Pore water evolution in oilfield sandstones: constraints from oxygen isotope microanalyses of quartz cement

Oxygen isotope microanalyses of authigenic quartz, in combination with temperatures of quartz precipitation constrained by fluid inclusion microthermometry and burial history modelling, are employed to trace the origin and evolution of pore waters in three distinct reservoirs of the Brae Formation in the Miller and Kingfisher Fields (North Sea). Oxygen isotope ratios of quartz cements were measured in situ in nine sandstone thin sections with a Cameca ims-4f ion microprobe. In conjunction with quartz cement paragenesis in the reservoirs, constrained from textural and cathodoluminescence (CL) microscopy studies, pore water evolution was reconstructed from the time of deposition of the sandstones in the Upper Jurassic until the present.CL photomicrographs of quartz overgrowths in the Brae Formation sandstones show three cement zones (A, B and C) which can be related to different oxygen isotope compositions: (1) the earliest, and thinnest, zone A (homogeneous CL pattern with probable δ¹⁸O values between +23‰ and +26‰—direct measurements were not possible) precipitated in the sandstones at temperatures <60 °C; (2) the second zone B (complex CL pattern and directly measured δ¹⁸O values between +15‰ and +18‰) precipitated in the sandstones most likely between 70 and 90 °C; (3) the third zone C (homogeneous CL pattern and directly measured δ¹⁸O values between +16‰ and +22‰) precipitated in the sandstones most likely at temperatures >90 °C. Calculated oxygen isotope compositions of pore waters show that zone A quartz cements, and enclosing concretionary calcite, precipitated from a meteoric-type fluid (∼−7‰) during shallow burial (<1.5 km). Zone B quartz cements precipitated from fluids which evolved in composition from a meteoric-type fluid (δ¹⁸O −7‰) to a more ¹⁸O-enriched fluid (δ¹⁸O −4‰) as burial continued to ∼3.0 km. Data from zone C quartz cements are consistent with further fluid evolution from δ¹⁸O −4‰ to basinal-type fluids with δ¹⁸O similar to the present-day formation water oxygen isotope composition (+0.6‰ at 4.0 km burial). A similar pore water evolution can be derived for all three reservoirs studied, indicating that hydrogeologic evolution was similar across sandstones of the whole Brae Formation.The quartz cement zones observed in the Brae Formation sandstones, and the pore water history derived for the area studied, is analogous to published petrographic and pore water evolution data from the nearby Brent Group reservoirs and from reservoirs located in the Haltenbanken area on the Atlantic margin offshore Norway. Considering quartz cement is a major porosity-occluding phase in many reservoir sandstones, and because pore waters both dissolve quartz and carry the dissolved silica to cementation sites, the data presented are valuable for improving the understanding and prediction of reservoir quality development in sandstones globally.     

Toward a quantitative model of metamorphic nucleation and growth

The formation of metamorphic garnet during isobaric heating is simulated on the basis of the classical nucleation and reaction rate theories and Gibbs free energy dissipation in a multi-component model system. The relative influences are studied of interfacial energy, chemical mobility at the surface of garnet clusters, heating rate and pressure on interface-controlled garnet nucleation and growth kinetics. It is found that the interfacial energy controls the departure from equilibrium required to nucleate garnet if attachment and detachment processes at the surface of garnet limit the overall crystallization rate. The interfacial energy for nucleation of garnet in a metapelite of the aureole of the Nelson Batholith, BC, is estimated to range between 0.03 and 0.3?J/m² at a pressure of ca. 3,500?bar. This corresponds to a thermal overstep of the garnet-forming reaction of ca. 30°C. The influence of the heating rate on thermal overstepping is negligible. A significant feedback is predicted between chemical fractionation associated with garnet formation and the kinetics of nucleation and crystal growth of garnet giving rise to its lognormal??shaped crystal size distribution.     

Numerical simulation of diffusion‐controlled nucleation and growth of porphyroblasts

This article presents the conceptual basis for a new numerical model of diffusion‐controlled nucleation and growth of porphyroblasts, describes its implementation, and illustrates the range of crystallization behaviours encompassed by it. The model differs from previous efforts principally in its ability to track explicitly the evolution in time and space of the chemical affinity for reaction in the intergranular medium, which provides a more accurate characterization of nucleation suppression in the vicinity of pre‐existing crystals and of growth suppression due to competition for nutrients among neighbouring crystals. Critical new features of these numerical simulations include: maintenance of local equilibrium for fluid in contact with reactants or products; persistence of reactants until they are eliminated by dissolution due to reaction progress and local diffusive flux; nucleation rates that vary as the local reaction affinity evolves; complex initial distributions of reactants if desired; and the flexibility to encompass any porphyroblast‐forming reaction for which changes in free energy as a function of time and temperature are specified. Model results reveal that radial growth rates remain proportional to the square‐root of time in diffusion systems buffered by persistent reactants; they document the interchangeable effects of diffusivity, porosity, and solubility on material fluxes and thus growth rates; and they illustrate the offsetting textural effects of rates of diffusion, nucleation, and heating. The initial distribution of reactants is found to exert a first‐order effect on crystal size distributions, confirming their limited utility for diagnosing crystallization mechanisms. These numerical simulations yield novel and rigorous confirmation of the textural effects of nucleation‐site saturation and variation in interconnected porosity, and reproduce with high fidelity much of the textural and chemical information gathered from natural specimens.     

河流相砂体的沉积微相特征--以济阳坳陷埕东北坡馆陶组砂体为例

本文以济阳坳陷埕东油田北坡馆陶组河流相砂岩为例,详细阐述了河流相砂体的沉积微相研究方法,将研究区的河流相砂体划分为曲流河、网状河和辫状河三种沉积相,并进一步划分为七类主要的沉积微相。通过单井剖面和井间剖面对比分析,研究沉积微相在垂向上和平面上的变化规律,在此基础上结合地震资料的精细解释,编制了研究区内不同砂层组沉积时期沉积微相平面展布图。     

Dissolution of illite in saline-acidic solutions at 25 °C

The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline-acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K_1.38Na_0.05)(Al_2.87Mg_0.46Fe³⁺_0.39Fe²⁺_0.28Ti_0.07)[Si_7.02Al_0.98]O₂₀(OH)₄ was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0-4.25 (H₂SO₄) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K⁺ release rate was observed at I = 0.25 in 2-4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na⁺ from the solution and K⁺ from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1-4 in the higher ionic strength experiments and at pH ?3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower R_Al (dissolution rate calculated from steady state Al release) than R_Si (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 (I = 0.25) and 0.36 (I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates.     

Plagioclase nucleation and growth kinetics in a hydrous basaltic melt by decompression experiments

Isothermal single-step decompression experiments (at temperature of 1075 °C and pressure between 5 and 50 MPa) were used to study the crystallization kinetics of plagioclase in hydrous high-K basaltic melts as a function of pressure, effective undercooling (ΔT _eff) and time. Single-step decompression causes water exsolution and a consequent increase in the plagioclase liquidus, thus imposing an effective undercooling (?T _eff), accompanied by increased melt viscosity. Here, we show that the decompression process acts directly on viscosity and thermodynamic energy barriers (such as interfacial-free energy), controlling the nucleation process and favoring the formation of homogeneous nuclei also at high pressure (low effective undercoolings). In fact, this study shows that similar crystal number densities (N _a) can be obtained both at low and high pressure (between 5 and 50 MPa), whereas crystal growth processes are favored at low pressures (5–10 MPa). The main evidence of this study is that the crystallization of plagioclase in decompressed high-K basalts is more rapid than that in rhyolitic melts on similar timescales. The onset of the crystallization process during experiments was characterized by an initial nucleation event within the first hour of the experiment, which produced the largest amount of plagioclase. This nucleation event, at short experimental duration, can produce a dramatic change in crystal number density (N _a) and crystal fraction (?), triggering a significant textural evolution in only 1 h. In natural systems, this may affect the magma rheology and eruptive dynamics on very short time scales.     

Variations in rates of nucleation and growth of biotite porphyroblasts

Differences in rates of nucleation and diffusion‐limited growth for biotite porphyroblasts in adjacent centimetre‐scale layers of a garnet‐biotite schist from the Picuris Mountains of New Mexico are revealed by variations in crystal size and abundance between two layers with strong compositional similarity. Relationships between fabrics recorded by inclusion patterns in biotite and garnet porphyroblasts are interpreted to reflect garnet growth following biotite growth, without substantial alteration of the biotite sizes. Sizes and locations of biotite crystals, obtained via high‐resolution X‐ray computed tomography, document that of the two adjacent layers, one has a larger mean crystal volume (9.5 × 10^?4v. 2.4 × 10^?4 cm³), fewer biotite crystals per unit volume (232 v. 576 crystals cm^?3), and a higher volume fraction of biotite (23%v. 14%). The two layers have similar mineral assemblages and mineral chemistry. Both layers show evidence for diffusional control of nucleation and growth. Pseudosection analysis suggests that the large‐biotite layer began to crystallize biotite at a temperature ～67 °C greater than the small‐biotite layer. Diffusion rates differed between layers, because of their different temperature ranges of crystallization, but this effect can be quantified. The bulk compositional difference between the layers, manifested in different modal amounts of biotite, has an effect on the biotite sizes that is also quantifiable and insufficient to account for the difference in biotite size. After these other possible causes of variation in crystal sizes have been eliminated, variability in nucleation and diffusion rates remain as the dominant factors responsible for the difference in porphyroblastic textures. Numerical simulations suggest that relative to the small‐biotite layer, the large‐biotite layer experienced elevated diffusion rates because of the higher crystallization temperature, as well as increased nucleation rates in order to achieve the observed size and number density of crystals. The simulations can replicate the observed textures only by invoking unreasonably large values for the thermal dependence of nucleation rates (activation energies), strongly suggesting that the observed textural differences arise from variations between layers in the abundance and energetics of potential nucleation sites.     

Model of nucleation and growth of crystals in cooling magmas

The nucleation and growth of liquidus phases in cooling magmas at constant rates are modeled taking into account homogeneous nucleation, diffusion-limited growth, and depletion of crystallizing component from melt, and the temperature-dependent diffusivity. The formulation of governing equations shows that four dimensionless parameters, whose physical meanings are the nucleation difficulty, the fusion enthalpy, the ratio of the growth rate to the cooling rate, and the activation energy of diffusion, control the crystallization phenomena. The nucleation behavior with time (or temperature) is determined primarily by the competition between increasing nucleation rate with cooling and the reduced supersaturation with depletion by progressive growth of crystals previously nucleated. The maximum nucleation rate and the number density of crystals increase with decreasing interfacial tension and diffusivity, and with increasing fusion enthalpy and cooling rate. Quantitative expressions of the time or temperature interval for which the nucleation remains appreciable, the peak nucleation rate, the number density of crystals and the mean crystal radius are derived as functions of controlling parameters, and can be used to estimate the cooling rate or other unknown parameters from the number density of crystals of a rock.     

Thermal profiles inferred from fluid inclusion and illite geothermometry from sandstones of the Athabasca basin: Implications for fluid flow and unconformity-related uranium mineralization

The Proterozoic Athabasca basin and underlying basement host numerous unconformity-related uranium deposits that were formed from extensive fluid circulation near the basement-cover interface. Although it is generally agreed that the mineralizing fluids were basinal brines, it is still unclear what driving forces were responsible for the circulation of the basinal fluids. Because different fluid flow driving forces are associated with different thermal profiles, knowing the basin-scale distribution of paleo-fluid temperatures can help constrain the fluid flow mechanism. This study uses fluid inclusions entrapped in quartz overgrowths and authigenic illite in sandstones from three drill cores (WC-79-1, BL-08-01, and DV10-001) in the central part of the Athabasca basin as thermal indicators of paleo-fluids in the basin. A total of 342 fluid inclusions in quartz overgrowths were studied for microthermometry. The homogenization temperatures (T_h) range from 50° to 235 °C, recording the minimum temperatures in various diagenetic stages. Temperatures estimated from illite geothermometry (121 points) range from 212° to 298 °C, which are systematically higher than (partly overlapping) the T_h values, suggesting that illite was precipitated in hotter fluids following the formation of quartz overgrowths. Neither the fluid inclusion T_h values nor the illite temperatures show systematic increase with depth in individual drill cores. This, together with the high illite temperatures that cannot be explained by burial at a normal geothermal gradient (35 °C/km), is interpreted to indicate that basin-scale fluid convection took place during the diagenetic history of the basin. Prolonged fluid convection is inferred to be responsible for delivering uranium (extracted from the basin or the upper part of the basement) to the unconformity, where uranium mineralization took place due to redox reactions associated with fluid-rock interaction or structurally controlled fluid mixing.     

Development of large‐scale seismites in Upper Cretaceous fluvial sandstones in a fault‐proximal setting

Large‐scale soft‐sediment deformation structures occur within fluvial sandstone bodies of the Upper Cretaceous Wahweap Formation in the Kaiparowits basin, southern Utah, USA. These structures represent an exceptional example of metre‐scale fault‐proximal, seismogenic load structures in nearly homogenous sandstones. The load structures consist of two types: large‐scale load casts and wedge‐shaped load structures. Large‐scale load casts penetrate up to 4·5 m into the underlying sandstone bed. Wedge‐shaped load structures include metre‐scale, parallel, sub‐vertical features and decimetre‐scale features along the periphery of the large‐scale load casts or other wedge‐shaped load structures. Wedge‐shaped load structures contain well‐developed, medial cataclastic shear deformation bands. All load structures contain pervasive well‐defined millimetre‐thick to centimetre‐thick internal laminae, oriented parallel to the outside form of the load structures and asymptotic to deformation bands. Both types of load structures formed because of an inverted density profile, earthquake‐triggered liquefaction and growth of irregularities (a Rayleigh–Taylor instability) on the sandstone–sandstone erosional contact. The internal laminae and deformation bands formed during deformation and clearly demonstrate polyphase deformation, recording a transition from liquefied to hydroplastic to brittle modes of deformation. Decimetre‐scale wedge‐shaped load structures on the edge of the large‐scale load casts probably formed towards the end of a seismic event after the sediment dewatered and increased the frictional contact of grains enough to impart strength to the sands. Metre‐scale wedge‐shaped load structures were created as the tips of downward foundering sediments were driven into fractures, which widened incrementally with seismic pulsation. With each widening of the fracture, gravity and a suction effect would draw additional sediment into the fracture. Superimposed laminae indicate a secondary syndeformational origin for internal laminae, probably by flow‐generated shearing and vibrofluidization mechanisms. Large‐scale and wedge‐shaped load structures, polyphase deformation and secondary laminae may characterize soft‐sediment deformation in certain fault‐proximal settings.     

The illite 'crystallinity'technique: a critical appraisal of its precision

Analysis of the precision of the illite 'crystallinity'technique shows that machine errors are <5%, while intra- and inter-sample errors are variable but are up to 12% and 14%, respectively (1σ). Consideration of this error analysis shows that the isocryst approach, which involves close contouring (e.g. 0.03 Δ2°) of illite 'crystallinity'data, has a very low degree of confidence (<0.5) and thus is not regarded as statistically valid. If contouring is to be undertaken with a high degree of confidence (>0.8) it is necessary that contours should be at intervals of 0.1 ΔΘ2°, which is equivalent to subdivision of the anchizone into upper and lower units. Where previous interpretations have relied upon an isocryst method of contouring at less than 0.1 ΔΘ2° the conclusions must be regarded as unsubstantiated.
Centrifuge separation of clay fractions (based on a Stokes'law application) gives separations in which a significant, but variable, percentage of grains have long axes greater than the size calculated. For the typical <2-μm fraction utilized, some 20% of grains lie in the 2–4-μm range, although the proportion is not believed to have a significant effect upon 'crystallinity'values. The formula is applicable for grain-sizes down to 0.5 μm. Illite 'crystallinity'values on samples prepared by an ultrasonic disaggregation method show a small increase on those prepared by ball mill crushing. The differences are minimal at the epi/anchizone level but increase to some 10% at the anchizone/diagenetic level. The effect on grade determinations is again thought to be minimal and indicates that concern over unsuitability of the ultrasonic disaggregation method is unfounded.     

Reaction‐induced nucleation and growth v. grain coarsening in contact metamorphic,impure carbonates

The understanding of the evolution of microstructures in a metamorphic rock requires insights into the nucleation and growth history of individual grains, as well as the coarsening processes of the entire aggregate. These two processes are compared in impure carbonates from the contact metamorphic aureole of the Adamello pluton (N‐Italy). As a function of increasing distance from the pluton contact, the investigated samples have peak metamorphic temperatures ranging from the stability field of diopside/tremolite down to diagenetic conditions. All samples consist of calcite as the dominant matrix phase, but additionally contain variable amounts of other minerals, the so‐called second phases. These second phases are mostly silicate minerals and can be described in a KCMASHC system (K₂O, CaO, MgO, Al₂O₃, SiO₂, H₂O, CO₂), but with variable K/Mg ratios. The modelled and observed metamorphic evolution of these samples are combined with the quantification of the microstructures, i.e. mean grain sizes and crystal size distributions. Growth of the matrix phase and second phases strongly depends on each other owing to coupled grain coarsening. The matrix phase is controlled by the interparticle distances between the second phases, while the second phases need the matrix grain boundary network for mass transfer processes during both grain coarsening and mineral reactions. Interestingly, similar final mean grain sizes of primary second phase and second phases newly formed by nucleation are observed, although the latter formed later but at higher temperatures. Moreover, different kinetic processes, attributed to different driving forces for growth of the newly nucleated grains in comparison with coarsening processes of the pre‐existing phases, must have been involved. Chemically induced driving forces of grain growth during reactions are orders of magnitudes larger compared to surface energy, allowing new reaction products subjected to fast growth rates to attain similar grain sizes as phases which underwent long‐term grain coarsening. In contrast, observed variations in grain size of the same mineral in samples with a similar T–t history indicate that transport properties depend not only on the growth and coarsening kinetics of the second phases but also on the microstructure of the dominant matrix phase during coupled grain coarsening. Resulting microstructural phenomena such as overgrowth and therefore preservation of former stable minerals by the matrix phase may provide new constraints on the temporal variation of microstructures and provide a unique source for the interpretation of the evolution of metamorphic microstructures.     

The generation of soil over sandstones in a periglacial environment

The work examines the chemical and physical processes that are likely to have contributed to forming the soil thickness across the Sherwood Sandstone outcrop in Nottinghamshire, England, UK. The similarity in the extent of chemical weathering across the interface of the loosely compacted sand that forms the soil and regolith and the non-durable rock underneath suggests that physical weathering processes are required as the final part of the weathering process, essential to breaking the clay cement that maintains the structural integrity of the non-durable rock. With prior knowledge that the outcrop was the input point for water currently in the aquifer with ages between 10 and 35,000 a, periglacial processes such as ‘frost cracking’ and ‘active zone development’ are considered major influences on soil thickness.     

Composition,nucleation, and growth of iron oxide concretions

Iron oxide concretions are formed from post depositional, paleogroundwater chemical interaction with iron minerals in porous sedimentary rocks. The concretions record a history of iron mobilization and precipitation caused by changes in pH, oxidation conditions, and activity of bacteria. Transport limited growth rates may be used to estimate the duration of fluid flow events. The Jurassic Navajo Sandstone, an important hydrocarbon reservoir and aquifer on the Colorado Plateau, USA, is an ideal stratum to study concretions because it is widely distributed, well exposed and is the host for a variety of iron oxide concretions.Many of the concretions are nearly spherical and some consist of a rind of goethite that nearly completely fills the sandstone porosity and surrounds a central sandstone core. The interior and exterior host-rock sandstones are similar in detrital minerals, but kaolinite and interstratified illite–smectite are less abundant in the interior. Lepidocrocite is present as sand-grain rims in the exterior sandstone, but not present in the interior of the concretions.Widespread sandstone bleaching resulted from dissolution of early diagenetic hematite grain coatings by chemically reducing water that gained access to the sandstone through fault conduits. The iron was transported in solution and precipitated as iron oxide concretions by oxidation and increasing pH. Iron diffusion and advection growth time models place limits on minimum duration of the diagenetic, fluid flow events that formed the concretions. Concretion rinds 2 mm thick and 25 mm in radius would take place in 2000 years from transport by diffusion and advection and in 3600 years if transport was by diffusion only. Solid concretions 10 mm in radius would grow in 3800 years by diffusion or 2800 years with diffusion and advection.Goethite (α-FeO (OH)) and lepidocrocite (γ-FeO (OH)) nucleated on K-feldspar grains, on illite coatings on sand grains, and on pore-filling illite, but not on clean quartz grains. Model results show that regions of detrital K-feldspar in the sandstone that consume H⁺ more rapidly than diffusion to the reaction site determine concretion size, and spacing is related to diffusion and advection rates of supply of reactants Fe²⁺, O₂, and H⁺.     

Analysis of faulting in porous sandstones

Faults in porous sandstones occur in three forms: deformation bands about 1-mm thick and tens of m long and across which offsets are a few mm; zones of deformation bands constituted of many closely spaced deformation bands across which offsets are a few cm or dm; and slip surfaces, that is, distinct surfaces within zones of deformation bands across which offsets are a few m to a few tens of m. Deformation bands represent highly localized deformation; analogous localization within a field of homogeneous deformation is theoretically possible in inelastic materials with certain ranges of constitutive parameters. Crushing and consolidation of sandstone within a band cause the material there to become stiffer than the surrounding porous sandstone. A zone of deformation bands behaves mesoscopically much as a stiff inclusion in a soft matrix. According to the constitutive model assumed to investigate the formation of deformation bands, an instability can develop, and strain increments within the zone of deformation bands can become boundlessly large when the far-field stresses reach critical values. This instability is here associated with the formation of slip surfaces.     

K‐Ar illite age constraints on the Proterozoic formation and reactivation history of a brittle fault in Fennoscandia

K‐Ar ages of authigenic illite from two drill‐core gouge samples of a fault in the Palaeoproterozoic basement of Finland record two distinct faulting events. The older sample yields apparent ages from 1240 ± 26 to 1006 ± 21 Ma for four grain size fractions between 6 and <0.1 μm. The second sample is structurally younger and yields statistically distinct ages ranging from 978 ± 20 to 886 ± 18 Ma. We interpret the ages of the <0.1 m fractions, which are the youngest, as representing the actual time of faulting. XRD analysis and age modelling exclude significant age contamination of the finest dated fractions with inherited host rock components. These results provide therefore an example of meaningful isotopic dating of illite‐type clay material formed during Precambrian faulting, demonstrate and constrain fault reactivation and give evidence for brittle Sveconorwegian Mesoproterozoic shortening and Neoproterozoic extension in Fennoscandia.