Water chemistry has been shown experimentally to affect the stability of water films and the sorption of organic oil components on mineral surfaces. When oil is displaced by water, water chemistry has been shown to impact oil recovery. At least two mechanisms could account for these effects, the water chemistry could change the charge on the rock surface and affect the rock wettability, and/or changes in the water chemistry could dissolve rock minerals and affect the rock wettability. The explanations need not be the same for oil displacement of water as for water imbibition and displacement of oil. This article investigates how water chemistry affects surface charge and rock dissolution in a pure calcium carbonate rock similar to the Stevns Klint chalk by constructing and applying a chemical model that couples bulk aqueous and surface chemistry and also addresses mineral precipitation and dissolution. We perform calculations for seawater and formation water for temperatures between 70 and 130 • C . The model we construct accurately predicts the surface potential of calcite and the adsorption of sulfate ions from the pore water. The surface potential changes are not able to explain the observed changes in oil recovery caused by changes in pore water chemistry or temperature. On the other hand, chemical dissolution of calcite has the experimentally observed chemical and temperature dependence and could account for the experimental recovery systematics. Based on this preliminary analysis, we conclude that although surface potential may explain some aspects of the existing spontaneous imbibitions data set, mineral dissolution appears to be the controlling factor.

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Effect of the aqueous chemistry on the mechanical strength of chalk has extensively been studied during the last decade. At high temperatures (∼130 • C), chalk exposed to seawater is significantly weaker compared to chalk exposed to distilled water when considering the hydrostatic yield strength and the following creep phase. The explanation of these experimental results must be of a chemical nature, as the density and viscosity of the aqueous phase vary little among these different brines. We present the results from simplified aqueous chemistry using MgCl 2 brines, and compare these results with seawater. Previous studies show that different ions, e.g. Ca 2+ , Mg 2+ , SO 4 2− in the injected brine, as well as the chalk mineralogy have an impact on the stability of the rock. We performed mechanical tests on chalk cores from Liège and Stevns Klint; it was found that these two outcrop chalks exhibit an unexpected difference in their mechanical responses when comparing cores flooded with NaCl and MgCl 2 at 130 • C. The results of this study show that the effects of magnesium seem to be governed not only by the differences in mineralogy, but also a time dependency on chalk deformation is additionally observed. Independent of the chalk type tested, the chemical analyses performed show that when MgCl 2 is flooded through the core, a significant loss of magnesium and a considerable additional amount of calcium are detected in the effluent. The experimental observations fit very well with the time-dependent chemical changes gained from the mathematical model of this study that accounts for transport effects (convection and molecular diffusion) as well as chemical processes such as precipitation/dissolution. Based on the calculations and chemical analyses, we argue that the loss of magnesium and the production of calcium cannot solely be a consequence of a substitution process. The calculations rather indicate that magnesium is precipitated forming new mineral 123 680 M. V. Madland et al. phases and in this process not only calcite, but also silicates are dissolved. The amount of dissolved calcium and silicon from the rock matrix is significant and could thus cause an additional deformation to take place. Both the retention of magnesium in the chalk core and the formation of newly precipitated magnesium-bearing carbonates and/or magnesium-bearing clay-like minerals after flooding with MgCl 2 brine were demonstrated using scanning electron microscopic methods. In addition, precipitation of anhydrite as a result of flooding with seawater-like brine was proven. The water-induced strain not only depends on the ion composition of the injected brine; moreover, the presence of non-carbonate minerals will most likely also have a significant influence on the mechanical behaviour of chalk.

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Summary North Sea chalk reservoirs are characterized as being purely biogenic and naturally fractured, having low matrix permeability and very high porosity (30 to 45%). The reservoir temperature is usually high, more than 90°C, and the wetting conditions appear to be moderately water-wet to neutral. Even though the permeability contrast between the matrix and fractures is significant, the injection of seawater has been a great success with the Ekofisk field as an example (estimated oil recovery is now approaching 50%). Seawater improves the water wetness of chalk, which increases the oil recovery by spontaneous imbibition and viscous displacement. During the primary production phase by pressure depletion, extensive compaction was observed and, at that time, it was regarded as an important drive mechanism for oil recovery. The compaction continued in the waterflooded areas even though the reservoir was repressurized by the injected seawater. The phenomenon has been described as water weakening of chalk, and production costs have increased because of the loss of wells and substitution of platforms. This paper gives an overview of the chemical aspects of the interaction between seawater and the chalk. Surface active components in seawater, such as Ca2+, Mg2+, and SO42-, will play an important role in both wettability modification and rock mechanics. In that sense, injection of seawater into chalk must be regarded as a tertiary-oil-recovery technique. Chemical models describing the wettabilty alteration and enhanced water weakening of chalk by seawater are suggested and presented.

Outcrop chalk of late Campanian age (Gulpen Formation) from Liège (Belgium) was flooded with MgCl 2 in a triaxial cell for 516 days under reservoir conditions to understand how the nonequilibrium nature of the fluids altered the chalks. The study is motivated by enhanced oil recovery (EOR) processes because dissolution and precipitation change the way in which oils are trapped in chalk reservoirs. Relative to initial composition, the first centimeter of the flooded chalk sample shows an increase in MgO by approximately 100, from a weight percent of 0.33% to 33.03% and a corresponding depletion of CaO by more than 70% from 52.22 to 14.43 wt.%. Except for Sr, other major or trace elements do not show a significant change in concentration. Magnesite was identified as the major newly grown mineral phase. At the same time, porosity was reduced by approximately 20%. The amount of Cl − in the effluent brine remained unchanged, whereas Mg 2+ was depleted and Ca 2+ enriched. The loss of Ca 2+ and gain in Mg 2+ are attributed to precipitation of new minerals and leaching the tested core by approximately 20%, respectively. Dramatic mineralogical and geochemical changes are observed with scanning electron microscopy-energy-dispersive x-ray spectroscopy, nano secondary ion mass spectrometry, x-ray diffraction, and whole-rock geochemistry techniques. The understanding of how fluids interact with rocks is important to, for example, EOR, because textural changes in the pore space affect how water will imbibe and expel oil from the rock. The mechanisms of dissolution and mineralization of fine-grained chalk can be described and quantified and, when understood, offer numerous possibilities in the engineering of carbonate reservoirs.

We report the complete chemical alteration of a Liège outcrop chalk core resulting from a 1072 flow-through experiment performed during mechanical compaction at 130°C. Chemical rock-fluid interactions alter the volumetric strain, porosity, and permeability in a nontrivial way. The porosity reduced only from 41.32% to 40.14%, even though the plug compacted more than 25%. We present a novel analysis of the experimental data, which demonstrates that the geochemical alteration does not conserve the volume of the solids, and therefore, the strain is partitioned additively into a pore volume and solid volume component. At stresses beyond yield, the observed deformation can be explained by grain reorganization reducing the pore space between grains and solid volume changes from the rock-fluid interactions. The mechanical and chemical effects are discussed in relation to the observed permeability development.

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