Microcrystalline Quartz Research Articles

The manufacture of natural hydraulic limes: Influence of raw materials' composition, calcination and slaking in the crystal-chemical properties of binders

This study aims to achieve an in-depth understanding of the manufacturing process of natural hydraulic lime (NHL) by assessing the influence of raw materials' chemical- mineralogical composition and the effect of the slaking process. NHLs with variable hydraulicity were manufactured using 56 raw materials from carbonate outcrops in Andalusia (Spain). This study shows that siliceous limestones with microcrystalline quartz generate hydraulic phases after calcination. However, when the amount of this reactive silica exceeds 18% by weight, CaO is not formed, and only calcium silicates appear. It was also found that slaking of NHL leads to partial hydration of the most reactive calcium silicates, reducing the expected reactivity of the lime. Instead, exposure of NHL quicklimes to environmental relative humidity promotes the formation of disordered portlandite and reduces the partial hydration of hydraulic phases. Our findings demonstrate that standard slaking can be replaced by alternative methods for the studied binders.

First report of Sansabaina acicula, an organic-cemented siliceous agglutinated foraminifera from the Early Permian glaciomarine Pebbley Beach Formation, Southern Sydney Basin, southeastern Australia

A ca 6 cm-thick microfossil coquina bed dominated by plastically deformed and siliceous tubular test fragments is described for the first time from the Lower Permian (Artinskian) Pebbley Beach Formation of coastal and glacial marine origin in the southern Sydney Basin, southeastern Australia. The test fragments are mostly very large, straight, smooth, nearly cylindrical in shape, and the test walls are composed mainly of homogenous microcrystalline quartz grains. This homogeneous siliceous test-wall microstructure is interpreted to have resulted from diagenetic alteration of what might have been originally organic-cemented, flexible (not rigid) and siliceous agglutinated walls. As such, this microscopic tubular test is identified as Sansabaina acicula, an organic-cemented siliceous-agglutinated foraminifera originally described from the Kungurian Quinnanie Shale in the Carnarvon Basin of Western Australia. The discovery of Sansabaina acicula supports the previous interpretation of the studied strata being deposited in a stressed marine shelf environment. G. R. Shi [guang@uow.edu.au], Sangmin Lee* [lsam@uow.edu.au], Paul F. Carr [pcarr@uow.edu.au] and Brian G. Jones [briangj@uow.edu.au], School of Earth, Atmospheric and Life Sciences, University of Wollongong, Northfields Avenue, NSW 2522 Australia David W. Haig [david.haig@uwa.edu.au], Oceans Institute, The University of Western Australia, 35 Stirling Highway, Perth, WA 6009, Australia.

Authigenic quartz reveals the triple oxygen isotope composition and diagenetic temperature of saline brines

Triple oxygen isotope compositions of authigenic minerals are an emerging tool for the reconstruction of fluid temperatures and the fluid isotopic composition. In this study, we analyzed euhedral authigenic quartz crystals from a halite deposit of the Upper Permian Zechstein evaporitic basin for their triple oxygen isotope composition using laser fluorination isotope ratio mass spectrometry. In the triple oxygen isotope space, additional information, such as the triple oxygen isotope composition of the ambient water, provides insights into equilibrium conditions during quartz formation that cannot be identified from δ18O alone. The triple oxygen isotope composition of authigenic quartz shows, that single oxygen isotope (δ18O) thermometry is not applicable for samples from evaporitic environments, where the fluids' δ18O deviates from dynamic oxygen isotope equilibrium. By combining the Craig and Gordon evaporation model with H2O – SiO2 triple oxygen isotope equilibrium fractionation, we reconstruct the formation temperature of authigenic quartz and the triple oxygen isotope composition of the marine-derived saline brine pore fluid in equilibrium with the quartz. We obtain temperatures of 90 to 130 °C that is interpreted as crystallization temperatures of microcrystalline quartz in pore fluid of halite during burial diagenesis. The triple oxygen isotope composition of authigenic quartz from evaporitic environments is suited as a geochemical tracer for fluid oxygen isotope compositions and ancient fluid or diagenetic temperatures.

The origin of Ordovician siliceous rocks and their deposition settings in the Northwest Tarim Basin, NW China

The siliceous rocks are well developed in Northwest Tarim Basin, which plays an important role in indicating its forming environment. In order to determine the origin of siliceous rock and its deposition settings, the paper studies the petrographic and geochemical characteristics of siliceous rock in well KP 1 and outcrops in Northwest Tarim Basin based on core observation, microscopic section identification and analysis of major and trace elements and rare earth elements. The Ordovician siliceous rocks of Northwest Tarim Basin are mainly developed in the middle and upper Penglaiba Formation and the bottom of the Yingshan Formation. Three types of cherts are identified, including cryptocrystalline silica, microcrystalline quartz and fibrous chalcedony depending on the mineral morphology. The terrigenous source is best evidenced by the high Ti (160∼310 ppm) and Al (1300∼3180 ppm), and positive δ30Si (0.9–3.6‰). Whereas, hydrothermal processes can be inferred from relative high content of V, Ni, Sr, Mo and Ba, and no obvious Ce and Eu anomaly. The chert of well KP 1 and Kuluxi profile is deposited in continental-margin settings, which is evidenced by its Al2O3/(Al2O3 + Fe2O3) (0.58–0.94, average of 0.81) and its Lan/Cen ratio (0.76–1.02, average of 0.93). The continental-margin settings are also evidenced by the close relation between silicification and dolomitization. Silicification is commonly well developed where dolomitization occurs, because the dolomitization mainly occurs in the regression background, where provides more terrigenous source silica to the sea water and results in more silicification. This study highlights the origin of Ordovician siliceous rocks and the outcome from this new contribution may provide useful guidelines for hydrocarbon exploration in the basin and other global analogues.

Enrichment mechanism of organic matter and silicon in lower Cambrian shale of the Yangtze Platform

Early Cambrian time witnessed accumulation of high-quality organic-rich siliceous shale deposits that comprise an especially promising shale gas exploration target, especially in China. The present study of the Cambrian Niutitang Formation of the shelf area of the Upper Yangtze Platform utilizes mineralogical and elemental geochemical data to aide in the paleoenvironment reconstruction of these organic-rich deposits. We are especially interested in elucidating organic carbon and silicon enrichment mechanisms of the Niutitang Formation that will benefit shale gas exploration and development of these deposits. The Niutitang Formation can be subdivided into three intervals based on lithology, gamma ray (GR) signature, and TOC abundance. Enriched TOC (average = 6.7%) and nano-size authigenic microcrystalline quartz (Qn) contents of Interval I deposits likely reflect deposition in an environment that experienced persistent euxinic and elevated organic matter delivery associated with enhanced paleoproductivity driven by hydrothermal activity. Interval II shale is interpreted to have accumulated under euxinic-ferruginous conditions that experienced the effects of robust paleoproductivity and diminished terrigenous input related to persistently warm, humid climatic conditions. Enriched TOC (average = 4.9%) and moderate microcrystalline quartz content of these deposits were likely the result of redox conditions and elevated paleoproductivity. Interval III strata appears to have accumulated under oxygenated bottom conditions that experienced moderate paleoproductivity, brackish water and elevated terrigenous detritus input driven by the establishment of cold, dry climatic conditions. The combined results of these conditions are diminished TOC content (average = 0.7%) and enrichment of the sediment in terrestrial quartz. The elevated content of authigenic quartz appears to have diminished the reservoir capacity of Niutitang Formation shale. Interval II organic-rich siliceous shale deposits of Upper Yangtze Platform shelf areas, which have the comparable authigenic microcrystalline quartz content, reservoir performance, and greater organic matter abundance as the rift trough, appear to comprise the stratigraphic horizon with the greatest exploration and development potential. Results of the present study offer theoretical guidance for future shale gas exploration and development efforts in geologically similar regions.

Exceptional In Situ Preservation of Chondrocranial Elements in a Coniacian Mosasaurid from Colombia

The first record of well-preserved chondrocranial elements in mosasaurids is here described. These elements are preserved in situ in a Coniacian skull found in north-central Colombia, inside a calcareous concretion. Based on a 3D model generated from computed tomography scans, we identified elements of the nasal and orbitotemporal regions. Our descriptions show that in this specimen, the chondrocranium was reduced, more so than in most lacertilians (including their closest recent relatives, the varanids), but not as severely as in snakes or amphisbaenians (which have an extremely reduced chondrocranium and limbs). The new evidence suggests that the reduction in the chondrocranium in mosasaurids could be related to modification of their limbs when adapting to aquatic environments, but also that in mosasaurids, the olfactory tract was reduced, and the optic muscle insertions occurred mainly in the interorbital septum. The exceptional preservation of the chondrocranial elements in the specimen is facilitated by a gray mineralization covering them. XRD analysis and thin section observations indicated that this mineralization is composed of microcrystalline quartz and calcite. We infer that this material was produced by a partial silicification process promoted by lower pH microenvironments associated with bacterial breakdown of non-biomineralized tissues during early diagenesis.

A multi-source proxies approach to identifying local processes in lower Permian black shale impacting on the sedimentary environment of eastern Palaeo-Tethys Ocean

Foreland basin tectonics along the eastern Palaeo-Tethys Ocean produced a complex and dynamic pattern of sediment delivery to adjacent basins. Environmental processes at the local scale significantly disrupt regional ones, making the analysis of sedimentary evolution difficult. This study investigated the Lower Permian Liangshan Formation black shale formed in such geological setting, rich in cherts with exceptionally high silica and fluctuating major and trace element concentrations, detected using XRD, XRF, and ICP-MS techniques. Different types of silica, including detrital quartz, recrystallised radiolaria, microcrystalline quartz, and quartz veins, were identified using SEM and SEM-CL imaging. Geochemical characterisation and enrichment pattern analyses indicated that the structural setting was characterised by proximity to the oceanic island arc, continental island arc, and passive margin, and the major zone of sediment accumulation was a semi-restricted back-arc basin under the subduction zone. The processes controlling sediment accumulation included hydrothermal activity, upwelling, biogenic silica, and terrestrial inputs. Although upwelling interfered with the mobility and migration of hydrothermal elements, it introduced abundant nutrients, and together with hydrothermal fluids, it contributed to the subsequent boom in siliceous organisms. Terrigenous inputs induced by land uplift significantly diluted the components from other sources. This multi-source proxies approach not only enables researchers to disentangle local from regional processes but also sheds light on how these diverse environmental forces interact within intricate earth systems, which enhance our comprehension of geologic history and inform ongoing studies focused on climate change mitigation strategies.

The Lower Silurian Longmaxi rapid-transgressive black shale and organic matter distribution on the Upper Yangtze Platform, China

The characteristics and formation of maximum flooding (MF) black shales are important aspects in defining the geology of fine-grained reservoirs. The MF black shales are located at the bottom of the Longmaxi Formation on the Upper Yangtze Platform, corresponding to graptolite zone LM1. Seismic interpretation, X-ray diffraction entire rock analysis, total organic carbon (TOC) tests, and field emission scanning electron microscopy analysis indicate that the MF black shales have an average content of 49.3% quartz (85% clay size), 10.5% calcite, 8.4% dolomite, and 23.4% clay minerals. The quartz content increases basinward, whereas the clay mineral content decreases. The shale has developed during rapid sea level rise, with a thickness of 0.5–2.8 m that gradually thickens basinward. The TOC content, averaging 5.4%, gradually decreases basinward, with four distinct stacking patterns. The mineral composition and thickness of the Longmaxi shale are related closely to rapid transgression, biology, and volcanism during the period of sedimentation. Rapid transgression has led to a decrease in terrestrial input and shale thickness. In addition, biological activity and volcanism have caused the prevalence of microcrystalline quartz. Shales with high TOC content are related to anoxic conditions, along with low sedimentation rates and high primary productivity. The combination of an anoxic water column, weak dilution, and enhanced organic matter (OM) supply have enhanced the preservation of the OM. The four TOC stacking patterns are related to the water depth. The supply of clay minerals decreases with increasing water depth, whereas the degradation and recycling of OM decrease the TOC content. The sediment accommodation increases with increasing water depth, resulting in four TOC stacking patterns.

Origin of quartz and its implications for different phase fluids in lacustrine shales from the Qingshankou Formation, southern Songliao Basin, China

Quartz, an important mineral that occurs in lacustrine shales, can be of different types and origins. Yet, only few studies have investigated how quartz from different sources contribute to phase fluids, such as adsorbed and free fluids present within shale matrix pores. This study integrates various experimental techniques, including X-ray diffraction analysis, geochemical analysis, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and high-frequency two-dimensional nuclear magnetic resonance analysis to quantitatively characterize the different phase fluids associated with various types of quartz occurring in the Qingshankou Formation shale. The characterization results indicated four distinct quartz types: silt-sized quartz, microcrystalline quartz linked with clay minerals, organism-skeletal quartz, and quartz aggregates comprising multiple crystals. The Fe–Al–Mn ternary diagram and SiO2 versus Zr scatter plot indicate that terrigenous clastic material is the primary source of SiO2 in shale quartz. Smectite-to-illite transition plays a pivotal role in authigenic quartz formation. Based on quartz concentration data obtained using major element analysis, we estimated the ranges of terrigenous clastic quartz, diagenetic quartz formed by the smectite-to-illite transition, and biogenic quartz concentrations to be from 55.49% to 92.03% (average 84.70%), 6.67%–20.30% (average 13.12%), and 0%–24.21% (average 2.17%), respectively. The solid organic matter in shale is affected by both terrigenous detrital quartz and authigenic quartz transformed from the clay in the basin. Authigenic quartz, formed by the smectite-to-illite transition, considerably enhances the development of solid organic matter in the Qingshankou Formation. By contrast, an abundance of terrigenous detrital quartz can lead to a dilution of the solid organic matter. Thus, this study provides the first direct evidence that along with a high value of bio-organic matter yield factor, the source of quartz plays a significant role in controlling organic matter abundance.

Estimation of the Transverse Wave Velocity in Siliceous Carbonate Reservoirs of the Dengying Formation in the Gaoshiti–Moxi Area, Sichuan Basin, China

Siliceous minerals of the Dengying Formation in the Gaoshiti–Moxi area in the central Sichuan Basin exhibit four types of quartz crystals (cryptocrystalline quartz, chalcedony, microcrystalline quartz, and megacrystalline quartz) and three structural types: cryptocrystalline, microcrystalline, and mosaic (laminated mosaic, window-hole interrupted mosaic, and arc-laminated mosaic). Siliceous minerals have a great influence on the storage performance of the reservoirs in the Dengying Formation. According to the petrophysical parameters of the Dengying Formation and porosity intersection diagrams, the siliceous dolomite and the reservoirs have low impedance characteristics, which makes it difficult to distinguish between them and leads to difficulties in the characterization and prediction of the reservoirs. The transverse wave velocity is favorable for reservoir characterization. Currently, the main method used to estimate the transverse wave velocity is petrophysical modeling, which establishes a relationship between the elastic and physical parameters of the reservoir. In this paper, the siliceous minerals in the dolomite in the study area are regarded as solid inclusions, and the calculation method of the rock matrix modulus is improved by using solid replacement. Then, an improved petrophysical model is constructed by combining the KT (Kuster–Toksöz) model, the DEM (Discrete Element Method) model, the Gassmann equation, and the Wood equation. The transverse wave velocity is estimated using the improved model under the constraint of the longitudinal wave velocity. The shapes of the transverse wave velocity curves obtained by the improved model and the deviations from the measured velocities are significantly better than those of the Xu–Payne model and other models. The results show that the improved model can effectively estimate the transverse wave velocity of the reservoir in this area, which provides a basis for future reservoir predictions in this area.

Genesis of Devonian volcanic-associated Lahn-Dill-type iron ores — part I: iron mobilisation and mineralisation style

Fe-oxide deposits of the Lahn-Dill-type in the eastern Rhenish Massif comprise haematite and quartz with minor siderite, magnetite, and calcite. The deposits are located in the hanging wall of thick volcaniclastic rock sequences and mark the Middle to Late Devonian boundary. Varying ore types with accompanying footwall rocks were sampled from two formerly important ore deposits, the Fortuna mine (Lahn syncline) and the Briloner Eisenberg mine (East Sauerland anticline), in order to elucidate the interplay of processes leading to ore formation. Deposit geology, petrography, and whole-rock geochemistry suggest that the ores formed by iron mobilisation from deeply altered footwall volcaniclastic rocks, subsequent venting of a modified H2O-CO2-Fe-rich and H2S-poor fluid, and precipitation on the seafloor (sedimentary-type), or locally by metasomatic replacement of wall rocks (replacement-type). Petrographic analysis to the sub-micron scale revealed that the sedimentary-type ores most likely formed from a Fe-Si-rich gel and accompanying maturation. Early gel textures include the presence of spherules, aggregates, tubes, and filamentous stalks consisting of nanocrystalline haematite dispersed in a matrix of microcrystalline quartz. Local diagenetic Fe3+ reduction within the gel is indicated by siderite replacement of haematite. Replacement-type ores formed due to a two-step process including coprecipitation of (precursor) haematite and carbonates and subsequent metasomatic replacement by haematite. These ore-forming processes took place during a time when several restricted shallow marine basins in the north-eastern Rheic Ocean were influenced by extensive volcanism and associated hydrothermal fluid flux. Examples of similar volcanic-associated Fe-oxide occurrences of Silurian to Carboniferous age can be categorised as being of Lahn-Dill-type ores as well.

Silicified unicellular green microalga as a significant oil source in the Late Paleozoic alkaline lake-playa deposit, Junggar Basin, NW China

Siliceous mudstones and chert-shale couplets are primary source rocks for many large paleo-oil reservoirs over the world. It is well established that photosynthetic organisms can be exceptionally well preserved in silica precipitates, but the fate of the trapped organic matter (OM) during burial remains poorly studied. Here, dense unicellular microbial fossils have been recently discovered in the cherts of the Late Paleozoic alkaline saline lake deposit in NW Junggar Basin, NW China. We use petrographic observations and organic geochemical analysis to study the origin of unicellular microbes and how silicified organic matter generate and expel hydrocarbons. A 300-m-long oil shale core shows overall low levels of porosity, permeability and total organic carbon contents (generally <0.5 wt%), but very high extracts (on average 0.26 wt%), suggesting that the rich extracts were mostly indigenous and the original organic matter had a high hydrocarbon conversion. Analysis of biomarkers and silicified fossils both suggest that the bio-precursor for the organic matter is a special green alga. Reconstruction of silica diagenesis of cherts indicates that both the trapped lipids and hydrocarbons in silicified microbial cells and extracellular polymeric substances had been effectively expelled out during the transformations of Opal-A to microcrystalline quartz and during OM thermal maturation. Exceptional OM preservation and effective oil expelling ways render siliceous source rocks as excellent unconventional hydrocarbon reservoirs.

PRE‐, SYN‐ AND POST‐TECTONIC DIAGENETIC EVOLUTION OF A CARBONATE RESERVOIR: A CASE STUDY OF THE LOWER CRETACEOUS FAHLIYAN FORMATION IN THE DEZFUL EMBAYMENT, ZAGROS FOLDBELT, SW IRAN

Lower Cretaceous carbonates of the Fahliyan Formation form prolific reservoir rocks at oilfields in the Dezful Embayment, central Zagros fold‐thrust belt, SW Iran. The carbonates have undergone significant diagenetic alteration in phases which can in general be linked to the pre‐, syn‐ and post‐tectonic evolution of the fold‐thrust belt. This paper investigates the impact of diagenetic processes on the reservoir quality of the carbonates using integrated petrographic, geochemical and sedimentological analyses of subsurface and outcrop samples of the formation. Diagenetic alterations include:(i) pre‐tectonic eogenesis in the marine and shallow‐burial realm, which resulted in micritization of allochems and cementation by equant and isopachous calcite rims and framboidal pyrite together with limited dolomitization and dissolution of metastable bioclasts. The isotopic compositions of micrite and early calcite cement depart from postulated values of Lower Cretaceous marine carbonates, signifying early stabilization of precursor metastable carbonate minerals and the possible effects of the incursion of meteoric waters and/or increasing burial temperatures;(ii) mesogenesis during the subsequent syn‐tectonic phase, which included Late Cretaceous ophiolite obduction at the northern margin of the Arabian Plate and the later Zagros orogeny in the Miocene‐Pliocene. Diagenetic modifications included the emplacement of hydrocarbons, the development of stylolites and fractures, and the precipitation of saddle dolomite, replacive rhombic dolomite, discrete pyrite, microcrystalline quartz, kaolin and anhydrite. The average stable isotope compositions of saddle dolomite (δ18O: ‐6.9 ‰ ± .9 and δ13C 0.5 ‰ ± 1.6, respectively) also reflects the influence of high temprature basinal fluids;and (iii) “late” (telogenetic, post‐tectonic) uplift‐related modification starting in the Pliocene, when the incursion of meteoric waters resulted in the formation of vugs, the calcitization of dolomite, and cementation by fracture‐filling blocky calcite. The negative δ18O and δ13C stable isotope values (average: ‐5.5 ‰ ± 1.5; and ‐3.6 ‰ ± 5.9, respectively) of late blocky calcite cement suggest the incursion of meteoric water into the system.This study demonstrates that diagenetic processes in carbonates in the Fahliyan Formation, which exerted a significant control on the distribution of secondary porosity, can be related to the tectonic evolution of the central Zagros fold‐thrust belt. Thus, constraining the diagenetic history of carbonate successions within the context of their wider tectonic evolution is important for the prediction of the spatial and temporal distribution of reservoir quality.

Relative Sea-Level Fluctuations during Rhuddanian–Aeronian Transition and Its Implication for Shale Gas Sweet Spot Forming: A Case Study of Luzhou Area in the Southern Sichuan Basin, SW China

Most scholars believe that transgression events can contribute positively to organic matter enrichment and shale gas sweet spot development, while whether or not regression events are conducive to shale gas sweet spot development remains to be further discussed. Variations in organic carbon content (TOC), and major and trace elements at the Rhuddanian–Aeronian stage in the Luzhou area, the southern margin of Sichuan Basin, were analyzed in this paper. We discuss differences in paleoenvironment organic matter enrichment and shale sweet spot development during transgression and regression. A transgressive system tract (TST) occurred during the early Rhuddanian stage, while early highstand system tracts (Ehst-1 and Ehst-2) occurred during the late Rhuddanian stage and Aeronian stage, and a late highstand system tract (LHST) developed during the late Aeronian stage. A rise in sea level during the TST in the upper Yangtze resulted in an anoxic environment, where a continuous upwelling current brought about a large number of nutrients in the seawater, significantly increasing paleoproductivity. Strong tectonic subsidence, weak chemical weathering, and a rising sea level together led to a low terrigenous debris supply in the catchment area. Therefore, paleoproductivity and redox conditions were the primary controlling factors of organic matter enrichment at the TST stage, with a clastic supply of secondary importance. With the advance of the Guangxi orogeny, the organic matter enrichment at the EHST-1, EHST-2, and LHST stages was mainly controlled by redox conditions and debris supply. A comparison of the key physical parameters and geochemical indicators of shale reservoirs from these four system tracts suggests that two shale sweet spot types (type I and II) were developed during the Rhuddanian–Aeronian stage, occurring in the TST and EHST-2 stages. High TOC and high microcrystalline quartz content are key to developing type I sweet spots, while enhanced anoxic conditions in the bottom water caused by ephemeral, small-scale sea level rises are the main determinant of class II sweet spots in the later EHST stage.

Origin of carbonate minerals and impacts on reservoir quality of the Wufeng and Longmaxi Shale, Sichuan Basin

The Ordovician-Silurian Wufeng and Longmaxi Shale in the Sichuan Basin were studied to understand the genesis and diagenetic evolution of carbonate minerals and their effects on reservoir quality. The results of geochemical and petrological analyses show that calcite grains have a negative Ce anomaly indicating they formed in the oxidizing environment of seawater. The high carbonate mineral contents in the margin of basin indicate that calcite grains and cores of dolomite grains appear largely to be of detrital origin. The rhombic rims of dolomite grains and dolomite concretions with the δ13C of –15.46‰ and the enrichment of middle rare earth elements were formed during the sulfate-driven anaerobic oxidation of methane. The calcite in radiolarian were related to the microbial sulfate reduction for the abundant anhedral pyrites and δ13C value of –11.34‰. Calcite veins precipitated in the deep burial stage with homogenization temperature of the inclusions ranging from 146.70 °C to 182.90 °C. The pores in shale are mainly organic matter pores with pore size mainly in the range of 1–20 nm in diameter. Carbonate minerals influence the development of pores through offering storage space for organic matter. When calcite contents ranging from 10% to 20%, calcite grains and cement as rigid framework can preserve primary pores. Subsequently, the thermal cracking of liquid petroleum in primary pores will form organic matter pores. The radiolarian were mostly partially filled with calcite, which combining with microcrystalline quartz preserved a high storage capacity.

Quartz Origins and Paleoenvironmental Controls on Organic Matter Accumulation of Marine Shale in the Ordovician Wulalike Formation, Northwestern Ordos Basin, China: Significance for Shale Gas Exploration

The Ordovician Wulalike marine siliceous shale is a notable hydrocarbon source rock in the Northwestern Ordos Basin. However, the causes of quartz and organic matter enrichment are still a mystery to experts. In this study, the organic geochemistry (maceral compositions, Rbitu, and TOC) and elemental geochemistry (major and trace elements) with mineralogy (XRD) and petrography were jointly acquired to systematically investigate the quartz origins and the paleoenvironment, and the main controlling factors for organic matter enrichment in the Wulalike shale. The results show that the organic matter is type I kerogen with low TOC concentrations (average 0.51%), and that the thermal evolution has reached mature and high mature stages (mean Requ is 1.08%). Three types of quartz are developed in Wulalike shale: biogenic quartz (average 63%) is the most dominant, followed by clastic quartz (average 31%) and microcrystalline quartz (average 6%). Babio and Ba/Al values indicate the low paleoproductivity, which is the primary cause for the low TOC found throughout the area. Redox indexes show the anoxic or dysoxic to oxic conditions from the bottom to the top of the section. Paleoclimate and paleowater depth proxies also changed from the bottom to the top. Various paleoenvironments and sedimentological evidence show that Wulalike shale went through the changing environments, and the early sedimentary environments were conducive to organic matter enrichment, leading to a relatively high TOC. The paleoproductivity and preservation conditions have an impact on organic matter enrichment. Based on the results of biogenic quartz distribution and sedimentary environments, it is considered that the bottom of the Wulalike Formation is the most favorable for shale gas exploration and development.

Siliceous Origin of the Cambrian Qiongzhusi Formation Shale in the Middle Part of the Upper Yangtze Platform: Significance of Organic Matter Enrichment.

The early Cambrian Qiongzhusi Formation shale is rich in organic matter and is a high-quality marine Source rock. However, the origin of Qiongzhusi Formation siliceous rocks is unknown, and the role of siliceous rocks in the process of organic matter enrichment or preservation is also lacking. This study combines thin section, scanning electron microscopy, SEM/EDS, major and trace element analysis, and N2 adsorption experiments to analyze and evaluate the shale of the Qiongzhusi Formation in the central region of the Sichuan Basin. The quartz types in the shale of the Qiongzhusi Formation are divided into four types, namely, bioclastic siliceous rocks, terrestrial detrital quartz, siliceous microcrystalline quartz particles, and microcrystalline quartz aggregates; at the same time, according to petrographic and geochemical parameters, the content of authigenic quartz in Qiongzhusi Formation shale decreases from top to bottom, and terrigenous detrital quartz tends to increase, and biogenic silicon accounts for the majority of authigenic quartz components; autogenous quartz has a positive impact on the pore structure of shale, providing sufficient pore space for the development of organic pores and protecting the internal pore network by forming intergranular pores as rigid frameworks. At the same time, it plays a crucial role in the enrichment and preservation of organic matter.

Origin of Silicate Spherules and Geochemistry of Re and Platinum-Group Elements Within Microfossil-Bearing Archean Chert from the 3.4 Ga Strelley Pool Formation, Western Australia.

Silicate spherules have been identified from the ca. 3.4 Ga-old Strelley Pool Formation (SPF) in the Pilbara Craton, Western Australia. Their origins and geochemical characteristics, including the Re and platinum-group elements of their host clastic layer and the overlying and underlying microfossil-bearing finely laminated carbonaceous cherts, were examined. The spherules have various morphologies (completely spherical to angular), sizes (∼20 to >500 μm), textures (layered, non-layered, and fibrous), mineralogy (various proportions of microcrystalline quartz, sericite, anatase and Fe-oxides), and chemistry (enriched in Ni and/or Cr), commonly with thin anatase-rich walls. Their host clastic layer is characterized by rip-up clasts, suggesting a suddenly occurring high-energy depositional environment, such as tsunamis. Although various origins other than asteroid impact were considered, none could unequivocally explain the features of the spherules. In contrast, non-layered spherical spherules that occur as individual framework grains or collectively comprise angular-shaped rock fragments appear to be more consistent with the asteroid impact origin. The calculated Re-Os age of the cherts (3331 ± 220 Ma) was consistent with the established age of the SPF (3426-3350 Ma), suggesting that the Re-Os system was not significantly disturbed by later metamorphic and weathering events.

Lithofacies Types and Physical Characteristics of Organic-Rich Shale in the Wufeng-Longmaxi Formation, Xichang Basin, China.

The shale of the Upper Ordovician Wufeng Formation and the Lower Silurian Longmaxi Formation in the Xichang Basin is the main replacement horizon for the shale gas exploration being conducted in the Sichuan Province, except for the Sichuan Basin. The fine identification and classification of the types of shale facies are important for shale gas exploration and development evaluation. However, the lack of systematic experimental studies on rock physical characteristics and micro-pore structures leads to a lack of physical evidence for the comprehensive prediction of shale sweet spots. Therefore, the present study used different means, such as core observation, total organic carbon content (TOC), helium porosity measurement, X-ray diffraction analysis, and mechanical properties analysis, in combination with the analysis of the whole rock mineral composition and characteristics of shale, for the identification and classification of the lithofacies of the shale layer, the systematic petrology and hardness measurement of the shale samples with different lithofacies, and discussion of the dynamic and static elastic properties of the shale samples and the control factors. It was revealed that nine types of lithofacies existed in the Wufeng Formation- the Long11 sub-member in the Xichang Basin, among which moderate organic carbon content-siliceous shale facies, moderate organic carbon content-mixed shale facies, and high-organic carbon content-siliceous shale facies were the best lithofacies with the optimum reservoir conditions, providing sufficient space for shale gas accumulation. The siliceous shale facies mainly developed organic pores and fractures, and the pore texture was excellent overall. The mixed shale facies mainly developed intergranular pores and mold pores, with a preference toward pore texture. The argillaceous shale facies mainly developed dissolution pores and interlayer fractures, and the pore texture was relatively poor. The geochemical characteristics of the organic-rich shale samples with TOC > 3.5% revealed that the sample was composed of microcrystalline quartz grains as the rock support framework, while the intergranular pores were located between the rigid quartz grains, which exhibited hard pores in the analysis of their mechanical properties. In the relatively organic-poor shale samples with TOC < 3.5%, the quartz source was mainly terrigenous clastic quartz, and the sample was composed of plastic clay minerals as the rock support skeleton, while the intergranular pores were located between argillaceous particles, which exhibited soft pores in the analysis of their mechanical properties. The difference in the rock fabric of the shale samples resulted in an ″initial increase followed by a decrease″ trend of velocity with quartz content, with the organic-rich shale samples exhibiting low velocity-porosity and velocity-organic matter content change rate, and the two kinds of rocks were easier to distinguish in the correlation diagram of the combined elastic parameters such as the P-wave impedance-Poisson ratio and the elastic modulus-Poisson ratio. The samples dominated by biogenic quartz exhibited greater hardness and brittleness, while the samples dominated by terrigenous clastic quartz exhibited lower hardness and brittleness. These results could serve as a basis for logging interpretation and seismic ″sweet spot″ prediction of high-quality shale gas reservoirs in Wufeng Formation-Member 1 of the Longmaxi Formation.

Geology, geochemistry, fluid inclusion data, stable isotope characteristics, and ore genesis of the Barout Aghaji gold deposit, NW Zanjan, Iran

The Barout Aghaji gold deposit is located ∼90 km northwest of Zanjan, within the Takab-Takht-e-Soleyman subzone of the Sanandaj-Sirjan metamorphosed-deformed zone. Ore-bearing quartz veins are hosted by Neoproterozoic amphibolite and Eocene to Oligocene granitic gneisses. Oligo-Miocene Upper Red Formation unconformably overlies the amphibolite and granitic gneisses. Field observations and petrographic studies show that two deformation stages occurred in this area. The first deformation stage was ductile, producing mylonitic and proto-mylonitic microstructures, but the second one was brittle, represented by sheeted quartz veins and veinlets. In the first stage, barren milky quartz veins occurred containing minor sulfide minerals, but dark to light gray ore-bearing quartz veins and veinlets are formed in the latter stage. The mineralized veins appear as massive microcrystalline quartz cut by sheeted quartz veins with comb, druse, and crustiform textures. The gold-bearing quartz veins contain as much as 3% sulfide minerals. Pyrite is the main sulfide mineral and is associated with minor chalcopyrite. Sulfides are commonly altered to hematite, goethite, and rarely malachite. Hydrothermal alteration around the quartz veins consists of silicification, pyritization, and sericitization. The whole-rock geochemistry of the collected samples from the granitic gneisses and quartz veins shows that Au is enriched in the quartz veins (average of 114 ppb) relative to host rocks (average of 22.5 ppb). Au shows strong positive correlations with As, Ba, Mo, Pb, Sc, Tl, Ag, and negative correlations with Cu, Bi, Se, and Te in the granitic gneisses. It also shows strong positive correlations with S, Hg, Th, Co, Bi, Pb, and Ag and negative correlations with P, V, Te, W, Sc, Zn in quartz veins. Four types of primary fluid inclusions were identified, including type I, two-phase aqueous-rich fluid inclusions (liquid > vapor; LV); type II, two-phase vapor-rich fluid inclusions (gas > liquid; VL); type III, three-phase fluid inclusions containing CO2 with clathrate formation (L1L2V); and type IV three-phase fluid inclusions (aqueous, vapor, and solid; LVS). The homogenization temperatures of fluid inclusions in auriferous quartz veins range from 199 −446 with a mode of 270–300 °C. Salinities range from 0.8 to 49.02 wt% NaCl Equiv. with two distinct populations at 0.8–8.5 and 31.1–49.02 wt% NaCl Equiv. The large variations in the homogenization temperatures and salinities can be attributed to the cooling and isothermal mixing of fluids. The δ34S values for four pyrites separated from auriferous quartz veins range from +2.9 to +7.1‰, with an average of 4.5‰. δ34S values of fluids in equilibrium with pyrite were calculated from +3.5 to +7.3‰, with an average of 5.4‰, indicating a metamorphic source for the sulfur using temperatures estimated from the fluid inclusion study. The Field observations, vein textures, mineralogy, ore geochemistry, fluid inclusion studies, and sulfur isotope data indicate that gold mineralization in the Barout Aghaji area has many similarities to orogenic and intrusion-related gold deposits, such that low salinity fluids derived from metamorphic rocks are mixed with high salinity fluid inclusions possibly derived from granitic gneisses during syn to post tectonic magmatism.