Structural defects in microcrystalline silica

The structure of the microcrystalline silica varieties chalcedony, flint, moganite, opal-C and -CT is characterized by X-ray powder diffractometry and transmission electron microscopy (TEM). The role of impurities is investigated by infrared spectroscopy and chemical analysis. Microcrystalline opal, chalcedony and flint have a disordered intergrowth structure composed of cristobalite and tridymite domains in opal, and quartz and moganite domains in chalcedony and flint. Each constituent phase has different cell dimensions and symmetry. The main impurity is water which is enriched at the intergrowth interfaces. Density and refractive indices of microcrystalline silica depend on the water content.     

玛瑙的结构、水含量和成因机制

玛瑙是一种隐晶质硅质岩石,主要由玉髓以及少量蛋白石、斜硅石和微晶石英等组成.其在世界各地分布广泛,质地坚硬细腻、色彩鲜艳多样、纹理交错、造型千姿百态,是一种平凡而美丽的宝石.本文结合国内外最新研究进展,对玛瑙矿物的结构、水含量和成因机制进行了综合评述.玛瑙以纹带构造为特征,其内部纹带花纹和化学组成呈韵律性变化,并在不同观察尺度表征出来.因此,玛瑙也被定义为条带状玉髓.然而,多数玛瑙实际上是由纤维状玉髓、同心环带状玉髓、水平条带状玉髓、微晶石英和自形石英晶体等组成,它们的相对含量与玛瑙的产地和形成过程密切相关.X射线衍射和电子背散射衍射(EBSD)测量数据揭示,玛瑙中的硅质矿物多发生定向生长,其中微晶石英a轴倾向于垂直韵律环带,c轴则近似平行韵律环带.傅立叶变换红外光谱(FTIR)测量表明,玛瑙含有少量分子水和羟基水,并且总水含量随着硅质矿物结晶度提高而降低.至今实验室仍然无法合成玛瑙,还不清楚玛瑙纹带构造的形成机制和过程.一种代表性假设认为,玛瑙中的纹带源于硅质热液沉淀作用或者硅胶原位结晶作用.但是,最近研究发现玛瑙纹带中共生矿物的结晶度、晶体取向和含水量具有系统差异,揭示其形成过程可能与成岩序列密切相关.将实验岩石学与定量显微结构观察以及多种矿物微区分析测试手段有机结合,深入研究玛瑙环带内部微量元素、水含量和晶体取向数据,获得其系统性变化特征及其内部联系,可以为玛瑙成因机制和形成过程研究提供重要数据支撑和关键性的约束条件.     

Solubility of silica polymorphs in electrolyte solutions, I. Activity coefficient of aqueous silica from 25° to 250°C, Pitzer''s parameterisation

Within the framework of Pitzer's specific interaction model, interaction parameters for aqueous silica in concentrated electrolyte solutions have been derived from Marshall and co-authors amorphous silica solubility measurements. The values, at 25°C, of the Pitzer interaction parameter (λ_SiO2(aq)−i) determined in this study are the following: 0.092 (i = Na⁺), 0.032 (K⁺), 0.165 (Li⁺), 0.292 (Ca²⁺, Mg²⁺), −0.139 (SO₄²⁻), and −0.009 (NO₃⁻). A set of polynomial equations has been derived which can be used to calculate λ_SiO2(aq)−i for these ions at any temperature up to 250°C. A linear relationship between the aqueous silica-ion interaction parameters (λ_SiO2(aq)−i) and the surface electrostatic field (Z_i/r_e,i) of ions was obtained. This empirical equation can be used to estimate, in first approximation, λ_SiO2(aq)−i if no measurements are available. From this parameterisation, the calculated activity coefficient of aqueous silica is 2.52 at 25°C and 1.45 at 250°C in 5 m NaCl solution. At lower concentrations, e.g. 2 m NaCl, the activity coefficient of silica is 1.45 at 25°C and 1.2 at 250°C. Hence, in practice, it is necessary to take into account the activity coefficient of aqueous silica (λ_SiO2(aq)≠1) in hydrothermal solutions and basinal brines where the ionic strength exceeds 1. A comparison of measured [Marshall, W.L., Chen, C.-T.A., 1982. Amorphous silica solubilities, V. Prediction of solubility behaviour in aqueous mixed electrolyte solutions to 300°C. Geochim. Cosmochim. Acta 46, 289–291.] and computed amorphous silica solubility, using this parameterisation, shows a good agreement. Because the effect of individual ions on silicate and silica polymorph solubilities are additive, the present study has permitted to derive Pitzer interaction parameters that allow a precise computation of γ_SiO2(aq) in the Na---K---Ca---Mg---Cl---SO₄---HCO₃---SiO₂---H₂O system, over a large range of salt concentrations and up to temperatures of 250°C.     

Origin and variability of a terminal Proterozoic primary silica precipitate,Athel Silicilyte,South Oman Salt Basin,Sultanate of Oman

The Precambrian–Cambrian Athel Silicilyte is a 400 m thick, salt‐encased siliceous succession in the South Oman Salt Basin. It is a self‐sourcing hydrocarbon reservoir and comprises up to 95% microcrystalline quartz and exhibits wavy discontinuous lamination, comprising thin, alternating organic‐rich and silica‐rich layers. Textures and geochemical fingerprinting indicate that it is a primary precipitate formed by microbially mediated precipitation of silica from sea water, within the water column at the sulphidic/oxic interface. The unique occurrence of the Athel Silicilyte in the terminal Proterozoic implies that optimal conditions for this style of silica precipitation occurred only briefly. Basin anoxia, coupled with the growth of microbial mats, low pH and high silica pore water saturations, created optimal chemical conditions for silica precipitation. Volumes of microcrystalline quartz are highest within the transgressive and early highstand systems tract and towards the centre of the Athel Basin. At the basin margins, and within the late highstand systems tract, volumes of microcrystalline quartz decreased as the volume of detrital sediment increased. Mass‐balance calculations indicate that silica‐enriched sea water would have been supplied to the basin by infrequent marine incursions that replenished ambient sea water in the upper part of the water column. In conclusion, precipitation of the Athel Silicilyte was driven by the coincidence of basin restriction, limited clastic input, availability of organic matter and water column anoxia. The observation that there are few documented examples of chert deposits younger than ca 700 Ma, prior to the Cambrian explosion, suggests that although silica budgets within marine basins probably remained high prior to the evolution of silica‐secreting organisms, direct precipitation from sea water was restricted. This is tentatively related to the gradual increase in alkalinity of sea water through the Palaeo‐Proterozoic and Meso‐Proterozoic, such that silica precipitation could only occur through the coincidence of basin anoxia and low siliciclastic input.     

TEM characterisation and interpretation of fabric and structural degree of order in microcrystalline SiO2 phases

Representative samples of the two fabric varieties of microcrystalline quartz, chalcedony and quartzine, from agates of different origin were investigated by transmission electron microscopy (TEM). Both varieties contain lamellar admixtures of the SiO₂ mineral moganite. The transitions from quartz to moganite within the fabric differ in a characteristic way. Whereas in quartzine the gradient between the structures is steep, the transition is more continuous in chalcedony. The morphology of moganite in chalcedony and quartzine is determined by the (101)-face; in pure moganite from Gran Canaria it is governed by the (110)-face.     

A proposed mechanism for the growth of chalcedony

The structural disparities that distinguish chalcedony from macrocrystalline quartz suggest that different crystallization mechanisms are operative during the growth of these two forms of silica. Although the paragenesis of chalcedony has provoked marked disagreement among researchers, a review of previous studies supports the idea that chalcedony can precipitate from slightly saturated aqueous solutions at relatively low temperatures (<100° C). These conditions for deposition suggest a model for chalcedony crystallization that involves the assembly of short-chain linear polymers via bridging silica monomers. This assembly occurs through a spiral growth mechanism activated by a screw dislocation withb=n/2 [110], wheren is an integer. The proposed model can account for a number of peculiarities that have been observed in chalcedony at the microstructural scale, such as: (1) the direction of fiber elongation along [110] rather than [001]; (2) the periodic twisting of chalcedony fibers about [110]; (3) the high density of Brazil twin composition planes; (4) the common intergrowth of moganite within chalcedony.     

Microzoning of agates as a reflection of their formation dynamics

Agates are natural hierarchicalal structural assemblies composed largely of silica minerals: chalcedony, quartz, and quartzine. Microstructural heterogeneities, most typical of those of agate-forming minerals, are characterized by variations in periods of helicoidal twisting of chalcedony and by micrometric rhythmic alternation of zones with a low refractive index within the matrix of normal chalcedony, quartz, and quartzine. A study of the degree of crystallization of chalcedony using the Barsanova-Yakovleva method showed that neither helicoidal twisting nor refractive index zoning brought about any significant disturbance in the chalcedony structure. Helicoidal twisting is a result of the stresses caused by substitution of Si⁴⁺ for Al³⁺ asymmetric with respect to chalcedony crystal. It is suggested that layering by the refractive index developed due to accumulation of small portions of gel consisting of high silica polymers at the front of crystal growth.     

Small angle neutron scattering by opals

Micro- and non-crystalline opals, chalcedony and flint show diffuse small angle neutron scattering (SANS). Precious opals give rise to two additional intensity maxima at very small scattering angles which are due to Bragg reflections from the closest packed non-crystalline silica spheres. A small angle texture diagram reveals that the closest packing is faulty. Synthetic non-crystalline opals yield much less intense small angle scattering due to lower contrast between silica spheres and interstitial cement or particles; in this case intensity maxima were not observed. The outer part of the scattering curves of opal-CT and microcrystalline quartz deviates from Porod's law. The specific surface of natural non-crystalline opals ranges from 0.006 to 0.018 nm^–1. In microcrystalline opals, the specific surface is about 10 times larger than in non-crystalline opals.     

Calculated thermodynamic properties of silica polymorphs

Accurate interatomic potentials have been employed to compute the phonon density of states of αquartz, stishovite and coesite polymorphs of silica. The temperature variation of several thermodynamic properties is calculated by using the phonon density of states to describe the vibrational entropy contribution to the free energy. Results for these polymorphs are in surprisingly good agreement with available experimental data. Moreover, the microscopic origin of quantitative differences in the heat capacity behavior of low and high density polymorphs is established.     

Opal and chalcedony speleothems on quartz sandstones in the Sydney region,southeastern Australia

Speleothems of silica are far rarer than those of calcite but occur in a range of types including stalactites, stalagmites and flowstones. This study has found a wider range and far greater number of silica speleothems on the quartz sandstones of the Sydney region than the small number of previous accounts had suggested. Speleothems on the Sydney region sandstones are composed of multiple layers of amorphous opal‐A and cryptocrystalline chalcedony. Silica slowly dissolved from detrital and diagenetic quartz and kaolinite clays of the host arenites is redeposited as opal‐A at the sandstone surface when groundwater evaporates. This amorphous silica converts over time by Ostwald‐type paragenesis to the cryptocrystalline form, but the expected intermediate opal‐CT phase has not been detected. The crystallisation of chalcedony at earth‐surface temperatures is generally believed to take an extremely long time and its presence makes these speleothems very significant, especially as it is reported in only a small number of silica speleothems elsewhere. Furthermore, a similar paragenetic silica‐‘ripening’ mechanism may also be involved in the low‐temperature earth‐surface formation of other crystalline silica deposits such as silcrete duricrusts and pedogenic quartz. Additional closely coupled laboratory and field investigations into the processes that control silica paragenesis under earth‐surface conditions are sorely needed.     

Glauconitization of detrital silica substrates in the Barton Formation (upper Eocene) of the Hampshire Basin, southern England

Upper Eocene detrital silica grains (chert and quartz) of the Hampshire Basin display alteration and replacement fabrics by glauconite. Silica grains have etched surfaces due to glauconitization which appear green in reflected light and thin section. Quartz grains were glauconitized by surface nucleation and replacement, which spreads from the margin with progressive glauconitization, replacing the quartz grain interior. Chert grains were glauconitized by surface replacement and nucleation internally along cracks and in pores. Different forms of glauconite are associated with the two minerals; glauconite associated with quartz is generally highly-evolved whereas glauconite associated with chert is of the evolved variety. This is interpreted as being due to different surface-reaction control mechanisms associated with the two forms of silica. There is no evidence to suggest that glauconite evolved in stages from a nascent form. Two crystalline morphological forms of glauconite are found associated with both quartz and chert. Glauconite growing within a confined space has a laminated morphology whilst glauconite occurring on the surface has a rosette morphology.     

Mineralogical and textural variation of silica minerals in hydrothermal flow-through experiments: Implications for quartz vein formation

We conducted hydrothermal flow-through experiments at 430 °C and 31 MPa to investigate the mechanism of silica precipitation on granite under crustal conditions. Two experiments were performed using different input solutions: a single-component Si solution, and a multi-component solution with minor Al, Na, and K. The degree of supersaturation with respect to quartz, Ω = C_Si/C_Si,Qtz,eq, where C_Si and C_Si,Qtz,eq indicate Si concentration in solutions and the solubility of quartz within water, respectively, decreased from 3-3.5 to <1.1 along the flow path. A variety of silica minerals formed during the experiments (opal-A, opal-C, chalcedony, and quartz), and their occurrences and modal abundances changed in response to Ω and the presence of additives in the solution.For near-equilibrium solutions (Ω < ∼1.2), silica precipitation occurred in a simple way in both experiments, being restricted to overgrowths on pre-existing quartz surfaces in the granite. At higher saturation levels (Ω > ∼1.2), silica minerals were deposited on other surfaces in addition to quartz. In the single-component experiment, the dominant silica minerals changed in the order of opal-A → opal-C → quartz with decreasing Si concentration along the flow path. In contrast, in the multi-component experiment, quartz and minor chalcedony formed throughout the entire reaction vessel. This finding indicates that impurities (Na, K, and Al) in the solutions inhibited the precipitation of opal and enhanced the direct nucleation of quartz. The systematic appearance of metastable silica minerals were examined by nucleation processes and macroscopic precipitation kinetics. Our experimental results indicate that different precipitation mechanisms yield contrasting textures, which in turn suggests that vein textures can be used as indicators of solution chemistry within the fracture.     

Quantitative study of geochemical processes in the Dogger aquifer,Paris Basin,France

The quantification of geochemical reactions in hydrothermal aquifers requires an exhaustive approach because of their interdependence. All chemical elements likely to have a quantitative influence on dissolution or precipitation reactions have to be taken into account. Geochemical constraints the number of which equals the number of the chemical elements, were determined with the help of chemical analyses of the solution. In the case study of the Dogger aquifer (Paris Basin, France), 12 elements are taken into account (Al, C, Cl, Ca, F, H, K, Mg, Na, O, S, Si). Three constraints apply to water-activity, neutrality and conservation of chloride in aqueous solutions. The determination of the remaining constraints was based on saturation indices, stability diagrams of minerals and partial pressure of carbon dioxide (pCO₂). The present-day solutions are at equilibrium with respect to nine minerals (albite, anhydrite, chalcedony, calcite, dolomite, fluorite, kaolinite, K-feldspar and illite or chlorite). Thus, it was demonstrated that the composition of these solutions (including computed pCO₂) is only a function of temperature and chloride content. Moreover, it was possible to test the validity of the geochemical system by computing its speciation and comparing these theoretical results with actual chemical analyses (pH and concentrations). Finally, geochemical simulations were used in predicting what quantities would be dissolved or precipitated, as either the temperature or the chlorinity varied. Although the rock is predominantly calcareous, these quantities could not be determined if the influence of the aluminosilicates were neglected. This chemical component approach with which one can pose and solve rigorously the chemical equilibrium problem constitutes a prerequisite for the quantitative study of geochemical processes related to fluid flow.     

A method of calculating quartz solubilities in aqueous sodium chloride solutions

The aqueous silica species that form when quartz dissolves in water or saline solutions are hydrated. Therefore, the amount of quartz that will dissolve at a given temperature is influenced by the prevailing activity of water. Using a standard state in which there are 1,000 g of water (55.51 moles) per 1,000 cm³ of solution allows activity of water in a NaCl solution at high temperature to be closely approximated by the effective density of water, p_e, in that solution, i.e. the product of the density of the NaCl solution times the weight fraction of water in the solution, corrected for the amount of water strongly bound to aqueous silica and Na⁺ as water of hydration. Generally, the hydration of water correction is negligible.The solubility of quartz in pure water is well known over a large temperature-pressure range. An empirical formula expresses that solubility in terms of temperature and density of water and thus takes care of activity coefficient and pressure-effect terms. Solubilities of quartz in NaCl solutions can be calculated by using that equation and substituting p_e, for the density of pure water. Calculated and experimentally determined quartz solubilities in NaCl solutions show excellent agreement when the experiments were carried out in non-reactive platinum, gold, or gold plus titanium containers. Reactive metal containers generally yield dissolved silica concentrations higher than calculated, probably because of the formation of metal chlorides plus NaOH and H₂. In the absence of NaOH there appears to be no detectable silica complexing in NaCl solutions, and the variation in quartz solubility with NaCl concentration at constant temperature can be accounted for entirely by variations in the activity of water.The average hydration number per molecule of dissolved SiO₂ in liquid water and NaCl solutions decreases from about 2.4 at 200°C to about 2.1 at 350°C. This suggests that H₄SiO₄ may be the dominant aqueous silica species at 350°C, but other polymeric forms become important at lower temperatures.     

Selective and reversible carbonate—silica replacements in Lower Cretaceous carbonate-bearing turbidites of the Eastern Alps

In the diagenetic history of calcareous sandstones, silicacementation and silicification may be followed by carbonatecementation and replacement and vice versa, and the change-over from one to the other may occur more than once. This is well illustrated by calcareous and siliciclastic turbidites of the Gault Formation (Aptian to Albian) of the Eastern Alps which have been interpreted as deep-sea trench plain and deep-sea fan deposits. In these turbidites silicification selectively affects ooids and a few other biogenic carbonate fragments rich in organic matter (algae and bryozoans) which form a small fraction of the bulk sediment. The type and sequence of diagenetic changes are largely controlled by host-rock composition and may vary vertically within individual beds as a result of compositional grading. In the carbonate turbidites, silicification follows widespread calcite cementation. The process is slow, resulting in relatively coarsely crystalline replacement quartz. In ooids with quartz nuclei, rim-quartz forms mostly monocrystalline ‘overgrowths’ by outward replacement of the concentrically laminated carbonate cortex. This type of silicification is often incomplete leaving parts of the ooid cortices unaffected. In quartz arenites and sublitharenites silicification precedes calcite cementation. There the process is rapid, forming microcrystalline quartz. Even if the ooid nucleus consists of quartz, a syntaxial ‘overgrowth’ does not normally form. The replacement quartz is almost always polycrystalline. Late-stage diagenetic calcite and dolomite which develop euhedral crystal shapes and cut across grain boundaries may replace the earlier secondary rim-quartz of the ooids as well as other minerals. Possible sources of the silica are pressure-solution of quartz, dissolution of opaline silica of radiolarian tests and of sponge spicules, and feldspar in the host bed. In a number of examples an increase in the degree of silicification can be observed towards the lower bedding planes of individual turbidites requiring an additional external source of silica which seems to necessitate cross-formational flow of pore solutions. Silicification in both the carbonate and the siliciclastic turbidites probably took place at about the same time; in the carbonate turbidites it was preceded, however, by calcite cementation, which significantly reduced porosity and permeability before silicification took place. The greater degree of alteration experienced by the Gault turbidites of the Falknis and Tasna Nappes, which are more internal structural units of the Alps (compared to the Flysch Zone of the Eastern Alps), is reflected by the growth of quartz ‘beards’ and spikes from the ooids in the direction perpendicular to maximum stress. This is the only case observed where the rim quartz of the ooids grows beyond the original grain boundaries.     

Silicified Precambrian evaporite nodules from Northern Norway: A preliminary report

Nodular silica concentrations reminiscent of evaporite bodies have been observed in the Late Precambrian (Riphean) Porsangerfjord Group in western Porsangerfjord, northern Norway. The nodules are individual or coalescent kidney-shaped bodies measuring a few centimetres across, and consist predominantly of megaquartz and of length-slow chalcedony. Length-fast chalcedony occurs only as a red layer present in some large nodules. Relics of a fibrous, felted or radiating texture are preserved in numerous crystals of megaquartz and quartzine.The quartz nodules are interpreted as silica-replaced, early diagenetic evaporite (anhydrite) bodies. The paleoclimatic importance of these Precambrian evaporites is briefly discussed and the significance of length-slow chalcedony as an indicator of evaporite environments is confirmed.     

Modeling the kinetics of silica nanocolloid formation and precipitation in geologically relevant aqueous solutions

The kinetics of the formation and precipitation of nanocolloidal silica from geologically relevant aqueous solutions is investigated. Changes in monomeric (SiO_2(mono)), nanocolloidal (SiO_2(nano)) and precipitated silica (SiO_2(ppt)) concentrations in aqueous solutions from pH 3 to 7, ionic strengths (IS) of 0.01 and 0.24 molal, and initial SiO₂ concentrations of 20.8, 12.5 and 4.2 mmolal (reported in [Icopini, G.A., Brantley, S.L., Heaney, P.J., 2005. Kinetics of silica oligomerization and nanocolloid formation as a function of pH and ionic strength at 25 °C. Geochim. Cosmochim. Acta69(2), 293-303.]) were fit using two kinetic models. The first model, termed the concentration model, is taken from Icopini et al. (2005) and assumes that the rate of change of SiO_2(mono) as a function of time has a fourth-order dependence on the concentration of SiO_2(mono) in solution. The second model, termed the supersaturation model, incorporates the equilibrium concentration of amorphous silica and predicts that polymerization will be a function of the degree of silica supersaturation in solution with respect to amorphous silica. While both models generally predicted similar rate constants for a given set of experimental conditions, the supersaturation model described the long-term equilibrium behavior of the SiO_2(mono) fraction more accurately, resulting in significantly better fits of the monomeric data. No difference was seen between the model fits of the nanocolloidal silica fraction. At lower pH values (3-4), a metastable equilibrium was observed between SiO_2(mono) and SiO_2(nano). This equilibrium SiO_2(mono) concentration was found to be 6 mmolal, or three times the reported solubility of bulk amorphous silica under the experimental conditions studied and corresponds to the predicted solubility of amorphous silica colloids approximately 3 nm in diameter. Atomic force microscopy was used to determine the average size of the primary nanocolloidal particles to be ∼3 nm, which is in direct agreement with the solubility calculations. Larger aggregates of the primary nanocolloids were also observed to range in size from 30 to 40 nm. This work provides the first kinetic models describing the formation and evolution of nanocolloidal silica in environmentally relevant aqueous solutions. Results indicate that nanocolloidal silica is an important species at low pH and neutral pH at low ionic strengths and may play a more important role in geochemical cycles in natural aqueous systems than previously considered.     

Geochemical processes controlling silica concentrations in groundwaters of the Salado River drainage basin, Argentina

Chemical analyses of dissolved silica in the shallow groundwater of the lower part of the Salado River drainage basin indicate that silica values averaged 60 ppm. The groundwaters are oversaturated in relation to quartz, Na-plagioclase, K-feldspar, and the weathering of quartz and aluminosilicates appear to have little control on silica concentrations in solution. Groundwater is undersaturated with respect to amorphous silica present in the loessic sediments, and these sediments are specially important in the control of the groundwater composition. The sources of amorphous silica are volcanic glass shards and biogenic silica derived from plant (silicophytoliths, diatom frustules) or animal remains (sponge spicules) also present in the Pampean loess. Silicophytoliths and diatoms have also been reported in A soil horizon samples. The dissolution of amorphous silica most likely controls the high dissolved silica concentrations in groundwater.     

Chert spheroids of the Monterey Formation,California (USA): early‐diagenetic structures of bedded siliceous deposits

Chert spheroids are distinctive, early‐diagenetic features that occur in bedded siliceous deposits spanning the Phanerozoic. These features are distinct in structure and genesis from similar, concentrically banded ‘wood‐grain’ or ‘onion‐skin’ chert nodules from carbonate successions. In the Miocene Monterey Formation of California (USA), chert spheroids are irregular, concentrically banded nodules, which formed by a unique version of brittle differential compaction that results from the contrasting physical properties of chert and diatomite. During shortening, there is brittle fracture of diatomite around, and horizontally away from, the convex surface of strain‐resistant chert nodules. Unlike most older siliceous deposits, the Monterey Formation still preserves all stages of silica diagenesis, thus retaining textural, mineralogical and geochemical features key to unravelling the origin of chert spheroids and other enigmatic chert structures. Chert spheroids found in opal‐A diatomite form individual nodules composed of alternating bands of impure opal‐CT chert and pure opal‐CT or chalcedony. With increased burial diagenesis, surrounding diatomite transforms to bedded porcelanite or chert, and spheroids no longer form discrete nodules, yet still display characteristic concentric bands of pure and impure microcrystalline quartz and chalcedony. Petrographic observations show that the purer silica bands are composed of void‐filling cement that precipitated in curved dilational fractures, and do not reflect geochemical growth‐banding in the manner of Liesegang phenomena invoked to explain concentrically banded chert nodules in limestone. Chertification of bedded siliceous sediment can occur more shallowly (< 100 m) and rapidly (< 1 Myr) than the bulk silica phase transitions forming porcelanite or siliceous shale in the Monterey Formation and other hemipelagic/pelagic siliceous deposits. Early diagenesis is indicated by physical properties, deformational style and oxygen‐isotopic composition of chert spheroids. Early‐formed cherts formed by pore‐filling impregnation of the purest primary diatomaceous beds, along permeable fractures and in calcareous–siliceous strata.     

Diagenesis in tertiary sandstones from Kettleman North Dome. California—II. Interstitial solutions: Distribution of aqueous species at 100°C and chemical relation to the diagenetic mineralogy

Interstitial brines from the Temblor and the McAdams sandstones at Kettleman are essentially NaCaCl solutions with subsidiary SO₄ and the total salinities are roughly 30,000 and 10,000 ppm, respectively. Activities of H⁺ and all other aqueous species have been calculated for 100°C (the in situ temperatures of the brines) from chemical analyses of the brines and 100-degree dissociation constants alone. The brine alkalinities measured at surface temperature appear to be too low when comparing them against alkalinities calculated from the measured pHs of the brines. Consequently, alkalinities calculated for 25°C were substituted for the measured ones in the calculation of the distribution of aqueous species at 100°C.Although the brines are nearly neutral (pH 6·3–d7·9) at surface temperature, their pHs calculated for 100°C range from 8·1 to 8·7 (± 0·35). These pHs and the 100-degree activities of the other aqueous species permit graphic representation of the brines on activity diagrams. Most brines fall at or near the boundaries between the stability fields of quartz, albite, microcline, mica, montmorillonite and anhydrite. Because these minerals are present as authigenic phases in the sandstones, the calculations suggest that the minerals are in stable equilibrium with the brines. By contrast, the calculations suggest that the brines are supersaturated by about three orders of magnitude with respect to calcite, also present in the sandstones. One possible explanation for this is kinetic inhibition of calcite crystallization by Mg²⁺ and SO₄^2? ions in the brines. Phosphatic pellets, glauconite and probably dolomite, pyrite and some kaolinite are early authigenic minerals preserved in the sandstones and they are not now in equilibrium with the brines, which are supersaturated with respect to dolomite and pyrite. The chemical relationship between the brines and the diagenetic minerals laumontite and sphene, also present in the Temblor Formation, cannot be assessed reliably until the thermodynamic properties of laumontite and of aqueous titanium complexes are well known.