Kinetic studies of the homogeneous abiotic reactions of several chlorinated aliphatic compounds in aqueous solution

The base mediated and neutral abiotic reactions of 4 chlorinated aliphatic compounds have been studied as a function of temperature and pH. Arrhenius parameters obtained for base mediated reactions were as follows: 1,1,2-trichloroethane, log₁₀A=14.36±0.55, E_a=95.6±3.6 kJ/mol; 1,1,1,2-tetrachloroethane, log₁₀A=14.56±0.33, E_a=101.4±2.1 kJ/mol; 1,2,3-trichloropropane, log₁₀A=13.31±0.53, E_a=95.9±3.5 kJ/mol. For the neutral reaction of 2,3-dichloro-1-propene the Arrhenius parameters were log₁₀A=10.2±1.3, E_a=98±9 kJ/mol. For 1,1,2-trichloroethane the product of the base mediated reaction was identified as 1,1-dichloroethene, in contrast to previous studies. 2,3-dichloro-1-propene was found as an intermediate in the base mediated reaction of 1,2,3-trichloropropane, with 2-chloro-2-propen-1-ol as the major final product. Results from the present study are compared to those found in previous work.     

Reaction kinetics of dolomite rim growth

Reaction rims of dolomite (CaMg[CO₃]₂) were produced by solid-state reactions at the contacts of oriented calcite (CaCO₃) and magnesite (MgCO₃) single crystals at 400 MPa pressure, 750–850 °C temperature, and 3–146 h annealing time to determine the reaction kinetics. The dolomite reaction rims show two different microstructural domains. Elongated palisades of dolomite grew perpendicular into the MgCO₃ interface with length ranging from about 6 to 41 µm. At the same time, a 5–71 µm wide rim of equiaxed granular dolomite grew at the contact with CaCO₃. Platinum markers showed that the original interface is located at the boundary between the granular and palisade-forming dolomite. In addition to dolomite, a 12–80 µm thick magnesio-calcite layer formed between the dolomite reaction rims and the calcite single crystals. All reaction products show at least an axiotactic crystallographic relationship with respect to calcite reactant, while full topotaxy to calcite prevails within the granular dolomite and magnesio-calcite. Dolomite grains frequently exhibit growth twins characterized by a rotation of 180° around one of the $[11\bar{2}0]$ equivalent axis. From mass balance considerations, it is inferred that the reaction rim of dolomite grew by counter diffusion of MgO and CaO. Assuming an Arrhenius-type temperature dependence, activation energies for diffusion of CaO and MgO are E _a (CaO) = 192 ± 54 kJ/mol and E _a (MgO) = 198 ± 44 kJ/mol, respectively.     

Fixation of CO2 by chrysotile in low-pressure dry and moist carbonation: Ex-situ and in-situ characterizations

A detailed study of low-pressure gas-solid carbonation of chrysotile in dry and humid environments has been carried out. The evolving structure of chrysotile and its reactivity as a function of temperature (300-1200 °C), humidity (0-10 mol %) and CO₂ partial pressure (20-67 mol %), thermal preconditioning, and alkali metal doping (Li, Na, K, Cs) have been monitored through in-situ X-ray photoelectron spectroscopy, isothermal thermogravimetry/mass spectrometry, ex-situ X-ray powder diffraction, and water and nitrogen adsorption/desorption. Based on chrysotile crystalline structure and its nanofibrilar orderliness, a multistep carbonation mechanism was elaborated to explain the role of water during chrysotile partial amorphisation, formation of periclase, brucite, and hydromagnesite crystalline phases, and surface passivation thereof, during humid carbonation. The weak carbonation reactivity was rationalized in terms of incongruent CO₂ van der Waals molecular diameters with the octahedral-tetrahedral lattice constants of chrysotile. This lack of reactivity appeared to be relatively indifferent to the facilitated water crisscrossing during chrysotile core dehydroxylation/pseudo-amorphisation and surface hydroxylation induced product stabilization during humid carbonation. Thermodynamic stability domains of the species observed at low pressure have been thoroughly discussed on the basis of X-ray powder diffraction patterns and X-ray photoelectron spectroscopy evidence. The highest carbon dioxide uptake occurred at 375 °C in moist atmospheres. On the basis of chrysotile fresh N₂ BET area, nearly 15 atoms out of 100 of the surface chrysotile brucitic Mg moiety have been carbonated at this temperature which was tantamount to the carbonation of about 2.5 at. % of the total brucitic Mg moiety in chrysotile. The carbonation of brucite (Mg(OH)₂) impurities coexisting in chrysotile was minor and estimated to contribute by less than 17.6 at. % of the total converted magnesium. The presence of cesium traces (3 Cs atoms per 100 Mg atoms) was found to boost chrysotile carbonation capacity by a factor 2.7.     

The accuracy of standard enthalpies and entropies for phases of petrological interest derived from density-functional calculations

The internal energies and entropies of 21 well-known minerals were calculated using the density functional theory (DFT), viz. kyanite, sillimanite, andalusite, albite, microcline, forsterite, fayalite, diopside, jadeite, hedenbergite, pyrope, grossular, talc, pyrophyllite, phlogopite, annite, muscovite, brucite, portlandite, tremolite, and CaTiO₃–perovskite. These thermodynamic quantities were then transformed into standard enthalpies of formation from the elements and standard entropies enabling a direct comparison with tabulated values. The deviations from reference enthalpy and entropy values are in the order of several kJ/mol and several J/mol/K, respectively, from which the former is more relevant. In the case of phase transitions, the DFT-computed thermodynamic data of involved phases turned out to be accurate and using them in phase diagram calculations yields reasonable results. This is shown for the Al₂SiO₅ polymorphs. The DFT-based phase boundaries are comparable to those derived from internally consistent thermodynamic data sets. They even suggest an improvement, because they agree with petrological observations concerning the coexistence of kyanite?+?quartz?+?corundum in high-grade metamorphic rocks, which are not reproduced correctly using internally consistent data sets. The DFT-derived thermodynamic data are also accurate enough for computing the P–T positions of reactions that are characterized by relatively large reaction enthalpies (>?100 kJ/mol), i.e., dehydration reactions. For reactions with small reaction enthalpies (a few kJ/mol), the DFT errors are too large. They, however, are still far better than enthalpy and entropy values obtained from estimation methods.     

基于等转化法及多元非线性拟合的高岭石非等温脱羟基动力学分析

采用Netzsch STA409PC同步热分析仪研究了苏州高岭石(KW125)在30℃~1 200℃间的热分解过程。采用"Netzsch Thermokinetics software"软件对其脱羟基机理进行了非等温动力学研究。基于等转化法评价了反应活化能及反应进程的依存关系。基于多元非线性拟合确定了最可能反应机理及动力学参数。研究结果表明:苏州高岭石在30℃~1200℃温度范围的热分解为脱羟基与相转变等两个阶段。其脱羟基(30℃~800℃)过程中活化能呈现三个变化:197.68 kJ/mol±12.95 kJ/mol→181.04kJ/mol±18.98kJ/mol→269.7kJ/mol±14.64kJ/mol。脱羟基反应遵循三步连续反应模型t:f,f;(D3-Fn-Fn),一个三维扩散(D3)反应,然后是两个n序列(Fn)反应。第一步,f(α)=3(1-α)^2/3/(2(1-(1-α)^1/3),E1=185.27 kJ/mol,logA=10.83s^-1;第二步,f(α)=(1-α)^n,n=1.75,E2=187.81 kJ/mol,logA=10.32s^-1;第三步,f(α)=(1-α)^n,n=4.4,E3=262.70 kJ/mol,logA=13.26s^-1。     

Settlement Due to Uniform Circular Load: On Finite Two-Layer System

Structures are commonly founded on layered soil deposits. In this study, settlement due to a circular load on a two-layer soil system overlying a rock stratum or a stiff soil deposit is estimated and compared with the values obtained using Steinbrenner’s and Finite element approaches. Design tables are proposed for settlements due to uniform circular loading (of radius equal to a) applied on two-layer soil system for top-layer thickness H ₁ = 0.2a–6.0a, bottom-layer thickness H ₂ = 1.0a–6.0a, moduli ratio of top and bottom layers E ₁ /E ₂ = 0.01–100 and Poisson’s ratio v = 0.2–0.5. The settlement factors from the study were also compared with the Ueshita and Meyerhof’s values for a finite top layer overlying a semi-infinite bottom layer. Results were compared with the observed settlement of a structure resting on a layered soil profile overlying a rock stratum. Proposed settlement of the two-layer system shows good agreement with these studies.     

Selective leaching of antimony and arsenic from mechanically activated tetrahedrite,jamesonite and enargite

In this study, the changes in surface area, morphology and leachability of antimony and arsenic from tetrahedrite, jamesonite and enargite mechanically activated by a high-energy planetary mill were investigated. It appears that the leaching of antimony from tetrahedrite and jamesonite and arsenic from enargite in alkaline solution of sodium sulphide is temperature-sensitive reaction. The temperature dependencies of all reactions were investigated in the interval 313–363 K. Resulting experimental activation energies were E_a = 111–182 kJ mol^− 1 for mechanically activated minerals. The values of E_a are characteristic for processes controlled by surface chemical reactions.     

Aqueous oxidation of trichloroethene (TCE): a kinetic analysis

An empirical kinetic rate law appropriate for many ground waters (neutral pH, aerobic) has been determined for the aqueous oxidation of trichloroethene (TCE), one of the most volumetrically important chlorinated hydrocarbon pollutants. Mass balances were monitored by measuring both the rate of disappearance of TCE and the rate of appearance of CO₂ and Cl⁻. Dilute buffer solutions were used to fix pH and stoichiometrically sufficient amounts of dissolved O₂ were used to make the reactions pseudo zero-order in O₂. Using a standard chemical kinetic approach, two orders-of-magnitude in initial TCE concentration were spanned and the resulting double-log plot (log concentration vs. log initial rate) was used to determine the rate constant (k=5.77±1.06×10⁻⁷ s⁻¹) and “true” (i.e., with respect to concentration, not time) reaction order (n_c=0.85±0.03) for the rate law. By determining rate constants over the temperature interval 343–373 K, the Arrhenius activation energy (E_a) for the reaction was determined to be 108.0±4.5 kJ/mol. The rate law and derived kinetic parameters may be used in reactive transport simulators in order to account for aqueous oxidation of TCE as a function of temperature.     

Hydration of periclase at 350 ∘C to 620 ∘C and 200 MPa: experimental calibration of reaction rate

The hydration of periclase to brucite was investigated experimentally. Single crystals of periclase machined to millimeter sized cubes with (100) surfaces were reacted with distilled water at temperatures of 350 to 620 ^°C and a pressure of 200 MPa for run durations of 5 to 40 minutes. Hydration produced a layer of brucite covering the surface of periclase. While the shrinking periclase largely retained its cube shape a surface roughness developed on the μm scale and eventually outward pointing spikes bounded by (111) faces emerged on the retreating faces of the periclase due to kinetic selection of less reactive (111) and (110) surfaces. The periclase to brucite conversion followed a linear rate law, where the reaction rate increased from 350 to 530 ^°C and then decreased towards higher temperature and finally vanished at about 630 ^°C, where periclase, brucite, and water are in equilibrium at 200 MPa. The overall kinetics of the hydration reaction is conveniently described in terms of a phenomenological interface mobility. Measuring the velocity of the hydration front relative to the lattice of the reactant periclase, the temperature dependence of its mobility is described by an Arrhenius relation with pre-exponential factor 1.7.10^?12 m ⁴/s.J and activation energy of E_A=55 kJ/mol.     

Adsorption kinetics and thermodynamics of organophosphorus profenofos pesticide onto Fe/Ni bimetallic nanoparticles

Bimetallic Fe/Ni nanoparticles were synthesized and used for the removal of profenofos organophosphorus pesticide from aqueous solution. These novel bimetallic nanoparticles (Fe/Ni) were characterized by scanning electron microscopy, energy-dispersive X-ray analysis spectroscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The effect of the parameters of initial pesticide concentration, pH of the solution, adsorbent dosage, temperature, and contact time on adsorption was investigated. The adsorbent exhibited high efficiency for profenofos adsorption, and equilibrium was achieved in 8 min. The Langmuir, Freundlich, and Temkin isotherm models were used to determine equilibrium. The Langmuir model showed the best fit with the experimental data (R ² = 0.9988). Pseudo-first-order, pseudo-second-order, and intra-particle diffusion models were tested to determine absorption kinetics. The pseudo-second-order model provided the best correlation with the results (R ² = 0.99936). The changes in the thermodynamic parameters of Gibb’s free energy, enthalpy, and entropy of the adsorption process were also evaluated. Thermodynamic parameters indicate that profenofos adsorption using Fe/Ni nanoparticles is a spontaneous and endothermic process. The value of the activation energy (E _a = 109.57 kJ/mol) confirms the nature of the chemisorption of profenofos onto Fe/Ni adsorbent.     

Kaolinite and smectite dissolution rate in high molar KOH solutions at 35° and 80°C

Experiments measuring kaolinite and smectite dissolution rates were carried out using batch reactors at 35° and 80°C. No potential catalysts or inhibitors were present in solution. Each reactor was charged with 1 g of clay of the ≤2 μm fraction and 80, 160 or 240 ml of 0.1–4 M KOH solution. An untreated but sized kaolinite from St. Austell and two treated industrial smectites were used in the experiments. One smectite is a nearly pure montmorillonite, while the second has a significant component of beidellitic charge (35%). The change in solution composition and mineralogy was monitored as a function of time. Initially, the 3 clays dissolved congruently. No new formed phases were observed by XRD and SEM during the pure dissolution stage. The kaolinite dissolution is characterized by a linear release of silica and Al as a function of the log of time. This relationship can be explained by a reaction affinity effect which is controlled by the octahedral layer dissolution. Far from equilibrium, dissolution rates are proportional to a^0.56±0.12_OH⁻ at 35°C and to a^0.81±0.12_OH⁻ at 80°C. The activation energy of kaolinite dissolution increases from 33±8 kJ/mol in 0.1 M KOH solutions to 51±8 kJ/mol in 3 M KOH solutions. In contrast to kaolinite, the smectites dissolve at much lower rates and independently of the aqueous silica or Al concentrations. The proportionality of the smectite dissolution rate constant at 35 and 80°C was a^0.15±0.06_OH⁻. The activation energy of dissolution appears to be independent of pH for smectite and is found to be 52±4 kJ/mol. The differences in behavior between the two kinds of minerals can be explained by structural differences. The hydrolysis of the tetrahedral and the octahedral layer appears as parallel reactions for kaolinite dissolution and as serial reactions for smectite dissolution. The rate limiting step is the dissolution of the octahedral layer in the case of kaolinite, and the tetrahedral layer in the case of smectite.     

High temperature dehydroxylation of muscovite-2M1: a kinetic study by in situ XRPD

Muscovite-2M₁ shows a major phase transition at about 800°C, which is generally attributed in the literature to the structural dehydroxylation process, although a number of structural models have been proposed for the dehydroxylated phase, and different transformation mechanisms have also been put forward. The observed first order transformation involves an increase in the cell volume, and it is not clear to date how the cell expansion is related to the loss of hydroxyl groups. The phase change has been re-investigated here by in situ high temperature powder diffraction, both in non-isothermal and isothermal modes, to combine for the first time the structural and the kinetic interpretation of the transformation. The results unequivocally confirm that the reaction taking place in the temperature range 700–1000°C is truly a dehydroxylation process, involving the nucleation and growth of the high temperature dehydroxylated phase, having Al in 5-fold coordination. Structural simulations of the basal peaks of the powder diffraction patterns indicate that the model originally proposed by Udagawa et al. (1974) for the dehydroxylated phase correctly describes the high temperature phase. The kinetic analysis of the isothermal data using an Avrami-type model yields values for the reaction order compatible with a reaction mechanism limited by a monodimensional diffusion step. Apparent activation energy of the process in vacuum is about 251 kJ/mol. Experiments carried out at temperatures much higher than the onset temperature of the reaction show that the dehydroxylation reaction overlaps with the reaction of formation of mullite, the final product in the reaction pathway. Received: 24 April 1998 / Revised, accepted: 12 October 1998     

Expansivity and compressibility of wadeite-type K2Si4O9 determined by in situ high T/P experiments, and their implication

Wadeite-type K₂Si₄O₉ was synthesized with a cubic press at 5.4 GPa and 900 °C for 3 h. Its unit-cell parameters were measured by in situ high-T powder X-ray diffraction up to 600 °C at ambient P. The T–V data were fitted with a polynomial expression for the volumetric thermal expansion coefficient (α_T = a ₀ + a ₁ T), yielding a ₀ = 2.47(21) × 10^?5 K^?1 and a ₁ = 1.45(36) × 10^?8 K^?2. Compression experiments at ambient T were conducted up to 10.40 GPa with a diamond-anvil cell combined with synchrotron X-ray radiation. A second-order Birch–Murnaghan equation of state was used to fit the P–V data, yielding K _T = 97(3) GPa and V ₀ = 360.55(9) Å³. These newly determined thermal expansion data and compression data were used to thermodynamically calculate the P–T curves of the following reactions: 2 sanidine (KAlSi₃O₈) = wadeite (K₂Si₄O₉) + kyanite (Al₂SiO₅) + coesite (SiO₂) and wadeite (K₂Si₄O₉) + kyanite (Al₂SiO₅) + coesite/stishovite (SiO₂) = 2 hollandite (KAlSi₃O₈). The calculated phase boundaries are generally consistent with previous experimental determinations.     

Interdiffusion of Mg–Fe in olivine at 1,400–1,600 °C and 1 atm total pressure

The interdiffusion coefficient of Mg–Fe in olivine (D _Mg–Fe) was obtained at 1,400–1,600 °C at the atmospheric pressure with the oxygen fugacity of 10^?3.5–10^?2 Pa using a diffusion couple technique. The D _Mg–Fe shows the anisotropy (largest along the [001] direction and smallest along the [100] direction), and its activation energy (280–320 kJ/mol) is ~80–120 kJ/mol higher than that estimated at lower temperatures. The D _Mg–Fe at temperatures of >1,400 °C can be explained by the cation-vacancy chemistry determined both by the Fe³⁺/Fe²⁺ equilibrium and by the intrinsic point defect formation with the formation enthalpy of 220–270 kJ/mol depending on the thermodynamical model for the Fe³⁺/Fe²⁺ equilibrium in olivine. The formation enthalpy of 220–270 kJ/mol for the point defect (cation vacancy) in olivine is consistent with that estimated from the Mg self-diffusion in Fe-free forsterite. The increase in the activation energy of D _Mg–Fe at >1,400 °C is thus interpreted as the result of the transition of diffusion mechanism from the transition metal extrinsic domain to the intrinsic domain at the atmospheric pressure.     

CO2 mineral sequestration by wollastonite carbonation

In this paper, we demonstrated a new approach to CO₂ mineral sequestration using wollastonite carbonation assisted by sulfuric acid and ammonia. Samples were characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and ²⁹Si nuclear magnetic resonance. The change in Gibbs free energy from ?223 kJ/mol for the leaching reaction of wollastonite to ?101 kJ/mol for the carbonation reaction indicated that these two reactions can proceed spontaneously. The leached and carbonated wollastonite showed fibrous bassanite and granular calcium carbonate, respectively, while the crystal structure of pristine wollastonite was destroyed and the majority of the Ca²⁺ in pristine wollastonite leached. The chemical changes in the phases were monitored during the whole process. A high carbonation rate of 91.1 % could be obtained under the action of sulfuric acid and ammonia at 30 °C at normal atmospheric pressure, indicating its potential use for CO₂ sequestration.     

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.     

Thermo-elastic behaviour of Be2BO3OH (hambergite) up to 7 GPa and 1,100 K

The thermo-elastic behaviour of Be₂BO₃(OH)_0.96F_0.04 (i.e. natural hambergite, Z = 8, a = 9.7564(1), b = 12.1980(2), c = 4.4300(1) Å, V = 527.21(1) ų, space group Pbca) has been investigated up to 7 GPa (at 298 K) and up to 1,100 K (at 0.0001 GPa) by means of in situ single-crystal X-ray diffraction and synchrotron powder diffraction, respectively. No phase transition or anomalous elastic behaviour has been observed within the pressure range investigated. P?V data fitted to a third-order Birch–Murnaghan equation of state give: V ₀ = 528.89(4) ų, K _T0 = 67.0(4) GPa and K′ = 5.4(1). The evolution of the lattice parameters with pressure is significantly anisotropic, being: K _T0(a):K _T0(b):K _T0(c) = 1:1.13:3.67. The high-temperature experiment shows evidence of structure breakdown at T > 973 K, with a significant increase in the full-width-at-half-maximum of all the Bragg peaks and an anomalous increase in the background of the diffraction pattern. The diffraction pattern was indexable up to 1,098 K. No new crystalline phase was observed up to 1,270 K. The diffraction data collected at room-T after the high-temperature experiment showed that the crystallinity was irreversibly compromised. The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α ₀ + α ₁ T ^?1/2. The refined parameters for Be₂BO₃(OH)_0.96F_0.04 are: α ₀ = 7.1(1) × 10^?5 K^?1 and α ₁ = ?8.9(2) × 10^?4 K ^?1/2 for the unit-cell volume, α ₀(a) = 1.52(9) × 10^?5 K^?1 and α ₁(a) = ?1.4(2) × 10^?4 K ^?1/2 for the a-axis, α ₀(b) = 4.4(1) × 10^?5 K^?1 and α ₁(b) = ?5.9(3) × 10^?4 K ^?1/2 for the b-axis, α ₀(c) = 1.07(8) × 10^?5 K^?1 and α ₁(c) = ?1.5(2) × 10^?4 K ^?1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α ₀(a):α ₀(b):α ₀(c) = 1.42:4.11:1. The main deformation mechanisms in response to the applied temperature, based on Rietveld structure refinement, are discussed.     

P–V Equations of State and the relative stabilities of serpentine varieties

Serpentines are hydrous phyllosilicates which form by hydration of Mg–Fe minerals. The reasons for the occurrence of the structural varieties lizardite and chrysotile, with respect to the variety antigorite, stable at high pressure, are not yet fully elucidated, and their relative stability fields are not quantitatively defined. In order to increase the database of thermodynamic properties of serpentines, the P–V Equations of State (EoS) of lizardite and chrysotile were determined at ambient temperature up to 10 GPa, by in situ synchrotron X-ray diffraction in a diamond-anvil cell. Neither amorphization nor hysteresis was observed during compression and decompression, and no phase transition was resolved in lizardite. In chrysotile, a reversible change in compression mechanism, possibly due to an unresolved phase transition, occurs above 5 GPa. Both varieties exhibit strong anisotropic compression, with the c axis three times more compressible than the others. Fits to ambient temperature Birch–Murnaghan EoS gave for lizardite V ₀=180.92(3) Å³, K ₀ = 71.0(19) GPa and K′ ₀=3.2(6), and for chrysotile up to 5 GPa, V ₀ = 730.57(31) Å³ and K ₀ = 62.8(24) GPa (K′ ₀ fixed to 4). Compared to the structural variety antigorite is stable at high pressure (HP) (Hilairet et al. 2006), the c axis is more compressible in these varieties, whereas the a and b axes are less compressible. These differences are attributed to the less anisotropic distribution of stiff covalent bonds in the corrugated structure of antigorite. The three varieties have almost identical bulk compressibility curves. Thus the compressibility has negligible influence on the relative stability fields of the serpentine varieties. They are dominated by first-order thermodynamic properties, which stabilizes antigorite at high temperature with respect to lizardite, and by out-of-equilibrium phenomena for metastable chrysotile (Evans 2004).     

Stability at high pressure, elastic behavior and pressure-induced structural evolution of “Al5BO9”, a mullite-type ceramic material

Elastic behavior and pressure-induced structural evolution of synthetic boron-mullite “Al₅BO₉” (a = 5.678(2) Å, b = 15.015(4) Å and c = 7.700(3) Å, space group Cmc2₁, Z = 4) were investigated up to 7.4 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase transition or anomalous compressional behavior occurred within the investigated P range. Fitting the P–V data with a truncated second-order (in energy) Birch-Murnaghan Equation-of-State (BM-EoS), using the data weighted by the uncertainties in P and V, we obtained: V ₀ = 656.4(3) Å³ and K _T0 = 165(7) GPa (β _V0 = 0.0061(3) GPa^?1). The evolution of the Eulerian finite strain versus normalized stress (f _E–F _E plot) leads to an almost horizontal trend, showing that a truncated second-order BM-EoS is appropriate to describe the elastic behavior of “Al₅BO₉” within the investigated P range. The weighted linear regression through the data points gives: F _E(0) = 159(11) GPa. Axial compressibility coefficients yielded: β _a  = 1.4(2) × 10^?3 GPa^?1, β _b  = 3.4(4) × 10^?3 GPa^?1, and β _c  = 1.7(3) × 10^?3 GPa^?1 (β _a :β _b :β _c  = 1:2.43:1.21). The highest compressibilities observed in this study within (100) can be ascribed to the presence of voids represented by five-membered rings of polyhedra: Al1–Al3–Al4–Al1–Al3, which allow accommodating the effect of pressure by polyhedral tilting. Polyhedral tilting around the voids also explains the higher compressibility along [010] than along [001]. The stiffer crystallographic direction observed here might be controlled by the infinite chains of edge-sharing octahedra running along [100], which act as “pillars”, making the structure less compressible along the a-axis than along the b- and c-axis. Along [100], compression can only be accommodated by deformation of the edge-sharing octahedra (and/or by compression of the Al–O bond lengths), as no polyhedral tilting can occur. In addition, a comparative elastic analysis among the mullite-type materials is carried out.     

Serpentinization at Burro Mountain,California

The Burro Mountain ultramafic complex, Monterey County, California, consists of dunites and peridotites which are partially or wholly serpentinized. Primary minerals in both rock types are olivine, enstatite, diopside, and picotite which upon alteration yield chrysotile, lizardite, brucite, magnetite, talc, tremolite, and carbonate. Electron microprobe analyses show that enstatite, En_85.8 to En_90.8, alters to “bastite” composed only of lizardite (5.0–12.0 weight percent FeO), whereas olivine, Fo_90.8 to Fo_91.6, forms lizardite+chrysotile+brucite with or without magnetite. The chrysotile ranges from 3.0 to 5.0 weight percent FeO, the brucite from 16.0 to 43.0 weight percent FeO. As Serpentinization proceeds, the alteration products are enriched in FeO relative to MgO. Serpentinization probably originates in a changing \(P_{O_2 }\)-T environment by two different reactions:

1. (a)
   Olivine+enstatite+H₂O+O₂?Mg, Fe⁺² chrysotile+Mg, Fe⁺³, Fe⁺² lizardite with or without magnetite.