Thermoluminescence of shock-loaded amethyst quartz

In natural amethyst samples subjected to shock pressures between 10 and 50 GPa (1 GPa=10⁹ Pa), thermoluminescence (TL) was observed after subsequent X-ray irradiation, in some cases even without high energy irradiation. The glow curves could be decomposed into at most five components of Gaussian shape, but no reliable activation energies could be determined from them, perhaps due to a wide distribution of trap depths. With increasing shock pressures traps of higher thermal stability were favored. Emission bands with maxima near 14000 cm^?1 were observed independent of shock pressure. They appear to be characteristic of defects created during the shock events, but it is uncertain whether the observed TL is connected with the iron impurities characteristic for amethyst. In natural amethyst samples of the same origin no TL could be observed, even after additional X-ray irradiation. It is concluded that TL in amethysts reported in the literature was actually caused by defects associated with aluminium impurities, not by destruction of Fe⁴⁺.     

Distinguishing natural from synthetic amethyst: the presence and shape of the 3595 cm−1 peak

Summary The infrared absorption spectrum of amethyst in the region of stretching vibrations of X–OH groups reveals several bands that have been used for the separation of natural from synthetic amethyst. The intensity and shape of these bands have been measured as a function of crystallographic orientation. Using a resolution of 0.5 cm⁻¹ the 3595 cm⁻¹ band is present in all infrared spectra of natural amethyst and in some rare synthetic ones. If present in synthetic amethyst, its full width at half maximum (FWHM) is about 7 cm⁻¹ whereas it is about 3 cm⁻¹ in all natural samples. This new criterion, unlike the previous ones, seems appropriate to separate natural from synthetic amethyst in all cases.     

Thermodynamic and magnetic properties of surface Fe<Superscript>3+</Superscript> species on quartz: effects of gamma-ray irradiation and implications for aerosol–radiation interactions

Samples of a natural amethyst, pulverized in air, and irradiated for gamma-ray doses from 0.14 to 70 kGy, have been investigated by powder electron paramagnetic resonance (EPR) spectroscopy from 90 to 294 K. The powder EPR spectra show that the surface Fe³⁺ species on the gamma-ray-irradiated quartz differ from its counterpart without irradiation in both the effective g value and the observed line shape, suggesting marked radiation effects. This suggestion is supported by quantitatively determined thermodynamic properties, magnetic susceptibility, relaxation times, and geometrical radius. In particular, the surface Fe³⁺ species on gamma-ray-irradiated quartz has larger Gibbs and activation energies than its non-irradiated counterpart, suggesting radiation-induced chemical reactions. The shorter phase-memory time (T _m) but longer spin–lattice relaxation time (T ₁) of the surface Fe³⁺ species on the gamma-ray-irradiated quartz than that without irradiation indicate stronger dipolar interactions in the former. Moreover, the calculated geometrical radius of the surface Fe³⁺ species on the gamma-ray-irradiated quartz is three orders of magnitude larger than that of its counterpart on the as-is sample. These results provide new insights into radiation-induced aerosol nucleation, with relevance to atmospheric cloud formation and global climate changes.     

Electron paramagnetic resonance spectroscopy of Fe<Superscript>3+</Superscript> ions in amethyst: thermodynamic potentials and magnetic susceptibility

Single-crystal and powder electron paramagnetic resonance (EPR) spectroscopic studies of natural amethyst quartz, before and after isochronal annealing between 573 and 1,173 K, have been made from 90 to 294 K. Single-crystal EPR spectra confirm the presence of two substitutional Fe³⁺ centers. Powder EPR spectra are characterized by two broad resonance signals at g = ~10.8 and 4.0 and a sharp signal at g = 2.002. The sharp signal is readily attributed to the well-established oxygen vacancy electron center E ₁′. However, the two broad signals do not correspond to any known Fe³⁺ centers in the quartz lattice, but are most likely attributable to Fe³⁺ clusters on surfaces. The absolute numbers of spins of the Fe³⁺ species at g = ~10.8 have been calculated from powder EPR spectra measured at temperatures from 90 to 294 K. These results have been used to extract thermodynamic potentials, including Gibbs energy of activation ΔG, activation energy E _a, entropy of activation ΔS and enthalpy of activation ΔH for the Fe³⁺ species in amethyst. In addition, magnetic susceptibilities (χ) have been calculated from EPR data at different temperatures. A linear relationship between magnetic susceptibility and temperature is consistent with the Curie–Weiss law. Knowledge about the stability and properties of Fe³⁺ species on the surfaces of quartz is important to better understanding of the reactivity, bioavailability and heath effects of iron in silica particles.     

Mineralisation of amethyst-bearing geodes in Ametista do Sul (Brazil) from low-temperature sedimentary brines: evidence from monophase liquid inclusions and stable isotopes

Fluid inclusion studies in combination with hydrogen, oxygen and sulphur isotope data provide novel insights into the genesis of giant amethyst-bearing geodes in Early Cretaceous Paraná continental flood basalts at Amestita do Sul, Brazil. Monophase liquid inclusions in colourless quartz, amethyst, calcite, barite and gypsum were analysed by microthermometry after stimulating bubble nucleation using single femtosecond laser pulses. The salinity of the fluid inclusions was determined from ice-melting temperatures and a combination of prograde and retrograde homogenisation temperatures via the density maximum of the aqueous solutions. Four mineralisation stages are distinguished. In stage I, celadonite, chalcedony and pyrite formed under reducing conditions in a thermally stable environment. Low δ³⁴S_V-CDT values of pyrite (?25 to ?32?‰) suggest biogenic sulphate reduction by organotrophic bacteria. During the subsequent stages II (amethyst, goethite and anhydrite), III (early subhedral calcite) and IV (barite, late subhedral calcite and gypsum), the oxidation state of the fluid changed towards more oxidising conditions and microbial sulphate reduction ceased. Three distinct modes of fluid salinities around 5.3, 3.4 and 0.3 wt% NaCl-equivalent characterise the mineralisation stages II, III and IV, respectively. The salinity of the stage I fluid is unknown due to lack of fluid inclusions. Variation in homogenisation temperatures and in δ¹⁸O values of amethyst show evidence of repeated pulses of ascending hydrothermal fluids of up to 80–90 °C infiltrating a basaltic host rock of less than 45 °C. Colourless quartz and amethyst formed at temperatures between 40 and 80 °C, while the different calcite generations and late gypsum precipitated at temperatures below 45 °C. Calculated oxygen isotope composition of the amethyst-precipitating fluid in combination with δD values of amethyst-hosted fluid inclusions (?59 to ?51?‰) show a significant ¹⁸O-shift from the meteoric water line. This ¹⁸O-shift, high salinities of the fluid inclusions with chloride-sulphate composition, and high δ³⁴S values of anhydrite and barite (7.5 to 9.9?‰) suggest that sedimentary brines from deeper parts of the Guaraní aquifer system must have been responsible for the amethyst mineralisation.     

The twinning microstructure and growth of amethyst quartz

The characteristic lamellar-twinning of the right-handed (R) and left-handed (L) structures in the major rhombohedral growth sectors of amethyst quartz has been studied by optical techniques, X-ray topography and transmission electron microscopy (TEM). The TEM observations show that the region of each Brewster fringe consists of fine-scale Brazil twin lamellae parallel to one of the r, z{10 \(\overline {\text{1}} \) 1} planes, and structural considerations suggest that it is one of the r-planes. The twin boundary corresponding to a Brewster fringe has the form of a zig-zag structure consisting of Brazil twin boundaries on two r{10 \(\overline {\text{1}} \) 1} planes, with one predominating. The Brewster fringes appear black between crossed polarizers because light travelling along the optic axis [001] passes through almost equal distances of R and L quartz, giving essentially zero optical rotation. From the visibility of the Brazil twin boundaries in electron micrographs and the visibility of the Brewster fringes in X-ray topographs, the fault vector R and the corresponding composition plane of the major Brazil twin associated with each Brewster fringe has been determined. The streaking of the Brewster fringes observed optically and in the X-ray topographs appears to be due to the stair-rod dislocations at the intersections of the Brazil twin boundaries. Experiments in which synthetic quartz was grown hydrothermally on untwinned seeds and on twinned amethyst seeds showed that the initiation of Brazil twins and the development of Brewster fringes was dependent upon the presence of iron in the growth solution.     

Structures,kinematic analysis,rheological parameters and temperature-pressure estimate of the Mesozoic Xingcheng-Taili ductile shear zone in the North China Craton

The NE to ENE trending Mesozoic Xingcheng-Taili ductile shear zone of the northeastern North China Craton was shaped by three phases of deformation. Deformation phase D₁ is characterized by a steep, generally E–W striking gneissosity. It was then overprinted by deformation phase D₂ with NE-sinistral shear with K-feldspar porphyroclasts forming a subhorizontal low-angle stretching lineation on a steep foliation. During deformation phase D₃, lateral motion accommodated by ENE sinistral strike-slip shear zones dominated. Associated fabrics developed at upper greenschist metamorphic facies conditions and show the deformation characteristics of middle- to shallow crustal levels. In some parts, the older structures have been in turn overprinted by late-stage sinistral D₃ shearing. Finite strain and kinematic vorticity in all deformed granitic rocks indicate a prolate ellipsoid (L-S tectonites) near plane strain. Simple shear-dominated general shear during D₃ deformation is probably of general significance. The quartz c-axis textures indicate prism-gliding with a dominant rhomb <a> slip and basal <a> slip system formed mainly at low-middle temperatures. Mineral deformation behavior, quartz c-axis textures, quartz grain size and the Kruhl thermometer demonstrate that the ductile shear zone developed under greenschist facies metamorphic conditions at deformation temperatures ranging from 400 to 500 °C. Dislocation creep is the main deformation mechanism at a shallow crustal level. Fractal analysis showed that the boundaries of recrystallized quartz grains had statistically self-similarities. Differential stresses deduced from dynamically recrystallized quartz grain size are at around 20–39 MPa, and strain rates in the order of 10⁻¹² to 10⁻¹⁴ s⁻¹. This indicates deformation of granitic rocks in the Xingcheng-Taili ductile shear zone at low strain rates, which is consistent with most other ductile shear zones. Hornblende-plagioclase thermometer and white mica barometer indicate metamorphic conditions of medium pressures at around ca. 3–5 kbar and temperatures of 400–500 °C within greenschist facies conditions. The main D₃ deformation of the ENE-trending sinistral strike-slip ductile shearing is related to the roll-back of the subducting Pacific plate beneath the North China Craton.     

Petrography and chemistry of SiO2 filling phases in the amethyst geodes from the Serra Geral Formation deposit,Rio Grande do Sul,Brazil

The filling process of amethyst-bearing geodes from Serra Geral Formation basalts, Brazil, is investigated by different methods performed on the SiO₂ filling phases. Image analysis of quartz–amethyst deposits suggests a single growing mechanism ruled by geometric selection of randomly oriented crystals. Microthermometry of fluid inclusions reveals formation temperature lower than 100 °C, probably lower than 50 °C, and fluid salinity as high as 3 mass% NaCl eq. Composition in REE and trace-elements measured by ICP-MS on acid-digested or laser-ablated samples indicates a common genesis for amethyst, quartz and chalcedony, as well as the absence of significant variations from one geode to another. ⁸⁷Sr/⁸⁶Sr data on chalcedony shows that both the host basalt or the Botucatu sandstone are possible silica sources. These data, combined with thermo-kinetic considerations, permit us to discuss the filling process. We argue in favor of the contribution of a mineralized fluid of hydrothermal origin producing a regional silica source which decreased with time. The observed mineral sequence is related to the depletion of silica in the solution.     

Aragonite from Mulanshan Glaucophane Schist: Implications for Regional Evolution of Southwestern Dabie Mountains, Central China

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天然与合成紫晶的红外和偏振拉曼光谱鉴定特征

天然紫晶与合成紫晶的鉴别是国内外珠宝鉴定实验室的一个难题,前人主要从双晶、色带、包裹体、红外吸收光谱特征等方面开展了研究。在利用红外光谱鉴别天然紫晶与合成紫晶时,不同的学者尚对3595cm-1或3543cm-1吸收峰作为诊断性还是指示性的判据存在不同认识。本文系统采集了典型的天然紫晶与合成紫晶样品,研究了利用红外光谱测试技术鉴别天然紫晶与合成紫晶的局限性,并尝试将偏振拉曼光谱应用于紫晶成因鉴别。结果表明:利用3595cm-1、3543cm-1红外吸收峰进行紫晶鉴别仅具有指示性意义,不能作为决定性的判定依据,偏振拉曼光谱可作为重要的补充。天然紫晶的偏振拉曼光谱(偏振方向:HH)均出现400cm-1的拉曼峰,而该峰在合成紫晶偏振拉曼光谱中缺失;合成紫晶的偏振拉曼光谱(偏振方向:HH)均具有795cm-1、448cm-1的拉曼峰,而这两个峰在天然紫晶偏振拉曼光谱中缺失。偏振拉曼光谱产生差异的原因可能与天然紫晶和合成紫晶内部晶格变形程度的不同有关。本文揭示的400cm-1、448cm-1和795cm-1偏振拉曼峰可作为鉴别紫晶成因的新依据。     

Trace element incorporation into quartz: A combined study by ICP-MS, electron spin resonance, cathodoluminescence, capillary ion analysis, and gas chromatography

Pegmatite quartz from different occurrences in Norway and Namibia was investigated by a combination of ICP-MS, Electron Spin Resonance (ESR), Capillary Ion Analysis (CIA) and Gas Chromatography (GC) to quantify trace elements in very low concentrations and to determine their position in the quartz structure.The studied quartz samples show similar geochemical characteristics with low contents of most trace elements. Remarkable are the elevated concentrations of Al (36-636 ppm), Ti (1.6-25.2 ppm), Ge (1.0-7.1 ppm), Na (5.2 to >50 ppm), K (1.6 to >100 ppm) and Li (2.1-165.6 ppm). These elements are preferentially incorporated into the quartz lattice on substitutional (Al, Ti, Ge) and interstitial (Li, Na, K) positions. Li⁺ was found to be the main charge compensating ion for Al, Ge and Ti, whereas some ppm of Na and K may also be hosted by fluid inclusions. Ti may be incorporated as substitutional ion for Si or bound on mineral microinclusions (rutile). The results of the ESR measurements show that there may be a redistribution of alkali ions during irradiation. The diamagnetic [AlO₄/M⁺]⁰ center transforms into the paramagnetic [AlO₄]⁰ center, whilst the compensating ions diffuse away and may be captured by the diamagnetic precursor centers of [GeO₄]⁰ and [TiO₄]⁰ to form paramagnetic centers ([TiO₄/Li⁺]⁰, [GeO₄/Li⁺]⁰).In general, fluid inclusions in pegmatite quartz can be classified as H₂O-CO₂-NaCl type inclusions with water as the predominant volatile. Among the main elements hosted by fluid inclusions in quartz are Na, K, NH₄, Ca, Mg and the anionic complexes Cl⁻, NO₃⁻, HCO₃⁻ and SO₄²⁻. Gas analysis of trapped fluids shows volatile components in the following order of abundance: H₂O > CO₂ > N₂(+) ≥ CH₄ > COS > C₂ and C₃ hydrocarbons. Additionally, traces of Co, Ni, Zn, Pb, and Cu were detected by CIA in fluid inclusions of some samples. There are indications that the REE and Rb are also bound in fluid inclusions, however, the concentrations of these elements are too low to be measured by CIA. Assuming that the REE preferentially occur in fluid inclusions, the typical chondrite normalized REE distribution patterns with tetrad effects and a distinct negative Eu anomaly would reflect the composition of the mineralizing fluid.For a number of elements, especially those with extremely low concentrations, the “type” of incorporation in quartz could not directly be determined. We conclude that these ions either are too large to substitute for the small Si⁴⁺ ion or they are not soluble in the mineralizing fluids to be hosted by fluid inclusions. Some of these elements, which are concentrated in the specific mineralization of certain pegmatites, are not present in elevated concentrations in the paragenetic pegmatite quartz itself. This was observed, for instance, for Be, Cs and Rb in the Li (Be-Cs-Rb) pegmatites of Rubicon or for Nb and Ta for Nb-Ta bearing pegmatites from Norway. It may be concluded that the concentrations of these trace elements in quartz do not reflect the mineralization and that these elements thus, cannot be used as petrogenetic indicator.     

TEM investigation of the crystal microstructures in a quartz-coesite assemblage of the western alps

Atransmission electron microscope (TEM) study of quartz-coesite inclusions in garnet in crustal rocks from the Western Alps is presented. Coesite shows a low dislocation density (<10⁷ cm^?2), and quartz a higher density of defects, Brasil twins (10⁴ cm^?1) and dislocations (10⁸ cm^?2). It is concluded that coesite has been not or only slightly plastically deformed and that the yield strength of coesite is higher than that of quartz. The large scale deformation implications are briefly discussed. TEM observations show no systematic topotactic relationship between the two polymorphs and their boundaries have a scalloped morphology which suggests that growth of quartz from coesite was controlled by a diffusion process.     

Chemical weathering in a tropical watershed,Luquillo Mountains,Puerto Rico III: quartz dissolution rates

The paucity of weathering rates for quartz in the natural environment stems both from the slow rate at which quartz dissolves and the difficulty in differentiating solute Si contributed by quartz from that derived from other silicate minerals. This study, a first effort in quantifying natural rates of quartz dissolution, takes advantage of extremely rapid tropical weathering, simple regolith mineralogy, and detailed information on hydrologic and chemical transport. Quartz abundances and grain sizes are relatively constant with depth in a thick saprolite. Limited quartz dissolution is indicated by solution rounding of primary angularity and by the formation of etch pits. A low correlation of surface area (0.14 and 0.42 m² g⁻¹) with grain size indicates that internal microfractures and pitting are the principal contributors to total surface area.Pore water silica concentration increases linearly with depth. On a molar basis, between one and three quarters of pore water silica is derived from quartz with the remainder contributed from biotite weathering. Average solute Si remains thermodynamically undersaturated with respect to recently revised estimates of quartz solubility (<180 μM) but exceeds estimated critical saturation concentrations controlling the initiation of etch pit formation (>17–81 μM). Etch pitting is more abundant on grains in the upper saprolite and is associated with pore waters lower in dissolved silica. Rate constants describing quartz dissolution increase with decreasing depth (from 10^−14.5–10^−15.1 mol m⁻² s⁻¹), which correlate with both greater thermodynamic undersaturation and increasing etch pit densities. Unlike for many aluminosilicates, the calculated natural weathering rates of quartz fall slightly below the rate constants previously reported for experimental studies (10^−12.4–10^−14.2 mol m⁻² s⁻¹). This agreement reflects the structural simplicity of quartz, dilute solutes, and near-hydrologic saturation.     

Size, speciation and lability of NOM-metal complexes in hyperalkaline cave dripwater

Transport of trace metals by natural organic matter (NOM) is potentially an important vector for trace metal incorporation in secondary cave precipitates [speleothems], yet little is known about the size distribution, speciation and metal binding properties of NOM in cave dripwaters. A hyperalkaline cave environment (ca. pH 11) was selected to provide information on colloid-metal interactions in cave waters, and to address the lack of high-pH data in natural systems in general. Colloidal (1 nm-1 μm) NOM in hyperalkaline cave dripwater from Poole’s Cavern, UK, was characterised by flow field-flow fractionation (FlFFF) coupled to UV and fluorescence detectors and transmission electron microscopy (TEM) coupled to X-ray energy-dispersive spectroscopy (X-EDS); trace-metal lability was examined by diffusive gradients in thin films (DGT). Colloidal aggregates and small particulates (>1 μm) imaged by TEM were morphologically heterogeneous with qualitative elemental compositions (X-EDS spectra; n = 41) consistent with NOM aggregates containing aluminosilicates, and iron and titanium oxides. Globular organic colloids, with diameters between ca. 1 and 10 nm were the most numerous colloidal class and exhibited high UV-absorbance (254 nm) and fluorescence intensity (320:400 nm excitation: emission) in optical regions characteristic of humic-like compounds. Metal binding with humic substances was modelled using the WHAM 6.1 (model VI) and visual MINTEQ 3.0 (NICA-Donnan) speciation codes. At pH 11, both models predicted dominant humic binding of Cu (ca. 100%) and minimal binding of Ni and Co (ca. <1-7%). A DGT depletion experiment (7 days duration) with the hyperalkaline dripwater showed that the available proportion of each metal was much lower than its total concentration. Metal availability for DGT in the initial stages (24 h) was consistent with weaker binding of alkaline earth metals by humic substances (Ba > Sr > V > Cu > Ni > Co), compared to the transition metals. Integrated over the entire experiment, the DGT-available proportion of transition metals (Ni > Cu & V >> Co) differed greatly from the expected hierarchy from WHAM and MINTEQ, indicating unusually strong complexation of Co. Total metal concentrations of Cu, Ni, and Co in raw and filtered PE1 dripwater samples (n = 53) were well correlated (Cu vs. Ni, R² = 0.8; Cu vs. Co, R² = 0.5) and were strongly reduced (> ca. 50%) by filtration at ca. 100 and 1 nm, indicating a common colloidal association. Our results demonstrate that soil-derived colloids reach speleothems, despite transport through a karst zone with potential for adsorption, and that NOM is a dominant complexant of trace metals in high pH speleothem-forming groundwaters.     

Grain boundary dissolution porosity in quartzofeldspathic ultramylonites: Implications for permeability enhancement and weakening of mid-crustal shear zones

Quartzofeldspathic ultramylonites from the Alpine Fault Zone, one of the world's major, active plate boundary-scale fault zones have quartz crystallographic preferred orientations (CPO) and abundant low-angle (<10° misorientation) boundaries, typical microstructures for dislocation creep-dominated deformation. Geometrically necessary dislocation density estimates indicate mean dislocation densities of ∼10⁹ cm⁻². A significant proportion (∼30%) of grain boundaries (>10° misorientation) are decorated by faceted pores, commonly with uniformly-oriented pyramidal shapes. Only grain boundaries with >10° misorientation angles in polymineralic aggregates are decorated by pores. Mean grain boundary pore densities are ∼5 × 10⁸ cm⁻². Grain boundary pores are dissolution pits generated during syn-deformational transient grain boundary permeability, nucleating on dislocation traces at dilatant grain boundary interfaces. They have not been removed by subsequent grain boundary closure or annealing. Pore decoration could have led to grain boundary pinning, triggering a switch in the dominant deformation mechanism to grain boundary sliding, which is supported by evidence of CPO destruction in matrix quartz. Pore-decorated grain boundaries have significantly reduced surface area available for adhesion and cohesion, which would reduce the tensile and shear strength of grain boundaries, and hence, the bulk rock. Grain boundary decoration also significantly decreased the mean distance between pores, potentially facilitating dynamic permeability. Consequently, these microstructures provide a new explanation for strain weakening and evidence of fluid flow along grain boundaries in mylonites at mid-crustal conditions.     

Charging time of tight gas in the Upper Paleozoic of the Ordos Basin,central China

The Upper Paleozoic section contains a tight gas sandstone reservoir (of 2.75 × 10¹² m³) in the Ordos Basin, central China. The measured porosities (< 10%) and permeabilities (generally < 1 mD) are the result of significant mechanical and chemical compaction and precipitation of carbonate, quartz and authigenic clay cements. Fluid inclusion geochemistry and kinetic modeling (generation of gaseous components and δ¹³C₁) were integrated to constrain the timing of gas charge into the tight reservoir. The modeling results indicate that the natural gases in the present reservoir are similar to gases liberated from quartz inclusions in both composition and stable carbon isotope values and also similar to gas generated from Upper Paleozoic coal. The similar geochemistry suggests that an important phase of quartz cementation must have occurred after gas emplacement in the reservoirs during regional uplift at the end of the Cretaceous. The latest carbonate cement, postdating quartz cementation, consumed most of the late CO₂ generated from coal at high maturity (R_O > 1.7%) and reduced the reservoir quality dramatically. On the contrary, tight sandstones from non-producing areas have fluid inclusions that were trapped in quartz cements much earlier. These data indicate that natural gas migrated into the Upper Paleozoic reservoir when it still retained high porosity and permeability. The reservoir continued to experience porosity and permeability reduction from continued quartz and carbonate cementation after gas charging due to low gas saturation. Comparison of the relative timing of gas charging with that of sandstone cementation can help to predict areas of risk during tight gas exploration and development.     

Role of molecular oxygen in the dissolution of siderite and rhodochrosite

The dissolution of siderite (FeCO₃) and rhodochrosite (MnCO₃) under oxic and anoxic conditions is investigated at 298 K. The anoxic dissolution rate of siderite is 10^−8.65 mol m⁻² s⁻¹ for 5.5 < pH < 12 and increases as [H⁺]^0.75 for pH < 5.5. The pH dependence is consistent with parallel proton-promoted and water hydrolysis dissolution pathways. Atomic force microscopy (AFM) reveals a change in pit morphology from rhombohedral pits for pH > 4 to pits elongated at one vertex for pH < 4. Under oxic conditions the dissolution rate decreases to below the detection limit of 10⁻¹⁰ mol m⁻² s⁻¹ for 6.0 < pH < 10.3, and hillock precipitation preferential to steps is observed in concurrent AFM micrographs. X-ray photoelectron spectroscopy (XPS) and thermodynamic analysis identify the precipitate as ferrihydrite. At pH > 10.3, the oxic dissolution rate is as high as 10^−7.5 mol m⁻² s⁻¹, which is greater than under the corresponding anoxic conditions. A fast electron transfer reaction between solution O₂ or [Fe³⁺(OH)₄]⁻ species and surficial >Fe^II hydroxyl groups is hypothesized to explain the dissolution kinetics. AFM micrographs do not show precipitation under these conditions. Anoxic dissolution of rhodochrosite is physically observed as rhombohedral pit expansion for 3.7 < pH < 10.3 and is chemically explained by parallel proton- and water-promoted pathways. The dissolution rate law is 10^−4.93[H⁺] + 10^−8.45 mol m⁻² s⁻¹. For 5.8 < pH < 7.7 under oxic conditions, the AFM micrographs show a tabular precipitate growing by preferential expansion along the a-axis, though the macroscopic dissolution rate is apparently unaffected. For pH > 7.7 under oxic conditions, the dissolution rate decreases from 10^−8.45 to 10^−9.0 mol m⁻² s⁻¹. Flattened hillock precipitates grow across the entire surface without apparent morphological influence by the underlying rhodochrosite surface. XPS spectra and thermodynamic calculations implicate the precipitate as bixbyite for 5.8 < pH < 7.7 and MnOOH (possibly feitnkechtite) for pH >7.7.     

Genesis of amethyst geodes in basaltic rocks of the Serra Geral Formation (Ametista do Sul,Rio Grande do Sul,Brazil): a fluid inclusion,REE, oxygen,carbon, and Sr isotope study on basalt,quartz, and calcite

In the Ametista do Sul area, Rio Grande do Sul, Brazil, amethyst-bearing geodes are hosted by a ~40- to 50-m-thick subhorizontal high-Ti basaltic lava flow of the Lower Cretaceous Paraná Continental Flood Basalt Province. The typically spherical cap-shaped, sometimes vertically elongated geodes display an outer rim of celadonite followed inwards by agate and colorless and finally amethystine quartz. Calcite formed throughout the whole crystallization sequence, but most commonly as very late euhedral crystals, sometimes with gypsum, in the central cavity. Fluid inclusions in colorless quartz and amethyst are predominantly monophase and contain an aqueous liquid. Two-phase liquid–vapor inclusions are rare. Some with a consistent degree of fill homogenize into the liquid between 95 and 98 °C. Ice-melting temperatures in the absence of a vapor phase between –4 and +4 °C indicate low salinities. Chondrite-normalized REE patterns of calcites are highly variable and show generally no systematic correlation with the paragenetic sequence. The oxygen isotope composition of calcites is very homogeneous (δ¹⁸O_VSMOW=24.9±1.1‰, n=34) indicating crystallization temperatures of less than 100 °C. Carbon isotope values of calcites show a considerable variation ranging from –18.7 to –2.9‰ (VPDB). The ⁸⁷Sr/⁸⁶Sr ratio of calcites varies between 0.706 and 0.708 and is more radiogenic than that of the host basalt (~0.705). The most likely source of silica, calcium, carbon, and minor elements in the infill of the geodes is the highly reactive interstitial glass of the host basalts leached by gas-poor aqueous solutions of meteoric origin ascending from the locally artesian Botucatú aquifer system in the footwall of the volcanic sequence. The genesis of amethyst geodes in basalts at Ametista do Sul, Brazil, is thus considered as a two-stage process with an early magmatic protogeode formation and a late, low temperature infill of the cavity. Editorial handling: A. Cheilletz     

Structural state and differusion of impurities in natural quartz of different genesis

Impurity inhomogeneities and other structural defects have been studied by means of transmission electron microscopy (TEM), X-ray microanalysis and electron paramagnetic resonance (EPR) in untreated and heat-treated quartz samples of three genetic types: hydrothermal, pegmatitic and magmatic. The impurities present are Al, Na and H₂O, which occupy tetrahedral (Al³⁺) or interstitial (Na⁺, H₂O) positions in the quartz lattice. Impurities form imperfections of various degrees of segregation: from point defects to micropores with a gas-liquid content. Their size, form, density and distribution in the lattice depend on the formation conditions of the quartz, the presence of dislocations and plane defects serving as sinks for the impurity atoms, and the heat treatment regime. Experimental data indicate that gas-liquid inclusions of dimensions up to some microns are the result of impurity segregation during postcrystallizational cooling. Crystalline quartz amorphizes upon electron irradiation. A model of structural water explaining experimentally observed features of this phenomenon is proposed whereby the water molecule, represented as a dipole, enters microregions of the silica lattice with a high impurity content and there forms a bond between ‘defective’ [SiO₃]^2? and [AlO₄]^5? tetrahedra. On irradiation, the Si---O donor-acceptor bonds trap nonelastically scattered electrons and are ruptured as a result. The water released by this lattice discontinuity forms microbubbles that diffuse along sinks into the larger micropores thus further increasing their volume.     

Al-related centers in relation to γ-irradiation

 The charge compensation problem for Si−Al substitution in Brazilian natural quartz is investigated in relation to γ-irradiation darkening response and impurity contents evaluated by atomic absorption spectrometry and infrared absorption spectroscopy. Al⁺³ in as-grown natural quartz is compensated by Li⁺ and H⁺ to form Al−Li and Al−OH centers. The content ratios (Al−Li)/(Al−OH) and Li/(broad OH band) depend on the environmental conditions of crystal growth and influence the formation of Al-hole centers due to γ-irradiation. Al−OH centers are the dominant Al-related centers in quartz from hydrothermal origin while Al−Li centers are dominant for that of pegmatitic origin. The formation of Al-hole centers is little in quartz with a high content of broad OH band which is from low temperature hydrothermal origin. Received May 23, 1995 / Revised, accepted May 8, 1996