Sulfur diffusion in rhyolite melts

 Diffusion rates for sulfur in rhyolite melt have been measured at temperatures of 800–1100° C, water contents of 0–7.3 wt%, and oxygen fugacities from the quartz-fayalite-magnetite buffer to air. Experiments involved dissolution of anhydrite or pyrrhotite into rhyolite melt over time scales of hours to days. Electron microprobe analysis was used to measure sulfur concentration profiles in the quenched glasses. Regression of the diffusion data in dry rhyolite melt gives D_sulfur=0.05·exp{−221±80RT}, which is one to two orders of magnitude slower than diffusion of other common magmatic volatiles such as H₂O, CO₂ and Cl^-. Diffusion of sulfur in melt with 7 wt% dissolved water is 1.5 to 2 orders of magnitude faster than diffusion in the anhydrous melt, depending on temperature. Sulfur is known to dissolve in silicate melts as at least two different species, S²⁻ and S⁶⁺, the proportions of which vary with oxygen fugacity; despite this, oxygen fugacity does not appear to affect sulfur diffusivity except under extremely oxidizing conditions. This result suggests that diffusion of sulfur is controlled by one species over a large range in oxygen fugacity. The most likely candidate for the diffusing species is the sulfide ion, S²⁻. Re-equilibration between S²⁻ and S⁶⁺ in oxidized melts must generally be slow compared to S²⁻ diffusion in order to explain the observed results. In a silicic melt undergoing degassing, sulfur will tend to be fractionated from other volatile species which diffuse more rapidly. This is consistent with analyses of tephra from the 1991 eruption of Mount Pinatubo, Philippines, and from other high-silica volcanic eruptions. Received: 26 April 1995 / Accepted: 1 November 1995     

Experimental investigation of H2O and Cl− solubilities in F-enriched silicate liquids; implications for volatile saturation of topaz rhyolite magmas

To interpret the degassing of F-bearing felsic magmas, the solubilities of H₂O, NaCl, and KCl in topaz rhyolite liquids have been investigated experimentally at 2000, 500, and ≈1 bar and 700° to 975 °C. Chloride solubility in these liquids increases with decreasing H₂O activity, increasing pressure, increasing F content of the liquid from 0.2 to 1.2 wt% F, and increasing the molar ratio of ((Al + Na + Ca + Mg)/Si). Small quantities of Cl⁻ exert a strong influence on the exsolution of magmatic volatile phases (MVPs) from F-bearing topaz rhyolite melts at shallow crustal pressures. Water- and chloride-bearing volatile phases, such as vapor, brine, or fluid, exsolve from F-enriched silicate liquids containing as little as 1 wt% H₂O and 0.2 to 0.6 wt% Cl at 2000 bar compared with 5 to 6 wt% H₂O required for volatile phase exsolution in chloride-free liquids. The maximum solubility of Cl⁻ in H₂O-poor silicate liquids at 500 and 2000 bar is not related to the maximum solubility of H₂O in chloride-poor liquids by simple linear and negative relationships; there are strong positive deviations from ideality in the activities of each volatile in both the silicate liquid and the MVP(s). Plots of H₂O versus Cl⁻ in rhyolite liquids, for experiments conducted at 500 bar and 910°–930 °C, show a distinct 90° break-in-slope pattern that is indicative of coexisting vapor and brine under closed-system conditions. The presence of two MVPs buffers the H₂O and Cl⁻ concentrations of the silicate liquids. Comparison of these experimentally-determined volatile solubilities with the pre-eruptive H₂O and Cl⁻ concentrations of five North American topaz and tin rhyolite melts, determined from melt inclusion compositions, provides evidence for the exsolution of MVPs from felsic magmas. One of these, the Cerro el Lobo magma, appears to have exsolved alkali chloride-bearing vapor plus brine or a single supercritical fluid phase prior to entrapment of the melt inclusions and prior to eruption. Received: 6 November 1995 / Accepted: 29 January 1998     

Electrical conductivity of hydrous basaltic melts: implications for partial melting in the upper mantle

The Earth’s uppermost asthenosphere is generally associated with low seismic wave velocity and high electrical conductivity. The electrical conductivity anomalies observed from magnetotelluric studies have been attributed to the hydration of mantle minerals, traces of carbonatite melt, or silicate melts. We report the electrical conductivity of both H₂O-bearing (0–6 wt% H₂O) and CO₂-bearing (0.5 wt% CO₂) basaltic melts at 2 GPa and 1,473–1,923 K measured using impedance spectroscopy in a piston-cylinder apparatus. CO₂ hardly affects conductivity at such a concentration level. The effect of water on the conductivity of basaltic melt is markedly larger than inferred from previous measurements on silicate melts of different composition. The conductivity of basaltic melts with more than 6 wt% of water approaches the values for carbonatites. Our data are reproduced within a factor of 1.1 by the equation log σ = 2.172 − (860.82 − 204.46 w ^0.5)/(T − 1146.8), where σ is the electrical conductivity in S/m, T is the temperature in K, and w is the H₂O content in wt%. We show that in a mantle with 125 ppm water and for a bulk water partition coefficient of 0.006 between minerals and melt, 2 vol% of melt will account for the observed electrical conductivity in the seismic low-velocity zone. However, for plausible higher water contents, stronger water partitioning into the melt or melt segregation in tube-like structures, even less than 1 vol% of hydrous melt, may be sufficient to produce the observed conductivity. We also show that ~1 vol% of hydrous melts are likely to be stable in the low-velocity zone, if the uncertainties in mantle water contents, in water partition coefficients, and in the effect of water on the melting point of peridotite are properly considered.     

Heterogeneous bubble nucleation in highly viscous silicate melts during instantaneous decompression from high pressure

The nucleation of H₂O bubbles in magmas has been proposed as a trigger for volcanic eruptions. To determine how bubbles nucleate heterogeneously in silicate melts, experiments were carried out in which high-silica rhyolitic melts were hydrated at 800 °C and either 50 or 125 MPa, and then decompressed by 20–91 MPa at temperatures that ranged between 550 and 700 °C, and held at the lower pressures for 10–720 s before being quenched. Bubbles nucleated in number densities (N_B) that vary between 3 × 10⁷ and 2 × 10⁸ cm^− 3. Blocky shaped magnetite or the ends of needle-shaped hematite acted as sites for nucleation, but only if a minimum super-saturation was exceeded, which increases with increasing melt viscosity. Bubbles did not nucleate along the lengths of hematite needles nor on plagioclase. Both the beginning and ending times of the nucleation event increases with increasing melt viscosity. Using nucleation theory predictions, neither the slower nucleation rates nor the changing activation of nucleation sites can be adequately explained by the differences in temperature, water diffusivity, or viscosity. Instead, the variations in nucleation kinetics are best explained by changes in surface tension between melt and vapor, resulting from the increasing polymerization of the melt at lower temperatures and water contents. Because only ∼ 10⁸ bubbles cm^− 3 nucleate on magnetite in the rhyolite melt used, almost regardless of experimental conditions, results from this study may not be directly comparable to vesicle numbers in volcanic pumice of different compositions.     

The Tarim picrite–basalt–rhyolite suite, a Permian flood basalt from northwest China with contrasting rhyolites produced by fractional crystallization and anatexis

We report major and trace element composition, Sr–Nd isotopic and seismological data for a picrite–basalt–rhyolite suite from the northern Tarim uplift (NTU), northwest China. The samples were recovered from 13 boreholes at depths between 5,166 and 6,333 m. The picritic samples have high MgO (14.5–16.8 wt%, volatiles included) enriched in incompatible element and have high ⁸⁷Sr/⁸⁶Sr and low ¹⁴³Nd/¹⁴⁴Nd isotopic ratios (εNd (t) = −5.3; Sr_i = 0.707), resembling the Karoo high-Ti picrites. All the basaltic samples are enriched in TiO₂ (2.1–3.2 wt%, volatiles free), have high FeOt abundances (11.27–15.75 wt%, volatiles free), are enriched in incompatible elements and have high Sr and low Nd isotopic ratios (Sr_i = 0.7049–0.7065; εNd (t) = −4.1 to −0.4). High Nb/La ratios (0.91–1.34) of basalts attest that they are mantle-derived magma with negligible crustal contamination. The rhyolite samples can be subdivided into two coeval groups with overlapping U–Pb zircon ages between 291 ± 4 and 272 ± 2 Ma. Group 1 rhyolites are enriched in Nb and Ta, have similar Nb/La, Nb/U, and Sr–Nd isotopic compositions to the associated basalts, implying that they are formed by fractional crystallization of the basalts. Group 2 rhyolites are depleted in Nb and Ta, have low Nb/La ratios, and have very high Sr and low Nd isotopic ratios, implying that crustal materials have been extensively, if not exclusively, involved in their source. The picrite–basalt–rhyolite suite from the NTU, together with Permian volcanic rocks from elsewhere Tarim basin, constitute a Large Igneous Province (LIP) that is characterized by large areal extent, rapid eruption, OIB-type chemical composition, and eruption of high temperature picritic magma. The Early Permian magmatism, which covered an area >300,000 km², is therefore named the Tarim Flood Basalt.     

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.     

Interdiffusion of Na,K,and Ca Between Granitic Melts and NaCl Liquid

This study is aimed at determining the diffusion coefficient of net-work modifiers (mainly Na, K, and Ca) in a two-phase melt-NaCl system, in which the melts are granitic and the system is NaCl-rich in composition. The diffusion coefficients of Na, K, and Ca were measured at the temperatures of 750 – 1400°C, pressures of 0.001 × 10⁸ – 2 × 10⁸ Pa, and initial H₂O contents of 0 wt% –6.9 wt% in the granitic melts. The diffusion coefficients of Fe and Mg were difficult to resolve. In all experiments a NaCl melt was present as well. In the absence of H₂O, the diffusion of net-work modifiers follows an Arrhanious equation at 1 × 10⁵ Pa: lgD_ca=−3. 88−5140/T, lgD_k =−3. 79−4040/T, and lgD_Na, =−4.99−3350/T, where D is in cm² /s andT is in K. The diffusion coefficients of Ca, Na, K, and Fe increase non-linearly with increasing H₂O content in the melt. The presence of about 2 wt% H₂O m the melt will lead to a dramatical increase in diffusivity, but higher H₂O content has only a minor effect. This change is probably the result of a change in the melt structure when H₂O is present. The diffusion coefficients measured in this study are significantly different from those in previous works. This may be understood in terms of the “transient two-liquid equilibrium” theory. Element interdiffusion depends not only on its concentration, but also on its activity co-efficient gradient, which is reflected by the distribution coefficient, of the two contacting melts.     

The effect of water on the viscosity of a haplogranitic melt under P-T-X conditions relevant to silicic volcanism

 The viscosities of hydrous haplogranitic melts synthesized by hydrothermal fusion at 2 kbar pressure and 800 to 1040° C have been measured at temperatures just above the glass transition and at a pressure of 1 bar using micropenetration techniques. The micropenetration viscometry has been performed in the viscosity range of 10⁹ Pa s to 10¹² Pa s. The samples ranged in water content from 0.4 to 3.5 wt%. For samples with up to 2.5 wt% H₂O, the water contents have been determined using infrared spectroscopy obtained before and after each viscometry experiment to be constant over the duration of the measurements. Above this water content a measurable loss of water occurs during the viscometry. The viscosity data illustrate an extremely nonlinear decrease in viscosity with added water. The viscosity drops drastically with the addition of 0.5 wt% of water and then shallows out at water contents of 2 wt%. An additional viscosity datum point obtained from the analysis of fluid inclusions in a water-saturated HPG8 confirms a near invariance of the viscosity with the addition of water between 2 and 6 wt%. These measurements may be compared directly with the data of Hess et al. (1995, in press) for the effects of excess alkali and alkaline earth oxides on the viscosity of HPG8 (also obtained at 1 bar). The viscosity of the melts, compared on an equivalent molar basis, increases in the order H₂O<(Li₂O<Na₂O< K₂O<Rb₂O,Cs₂O<BaO<SrO<CaO<MgO< BeO). The extraordinary decrease in melt viscosity with added water is poorly reproduced by the calculation scheme of Shaw (1972) for the range of water contents investigated here. The speciation of water in the quenched glasses can be used to quantify the dependence of the viscosity on hydroxyl content. Considering only the hydroxyl groups as active fluidizers in the hydrous melts the nonlinearity of the viscosity decrease and the difference with the effects of the alkali oxides becomes larger. Consequences for degassing calcalkaline rhyolite are discussed. Received: 17 August 1995/Accepted: 8 January 1996     

Viscosity of flux-rich pegmatitic melts

Viscosity experiments were conducted with two flux-rich pegmatitic melts PEG0 and PEG2. The Li₂O, F, B₂O₃ and P₂O₅ contents of these melts were 1.04, 4.06, 2.30 and 1.68 and 1.68, 5.46, 2.75 and 2.46 wt%, respectively. The water contents varied from dry to 9.04 wt% H₂O. The viscosity was determined in internally heated gas pressure vessels using the falling sphere method in the temperature range 873–1,373 K at 200 and 320 MPa pressure. At 1,073 K, the viscosity of water-rich (~9 wt% H₂O) melts is in the range of 3–60 Pa s, depending on the melt composition. Extrapolations to lower temperature assuming an Arrhenian behavior indicate that highly fluxed pegmatite melts may reach viscosities of ~30 Pa s at 773 K. However, this value is a minimum estimation considering the strongly non-Arrhenian behavior of hydrous silicate melts. The experimentally determined melt viscosities are lower than the prediction of current models taking compositional parameters into account. Thus, these models need to be improved to predict accurately the viscosity of flux-rich water bearing melts. The data also indicate that Li influences significantly the melt viscosity. Decreasing the molar Al/(Na + K + Li) ratio results in a strong viscosity decrease, and highly fluxed melts with low Al/(Na + K + Li) ratios (~0.8) have a rheological behavior which is very close to that of supercritical fluids.     

Kinetics of heterogeneous bubble nucleation in rhyolitic melts: implications for the number density of bubbles in volcanic conduits and for pumice textures

We performed decompression experiments to simulate the ascent of a phenocryst-bearing rhyolitic magma in a volcanic conduit. The starting materials were bubble-free rhyolites water-saturated at 200 MPa–800°C under oxidizing conditions: they contained 6.0 wt% dissolved H₂O and a dense population of hematite crystals (8.7 ± 2 × 10⁵ mm⁻³). Pressure was decreased from the saturation value to a final value ranging from 99 to 20 MPa, at constant temperature (800°C); the rate of decompression was either 1,000 or 27.8 kPa/s. In all experiments, we observed a single event of heterogeneous bubble nucleation beginning at a pressure P _N equal to 63 ± 3 MPa in the 1,000 kPa/s series, and to 69 ± 1 MPa in the 27.8 kPa/s series. Below P _N, the degree of water supersaturation in the liquid rapidly decreased to a few 0.1 wt%, the nucleation rate dropped, and the bubble number density (BND) stabilized to a value strongly sensitive to decompression rate: 80 mm⁻³ at 27.8 kPa/s vs. 5,900 mm⁻³ at 1,000 kPa/s. This behaviour is like the behavior formerly described in the case of homogeneous bubble nucleation in the rhyolite-H₂O system and in numerical simulations of vesiculation in ascending magmas. Similar degrees of water supersaturation were measured at 27.8 and 1,000 kPa/s, implying that a faster decompression rate does not result in a larger departure from equilibrium. Our experimental results imply that BNDs in acid to intermediate magmas ascending in volcanic conduits will depend on both the decompression rate and the number density of phenocrysts, especially the number density of magnetite microphenocrysts (1–100 mm⁻³), which is the only mineral species able to reduce significantly the degree of water supersaturation required for bubble nucleation. Very low BNDs (≈1 mm⁻³) are predicted in the case of effusive eruptions ( ≈ 0.1 kPa/s). High BNDs (up to 10⁷ mm⁻³) and bimodal bubble size distributions are expected in the case of explosive eruptions: (1) a relatively small number density of bubbles (1–100 mm⁻³) will first nucleate in the lower part of the conduit ( ≈ 10 kPa/s), either at high pressure on magnetite or at lower pressure on quartz and feldspar (or by homogeneous nucleation in the liquid) and (2) then, extreme decompression rates near the fragmentation level ( ≈ 10³ kPa/s) will trigger a major nucleation event leading to the multitude of small bubbles, typically a few micrometers to a few tens of micrometers in diameter, which characterizes most silicic pumices.     

Differentiation and crystallization conditions of basalts from the Kerguelen large igneous province: an experimental study

Phase relations of basalts from the Kerguelen large igneous province have been investigated experimentally to understand the effect of temperature, fO₂, and fugacity of volatiles (e.g., H₂O and CO₂) on the differentiation path of LIP basalts. The starting rock samples were a tholeiitic basalt from the Northern Kerguelen Plateau (ODP Leg 183 Site 1140) and mildly alkalic basalt evolved from the Kerguelen Archipelago (Mt. Crozier on the Courbet Peninsula), representing different differentiation stages of basalts related to the Kerguelen mantle plume. The influence of temperature, water and oxygen fugacity on phase stability and composition was investigated at 500 MPa and all experiments were fluid-saturated. Crystallization experiments were performed at temperatures between 900 and 1,160°C under oxidizing (log fO₂ ~ ΔQFM + 4) and reducing conditions (log fO₂ ~ QFM) in an internally heated gas-pressure vessel equipped with a rapid quench device and a Pt-Membrane for monitoring the fH₂. In all experiments, a significant influence of the fO₂ on the composition and stability of the Mg/Fe-bearing mineral phases could be observed. Under reducing conditions, the residual melts follow a tholeiitic differentiation trend. In contrast, melts have high Mg# [Mg²⁺/(Mg²⁺ + Fe²⁺)] and follow a calk-alkalic differentiation trend at oxidizing conditions. The comparison of the natural phenocryst assemblages with the experimental products allows us to constrain the differentiation and pre-eruptive conditions of these magmas. The pre-eruptive temperature of the alkalic basalt was about 950–1,050°C. The water content of the melt was below 2.5 wt% H₂O and strongly oxidizing conditions (log fO₂ ~ ΔQFM + 2) were prevailing in the magma chamber prior to eruption. The temperature of the tholeiitic melt was above 1,060°C, with a water content below 2 wt% H₂O and a log fO₂ ~ ΔQFM + 1. Early fractionation of clinopyroxene is a crucial step resulting in the generation of silica-poor and alkali-rich residual melts (e.g., alkali basalt). The enrichment of alkalis in residual melts is enhanced at high fO₂ and low aH₂O.     

Solubility of manganotantalite, zircon and hafnon in highly fluxed peralkaline to peraluminous pegmatitic melts

The behavior of tantalum and zirconium in pegmatitic systems has been investigated through the determination of Ta and Zr solubilities at manganotantalite and zircon saturation from dissolution and crystallization experiments in hydrous, Li-, F-, P- and B-bearing pegmatitic melts. The pegmatitic melts are synthetic and enriched in flux elements: 0.7–1.3 wt% Li₂O, 2–5.5 wt% F, 2.8–4 wt% P₂O₅ and 0–2.8 wt% B₂O₃, and their aluminum saturation index ranges from peralkaline to peraluminous (ASI_Li = Al/[Na + K + Li] = 0.8 to 1.3) with various K/Na ratios. Dissolution and crystallization experiments were conducted at temperatures varying between 700 and 1,150°C, at 200 MPa and nearly water-saturated conditions. For dissolution experiments, pure synthetic, end member manganotantalite and zircon were used in order to avoid problems with slow solid-state kinetics, but additional experiments using natural manganotantalite and zircon of relatively pure composition (i.e., close to end member composition) displayed similar solubility results. Zircon and manganotantalite solubilities considerably increase from peraluminous to peralkaline compositions, and are more sensitive to changes in temperature or ASI of the melt than to flux content. A model relating the enthalpy of dissolution of manganotantalite to the ASI_Li of the melt is proposed: ∆H _diss (kJ/mol) = 304 × ASI_Li − 176 in the peralkaline field, and ∆H _diss (kJ/mol) = −111 × ASI_Li + 245 in the peraluminous field. The solubility data reveal a small but detectable competitivity between Zr and Ta in the melt, i.e., lower amounts of Zr are incorporated in a Ta-bearing melt compared to a Ta-free melt under the same conditions. A similar behavior is observed for Hf and Ta. The competitivity between Zr (or Hf) and Ta increases from peraluminous to peralkaline compositions, and suggests that Ta is preferentially bonded to non-bridging oxygens (NBOs) with Al as first-neighbors, whereas Zr is preferentially bonded to NBOs formed by excess alkalies. As a consequence Zr/Ta ratios, when buffered by zircon and manganotantalite simultaneously, are higher in peralkaline melts than in peraluminous melts.     

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.     

Effects of nitrogen fertilization on soil respiration in temperate grassland in Inner Mongolia,China

Nitrogen addition to soil can play a vital role in influencing the losses of soil carbon by respiration in N-deficient terrestrial ecosystems. The aim of this study was to clarify the effects of different levels of nitrogen fertilization (HN, 200 kg N ha⁻¹ year⁻¹; MN, 100 kg N ha⁻¹ year⁻¹; LN, 50 kg N ha⁻¹ year⁻¹) on soil respiration compared with non-fertilization (CK, 0 kg N ha⁻¹ year⁻¹), from July 2007 to September 2008, in temperate grassland in Inner Mongolia, China. Results showed that N fertilization did not change the seasonal patterns of soil respiration, which were mainly controlled by soil heat-water conditions. However, N fertilization could change the relationships between soil respiration and soil temperature, and water regimes. Soil respiration dependence on soil moisture was increased by N fertilization, and the soil temperature sensitivity was similar in the treatments of HN, LN, and CK treatments (Q ₁₀ varied within 1.70–1.74) but was slightly reduced in MN treatment (Q ₁₀ = 1.63). N fertilization increased soil CO₂ emission in the order MN > HN > LN compared with the CK treatment. The positive effects reached a significant level for HN and MN (P < 0.05) and reached a marginally significant level for LN (P = 0.059 < 0.1) based on the cumulative soil respiration during the 2007 growing season after fertilization (July–September 2007). Furthermore, the differences between the three fertilization treatments and CK reached the very significant level of 0.01 on the basis of the data during the first entire year after fertilization (July 2007–June 2008). The annual total soil respiration was 53, 57, and 24% higher than in the CK plots (465 g m⁻² year⁻¹). However, the positive effects did not reach the significant level for any treatment in the 2008 growing season after the second year fertilization (July–September 2008, P > 0.05). The pairwise differences between the three N-level treatments were not significant in either year (P > 0.05).     

Rb−Sr and Ar−Ar systematics of Malani volcanic rocks of southwest Rajasthan: Evidence for a younger post-crystallization thermal event

A new Rb−Sr age of 779±10 Ma has been obtained for a suite of andesite-daciterhyolite from the Malani Igneous Province of southwestern Rajasthan, dated earlier at 745±10 Ma by Crawford and Compston (1970). The associated basalts may be slightly younger than the felsic volcanics and have a mantle source. The felsic volcanics on the other hand were most probably derived by fractional crystallization of a crustal magma (Srivastavaet al 1989a, b).⁴⁰Ar−³⁹Ar systematics of three samples viz., a basalt, a dacite and a rhyolite show disturbed age spectra indicating a thermal event around 500–550 Ma ago. This secondary thermal event is quite wide-spread and possibly related to the Pan-African thermo-tectonic episode observed in the Himalayas and south India.     

Low T heat capacity measurements and new entropy data for titanite (sphene): implications for thermobarometry of high-pressure rocks

The accepted standard state entropy of titanite (sphene) has been questioned in several recent studies, which suggested a revision from the literature value 129.3 ± 0.8 J/mol K to values in the range of 110–120 J/mol K. The heat capacity of titanite was therefore re-measured with a PPMS in the range 5 to 300 K and the standard entropy of titanite was calculated as 127.2 ± 0.2 J/mol K, much closer to the original data than the suggested revisions. Volume parameters for a modified Murgnahan equation of state: V _P,T  = V ₂₉₈° × [1 + a°(T − 298) − 20a°(T − 298)] × [1 – 4P/(K ₂₉₈ × (1 – 1.5 × 10⁻⁴ [T − 298]) + 4P)]^1/4 were fit to recent unit cell determinations at elevated pressures and temperatures, yielding the constants V ₂₉₈° = 5.568 J/bar, a° = 3.1 × 10⁻⁵ K⁻¹, and K = 1,100 kbar. The standard Gibbs free energy of formation of titanite, −2456.2 kJ/mol (∆H°_f = −2598.4 kJ/mol) was calculated from the new entropy and volume data combined with data from experimental reversals on the reaction, titanite + kyanite = anorthite + rutile. This value is 4–11 kJ/mol less negative than that obtained from experimental determinations of the enthalpy of formation, and it is slightly more negative than values given in internally consistent databases. The displacement of most calculated phase equilibria involving titanite is not large except for reactions with small ∆S. Re-calculated baric estimates for several metamorphic suites yield pressure differences on the order of 2 kbar in eclogites and 10 kbar for ultra-high pressure titanite-bearing assemblages.     

Systematic study of hydrogen incorporation into Fe-free wadsleyite

The H₂O content of wadsleyite were measured in a wide pressure (13–20 GPa) and temperature range (1,200–1,900°C) using FTIR method. We confirmed significant decrease of the H₂O content of wadsleyite with increasing temperature and reported first systematic data for temperature interval of 1,400–1,900°C. Wadsleyite contains 0.37–0.55 wt% H₂O at 1,600°C, which may be close to its water storage capacity along average mantle geotherm in the transition zone. Accordingly, water storage capacity of the average mantle in the transition zone may be estimated as 0.2–0.3 wt% H₂O. The H₂O contents of wadsleyite at 1,800–1,900°C are 0.22–0.39 wt%, indicating that it can store significant amount of water even under the hot mantle environments. Temperature dependence of the H₂O content of wadsleyite can be described by exponential equation C_{\textH2 \textO} = 6 3 7.0 7 \texte ^{- 0.00 4 8T} , C_{{{\text{H}}_{2} {\text{O}}}} = 6 3 7.0 7 {\text{e}}^{ - 0.00 4 8T} , where T is in °C. This equation is valid for temperature range 1,200–2,100°C with the coefficient of determination R ² = 0.954. Temperature dependence of H₂O partition coefficient between wadsleyite and forsterite (D _wd/fo) is complex. According to our data apparent D_wd/fo decreases with increasing temperature from D _wd/fo = 4–5 at 1,200°C, reaches a minimum of D _wd/fo = 2.0 at 1,400–1,500°C, and then again increases to D _wd/fo = 4–6 at 1,700–1,900°C.     

Mineralogy of telluride-bearing epithermal ores in the Kassiteres-Sappes area, western Thrace, Greece

Summary The Kassiteres-Sappes district represents a multi-centered, porphyry-epithermal system developed during the Oligocene to Miocene at a composite calc-alkaline to high-K calc-alkaline volcanic edifice. Precious and base metal mineralization postdates the emplacement of dacite and rhyolite porphyries and is partly superimposed on earlier microdiorite-related porphyry-style mineralization exposed at the Koryfes Hill prospect. A second mineralized porphyry-type system genetically related to a dacite porphyry body developed near the St Demetrios deposit. Tellurides occur mainly at the St Barbara prospect and the St Demetrios deposit. Based on petrographic, electron microprobe, and scanning electron microscope analyses, hessite, petzite, sylvanite, altaite, stützite and native tellurium occur in the St Barbara prospect. These tellurium-bearing minerals are hosted in intermediate-sulfidation type veins and accompanied by pyrite, chalcopyrite, tetrahedrite-group minerals, galena and native gold/electrum. The St Demetrios mineralization includes hessite, altaite, stützite, and tetradymite in close spatial relation to a high-sulfidation assemblage composed of enargite, chalcopyrite, goldfieldite, and native gold. Tellurides were deposited at logfTe₂ values of −8.5 to −7.1 and logfS₂ values of −10.7 to −7.9 (275 °C). The ore systems are characterized by Au, Ag, Te, Bi, and Mo, which suggests a magmatic contribution to the mineralizing fluids. Ore-forming components were likely derived from both the dacite and rhyolite porphyries.     

The geodynamics of collision of a microplate (Chilenia) in Devonian times deduced by the pressure–temperature–time evolution within part of a collisional belt (Guarguaraz Complex,W-Argentina)

The Guarguaraz Complex in West Argentina formed during collision between the microplate Chilenia and South America. It is composed of neritic clastic metasediments with intercalations of metabasic and ultrabasic rocks of oceanic origin. Prograde garnet growth in metapelite and metabasite occurred between 1.2 GPa, 470°C and 1.4 GPa, 530°C, when the penetrative s₂-foliation was formed. The average age of garnet crystallization of 390 ± 2 Ma (2σ) was determined from three four-point Lu–Hf mineral isochrones from metapelite and metabasite samples and represents the time of collision. Peak pressure conditions are followed by a decompression path with slight heating at 0.5 GPa, 560°C. Fluid release during decompression caused equilibration of mineral compositions at the rims and also aided Ar diffusion. An ⁴⁰Ar/³⁹Ar plateau age of white mica at 353 ± 1 Ma (1σ) indicates the time of cooling below 350–400°C. These temperatures were attained at pressures of 0.2–0.3 GPa, indicative of an average exhumation rate of ≥1 mm/a for the period 390–353 Ma. Late hydrous influx at 0.1–0.3 GPa caused pervasive growth of sericite and chlorite and reset the Ar/Ar ages of earlier coarse-grained white mica. At 284–295 Ma, the entire basement cooled below 280°C (fission track ages of zircon) after abundant post-collisional granitoid intrusion. The deeply buried epicontinental sedimentary rocks, the high peak pressure referring to a low metamorphic geotherm of 10–12°C/km, and the decompression/heating path are characteristics of material buried and exhumed within a (micro) continent–continent collisional setting.     

Annual variations in the surface radiation budget and soil water and heat content in the Upper Yellow River area

Measurements taken between July 2006 to May 2007 at the Maqu station in the Upper Yellow River area were used to study the surface radiation budget and soil water and heat content in this area. These data revealed distinct seasonal variations in downward shortwave radiation, downward longwave radiation, upward longwave radiation and net radiation, with larger values in the summer than in winter because of solar altitudinal angle. The upward shortwave radiation factor is not obvious because of albedo (or snow). Surface albedo in the summer was lower than in the winter and was directly associated with soil moisture and solar altitudinal angle. The annual averaged albedo was 0.26. Soil heat flux, soil temperature and soil water content changed substantially with time and depth. The soil temperature gradient was positive from August to February and was related to the surface net radiation and the heat condition of the soil itself. There was a negative correlation between soil temperature gradient and net radiation, and the correlation coefficient achieved a significance level of 0.01. Because of frozen state of the soil, the maximum soil thermal conductivity value was 1.21 W m⁻¹°C⁻¹ in January 2007. In May 2007, soil thermal conductivity was 0.23 W m⁻¹°C⁻¹, which is the lowest value measured in the study, likely due to the fact that the soil was drier then than in other months. The soil thermal conductivity values for the four seasons were 0.27, 0.38, 0.55 and 0.83 W m⁻¹°C⁻¹, respectively.