Factors affecting preservation of coesite in ultrahigh‐pressure metamorphic rocks: Insights from TEM observations of dislocations within kyanite

To understand the preservation of coesite inclusions in ultrahigh‐pressure (UHP) metamorphic rocks, an integrated petrological, Raman spectroscopic and focussed ion beam (FIB) system–transmission electron microscope (TEM) study was performed on a UHP kyanite eclogite from the Sulu belt in eastern China. Coesite grains have been observed only as rare inclusions in kyanite from the outer segment of garnet and in the matrix. Raman mapping analysis shows that a coesite inclusion in kyanite from the garnet rim records an anisotropic residual stress and retains a maximum residual pressure of ~0.35 GPa. TEM observations show quartz is absent from the coesite inclusion–host kyanite grain boundaries. Numerous dislocations and sub‐grain boundaries are present in the kyanite, but dislocations are not confirmed in the coesite. In particular, dislocations concentrate in the kyanite adjacent to the boundary with the coesite inclusion, and they form a dislocation concentration zone with a dislocation density of ~10⁹ cm^?2. A high‐resolution TEM image and a fast Fourier transform‐filtered image reveal that a tiny dislocation in the dislocation concentration zone is composed of multiple edge dislocations. The estimated dislocation density in most of the kyanite away from the coesite inclusion–host kyanite grain boundaries is ~10⁸ cm^?2, being lower than that in kyanite adjacent to the coesite. In the case of a coesite inclusion in a matrix kyanite, using Raman and TEM analyses, we could not identify any quartz at the grain boundaries. Dislocations are not observed in the coesite, but numerous dislocations and stacking faults are developed in the kyanite. The estimated overall dislocation density in the coesite‐bearing matrix kyanite is ~10⁸ cm^?2, but a high dislocation density region of ~10⁹ cm^?2 is also present near the coesite inclusion–host kyanite grain boundaries. Inclusion and matrix kyanite grains with no coesite have dislocation densities of ≤10⁸ cm^?2. Dislocation density is generally reduced during an annealing process, but our results show that not all dislocations in the kyanite have recovered uniformly during exhumation of the UHP rocks. Hence, one of the key factors acting as a buffer to inhibit the coesite to quartz transformation is the mechanical interaction between the host and the inclusion that lead to the formation of dislocations in the kyanite. The kyanite acts as an excellent pressure container that can preserve coesite during the decompression of rocks from UHP conditions. The search for and study of inclusions in kyanite may be a more suitable approach for tracing the spatial distribution of UHP metamorphic rocks.     

Raman microprobe (RMP) determinations of natural and synthetic coesite

Raman microprobe (RMP) spectra of synthetic coesiste and three natural coesites from eclogite — facies rocks are provided and evaluated for characterisation purposes. The main coesite line lies at 521 cm^?1 and the other characteristic lines attributed to coesite occur at 117, 177 and 271 cm^?1. Two petrologically useful applications were (a) the confirmation of the coesite structure in very small natural crystals deduced to be coesite from petrographic observations only, and (b) the recognition of sub-microscopic crystallites of quartz in incipiently — transformed coesite in all the natural samples.     

Pressure-induced incipient amorphization of α-quartz and transition to coesite in an eclogite from Antarctica: a first record and some consequences

Monocrystalline quartz inclusions in garnet and omphacite from various eclogite samples from the Lanterman Range (Northern Victoria Land, Antarctica) have been investigated by cathodoluminescence (CL), Raman spectroscopy and imaging, and in situ X‐ray (XR) microdiffraction using the synchrotron. A few inclusions, with a clear‐to‐opalescent lustre, show ‘anomalous’ Raman spectra characterized by weak α‐quartz modes, the broadening of the main α‐quartz peak at 465 cm^?1, and additional vibrations at 480–485, 520–523 and 608 cm^?1. CL and Raman imaging indicate that this ‘anomalous’α‐quartz occurs as relicts within ordinary α‐quartz, and that it was preserved in the internal parts of small quartz inclusions. XR diffraction circular patterns display irregular and broad α‐quartz spots, some of which show an anomalous d‐spacing tightening of ～2%. They also show some very weak, hazy clouds that have d‐spacing compatible with coesite but not with α‐quartz. Raman spectrometry and XR microdiffraction characterize the anomalies with respect to α‐quartz as (i) a pressure‐induced disordering and incipient amorphization, mainly revealed by the 480–485 and 608‐cm^?1 Raman bands, together with (ii) a lattice densification, evidenced by d‐spacing tightening; (iii) the cryptic development of coesite, 520–523 cm^?1 being the main Raman peak of coesite and (iv) Brazil micro‐twinning. This ‘anomalous’α‐quartz represents the first example of pressure‐induced incipient amorphization of a metastable phase in a crustal rock. This issue is really surprising because pressure‐induced amorphization of metastable α‐quartz, observed in impactites and known to occur between 15 and 32 GPa during ultrahigh‐pressure (UHP) experiments at room temperature, is in principle irrelevant under normal geological P–T conditions. A shock (due to a seism?) or a local overpressure at the inclusion scale (due to expansion mismatch between quartz and its host mineral) seem the only geological mechanisms that can produce such incipient amorphization in crustal rocks. This discovery throws new light on the modality of the quartz‐coesite transition and on the pressure regimes (non‐lithostatic v. lithostatic) during high‐pressure/UHP metamorphism. In particular, incipient amorphization of quartz could favour the quartz‐coesite transition, or allow the growth of metastable coesite, as already experimentally observed.     

Raman spectroscopy of natural silica in Chicxulub impactite,MexicoSpectroscopie Raman de silices naturelles dans l'impactite de Chicxulub,Mexique

A series of natural silica impactite samples from Chicxulub (Mexico) was investigated by Raman microprobe (RMP) analysis. The data yield evidence for high-pressure shock metamorphism in the rock. The impactite contains three polymorphs of silica: the original α-quartz, and two high-pressure varieties – coesite and disordered quartz representing various degrees of crystallinity. We found systematic changes in frequencies and half-widths of the Raman bands, caused by increasing irregularities of bond-lengths and bond-angles and a general breaking-up of the structure as a result of impact events. Therefore, RMP is an adequate tool for measuring the crystallinity of disordered quartz. The half-width Γ and the frequency ω of the symmetric SiOSi stretching vibrational band (A₁ mode) of the SiO₄ tetrahedra are the most amenable parameters for estimating the degree of crystallinity. In well-crystallized quartz, Γ=5 cm^?1 and ω=464 cm^?1, while in highly disordered quartz this line shifts up to ω=455 cm^?1 and broadens up to Γ=30 cm^?1. The Raman lineshapes appear to depend strongly on the degree of lattice disorder subsequent to impact events. To cite this article: M. Ostroumov et al., C. R. Geoscience 334 (2002) 21–26     

Quartz paramorphs after former stishovite in UHP eclogite from the South Altyn Tagh,Western China and its Significance

The long prism/needle‐shaped polycrystalline quartz aggregates and square/parallelogram‐shaped singlephase quartz inclusions in omphacite and garnet of ultrahigh pressure eclogite were first discovered from the Jiangalesayi area, South Altyn UHP belt. Based on their morphology, these quartz inclusions are quartz paramorphs after stishovite. The minimum peak pressure of the eclogite is estimated to be >8–9 GPa at 800– 1000 °C based on the stability field of stishovite. This new evidence, together with previous stishovite exsolution microstructure in the gneiss from the same region, suggests an ultra‐deep subduction and exhumation of the South Altyn continental rocks to/from mantle depths in stishovite stability field. Evidence of ultra‐deep subduction of continental materials might be more common and diverse than previous thought. Exhumation of subducted continental rocks from≥300 km has been considered impossible because they are denser than mantle at these depths. How did the stishovite bearing continental rocks of the South Altyn exhumated? As we all know, the densities of stishovite (4.3 g/cm³) are much higher than coesite (2.9 g/cm³), and stishovite transforms into coesite with temperature increases. Density calculations were performed for subducted continental rocks along phase transition of stishovite to coesite, using the third‐order Birch‐Murnaghan equation of state based on mineral fractions obtained from experiments and Perple_X. The results show that the density of Siliceous rocks decrease remarkably, lower than the surrounding mantle in coesite stability field, whereas the density of Oligosiliceous and Silicon unsaturated rocks is higher than surrounding mantle. Thus, we propose that the thermal induced transformation could provide an initial driven force for the exhumation of ultra‐deep subducted silica‐enriched felsic continental rocks. Temperature increase could be derived from an increased geothermal gradient from convective mantle or mantle plume. Mafic to ultra‐mafic rocks and silica‐deficient rocks may be captured by the upwelling subducted continental rocks and exhumated together.     

On the survival of intergranular coesite in UHP eclogite

Coesite is typically found as inclusions in rock‐forming or accessory minerals in ultrahigh‐pressure (UHP) metamorphic rocks. Thus, the survival of intergranular coesite in UHP eclogite at Yangkou Bay (Sulu belt, eastern China) is surprising and implies locally “dry” conditions throughout exhumation. The dominant structures in the eclogites at Yangkou are a strong D₂ foliation associated with tight‐to‐isoclinal F₂ folds that are overprinted by close‐to‐tight F₃ folds. The coesite‐bearing eclogites occur as rootless intrafolial isoclinal F₁ fold noses wrapped by a composite S₁–S₂ foliation in interlayered phengite‐bearing quartz‐rich schists. To evaluate controls on the survival of intergranular coesite, we determined the number density of intergranular coesite grains per cm² in thin section in two samples of coesite eclogite (phengite absent) and three samples of phengite‐bearing coesite eclogite (2–3 vol.% phengite), and measured the amount of water in garnet and omphacite in these samples, and also in two samples of phengite‐bearing quartz eclogite (6–7 vol.% phengite, coesite absent). As coesite decreases in the mode, the amount of primary structural water stored in the whole rock, based on the nominally anhydrous minerals (NAMs), increases from 107/197 ppm H₂O in the coesite eclogite to 157–253 ppm H₂O in the phengite‐bearing coesite eclogite to 391/444 ppm H₂O in the quartz eclogite. In addition, there is molecular water in the NAMs and modal water in phengite. If the primary concentrations reflect differences in water sequestered during the late prograde evolution, the amount of fluid stored in the NAMs at the metamorphic peak was higher outside of the F₁ fold noses. During exhumation from UHP conditions, where NAMs became H₂O saturated, dehydroxylation would have generated a free fluid phase. Interstitial fluid in a garnet–clinopyroxene matrix at UHP conditions has dihedral angles >60°, so at equilibrium fluid will be trapped in isolated pores. However, outside the F₁ fold noses strong D₂ deformation likely promoted interconnection of fluid and migration along the developing S₂ foliation, enabling conversion of some or all of the intergranular coesite into quartz. By contrast, the eclogite forming the F₁ fold noses behaved as independent rigid bodies within the composite S₁–S₂ foliation of the surrounding phengite‐bearing quartz‐rich schists. Primary structural water concentrations in the coesite eclogite are so low that H₂O saturation of the NAMs is unlikely to have occurred. This inherited drier environment in the F₁ fold noses was maintained during exhumation by deformation partitioning and strain localization in the schists, and the fold noses remained immune to grain‐scale fluid infiltration from outside allowing coesite to survive. The amount of inherited primary structural water and the effects of strain partitioning are important variables in the survival of coesite during exhumation of deeply subducted continental crust. Evidence of UHP metamorphism may be preserved in similar isolated structural settings in other collisional orogens.     

Pressure dependence of hydroxyl solubility in coesite

 The solubility of hydroxyl in coesite was investigated in multianvil experiments performed at 1200 °C over the nominal pressure range 5–10 GPa, at an f _O2 close to the Ni-NiO buffer. The starting material for each experiment was a cylinder of pure silica glass plus talc, which dehydrates at high P and T to provide a source of water and hydrogen (plus enstatite and excess SiO₂). Fourier-transform infrared (FTIR) spectra of the recovered coesite crystals show five sharp bands at 3606, 3573, 3523, 3459, and 3299 cm⁻¹, indicative of structurally bonded hydrogen (hydroxyl). The concentration of hydrogen increases with pressure from 285 H/10⁶ Si (at 5 GPa) to 1415 H/10⁶ Si (at 10 GPa). Assuming a model of incorporation by (4H)_Si defects, the data are fit well by the equation C _OH=Af ² _H2<\INF>Oexp(−PΔV/RT), with A=4.38 H/10⁶ Si/GPa, and ΔV=20.6 × 10⁻⁶ m³ mol⁻¹. An alternative model entailing association of hydrogen with cation substitution can also be used to fit the data. These results show that the solubility of hydroxyl in coesite is approximately an order of magnitude lower than in olivines and pyroxenes, but comparable to that in pyropic garnet. However, FTIR investigations on a variety of ultrahigh pressure metamorphic rocks have failed in all cases to detect the presence of water or hydrogen in coesite, indicating either that it grew in dry environments or lost its hydrogen during partial transformation to quartz. On the other hand, micro-FTIR investigations of quartz crystals replacing coesite show that they contain varying amounts of H₂O. These results support the hypothesis that preservation of coesite is not necessarily linked to fast exhumation rates but is crucially dependent on limited fluid infiltration during exhumation. Received: 23 August 1999 / Accepted: 10 April 2000     

Study of the star-forming region L379 IRS3 in CH<Subscript>3</Subscript>OH and CS

A molecular cloud and high-velocity outflow associated with the star-forming region L379 IRS3 have been mapped in the 6_?1-5₀E methanol and CS (3-2) lines using the 12-meter Kitt Peak telescope. The estimated CS column density and abundance in the molecular cloud are 8×10¹⁴ cm^?2 and 4×10^?9, respectively. LVG modeling of the methanol emission constrains the gas density in the cloud to (1–4)×10⁵ cm^?3 and the gas kinetic temperature to 20–45 K. The upper limit on the density of the high-velocity gas is 10⁵ cm^?3.     

Olivine as an in situ piezometer in high pressure apparatus

The deviatoric stress produced in a large-volume, high-pressure apparatus of the girdle-anvil type has been estimated from the density of free dislocations induced in natural olivine single crystals (initial density of 2×10⁶ cm^?2). Experiments at maximum pressure P=40 kbar and temperature T=1050°C for t=1 h in NaCl cell assemblies and various P-T paths yield specimens whose dislocation densities are unchanged from this initial value, implying that the deviatoric stress was less than 140 bar. In BN cell assemblies, the recovered specimen from high P-T experiments exhibit much higher densities of dislocations (～10⁹ cm^?2) which have been produced by steady-state plastic deformation of the olivine crystals under a deviatoric stress of ～3 kbar. This value of deviatoric stress in BN has been corroborated by observations of the subgrain size and recrystallized grain size in specimens of longer run duration (3 h).     

Timing of Himalayan ultrahigh-pressure metamorphism: sinking rate and subduction angle of the Indian continental crust beneath Asia

Coesite relics were discovered as inclusions in clinopyroxene in eclogite and as inclusions in zircon in felsic and pelitic gneisses from Higher Himalayan Crystalline rocks in the upper Kaghan Valley, north‐west Himalaya. The metamorphic peak conditions of the coesite‐bearing eclogites are estimated to be 27–32 kbar and 700–770 °C, using garnet–pyroxene–phengite geobarometry and garnet–pyroxene geothermometry, respectively. Cathodoluminescence (CL) and backscattered electron (BSE) imaging distinguished three different domains in zircon: inner detrital core, widely spaced euhedral oscillatory zones, and thin, broadly zoned outermost rims. Each zircon domain contains a characteristic suite of micrometre‐sized mineral inclusions which were identified by in situ laser Raman microspectroscopy. Core and mantle domains contain quartz, apatite, plagioclase, muscovite and rutile. In contrast, the rim domains contain coesite and minor muscovite. Quartz inclusions were identified in all coesite‐bearing zircon grains, but not coexisting with coesite in the same growth domain (rim domain). ²⁰⁶Pb/²³⁸U zircon ages reveal that the quartz‐bearing mantle domains and the coesite‐bearing rim were formed at c. 50 Ma and 46.2 ± 0.7 Ma, respectively. These facts demonstrate that the continental materials were buried to 100 km within 7–9 Myr after initiation of the India–Asia collision (palaeomagnetic data from the Indian oceanic floor supports an initial India‐Asia contact at 55–53 Ma). Combination of the sinking rate of 1.1–1.4 cm year^?1 with Indian plate velocity of 4.5 cm year^?1 suggests that the Indian continent subducted to about 100 km depth at an average subduction angle of 14–19°.     

Analytical methods for measuring the parameters of interstellar gas using methanol observations

The excitation of methanol in the absence of external radiation is analyzed, and LTE methods for probing interstellar gas considered. It is shown that rotation diagrams correctly estimate the gas kinetic temperature only if they are constructed using lines whose upper levels are located in the same K-ladders, such as the J₀?J_?1E lines at 157 GHz, the J₁?J₀E lines at 165 GHz, and the J₂?J₁E lines at 25 GHz. The gas density must be no less than 10⁷ cm^?3. Rotation diagrams constructed from lines with different K values for their upper levels (e.g., 2_K?1_K at 96 GHz, 3_K?2_K at 145 GHz, 5_K?4_K at 241 GHz) significantly underestimate the temperature, but enable estimation of the density. In addition, diagrams based on the 2_K?1_K lines can be used to estimate the methanol column density within a factor of about two to five. It is suggested that rotation diagrams should be used in the following manner. First, two rotation diagrams should be constructed, one from the lines at 96, 145, or 241 GHz, and another from the lines at 157, 165, or 25 GHz. The former diagram is used to estimate the gas density. If the density is about 10⁷ cm^?3 or higher, the latter diagram reproduces the temperature fairly well. If the density is around 10⁶ cm^?3, the temperature obtained from the latter diagram should be multiplied by a factor of 1.5–2. If the density is about 10⁵ cm^?3 or lower, then the latter diagram yields a temperature that is lower than the kinetic temperature by a factor of three or more, and should be used only as a lower limit for the kinetic temperature. The errors in the methanol column density determined from the integrated intensity of a single line can be more than an order of magnitude, even when the gas temperature is well known. However, if the J₀?(J ? 1)₀E lines, as well as the J₁?(J ? 1)₁A⁺ or A^? lines are used, the relative error in the column density is no more than a factor of a few.     

The thermodynamic properties and phase relations of some minerals in the system CaO-AI2O3-SiO2-H2O

The heat capacities of lawsonite, margante, prehnite and zoisite have been measured from 5 to 350 K with an adiabatic-shield calorimeter and from 320 to 999.9 K with a differential-scanning calorimeter. At 298.15 K, their heat capacities, corrected to end-member compositions, are 66.35, 77.30, 79.13 and 83.84 cal K^?1 mol^?1; their entropies are 54.98, 63.01, 69.97 and 70.71 cal K^?1 mol^?1, respectively. Their high-temperature heat capacities are described by the following equations (in calories, K, mol): Lawsonite (298–600 K): Cp° = 66.28 + 55.95 × 10^?3T ? 15.27 × 10⁵T^?2 Margarite (298–1000 K): Cp° = 101.83 + 24.17 × 10^?3T ? 30.24 × 10⁵T^?2 Prehnite (298–800 K): Cp° = 97.04 + 29.99 × 10^?3T ? 25.02 × 10⁵T^?2 Zoisite (298–730 K): Cp° = 98.92 + 36.36 × 10^?3T ? 24.08 × 10⁵T^?2 Calculated Clapeyron slopes for univariant equilibria in the CaO-Al₂O₃-SiO₂-H₂O system compare well with experimental results in most cases. However, the reaction zoisite + quartz = anorthite + grossular + H₂O and some reactions involving prehnite or margarite show disagreements between the experimentally determined and the calculated slopes which may possibly be due to disorder in experimental run products. A phase diagram, calculated from the measured thermodynamic values in conjunction with selected experimental results places strict limits on the stabilities of prehnite and assemblages such as prehnite + aragonite, grossular + lawsonite, grossular + quartz, zoisite + quartz, and zoisite + kyanite + quartz. The presence of this last assemblage in eclogites indicates that they were formed at moderate to high water pressure.     

OH defects in quartz in granitic systems doped with spodumene,tourmaline and/or apatite: experimental investigations at 5–20 kbar

The incorporation of OH defects in quartz as a function of Li content in the bulk system and pressures was investigated. Quartz crystals were grown in water-saturated granitic systems, containing various amounts Li, B and P, supplied as accessory phases such as spodumene, tourmaline or apatite in the starting mixtures. High pressure experiments were performed at temperatures between 900 and 1100 °C, and pressures between 5 and 20 kbar with a piston cylinder apparatus, and the synthesized quartz crystals were analyzed by IR spectroscopy, electron microprobe and LA-ICP-MS spectroscopy. All IR absorption spectra revealed absorption features that can be assigned to AlOH (3313, 3379 and 3431 cm^?1) and (4H)_Si defects (3585 cm^?1), whereas quartz grown in the Li and B systems exhibited two additional bands related, respectively, to LiOH (3483 cm^?1) and BOH defects (3596 cm^?1). It was further observed that LiOH incorporation increases with higher spodumene content in the starting material and decreases with pressure, until no LiOH defects are observed at pressure higher than 15 kbar. Specifically, the most pronounced reduction of LiOH defects occurs in a rather narrow pressure interval (10–15 kbar) close to the high-quartz/low-quartz transition. However, the link between the transition and the defect incorporation remains unclear. Li total concentrations always exceed the Li-coupled LiOH defects, suggesting the simultaneous presence of dry AlLi defects. Results of this study suggest that LiOH defects are detectable only in quartz crystals grown from middle and upper crustal sections (such as hydrothermal quartz) and not in quartz from deep roots of orogenic granitoids.     

Extrinsic and intrinsic mode of hydrogen occurrence in natural olivines: FTIR and TEM investigation

Olivine crystals from two mantle nodules in kimberlites (pipe Udachnaya and pipe Obnazennaya, Yakutiya, Siberia) were investigated using EMP, TEM, AEM and FTIR techniques to determine the mode of hydrogen occurrence in olivine. Olivine contains three types of nanometer-sized inclusions: “large” inclusions of hexagonal-like shape up to several hundred nm in size (1), lamellar defects (2) and small inclusions of hexagon-like shape up to several 10?nm in size (3). Lamellar defects and small inclusions are considered to be a “hydrous” olivine. All three types of inclusions contain OH^? or water, but they are different with respect to their phase composition. In “large” inclusions (1) hydrous magnesium silicates, such as serpentine?+?talc (“kerolite”?) and 10-Å phase?+?talc were identified. Lamellar defects (2) and small inclusions (3) are depleted in Mg and Fe compared to the olivine matrix, while the silica content is the same as that of olivine. Modulations in the periodicity of the olivine structure are observed in SAED patterns and HREM images of (2) and (3). The superperiodicity can be referred to OH^?-bearing point defect ordering in the olivine structure. If this is the case, the material of both lamellar defects and small inclusions can be assumed to be a “hydrous olivine” Mg_{2– x} v _x SiO₄H_{2 x} with a cation-deficient olivine crystal structure. Thus, both an extrinsic mode of hydrogen occurrence in olivine, such as nanometer-sized inclusions of OH^?-bearing magnesium silicates, and an intrinsic mode of hydrogen incorporation into the olivine structure, such as “hydrous olivine” in itself, were found. The data obtained here show that the OH absorption bands observed in olivine spectra at 3704(3717) and 3683(3688) cm^?1 can be unambiguously identified with serpentine; the band at 3677(3676) cm^?1 can be associated with talc. The absorption bands observed at 3591 and 3660?cm^?1 in olivine match those of the 10-Å phase at 3594, 3662 and 3666?cm^?1.     

Helium measurements of pore fluids obtained from the San Andreas Fault Observatory at Depth (SAFOD, USA) drill cores

⁴He accumulated in fluids is a well established geochemical tracer used to study crustal fluid dynamics. Direct fluid samples are not always collectable; therefore, a method to extract rare gases from matrix fluids of whole rocks by diffusion has been adapted. Helium was measured on matrix fluids extracted from sandstones and mudstones recovered during the San Andreas Fault Observatory at Depth (SAFOD) drilling in California, USA. Samples were typically collected as subcores or from drillcore fragments. Helium concentration and isotope ratios were measured 4?C6 times on each sample, and indicate a bulk ⁴He diffusion coefficient of 3.5?±?1.3?×?10^?C8 cm²?s^?C1 at 21°C, compared to previously published diffusion coefficients of 1.2?×?10^?C18 cm²?s^?C1 (21°C) to 3.0?×?10^?C15 cm²?s^?C1 (150°C) in the sands and clays. Correcting the diffusion coefficient of ⁴He_water for matrix porosity (??3%) and tortuosity (??6?C13) produces effective diffusion coefficients of 1?×?10^?C8 cm^2?s^?C1 (21°C) and 1?×?10^?C7 (120°C), effectively isolating pore fluid ⁴He from the ⁴He contained in the rock matrix. Model calculations indicate that <6% of helium initially dissolved in pore fluids was lost during the sampling process. Complete and quantitative extraction of the pore fluids provide minimum in situ porosity values for sandstones 2.8?±?0.4% (SD, n?=?4) and mudstones 3.1?±?0.8% (SD, n?=?4).     

A mapping of the electron localization function for the silica polymorphs: evidence for domains of electron pairs and sites of potential electrophilic attack

The electron localization function, η, evaluated for first-principles geometry optimized model structures generated for quartz and coesite, reveals that the oxide anions are coordinated by two hemispherically shaped η-isosurfaces located along each of the SiO bond vectors comprising the SiOSi angles. With one exception, they are also coordinated by larger banana-shaped isosurfaces oriented perpendicular to the plane centered in the vicinity of the apex of each angle. The hemispherical isosurfaces, ascribed to domains of localized bond-pair electrons, are centered ～0.70 Å along the bond vectors from the oxide anions and the banana-shaped isosurfaces, ascribed to domains of localized nonbonding lone-pair electrons, are centered ～0.60 Å from the apex of the angle. The oxide anion comprising the straight SiOSi angle in coesite is the one exception in that the banana-shaped isosurface is missing; however, it is coordinated by two hemispherically shaped isosurfaces that lie along the bond vectors. In the case of a first-principles model structure generated for stishovite, the oxide anion is coordinated by five hemispherically shaped η-isosurfaces, one located along each of the three SiO bond vectors (ascribed to domains of bonding-electron pairs) that are linked to the anion with the remaining two (ascribed to domains of nonbonding-electron pairs) located on opposite sides of the plane defined by three vectors, each isosurface at a distance of ～0.5 Å from the anion. The distribution of the five isosurfaces is in a one-to-one correspondence with the distribution of the maxima displayed by experimental Δρ and theoretical ??²ρ maps. Isosurface η maps calculated for quartz and the (HO) ₃ SiOSi(OH) ₃ molecule also exhibit maxima that correspond with the (3,?3) maxima displayed by distributions of ??²ρ. Deformation maps observed for the SiOSi bridges for the silica polymorphs and a number of silicates are similar to that calculated for the molecule but, for the majority, the maxima ascribed to lone-pair features are absent. The domains of localized nonbonding-electron pair coordinating the oxide anions of quartz and coesite provide a basis for explaining the flexibility and the wide range of the SiOSi angles exhibited by the silica polymorphs with four-coordinate Si. They also provide a basis for explaining why the SiO bond length in coesite decreases with increasing angle. As found in studies of the interactions of solute molecules with a solvent, a mapping of η-isosurfaces for geometry-optimized silicates is expected to become a powerful tool for deducing potential sites of electrophilic attack and reactivity for Earth materials. The positions of the features ascribed to the lone pairs in coesite correspond with the positions of the H atoms recently reported for an H-doped coesite crystal.     

Isovolumetric geochemical investigation of a buried granite saprolite near Columbia,SC, U.S.A.

Saprolites are residual soils which preserve the textures of their parent rocks and thus have evolved by an isovolumetric process of weathering (MILLOT, 1970, The Geology of Clays, Springer). Using bulk density, saprolite elemental analyses can be converted to units of g cm^?3. Furthermore, an empirical reaction progress diagram can be constructed for a suite of saprolite samples by plotting element concentrations (in g cm^?3) against bulk density (B.D.). Our data for a granite saprolite show that Al₂O₃ and SiO₂ decrease in a linear fashion from B.D. 2.1g cm^?3 to 1.5g cm^?3 but that K₂O follows a curvilinear trend such that it decreases from 75% of its fresh rock value at B.D. 1.6 g cm^?3 to nearly zero at B.D. 1.5 g cm^?3. The only hypothetical reaction paths that are compatible with these B.D. vs A1₂O₃, SiO₂ and K₂O constraints are those in which orthoclase alters to kaolinite through an intermediate potassium phase similar to KAl₃Si₃O₁₀(OH)₂ or KAl₂Si₂O₆(OH)₃ (hypothetical K-kaolinite). Normative mineral calculations, X-ray diffraction data and structural H₂O data are employed to test this conclusion.     

Origins and properties of the quasi-stationary slow solar wind

Comparisons of the brightness distributions of the white corona observed at distances of several solar radii with solar wind velocities derived from interplanetary-scintillation observations, as well as analyses of solar wind data obtained on spacecraft from December 1994 to June 1995, indicate that the fast solar wind can contain plasma with velocities V ≈ 300–450 km/s, approaching those typical for the slow solar wind that flows in the streamer belt and chains of streamers. At the same time, certain other parameters, first and foremost the plasma density N and ratio T/N ^0.5 (where T is the temperature), indicate that these two flows differ considerably. The slow solar wind flowing in the streamer belt and chains displays high densities N > 10 ± 2 cm^?3 and low T/N ^0.5 < 1.7 × 10⁴ K cm^3/2 at the Earth’s orbit. The number of slow solar-wind sources observed in chains can be comparable with the number observed in the belt. The fast solar wind flowing from coronal holes always displays low densities N≤ 8 cm^?3 and high T/N ^0.5 > 1.7 × 10⁴ K cm^3/2. These properties probably indicate different origins of the fast and slow solar winds.