Diagenetic Stage Research Articles

Micro-facies characterization of the Cane Creek Shale, Paradox Basin, Utah: implications of diagenetic controls on reservoir quality

The fine-grained Pennsylvanian Cane Creek Shale of the Paradox Formation, Paradox Basin, Utah exhibits relatively thin cyclic interbeds of contrasting lithologies including fine sandstone to siltstone, organic-rich carbonate and dolomitic mudstone, and evaporites. As such, it provides a unique opportunity to evaluate micro-facies and the fluid storage capacity potential of mixed fine-grained systems. Micro-facies descriptions were performed using core and petrographic analyses, including scanning electron microscopy with energy dispersive spectroscopy. The study leverages core-based porosity and permeability data, as well as previous core description. These data are used together to explore mineralogical depositional and diagenetic controls on porosity and permeability. Twelve micro-facies were described based on sedimentological textures, grain size, lithology, and mineralogy categorized into three groups: 1) sandstone to siltstone, 2) mudstone, and 3) evaporitic micro-facies. Sandstone to siltstone micro-facies exhibit variable porosity and permeability. Porosity connectivity is dependent on the degree of authigenic cementation and compaction that negatively impacts porosity. Mudstone micro-facies show less variability in porosity and permeability; and are characterized by carbonate content, organic-matter, and clay nanopores. The development of early carbonate grains maintains porosity in mudstone and dolomitic siltstone micro-facies. Evaporitic micro-facies represented by evaporitic sabkha-like conditions are characterized by pore-reducing anhydrite and halite cement. A diagenetic paragenetic sequence was developed to assess the timing and impact of mineralogy on reservoir quality. Early (eogenetic), Middle (mesogenetic), and Late (telogenetic) stages correspond with diagenetic stages and known tectonic basin events. Syndepositional dolomite and diagenetic illite/smectite authigenic cements are the main controls on reservoir quality and have opposing effects related to porosity and permeability by preserving early pore space or reducing porosity and permeability.

Coupled Effects of Paleofluid Evolution on Ultra-deep Microbialite Reservoir Modification: A case study of the upper Ediacaran Deng-2 Member within the Penglai area of central Sichuan Basin, SW China

Paleofluid-rock interaction results in the modification of the ultra-deep reservoir quality, but the coupling effects of the paleofluid evolution on reservoir quality modification are still underestimated. Here, the multi-stage dolomite cements have been studied by means of core observations, thin section identification, fluid inclusions, and in situ elements and isotopic analyses in order to reaveal the paleofluid evolution processes and their effects on the reservoir quality. The fibrous dolomite cement (FDC) and bladed dolomite cement (BDC) both have similar geochemical properties and homogenization temperature (Th) to the matrix dolostone. Subsequent early silicification occurs (QZ1). However, silt- to fine-sized crystalline dolomite cement (CD2) has higher concentration of Fe and medium rare earth element, more negative δ18O than for FDC and BDC, and 103.4 to 150.2 °C in Th. The first petroleum charge episode solid bitumen 1 (SB1) followed the CD2. The medium to coarse sized crystalline dolomite cement (CD3) is characterized by the higher Mn and lower Sr concentration than CD2, positive δEu anomaly, negative δ13C and δ18O, high 87Sr/86Sr ratio and 138.9 °C to 184.3 °C in Th. The solid bitumen 2 (SB2) occurs after CD3. Subsequently, the saddle dolomite (SD) has higher Fe and Mn concentration and lower Na and Sr than others cement, δEu positive anomaly, negative δ13C and δ18O, high 87Sr/86Sr ratio and 177.5 °C to 243.6 °C in Th. Eventually massive silicification (QZ2) took place. The FDC, BDC, QZ1 and SB1 formed in the early diagenetic stage and have little negative effect on the reservoir quality. But the CD2 and CD3 dramatically decreased the reservoir quality related to a quantity of hydrothermal fluids entrance in the mesodiagenetic stage along the strike-slip faults and the unconformity surface at top of the Deng-2 Member during the late stage of the Caledonian orogeny. The reservoir spaces were retained and enlarged during the late diagenetic stage when the peak petroleum charge occurred, massive silicification and thermochemical sulphate reduction took place with SB2, SD and QZ2 being formed. The research outcome may update our understanding on the retention mechanism and the insights for further hydrocarbon exploration of Precambrian ultra-deep microbial reservoirs.

The mechanism of dolomitization in a stromatolite mound in the late Cambrian Chaomidian Formation, Shandong Province, China

Clarifying the mechanism of dolomitization is of pivotal importance and represents a burning issue among geologists. A comprehensive model to define the genesis of dolomitization in the Cambrian Chaomidian Formation carbonates is still lacking. In the highly focused study, the advanced integration of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), clumped isotope and carbon/oxygen isotope analyses was used to reveal complex interactions between the genesis and dolomitization of a stromatolite mound in the late Cambrian Chaomidian Formation of China. The results show that the dolomite content increases from bottom to top, along with a shift in lithology from limestone to dolostone. Additionally, as we moved from the base to the summit of the stromatolite mound, the Fe, Mn, and Na contents increase with increasing Mg levels, whereas the δ13C and δ18O values became more positive. Conversely, the levels of Sr and total rare earth elements (REEs) gradually decreased. The dolomite grains in the stromatolite mound are micritic and euhedral to subhedral, with foggy cores and bright edges and low cation ordering. The stromatolite limestone, dolostone, and underlying lime mudstone samples exhibit similar REE patterns: light REE enrichment, heavy REE loss, negative δEu anomalies, and weak negative δCe anomalies. The δ13C and δ18O values fall within the late Cambrian seawater range, suggesting that dolomitizing fluids originated mainly from concentrated seawater and migrated from top to bottom. The δ18O values indicate lower dolomite formation temperatures than calcite formation temperatures, supporting dolomitization during the penecontemporaneous diagenetic stage. Petrographic evidence reveals the presence of pyrite, indicating sulfate-reducing bacterial activity during diagenesis. XPS analysis revealed similar organic functional groups in both the stromatolite limestone and the dolostone, including C-(C = O)-O, C–C/C-(C–H), C-O and C-N. However, the dolostone spectrum exhibited a larger C-OH/C-O peak area, suggesting significant microbial organic matter involvement in dolomite formation. While a kinetic obstacle is recognized as a primary cause of dolomite formation, this study also suggested that microbial activity weakened this obstacle during diagenesis. Thus, microbial metabolism or cyanobacterial decomposition facilitates dolomite formation during the penecontemporaneous diagenetic stage.

Influence of climate and marine transgression on Mesozoic–Cenozoic diagenesis of clastic rocks in the Tabei Uplift, Tarim Basin, China

The Mesozoic–Cenozoic clastic rocks in the Tabei Uplift form one of the most hydrocarbon-rich zones in the Tarim Basin of China. Understanding how diagenesis has affected the petrophysical properties of the sandstone is crucial for developing regional exploration strategies. Although most studies have investigated the physical conditions during sedimentation and chemical processes during diagenesis, the hydrochemical environment during sedimentation and subsequent diagenesis has received little attention. This study employed petrographic observations, paleo-geothermal reconstructions, and paleoenvironmental analysis to constrain the regional climatic conditions, hydrochemical environment of deposition, and diagenetic features of clastic rocks in the Tabei Uplift. The sandstone at depths of 3500–6000 m is located mainly in the A phase of the middle diagenetic stage, and exhibits three types of diagenesis. Triassic–Jurassic sandstones are dominated by silica, kaolinite, and chlorite cements, Cretaceous sandstones by mainly carbonate cements, and Paleogene sandstones by carbonate and evaporite cements. These diagenetic stages correspond to paleoclimatic changes during the earliest Late Jurassic and the maximum marine transgressions of the Proto-Tethys during the Paleogene, thereby highlighting the influence of climatic change and transgressions on the water conditions during deposition and the type of diagenesis.

Insights into the formation and growth of authigenic chlorite in sandstone: Analysis of mineralogical and geochemical characteristics from Shaximiao Formation, Sichuan Basin, SW China

Chlorite is a widely distributed clay mineral in sandstone reservoirs, attracting significant attention due to its complex physicochemical properties and unique reservoir significance. The Shaximiao Formation in the Sichuan Basin, SW China, features abundant diagenetic chlorite, offering valuable insights into chlorite growth theories. Petrographic observations and electron probe analyses reveal that the formation of authigenic chlorite resembles a continuous, staged growth process, akin to tree growth. This process encompasses stages from depositional smectite clay (seeding) to inner-layer chlorite formation (germination), outer-layer chlorite development (branching), and pore-filling chlorite precipitation (blooming). During the initial burial, depositional smectite (seeds) transforms into low-Fe, low-Mg inner-layer chlorite (germination) under the influence of Fe and Mg ions in the original formation water. In the early diagenetic stage, volcanic detritus and biotite alteration release substantial Fe2+ and Mg2+, fostering the growth of outer-layer chlorite (branching) on the inner-layer chlorite. In the middle diagenetic stage, volcanic detritus releases Ca2+, Fe2+, and Mg2+ under the influence of organic acids, leading to supersaturation of Si4+, Al3+, Fe2+, and Mg2+ in pore water, which directly crystallizes into highly euhedral pore-filling chlorite (blooming). The presence of precursor smectite is fundamental to this process, while sufficient Fe and Mg sources are crucial for chlorite formation.

Carbon–sulfur–calcium isotopic variability of lower Cambrian shale-hosted carbonate concretions: Insights into growth mechanisms and calcium cycling

Marine calcium cycling is closely linked with carbon cycling in the ocean, in which authigenic carbonates precipitated in sediments play a non-negligible role. However, calcium cycling during authigenic carbonate precipitation in organic-rich, shaly sediments in geological history remains underexplored. This study focuses on carbonate concretions (aggregates of authigenic carbonates) in the lower Cambrian Niutitang Formation, South China, to provide insights into calcium cycling during their growth. Sedimentological and mineralogical observations suggest that these concretions were formed through concentric growth by authigenic calcite and pyrite precipitation during the early diagenetic stage. Geochemical analyses reveal internal variations in “M-shaped” δ13Ccarb trends (from −11.9 ‰ to −4.4 ‰) and diverse δ34Spyr trends (from 4.7 ‰ to 14.0 ‰) along core-to-rim transects. These findings suggest formation through microbial sulfate reduction by organic matter in a shallow depth beneath the sediment–water interface. In contrast to the dynamic δ13Ccarb and δ34Spyr variations and multi-stage concentric growth, these carbonate concretions display nearly uniform δ44/40Cacarb values (from 0.80 ‰ to 1.03 ‰, average 0.96 ± 0.06 ‰, 1SD) and consistent internal trends, which are further attributed to strongly seawater-buffered porewater calcium geochemistry and small calcium isotope fractionation due to calcite precipitation at slow rates. This study confirms that early diagenetic carbonate concretions in the lower Cambrian Niutitang Formation are characterized by much heavier δ44/40Ca values compared to coeval shallow platform carbonates. In light of abundant authigenic carbonates observed in the lower Cambrian successions, their roles in calcium isotope mass balance in the early Cambrian ocean warrant further investigation in the future. Therefore, early diagenetic carbonate concretions in black shales could provide valuable insights into porewater and seawater calcium isotope signals, as well as early diagenetic and marine calcium cycling in geological history.

Diagenetic evolution and cementation mechanism in deep Carbonate reservoirs: A case study of Dengying Fm. 2 in Penglai, Sichuan Basin, China

The Dengying Formation in the Penglai region of the Sichuan Basin is renowned for hosting high-quality dolomite reservoirs. However, the understanding of their formation mechanisms and spatial distribution patterns remains enigmatic. This study undertakes a comprehensive petrographic analysis of the second member of the Dengying Formation, primarily focusing on its burial history, reservoir characteristics, and an examination of the types, stages, and developmental patterns of cementation within the dolomite reservoir. This is achieved through the application of isotopic geochemistry, inclusion temperature analysis, and laser U-Pb dating. The findings reveal that cements within the second member of the Dengying Formation predominantly occur in pores and fractures, often exhibiting euhedral and subhedral morphologies. These cements also exhibit evidence of replacing original non-skeletal grains and micrites in semi-euhedral and other forms. Broadly, the cements can be classified into four types: calcium cement (the most abundant), dolomite cement, quartz, and pyrite. The formation of calcareous and siliceous cements closely aligns with the sedimentation and burial processes of the Dengying Formation as a whole. The early to late stages of early-middle diagenesis play a crucial role in the formation of dolomite within the second member. Notably, the degree of euhedral dolomite formation directly correlates with the specific diagenetic stage. Our research indicates that the development of high-quality reservoirs in deep-to-ultra-deep microbial dolomites is a result of complex multi-factor interactions and multi-stage discontinuous modifications, leading to strong heterogeneity within the reservoirs. Microbial dolomite carbonates inherently exhibit high initial porosity, with the favorable sedimentary facies serving as the fundamental basis for reservoir development. Dissolution processes during the syngenetic and quasi-syngenetic periods, in conjunction with epigenetic karstification, further augment porosity and expand the reservoir's capacity. During burial and deep burial stages, various acidic fluids play a pivotal role in preserving and modifying the early-formed pores. In the deep environment characterized by high temperature and pressure, microbial dolomite reservoirs undergo intricate diagenetic evolution and possess complex pore preservation mechanisms. Remarkably, even under exceptional ultra-deep conditions, high-quality microbial dolomite carbonate reservoirs can still develop and be preserved, presenting significant potential for oil and gas exploration.

New Advance in the Study of Shale Oil Generation Peak Determination and Diagenetic Pore Evolution

Shale formations globally are widely distributed with abundant resources and varied thermal maturation ranges. However, the understanding of shale’s oil generation peak, diagenetic stages, and pore evolution remains incomplete. This study investigates shale samples of varying maturities and organic matter content from representative oil and gas basins in China and the United States. Comprehensive characterization was conducted using thermal simulation, rock X-ray diffraction analysis, N2 and CO2 adsorption, and mercury injection analysis. The study delineates the hydrocarbon generation process in shale, identifies the oil generation threshold, determines the peak oil generation, and categorizes shale’s diagenetic stages based on clay minerals and pore evolution. The results indicate: (1) highly mature shale exhibits delayed hydrocarbon expulsion and peak oil generation, starting at Ro values greater than 0.75% and reaching peak oil generation at Ro levels surpassing 1.2%. In contrast, peak oil generation in less mature shale initiates at Ro values of 1.1%, providing a more precise depiction of the shale’s diagenetic evolution stages; (2) the higher the TOC content of shale, the greater its hydrocarbon generation capacity, showing a robust positive correlation between hydrocarbon generation and TOC; (3) the diagenesis and pore evolution of shale can be categorized into four distinct stages: the early diagenesis stage (Ro < 0.5%), dominated by mesopores, and with reduced pore volume and surface area; the middle diagenesis stage A (0.5%–1.1%), where shale pore volume has been enhanced while the surface area has been reduced; the middle diagenesis stage B (1.1%–2.0%), where an initial decrease followed by an increase in mesopore volume occurs, along with a modest increase in macropores; and the late diagenesis stage (Ro > 2.0%), with increased organic pores and microfractures, while both pore volume and surface area expand. The study suggests that a Ro of 1.1% marks the peak oil generation period for shale, occurring during the early stage of middle diagenesis, characterized by larger pore volume and surface area, crucial for shale oil and gas enrichment.

Diagenesis and reservoir quality evolution of estuarine sandstones: Insights from the Cenomanian-Turonian Yolde Formation, northern Benue Trough, NE Nigeria

Estuarine sandstones often exhibit complex diagenetic pathways due to the interaction of fluvial and shallow marine processes, resulting in significant reservoir heterogeneities. The Yolde Formation is an important petroleum reservoir in the Northern Benue Trough, NE Nigeria. However, diagenetic and reservoir quality evolution of the formation are still poorly understood. This study utilizes thin-section petrography, XRD, SEM, and fluid inclusion microthermometry to analyse the composition, diagenesis, and reservoir quality of the sandstones. Results show that the sandstones are mainly arkose and subarkose in composition; they are generally well-sorted and vary in grain size from very fine-to coarse-grained. Three diagenetic stages are identified: early, middle, and late. The early stage includes feldspar dissolution, formation of kaolinite, development of clay coating, and mechanical compaction. The middle stage comprises the formation of authigenic chlorite and Fe-oxide cements. The late-stage diagenesis involves illitization of kaolinite, formation of dickite, albitization of K-feldspar, and precipitation of quartz overgrowths. The diagenetic evolution of the sandstones was strongly controlled by their compositional makeup. The feldspathic nature of the sandstones resulted in the formation of kaolinite, illite, and quartz overgrowths, through feldspar dissolution and silica supply. The inner and middle estuarine facies have inhibited the development of quartz overgrowths due to well-developed clay coatings, whereas the outer estuarine facies were well-cemented by quartz overgrowths due to lack of clay coatings. Illitic clay coatings were found to be effective in preventing quartz cementation. Fluid inclusion analysis reveals that the formation temperatures of the quartz overgrowths range from 98 °C to 135.5 °C, corresponding to burial depths ranging between 2.3 and 3.5 km. These findings would provide useful insights that would reduce the risks of exploration of the sandstones and also supplies potential input data for forward diagenetic modelling of their subsurface equivalents in similar depositional settings elsewhere.

Evolution of pore structure and diagenetic stages of late Permian shales in the Lower Yangtze Region, South China

This study examines the evolution characteristics of shale pores in the Late Permian Longtan Formation located in the Lower Yangtze region of South China. The complete process of thermal evolution of the samples was achieved through thermal simulation experiments while identifying qualitatively the pore types and their development characteristics using field emission-scanning electron microscope (FE-SEM). Quantitative analysis of pore size distribution was conducted through mercury intrusion capillary pressure (MICP), nitrogen (N2) and carbon dioxide (CO2) adsorption experiments. The paper comprehensively analyzed the pore evolution characteristics and controlling factors of shale in the study area, with an analysis of diagenetic differences. Findings reveal that during the pore evolution process, both morphology and pore size are influenced by thermal maturity. The pore volume is dominated by mesopores and macropores, while the specific surface area is mainly dominated by mesopores and micropores. Thermal evolution promotes the formation of micropores and mesopores but hinders the development of macropores. Moreover, clay minerals transformation and mineral dissolution make certain contributions to the development of micropores. The diagenesis in the study area is controlled primarily by the pyrolysis of organic matter. Pyrite and clay minerals are the first to dissolve, followed by calcite and quartz. Five stages of evolution characterization have been identified from low-mature stage (Ro = 0.88 %) to overmature stage (Ro = 3.35 %) in combination with diagenesis. The development of pore structure and its influencing factors vary across different stages. The influencing factors mainly include hydrocarbon generation from organic matter, compaction, mineral transformation, and dissolution. The process of hydrocarbon generation in organic matter occurs throughout the entire pore evolution process, resulting in the development of numerous micropores and mesopores. Compaction primarily impacts pore development during the early diagenetic stage, causing a substantial transition of primary mineral pores from macropores to mesopores. Mineral transformation and dissolution take place during and after the middle diagenetic stage. The former governs the development of mesopore-sized clay interlayer pores, while the latter primarily generates micropores.

Investigating the impact of paleoclimatic conditions and diagenesis on the genesis of Permian Continental Red Beds: A case study from the Bohemian Massif, Czechia

The processes responsible for reddening of Continental Red Beds (CRBs) and the relationship between color variation and paleoenvironmental conditions are presented focusing on a comprehensive multi-proxy study of Permian sediments in the Bohemian Massif, Czechia. The investigation incorporates facies analysis, quantitative color assessment using diffuse Vis-spectral reflectance (DRS), optical and electron microprobe microscopy, bulk-rock (XRF and XRD), and in-situ geochemistry (laser-ablation ICP-MS). Results indicate a progressive drying trend from the Cisuralian to Guadalupian series in studied continental red sediments. Different facies indicate the change of the sedimentary environment from a deep lacustrine environment (lower part of Rudník Member, Cisuralian) to a fluvial floodplain and eolian environment (Trutnov Formation, Guadalupian). Examination of the three major categories (white, gray–green and red sediments) identified in the studied continental red beds indicates that diagenetic alteration of clay minerals and biotite was the main source of iron fueling the growth of hematite responsible for their red color. Early diagenetic processes and paleoenvironmental conditions, particularly the oxidizing or reducing conditions play a key role in the red sediment formation. It is suggested that later diagenetic stages are incapable of coloring non-red, iron-rich sediments formed in deep anoxic lacustrine environments. Microbial activities and reducing fluids have been identified as the main factors in the formation of gray–green sediments forming distinct reduction zones. The reduction spots formed during the early stages of diagenesis (eodiagenesis), and they were likely never red. In contrast, reduction strips, initially exhibiting a red hue, underwent a color change during more advanced stages of diagenesis (mesodiagenesis).

Unlocking the geochemical features of the Paleocene southern Pacific Ocean using carbon isotopes and biolipids

Little is known about the Paleocene in the southern Pacific Ocean due to scarce marine records. Here, we present a systematic geochemical investigation using biomarkers, carbonate content, and carbon isotopes of a set of early Paleocene deep-sea cores from International Ocean Discovery Program Expedition 378 Site U1553. The results provide a new Paleocene biomarker profile for the Campbell Plateau, New Zealand. The occurrence and distribution of a series of hopenes, ββ hopanes, sterenes and biomarker-based maturity parameters indicate that these organically-lean sediments are in an early diagenetic stage, with an equivalent vitrinite reflectance of approximately 0.4%. Biomarker data (e.g., gammacerane index and homohopane index), carbonate carbon isotopes (−27.9 ‰ to +2.0 ‰) combined with onboard data (sulphur and methane contents) indicate that the redox properties of the Paleocene southern Pacific Ocean changed from an oxidising-anoxic transition zone to a more reducing marine environment (water depth > 1000 m). The sources of the organic matter are diverse, including algae, bacteria, diatoms, dinoflagellates, and higher plants, but are dominated by aquatic organisms. Our new biomarker record bridges a Paleocene biosphere knowledge gap in the high latitude South Pacific.

Genesis of Carboniferous aluminous-bearing strata in the northern part of the North China Craton: A case study of the Xingxian bauxite deposit

More than five billion tons of karstic bauxites were formed in the North China Craton (NCC) during the Late Carboniferous period. Compared to the bauxite ore, the genesis of the entire aluminous-bearing strata has received less attention. In this study, we conducted geological, mineralogical, and geochemical analyses on core samples from the aluminous-bearing strata located in Xingxian area, situated within the northern NCC, aiming to elucidate the genetic process of these formations. The aluminous-bearing strata consist of a bauxite layer (diaspore–anatase–kaolinite–florencite) sandwiched between the upper sandy claystone horizon (kaolinite–illite–quartz) and the lower berthierine-bearing claystone horizon (berthierine–diaspore–hematite–goethite). Based on the upper continental crust-normalized patterns of rare earth elements and yttrium (REY), immobile trace element ratios, mineral inheritance diagrams, and previous findings, it is suggested that the lower berthierine-bearing claystone was weathered from the impure limestone at the bottom, whereas the upper bauxite and sandy claystone mainly originated from intermediate-felsic igneous rocks of the northern margin of the NCC, granite from the North Qinling Orogenic Belt, and aluminosilicate rocks of the surrounding paleo-uplifts. During the early diagenetic stage, the berthierine was transformed under alkaline and reducing conditions from iron-rich clays (composed of clay minerals, ferric minerals, etc.) formed in acidic and oxidizing conditions from the underlying impure limestone. The coexistence of berthierine with low-temperature stability and diaspore is observed in the berthierine-bearing claystone, which precludes a high-temperature origin of diaspore in the aluminous-bearing strata. Moreover, diaspore is characterized by a small crystal size and is usually poorly crystallized, suggesting a supergene precipitation-diagenesis origin. The paragenetic minerals assemblages (e.g., diaspore, berthierine, goethite, hematite, etc.) suggest that the aluminous-bearing strata primarily formed in a transition zone nearer to the phreatic environment. Large-scale volcanism and warm, humid climatic conditions accelerated the decomposition of allochthonous weathering materials, resulting in the downward migration of metal ions. These ions then precipitated in a reducing and weakly alkaline environment, giving rise to form bauxite ore dominated by diaspore, anatase, and REY minerals.

Nitrogen isotope homogenization of dissolved ammonium with depth and 15N enrichment of ammonium during incorporation into expandable layer silicates in organic-rich marine sediment from Guaymas Basin, Gulf of California

Sedimentary nitrogen isotopic ratios are used as a proxy for ancient biogeochemical cycles on Earth's surface. It is generally accepted that sediment hole tops record primary signatures because organic nitrogen (ON) is predominant in this part of the hole. In contrast to such early to middle diagenetic stages, it is well known that heavier nitrogen isotope 15N tends to enrich in sedimentary rocks during later diagenetic and metamorphic stages. However, there are some critical gaps in our understanding of nitrogen isotopic alteration associated with abiotic processes during early-middle diagenesis. In this study, we examined the isotope ratios of ammonium nitrogen in interstitial water (IW) and total nitrogen (TN), including exchangeable ammonium and mineral nitrogen, in the solid-phase of organic-rich-sediment recovered by International Ocean Discovery Program (IODP) Expedition 385 cores drilled in the Guaymas Basin, Gulf of California, that contained ammonium-rich IW. The isotopic ratios (δ15N value) of TN are the most variable with depth compared to any other type of nitrogen. This variation can be interpreted as reflecting changes in the water mass environment in the basin caused by glacial–interglacial climate changes, modifying the δ15N values of the marine primary producers. Thus, the δ15N value of TN is a proxy for environmental change in the basin, while each component of TN shows different trends. The δ15N values of IW and exchangeable ammonium did not exhibit significant changes with depth, but the latter values are about 3 ‰ enriched in 15N. This may be due to advective transport of solute into adjacent layers followed by the formation of an isotopic equilibrium between IW and exchangeable ammonium in the case of fast sediment accumulation rate. The δ15N value of exchangeable ammonium is the highest among the other types of nitrogen with one exception, where the δ15N value of TN is the highest. The calculated δ15N values of ON based on mass balance are almost the same as those of associated TN in the shallow sediment layers (< 150 m below seafloor), but the difference in the δ15N values of TN and ON are significant in the deeper layers, where proportions of ON contents are <50%. In particular, in the layer where the δ15N value of TN is the highest, that of ON shows an even higher value and the difference reaches 3.5 ‰. The δ15N values of mineral nitrogen are similar to that of IW ammonium except the surface layers. Under such conditions, when δ15N value of TN is intermediate between those of mineral nitrogen and exchangeable ammonium, calculated δ15N value of ON is close to that of TN. On the other hand, if δ15N value of TN is out of the range between mineral nitrogen and exchangeable ammonium, it causes further difference in δ15N value of ON. It means that the fluctuation of δ15N values of TN is reduced relative to those of ON through depth. It has been considered that δ15N value of TN in sediment is similar to that of ON, and changes in the δ15N value of TN due to diagenesis are limited, but in such environment ON fluctuations over depth may be slightly underestimated.

Diagenetic controls on the quality of shallow marine sandstones: An example from the Cambro-Ordovician Saq Formation, central Saudi Arabia

The Saq Formation is the most important Paleozoic aquifer in central and northern Saudi Arabia. However, owing to the continued depletion of the aquifers and the great depths to which the aquifers are buried in undrilled/underexplored regions, the aquifers porosity and permeability are increasingly becoming an issue of concern. Here, we employed thin-section petrography, petrophysical measurements, X-ray diffraction and scanning electron microscopic analyses, and fluid inclusion microthermometry to investigate the composition and diagenetic evolution of the Saq sandstones. The results of this study indicate that the sandstones are mainly quartz arenite in composition, mostly well sorted, and ranged in grain size from silt to coarse-grained sandstones. We observed three diagenetic stages (early, middle, and late) that impacted the porosity evolution of the Saq sandstones. Mechanical compaction, formation of authigenic kaolinite, and infiltration of smectitic clays occurred during early shallow burial diagenesis. The middle (deep-burial) diagenesis was dominated by mechanical and chemical compaction, formation of authigenic quartz overgrowths, transformation of kaolinite and smectite into illite, and precipitation of late calcite. The late (uplift-related) diagenesis resulted in the formation of authigenic kaolinite, dissolution of the late calcite, and the formation of predominantly pore-filling Fe-oxide (goethite) cement. Fluid inclusion results of this study show that quartz cement mostly formed at temperatures ranging between 151 °C and 175 °C and reached up to 272 °C, with, at least, two phases of overgrowth development. The overall high amounts of rigid grain contents (>65 %), low detrital matrix (<10 %), and coarser grain size have maintained the Saq sandstone quality (average permeability = 2100 mD) despite having been buried to great depths. The findings of this study provide useful insights into the diagenetic evolution of the Saq Formation, which has provided important input data for forward diagenetic modelling of their subsurface equivalent in Saudi Arabia and sandstones of similar depositional settings elsewhere.

The joint controls of tectonism, sedimentation and diagenesis on reservoir quality in the East China Sea Basin

Variation in reservoir quality is especially important in low-permeability and tight sandstone reservoirs. By using log, seismic and core test data, we developed a method that uses tectonism, sedimentation and diagenesis to evaluate sweet spot distribution of the third (Mbr 3), fourth (Mbr 4) and fifth (Mbr 5) members of the Oligocene Huagang Formation in the Xihu Depression, East China Sea Basin. Sweet spot maps of the Mbr 3, Mbr 4 and Mbr 5 sandstone reservoirs were compiled by superposing tectonic locations, depositional microfacies and diagenetic facies. Sweet spots were classified into three types. Mbr 3 exhibits type I and type II sweet spots, Mbr 4 exhibits type I, type II and type III sweet spots, and Mbr 5 exhibits type II and type III sweet spots. In the Oligocene, tectonism and climatic controlled the depositional microfacies, sandstone grain size and clastic composition of the Mbr 5, Mbr 4 and Mbr 3 members, which were deposited in a braided river delta setting that ranged from delta-front distal part to proximal part. From late Oligocene to present, along with depositional microfacies, diagenetic stage, diagenetic facies and reservoir properties, the joint control of tectonism, sedimentation and diagenesis determined the distribution of diagenetic facies, and was used to develop a synthetic pattern for reservoir quality variation.

Mineralogical and geochemical studies on the Qianjiadian deposit, Songliao Basin, NE China: Insights into multiple metallogenic processes in the sandstone-type uranium deposit

Sandstone-type uranium deposits usually exhibit a range of metallogenic mechanisms. To gain insights into the nature, genetic relationships, and mineralization mechanisms of uranium and associated minerals, representative samples from the Qianjiadian uranium deposit in the Songliao Basin were investigated through detailed mineralogical, elemental geochemical, and in-situ sulfur isotopic analyses. The results provided invaluable information on the various stages of uranium mineralization. During the early diagenetic stage, uranium mineralization occurred in the local organic matter (OM)-enriched sites (TOC = 0.70 ∼ 2.05 %) in the Yaojia Formation. The paragenetic relationship revealed that uranium was firstly precipitated as pitchblende along with the biogenetic framboidal pyrite (δ34S values ranging from −44.1 ‰ to −1.8 ‰) through bacterial sulfate reduction (BSR) process. Simultaneously, organic acids generated through biodegradation of OM caused an acidic fluid condition and subsequent dissolution of feldspars, resulting in the production of kaolinite intergrowth with pitchblende. During the late diagenetic stage, the ore-forming fluid turned alkaline, leading to the conversion of pitchblende into coffinite, with elevated elements such as Si, P, Ca, Zr, and Y in the altered phase. In addition to the contribution of OM and sulfate-reducing bacteria (SRB), pyrite was confirmed as a reducing agent manifested by its replacement by uranium minerals and the Fe-oxide produced along the boundaries. The diagenetic uranium enrichment is mainly hosted in the gray sandstone that experienced reduced alteration of deep hydrocarbons, resulting in pervasive kaolinization and promotion of reduction potential. A significant amount of uranium was fixed by adsorption, as evidenced by the rare observation of independent uranium minerals, but the higher whole-rock U content (U = 133.5 ∼ 394.0 ppm) and the detection of U signal in micro-XRF analysis and EPMA data (U content in representative kaolinite ranges from bld to 0.74 wt%). Overall, the formation of sandstone-type uranium deposits is a long-term and multi-stage process. The early enriched uranium during synsedimentary-diagenetic stages is non-negligible and can even result in an appreciable amount of mineralization, further serving as an important source for the subsequent secondary enrichment.

Types, composition and diagenetic evolution of authigenic clay minerals in argillaceous limestone of sepiolite-bearing strata: A case study of Mao-1 Member of Middle Permian Maokou Formation, eastern Sichuan Basin, SW China

The types, occurrence and composition of authigenic clay minerals in argillaceous limestone of sepiolite-bearing strata of the first member of the Middle Permian Maokou Formation (Mao-1 Member) in eastern Sichuan Basin were investigated through outcrop section measurement, core observation, thin section identification, argon ion polishing, X-ray diffraction, scanning electron microscope, energy spectrum analysis and laser ablation-inductively coupled plasma-mass spectrometry. The diagenetic evolution sequence of clay minerals was clarified, and the sedimentary-diagenetic evolution model of clay minerals was established. The results show that authigenic sepiolite minerals were precipitated in the Si4+ and Mg2+-rich cool aragonite sea and sepiolite-bearing strata were formed in the Mao-1 Member. During burial diagenesis, authigenic clay minerals undergo two possible evolution sequences. First, from the early diagenetic stage A to the middle diagenetic stage A1, the sepiolite kept stable in the shallow-buried environment lack of Al3+. It began to transform into stevensite in the middle diagenetic stage A2, and then evolved into disordered talc in the middle diagenetic stage B1 and finally into talc in the period from the middle diagenetic stage B2 to the late diagenetic stage. Thus, the primary diagenetic evolution sequence of authigenic clay minerals, i.e. sepiolite–stevensite–disordered talc–talc, was formed in the Mao-1 Member. Second, in the early diagenetic stage A, as Al3+ carried by the storm and upwelling currents was involved in the diagenetic process, trace of sepiolite started to evolve into smectite, and a part of smectite turned into chlorite. From the early diagenetic stage B to the middle diagenesis stage A1, a part of smectite evolved to illite/smectite mixed layer (I/S). The I/S evolved initially into illite from the middle diagenesis stage A2 to the middle diagenesis stage B2, and then totally into illite in the late diagenesis stage. Thus, the secondary diagenetic evolution sequence of authigenic clay minerals, i.e. sepiolite–smectite–chlorite/illite, was formed in the Mao-1 Member. The types and evolution of authigenic clay minerals in argillaceous limestone of sepiolite-bearing strata are significant for petroleum geology in two aspects. First, sepiolite can adsorb and accumulate a large amount of organic matters, thereby effectively improving the quality and hydrocarbon generation potential of the source rocks of the Mao-1 Member. Second, the evolution from sepiolite to talc is accompanied by the formation of numerous organic matter pores and clay shrinkage pores/fractures, as well as the releasing of the Mg2+-rich diagenetic fluid, which allows for the dolomitization of limestone within or around the sag. As a result, the new assemblages of self-generation and self-accumulation, and lower/side source and upper/lateral reservoir, are created in the Middle Permian, enhancing the hydrocarbon accumulation efficiency.

Pyrite Characteristics in Lacustrine Shale and Implications for Organic Matter Enrichment and Shale Oil: A Case Study from the Triassic Yanchang Formation in the Ordos Basin, NW China.

Pyrite is widely distributed in lacustrine shales and has become a research focus in unconventional oil and gas exploration. Pyrite morphology is useful for identifying different types of organic matter and assessing shale oil enrichment in organic-rich shale. Abundant pyrite is developed in the source rocks from the Chang 7 Member of the Yanchang Formation in the Ordos Basin, NW China. However, the relationship between different pyrite types and the differential enrichment of shale oil still needs to be clarified. The organic geochemistry, petrology, and isotopic composition of the Chang 7 Member samples were analyzed. The significance of pyrite types and sulfur isotopic compositions as indicators of depositional environments and shale oil enrichment was emphasized. The Chang 7 shales contain three pyrite morphologies, framboidal pyrite (type A), spherulitic pyrite (type B), and euhedral and anhedral pyrite (type C), and their aggregates. The sulfur isotopic compositions of pyrite (δ34Spy) in Chang 7 shales with different pyrite types exhibited regular patterns. The δ34S values of types A, B, and C pyrites were sequentially positive overall (average values are -2.739, 2.201, and 7.487‰ in sequence), indicating that type A pyrite was formed during the syn-sedimentary to early diagenetic stage and types B and C pyrites were formed during the early to middle diagenetic stage. Types A, B, and C pyrites showed sequentially increasing kerogen type index values and kerogen carbon isotope values (mean values of -31.59, -28.70, and -26.45‰, successively), indicating that the horizons where types A, B, and C pyrites developed correspond to types I, II, and III organic matter, respectively. Strong correlations between the pyrite content and oil components reveal that pyrite indicates shale oil enrichment. Moreover, variations in pyrite type significantly influenced the enrichment behavior of shale oil. Types A and B pyrites contributing to reservoir space showed shale oil enrichment. They promoted saturated hydrocarbon enrichment at >15% pyrite content, whereas type C pyrite did not indicate shale oil enrichment. These findings provide new insights into the differential enrichment of organic matter and shale oil and valuable guidance for the large-scale exploration and development of shale oil resources.

Review of bacterial sulfate reduction in lacustrine deposition and its identification in the Jimsar Sag, Junggar Basin

Bacterial sulfate reduction (BSR) is the interaction between sulfates and organic matter that bacteria participate in during the early diagenetic stage. It is one of the important biogeochemical processes that affect the formation of sulfides and sulfur cycling. Due to the lack of sulfate in the lakes, there is relatively little research on lacustrine bacterial sulfate reduction (LBSR), and related research mainly focuses on marine sedimentation. Marine incursion and volcanic ash may bring sulfate to lakes, providing a possibility for the occurrence of LBSR. The process, main influencing factors, and identification methods of BSR are summarized systematically. Through comprehensive analysis, it is believed that the occurrence depth of LBSR is relatively shallow (about 10 cm). Sulfate concentration, total organic matter, and sulfate reducing bacteria activity are the main controlling factors of BSR. The petrological and geochemical characteristics of the product are commonly used indicators to determine whether BSR occurs. The Jimsar Sag is one of the important shale oil rich areas in China. Taking Jimsar Sag as an example, the identification of LBSR was attempted. Based on the characteristics of framboidal pyrite, columnar calcite, and fine-grained dolomite, comprehensive analysis suggests that LBSR has occurred in the Lucaogou Formation of the Jimsar Sag. BSR has a significant effect on the degradation of organic matter, and TOC is usually lower in areas with higher intensity. Therefore, BSR has impact on the enrichment of organic matter in shale. The relevant research may have reference significance for the enrichment of lacustrine organic matter and shale oil exploration.