Paleoenvironmental insights from the deposition and diagenesis of Aptian pre-salt magnesium silicates from the Lula Field, Santos Basin, Brazil

ABSTRACT Since the discovery of giant Aptian pre-salt reservoirs in Brazilian margin basins, the study of lacustrine carbonates has drawn great attention from the scientific community. Comparatively, minor attention was given to the characterization and genesis of the Mg-silicates (e.g., stevensite, kerolite) which are commonly associated with these carbonates. A systematic petrological study was performed in the Aptian Barra Velha Formation (BVF) within distinct structural compartments of the giant Lula Field in the Santos Basin, in order to recognize the patterns of primary formation and diagenetic alteration of these Mg-silicates. Mg-silicates occur as peloids, ooids, intraclasts, and fine-grained laminated deposits, either mixed in variable proportions with other particles, such as carbonate bioclasts and volcanic rock fragments, or constituting specific intrabasinal deposits. In the BVF interval, clay peloids and laminated deposits are associated with spherulitic and fascicular calcite aggregates, as substrate and hosts for these precipitates. Ooids are interpreted as formed at the sediment–water interface by the nucleation of concentric envelopes on the surface of particles (heterogeneous nucleation), through repeated rolling under gentle wave and current action. Laminated deposits, interpreted as precipitated directly from the water column (homogeneous nucleation) in highly supersaturated and low-hydrodynamic-energy environments, constitute extensive deposits in the BVF. Peloids were probably formed in intermediate energy conditions. Some ooidal arenites show porosity from the dehydration and contraction, and/or the dissolution of ooids. In some rocks, these pores are filled with fibrous calcite, while the remaining Mg-silicates are replaced by dolomite, calcite, or silica. A similar diagenetic pattern occurs in the laminated deposits, where magnesite and dolomite fill shrinkage pores formed along their characteristic wavy laminae. Owing to their elevated solubility, most of the Mg-silicates were dissolved, or intensely replaced by calcite, dolomite, or silica. The detailed petrologic analysis indicates that the original volumes of Mg-silicates were substantially larger, and that their deposition was widespread in the basin, including on structurally high areas. The types and intensity of diagenetic alteration of the Mg-silicate deposits are distinct for each structural compartment, being more intense towards the highs and closer to the overlying evaporites, which imposed a strong influence on reservoir quality.

Mineralogy and diagenesis of Mars-analog paleosols from eastern Oregon, USA

Ancient (4.1-3.7-billion-year-old) layered sedimentary rocks on Mars are rich in clay minerals which formed from aqueous alteration of the Martian surface. Many of these sedimentary rocks appear to be composed of vertical sequences of Fe/Mg clay minerals overlain by Al clay minerals that resemble paleosols (ancient, buried soils) from Earth. The types and properties of minerals in paleosols can be used to constrain the environmental conditions during formation to better understand weathering and diagenesis on Mars. This work examines the mineralogy and diagenetic alteration of volcaniclastic paleosols from the Eocene-Oligocene (43-28 Ma) Clarno and John Day Formations in eastern Oregon as a Mars-analog site. Here, paleosols rich in Al phyllosilicates and amorphous colloids overlie paleosols with Fe/Mg smectites that altogether span a sequence of ~500 individual profiles across hundreds of meters of vertical stratigraphy. Samples collected from three of these paleosol profiles were analyzed with visible/near-infrared (VNIR) spectroscopy, X-ray diffraction (XRD), and evolved gas analysis (EGA) configured to operate like the SAM-EGA instrument onboard Curiosity Mars Rover. Strongly crystalline Al/Fe dioctahedral phyllosilicates (montmorillonite and nontronite) were the major phases identified in all samples with all methods. Minor phases included the zeolite mineral clinoptilolite, as well as andesine, cristobalite, opal-CT and gypsum. Evolved H2O was detected in all samples and was consistent with adsorbed water and the dehydroxylation of a dioctahedral phyllosilicate, and differences in H2O evolutions between montmorillonite and nontronite were readily observable. Detections of hematite and zeolites suggested paleosols were affected by burial reddening and zeolitization, but absence of illite and chlorite suggest that potash metasomatism and other, more severe diagenetic alterations had not occurred. The high clay mineral content of the observed paleosols (up to 95 wt. %) may have minimized diagenetic alteration over geological time scales. Martian paleosols rich in Al and Fe smectites may have also resisted severe diagenetic alteration, which is favorable for future in-situ examination. Results from this work can help distinguish paleosols and weathering profiles from other types of sedimentary rocks in the geological record of Mars.

Microporosity of the Shuaiba Formation: The Link Between Depositional Character and Diagenesis in Sharjah, United Arab Emirates

Objectives/Scope This study focuses on assessing the uncertainties related to sedimentological heterogeneity and the diagenetic variability within the gas-condensate reservoirs of the Shuaiba Formation, Sharjah, United Arab Emirates. Methods, Procedures, Process For characterizing the sedimentology of the Shuaiba Formation, a lithofacies scheme has been developed on the basis of Dunham's (1962) and Embry & Klovan classification (1971). The lithofacies are grouped on the basis of their genetic relationships which also correspond to their depositional environment, and are designated as lithofacies associations. A pore-scale fabric/textural investigation was completed using conventional thin-section microscopy and Scanning Electron Microscopy (SEM). Results, Observations, Conclusions The Shuaiba sediments are characterized by skeletal-rich wackestone/packstones to floatstones deposited in an inner ramp setting. The stacking pattern of the inner ramp deposits define broad third order trends observed across the studied field.These trends are relatable to the regional sequence stratigraphic framework of Sharland et al. (2001). In higher order sequences, lateral variations in lithology occur, defining the reservoir heterogeneity, which are most likely forced by topographic/hydrodynamic variation as well as sea level changes. Reservoir quality distribution is controlled by various factors, including the depositional texture and allochem assemblage (abundance, type, and size). Diagenetic alteration of the textures played an important role in determining overall reservoir quality. The pore enhancing phases are defined by dissolution events, where later stage dissolution was the dominant phase to enhance micropores and also to create meso- to macropores which partially to completely negated the effect of previous cementing phases. In these Shuaiba deposits, the porosity comprises common matrix-hosted as well as grain-hosted micropores along with variably distributed intraparticle and rare mouldic meso- to macropores. The measured porosity ranges from very poor to moderate (0.5-17%) while permeability is very low to low (<0.001-1.49 mD). The detailed petrographic analysis highlighted that changes in micritic fabric shows a variation in the reservoir properties. From SEM observations, it was noted that microcrystalline calcite crystals of polyhedral to sub-rounded morphologies with intercrystalline contacts ranging from facial to sub-punctic, which display relatively a good microporosity developement, whereas crystals that show anhedral compact character with coalescent/fused intercrystalline contacts are rarely associated with any microporosity. Novel/Additive Information In addition to SEM characterization, porosity data and elastic properties (e.g., Young's moduli) generated from the interpretation of the well-log data, were used to investigate the prospective relationship between the microporous carbonates and elastic properties. The comparisons highlight that an increase in porosity values results in a decrease of Young's moduli values, thereby reflecting a decrease in the stiffness of the rock. On the other hand, the increase in porosity maybe linked to the evolution of anhedral, compact, micritic fabric to polyhedral/sub-rounded micritic fabric. The understanding of this relationship provides a powerful tool to be utilized in reservoir architecture prediction based on integrating the sedimentological framework and diagenetic overprint.

The Diagenetic Alteration of the Carbonate Rocks from the Permian Qixia Formation as Response to Two Periods of Hydrothermal Fluids Charging in the Central Uplift of Sichuan Basin, SW China

The hydrothermal fluid–carbonate rock reaction is frequently regarded to occur in deep-burial diagenesis, and the hydrothermal dissolution is usually distributed and takes place along the faults. Previous studies have suggested that there was hydrothermal fluid activity locally in the Permian Qixia Formation in Sichuan Basin, likely related to the Emeishan basalt eruption. However, the effect of hydrothermal fluids on the carbonate rocks of the Qixia Formation in the central uplift of Sichuan Basin is still unclear. Based on the characteristics and geochemical parameters of the diagenetic minerals, this study aims to reveal the diagenetic alteration related to the hydrothermal fluid–rock reaction in the Qixia Formation and reestablish the diagenetic evolution by using the timing of diagenetic mineral precipitation. The methods include petrographic observation; trace and rare earth element (REE) analysis; C, O and Sr isotope measurement; fluid inclusion temperature measurement and cathodoluminescence analysis. According to the petrographic characteristics, the dolostones are mainly of crystalline structure, namely fine-medium crystalline dolostone, meso-coarse crystalline dolostone, and coarse crystalline dolostone, with the cathodoluminescence color becoming brighter in that order. The limestones from the Qixia Formation are of the bioclastic limestone type, with no cathodoluminescence color. Compared with dolostones, limestones have higher Sr content, lower Mn content, and heavier oxygen isotopes. With the crystalline size of dolostone becoming coarser, the oxygen isotopes of dolostones tend to become lighter. The meso-coarse crystalline dolostone has the highest Mn content and negative carbon isotope. Both limestones and dolostones have an obvious positive Eu anomaly in the Qixia Formation. However, the REE patterns of fine-medium crystalline dolostones are very different from those of meso-coarse crystalline dolostone. It is credible that there were two periods of hydrothermal fluid charging, with different chemical compositions. The first period of hydrothermal fluids could laterally migrate along the sequence boundary. Fine-medium crystalline dolostones were almost completely distributed below the sequence boundary and were dolomitized during the shallow burial period. As products of the hydrothermal fluid–dolostone reaction, the saddle-shaped dolomites in the meso-coarse crystalline dolostones were the evidence of the second period of hydrothermal fluids. As a result, the dolomitization model was established according to the timing of diagenetic mineral precipitation, which can improve the geological understanding of the effect of hydrothermal fluid activities on the carbonate rocks in the Qixia Formation.

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.

Manuscript Title: Mechanical and Microstructural Studies of Volcanic Ash Beds in Unconventional Reservoirs

Volcanic ash beds are thin layers commonly observed in the Eagle Ford, Niobrara and, Vaca Muerta formations. Because of their differences in composition, sedimentary structures, and diagenetic alteration, they exhibit a significant contrast in mechanical properties with respect to surrounding formation layers. This can impact hydraulic fracturing, affecting fracture propagation and fracture geometry. Quantifying the mechanical properties of ash beds becomes significant; however, it is a challenge with traditional testing methods. Common logging fails to identify the ash beds, and core plug testing is not possible because of their friability. In this study, nanoindentation was used to measure the mechanical properties (Young's modulus, creep, and anisotropy) in Eagle Ford ash beds, and to determine the contrast with the formation matrix properties. Two separate ash beds of high clay and plagioclase composition were epoxied in an aluminum tray and left for 48 hours curing time. Horizontal and vertical samples of ash beds were acquired and mounted on a metal stub, followed by polishing and broad beam ion milling. Adjacent samples were also prepared for high-resolution Scanning Electron Microscope (SEM) microstructural analysis. The Young's modulus in ash beds ranged from 12 to 24 GPa, with the horizontal direction Young's modulus being slightly greater than that of the vertical samples. The Young's modulus contrast with adjacent layers was calculated to be 1:2 with clay-rich zones and 1:4 with calcite rich zones. The creep deformation rate was three times higher for ash beds compared to other zones. Using Backus averaging, it was determined that the presence of ash beds can increase the anisotropy in the formation by 15-25%. SEM results showed a variation in microstructure between the ash beds with evidence of diagenetic conversion of rhyolitic material into clays. Key differences between the two ash beds were due to the presence of plagioclase and the occurrence of porosity within kaolinite. Overall porosity varied between the two ash beds and adjacent carbonate layers showing a significant increase in porosity. Understanding the moduli contrast between adjacent layers can improve the hydraulic fracturing design when ash beds are encountered. In addition, the presence of these beds can lead to proppant embedment and loss in fracture connectivity. These results can be used for improving geomechanical models.

Long-term experimental diagenesis of aragonitic biocarbonates: from organic matter loss to abiogenic calcite formation

Carbonate biological hard tissues are valuable archives of environmental information. However, this information can be blurred or even completely lost as hard tissues undergo diagenetic alteration. This is more likely to occur in aragonitic skeletons because bioaragonite commonly transforms into calcite during diagenesis. For reliably using aragonitic skeletons as geochemical proxies, it is necessary to understand in depth the diagenetic alteration processes that they undergo. Several works have recently investigated the hydrothermal alteration of aragonitic hard tissues during short term experiments at high temperatures (T > 160 °C). In this study, we conduct long term (4 and 6 months) hydrothermal alteration experiments at 80 °C using burial-like fluids. We document and evaluate the changes undergone by the outer and inner layers of Arctica islandica shell, the prismatic and nacreous layers of Haliotis ovina shell, and the skeleton of Porites sp. combining a variety of analytical tools (X-ray diffraction, thermogravimetry analysis, laser confocal microscopy, scanning electron microscopy, electron backscatter diffraction and atomic force microscopy). We demonstrate that this approach is the most adequate to trace subtle, diagenetic alteration-related changes in aragonitic biocarbonates. Furthermore, we unveil that the diagenetic alteration of aragonitic hard tissues is a complex multi-step process where major changes occur even at the low temperature used in this study and well before any aragonite into calcite transformation takes place. Alteration starts with biopolymer decomposition and concomitant generation of secondary porosity. These processes are followed by abiogenic aragonite precipitation that partially or totally obliterates the secondary porosity. Only afterwards any transformation of aragonite into calcite takes place. The kinetics of the alteration is highly dependent on primary microstructural features of the aragonitic biomineral. While the skeleton of Porites sp. remains virtually unaltered within the time spam of the experiments, Haliotis ovina nacre undergoes extensive abiogenic aragonite precipitation, the outer and inner layers of Arctica islandica shell are significantly affected by aragonite transformation into calcite and this transformations extensive in the case of the prismatic layer of Haliotis ovina shell. Our results suggest that most aragonitic fossil archives may be overprinted, even those free of clear diagenetic alteration signs. This finding may have major implications for the use of these archives as geochemical proxies.

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.