Plastic-deformati on mechanisms in quartz: The effect of water

High-temperature and pressure-deformation experiments indicate that small amounts of water strongly affect the plastic-deformation mechanisms that operate in quartz. Inherently dry natural quartz crystals exhibit a transition from T = (0001), to , t = [0001] glide at approximately 700° C at a strain rate of 8 · 10⁻⁶ sec⁻¹. The transition temperature decreases with decreasing strain rate. When water is diffused into dry natural crystals at high temperature, duplex slip occurs on the systems (0001), 112̄0and either {112̄0}, [0001] or {101̄0}, [0001] depending on which of the latter systems is most highly stressed.Hydrothermally grown synthetic quartz crystals contain relatively large amounts of structurally bound water. In these crystals, a transition occurs from (0001), 112̄0 to dominantly pencil glide in the [0001] and possibly 112̄3 directions. The transition temperature is strongly dependent on the water content of the crystals, and coincides with the hydrolytic weakening temperature defined by Griggs and Blacic for these crystals. Inhomogeneous distribution of water in the synthetic crystals controls the distribution of plastic strain and may, in part, control the orientation of subbasal deformation lamellae in these.It is suggested that anisotropic diffusion of H-OH in quartz may be responsible for the operation of the [0001] pencil-glide system in the hydrolytic weakening regime. Crystal structure anisotropy may also play a role in the slip-system transition through its influence on the Peierls stress, and this is most likely the dominant factor in the dry crystals.     

Evolution of fluid chemistry in quartz compaction systems: Experimental investigations and numerical modeling

The evolution of fluid chemistry in compacting rock is controlled by coupled chemical processes and rock deformation. In order to characterize this evolution, we conducted water-rock interaction experiments using quartz aggregates at 150 °C and effective pressure of 34.5 MPa. A coupled fluid flow, chemical reaction, and creep compaction model is developed, in which both free-surface reaction and grain-contact dissolution are considered as system volume and porosity evolve.The direct experimental measurement and numerical modeling indicate that effective pressure has significant effects on pore-fluid chemistry. At the early stages of compaction, pore fluids are supersaturated with respect to bulk quartz. With increasing compaction and time, solute concentrations gradually decrease to saturated conditions. Supersaturation is caused mainly by dissolution of ultrafines and high-energy, unstable surfaces which are produced by stress concentrations at grain contacts during the very early stages of compaction. Grain-contact dissolution also contributes to the solute increase in pore fluid in the early stage of compaction, but the effect is small compared to that of ultrafines and unstable surfaces and only slight supersaturation can be produced by it. The gradual decrease in pore-fluid concentration is related to the mechanical removal of ultrafines by pore-fluid flow and the dissolution of ultrafines and unstable surfaces. It also results from the lessening of grain-contact dissolution.Pore fluids in compacting sedimentary basins of quartz sandstone are nearly saturated throughout most of diagenetic processes. Ultrafines and unstable surfaces produced by stress appear not to be the major sources of quartz cement.     

ESEEM of industrial quartz powders: insights into crystal chemistry of Al defects

A set of raw industrial materials, that is, pure quartz and quartz-rich mixtures, were investigated through electron paramagnetic resonance and electron spin echo-envelope modulation spectroscopies, with the aim of evaluating the effective role played by defect centres and of assessing whether they can be used to monitor changes in the physical properties of quartz powders with reference to their health effects. The obtained results point to two interactions of the Al defect centres with H⁺, hosted in sites within the channels parallel and perpendicular to the c axis of quartz, respectively. These two Al/H⁺ (h_Al) centres exhibit a weak chemical bond, and their relative amounts appear to be modified/controlled by the thermo-mechanical processes underwent by powders. Indeed, a mechanically promoted inter-conversion between the two kinds of site is suggested. As a consequence, the h_Al centres are effective in monitoring even modest activations of powders, through thermal or mechanical processes, and they are also supposed to play a specific, relevant role in quartz reactivity during the considered industrial processes.     

The influence of groundwater chemistry on arsenic concentrations and speciation in a quartz sand and gravel aquifera)

We examined the chemical reactions influencing dissolved concentrations, speciation, and transport of naturally occurring arsenic (As) in a shallow, sand and gravel aquifer with distinct geochemical zones resulting from land disposal of dilute sewage effluent. The principal geochemical zones were: (1) the uncontaminated zone above the sewage plume [350 μM dissolved oxygen (DO), pH 5.9]; (2) the suboxic zone (5 μM DO, pH 6.2, elevated concentrations of sewage-derived phosphate and nitrate); and (3) the anoxic zone [dissolved iron(II) 100–300 μM, pH 6.5–6.9, elevated concentrations of sewage-derived phosphate]. Sediments are comprised of greater than 90% quartz but the surfaces of quartz and other mineral grains are coated with nanometer-size iron (Fe) and aluminum (Al) oxides and/or silicates, which control the adsorption properties of the sediments. Uncontaminated groundwater with added phosphate (620 μM) was pumped into the uncontaminated zone while samples were collected 0.3 m above the injection point. Concentrations of As(V) increased from below detection (0.005 μM) to a maximum of 0.07 μM during breakthrough of phosphate at the sampling port; As(III) concentrations remained below detection. These results are consistent with the hypothesis that naturally occurring As(V) adsorbed to constituents of the coatings on grain surfaces was desorbed by phosphate in the injected groundwater. Also consistent with this hypothesis, vertical profiles of groundwater chemistry measured prior to the tracer test showed that dissolved As(V) concentrations increased along with dissolved phosphate from below detection in the uncontaminated zone to approximately 0.07 and 70 μM, respectively, in the suboxic zone. Concentrations of As(III) were below detection in both zones. The anoxic zone had approximately 0.07 μM As(V) but also had As(III) concentrations of 0.07–0.14 μM, suggesting that release of As bound to sediment grains occurred by desorption by phosphate, reductive dissolution of Fe oxides, and reduction of As(V) to As(III), which adsorbs only weakly to the Fe-oxide-depleted material in the coatings. Results of reductive extractions of the sediments suggest that As associated with the coatings was relatively uniformly distributed at approximately 1 nmol/g of sediment (equivalent to 0.075 ppm As) and comprised 20%-50% of the total As in the sediments, determined from oxidative extractions. Quartz sand aquifers provide high-quality drinking water but can become contaminated when naturally occurring arsenic bound to Fe and Al oxides or silicates on sediment surfaces is released by desorption and dissolution of Fe oxides in response to changing chemical conditions.

     

The equilibration of high-angle grain boundaries in dynamically recrystallized quartz: the effect of crystallography and temperature

Dynamically recrystallized and sutured quartz grains from metamorphic rocks with different strain intensities and temperature conditions ranging from ca. 350°C to ca. 700°C have been studied. Universal-stage measurements on quartz–quartz high-angle grain boundaries show that they are never curved but always consist of straight segments which preferentially occupy specific crystallographic orientations in relation to both neighboring crystals. With increasing temperature the segments preferentially concentrate in a decreasing number of orientations, mainly near the rhombohedral {101̄1} planes. The crystallographic data and the observations on grain boundary geometries suggest that: (i) grain boundary orientations are strongly crystallographically controlled, (ii) this control is the main factor on the textural equilibration of quartz–quartz grain boundaries in metamorphic rocks, and (iii) grain boundaries from dynamically recrystallized quartz should be regarded as annealed and equilibrated fabrics that are stable against subsequent annealing as long as the material is not re-deformed.     

The proportional effect in gold-bearing quartz veins of the Kekura deposit,East Chukotka

The proportional mineralization effect was detected in the gold mineralization variability at the Kekura deposit. The presence of this effect complicates data interpretation and influences the methodology for studying the variography of the deposit. This paper presents a technique for the detection of this effect and methods for smoothing out this effect for further work with variography.     

The stress-sensitivity of quartz in tectonites

Petrofabric investigation of five crossbedded quartzites shows an essentially isotropic fabric in three cases, and preferred orientation together with parallel texture in the remaining two. Crossbedding is undistorted in all five. Recrystallization by solution and re-deposition could satisfactorily explain the three isotropic fabrics. Low-magnitude shear of short duration, coupled with extremely sensitive response of quartz to deformation, is the preferred explanation for the quartzites showing preferred orientation.At a higher metamorphic level in a sheared granite, stress-sensitive quartz and stress-insensitive feldspar are contrasted and, in view of their analogous crystal structures, the apparent anomaly in deformation behavior is noted.With 2 figures.     

The thermodynamics of water in quartz

The thermodynamic model of Doukhan and Trepied (1985) for water solubility in quartz, based on the (4H)_Si substitution, has been developed to take into account the variation in oxygen fugacity under different buffering conditions, as well as the solubility of the quartz in the water. An evaluation of the thermodynamic parameters has then been made using analogous data on grossular and hydrogrossular. This evaluation, although approximate, leads to predicted solubilities that are lower than some published experimental values but are consistent with other observations indicating that the solubility is relatively low, less than 100H/10⁶ Si at most, even at the highest temperatures and pressures. The predictions give a monotonically increasing solubility with increasing temperature at given pressure, and an increase in solubility with increasing pressure at given temperature up to a maximum, beyond which the solubility decreases with further increase in pressure. The variation of solubility with oxygen fugacity at fixed pressure and temperature broadly mirrors the observations of Ord and Hobbs (1986) although not predicting the finer details. An interstitial H₂O model is also considered and shown to be probably less important as a mechanism for water solubility than the (4H)_Si mechanism. Hydrogen/alkali exchange depends on hydrogen fugacity rather than water fugacity and is predicted to be more important at lower oxygen fugacities.     

Millennial timescale resolution of rhyolite magma recharge at Tarawera volcano: insights from quartz chemistry and melt inclusions

Most rhyolite eruption episodes of Tarawera volcano have emitted several physiochemically distinct magma batches (∼1–10 km³). These episodes were separated on a millennial timescale. The magma batches were relatively homogeneous in temperature and composition at pumice scale (>4 cm), but experienced isolated crystallisation histories. At the sub-cm scale, matrix glasses have trace element compositions (Sr, Ba, Rb) that vary by factors up to 2.5, indicating incomplete mixing of separate melts. Some quartz-hosted melt inclusions are depleted in compatible trace elements (Sr, Ti, Ba) compared to enclosing matrix glasses. This could reflect re-melting of felsic crystals deeper in the crystal pile. Individual quartz crystals display a variety of cathodoluminescence brightness and Ti zoning patterns including rapid changes in melt chemistry and/or temperature (∼50–100°C), and point to multi-cycle crystallisation histories. The Tarawera magma system consisted of a crystal-rich mass containing waxing and waning melt pockets that were periodically recharged by silicic melts driven by basaltic intrusion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Dissolution of silica from montmorillonite: effect of solution chemistry

The rate of silica removal from two montmorillonites (Chambers and Polkville) has been measured as a function of time, temperature, solution composition, and exchange ion on the clay. Silica removal rate increased with temperature from 200 to 350°C, decreased with time, and could be approximated initially by a parabolic rate law. Solution composition influenced silica removal rate by determining the exchange population of the clay; silica removal is most rapid when K-exchange ions are present. Thus increasing the concentration of K⁺ accelerated silica removal, whereas increasing the concentration of Na⁺, Ca²⁺, and Mg²⁺ inhibited silica removal. Activation energies for silica removal range from 5 to 10 kcal/mol. The largest values are associated with the largest concentrations of inhibitor ions in solution. Activation energies of this magnitude suggest that the rate-limiting step for silica removal is transport through a hydrated, expanded interlayer space. Application of experimental results to diagenesis in moderately to deeply buried sediments suggests that K⁺ uptake by montmorillonite may precede and accelerate illite formation.     

The investigation of defects in shock-metamorphosed quartz

The shock-metamorphosed quartz exhibits thermal luminescence (TL) with maxima at 365 nm, 470 nm and 610–680 nm. By electron paramagnetic resonance (EPR) analysis E₁ type electron centers and hole centers have been found which originate from vacancies including those from the substitution of Al³⁺ and/or Fe³⁺, for Si⁴⁺. The EPR and TL spectra may be interpreted mainly in terms of vacancy type defects associated with dislocations in the crystal structure of quartz.     

The non-mass-dependent oxygen isotope effect in the electrodissociation of carbon dioxide: A step toward understanding NoMaD chemistry

A non-mass dependent (NoMaD) oxygen isotope effect is demonstrated in the dissociation of CO₂ similar to that observed in the electrosynthesis of ozone. The molecular oxygen produced carries the signature of two separate isotopic fractionation processes; a mass-dependent fractionation probably due to CO₂ + O isotopic exchange, and a secondary NoMaD fractionation (δ¹⁷O = 0.97 ± 0.09δ¹⁸O, with the O₂ depleted in ¹⁷O and ¹⁸O). It is suggested that the effect is due to either the formation or relaxation of ozone in an excited electronic state. This represents the latest advance in the understanding of chemical NoMaD effects which may be essential to the explanation of non-mass-dependent fractionations observed in meteorites.     

石英道芬双晶对晶格优选取向及变形机制的贡献和意义

矿物是岩石圈最基本的物质组成,其变形行为、特性和物理/化学过程直接影响着大陆岩石圈的力学强度和流变学性质。石英是地壳主要的组成矿物之一,对其变形机理及制约因素的研究,是理解地壳流变学性质的关键。石英中的道芬双晶在晶体形态上表现出沿c轴方向的6次对称,早期研究认为其只能形成于α-和β-石英的相变过程中,越来越多的研究发现,机械应力诱发的道芬双晶对温度和应力具有一定的依赖性。通过对高黎贡剪切带内变形石英的EBSD组构分析并结合前人的研究,发现石英道芬双晶对晶内塑性应变的分布及其不同滑移系的激活起着重要作用。α-石英晶体中菱面方向比方向具有更高柔度,即更适应变形。在外力作用下,石英道芬双晶通过菱面和上的弹性性质差异,即相比方向,在压缩方向(σ₁)上代表晶面方向的极点更多地聚集在方向,形成一种较为少见的菱面晶格优选取向。由此可见,道芬双晶是石英塑性变形过程中的一种特殊的流变弱化机制,其不仅使得晶体发生可恢复的结构弱化,还通过动态重结晶作用和颗粒边界...     

The effect of tissue structure and soil chemistry on trace element uptake in fossils

Trace element profiles for common divalent cations (Sr, Zn, Ba), rare-earth elements (REE), Y, U, and Th were measured in fossil bones and teeth from the c. 25 ka Merrell locality, Montana, USA, by using laser-ablation ICP-MS. Multiple traverses in teeth were transformed into 2-D trace element maps for visualizing structural influences on trace element uptake. Trace element compositions of different soils from the fossil site were also analyzed by solution ICP-MS, employing progressive leaches that included distilled H₂O, 0.1 M acetic acid, and microwave digestion in concentrated HCl-HNO₃. In teeth, trace element uptake in enamel is 2-4 orders of magnitude slower than in dentine, forming an effective trace element barrier. Uptake in dentine parallel to the dentine-enamel interface is enhanced by at least 2 orders of magnitude compared to transverse, causing trace element “plumes” down the tooth core. In bone, U, Ba and Sr are nearly homogeneous, implying diffusivities ∼5 orders of magnitude faster than in enamel and virtually complete equilibration with host soils. In contrast all REE show strong depletions inward, with stepwise linear segments in log-normal or inverse complementary error function plots; these data require a multi-medium diffusion model, with about 2 orders of magnitude difference in slowest vs. fastest diffusivities. Differences in REE diffusivities in bone (slow) vs. dentine (fast) reflect different partition coefficients (K_d’s). Although acid leaches and bulk digestion of soils yield comparable fossil-soil K_d’s among different elements, natural solutions are expected to be neutral to slightly basic. Distilled H₂O leachates instead reveal radically different K_d’s in bone for REE than for U-Sr-Ba, suggest orders of magnitude lower effective diffusivities for REE, and readily explain steep vs. flat profiles for REE vs. U-Sr-Ba, respectively. Differences among REE K_d’s and diffusivities may explain inward changes in Ce anomalies. Acid washes and bulk soil compositions yield misleading K_d’s for many trace elements, especially the REE, and H₂O-leaches are preferred. Patterns of trace element distributions indicate diagenetic alteration at all scales, including enamel, and challenge the use of trace elements in paleodietary studies.     

The amethyst-citrine dichromatism in quartz and its origin

The occurrence of the amethyst-citrine dichromatism in natural and mainly synthetic quartz crystals was studied as a function of their growth conditions. It has been found experimentally that the origin of the coloration is related to the variable dependence of the incorporation of the amethyst- and citrine-producing impurities on the crystallographic direction and growth rates of the faces and also to the effect the charge compensators have on the thermal stability of the amethyst color centers.     

TitaniQ under pressure: the effect of pressure and temperature on the solubility of Ti in quartz

Quartz and rutile were synthesized from silica-saturated aqueous fluids between 5 and 20 kbar and from 700 to 940°C in a piston-cylinder apparatus to explore the potential pressure effect on Ti solubility in quartz. A systematic decrease in Ti-in-quartz solubility occurs between 5 and 20 kbar. Titanium K-edge X-ray absorption near-edge structure (XANES) measurements demonstrate that Ti⁴⁺ substitutes for Si⁴⁺ on fourfold tetrahedral sites in quartz at all conditions studied. Molecular dynamic simulations support XANES measurements and demonstrate that Ti incorporation onto fourfold sites is favored over interstitial solubility mechanisms. To account for the P–T dependence of Ti-in-quartz solubility, a least-squares method was used to fit Ti concentrations in quartz from all experiments to the simple expression

The effect of medium chemistry on the solubility and morphology of brushite crystals

An experimental study of the particulars of the solubility and crystallization of brushite Ca(HPO₄) · 2H₂O from aqueous solution in conditions of a variable pH (6.0–3.0) and the contents of impurity ions (K⁺, Na⁺, NH ₄ ⁺ , Mg²⁺, SO ₄ ^2? , CO ₃ ^2? ) has been conducted. It is established that brushite solubility markedly rises with a decrease in pH from 6 to 3 and slightly rises with an increase in Mg²⁺ and SO ₄ ^2? concentrations. The enrichment in K⁺, Na⁺, and NH ₄ ⁺ does not affect brushite solubility. The changeable chemistry of the medium results in variation of the synthetic crystal habit, from rhombic tabular to thickened prismatic crystals.