The solubility of BaCO3(cr) (witherite) in CO2-H2O solutions between 0 and 90°C,evaluation of the association constants of BaHCO3+(aq) and BaCO30(aq) between 5 and 80°C,and a preliminary evaluation of the thermodynamic properties of Ba2+(aq)

One hundred and fifty new measurements of the solubility of witherite were used to evaluate the equilibrium constant of the reaction BaCO₃(cr) = Ba²⁺(aq) + CO₃²⁻(aq) between 0 and 90°C and 1 atm total pressure. The temperature dependence of the equilibrium constant is given by logK = 607.642 + 0.121098T − 20011.25/T − 236.4948 logT where T is in degrees Kelvin. The logK of BaCO₃(cr), the Gibbs energy, the enthalpy and entropy of the reaction at 298.15 K are −8.562, 48.87 kJ · mol⁻¹, 2.94 kJ · mol⁻¹ and −154.0 J · mol⁻¹ · K⁻¹, respectively. The equilibrium constants are consistent with an aqueous model that includes the ion pairs BaHCO₃⁺(aq) and BaCO₃⁰(aq) Three different methods were used to evaluate the association constant of BaHCO₃⁺(aq), and all yielded similar results. The temperature dependence of the association constant for the reaction Ba²⁺(aq) + HCO₃⁻(aq) = BaHCO₃⁺(aq) is given by logK_BaHCO3⁺ = −3.0938 + 0.013669T.The log of the association constant, the Gibbs energy, the enthalpy and entropy of the reaction at 298.15°K are 0.982, −5.606 kJ · mol⁻¹, 23.26 kJ · mol⁻¹ and 96.8 J · mol⁻¹ · K⁻¹, respectively. The temperature dependence of the equilibrium constant for the reaction Ba²⁺(aq) + CO²⁻₃(aq) = BaCO₀³(aq) is given by logK_BaCO3⁰ = 0.113 + 0.008721T.The log of the association constant, the Gibbs energy, the enthalpy and entropy of the reaction at 298.15° K are 2.71, −15.49 kJ · mol⁻¹, 14.84 kJ · mol⁻¹ and 101.7 J· mol⁻¹ · K⁻¹.The above model leads to reliable calculations of the aqueous speciation and solubility of witherite in the system BaCO₃-CO₂-H₂O from 0 to more than 90°C. Literature data on witherite solubility were re-evaluated and compared with the results of this study.Problems in the thennodynamic selections of Ba compounds are considered. Newer data require the revision of Δ_fH° and Δ_fG° of Ba²⁺(aq) to −532.5 and −555.36 kJ · mol⁻¹, respectively, for agreement with solubility data.     

New high-pressure phases in BaCO<Subscript>3</Subscript>

Barium carbonate (BaCO₃) was examined in a diamond anvil cell up to a pressure of 73 GPa using an in situ angle-dispersive X-ray diffraction technique. Three new phases of BaCO₃ were observed at pressures >10 GPa. From 10 to 24 GPa, BaCO₃-IV had a post-aragonite structure with space group Pmmn. There are two molecules in a single unit cell (Z = 2) of the orthorhombic phase, which is same as the high-pressure phases of CaCO₃ and SrCO₃. The isothermal bulk modulus of BaCO₃-IV is K ₀ = 84(4) GPa, with V ₀ = 129.0(7) Å³ when K ₀′ = 4. The c axis of the unit cell parameter is less compressible than the a and b axes. The relative change in volume that accompanies the transformation between BaCO₃-III and BaCO₃-IV is ～6%. BaCO₃-V, which has an orthorhombic symmetry, was synthesized at 50 GPa. As the pressure increases, BaCO₃-V is transformed into tetragonal BaCO₃-VI. This transformation is likely to be second order, because the diffraction pattern of BaCO₃-V is similar to that of BaCO₃-VI, and some single peaks in BaCO₃-VI become doublets in BaCO₃-V. After decompression, the new high-pressure phases transform into BaCO₃-II. Our findings resolve a dispute regarding the stable high-pressure phases of BaCO₃.     

The heat capacity of two natural chlorite group minerals derived from differential scanning calorimetry

The heat capacity of natural chamosite (X_Fe=0.889) and clinochlore (X_Fe=0.116) were measured by differential scanning calorimetry (DSC). The samples were characterised by X-ray diffraction, microprobe analysis and Mössbauer spectroscopy. DSC measurements between 143 and 623?K were made following the procedure of Bosenick et?al. (1996). The fitted data for natural chamosite (CA) in J?mol^?1?K^?1 give: C _p,CA = 1224.3–10.685?×?10³?×?T ^??0.5???6.4389?× 10⁶?×T ^??2?+?8.0279?×?10⁸?×?T ^??3 and for the natural clinochlore (CE): C _p,CE = 1200.5–10.908?×?10³?×T ^??0.5?? 5.6941?×?10⁶?×?T ^??2?+?7.1166?×?10⁸?×?T ^??3. The corrected C _p-polynomial for pure end-member chamosite (Fe₅Al)[Si₃AlO₁₀](OH)₈ is C _p,CAcor = 1248.3–11.116?× 10³?×?T ^??0.5???5.1623?×?10⁶?×?T ^??2?+?7.1867?×?10⁸×T ^??3 and the corrected C _p-polynomial for pure end-member clinochlore (Mg₅Al)[Si₃AlO₁₀](OH)₈ is C _p,CEcor = 1191.3–10.665?×?10³?×?T ^??0.5???6.5136?×?10⁶?×?T ^??2?+ 7.7206?×?10⁸?×?T ^??3. The corrected C _p-polynomial for clinochlore is in excellent agreement with that in the internally consistent data sets of Berman (1988) and Holland and Powell (1998). The derived C _p-polynomial for chamosite (C _p,CAcor) leads to a 4.4% higher heat capacity, at 300?K, compared to that estimated by Holland and Powell (1998) based on a summation method. The corrected C _p-polynomial (C _p,CAcor) is, however, in excellent agreement with the computed C _p-polynomial given by Saccocia and Seyfried (1993), thus supporting the reliability of Berman and Brown's (1985) estimation method of heat capacities.     

Experimental study of subsolidus phase relations and mixing properties of pyroxene in the system CaO-Al2O3-SiO2

Subsolidus phase relations in the system CaO-Al₂O₃-SiO₂ (CAS) were experimentally determined with tight reversals of several univariant curves and with 14 equilibration experiments containing the assemblage pyroxene + anorthite, where pyroxene is a binary solid solution of Ca-Tschermak (CaTs-CaAl₂SiO₆) and Ca-Eskola (CaEs-Ca_0.5AlSi₂O₆) endmembers.Reversals were obtained on the following reactions (bar, °C): 3An = Gr + 2Ky + Q (P = 22T ? 700), 3An + Cor = Gr + 3Ky (P = 21.8T ? 950), 3CaTs= Gr + 2Cor(P = 55T ? 53900), and 6CaTs_{(1 ? x)}CaEs_x = 2(1 ? 2x)Gr + 4(1 ? 2x)Cor + 9xAn. Observed slopes indicate 9.8 J/mol · K of Al-Si disorder in Ca-Tschermak pyroxene and 5.3 J/mol·K of Al-Si disorder in anorthite, at 1300°C. It is suggested that Al-Si disorder in anorthite increases by 1.9 J/mol · K from 700°C to 1300°C.Compositions of CaTs-CaEs pyroxene in equilibrium with anorthite and PbO-rich liquid were experimentally determined at 1400–1430°C and 22.7–30.8 kbar. Microprobe measurements gave compositions which are consistent with an ideal pyroxene solution and the following parameters for the reaction 3An = 2CaTs + 2CaEs (J, bar, K): 2RTln(X_CaTs · X_CaEs) + 60200 + 86.4T ? (5.06 + 13 × 10^?7P)P = 0, resulting in ΔH⁰_j = ?39.8 kJ/mol and S⁰ = 461.8 J/mol · K for the Ca-Eskola endmember at 1300°C. The obtained properties of the Ca-Eskola component are necessary for thermobarometry based on pyroxene bearing assemblages containing plagioclase, quartz, or kyanite.     

Thermodynamics and crystal chemistry of the hematite–corundum solid solution and the FeAlO3 phase

High-temperature oxide-melt calorimetry and Rietveld refinement of powder X-ray diffraction patterns were used to investigate the energetics and structure of the hematite–corundum solid solution and ternary phase FeAlO₃ (with FeGaO₃ structure). The mixing enthalpies in the solid solution can be described by a polynomial ΔH_mix=WX _hem(1?X _hem) with W=116 ± 10 kJ mol^?1. The excess mixing enthalpies are too positive to reproduce the experimental phase diagram, and excess entropies in the solid solution should be considered. The hematite–corundum solvus can be approximately reproduced by a symmetric, regular-like solution model with ΔG _excess=(W _H ?TW _S )X _hem X _cor, where W _H= 116 ± 10 kJ mol^?1 and W _S =32 ± 4 J mol^?1 K^?1. In this model, short-range order (SRO) of Fe/Al is neglected because SRO probably becomes important only at intermediate compositions close to Fe:Al=1:1 but these compositions cannot be synthesized. The volume of mixing is positive for Al-hematite but almost ideal for Fe-corundum. Moreover, the degree of deviation from Vegard's law for Al-hematite depends on the history of the samples. Introduction of Al into the hematite structure causes varying distortion of the hexagonal network of oxygen ions while the position of the metal ions remains intact. Distortion of the hexagonal network of oxygen ions attains a minimum at the composition (Fe_0.95Al_0.05)₂O₃. The enthalpy of formation of FeAlO₃ from oxides at 298 K is 27.9 ± 1.8 kJ mol^?1. Its estimated standard entropy (including configurational entropy due to disorder of Fe/Al) is 98.9 J mol^?1 K^?1, giving the standard free energy of formation at 298 K from oxides and elements as +19.1 ± 1.8 and ?1144.2 ± 2.0 kJ mol^?1, respectively. The heat capacity of FeAlO₃ is approximated as C _p (T in K)= 175.8 ? 0.002472T ? (1.958 × 10⁶)/T ²? 917.3/T ^0.5+(7.546 × 10^?6) T ² between 298 and 1550 K, based on differential scanning calorimetric measurements. No ferrous iron was detected in FeAlO₃ by Mössbauer spectroscopy. The ternary phase is entropy stabilized and is predicted to be stable above about 1730 ± 70 K, in good agreement with the experiment. Static lattice calculations show that the LiNbO₃-, FeGaO₃-, FeTiO₃-, and disordered corundum-like FeAlO₃ structures are less stable (in the order in which they are listed) than a mechanical mixture of corundum and hematite. At high temperatures, the FeGaO₃-like structure is favored by its entropy, and its stability field appears on the phase diagram.     

Stability and equation of state of post-aragonite BaCO3

At ambient conditions, witherite is the stable form of BaCO₃ and has the aragonite structure with space group Pmcn. Above ~10 GPa, BaCO₃ adopts a post-aragonite structure with space group Pmmn. High-pressure and high-temperature synchrotron X-ray diffraction experiments were used to study the stability and equation of state of post-aragonite BaCO₃, which remained stable to the highest experimental P–T conditions of 150 GPa and 2,000 K. We obtained a bulk modulus K ₀ = 88(2) GPa with $K'$  = 4.8(3) and V ₀ = 128.1(5) ų using a third-order Birch-Murnaghan fit to the 300 K experimental data. We also carried out density functional theory (DFT) calculations of enthalpy (H) of two structures of BaCO₃ relative to the enthalpy of the post-aragonite phase. In agreement with previous studies and the current experiments, the calculations show aragonite to post-aragonite phase transitions at ~8 GPa. We also tested a potential high-pressure post–post-aragonite structure (space group C222 ₁ ) featuring four-fold coordination of oxygen around carbon. In agreement with previous DFT studies, ΔH between the C222 ₁ structure and post-aragonite (Pmmn) decreases with pressure, but the Pmmn structure remains energetically favorable to pressures greater than 200 GPa. We conclude that post–post-aragonite phase transformations of carbonates do not follow systematic trends observed for post-aragonite transitions governed solely by the ionic radii of their metal cations.     

Elasticity of CaSnO3 perovskite

The elastic properties of CaSnO₃ perovskite have been measured by both ultrasonic interferometry and single-crystal X-ray diffraction at high pressures. The single-crystal diffraction data collected using a diamond-anvil cell show that CaSnO₃ perovskite does not undergo any phase transitions at pressures below 8.5?GPa at room temperature. Ultrasonic measurements in the multianvil press to a maximum pressure of ～8?GPa at room temperature yielded S- and P-wave velocity data as a function of pressure. For a third-order Birch-Murnaghan EoS the adiabatic elastic moduli and their pressure derivatives determined from these velocity data are K _S0=167.2±3.1?GPa, K ^′ _S0=4.89±0.17, G ₀=89.3±1.0?GPa, G ^′ ₀=0.90±0.02. The quoted uncertainties include contributions from uncertainties in both the room pressure length and density of the specimen, as well as uncertainties in the pressure calibration of the multianvil press. Because the sample is a polycrystalline specimen, this value of K _S0 represents an upper limit to the Reuss bound (conditions of uniform stress) on the elastic modulus of CaSnO₃ perovskite. If the value of αγT is assumed to be 0.01, the value of K _S0 corresponds to K _T0=165.5±3.1?GPa. The 10 P-V data obtained by single-crystal diffraction were fit with a third-order Birch–Murnaghan equation-of-state to obtain the parameters V ₀=246.059±0.013 ų, K _T0=162.6±1.0?GPa, K ^′ _T0=5.6±0.3. Because single-crystal measurements under hydrostatic conditions are made under conditions of uniform stress, they yield bulk moduli equivalent to the Reuss bound on a polycrystalline specimen. The results from the X-ray and ultrasonic experiments are therefore consistent. The bulk modulus of CaSnO₃ perovskite lies above the linear trend of K ₀ with inverse molar volume, previously determined for Ca perovskites. This prevents an estimation of the bulk modulus of CaSiO₃ perovskite by extrapolation. However, our value of G ₀ for CaSnO₃ perovskite combined with values for CaTiO₃ and CaGeO₃ forms a linear trend of G ₀ with octahedral tilt angle. This allows a lower bound of 150?GPa to be placed on the shear modulus of CaSiO₃ by extrapolation.     

Unit-cell dimensions and tetrahedral-site ordering in synthetic gallium albite (NaGaSi3O8)

The tetrahedral-site order-disorder transformation in gallium albite (NaGaSi₃O₈) has been investigated using Rietveld structure refinement. Study of gallium-substituted albite (in contrast to pure albite [NaAlSi₃O₈]) is facilitated by a relatively rapid order-disorder transformation and the large difference in X-ray scattering efficiencies of gallium and silicon. High albite-structure NaGaSi₃O₈, grown in a Na₂WO₄ flux, was ordered by hydrothermal annealing below 820° C and dry annealing above 820° C, to avoid melting, using a load pressure of approximately 1 kbar. Equilibration of the order-disorder reaction has been verified by three independent reversals of ordering. The transformation between low gallium albite and high gallium albite occurs over the temperature range 890° C 970° C. The gallium content of the T ₁o site increases continuously with decreasing temperature. The gallium contents of the T ₁m and T ₂m sites decrease smoothly with increasing ordering while the gallium content of the T ₂o site decreases, then increases and then decreases again with decreasing temperature. Unit-cell parameters and the triclinic obliquity vary throughout the order-disorder transformation and undergo abrupt changes at 913±3° C and 937±3° C. These abrupt changes correlate with changes in the gallium content of the T ₂o site, the X and Z ordering parameters and the configurational entropy. The order-disorder transformation in gallium-aluminum albite (NaGa_0.5Al_0.5Si₃O₈) occurs in the temperature range 765° C-850° C, at a temperature intermediate to the transformation in albite (50% order at about 680±20° C) and gallium albite.     

http://www.sciencedirect.com/science/article/pii/S1674987112000643

Incipient charnockites represent granulite formation on a mesoscopic scale and have received considerable attention in understanding fluid processes in the deep crust.Here we report new petrological data from an incipient charnockite locality at Rajapalaiyam in the Madurai Block,southern India,and discuss the petrogenesis based on mineral phase equilibrium modeling and pseudosection analysis. Rajapalaiyam is a key locality in southern India from where diagnostic mineral assemblages for ultrahigh-temperature（UHT） metamorphism have been reported.Proximal to the UHT rocks are patches and lenses of charnockite（Kfs + Qtz + Pl + Bt + Opx + Grt + Ilm） occurring within Opx-free Grt-Bt gneiss（Kfs + Pl + Qtz + Bt + Grt + Ilm + Mt） which we report in this study.The application of mineral equilibrium modeling on the charnockitic assemblage in NCKFMASHTO system yields a p-T range of～820℃and～9 kbar.Modeling of the charnockite assemblage in the MnNCKFMASHTO system indicates a slight shift of the equilibrium condition toward lower p and T（～760℃and～7.5 kbar）. which is consistent with the results obtained from geothermobarometry（710—760℃,6.7—7.5 kbar）. but significantly lower than the peak temperatures（>1000℃） recorded from the UHT rocks in this locality,suggesting that charnockitization is a post-peak event.The modeling of T versus molar H₂O content in the rock（M（H₂O）） demonstrates that the Opx-bearing assemblage in charnockite and Opxfree assemblage in Grt-Bt gneiss are both stable at M（H₂O） = 0.3 mol%-0.6 mol%.and there is no significant difference in water activity between the two domains.Our finding is in contrast to the previous petrogenetic model of incipient charnockite formation which envisages lowering of water activity and stabilization of orthopyroxene through breakdown of biotite by dehydration caused by the infiltration of CO₂-rich fluid.T-X_Fe³⁺（= Fe₂O₃/（FeO + Fe₂O₃） in mole） pseudosections suggest that the oxidation condition of the rocks played a major role on the stability of orthopyroxene:Opx is stable at X_Fe³⁺ <0.03 in charnockite.while Opx-free assemblage in Grt-Bt gneiss is stabilized at X_Fe³⁺ >0.12.Such low oxygen fugacity conditions of X_Fe³⁺ <0.03 in the charnockite compared to Grt-Bt gneiss might be related to the infiltration of a reduced fluid（e.g.,H₂O + CH₄） during the retrograde stage.     

A high P-T single-crystal X-ray diffraction study of thermoelasticity of MgSiO3 orthoenstatite

P-V-T data of MgSiO₃ orthoenstatite have been measured by single-crystal X-ray diffraction at simultaneous high pressures (in excess of 4.5 GPa) and temperatures (up to 1000 K). The new P-V-T data of the orthoenstatite, together with previous compression data and thermal expansion data, are described by a modified Birch-Murnaghan equation of state for diverse temperatures. The fitted thermoelastic parameters for MgSiO₃ orthoenstatite are: thermal expansion ?α/?P with values of a=2.86(29)×10^-5 K^-1 and b=0.72(16)×10^-8 K^-2; isothermal bulk modulus K _{T o} =102.8(2) GPa; pressure derivative of bulk modulus K′=?K/?P=10.2(1.2); and temperature derivative of bulk modulus K=?K/?T=-0.037(5) GPa/K. The derived thermal Grüneisen parameter is γ _th=1.05 for ambient conditions; Anderson-Grüneisen parameter is δ _{T o} =11.6, and the pressure derivative of thermal expansion is ?α/?P=-3.5×10^-6K^-1 GPa^-1. From the P-V-T data and the thermoelastic equation of state, thermal expansions at two constant pressures of 1.5 GPa and 4.0 GPa are calculated. The resulting pressure dependence of thermal expansion is Δα/ΔP=-3.2(1)× 10^-6 K^-1 GPa^-1. The significantly large values of K′, K, δ _T and ?α/?P indicate that compression/expansion of MgSiO₃ orthoenstatite is very sensitive to changes of pressure and temperature.     

In situ observation of crystal growth in a basalt melt and the development of crystal size distribution in igneous rocks

The speciation of CO₂ in dacite, phonolite, basaltic andesite, and alkali silicate melt was studied by synchrotron infrared spectroscopy in diamond anvil cells to 1,000 °C and more than 200 kbar. Upon compression to 110 kbar at room temperature, a conversion of molecular CO₂ into a metastable carbonate species was observed for dacite and phonolite glass. Upon heating under high pressure, molecular CO₂ re-appeared. Infrared extinction coefficients of both carbonate and molecular CO₂ decrease with temperature. This effect can be quantitatively modeled as the result of a reduced occupancy of the vibrational ground state. In alkali silicate (NBO/t = 0.98) and basaltic andesite (NBO/t = 0.42) melt, only carbonate was detected up to the highest temperatures studied. For dacite (NBO/t = 0.09) and phonolite melts (NBO/t = 0.14), the equilibrium CO₂ + O^2? = CO₃ ^2? in the melt shifts toward CO₂ with increasing temperature, with ln K = ?4.57 (±1.68) + 5.05 (±1.44) 10³ T ^?1 for dacite melt (ΔH = ?42 kJ mol^?1) and ln K = ?6.13 (±2.41) + 7.82 (±2.41) 10³ T ^?1 for phonolite melt (ΔH = ?65 kJ mol^?1), where K is the molar ratio of carbonate over molecular CO₂ and T is temperature in Kelvin. Together with published data from annealing experiments, these results suggest that ΔS and ΔH are linear functions of NBO/t. Based on this relationship, a general model for CO₂ speciation in silicate melts is developed, with ln K = a + b/T, where T is temperature in Kelvin and a = ?2.69 ? 21.38 (NBO/t), b = 1,480 + 38,810 (NBO/t). The model shows that at temperatures around 1,500 °C, even depolymerized melts such as basalt contain appreciable amounts of molecular CO₂, and therefore, the diffusion coefficient of CO₂ is only slightly dependent on composition at such high temperatures. However, at temperatures close to 1,000 °C, the model predicts a much stronger dependence of CO₂ solubility and speciation on melt composition, in accordance with available solubility data.     

Experimentally determined compositions of diopside-jadeite pyroxene in equilibrium with albite and quartz at 1200–1350°C and 15–34 kbar

Equilibrium compositions of diopside-jadeite pyroxene coexisting with albite and quartz were experimentally determined at 25 different P-T conditions, using an electron microprobe for analysis. The new data and the 600°C data of Holland (1983) provided the following mixing properties of the diopside (Di)-jadeite (Jd) solid solution (J, K): G^xs = X_JdX_Di[12600 ? 9.45T + (12600 ? 7.6T)(X_Jd ? X_Di) ? (21400 ? 16.2T)(X_Jd ? X_Di)²]. The Di-Jd solution is close to ideal above 1000°C but immiscible below 565°C. The Di-Jd solvus is slightly asymmetric with the crest at composition Di_42.4Jd_57.6. Excess enthalpy is positive but smaller than indicated by the enthalpy of solution measurements of Woodet al. (1980). Disorder in the Di-Jd solution is significantly smaller than complete disorder implied by the ionic two-site model.     

Estimating the Density and Compressibility of Seawater to High Temperatures Using the Pitzer Equations

The density and compressibility of seawater solutions from 0 to 95 °C have been examined using the Pitzer equations. The apparent molal volumes (X = V) and compressibilities (X = κ) are in the form $$ X_{\phi } = \bar{X}^{0} + A_{X} I/(1.2 \, m)\ln (1 + 1.2 \, I^{0.5} ) + \, 2{\text{RT }}m \, (\beta^{(0)X} + \beta^{(1)X} g(y) + C^{X} m) $$ where $ \bar{X}^{0} $ is the partial molal volume or compressibility, I is the ionic strength, m is the molality of sea salt, A_X is the Debye–Hückel slope for volume (X = V) or adiabatic compressibility (X = κ _s), and g(y) = (2/y ²)[1 ? (1 + y) exp(?y)] where y = 2I ^0.5. The values of the partial molal volume and compressibility ( $ \bar{X}^{0} $ ) and Pitzer parameters (β ^(0)X , β ^(1)X and C ^X ) are functions of temperature in the form $$ Y^{X} = \sum_{i} a_{i} (T-T_{\text{R}} )^{i} $$ where a _i are adjustable parameters, T is the absolute temperature in Kelvin, and T _R = 298.15 K is the reference temperature. The standard errors of the seawater fits for the specific volumes and adiabatic compressibilities are 5.35E?06 cm³ g^?1 and 1.0E?09 bar^?1, respectively. These equations can be combined with similar equations for the osmotic coefficient, enthalpy and heat capacity to define the thermodynamic properties of sea salt to high temperatures at one atm. The Pitzer equations for the major components of seawater have been used to estimate the density and compressibility of seawater to 95 °C. The results are in reasonable agreement with the measured values (0.010E?03 g cm^?3 for density and 0.050E?06 bar^?1 for compressibility) from 0 to 80 °C and salinities from 0 to 45 g kg^?1. The results make it possible to estimate the density and compressibility of all natural waters of known composition over a wide range of temperature and salinity.     

Analysis of factors controlling soil N2O emission by principal component and path analysis method

Nitrous oxide (N₂O) is a potent greenhouse gas. Mitigating N₂O emission is critical for combating global climate change and improving the ecological environment. Many studies have focused on factors affecting N₂O emission from agricultural soils, but rarely on the relationship among these factors. In the present study, continuous measurement on N₂O emission was conducted in a maize system in Griffith, Australia and the relationships between N₂O emission, soil properties and weather conditions were examined. Principal component analysis and path analysis were used to analyze these data in correlation coefficient and the direct and indirect effects to N₂O emission. Results indicated that (1) the major factors affecting N₂O emission were WFPS, mineralized nitrogen (Mineral N), daily mean temperature (T _mean) and CO₂ concentration. The factors of direct influence N₂O emission were following Mineral N, CO₂, WFPS, and T _mean. The indirect influence N₂O emission was following T _mean, WFPS, Mineral N, and CO₂ concentration. (2) The standard multiple regression describing the relationship between N₂O emission and its major factors were Y = ?37.162 + 0.5267 X ₁ + 0.4331 X ₂ + 0.3014 X ₃ + 0.2392 X ₄ (r = 0.924, p < 0.01, n = 151), where Y is N₂O emission, X ₁ is Mineral N, X ₂ is CO₂, X ₃ is WFPS and X ₄ is T _mean. (3) N₂O emission from agricultural soils can be monitored and mitigated through improved management practices such as irrigation, straw retention and fertilizer application.     

Pressure dependence of Néel transition in (Mg,Fe)O

Pressure dependence of Néel temperature (T _N) in (Mg_0.20Fe_0.80)O, (Mg_0.25Fe_0.75)O, and (Mg_0.30Fe_0.70)O was newly measured up to 1.14 GPa, using superconducting quantum interference device magnetometer and piston–cylinder-type pressure cell under hydrostatic condition. The dT _N/dP values of (Mg_0.20Fe_0.80)O, (Mg_0.25Fe_0.75)O, and (Mg_0.30Fe_0.70)O were determined as 4.0 ± 0.3, 2.7 ± 0.3, and 4.4 ± 0.4 K/GPa, respectively, in linear approximation; however, the T _N deviated from the linearity under nonhydrostatic conditions. The compositional dependence of dT _N/dP in (Mg_1?X Fe _X )O showed a rapid decay with increasing Mg components at X ≥ 0.75 and the trend ended at X = 0.70. The estimated Néel transition pressure at room temperature by extrapolating these linearities are very similar to the rhombohedral distortion determined by previous X-ray diffraction studies for X ≥ 0.75, which suggests that the rhombohedral phase of (Mg_1?X Fe _X )O (X ≥ 0.75) at room temperature is antiferromagnetic under hydrostatic conditions.     

Hydrostatic compression of ilmenite phase of ZnSiO3 and MgGeO3

Accurate measurements of cell parameters were performed on the ilmenite phases of ZnSiO₃ and MgGeO₃ using an X-ray diffraction method under hydrostatic conditions. The linear changes in cell parameter are represented by 1?a/a ₀=(1.06±0.04)×10^?4 P(kbar) and 1?c/c ₀=(2.11±0.04)×10^?4 P for ZnSiO₃, and 1?a/a ₀=(1.37±0.03)×10^?4 P and 1?c/c ₀=(2.05±0.04)×10^?4 P for MgGeO₃. A least-squares calculation using the first-order Birch-Murnaghan equation gives K _T =2.16±0.02 Mbar and K _T =1.87±0.02 Mbar for ZnSiO₃ and MgGeO₃, respectively. Elastic systematics assuming K _T V _m =constant give a predicted value K _T =2.14 Mbar for the ilmenite phase of MgSiO₃.     

Dissociation constants of calcite and CaHC03+ from 0 to 50°C

From conductance measurements, the negative logarithm of the dissociation constant of the CaHCO₃₊ ion pair, pK(CaHCO₃⁺), is 0.7, 1.0 and 1.35 within ±0.05 units at 0, 25 and 60°C, respectively. A revaluation of published and unpublished data yields pK(CaCO₃⁰) ≈ 3.2 at 25°C. Use of these pK's to compute the dissociation constant of calcite (Kc) from published calcite solubility measurements in pure water gives pKc values which increase markedly with ionic strength. However, if the ion pairs are ignored, computed pKc values are nearly constant with ionic strength. All reasonable attempts to eliminate the trend in pKc by adjusting ion activity coefficients, and/or values of K(CaCO₃⁰) failed, so the dilemma remains. Kc values computed from the most reliable published calcite solubility data are in good agreement with such values based on solubility data measured in this study at 5, 15, 35 and 50°C. Study results ignoring ion pairs are accurately represented by the equation log Kc = 13.870 — (3059/T) ?0.04035T, and correspond to ?8.35, ?8.42, and ?8.635 at 0, 25 and 50°C, respectively. The logarithmic expression leads to ΔH_r^o = ?2420 ± 300 cal/mol, ΔCp = ?110 ± 2 cal/deg mol, and ΔS_r^o = ?46.6 ± 1.0 cal/deg mol for the calcite dissociation reaction at 25°C. The dependence of Kc on temperature when CaCO₃⁰ and CaHCO₃⁺ are assumed, is described by log Kc = 13.543 ? (3000/T) ? 0.0401T which yields ?8.39, ?8.47, and -8.70 at 0, 25 and 50°C. This gives ΔH_r^o = ?2585 ± 300 cal/mol, ΔCp = ?109 ± 2 cal/deg mol, and ΔS_r⁰ = ?47.4 ± 1.0 cal/deg mol at 25°C.     

Crystal structure, Raman and FTIR spectroscopy, and equations of state of OH-bearing MgSiO3 akimotoite

MgSiO₃ akimotoite is stable relative to majorite-garnet under low-temperature geotherms within steeply or rapidly subducting slabs. Two compositions of Mg–akimotoite were synthesized under similar conditions: Z674 (containing about 550 ppm wt H₂O) was synthesized at 22 GPa and 1,500 °C and SH1101 (nominally anhydrous) was synthesized at 22 GPa and 1,250 °C. Crystal structures of both samples differ significantly from previous studies to give slightly smaller Si sites and larger Mg sites. The bulk thermal expansion coefficients of Z674 are (153–839 K) of a ₁ = 20(3) × 10^?9 K^?2 and a ₀ = 17(2) × 10^?6 K^?1, with an average of α ₀ = 27.1(6) × 10^?6 K^?1. Compressibility at ambient temperature of Z674 was measured up to 34.6 GPa at Sector 13 (GSECARS) at Advanced Photon Source Argonne National Laboratory. The second-order Birch–Murnaghan equation of state (BM2 EoS) fitting yields: V ₀ = 263.7(2) Å³, K _T0 = 217(3) GPa (K′ fixed at 4). The anisotropies of axial thermal expansivities and compressibilities are similar: α _a  = 8.2(3) and α _c  = 10.68(9) (10^?6 K^?1); β _a  = 11.4(3) and β _c  = 15.9(3) (10^?4 GPa). Hydration increases both the bulk thermal expansivity and compressibility, but decreases the anisotropy of structural expansion and compression. Complementary Raman and Fourier transform infrared (FTIR) spectroscopy shows multiple structural hydration sites. Low-temperature and high-pressure FTIR spectroscopy (15–300 K and 0–28 GPa) confirms that the multiple sites are structurally unique, with zero-pressure intrinsic anharmonic mode parameters between ?1.02 × 10^?5 and +1.7 × 10^?5 K^?1, indicating both weak hydrogen bonds (O–H···O) and strong OH bonding due to long O···O distances.     

Behavior of 10-Å phase at low temperatures

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