The Central Luconia Miocene carbonate platform represents one of the largest regions of Liquified Natural Gas (LNG) production in the world. Although several studies have been conducted, the reservoir diagenesis of this gas-producing region remains poorly understood. To address this issue, a comprehensive and systematic diagenetic study has now been undertaken. Methodologies used included petrography, X-ray diffractometry (XRD), scanning electron microscopy (SEM), backscattered electron microscopy (BSEM), and cathodoluminescent microscopy (CL). Other technologies included elemental analysis using electron probe microanalyzer (EPMA), fluid inclusion microthermometry (FIM), and stable C, O, S, and Sr isotope analyses. The resulting datasets have been integrated so that the paleodiagenetic fluid flow, cementation history, and potential late-stage high-temperature hydrothermal corrosive fluids can be assessed with respect to the effect on reservoir potential. The results show that the reservoirs have undergone a complex diagenetic evolution over time. Six stages of calcite cementation (Cal-1 to Cal-6), four stages of dolomitization (Dol-1 to Dol-4), and one stage of dedolomitization (Ded-1) have occurred. Three phases of major dissolution and several minor late burial diagenetic events, such as fluorite and anhydrite replacement, pyritization, and kaolinite bridging have also been recognized. Each stage is characterized by different crystal habits, cathodoluminescent characteristics, elemental compositions, and isotopic signatures, indicating their precipitation took place at different temperatures and diagenetic environments. The early surface to shallow burial calcites (Cal-1 to Cal-4) and dolomites (Dol-1 to Dol-2) were mainly precipitated in marine, phreatic, and possible mixing water environments at relatively low temperatures (<50° C). The late calcites (Cal-5 and Cal-6), dolomites (Dol-3 and Dol-4), and dedolomite (Ded-1) were precipitated at higher temperatures (85–130° C). The late stages of dolomite (Dol-3 and Dol-4) have narrow distribution of δ 18 O[−5.29 to −6.03‰ Peedee Belemnite (PDB) scale], and δ 13 C (0.64 to −3.65‰ PDB) isotope values have been interpreted as precipitating from dolomitizing fluid that may be associated with deep burial and hydrothermal conditions. Fluid inclusion homogenization temperatures (Th) range from 125° to 130° C, and the melting temperatures of ice (Tm) range from −2.60° to −3.30° C, corresponding to a salinity of 4.34 to 5.41% weight NaCl equivalent. This interpretation also is consistent with the presence of large saddlelike dolomite and high-temperature minerals in the deeper part of the reservoirs. Three main phases of dissolution that enhanced the porosity occurred during the subaerial exposure of the platforms. The reservoir properties were enhanced further by early dolomitization, followed by hydrothermal-related corrosive fluids at high temperatures (>130° C) that possibly migrated upward from deep-seated areas underneath the reservoir via faults prior to hydrocarbon migration. This late diagenetic fluid flow was constrained by porous and nonporous layers formed during deposition and early diagenesis. These fluids created high porosity (up to 40%) and permeability (exceeding 1000 mD) within the hydrocarbon reservoirs.

Abstract: Constraining basin thermal history is a key part of reservoir characterization in carbonate rocks. Conventional palaeothermometric approaches cannot always be used: fluid inclusions may be reset or not present, while δ 18 O palaeothermometry requires an assumption on the parent fluid composition. The clumped isotope palaeothermometer, however, is a promising technique for constraining the thermal history of basins. In this study, we test if clumped isotopes record temperatures of recrystallization in deeply-buried dolomitic reservoirs, through comparison with fluid-inclusion data. The studied reservoir is the Cretaceous Pinda Formation, offshore Angola, a deeply-buried dolomitized sedimentary carbonate hydrocarbon reservoir. It provides an ideal test case as samples from industry wells are available over a relatively wide burial depth range of c. 2000–4000 m below seafloor (mbsf) and the constituent dolomites are relatively homogeneous. Across this depth range, fluid-inclusion homogenization temperatures for the Pinda Formation record a range of temperatures from c. 110 to 170°C, increasing with depth. These closely match present-day ambient well temperatures, indicating recent resetting of the fluid inclusions. Clumped isotopes, however, record temperatures significantly ( c. 20–60°C) below fluid-inclusion and well temperatures for the seven samples analysed. The deepest five samples ( c. 2800–3700 mbsf) record clumped isotope temperatures of around 100–120°C, interpreted to represent a deep burial recrystallization event responsible for a massive (re)dolomitization of the reservoir. The lower clumped isotope temperatures (65 and 82°C) of the shallower (2055 and 2740 mbsf) samples are interpreted to represent physical mixing of two dolomite generations due to incomplete burial recrystallization of an early shallow dolomite. Determination of temperature through clumped isotopes allows calculation of the parent fluid δ 18 O values. In the five deepest samples, the fluid δ 18 O values of 3.7–6.5‰ cluster around the modern-day porewater composition (5‰), suggesting that burial dolomitization occurred in the presence of evolved brine. Mineral δ 18 O values of c . −7 to −4.5‰ are lower than pristine Cretaceous marine dolomite and are in accordance with burial recrystallization. Clumped isotopes are therefore interpreted to record temperatures corresponding to open-system burial recrystallization events. This study shows that clumped isotopes are a valuable tool in characterizing the thermal history of deeply-buried (>2000 m) carbonate hydrocarbon reservoirs. Supplementary material: All standard and sample data are available at https://doi.org/10.6084/m9.figshare.c.3945184

Abstract: Accurate determination of the thermal history of sedimentary basins is critical to constrain the timing of diagenetic processes. Here, clumped isotope palaeothermometry is used to estimate minimum burial depth of the Lower Cretaceous Qishn Formation in east central Oman. Fossil oysters were collected in a soft argillaceous unit, thin-sectioned, and studied under petrographical and cathodoluminescence microscopy, revealing a variable state of shell preservations with early silica replacement of carbonate and late-stage calcite cementation. Clumped isotopes values varied from 0.602 to 0.666‰, with the best-preserved oyster shell yielding a temperature of 37 ± 4°C and a calculated oxygen isotope ratio in seawater (δ 18 O seawater ) compatible with Cretaceous seawater having experienced moderate evaporation (1.0–1.5‰ VSMOW). The new minimum estimates for the burial depth of the Qishn Formation is 1.0–1.2 km, based on the temperature difference between the well-preserved oyster and the partially neomorphosed oyster recording the highest burial temperature (63 ± 4°C). This is in excess of what was predicted by previous studies (<400 m), but compatible with conodonts alteration index temperatures (<80°C). This study highlights the potential of clumped isotopes as a quantitative tool to estimate temperature and burial depth in fine-grained carbonate succession where fluid inclusions are absent, and offers a new tool to constrain the thermal histories of sedimentary basins.

Abstract The temporal variability of geochemical proxies can be used in time intervals characterized by global changes in marine chemistry to achieve improved stratigraphic correlation. The application of this approach in rocks lithified by cementation requires particular attention, as the original isotopic signature may have been modified by diagenetic processes and, when bulk samples are used could reflect facies-specific compositional changes as opposed to primary changes in the water column. This paper examines sedimentological and chemostratigraphic records from outcrops in the central Mediterranean and cores drilled on the Marion Plateau by the Ocean Drilling Program (ODP) Leg 194, where heterozoan carbonates accumulated during the Miocene. Specifically, the paper addresses how facies and preservation of original marine signatures differentially affect the quality of the dataset. The analysis indicates that, in general, heterozoan systems, relative to their tropical counterparts, show good preservation of marine signatures. Chemostratigraphy offers a viable low-resolution alternative for dating platform sediments considering the general lack of biostratigraphic markers in these settings. It is stressed, however, that care must be taken when interpreting these values, especially when the dataset is at a low resolution or when post-depositional dolomitization took place. Furthermore, chemostratigraphy in shallow-water environments cannot be done without detailed facies analysis, as facies changes may impact bulk-rock stable isotope values.