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.
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.
Calcareous dinoflagellates are considered to be a monophyletic group of peridinoid taxa that have the potential to produce calcified exoskeletal structures during the life cycle, or that derive from such forms. Frequently, these calcareous bodies are excellently preserved in the fossil record and have received increased attention during the past three decades with regard to their use in biostratigraphy, climate and environmental reconstruction. Fossil and extant taxa have been classified in various, partly concurring, systematic concepts, using character complexes of the theca, cyst wall ultrastructure and archaeopyle/operculum morphology. The significance of such character complexes is briefly discussed in the light of molecular data that have been accumulated during the past decade. Over the years, the number of published taxonomic names has increased, partly due to nomenclatural changes. We propose that the entirety of calcareous dinoflagellates, and non-calcareous relatives derived from them, is accommodated in a single family of the order Peridiniales, the Thoracosphaeraceae, combining the former segregated taxonomic units Calciodinelloideae, a subfamily within Peridiniaceae, and Thoracosphaerales, a separate dinoflagellate order. As a result of a meeting of calcareous dinoflagellate specialists, we outline major subjects that are in need of re-investigation and -evaluation (an Agenda for Calcareous Dinoflagellate Research). In order to contribute to a consistent and stable nomenclature and taxonomy of calcareous dinoflagellates, we list 97 published generic names assigned to known calcareous dinoflagellates in a nomenclatural synopsis, with species names indicating their types and information on type locality and stratigraphy. We evaluate the status of these names-whether validly published and, if so, whether legitimate-, a crucial first step for any revisionary work in the future.
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