An Analytical TOOLBOX for the Characterization of Chalks and Other Fine-Grained Rock Types within Enhanced Oil Recovery Research and Its Application—A Guideline

Analyses of fine-grained rocks like shales, cherts, and specifically chalk are challenging with regards to spatial resolution. We propose a “toolbox” to understand mineralogical alteration in chalk, especially those induced by non-equilibrium fluids or polymers and silicates during production of hydrocarbons. These data are fundamental in experiments related to improved/enhanced oil recovery (IOR/EOR) research with the aim to increase hydrocarbon production in a sustainable and environmentally friendly process. The ‘toolbox’ methods analyse rock–fluid or polymer–rock interaction and can be applied to any fine-grained rock type. In our ‘toolbox’, we include methods for routine analysis and evaluate the economic side of the usage together with the complexity of application and the velocity of data acquisition. These methods are routine methods for identification and imaging of components at the same time by chemical or crystallographic means and here applied to petroleum geology. The ‘toolbox’ principle provides a first workflow to develop a road map with clear focus on objectives for maximizing EOR. Most importantly, the methods provide a robust dataset that can identify mineralogical properties and alterations in very fine-grained rocks over several scales (nanometer-decimeter).publishedVersio

The missing link of Rodinia break up in western South America: A petrographical, geochemical, and zircon Pb-Hf isotope study of the volcanosedimentary Chilla beds (Altiplano, Bolivia)

The assembly of Rodinia involved the collision of eastern Laurentia with southwestern Amazonia at ca. 1 Ga. The tectonostratigraphic record of the central Andes records a gap of ∼300 m.y. between 1000 Ma and 700 Ma, i.e., from the beginning of the Neoproterozoic Era to the youngest part of the Cryogenian Period. This gap encompasses the time of final assembly and breakup of the Rodinia supercontinent in this region. We present new petrographic and whole-rock geochemical data and U-Pb ages combined with Hf isotope data of detrital zircons from the volcanosedimentary Chilla beds exposed on the Altiplano southwest of La Paz, Bolivia. The presence of basalt to andesite lavas and tuffs of continental tholeiitic affinity provides evidence of a rift setting for the volcanics and, by implication, the associated sedimentary rocks. U-Pb ages of detrital zircons (n = 124) from immature, quartz-intermediate sandstones have a limited range between 1737 and 925 Ma. A youngest age cluster (n = 3) defines the maximum depositional age of 925 ± 12 Ma. This is considered to coincide with the age of deposition because Cryogenian and younger ages so typical of Phanerozoic units of this region are absent from the data. The zircon age distribution shows maxima between 1300 and 1200 Ma (37% of all ages), the time of the Rondônia–San Ignacio and early Sunsás (Grenville) orogenies in southwestern Amazonia. A provenance mixing model considering the Chilla beds, Paleozoic Andean units, and data from eastern Laurentia Grenville sources shows that >90% of the clastic input was likely derived from Amazonia. This is also borne out by multidimensional scaling (MDS) analysis of the data. We also applied MDS analysis to combinations of U-Pb age and Hf isotope data, namely εHf(t) and 176Hf/177Hf values, and demonstrate again a very close affinity of the Chilla beds detritus to Amazonian sources. We conclude that the Chilla beds represent the first and hitherto only evidence of Rodinia breakup in Tonian time in Andean South America.publishedVersio

Water Weakening of Artificially Fractured Chalk, Fracture Modification and Mineral Precipitation during Water Injection—An Experimental Study

This experiment was designed to study the water-weakening effect of artificially fractured chalk caused by the injection of different compositions of brines under reservoir conditions replicating giant hydrocarbon reservoirs at the Norwegian Continental Shelf (NCS). NaCl, synthetic seawater (SSW), and MgCl2, with same ionic strength, were used to flood triaxial cell tests for approximately two months. The chalk cores used in this experiment originate from the Mons basin, close to Obourg, Belgium (Saint Vast Formation, Upper Cretaceous). Three artificially fractured chalk cores had a drilled central hole parallel to the flooding direction to imitate fractured chalk with an aperture of 2.25 (±0.05) mm. Two additional unfractured cores from the same sample set were tested for comparison. The unfractured samples exposed a more rapid onset of the water-weakening effect than the artificially fractured samples, when surface active ions such as Ca2+, Mg2+ and SO42− were introduced. This instant increase was more prominent for SSW-flooded samples compared to MgCl2-flooded samples. The unfractured samples experienced axial strains of 1.12% and 1.49% caused by MgCl2 and SSW, respectively. The artificially fractured cores injected by MgCl2 and SSW exhibited a strain of 1.35% and 1.50%, while NaCl showed the least compaction, at 0.27%, as expected. Extrapolation of the creep curves suggested, however, that artificially fractured cores may show a weaker mechanical resilience than unfractured cores over time. The fracture aperture diameters were reduced by 84%, 76%, and 44% for the SSW, MgCl2, and NaCl tests, respectively. Permeable fractures are important for an effective oil production; however, constant modification through compaction, dissolution, and precipitation will complicate reservoir simulation models. An increased understanding of these processes can contribute to the smarter planning of fluid injection, which is a key factor for successful improved oil recovery. This is an approach to deciphering dynamic fracture behaviours.publishedVersio

Ermittlung der Kosten und Nutzen von Verkehr in Sachsen – Hauptstudie: Abschlussbericht, Im Auftrag des Freistaates Sachsen vertreten durch das Sächsische Landesamt für Umwelt und Geologie (LfUG)

Gegenstand der Studie ist die Analyse der externen Kosten von Verkehr im Freistaat Sachsen. Die relevanten Daten wurden zusammengestellt, monetarisiert und im GIS visualisiert, so dass als Ergebnis die externen Kosten für den Straßen-, Schienen- und Luftverkehr sowie die Binnenschifffahrt für das Jahr 1999 gemeindefein vorliegen. Die Summe der absoluten externen Kosten des Verkehrs in Sachsen beträgt für das Jahr 1999 ca. 8,7 Mrd. €, woraus sich pro Einwohner ein Wert von ca. 2.000 € pro Jahr ergibt. Einen Teil dieser Kosten trägt die Gesellschaft als Ganzes, aber auch andere Regionen und künftige Generationen werden damit belastet. Mit Abstand für den größten Teil der externen Kosten ist der Straßen- und hier der Pkw-Verkehr verantwortlich mit 95 Prozent der gesamten Kosten. Der Schienenverkehr verursacht ca. vier Prozent der externen Kosten, die Anteile des Flugverkehrs und der Binnenschifffahrt mit je ca. einem halben Prozent sind vernachlässigbar (auf Grund der Inlandsbetrachtung). Betrachtet man die einzelnen Kostenkomponenten, so sind die externen Unfallkosten am größten, gefolgt von den Kosten der Luftverschmutzung und der Klimafolgen. Der zweite Schwerpunkt der vorliegenden Studie lag auf der Erarbeitung eines Überblicks über Strategien zur Internalisierung der externen Kosten. Zu diesem Zweck wurden für jede Kostenkomponente auf den Ebenen Bund/EU, Land und Kommune Maßnahmen zusammengestellt, welche die einzelnen Akteure zur Verringerung der externen Kosten ergreifen können

Permeability evolution of shear failing chalk cores under thermochemical influence

Development of petroleum reservoirs, including primary depletion of the pore pressure and repressurization during water injection naturally, leads to changes in effective stresses of the formations. These changes impose mechanical deformation of the rock mass with subsequent altering of its petrophysical properties. Besides mechanical compaction, chalk reservoirs on the Norwegian Continental Shelf also seem susceptible to mineralogical and textural changes as an effect of the injecting fluid’s chemical composition and temperature. Understanding such chemical and thermal effects and how they interplay with the mechanical response to changes in effective stresses could contribute to improved prediction of permeability development during field life. This article presents results from mechanical testing of chalk cores of medium-porosity (32%) outcrop chalk (Niobrara Formation, Kansas) in triaxial cells. The experimental setup allows systematic combinations of fluctuating deviatoric stress, temperature (50 and 130 °C), and injecting fluid (calcite-equilibrated sodium chloride, calcite-equilibrated sodium sulfate, and reactive synthetic seawater) intended to replicate in situ processes, relevant to the North Sea chalk reservoirs. Deviatoric loading above yield resulted in a shear failure with a steeply dipping fracture of the core and a simultaneous increase in permeability. This occurred regardless of the brine composition. The second and third deviatoric loadings above yield did not have the same strong effect on permeability. During creep and unloading, the permeability changes were minor such that the end permeability remained higher than the initial values. However, sodium sulfate-injected cores retained most of the permeability gain after shear fracturing compared to sodium chloride and synthetic seawater series at both temperatures. Synthetic seawater-injected cores registered the most permeability loss compared to the other brines at 130 °C. The results indicate that repulsive forces generated by sulfate adsorption contribute to maintain the fracture permeability.publishedVersio

Mineralogy and geochemistry of reservoir and non-reservoir chalk from the Norwegian continental shelf

A first and detailed study of the geochemistry and mineralogy characterizing the North Sea reservoir and non-reservoir chalk is provided in this work. The study is based on 185 cores from exploration and development wells in the North Sea. The cores related to reservoir development have different flooding status – unflooded or waterflooded at various temperatures – and are directly sampled from the Ekofisk field. Optical petrography shows a micritic carbonate matrix, with grains represented by various microfossils such as foraminifers and sponge spicules. Scanning electron microscopy (SEM) reveals post-depositional calcite precipitation and cementation. Dolomite is found only in the reservoir samples, but it is discussed as a diagenetic feature, unrelated to the hydrocarbon content or EOR exposure. The non-carbonate minerals observed with BSE-SEM and XRD include mostly quartz but also smectite, illite, kaolinite, mica, and pyrite. The abundance of clastic input varies, and there is a clear decrease in porosity stratigraphically downwards, with stronger cementation and higher compaction. δ13C reflects primary trends for Upper Cretaceous stages while δ18O in all samples is lower than the secular global isotopic values for this period. However, the δ18O values are not sufficiently low to imply a strong diagenetic overprint, but rather suggest the influence of a secondary fluid. This fluid cannot be a hydrocarbon-rich one, nor EOR fluids, as non-reservoir samples, as well as flooded and unflooded reservoir samples show very similar stable isotope values.publishedVersio

Mineralogical alterations in calcite powder flooded with MgCl2 to study Enhanced Oil Recovery (EOR) mechanisms at pore scale

Seawater injection into chalk-reservoirs on the Norwegian Continental Shelf has increased the oil recovery and reduced seabed subsidence, but not eliminated it. Therefore, understanding rock–fluid interactions is paramount to optimize water injection, predict and control water-induced compaction. Laboratory experiments on onshore and reservoir chalks have shown the need to simplify the aqueous chemistry of the brine, and also the importance of studying the effect of primary mineralogy of chalk to understand which ions interact with the minerals present. In this study, the mineralogy of the samples tested, are simplified. These experiments are carried out on pure calcite powder (99.95%), compressed to cylinders, flooded with MgCl2, at 130 °C and 0.5 MPa effective stress, for 27 and 289 days. The tested material was analysed by scanning and transmission electron microscopy, along with whole-rock geochemistry. The results show dissolution of calcite followed by precipitation of magnesite. The occurrence and shape of new-grown crystals depend on flooding time and distance from the flooding inlet of the cylinder. Crystals vary in shape and size, from a few nanometres up to 2 μm after 27 days, and to over 10 μm after 289 days of flooding and may crystallize as a single grain or in clusters. The population and distribution of new-grown minerals are found to be controlled by nucleation- and growth-rates along with advection of the injected fluid through the cores. Our findings are compared with in-house experiments on chalks, and allow for insight of where, when, and how crystals preferentially grow

Evaluation of the compositional changes during flooding of reactive fluids using scanning electron microscopy, nano-secondary ion mass spectrometry, x-ray diffraction, and whole-rock geochemistry

Outcrop chalk of late Campanian age (Gulpen Formation) from Liège (Belgium) was flooded with MgCl2 in a triaxial cell for 516 days under reservoir conditions to understand how the non-equilibrium 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 Mg2+ was depleted and Ca2+ enriched. The loss of Ca2+ and gain in Mg2+ 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.acceptedVersio