,273 K, respectively, with energy-dispersive synchrotron X-ray diffraction using a DIA-type, cubic-anvil apparatus (SAM85). Unit-cell dimensions were derived from the Le Bail full profile refinement technique, and the results were fitted using the third-order Birth-Murnaghan equation of state. The derived bulk modulus \( K_{T0} \) at ambient pressure and temperature is 168.3 ± 7.1 GPa with a pressure derivative \( K_{T0}^{\prime } \) = 5.4 ± 0.7. All of the high temperature data, combined with previous experimental data, are fitted using the high-temperature Birch-Murnaghan equation of state, the thermal pressure approach, and the Mie-Grüneisen-Debye formalism. The refined thermoelastic parameters for CaIrO₃ ppv are: temperature derivative of bulk modulus \( (\partial K_{T} /\partial T)_{P} \) = ?0.038 ± 0.011 GPa K^?1, \( \alpha K_{T} \) = 0.0039 ± 0.0001 GPa K^?1, \( \left( {\partial K_{T} /\partial T} \right)_{V} \) = ?0.012 ± 0.002 GPa K^?1, and \( \left( {\partial^{2} P/\partial T^{2} } \right)_{V} \) = 1.9 ± 0.3 × 10^?6 GPa² K^?2. Using the Mie-Grüneisen-Debye formalism, we obtain Grüneisen parameter \( \gamma_{0} \) = 0.92 ± 0.01 and its volume dependence q = 3.4 ± 0.6. The systematic variation of bulk moduli for several oxide post-perovskites can be described approximately by the relationship K _T0  = 5406.0/V(molar) + 5.9 GPa.     

Experimental determination of liquidus H<Subscript>2</Subscript>O contents of haplogranite at deep-crustal conditions

The liquidus water content of a haplogranite melt at high pressure (P) and temperature (T) is important, because it is a key parameter for constraining the volume of granite that could be produced by melting of the deep crust. Previous estimates based on melting experiments at low P (≤0.5 GPa) show substantial scatter when extrapolated to deep crustal P and T (700–1000 °C, 0.6–1.5 GPa). To improve the high-P constraints on H₂O concentration at the granite liquidus, we performed experiments in a piston–cylinder apparatus at 1.0 GPa using a range of haplogranite compositions in the albite (Ab: NaAlSi₃O₈)—orthoclase (Or: KAlSi₃O₈)—quartz (Qz: SiO₂)—H₂O system. We used equal weight fractions of the feldspar components and varied the Qz between 20 and 30 wt%. In each experiment, synthetic granitic composition glass + H₂O was homogenized well above the liquidus T, and T was lowered by increments until quartz and alkali feldspar crystalized from the liquid. To establish reversed equilibrium, we crystallized the homogenized melt at the lower T and then raised T until we found that the crystalline phases were completely resorbed into the liquid. The reversed liquidus minimum temperatures at 3.0, 4.1, 5.8, 8.0, and 12.0 wt% H₂O are 935–985, 875–900, 775–800, 725–775, and 650–675 °C, respectively. Quenched charges were analyzed by petrographic microscope, scanning electron microscope (SEM), X-ray diffraction (XRD), and electron microprobe analysis (EMPA). The equation for the reversed haplogranite liquidus minimum curve for Ab_36.25Or_36.25Qz_27.5 (wt% basis) at 1.0 GPa is \(T = - 0.0995 w_{{{\text{H}}_{ 2} {\text{O}}}}^{ 3} + 5.0242w_{{{\text{H}}_{ 2} {\text{O}}}}^{ 2} - 88.183 w_{{{\text{H}}_{ 2} {\text{O}}}} + 1171.0\) for \(0 \le w_{{{\text{H}}_{ 2} {\text{O}}}} \le 17\) wt% and \(T\) is in °C. We present a revised \(P - T\) diagram of liquidus minimum H₂O isopleths which integrates data from previous determinations of vapor-saturated melting and the lower pressure vapor-undersaturated melting studies conducted by other workers on the haplogranite system. For lower H₂O (<5.8 wt%) and higher temperature, our results plot on the high end of the extrapolated water contents at liquidus minima when compared to the previous estimates. As a consequence, amounts of metaluminous granites that can be produced from lower crustal biotite–amphibole gneisses by dehydration melting are more restricted than previously thought.     

Phase diagram and thermodynamic properties of AIPO<Subscript>4</Subscript> based on first-principles calculations and the quasiharmonic approximation

We calculated the phase diagram of \(\hbox {AlPO}_{4}\) up to 15 GPa and 2,000 K and investigated the thermodynamic properties of the high-pressure phases. The investigated phases include the berlinite, moganite-like, \(\hbox {AlVO}_{4},\, P2_1/c\), and \(\hbox {CrVO}_{4}\) phases. The computational methods used include density functional theory, density functional perturbation theory, and the quasiharmonic approximation. The investigated thermodynamic properties include the thermal equation of state, isothermal bulk modulus, thermal expansivity, and heat capacity. With increasing pressure, the ambient phase berlinite transforms to the moganite-like phase, and then to the \(\hbox {AlVO}_{4}\) and \(P2_1/c\) phases, and further to the \(\hbox {CrVO}_{4}\) phase. The stability fields of the \(\hbox {AlVO}_{4}\) and \(P2_1/c\) phases are similar in pressure but different in temperature, as the \(\hbox {AlVO}_{4}\) phase is stable at low temperatures, whereas the \(P2_1/c\) phase is stable at high temperatures. All of the phase relationships agree well with those obtained by quench experiments, and they support the stabilities of the moganite-like, \(\hbox {AlVO}_{4}\), and \(P2_1/c\) phases, which were not observed in room-temperature compression experiments.     

New Zr–Hf Geothermometer for Magmatic Zircons

A geothermometer equation \(T = \frac{{1531}} {{\ln K_d + 0.883}}\), where \(K_{\dot d} = \frac{{X_{Zr}^S X_{Hf}^m }} {{X_{Zr}^m X_{Hf}^s }}\) [X _j ⁱ is the concentration (in ppm) of component i in phase j] is the Zr and Hf distribution coefficient between melt and zircon, and T is temperature in K, was derived by thermodynamic processing of literature experimental data on Zr and Hf distribution between acid melts (m) and zircon (s) and on the solubility of zircon and hafnon in the melts with variable silica content. In calculations with this equations, we assumed the Zr concentration in zircon to be constant: 480000 ppm. It is shown that the commonly observed increase in Hf concentration from the cores to margins of magmatic zircon crystals is caused by the fractional crystallization of zircon. For differentiated acid magmatic series, the initial crystallization temperature of zircon in the least silicic cumulates should be evaluated using the cores of large zircon grains with the highest Zr/Hf ratio. Application of the geothermometer for mafic and intermediate rocks may be hampered due to simultaneous crystallization of zircon with some other ore and mafic minerals relatively enriched in Zr and Hf. The newly derived geothermometer has some advantages over other indicators of the crystallization temperature of magmatic zircon based on the zircon saturation index (Watson and Harrison, 1983; Boehnke et al., 2013) and on Ti concentration in this mineral (Ferry and Watson, 2007) as it does not depend on the major-oxide melt composition and on the accuracy of the estimated SiO₂ and TiO₂ activities in the melts. Calculations of the Zr and Hf fractionation trends in the course of zircon crystallization in granitoid melts allow one to evaluate the temperature at which more evolved melt portions were segregated.     

Hydroxylborite,Mg<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)(OH)<Subscript>3</Subscript>, a new mineral species and isomorphous series fluoborite-hydroxylborite

Hydroxylborite, a new mineral species, an analogue of fluoborite with OH > F, has been found at the Titovsky deposit (57°41′N, 125°22′E), the Chersky Range, Dogdo Basin, Sakha-Yakutia Republic, Russia. Prismatic crystals of the new mineral are dominated by the {10\(\overline 1 \)0} faces without distinct end forms and reach (1?1.5) × (0.1?0.2) mm in size. Radial aggregates of such crystals occur in the mineralized marble adjacent to the boron ore (suanite-kotoite-ludwigite). Calcite, dolomite, Mg-rich ludwigite, kotoite, szaibelyite, clinohumite, magnetite, serpentine, and chlorite are associated minerals. Hydroxylborite is transparent colorless, with a white streak and vitreous luster. The new mineral is brittle. The Mohs’ hardness is 3.5. The cleavage is imperfect on {0001}. The density measured with equilibration in heavy liquids is 2.89(1) g/cm³; the calculated density is 2.872 g/cm³. The wave numbers of the absorption bands in the IR spectrum of hydroxylborite are (cm^?1; sh is shoulder): 3668, 1233, 824, 742, 630sh, 555sh, 450sh, and 407. The new mineral is optically uniaxial, negative, ω = 1.566(1), and ε = 1.531(1). The chemical composition (electron microprobe, H₂O measured with the Penfield method, wt %) is 18.43 B₂O₃, 65.71 MgO, 10.23 F, 9.73 H₂O, 4.31-O = F₂, where the total is 99.79. The empirical formula calculated on the basis of 6 anions pfu is as follows: Mg_3.03B_0.98[(OH)_2.00F_1.00]O_3.00. Hydroxylborite is hexagonal, and the space group is P6₃/m. The unit-cell dimensions are: a = 8.912(8) Å, c = 3.112(4) Å, V = 214.05(26) ų, and Z = 2. The strongest reflections in the X-ray powder pattern [d, Å (I, %)(hkil)] are: 7.69(52)(01\(\overline 1 \)0), 4.45(82)(11\(\overline 2 \)0), 2.573(65)(03\(\overline 3 \)0), 2.422(100)(02\(\overline 2 \)1), and 2.128(60)(12\(\overline 3 \)1). The compatibility index 1 ? (K _p/K _c) is 0.038 (excellent) for the calculated density and 0.044 (good) for the measured density. The type material of hydroxylborite is deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow (inventory number 91968) and the Geological Museum of the All-Russia Institute of Mineral Resources, Moscow (inventory number M-1663).     

Laboratory parallel-beam transmission X-ray powder diffraction investigation of the thermal behavior of nitratine NaNO<Subscript>3</Subscript>: spontaneous strain and structure evolution

Present work provides in-situ structural data at a fine temperature scale from RT to the melting point of nitratine, NaNO₃. From the analysis of log e ₃₃ versus log t plots, it is possible to prove that an univocal indication on the R \( \overline{3} \) c (low temperature, LT) → R \( \overline{3} \) m (high temperature, HT) transition mechanism cannot be obtained because of the relevant role played by the arbitrary assumptions required for defining the c ₀ dependence from temperature of the HT phase. This is due to the occurrence of excess thermal expansion for the HT phase. A significantly better fit for an Ising-spin structural model over a non-Ising rigid-body one has been obtained for the LT phase. Moreover, the Ising model led to a smooth variation of the oxygen site x fractional coordinate throughout the transition. The structure of the HT polymorph has been successfully refined considering an oxygen site at x, 0, ½, with 50% occupancy. Such model was the only acceptable one from the crystal chemical point of view as the alternative model (oxygen site at x, y, z with 25% occupancy) led to unrealistically aplanar \( {\text{NO}}_{3}^{ - } \) groups.     

Fluid regime and origin of gold-bearing rodingites from the Karabash alpine-type ultrabasic massif,Southern Ural

The rodingites of the Karabash Massif are distinguished by the presence of native cupriferous gold. This zonal hydrothermal-metasomatic complex was formed in three stages. The inner zone of rodingite proper is made up of chlorite-andradite-diopside rocks of stage 1, which are cut by diopside veinlets of stage 2 and calcite veinlets of stage 3. The intermediate zone consists of chloritolites, which give way to the antigorite and chrysotile-lizardite serpentinites of the outer zone. Thermometric and cryometric studies and gas chromatography showed that the gold-bearing rodingites of stages 1 and 2 were formed at t = 420–470°C, P = 2–3 kbar, and \(X_{CO_2 } \) = 0.001–0.02, i.e., under conditions typical of rodingite formation. The final stage was accompanied by a decrease in P-T parameters (0.5–1.0 kbar and 230–310°C) and an increase in \(X_{CO_2 } \) up to 0.04. The rodingite-forming fluid was extremely rich in water (\(X_{H_2 O} \) = 0.942–0.981) and contained hydrogen as the major gas component (\(X_{H_2 } \) = 0.012–0.023); its composition was essentially chloride-magnesium with minor amounts of CaCl₂ and FeCl₂ and a low salinity of 2.6–8.0 wt % NaCl equiv. The rodingite minerals showed the following isotopic characteristics (‰): δ¹⁸O from 5.5 to 6.6 and δD from 42.8 to ?44.3 for chlorite, δ¹⁸0 from 2.0 to 3.8 for andradite, δ¹⁸O from 6.0 to 6.6 for diopside, and δ¹⁸O from 10.6 to 11.4 and δ¹³C from 0.1 to ?1.8 for calcite. The chloritolite is characterized by δ¹⁸O from 5.9 to 6.6 and δD from ?49.8 to ?64.4; the antigorite serpentinite shows δ¹⁸O=6.5 and δD=?65.2; and the antigoritized chrysotile-lizardite serpentinite shows δ¹⁸O from 6.8 to 6.9 and δD from ?127 to ?128. The calculated isotopic composition of fluid in equilibrium with various rocks suggested its metamorphic origin. It was formed from the water released during dehydration of oceanic serpentinites, from the components of ultrabasic and basic magmatic rocks, and, at the final stage, from marine carbon.     

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.     

An experimental study of Fe–Ni exchange between sulfide melt and olivine at upper mantle conditions: implications for mantle sulfide compositions and phase equilibria

The behavior of nickel in the Earth’s mantle is controlled by sulfide melt–olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity conditions. In this study, we constrain the Fe–Ni composition of molten sulfide in the Earth’s upper mantle via sulfide melt–olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt \(X_{{{\text{Ni}}}}^{{{\text{Sulfide}}}}=\frac{{{\text{Ni}}}}{{{\text{Ni}}+{\text{Fe}}}}\) (atomic ratio) ranging from 0 to 0.94. To verify the approach to equilibrium and to explore the effect of \({f_{{{\text{O}}_{\text{2}}}}}\) on Fe–Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baró et al., Nucl Instrum Methods Phys Res B 100:31–46, 1995), “zero time” experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0?±?1.0 log units more reduced than the fayalite–magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ ??1 or more oxidized (suite 4). For the reduced (suites 1–3) experiments, Fe–Ni distribution coefficients \(K_{{\text{D}}}^{{}}=\frac{{(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}/X_{{{\text{Fe}}}}^{{{\text{sulfide}}}})}}{{(X_{{{\text{Ni}}}}^{{{\text{olivine}}}}/X_{{{\text{Fe}}}}^{{{\text{olivine}}}})}}\) are small, averaging 10.0?±?5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of K_D (21.1–25.2). Compared to previous determinations at 100 kPa, values of K_D from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem attributable to differences in temperature and pressure between experimental studies. It may be related in part to the effects of metal/sulfur ratio in sulfide melt. Application of these results to the composition of molten sulfide in peridotite indicates that compositions are intermediate in composition (\(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}\)?~?0.4–0.6) in the shallow mantle at 50 km, becomes more Ni rich with depth as the O content of the melt diminishes, reaching a maximum (0.6–0.7) at depths near 80–120 km, and then becomes more Fe rich in the deeper mantle where conditions are more reduced, approaching (\(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}\)?~?0.28)?>?140 km depth. Because Ni-rich sulfide in the shallow upper mantle melts at lower temperature than more Fe-rich compositions, mantle sulfide is likely molten in much of the deep continental lithosphere, including regions of diamond formation.     

H<Subscript>2</Subscript>O solubility in basalt at upper mantle conditions

This study presents a new experimental approach for determining H₂O solubility in basaltic melt at upper mantle conditions. Traditional solubility experiments are limited to pressures of ~600 MPa or less because it is difficult to reliably quench silicate melts containing greater than ~10 wt% dissolved H₂O. To overcome this limitation, our approach relies on the use of secondary ion mass spectrometry to measure the concentration of H dissolved in olivine and on using the measured H in olivine as a proxy for the concentration of H₂O in the co-existing basaltic melt. The solubility of H₂O in the melt is determined by performing a series of experiments at a single pressure and temperature with increasing amounts of liquid H₂O added to each charge. The point at which the concentration of H in the olivine first becomes independent of the amount of initial H₂O content of the charge (added + adsorbed H₂O) indicates its solubility in the melt. Experiments were conducted by packing basalt powder into a capsule fabricated from San Carlos olivine, which was then pressure-sealed inside a Ni outer capsule. Our experimental results indicate that at 1000 MPa and 1200 °C, the solubility of H₂O in basaltic melt is 20.6 ± 0.9 wt% (2 × standard deviation). This concentration is considerably higher than predicted by most solubility models but defines a linear relationship between H₂O fugacity and the square of molar H₂O solubility when combined with solubility data from lower pressure experiments. Further, our solubility determination agrees with melting point depression determined experimentally by Grove et al. (2006) for the H₂O-saturated peridotite solidus at 1000 MPa. Melting point depression calculations were used to estimate H₂O solubility in basalt along the experimentally determined H₂O-saturated peridotite solidus. The results suggest that a linear relationship between H₂O fugacity and the square of molar solubility exists up to ~1300 MPa, where there is an inflection point and solubility begins to increase less strongly with increasing H₂O fugacity.     

Physico-chemical conditions of four calc-alkaline granitoid plutons of Chhotanagpur Gneissic Complex,eastern India: Tectonic implications

Petrography and mineralogy of four calc-alkaline granitoid plutons Agarpur, Sindurpur, Raghunathpur and Sarpahari located from west to east of northern Purulia of Chhotanagpur Gneissic Complex, eastern India, are investigated. The plutons, as a whole, are composed of varying proportions of Qtz–Pl–Kfs–Bt–Hbl±Px–Ttn–Mag–Ap–Zrn±Ep. The composition of biotite is consistent with those of calc-alkaline granitoids. Hornblende–plagioclase thermometry, aluminium-in-hornblende barometry and the assemblage sphene–magnetite–quartz were used to determine the P, T and \(f_{\mathrm{O}_2}\) during the crystallisation of the parent magmas in different plutons. The plutons are crystallised under varying pressures (6.2–2.4 kbar) and a wide range of temperatures (896–\(718{^{\circ }}\hbox {C}\)) from highly oxidised magmas (log \(f_{\mathrm{O}_2}\) \(-11.2\) to \(-15.4\) bar). The water content of the magma of different plutons varied from 5.0 to 6.5 wt%, consistent with the calc-alkaline nature of the magma. Calc-alkaline nature, high oxygen fugacity and high \(\hbox {H}_{2}\hbox {O}_{{\mathrm{melt}}}\) suggest that these plutons were emplaced in subduction zone environment. The depths of emplacement of these plutons seem to increase from west to east. Petrologic compositions of these granitoids continuously change from enderbite (opx-tonalite: Sarpahari) in the east to monzogranite (Raghunathpur) to syenogranite (Sindurpur) to alkali feldspar granite (Agarpur) in the west. The water contents of the parental magmas of different plutons also increase systematically from east to west. No substantial increase in the depth of emplacement is found in these plutons lying south and north of the major shear zone passing through the study area suggesting the strike-slip nature of the east–west shear zone.     

Experimental study of fluorine and chlorine contents in mica (biotite) and their partitioning between mica,phonolite melt,and fluid

This paper reports the results of a study of the composition of mica (biotite) crystallizing in the system of phonolite melt-Cl- and F-bearing aqueous fluid at T ～ 850°C, P = 200 MPa, and \(f_{O_2 } \) = Ni-NiO, as well as data on F and Cl partitioning between coexisting phases. It was established that Cl content in mica is significantly lower than in phonolite melt and, especially, in fluid. Fluorine shows a different behavior in this system: its content in mica is always higher than in phonolite melt but lower than in fluid. The mica-melt partition coefficients of Cl and F also behave differently. The Cl partition coefficient gradually increases from 0.17 to 0.33 with increasing Cl content in the system, whereas the partition coefficient of F sharply decreases from 3.0 to 1.0 with increasing total F content. The apparent partition coefficients of F between biotite and groundmass (melt) in various magmatic rocks are usually significantly higher than the experimental values. It was supposed that the higher ^Bt/glassD_F values in natural samples could be related to the influence of later oxidation reactions, reequilibration of biotite at continuously decreasing \(f_{H_2 O} \)/f _HF ratio, and an increase in this coefficients with decreasing total F content in the system.     

Equation of state of synthetic qandilite Mg<Subscript>2</Subscript>TiO<Subscript>4</Subscript> at ambient temperature

Using a diamond-anvil cell and synchrotron X-ray diffraction, the compressional behavior of a synthetic qandilite Mg_2.00(1)Ti_1.00(1)O₄ has been investigated up to about 14.9 GPa at 300 K. The pressure–volume data fitted to the third-order Birch–Murnaghan equation of state yield an isothermal bulk modulus (K _T0) of 175(5) GPa, with its first derivative \(K_{T0}^{{\prime }}\) attaining 3.5(7). If \(K_{T0}^{{\prime }}\) is fixed as 4, the K _T0 value is 172(1) GPa. This value is substantially larger than the value of the adiabatic bulk modulus (K _S0) previously determined by an ultrasonic pulse echo method (152(7) GPa; Liebermann et al. in Geophys J Int 50:553–586, 1977), but in general agreement with the K _T0 empirically estimated on the basis of crystal chemical systematics (169 GPa; Hazen and Yang in Am Miner 84:1956–1960, 1999). Compared to the K _T0 values of the ulvöspinel (Fe₂TiO₄; ~148(4) GPa with \(K_{T0}^{{\prime }} = 4\)) and the ringwoodite solid solutions along the Mg₂SiO₄–Fe₂SiO₄ join, our finding suggests that the substitution of Mg²⁺ for Fe²⁺ on the T sites of the 4–2 spinels can have more significant effect on the K _T0 than that on the M sites.     

A seismological overview of the April 25, 2015 M<Subscript>w</Subscript>7.8 Nepal earthquake

This paper aims to determine the damage distribution and to analyze the available strong motion records of the April 25, 2015 Nepal earthquake and its eight aftershocks. For this purpose, an earthquake investigation team was dispatched to Nepal from May 6 to 11, 2015 to evaluate the damages of the epicentral region and the four affected cities containing Kathmandu, Bhaktapur, Gorkha, and Pokhara. Based on the observations from the damages to the built environment, an iso-intensity map is prepared on the EMS-98 intensity scale in which the maximum intensity in the epicentral region is estimated to be about VIII. However, based on the geological and geotechnical evidences such as landslide volumes and ground fissures, the maximum intensity can be inferred about IX or X on the International Union for Quaternary Research (INQUA) intensity scale. In addition, the available strong motion data of the 2015 Nepal mainshock and its eight large aftershocks recorded at the KATNP accelerometric station in Kathmandu were processed and analyzed. In order to investigate the probable site effects, the Fourier amplitude spectra (FAS) of the horizontal north-south (N) and east-west (E) components and the average of them (H _avg) were divided to the FAS of the vertical (Z) component and thus, the \( \raisebox{1ex}{$ N$}\!\left/ \!\raisebox{-1ex}{$ Z$}\right. \), \( \raisebox{1ex}{$ E$}\!\left/ \!\raisebox{-1ex}{$ Z$}\right. \), \( \raisebox{1ex}{${H}_{\mathrm{avg}}$}\!\left/ \!\raisebox{-1ex}{$ Z$}\right. \) spectral ratios were calculated. Based on these horizontal to vertical spectral ratios, a low-frequency peak at about 0.2–0.3 Hz (3.5–5-s period) is observed clearly in all the records. Accordingly, the repeated results might imply site amplification due to the thick alluvial deposits and the high groundwater level at the KATNP accelerometric station within the Kathmandu basin. It should be noted that all the horizontal to vertical spectral ratios of the aftershocks show a high peak at around 1.5–3 Hz, which is missed in the horizontal to vertical spectral ratio of the mainshock. On the other hand, considering the low angle of the causative fault plane, a near-source directivity effect on the fault normal direction (here, the vertical component) of the April 25, 2015 mainshock rupture may exist. Therefore, vertical to horizontal spectral ratios (\( \raisebox{1ex}{$ Z$}\!\left/ \!\raisebox{-1ex}{$ N$}\right. \) and \( \raisebox{1ex}{$ Z$}\!\left/ \!\raisebox{-1ex}{$ E$}\right. \)) were also calculated to find the vertical peak more clearly. The figures confirmed a peak at the frequency of 1.5–3 Hz in the mainshock spectra which is not repeated on the aftershock spectra and thus can probably be attributed as the pulse of directivity effect toward Kathmandu. This inferred directivity pulse can be also well distinguished on the velocity and displacement time histories of the mainshock.     

Trend analysis of evapotranspiration over India: Observed from long-term satellite measurements

Owing to the lack of consistent spatial time series data on actual evapotranspiration (ET), very few studies have been conducted on the long-term trend and variability in ET at a national scale over the Indian subcontinent. The present study uses biome specific ET data derived from NOAA satellite’s advanced very high resolution radiometer to investigate the trends and variability in ET over India from 1983 to 2006. Trend analysis using the non-parametric Mann–Kendall test showed that the domain average ET decreased during the period at a rate of \(0.22\,\hbox {mm year}^{-1}\). A strong decreasing trend (\(m = -1.75\, \hbox {mm year}^{-1}\), \(F = 17.41\), \(P\) 0.01) was observed in forest regions. Seasonal analyses indicated a decreasing trend during southwest summer monsoon (\(m= -0.320\, \hbox {mm season}^{-1}\,\hbox {year}^{-1})\) and post-monsoon period (\(m= -0.188\, \hbox {mm season}^{-1 }\,\hbox {year}^{-1})\). In contrast, an increasing trend was observed during northeast winter monsoon (\(m = 0.156 \,\hbox {mm season}^{-1 }\,\hbox {year}^{-1})\) and pre-monsoon (\(m = 0.068\, \hbox {mm season}^{-1 }\,\hbox {year}^{-1})\) periods. Despite an overall net decline in the country, a considerable increase ( \(4 \,\hbox {mm year}^{-1}\)) was observed over arid and semi-arid regions. Grid level correlation with various climatic parameters exhibited a strong positive correlation (\(r \!>\!0.5\)) of ET with soil moisture and precipitation over semi-arid and arid regions, whereas a negative correlation (\(r\) \(-0.5\)) occurred with temperature and insolation in dry regions of western India. The results of this analysis are useful for understanding regional ET dynamics and its relationship with various climatic parameters over India. Future studies on the effects of ET changes on the hydrological cycle, carbon cycle, and energy partitioning are needed to account for the feedbacks to the climate.     

The effect of liquid composition on the partitioning of Ni between olivine and silicate melt

We report the results of experiments designed to separate the effects of temperature and pressure from liquid composition on the partitioning of Ni between olivine and liquid, \(D_{\text{Ni}}^{\text{ol/liq}}\). Experiments were performed from 1300 to 1600 °C and 1 atm to 3.0 GPa, using mid-ocean ridge basalt (MORB) glass surrounded by powdered olivine in graphite–Pt double capsules at high pressure and powdered MORB in crucibles fabricated from single crystals of San Carlos olivine at one atmosphere. In these experiments, pressure and temperature were varied in such a way that we produced a series of liquids, each with an approximately constant composition (~12, ~15, and ~21 wt% MgO). Previously, we used a similar approach to show that \(D_{\text{Ni}}^{\text{ol/liq}}\) for a liquid with ~18 wt% MgO is a strong function of temperature. Combining the new data presented here with our previous results allows us to separate the effects of temperature from composition. We fit our data based on a Ni–Mg exchange reaction, which yields \(\ln \left( {D_{\text{Ni}}^{\text{molar}} } \right) = \frac{{ -\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } }}{RT} + \frac{{\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } }}{R} - \ln \left( {\frac{{X_{\text{MgO}}^{\text{liq}} }}{{X_{{{\text{MgSi}}_{ 0. 5} {\text{O}}_{ 2} }}^{\text{ol}} }}} \right).\) Each subset of constant composition experiments displays roughly the same temperature dependence of \(D_{\text{Ni}}^{\text{ol/liq}}\) (i.e.,\(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\)) as previously reported for liquids with ~18 wt% MgO. Fitting new data presented here (15 experiments) in conjunction with our 13 previously published experiments (those with ~18 wt% MgO in the silicate liquid) to the above expression gives \(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = 3641 ± 396 (K) and \(\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = ? 1.597 ± 0.229. Adding data from the literature yields \(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = 4505 ± 196 (K) and \(\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = ? 2.075 ± 0.120, a set of coefficients that leads to a predictive equation for \(D_{\text{Ni}}^{\text{ol/liq}}\) applicable to a wide range of melt compositions. We use the results of our work to model the melting of peridotite beneath lithosphere of varying thickness and show that: (1) a positive correlation between NiO in magnesian olivine phenocrysts and lithospheric thickness is expected given a temperature-dependent \(D_{\text{Ni}}^{\text{ol/liq}} ,\) and (2) the magnitude of the slope for natural samples is consistent with our experimentally determined temperature dependence. Alternative processes to generate the positive correlation between NiO in magnesian olivines and lithospheric thickness, such as the melting of olivine-free pyroxenite, are possible, but they are not required to explain the observed correlation of NiO concentration in initially crystallizing olivine with lithospheric thickness.     

Arsenic in shallow groundwater of Bangladesh: investigations from three different physiographic settings

Occurrences of arsenic (As) in the Bengal Basin of Bangladesh show close relationships with depositional environments and sediment textures. Hydrochemical data from three sites with varying physiography and sedimentation history show marked variations in redox status and dissolved As concentrations. Arsenic concentration in groundwater of the Ganges Flood Plain (GFP) is characteristically low, where high Mn concentrations indicate redox buffering by reduction of Mn(IV)-oxyhydroxides. Low DOC, \( {\text{HCO}}^{ - }_{3} \), \( {\text{NH}}^{ + }_{4} \) and high \( {\text{NO}}^{ - }_{3} \) and \( {\text{SO}}^{{2 - }}_{4} \) concentrations reflect an elevated redox status in GFP aquifers. In contrast, As concentration in the Ganges Delta Plain (GDP) is very high along with high Fe and low Mn. In the Meghna Flood Plain (MFP), moderate to high As and Fe concentrations and low Mn are detected. Degradation of organic matter probably drives redox reactions in the aquifers, particularly in MFP and GDP, thereby mobilising dissolved As. Speciation calculations indicate supersaturation with respect to siderite and vivianite in the groundwater samples at MFP and GDP, but groundwater in the GFP wells is generally supersaturated with respect to rhodochrosite. Values of log P_CO2 at MFP and GDP sites are generally higher than at the GFP site. This is consistent with Mn(IV)-redox buffering suggested at the GFP site compared to Fe(III)-redox buffering at MFP and GDP sites.     

The effect of H<Subscript>2</Subscript>O on the olivine liquidus of basaltic melts: experiments and thermodynamic models

We designed and carried out experiments to investigate the effect of H₂O on the liquidus temperature of olivine-saturated primitive melts. The effect of H₂O was isolated from other influences by experimentally determining the liquidus temperatures of the same melt composition with various amounts of H₂O added. Experimental data indicate that the effect of H₂O does not depend on pressure or melt composition in the basaltic compositional range. The influence of H₂O on melting point lowering can be described as a polynomial function This expression can be used to account for the effect of H₂O on olivine-melt thermometers, and can be incorporated into fractionation models for primitive basalts. The non-linear effect of H₂O indicates that incorporation of H₂O in silicate melts is non-ideal, and involves interaction between H₂O and other melt components. The simple speciation approach that seems to account for the influence of H₂O in simple systems (albite-H₂O, diopside-H₂O) fails to describe the mixing behavior of H₂O in multi-component silicate melts. However, a non-ideal solution model that treats the effect of H₂O addition as a positive excess free energy can be fitted to describe the effect of melting point lowering.