Applications of geochemistry and basin modeling in the diagenetic evaluation of Paleocene sandstones, Kupe Field, New Zealand

ABSTRACT Paleocene sandstones in the Kupe Field of Taranaki Basin, New Zealand, are subdivided into two diagenetic zones, an upper kaolinite–siderite (K-S) zone and a lower chlorite–smectite (Ch-Sm) zone. Petrographic observations show that the K-S zone has formed from diagenetic alteration of earlier-formed Ch-Sm sandstones, whereby biotite and chlorite–smectite have been altered to form kaolinite and siderite, and plagioclase has reacted to form kaolinite and quartz. These diagenetic zones can be difficult to discriminate from downhole bulk-rock geochemistry, which is largely due to a change in element-mineral affinities without a wholesale change in element abundance. However, some elements have proven useful for delimiting the diagenetic zones, particularly Ca and Na, where much lower abundances in the K-S zone are interpreted to represent removal of labile elements during diagenesis. Multivariate analysis has also proven an effective method of distinguishing the diagenetic zones by highlighting elemental affinities that are interpreted to represent the principal diagenetic phases. These include Fe-Mg-Mn (siderite) in the K-S zone, and Ca-Mn (calcite) and Fe-Mg-Ti-Y-Sc-V (biotite and chlorite–smectite) in the Ch-Sm zone. Results from this study demonstrate that the base of the K-S zone approximately corresponds to the base of the current hydrocarbon column. An assessment with 1D basin models and published stable-isotope data show that K-S diagenesis is likely to have occurred during deep-burial diagenesis in the last 4 Myr. Modeling predicts that CO2-rich fluids were generating from thermal decarboxylation of intraformational Paleocene coals at this time, and accumulation of high partial pressures of intraformational CO2 in the hydrocarbon column is considered a viable catalyst for the diagenetic reactions. Variable CO2 concentrations and residence times are interpreted to be the reason for different levels of K-S diagenesis, which is supported by a clear relationship between the presence or absence of a well-developed K-S zone and the present-day reservoir-corrected CO2 content.

Relating Acoustic Anisotropy to Kerogen Content in Unconventional Formations - A Case Study in A Kerogen-Rich Unconventional Carbonate

The mechanical and petrophysical behavior of organic-rich carbonates (ORC) is affected significantly by burial diagenesis and the thermal maturation of their organic matter. Therefore, establishing Rock Physics (RP) relations and appropriate models can be valuable in delineating the spatial distribution of key rock properties such as the total organic carbon (TOC), porosity, water saturation, and thermal maturity in the petroleum system. These key rock properties are of most importance to evaluate during hydrocarbon exploration and production operations when establishing a detailed subsurface model is critical. High-resolution reservoir models are typically based on the inversion of seismic data to calculate the seismic layer properties such as P- and S-wave impedances (or velocities), density, Poisson's ratio, Vp/Vs ratio, etc. If velocity anisotropy data are also available, then another layer of data can be used as input for the subsurface model leading to a better understanding of the geological section. The challenge is to establish reliable geostatistical relations between these seismic layer measurements and petrophysical/geomechanical properties using well logs and laboratory measurements. In this study, we developed RP models to predict the organic richness (TOC of 1-15 wt%), porosity (7-35 %), water saturation, and thermal maturity (Tmax of 420-435⁰C) of the organic-rich carbonate sections using well logs and laboratory core measurements derived from the Ness 5 well drilled in the Golan Basin (950-1350 m). The RP models are based primarily on the modified lower Hashin-Shtrikman bounds (MLHS) and Gassmann's fluid substitution equations. These organic-rich carbonate sections are unique in their relatively low burial diagenetic stage characterized by a wide range of porosity which decreases with depth, and thermal maturation which increases with depth (from immature up to the oil window). As confirmation of the method, the levels of organic content and maturity were confirmed using Rock-Eval pyrolysis data. Following the RP analysis, horizontal (HTI) and vertical (VTI) S-wave velocity anisotropy were analyzed using cross-dipole shear well logs (based on Stoneley waves response). It was found that anisotropy, in addition to the RP analysis, can assist in delineating the organic-rich sections, microfractures, and changes in gas saturation due to thermal maturation. Specifically, increasing thermal maturation enhances VTI and azimuthal HTI S-wave velocity anisotropies, in the ductile and brittle sections, respectively. The observed relationships are quite robust based on the high-quality laboratory and log data. However, our conclusions may be limited to the early stages of maturation and burial diagenesis, as at higher maturation and diagenesis the changes in physical properties can vary significantly.

The Paleoproterozoic Kombolgie Subgroup (1.8 Ga), McArthur Basin, Australia: Sequence stratigraphy, basin evolution, and unconformity-related uranium deposits following the Great Oxidation Event

ABSTRACT Proterozoic continental sedimentary basins contain a unique record of the evolving Earth in their sedimentology and stratigraphy and in the large-scale, redox-sensitive mineral deposits they host. The Paleoproterozoic (Stratherian) Kombolgie Basin, located on the Arnhem Land Plateau, Northern Territory, is an exceptionally well preserved, early part of the larger McArthur Basin in northern Australia. This intracratonic basin is filled with 1 to 2 km-thick, relatively undeformed, nearly flat-lying, siliciclastic rocks of the Kombolgie Subgroup. Numerous drill cores and outcrop exposures from across the basin allow sedimentary fabrics, structures, and stratigraphic relationships to be studied in great detail, providing an extensive stratigraphic framework and record of basin development and evolution. Tectonic events controlled the internal stratigraphic architecture of the basin and led to the formation of three unconformity-bounded sequences that are punctuated by volcanic events. The first sequence records the onset of basin formation and is comprised of coarse-grained sandstone and polymict lithic conglomerate deposited in proximal braided rivers that transported sediment away from basin margins and intra-basin paleohighs associated with major uranium mineralization. Paleo-currents in the upper half of this lower sequence, as well as those of overlying sequences, are directed southward and indicate that the major intra-basin topographic highs no longer existed. The middle sequence has a similar pattern of coarse-grained fluvial facies, followed by distal fluvial facies, and finally interbedded marine and eolian facies. An interval marked by mud-rich, fine-grained sandstones and mud-cracked siltstones representing tidal deposition tops this sequence. The uppermost sequence is dominated by distal fluvial and marine facies that contain halite casts, gypsum nodules, stromatolites, phosphate, and “glauconite” (a blue-green mica group mineral), indicating a marine transgression. The repeating pattern of stratigraphic sequences initiated by regional tectonic events produced well-defined coarse-grained diagenetic aquifers capped by intensely cemented distal fluvial, shoreface, eolian, and even volcanic units, and led to a well-defined heterogenous hydrostratigraphy. Basinal brines migrated within this hydrostratigraphy and, combined with paleotopography, dolerite intrusion, faulting, and intense burial diagenesis, led to the economically important uranium deposits the Kombolgie Basin hosts. Proterozoic sedimentary basins host many of Earth's largest high-grade iron and uranium deposits that formed in response to the initial oxygenation of the hydrosphere and atmosphere following the Great Oxygenation Event. Unconformity-related uranium mineralization like that found in the Kombolgie Basin highlights the interconnected role that oxygenation of the Earth, sedimentology, stratigraphy, and diagenesis played in creating these deposits.

Million-year-scale alternation of warm–humid and semi-arid periods as a mid-latitude climate mode in the Early Jurassic (late Sinemurian, Laurasian Seaway)

Clay mineral and stable isotope (C, O) data are reported from the upper Sinemurian (Lower Jurassic) of the Cardigan Bay Basin (Llanbedr–Mochras Farm borehole, northwestern Wales) and the Paris Basin (Montcornet borehole, northern France) to highlight the prevailing environmental and climatic conditions. In both basins, located at similar palaeolatitudes of 30–35∘ N, the clay mineral assemblages comprise chlorite, illite, illite–smectite mixed layers (R1 I-S), smectite, and kaolinite in various proportions. Because the influence of burial diagenesis and authigenesis is negligible in both boreholes, the clay minerals are interpreted to be derived from the erosion of the Caledonian and Variscan massifs, including their basement and pedogenic cover. In the Cardigan Bay Basin, the variations in the proportions of smectite and kaolinite are inversely related to each other through the entire upper Sinemurian. As in the succeeding Pliensbachian, the upper Sinemurian stratigraphic distribution reveals an alternation of kaolinite-rich intervals reflecting strong hydrolysing conditions and smectite-rich intervals indicating a semi-arid climate. Kaolinite is particularly abundant in the upper part of the obtusum zone and in the oxynotum zone, suggesting more intense hydrolysing conditions likely coeval with warm conditions responsible for an acceleration of the hydrological cycle. In the north of the Paris Basin, the succession is less continuous compared to the Cardigan Bay Basin site, as the oxynotum zone and the upper raricostatum zone are either absent or highly condensed. The clay assemblages are dominantly composed of illite and kaolinite without significant stratigraphic trends, but a smectite-rich interval identified in the obtusum zone is interpreted as a consequence of the emersion of the London–Brabant Massif following a lowering of sea level. Following a slight negative carbon isotope excursion at the obtusum–oxynotum zone transition, a long-term decrease in δ13Corg from the late oxynotum–early raricostatum zones is recorded in the two sites and may precede or partly include the negative carbon isotope excursion of the Sinemurian–Pliensbachian Boundary Event, which is recognised in most basins worldwide and interpreted to signify a late pulse of the Central Atlantic Magmatic Province volcanism.

The Teena Zn-Pb Deposit (McArthur Basin, Australia). Part II: Carbonate Replacement Sulfide Mineralization During Burial Diagenesis—Implications for Mineral Exploration

The Teena Zn-Pb deposit is located in the Carpentaria Zn Province (Australia), which contains some of the largest clastic dominant (CD-type) massive sulfide Zn-Pb deposits in the world. The timing of the main stage of hydrothermal sulfide mineralization in the Teena subbasin is constrained to the midstage of burial diagenesis, during a period of short-lived regional extension. To distinguish hydrothermal alteration from spatially and temporally overlapping burial diagenetic alteration, and to establish the primary controls on hydrothermal mass transfer, it is necessary to evaluate the various foot- and hanging-wall alteration assemblages that formed between early- (eogenesis) and late- (mesogenesis) stage diagenesis. To achieve this, we have statistically evaluated a large lithogeochemistry dataset (n >2,500) and selected a subset (n = 65) of representative samples for detailed mineralogical (X-ray diffraction, illite crystallinity) and petrographic (scanning electron microscopy) analyses; hyperspectral core imaging data were then used to upscale key paragenetic observations. We show that sulfide mineralization was predated by multiple diagenetic alteration assemblages, including stratiform pyrite, dolomite nodules and cement, disseminated hematite and authigenic K-feldspar. These assemblages formed during eogenesis in multiple subbasins across the broader McArthur Basin and are not part of the synmineralization alteration footprint. Whereas pyrite and dolomite formed primarily from the in situ degradation of organic matter, feldspar authigenesis was the product of K metasomatism that was focused along permeable coarse-grained volcaniclastic sandstone beds within the host-rock sequence. The immature volcaniclastic input is broadly representative of the siliciclastic compositional end member in the subbasin, which formed the protolith for phyllosilicate (illite, phengite, chlorite) formation during burial diagenesis. There is no evidence of extensive phyllosilicate alteration in any of the geochemical, mineralogical (illite crystallinity), or petrographic datasets, despite some evidence of K-feldspar replacement by sphalerite in the Lower and Main mineralized lenses. Rather, the high Zn grades formed via dolomite replacement, which is resolvable from a chemical mass balance analysis and consistent with petrographic observations. There are significant exploration implications associated with carbonate-replacement sulfide mineralization during mesogenesis: (1) the capacity for secondary porosity generation in the host rock is as important as its sulfate-reducing capacity; (2) hydrothermal mineralization has a short-range cryptic lateral and vertical synmineralization alteration footprint due to acid neutralization by a carbonate-rich protolith; and (3) the distribution and chemistry of premineralization phases (e.g., pyrite, dolomite nodules) cannot be directly related to the mineralization footprint, which is localized to the 4th-order subbasin scale. Future exploration for this deposit style should therefore be focused on identifying units that contain a mixture of organic carbon and carbonate in the protolith, at favorable stratigraphic redox boundaries, and proximal to feeder growth faults.

Rock alteration at the post-Variscan nonconformity: implications for Carboniferous–Permian surface weathering versus burial diagenesis and paleoclimate evaluation

A nonconformity refers to a hiatal surface located between metamorphic or igneous rocks and overlying sedimentary or volcanic rocks. These surfaces are key features with respect to understanding the relations among climate, lithosphere and tectonic movements during ancient times. In this study, the petrological, mineralogical and geochemical characteristics of Variscan basement rock as well as its overlying Permian volcano-sedimentary succession from a drill core in the Sprendlinger Horst, Germany, are analyzed by means of polarization microscopy, and environmental scanning electron microscope, X-Ray diffraction, X-ray fluorescence and inductively coupled plasma mass spectrometry analyses. In the gabbroic diorite of the basement, the intensity of micro- and macro-fractures increases towards the top, indicating an intense physical weathering. The overlying Permian volcanic rock is a basaltic andesite that shows less intense physical weathering compared with the gabbroic diorite. In both segments, secondary minerals are dominated by illite and a mixed-layer phase of illite and smectite (I–S). The corrected chemical index of alteration (CIA) and the plagioclase index of alteration (PIA) indicate an intermediate to unweathered degree in the gabbroic diorite and an extreme to unweathered degree in the basaltic andesite. The τ values for both basaltic andesite and gabbroic diorite indicate an abnormal enrichment of K, Rb and Cs that cannot be observed in the overlying Permian sedimentary rocks. Accompanying minerals such as adularia suggest subsequent overprint by (K-rich) fluids during burial diagenesis which promoted the conversion from smectite to illite. The overall order of element depletion in both basaltic andesite and gabbroic diorite during the weathering process is as follows: large-ion lithophile elements (LILEs) > rare earth elements (REEs) > high-field-strength elements (HFSEs). Concerning the REEs, heavy rare earth elements (HREEs) are less depleted than light rare earth elements (LREEs). Our study shows that features of supergene physical and chemical paleo-weathering are well conserved at the post-Variscan nonconformity despite hypogene alteration. Both can be distinguished by characteristic minerals and geochemical indices. Based on these results, a new workflow to eliminate distractions for paleoclimate evaluation and evolution is developed.

Clay mineral formation in Permian rocks of a geothermal borehole at Northern Upper Rhine Graben, Germany

Hydrothermally altered rhyolite rocks in the Permian Donnersberg Formation of a geothermal borehole in the Northern Upper Rhine Graben (Germany) were investigated to find out answers for the low hydraulic conductivity of the rocks. The composition of clay minerals and the temperature of smectite–illite transformation were carried out using X-ray diffraction, X-ray fluorescence, transmission electron microscopy, Fourier transform infrared spectroscopy, and polarized-light microscopy analyses. Clay mineral (CM) composition includes illite/muscovite (1M and 2M1 polytypes), illite–smectite interstratifications (IS-ml), smectite, and chlorite; and non-clay minerals such as quartz, feldspars, epidote, calcite, dolomite, and hematite were detected. The 2M1-polytype mica might be the only primary sheet silicates from the parent rocks, while the others occur as authigenic neo-formed CMs under heat flow and geothermal gradient. The development of CMs indicates different mechanisms of illitization and smectitization. Based on the texture, morphology, structure/polytype, and chemistry of rocks and minerals, in particular CMs, the study grouped the CM formation into three transformation processes: smectitization during magma cooling and possible contact metamorphisms with decreasing and low temperature, smectite illitization controlled by burial diagenesis and hydrothermal alteration, and illite smectitization followed exhumation and Cenozoic subsidence with decreasing temperature. The rhyolites were altered to all of the orders IS-R0, IS-R1, and IS-R3 by the dissolution-precipitation and layer-to-layer mechanisms. The first one supported small xenomorphic plates and flakes of 1Md, elongated particles of 1M, and pseudo-hexagonal forms of 2M1. The second one could lead to the platy particles of 1Md and 2M1 polytypes. The dominant temperature range for the transformation in the area has been 140–170 °C– ~ 230 °C.

Evolution of calcite microcrystal morphology during experimental dissolution

Phanerozoic limestones are composed of low-Mg calcite microcrystals (i.e., micrite) that typically measure between 1 and 9 μm in diameter. These microcrystals, which host most of the microporosity in subsurface reservoirs, are characterized by a variety of microtextures. Despite the overwhelming consensus that calcite microcrystals are diagenetic, the origin of the various textures is widely debated. The most commonly reported texture is characterized by polyhedral and rounded calcite microcrystals, which are interpreted to form via partial dissolution of rhombic microcrystals during burial diagenesis. A proposed implication of this model is that dissolution during burial is responsible for significant porosity generation. This claim has been previously criticized based on mass-balance considerations and geochemical constrains. To explicitly test the dissolution model, a series of laboratory experiments were conducted whereby various types of calcites composed of rhombic and polyhedral microcrystals were partially dissolved under a constant degree of undersaturation, both near and far-from-equilibrium. Our results indicate that calcite crystals dissolved under far-from-equilibrium conditions develop rounded edges and corners, inter-crystal gulfs (narrow grooves or channels between adjacent crystals), and a few etch pits on crystal faces—observations consistent with the burial-dissolution hypothesis. Crystals dissolved under near-equilibrium conditions, in contrast, retain sharp edges and corners and develop ledges and pits—suggesting that dissolution occurs more selectively at high-energy sites. These observations support the longstanding understanding that far-from-equilibrium dissolution is transport-controlled, and near-equilibrium dissolution is surface-controlled. Our results also show that while the rhombic calcite crystals may develop rounded edges and corners when dissolved under far-from-equilibrium conditions the crystals themselves do not become spherical. By contrast, polyhedral crystals not only develop rounded edges and corners when dissolved under far-from-equilibrium conditions but become nearly spherical with continued dissolution. Collectively, these observations suggest that rounded calcite microcrystals more likely form from a precursor exhibiting an equant polyhedral texture, rather than from a euhedral rhombic precursor as previously proposed. Lastly, the observation that calcite crystals developed rounded edges and corners and inter-crystal gulfs after only 5% dissolution indicates that the presence of such features in natural limestones need not imply that significant porosity generation has occurred.

Rock alteration at the post-Variscan nonconformity: implications for Carboniferous-Permian surface weathering versus burial diagenesis and paleoclimate evaluation

A nonconformity refers to a hiatal surface located between metamorphic or igneous rocks and overlying sedimentary or volcanic rocks. Those surfaces are key features to understand the relations among climate, lithosphere and tectonic movements during ancient time. In this study, the petrological, mineralogical, and geochemical characteristics of Variscan basement rock and its overlying Permian volcano-sedimentary succession from a drill core in the Sprendlinger Horst, Germany are analyzed by means of polarization microscopy, and environmental scanning electron microscope, X-Ray diffraction, X-ray fluorescence and Inductively Coupled Plasma Mass Spectrometry analyses. In the gabbroic diorite of the basement, the intensity of micro- and macro-fractures increases towards the top indicating an intense physical weathering. The overlying Permian volcanic rock is a basaltic andesite which shows less intense physical weathering compared to the gabbroic diorite. In both segments, secondary minerals are dominated by illite and a mix-layer phase of illite and smectite (I/S). The corrected chemical index of alteration (CIA) and the plagioclase index of alteration (PIA) indicate an intermediate to unweathered degree in the gabbroic diorite and an extreme to unweathered degree in the basaltic andesite. The τ value for both basaltic andesite and gabbroic diorite indicate an abnormal enrichment of K, Rb, and Cs that cannot be observed in the overlying Permian sedimentary rocks. Accompanying hydrothermal minerals such as adularia suggest subsequent overprint by (K-rich) hydrothermal fluids during burial diagenesis which promoted the conversion from smectite to illite. The overall order of element depletion in both basaltic andesite and gabbroic diorite during the weathering process is as follows: Large Ion Lithophile Elements (LILE) > Rear earth elements (REE) > High Field Strength Element (HFSE). Concerning the REE, heavy rare earth elements (HREE) are less depleted than light rare earth elements (LREE). Our study shows that features of supergene physical and chemical paleo-weathering are well conserved at the post-Variscan nonconformity despite hypogene alteration. Both can be distinguished by characteristic minerals and geochemical indices, with the results, a new workflow to eliminate distractions for paleoclimate evaluation and evolution is well developed.