The effect of alkalis and polymerization on the solubility of H<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> in alkali-rich silicate melts

The effect of alkalis on the solubility of H₂O and CO₂ in alkali-rich silicate melts was investigated at 500 MPa and 1,250 °C in the systems with H₂O/(H₂O + CO₂) ratio varying from 0 to 1. Using a synthetic analog of phonotephritic magma from Alban Hills (AH1) as a base composition, the Na/(Na + K) ratio was varied from 0.28 (AH1) to 0.60 (AH2) and 0.85 (AH3) at roughly constant total alkali content. The obtained results were compared with the data for shoshonitic and latitic melts having similar total alkali content but different structural characteristics, e.g., NBO/T parameter (the ratio of non-bridging oxygens over tetrahedrally coordinated cations), as those of the AH compositions. Little variation was observed in H₂O solubility (melt equilibrated with pure H₂O fluid) for the whole compositional range in this study with values ranging between 9.7 and 10.2 wt. As previously shown, the maximum CO₂ content in melts equilibrated with CO₂-rich fluids increases strongly with the NBO/T from 0.29 wt % for latite (NBO/T = 0.17) to 0.45 wt % for shoshonite (NBO/T = 0.38) to 0.90 wt % for AH2 (NBO/T = 0.55). The highest CO₂ contents determined for AH3 and AH1 are 1.18 ± 0.05 wt % and 0.86 ± 0.12 wt %, respectively, indicating that Na is promoting carbonate incorporation stronger than potassium. At near constant NBO/T, CO₂ solubility increases from 0.86 ± 0.12 wt % in AH1 [Na/(Na + K)] = 0.28, to 1.18 ± 0.05 wt % in AH3 [Na/(Na + K)] = 0.85, suggesting that Na favors CO₂ solubility on an equimolar basis. An empirical equation is proposed to predict the maximum CO₂ solubility at 500 MPa and 1,100–1,300 °C in various silicate melts as a function of the NBO/T, (Na + K)/∑cations and Na/(Na + K) parameters: \({\text{wt}}\% \;{\text{CO}}_{2} = - 0.246 + 0.014\exp \left( {6.995 \cdot \frac{\text{NBO}}{T}} \right) + 3.150 \cdot \frac{{{\text{Na}} + {\text{K}}}}{{\varSigma {\text{cations}}}} + 0.222 \cdot \frac{\text{Na}}{{{\text{Na}} + {\text{K}}}}.\) This model is valid for melt compositions with NBO/T between 0.0 and 0.6, (Na + K)/∑cation between 0.08 and 0.36 and Na/(Na + K) ratio from 0.25 to 0.95 at oxygen fugacities around the quartz–fayalite–magnetite buffer and above.     

The effects of petroleum-contaminated soil on photosynthesis of <Emphasis Type="Italic">Amorpha fruticosa</Emphasis> seedlings

A pot experiment was conducted to monitor the dynamic response of photosynthesis of Amorpha fruticosa seedlings to different concentrations of petroleum-contaminated soils from April to September. The results showed that the photosynthetic rates, stomatal conductance and transpiration rate of seedlings significantly decreased in 5–20 g kg^?1 petroleum-contaminated soil during the three given sampling period of July 31 (early), August 30 (mid-term) and September 29 (late). However, the intercellular CO₂ concentration significantly increased in 10 g kg^?1 contaminated soil, while declined in 20 g kg^?1 contaminated soil during the early sampling period as well as in 20 g kg^?1 contaminated soil during the late sampling period. The leaf relative water content of seedlings significantly increased in 20 g kg^?1 contaminated soil during the early sampling period, while it dropped dramatically in 15–20 g kg^?1 contaminated soil during the late sampling period. The contents of chlorophyll a, chlorophyll b and the total chlorophyll of seedlings showed a sharp decline during the three sampling periods in contaminated soil. Comprehensively, considering the negative effects of petroleum on the photosynthesis, growth performance and remediation effect on petroleum of A. fruticosa seedlings, this plant was tolerant of petroleum-contaminated soil and was potentially useful for the phytoremediation of petroleum-contaminated sites in northern Shaanxi, China.     

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.     

Experimental study of the dehydration of 10-Å phase,with implications for its H<Subscript>2</Subscript>O content and stability in subducted lithosphere

The 10-Å phase (TAP) is a hydrous magnesium silicate that forms from the reaction of talc with H₂O at high pressures. Its high-pressure, low-temperature stability means that it could be a storage site for H₂O in subduction zones. We have determined the position of the TAP dehydration reaction, TAP = enstatite + coesite + H₂O, in phase-equilibrium experiments from 5.0 to 7.1 GPa. Because previous studies had suggested that the composition of TAP is a function of synthesis duration, we used a TAP sample that was synthesised for 392 h. Over the pressure interval of our experiments, the dehydration reaction is isothermal, occurring at a temperature of ~690°C. It is coincident, within experimental uncertainty, with the position of the dehydration reaction of TAP synthesised in short experiments (up to 46 h). Above 7.5 GPa, TAP breaks down to enstatite + stishovite + H₂O. This reaction has a negative dP/dT and terminates at an invariant point involving the 3.65-Å phase at ~9.5 GPa, 500°C. The zero volume change implied by the isothermal reaction TAP = enstatite + coesite + H₂O was used to calculate the interlayer H₂O content of TAP along the reaction. A best-fit H₂O content of 1 H₂O pfu was obtained. This H₂O content is independent of TAP synthesis conditions, suggesting that variations in previously measured H₂O contents of TAP occur during quenching and decompression of the samples. The stability of TAP in the Earth is probably limited to cold subduction zones, but in these, it could persist to 300 km depth.     

Lawsonite- and glaucophane-bearing blueschists from NW Qiangtang,northern Tibet,China: mineralogy,geochemistry, geochronology,and tectonic implications

The occurrence of high-pressure (HP) blueschists within the central Qiangtang terrane of northern Tibet has a significant bearing on plate-suturing processes. In order to contribute to the ongoing debate on whether the central Qiangtang metamorphic belt represents an in situ suture within the Qiangtang terrane, we examined lawsonite- and glaucophane-bearing blueschists from the northwest Qiangtang area (84° 10′–85° 30′ E, 34°10′–34° 45′ N). All studied rocks are metapelites, metasandstones, or metabasalts, characterized by lawsonite + glaucophane + phengite, lawsonite + glaucophane + epidote + albite + quartz, or glaucophane + phengite + quartz assemblages. The meta-mafic rocks contain very high TiO₂ and low Al₂O₃ contents. They are typified by abundant ferromagnesian trace elements, and an absence of Eu anomalies and Nb–Ta deletions; all the above features indicate that these mafic rocks represent oceanic island basalt (OIB) protoliths. Most of the metasediments contain high SiO₂, moderate Al₂O₃ + K₂O, and low TiO₂ + Na₂O. They display high CIA (chemical index of alteration) values (74% ± 5%) and distinctly negative Eu anomalies (Eu/Eu* = 0.64 ± 0.05). This, along with their high field strength elemental characteristics, indicates that they were deposited in a passive continental margin environment, intercalated with OIB-type basalts. We estimate the peak metamorphic conditions for these blueschists as T = 330–415°C and P = 9–11.5 kbar. This HP event occurred at ca. 242 Ma, indicated by a well-defined ⁴⁰Ar/³⁹Ar plateau age for glaucophane. Retrograde metamorphism occurred at T = 280–370°C, P = 6.5–9.5 kbar, t = ca. 207 Ma (⁴⁰Ar/³⁹Ar dating of phengite). Therefore, a cold subduction (geotherm ～8°C/km) attended the passive continental margin during the Triassic when the eastern Qiangtang collided with the western Qiangtang. The northwest Qiangtang HP metamorphic belt is an extension of the central Qiangtang metamorphic belt that defines the suture between eastern and western Qiangtang, and indicates an anticlockwise, diachronous closure of the Shuanghu Palaeo-Tethys.     

Alkali in phlogopite and amphibole and their effects on phase relations in metasomatized peridotites: a high-pressure study

Subsolidus phase relations for a K-doped lherzolite are investigated in the model system K₂O–Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O at 1.5–6.0 GPa and 680–1,000°C. Phlogopite is ubiquitous and coexists with Ca-amphibole up to 3.2 GPa and 900°C. High-pressure phlogopites show a peculiar mineral chemistry dependent on pressure: e.g., at 5.5 GPa and 680°C, excess of Si (up to 3.4 apfu) coupled with deficiency in Al (as low as 0.58 apfu) and K + Na (as low as 0.97 apfu), suggest a significant amount of a talc/10 Å phase component ([v]^XIISi₁K_?1Al _?1 ^IV , where [v]^XII is interlayer vacancy). Mixed layering or solid solution relations between high-pressure phlogopites and the 10 Å phase, Mg₃Si₄O₁₀(OH)₂ nH₂O, are envisaged. Phlogopite modal abundance, derived by weighted least squares, is maximum at high-pressure and relative low-temperature conditions and therefore along the slab–mantle interface (10.3 ± 0.7 wt.%, at 4.8 GPa, 680°C). In phlogopite-bearing systems, Ca-amphibole breaks down between 2.5 and 3.0 GPa, and 1,000°C, through the water conservative reaction 5(pa + 0.2 KNa_?1) + 17en + 15phl = (10di + 4jd) + 5py + 12fo + 20(phl + 0.2 talc), governed by bulk composition and pressure-dependent variations of K/OH in K-bearing phases and as a result, it does not necessarily imply a release of fluid.     

Crystallization conditions of peraluminous charnockites: constraints from mineral thermometry and thermodynamic modelling

Most igneous charnockites are interpreted to have crystallized at hot and dry conditions, i.e. at >800?°C and <3 wt.% H₂O and with an important CO₂ component in the system. These charnockites are metaluminous to weakly peraluminous and their formation involves a significant mantle-derived component. This study, in contrast, investigates the crystallization conditions of strongly peraluminous, metasediment-sourced charnockites from the Qinzhou Bay Granitic Complex, South China. To constrain the temperature-melt H₂O crystallization paths for the studied peraluminous charnockites, petrographic characterization was combined with fluid inclusion compositional data, mineral thermometry, and thermodynamic modelling. The uncertainties of the thermodynamic modelling in reconstructing the crystallization conditions of the granitic magmas have been evaluated by comparison between modelled and experimental phase relations for a moderately evolved, peraluminous granite (~70 wt.% SiO₂). The comparison suggests that the modelling reproduces the experimentally derived phase saturation boundaries with uncertainties of 20–60?°C and 0.5–1 wt.% H₂O for systems with ≤1–2 wt.% initial melt H₂O at ~0.2 GPa. For the investigated natural systems, the thermometric estimates and modelling indicate that orthopyroxene crystallized at relatively low temperature (750–790?±?30?°C) and moderately high to high melt H₂O content (3.5–5.6?±?0.5 wt.%). The charnockites finally solidified at relatively “cold” and “wet” conditions. This suggests that thermodynamic modelling affords a possible approach to constrain charnockite crystallization as tested here for peraluminous, moderately low pressure (≤0.3 GPa), and overall H₂O-poor systems (≤1–2 wt.% H₂O total), but yields results with increasing uncertainty for high-pressure or H₂O-rich granitic systems.     

Origin of peraluminous minerals (corundum,spinel, and sapphirine) in a highly calcic anorthosite from the Sittampundi Layered Complex,Tamil Nadu,India

The highly calcic anorthosite (An_>95) from the Sittampundi Layered Complex (SLC) develops corundum, spinel and sapphirine that are hitherto not reported from any anorthositic rocks in the world. Petrological observations indicate the following sequence of mineral growth: plagioclase_matrix → corundum; clinopyroxene → amphibole; corundum + amphibole → plagioclase_corona + spinel; and spinel + corundum → coronitic sapphirine. Phase relations in the CaO–Na₂O–Al₂O₃–SiO₂–H₂O (CNASH) system suggest that corundum was presumably developed through vapour present incongruent melting of the highly calcic plagioclase during ultra-high temperature (UHT) metamorphism (T ≥ 1000 °C, P ≥ 9 kbar). Topological constraints in parts of the Na₂O–CaO–MgO–Al₂O₃–SiO₂–H₂O (NCMASH) system suggest that subsequent to the UHT metamorphism, aqueous fluid(s) permeated the rock and the assemblage corundum + amphibole + anorthite + clinozoisite was stabilized during high-pressure (HP) metamorphism (11 ± 2 kbar, 750 ± 50 °C). Constraints of the NCMASH topology and thermodynamic and textural modeling study suggest that coronitic plagioclase and spinel formed at the expense of corundum + amphibole during a steeply decompressive retrograde P–T path (7–8 kbar and 700–800 °C) in an open system. Textural modeling studies combined with chemical potential diagrams (μSiO₂–μMgO) in the MASH system support the view that sapphirine also formed from due to silica and Mg metasomatism of the precursor spinel ± corundum, on the steeply decompressive retrograde P–T path, prior to onset of significant cooling of the SLC. Extremely channelized fluid flow and large positive solid volume change of the stoichiometrically balanced sapphirine forming reaction explains the localized growth of sapphirine.     

Field-scale evaluation of the chemical–biological stabilization process for the remediation of hydrocarbon-contaminated soil

Developing countries face the challenge of growing their economy while reducing the negative environmental impacts of industry, thus requiring treatment technologies that are economical and effective. One recent technology developed in the tropical part of Mexico for the remediation of petroleum-contaminated soil was tested in this scale-up project at an industrial level, whereas previously it had only been tested at laboratory scale; 150 m³ of bentonitic mud, contaminated with weathered hydrocarbons (3.4°API) at ~50,000 ppm, was treated with 4 % Ca(OH)₂, 4 % organic amendment, and a fine-root tropical grass. Hydrocarbons in soil and in leachates, as well as pH, and acute toxicity (Microtox) were monitored for 28.8 months. At the end of the study, basal respiration, root density, and earthworm toxicity were also measured. The hydrocarbon concentration in soil was reduced to 45 %, and toxicity was eliminated. Hydrocarbons in leachates were reduced to ~1 mg/l, safe for human consumption. The pH adjustment depended on low soil moisture and was stabilized at 7.1. Intense revegetation resulted in good root density, within 90 % of nearby uncontaminated soil under pasture. Basal respiration was increased to levels comparable to uncontaminated tropical soils with agricultural use, pasture and gallery forest. At an industrial scale, strict moisture control was necessary for good pH stabilization. By controlling these conditions and applying this novel treatment process, it was possible to transform a heavily contaminated geological material into a non-toxic, fertile, soil-like substrate capable of maintaining a complete vegetative cover and microbial activity comparable to similar soils in a tropical environment.     

Titanium- and water-rich metamorphic olivine in high-pressure serpentinites from the Voltri Massif (Ligurian Alps,Italy): evidence for deep subduction of high-field strength and fluid-mobile elements

Titanium- and water-rich metamorphic olivine (Fo 86–88) is reported from partially dehydrated serpentinites from the Voltri complex, Ligurian Alps. The rocks are composed of mostly antigorite and olivine in addition to magnetite, chlorite, clinopyroxene and Ti-clinohumite. In situ secondary ion mass spectrometry (SIMS) data show that metamorphic olivine has very high and strongly correlated H₂O (up to 0.7 wt%) and TiO₂ contents (up to 0.85 wt%). Ti-rich olivine shows colourless to yellow pleochroism. Olivine associated with Ti-clinohumite contains low Ti, suggesting that Ti-rich olivine is not the breakdown product of Ti-clinohumite. Fourier transform infrared spectroscopy (FTIR) absorption spectra show peaks of serpentine, Ti-clinohumite and OH-related Si vacancies. Combining FTIR and SIMS data, we suggest the presence of clustered planar defects or nanoscale exsolutions of Ti-clinohumite in olivine. These defects or exsolutions contain more H₂O (x ~ 0.1 in the formula 4Mg₂SiO₄·(1?x)Mg(OH,F)₂·xTiO₂) than Ti-clinohumite in the sample matrix (x = 0.34–0.46). In addition to TiO₂ and H₂O, secondary olivine contains significant Li (2–60 ppm), B (10–20 ppm), F (10–130 ppm) and Zr (0.9–2.1 ppm). It is enriched in ¹¹B (δ¹¹B = +17 to +23 ‰). Our data indicate that secondary olivine may play a significant role in transporting water, high-field strength and fluid-mobile elements into the deeper mantle as well as introduce significant B isotope anomalies. Release of hydrogen from H₂O-rich olivine subducted into the deep mantle may result in strongly reduced mantle domains.     

C–O–H–N fluids in quartz segregations from a major ductile shear zone: the Berzosa fault, Spanish Central System

Abstract The Berzosa fault is a major ductile shear zone, the Berzosa Shear Zone (BSZ), which separates the ‘Ollo de Sapo’anticline from the inner higher-grade crystalline axis of the Iberian Hercynian Belt. This shear zone is the site of abundant early kinematic quartz (± Al-silicates) segregations, rich in fluid inclusions. Host rocks are medium-grade staurolite schists and sillimanite gneisses. Fluid inclusions in selected quartz segregations across the Berzosa shear zone have been studied by microthermometric methods as well as, in some instances, by Raman analysis. The recorded fluid inclusion history begins at the end of an intense secondary recrystallization period during late-peak metamorphic conditions and lasts until late in the uplift history of the zone. Three types of inclusions have been found, which in a time sequence are: CO₂± H₂O; H₂O+salt (B-type); and, N₂+CH₄. Three types of B inclusion may be distinguished in turn, depending on whether they were trapped during an earlier dynamic-recovery phase (B₁-type), formed later as intergranular trails (B₂-type), or were trapped apparently along with N₂+CH₄ in clusions from a heterogeneous fluid (B₃-type). Considerations from isochores confirm that CO₂± H₂O inclusions were trapped during late-peak and high-T retrograde metamorphic conditions (in the range 650–500°C and 5–2 kbar), whilst N₂+CH₄ inclusions, along with the B₃-type of inclusions, formed at low-pressures (<1 kbar) and temperatures (± 300°C). B₂-type inclusions were trapped chronologically between these two in a period in which strong inverse lateral thermal gradients developed in the zone. Inferred P-T paths for the area are convex to the T-axis.     

The thermodynamic properties of H2O in magnesium and iron cordierite

 The equilibrium water content of cordierite has been measured for 31 samples synthesized at pressures of 1000 and 2000 bars and temperatures from 600 to 750° C using the cold-seal hydrothermal technique. Ten data points are presented for pure magnesian cordierite, 11 data points for intermediate iron/magnesium ratios from 0.25 to 0.65 and 10 data points for pure iron cordierite. By representing the contribution of H₂O to the heat capacity of cordierite as steam at the same temperature and pressure, it is possible to calculate a standard enthalpy and entropy of reaction at 298.18° K and 1 bar for, (Mg,Fe)₂Al₄Si₅O₁₈+H₂O ⇄ (Fe,Mg)₂Al₄Si₅O₁₈.H₂O Combining the 31 new data points with 89 previously published experimental measurements gives: ΔH ^° _r =–37141±3520 J and ΔS ^° _r =–99.2±4 J/degree. This enthalpy of reaction is within experimental uncertainty of calorimetric data. The enthalpy and entropy of hydration derived separately for magnesian cordierite (–34400±3016 J, –96.5±3.4 J/degree) and iron cordierite (–39613±2475, –99.5±2.5 J/degree) cannot be distinguished within the present experimental uncertainty. The water content as a function of temperature, T(K), and water fugacity, f(bars), is given by n _H2O=1/[1+1/(K ⋅ f _H2O)] where the equilibrium constant for the hydration reaction as written above is, ln K=4466.4/T–11.906 with the standard state for H₂O as the gas at 1 bar and T, and for cordierite components, the hydrous and anhydrous endmembers at P and T. Received: 2 August 1994/Accepted: 7 February 1996     

Experimental study into the petrogenesis of crystal-rich basaltic to andesitic magmas at Arenal volcano

Arenal volcano is nearly unique among arc volcanoes with its 42 year long (1968–2010) continuous, small-scale activity erupting compositionally monotonous basaltic andesites that also dominate the entire, ~7000 year long, eruptive history. Only mineral zoning records reveal that basaltic andesites are the result of complex, open-system processes deriving minerals from a variety of crystallization environments and including the episodic injections of basalt. The condition of the mafic input as well as the generation of crystal-rich basaltic andesites of the recent, 1968–2010, and earlier eruptions were addressed by an experimental study at 200 MPa, 900–1,050 °C, oxidizing and fluid-saturated conditions with various fluid compositions [H₂O/(H₂O + CO₂) = 0.3–1]. Phase equilibria were determined using a phenocryst-poor (~3 vol%) Arenal-like basalt (50.5?wt% SiO₂) from a nearby scoria cone containing olivine (Fo₉₂), plagioclase (An₈₆), clinopyroxene (Mg# = 82) and magnetite (X_ulvö = 0.13). Experimental melts generally reproduce observed compositional trends among Arenal samples. Small differences between experimental melts and natural rocks can be explained by open-system processes. At low pressure (200 MPa), the mineral assemblage as well as the mineral compositions of the natural basalt were reproduced at 1,000 °C and high water activity. The residual melt at these conditions is basaltic andesitic (55 wt% SiO₂) with 5 wt% H₂O. The evolution to more evolved magmas observed at Arenal occurred under fluid-saturated conditions but variable fluid compositions. At 1,000 °C and 200 MPa, a decrease of water content by approximately 1 wt% induces significant changes of the mineral assemblage from olivine + clinopyroxene + plagioclase (5 wt% H₂O in the melt) to clinopyroxene + plagioclase + orthopyroxene (4 wt% H₂O in the melt). Both assemblages are observed in crystal-rich basalt (15 vol%) and basaltic andesites. Experimental data indicate that the lack of orthopyroxene and the presence of amphibole, also observed in basaltic andesitic tephra units, is due to crystallization at nearly water-saturated conditions and temperatures lower than 950 °C. The enigmatic two compositional groups previously known as low- and high-Al₂O₃ samples at Arenal volcano may be explained by low- and high-pressure crystallization, respectively. Using high-Al as signal of deeper crystallization, first magmas of the 1968–2010 eruption evolved deep in the crust and ascent was relatively fast leaving little time for significant compositional overprint by shallower level crystallization.     

Volatiles contents, degassing and crystallisation of intermediate magmas at Volcan de Colima, Mexico, inferred from melt inclusions

In volatile-saturated magmas, degassing and crystallisation are interrelated processes which influence the eruption style. Melt inclusions provide critical information on volatile and melt evolution, but this information can be compromised significantly by post-entrapment modification of the inclusions. We assess the reliability and significance of pyroxene-hosted melt inclusion analyses to document the volatile contents (particularly H₂O) and evolution of intermediate arc magmas at Volcán de Colima, Mexico. The melt inclusions have maximal H₂O contents (≤4 wt%) consistent with petrological estimates and the constraint that the magmas crystallised outside the amphibole stability field, demonstrating that pyroxene-hosted melt inclusions can preserve H₂O contents close to their entrapment values even in effusive eruptions with low effusion rates (0.6 m³ s^?1). The absence of noticeable H₂O loss in some of the inclusions requires post-entrapment diffusion coefficients (≤1 × 10^?13 m² s^?1) at least several order of magnitude smaller than experimentally determined H⁺ diffusion coefficient in pyroxenes. The H₂O content distribution is, however, not uniform, and several peaks in the data, interpreted to result from diffusive H₂O reequilibration, are observed around 1 and 0.2 wt%. H₂O diffusive loss is also consistent with the manifest lack of correlations between H₂O and CO₂ or S contents. The absence of textural evidence supporting post-entrapment H₂O loss suggests that diffusion most likely occurred via melt channels prior to sealing of the inclusions, rather than through the host crystals. Good correlation between the melt inclusion sealing and volcano-tectonic seismic swarm depths further indicate that, taken as a whole, the melt inclusion population accurately records the pre-eruptive conditions of the magmatic system. Our data demonstrate that H₂O diffusive loss is a second-order process and that pyroxene-hosted melt inclusions can effectively record the volatile contents and decompression-induced crystallisation paths of vapour-saturated magmas.     

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.     

The solubility of Gd<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript> and the hydrolysis of Gd<Superscript>3+</Superscript> in acidic solutions at 250°C and saturation vapor pressure

The solubility of Gd₂Ti₂O₇ ceramic in acidic solutions (HCl and HClO₄) was studied at 250°C and saturation vapor pressure within pH 2.5–5.2. The dissolution process occurs mainly via two reactions: 0.5 Gd₂Ti₂O_7(cr) + 3H⁺ = Gd³⁺ + TiO_2(cr) + 1.5 H₂O at pH < 3 and 0.5Gd₂Ti₂O₇(cr) + H⁺ + 0.5H₂O = Gd(OH) ₂ ⁺ TiO₂(cr) at pH 3–5. The thermodynamic equilibrium constants were calculated at the 0.95 confidence level as log K ₍₁₎ ^o = 4.12 ± 0.47; = ?0.97 ± 0.16 at 250°C. It was shown that Gd³⁺ undergoes hydrolysis in solutions with pH > 3, and the species Gd(OH) ₂ ⁺ dominates up to at least pH 5. At pH < 3, Gd occurs in solutions as Gd³⁺. The second constant of Gd³⁺ hydrolysis was determined at 250°C as K ^o = ?5.09 ± 0.5, and the thermodynamic characteristics of the initial Gd₂Ti₂O₇ solid phase were determined: S _298.15 ^o = 251.4 J/(mol K) and ΔfG _298.15 ^o = ?3630 ± 10 kJ/mol.     

Static elasticity of cordierite II: effect of molecular CO2 channel constituents on the compressibility

Two natural CO₂-rich cordierite samples (1.00 wt% CO₂, 0.38 wt% H₂O, and 1.65 wt% CO₂, 0.15 wt% H₂O, respectively) were investigated by means of Raman spectroscopy and single-crystal X-ray diffraction at ambient and high pressures. The effect of heavy-ion irradiation (Au 2.2 GeV, fluence of 1 × 10¹² ions cm^?2) on the crystal structure was investigated to characterize the structural alterations complementary to results reported on hydrous cordierite. The linear CO₂ molecules sustained irradiation-induced breakdown with small CO₂-to-CO conversion rates in contrast to the distinct loss of channel H₂O. The maximum CO₂ depletion rate corresponds to ~12 ± 5 % (i.e. ~0.87 and ~1.49 wt% CO₂ according to the two samples, respectively). The elastic properties of CO₂-rich cordierite reveal stiffening due to the CO₂ molecules (non-irradiated: isothermal bulk modulus K ₀ = 120.3 ± 3.7 GPa, irradiated: K ₀ = 109.7 ± 3.7 GPa), but show the equivalent effect of hydrous cordierite to get softer when irradiated. The degree of anisotropy of axial compressibilities and the anomalous elastic softening at increasing pressure agrees with those reported for hydrous cordierite. Nevertheless, the experimental high-pressure measurements using ethanol–methanol reveal a small hysteresis between compression and decompression, together with the noticeable effect of pressure-induced over-hydration at pressures between 4 and 5 GPa.     

Solubility of Ca6[Al(OH)6]2(CrO4)3·26H2O,the chromate analog of ettringite; 5–75°C

Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O, the chromate analog of the sulfate mineral ettringite, was synthesized and characterized by X-ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analyses, energy dispersive X-ray spectrometry, and bulk chemical analyses. The solubility of the synthesized solid was measured in a series of dissolution and precipitation experiments conducted at 5–75°C and at initial pH values between 10.5 and 12.5. The ion activity product (IAP) for the reaction Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O⇌6Ca²⁺+2Al(OH)⁻₄+3CrO²⁻₄+4OH⁻+26H₂O varies with pH unless a CaCrO_4(aq) complex is included in the speciation model. The log K for the formation of this complex by the reaction Ca²⁺+CrO²⁻₄=CaCrO_4(aq) was obtained by minimizing the variance in the IAP for Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O. There is no significant trend in the formation constant with temperature and the average log K is 2.77±0.16 over the temperature range 5–75°C. The log solubility product (log K_SP) of Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O at 25°C is −41.46±0.30. The temperature dependence of the log K_SP is log K_SP=A−B/T+D log(T) where A=498.94±48.99, B=27,499±2257, and D=−181.11±16.74. The values of ΔG⁰_r,298 and ΔH⁰_r,298 for the dissolution reaction are 236.6±3.9 and 77.5±2.4 kJ mol⁻¹. the values of ΔC⁰_P,r,298 and ΔS⁰_r,298 are −1506±140 and −534±83 J mol⁻¹ K⁻¹. Using these values and published standard state partial molal quantities for constituent ions, ΔG⁰_f,298=−15,131±19 kJ mol⁻¹, ΔH⁰_f,298=−17,330±8.6 kJ mol⁻¹, ΔS⁰₂₉₈=2.19±0.10 kJ mol⁻¹ K⁻¹, and ΔC⁰_Pf,298=2.12±0.53 kJ mol⁻¹ K⁻¹, were calculated.     

Improving microbial oil production with standard and native oleaginous yeasts by using Taguchi design

Production of microbial oil has attracted a great attention in recent years. The potential of lipid production by the yeast strains is the reason for using microorganisms for biodiesel production. Microbial lipid has high similarity to the oil obtained from plants and animals in type and composition. Production of oil from yeasts must be economical, so optimization of the cultivation condition to reach higher production must be done. Native oleaginous yeast, Cryptococcus albidus, was isolated from soil by the nitrogen-limited medium and screened by Nile red staining. Yarrowia lipolytica DSM 8218 was used for lipid production as a standard strain. C. albidus was an excellent oleaginous yeast, and the lipid quantity, dry biomass and lipid productivity of this strain were 11.81 g/l, 19.65 g/l and 60.1 %, respectively, in shaking flask cultivation at 150 rpm and 25 °C in nitrogen-limited medium containing per liter 75 g glucose, 1 g (NH₄)₂SO₄, 1 g yeast extract, 3 g KH₂PO₄, 1.5 g MgSO₄.7H₂O, 0.15 g CaCl₂, 0.06 g MnSO₄.H₂O, 0.02 g ZnSO₄.7H₂O and 0.15 g FeCl₃.6H₂O with pH adjusted to 6.5. Fourier transform infrared spectroscopy was used for analyzing and confirming the production of microbial oil in this study.     

Nitrous oxide (N<Subscript>2</Subscript>O) emissions from a mesotrophic reservoir on the Wujiang River,southwest China

Aquatic ecosystems have been identified as a globally significant source of nitrous oxide (N₂O) due to continuous active nitrogen involvement, but the processes and influencing factors that control N₂O production are still poorly understood, especially in reservoirs. For that, monthly N₂O variations were monitored in Dongfeng reservoir (DFR) with a mesotrophic condition. The dissolved N₂O concentration in DFR displayed a distinct spatial–temporal pattern but lower than that in the eutrophic reservoirs. During the whole sampling year, N₂O saturation ranging from 144% to 640%, indicating that reservoir acted as source of atmospheric N₂O. N₂O production is induced by the introduction of nitrogen (NO₃ ^?, NH₄ ⁺) in mesotrophic reservoirs, and is also affected by oxygen level and water temperature. Nitrification was the predominate process for N₂O production in DFR due to well-oxygenated longitudinal water layers. Mean values of estimated N₂O flux from the air–water interface averaged 0.19 µmol m^?2 h^?1 with a range of 0.01–0.61 µmol m^?2 h^?1. DFR exhibited less N₂O emission flux than that reported in a nearby eutrophic reservoir, but still acted as a moderate N₂O source compared with other reservoirs and lakes worldwide. Annual emissions from the water–air interface of DFR were estimated to be 0.32 × 10⁵ mol N–N₂O, while N₂O degassing from releasing water behind the dam during power generation was nearly five times greater. Hence, N₂O degassing behind the dam should be taken into account for estimation of N₂O emissions from artificial reservoirs, an omission that historically has probably resulted in underestimates. IPCC methodology should consider more specifically N₂O emission estimation in aquatic ecosystems, especially in reservoirs, the default EF5 model will lead to an overestimation.