Organic Shale Research Articles

Depositional Heterogeneities and Brittleness of Mudstone Lithofacies in the Marcellus Subgroup, Appalachian Basin, New York, U.S.A.

Organic-rich rocks of the Marcellus subgroup in the study area consist of a diverse suite of mudstone lithofacies that were deposited in distinct facies belts. Lithofacies in the succession range in composition from argillaceous to siliceous, calcareous, and carbonaceous mudstone. Heterogeneities in the succession occurs in the form of varying mineralogical composition, slightly bioturbated to highly bioturbated chaotic matrix, organic-rich and organic-lean laminae, scattered fossil shells in the matrix, and fossils acting as lamination planes. Lithofacies were deposited in three facies belts from the proximal to the distal zone of the depositional system. Bedded siliceous mudstone (BSM) facies occur in the proximal facies belt and consists of a high quartz content in addition to clay minerals and pyrite. In the medial part of the facies belt lies the laminated argillaceous mudstone (LAM), bedded calcareous mudstone (BCaM), and bedded carbonaceous mudstone (BCM). The size of detrital mineral grains in the lithofacies of the medial facies belt is larger than bedded argillaceous mudstone (BAM) of the distal facies belt, characterized by clay-rich matrix with occasional fossil shells and horizontally aligned fossils. Two types of horizontal traces and one type of fecal string characterize the proximal mud-stone facies, whereas only single horizontal trace fossil is found in the mudstones of the medial and distal facies belt. Parallel alignment of fossil shells and fossil lags in lithofacies indicate that bed-load transport was active periodically from the proximal source of the depositional system. Bioturbation has heavily affected all of the lithofacies and presence of mottled burrows as well as Devonian fauna indicate that oxic to dysoxic conditions prevailed during deposition. The deposition of this organic-rich mudstone succession through dynamic processes in an overall oxic to dysoxic environment is different from conventional anoxic depositional models interpreted for most of the organic rich black shales worldwide. Total organic content (TOC) varies from top to bottom in the succession and is highest in BCM facies. The brittleness index, calculated on the basis of mineralogy, allowed classification of the lithofacies into three distinct zones, i.e., a brittle zone, a less brittle zone, and a ductile zone with a general proximal to distal decrease in the brittle behavior due to a decrease in the size of the sediments.

Biostratigraphy and reservoir characteristics of the Ordovician Wufeng Formation—Silurian Longmaxi Formation shale in the Sichuan Basin and its surrounding areas, China

Through graptolite identification in profiles, graptolite zone division, contour map compilation, and analysis of mineral composition, TOC content, lamina distribution features of shale samples, the biostratigraphic and reservoir characteristics of Ordovician Wufeng Formation—Silurian Longmaxi Formation in the Sichuan Basin and its peripheral are sorted out. There are 4 graptolite zones (WF1 to WF4) in Wufeng Formation and 9 (LM1 to LM9) in Longmaxi Formation, and the different graptolite zones can be calibrated by lithology and electrical property. The shale layers of these graptolite zones have two depocenters in the southwest and northeast, and differ in mineral composition, TOC, and lamina types. Among them, the graptolite zones of lower WF2 and WF4 are organic matter-poor massive hybrid shale, the upper part of WF1–WF2 and WF3 have horizontal bedding hybrid shale with organic matter, the LM1–LM4 mainly consist of organic-rich siliceous shale with horizontal bedding, and the LM5–LM9 graptolite zones consist of organic-lean hybrid shale with horizontal bedding. The mineral composition, TOC and lamina types of shale depend on the paleo-climate, paleo-water oxidation-reduction conditions, and paleo-sedimentation rate during its deposition. Deposited in oxygen-rich warm water, the lower parts of WF1 and WF2 graptolite zones have massive bedding, low TOC and silicon content. Deposited in cooler and oxygen-rich water, the WF4 has massive bedding, high calcium content and low TOC. Deposited in anoxic water with low rate, the upper part of WF2, WF3, and LM1–LM4 are composed of organic rich siliceous shale with horizontal bedding and high proportion of silt laminae. Deposited in oxygen rich water at a high rate, the graptolite zones LM5–LM9 have low contents of organic matter and siliceous content and high proportions of silt lamina.

Upper Jurassic to Lower Cretaceous source rocks in the Norwegian Barents Sea, part II: Insights from open- and closed-system pyrolysis experiments

The petroleum generation potential of Upper Jurassic to Lower Cretaceous organic rich shales from the southwestern Barents Sea was evaluated using bulk and quantitative pyrolysis analysis. Fifteen thermally-immature samples from the Hekkingen Formation with differing organic facies, as defined by maceral composition, were subjected to total organic carbon, Rock-Eval pyrolysis, pyrolysis gas chromatography, bulk kinetics, and micro-scale sealed vessel pyrolysis analyses. The results were employed to characterize differences in source rock kerogens, gross petroleum type, and the compositional evolution of the generated fluids as well as their physical properties (i.e. gas to oil ratio, saturation pressure, and formation volume factor) as a function of increasing maturity.The investigated samples contain varying proportions of kerogen type II and III. Heterogeneities in the kerogen composition result in different orders of thermal stability, with the onset of petroleum generation predicted to occur over a high and broad temperature range from 123 °C to 144 °C (at 3.3C⁰/Ma). Reduced kerogen stability associated with elevated sulfur contents is only documented in a few samples. Most of the analyzed samples have the potential to generate low GOR oils of an intermediate to aromatic, low wax paraffinic-naphthenic-aromatic (P–N-A) composition and variable amounts of wet gas. Petroleums of similar compositional and physical properties are predicted to have been generated from the natural maturation sequence of various organic facies in thermally mature areas of the Hammerfest Basin and the Ringvassøy-Loppa High and Bjørnøyrenna fault complexes. Vitrinite-rich sources in the Fingerdjupet Sub-basin and the Troms-Finnmark Fault Complex have potential for gas and condensate generation.

Organic matter heterogeneity and shale oil significance in Triassic Zhangjiatan shale, Ordos Basin, China

Organic matter heterogeneity exerts an important impact on the generation, evaluation, and exploitation of shale oil resources. In the past, only a limited number of analytical samples that represented the contribution or influence of high or low organic matter abundance intervals were used to represent an entire set of thick source rocks, and based on this limitation, occasionally researchers have reached incorrect conclusions. Here, the heterogeneity of organic matter and its significance to shale oil in the Triassic Zhangjiatan shale of the Ordos Basin were discussed based on sedimentary and geochemical analyses. Our results indicate that (1) the Chang 73 shale within the study area is characterized by high abundance, good quality, strong heterogeneity, and segmented enrichment in the vertical profile. The primary organic matter type was type II1, and this was followed by types I, II2, and III that exhibited three changing trends in the vertical profile. Organic matter maturity is primarily at the immature stage. (2) Additionally, we observed that the organic matter heterogeneity of Chang 73 shale was related to changes in lithology, sedimentary environment, paleoproductivity, terrigenous influence, and event action (such as volcanism and hydrothermal processes). The abundance of organic matter is the result of the coupling control of these processes. In the process of organic matter deposition, if volcano or hydrothermal activities occurred, the organic matter was abnormally enriched, and the total organic carbon content exceeded 20% and could even be as high as 40%. (3) Finally, we observed at least nine enrichment layers that were controlled by the coupling of different geological factors, and there were four potential target resource layers corresponding to the hydrothermal sedimentary area.

A Molecular Dynamics Investigation on Methane Flow and Water Droplets Sliding in Organic Shale Pores with Nano-structured Roughness

Roughness of surfaces significantly influences how methane and water flow in shale nanopores. We perform molecular dynamics simulations to investigate the influence of surface roughness on pore-scale transport of pure methane as well as of two-phase methane–water systems with the water sliding as droplets over the pore surface. For single-phase methane flow, surface roughness shows a limited influence on bulk methane density, while it significantly reduces the methane flow capacity. In methane–water systems, the mobility of water is a strong function of surface roughness including a clear transition between immobile and mobile water droplets. For cases with mobile water, droplet sliding speeds were correlated with pressure gradient and surface roughness. Sliding water droplets hardly deform, i.e., there is little difference between their advancing and receding contact angle with structured roughness.

Absolute adsorption of light hydrocarbons on organic-rich shale: An efficient determination method

Absolute adsorption has been found being more accurate than directly measured excess adsorption value for estimating the in-situ shale gas-in-place storage. To obtain accurate absolute adsorption, traditional methods determined the adsorbed gas density using complicated molecular simulation methods, which is employed to correct the measured excess value. In this work, excess adsorption, which is deemed to be inaccurate in previous work, of CH4 and C3H8 is first measured on three typical shale rocks. The adsorbed-layer density is then reasonably calculated using the simplified local density theory (SLD) to obtain corresponding absolute adsorption of CH4 and C3H8. It is found that the adsorbed layer density calculated from SLD theory is comparable to that obtained from molecular simulation methods, while it is more efficient for the density computation. Compared to CH4, C3H8 presents stronger adsorption capacity on shale rocks, suggesting that C3H8 is more affinity to organic shale. The CH4′s absolute adsorption is stronger than its excess value and their deviation enlarges as pressure increases, while absolute adsorption for C3H8 is found to be more or less the same with the measured excess value. The importance of this work lies in that we propose a new method for efficiently obtaining the adsorbed-layer density, which is crucial for accurately determining gas and oil storage in shale reservoirs.

Determining crack initiation stress in unconventional shales based on strain energy evolution

Abstract Determining the crack initiation stress (Ci) for unconventional shale rocks is of critical importance in describing the entire failure process of unconventional shale reservoirs. We propose a new method to identify Ci values based on triaxial failure tests on four organic shale samples, attempting to improve the shortcomings of other methods. The new method is based on the relationship between crack development and strain energy evolution (SEE). Additionally, the proposed SEE method is compared with three widely used methods, including crack volumetric strain (CVS), moving point regression (MPR) and the lateral strain response (LSR), intending to examine the performance of different methods. The contrastive results indicate that the LSR method cannot determine Ci when the rock ruptures without volumetric dilatancy, which frequently occurs in the compression process of organic shales. Ci values obtained using the SEE method are consistent with those from the CVS and MPR methods. However, the proposed SEE method with a solid physical basis is more objective and stable than the CVS and MPR methods. The proposed method, from one aspect, compensates for the shortcomings of other methods when facing different failure modes in organic shales. From the other aspect, it provides a way to precisely determine Ci values for applications in wellbore stability evaluation and hydraulic fracturing design.

Grid filtering method for shale reservoir 3-D property modeling using horizontal well data

Wells drilled in the core area of shale reservoir are predominantly horizontal compared to vertical wells in conventional reservoirs. Due to the different features of data in horizontal and vertical wells, the 3-D property modeling of shale reservoirs is distinct from the conventional reservoirs. Lateral drilling usually leads to the repeated sampling in the specific vertical intervals and the missing sampling in the bottom part of the shale reservoir. This biased sampling distorts the distribution characteristics in well data from the real reservoir properties. Moreover, because of the large inclination angle in the laterals, it is so common to penetrate only the upper or lower part of the grid. Given that the same method is utilized to assign well values to these partially penetrated girds and fully penetrated grids, the assigned value in these partially penetrated grids fail to represent the reservoir property in the associated grid layer. Therefore, we developed a grid filtering method to solve the issues arised from the biased sampling and the partially penetrated grids. It includes five parts: (1) divide wellbore into multiple well segments using formation top data; (2) recognize the type of well segments and well-penetrated grids to generate a grid filter; (3) process the log-format data of each complete sampling segment using the grid filter; (4) generate one dataset for analyzing distribution features and another dataset as the control points of geostatistic simulation algorithms; (5) build the 3-D property models using the analyzed distribution features and the control points as the input. By generating two independent datasets, we achieved the maximum utilization of log-format data in horizontal wells and eliminated the biased sampling effect. The total organic carbon content and shale lithofacies in the JY-1 district, Jiaoshiba Area, Eastern Sichuan Basin, were used to demonstrate our method.

Seismic Characteristics of Mud Diapir in Song Hong Basin, Offshore Vietnam

Seismic characteristics of mud diapir has been investigate over an area of 3900 km2, located in the central part of Song Hong basin, using four 2D seismic lines. There are six mud diapirs and three mud pipes have been documented. The core of the diapir is characterized as a zone of chaotic, disrupted seismic reflection, with the amplitude reflection ranging from low the high. High amplitude reflections are distributed in the top of the some diapir, which is possibly related to the gas accumulation. They are in different sizes, shapes, and the relationship with surrounding rock. They are characterized as deep sourced, high energy rooting from Oligocene/early Miocene shale layers. This organic rich shale rocks are in the oil and gas windows, thus their hydrocarbon generation combining with the tectonic inversion during Miocene make the overpressured shale and therefore rising the diaipirs. The area has experienced several phases of eruption in Middle Miocene, Late Miocene, Late Pliocene and Present day. The discovery and identification of the occurrence of mud diapirs implied a great potential for prediction of structural traps in the central part of the Red River Basin.

Organic geochemical characteristics and shale oil potential of the middle Eocene early-mature shale in the Nanpu Sag, Bohai Bay Basin, Eastern China

The decline of proven conventional petroleum resources in the shallow portions of the Nanpu sag has shifted attention to the exploration of deep unconventional oil and gas resources there, especially the shale oil resources in the middle Eocene shales of the Shahejie Formation (MES shales). In this study, to assess the oil potential of the MES shales, we carried out a systematical geochemical and basin modeling characterization. The results show that the MES shales have low maturity and are at the early stage of hydrocarbon generation, with a mean vitrinite reflectance of 0.64% and low ratio of C27 18α(H)-22, 29, 30-trisnorneohopane to C27 17α(H)-22, 29, 30-trisnorhopane (0.44–1.18). The MES shales contain abundant organic matter (OM), with an average total organic carbon content of 2.21 wt %. Biomarker analyses show that the OM in the MES shales derived mainly from floating macrophyte and aquatic algae, microalgae and bacteria. The sapropelinite group in the MES shales is predominant in the organic macerals, and the kerogen is sapropelic and dominated by types I and II1. Biomarker analyses also reveal that the MES shales were deposited in the stratified water column as suggested by the presence of gammacerane, under relatively warm and wet climatic conditions. The anoxic conditions built up in the water column facilitated the OM preservation, although slight microbial degradation resulted in relatively high carbon preference index values. Modeling results based on geochemical data and basin analyses show that considerable quantities of hydrocarbons remain in the low-maturity MES shales. The preliminary estimate of the quantity of shale oil resources in the Gaoliu area of Nanpu sag is approximately 1.78 × 108 t. Nanpu sag have good shale oil potential, and shale oil exploration may be more feasible for MES shales, especially in the context of in-situ heating technology.

Geochemical Characteristics of the Middle Devonian Dacaozi-Tanshanping Shale Strata in the Yanyuan Basin, Southwest China: Implications for Organic Matter Accumulation and Preservation

How the geochemical characteristics of organic matter shale for the carbonate platform facies remain uncertain, which restricts an integrated reconstruction of the model of organic matter accumulation and preservation. Here, we present new results from element geochemical fingerprinting and integrated analyses of paleoclimate, paleoproductivity, paleoredox environment, and terrigenous input of the targeted Middle Devonian Tanshanping and Dacaozi Formations in the Ninglang-Yanyuan Basin, Southwest China. It is worth noting that although the carbonate platform connects with the open sea partially, the redox environment will not be completely controlled by relative sea level variations. Specially, the paleoclimate, paleoproductivity, and paleoredox conditions are the main controlling factors of the accumulation and preservation of organic matter. In view of the paleoclimate indexes, we suggest that both a relatively warm-humid climate characterized by intensified chemical weathering conditions and a higher terrigenous input are identified as two major drivers forcing the reductive environment in the sedimentary waterbody. Finally, a comprehensive model is established for providing new insights into the mechanism of organic matter accumulation and preservation for the carbonate platform facies. The paleoredox environment, paleoproductivity, paleoclimate, and terrigenous input are believed to have exerted a very considerable force on reconstructing the model of organic matter accumulation and preservation for the carbonate platform facies. Specially, the coupling interactions between the paleoproductivity and redox condition are thus also stressed. We found that the preservation condition is much more important than the paleoproductivity, resulting in the degree of organic matter enrichment. Even if the paleoproductivity of a sedimentary waterbody of a depositional period of the Dacaozi Formation was higher, the TOC concentrations were relatively low due to the poor preservation condition by fall of the sea level and increase of the terrigenous input. In another aspect, the better preservation condition of the Tanshanping Formation makes the TOC concentrations higher in the case of lower paleoproductivity in the sedimentary waterbody.

Geochemical characteristics and geological significance of humid climate events in the Middle-Late Triassic (Ladinian-Carnian) of the Ordos Basin, central China

Many Middle-Late Triassic (Ladinian-Carnian) global and local humid climate events that impacted on global palaeontological evolution and mineral distribution have been recorded in the rocks. The lacustrine sedimentary sequence of the Yanchang Formation in the Ordos Basin in the northeastern Tethys region may be an important example of control by global humid climate events. As revealed by an established chronostratigraphic framework and the study of organic carbon isotopes, elemental geochemistry and clay minerals, the Chang 7 Member of the Yanchang Formation was deposited in the Ladinian-Carnian, and the high total organic carbon (TOC) and total nitrogen (TN) contents indicate the high productivity of the ancient lake. The observed elemental ratios (Sr/Cu, Rb/Sr and Al2O3/MgO) and high contents of mixed-layer smectite indicate humid climate events in the Chang 73 and Chang 71 members. The increases in weathering degree, surface temperature and terrigenous clastic material input indicate enhancement of the hydrological cycle driven by a warm-humid climate. The arid-wet transitions, the negative excursions of the studied organic carbon isotope and the temperature fluctuations during the deposition of the Chang 73 and Chang 71 members of the Yanchang Formation are consistent with the Carnian humid event (CHE) and Ladinian-Carnian humid interval (L-CHI). The palaeontological diversity and the development of organic shales, turbidity currents and sandy debris flows in the Chang 7 Member may represent the continental sedimentary responses to coeval global humid climate events. The isochronous eruptions of volcanoes around the Ordos Basin may have intensified the global greenhouse effect and become an important factor driving the multi-stage humid climate events in the Ordos Basin.

Study of a Polyamine Inhibitor Used for Shale Water-Based Drilling Fluid.

Here, we report a water-soluble shale inhibitor for inhibiting shale hydrate formation. The copolymer denoted as thermogravimetric analysis (TGA) was synthesized via triethanolamine, two maleic anhydrides, and glacial acetic acid. The infrared (IR) and gas chromatography (GC) results indicated that TGA is a low molecular weight polymer inhibitor (IR) and is the most commonly used method to identify compounds and molecular structures qualitatively. It is mainly used to study the molecular structure of organic substances and conduct qualitative and quantitative analyses of organic compounds. The main function of GC is for polymer molecular weight analysis. With the aid of shale rolling recovery experiments, particle size distribution experiments, triaxial stress experiment methods, bentonite slurry rate inhibition experiments, and thermogravimetric experiments to evaluate TGA inhibition characteristics, the inhibition effect of TGA is better than that of the traditional inorganic salt inhibitor KCl, polymer amine inhibitor UHIB, and organic cationic shale inhibitor NW-1. When the mass fraction is 0.2%, the cutting recovery rate increases from 18.3 to 94.1%. The compressive strength of the shale core after adding 1% TGA inhibitor is 177.9 MPa, which is close to the original core compressive strength of 186.5. The wet sodium montmorillonite crystal layer spacing after treatment with 0.5%, 1.5%, and 3% TGA aqueous solution is 1.38, 1.35, and 1.35 nm, respectively, and the sodium montmorillonite crystal layer spacing after diesel treatment is 1.34 nm, indicating that the inhibitory effect of TGA on sodium montmorillonite is equivalent to that of diesel and that TGA can effectively inhibit the hydration and dispersion of sodium montmorillonite. At the same time, the crystal layer spacing and the weight loss rate of sodium montmorillonite modified by TGA inhibitors did not change significantly after adsorption of deionized water, which proved that TGA inhibitors could be adsorbed in the crystal layer space of sodium montmorillonite to inhibit hydration and dispersion of sodium montmorillonite. Field test results show that TGA can significantly improve the inhibition performance of the field drilling fluid, and the effect is better than the strong conventional inhibition water-based drilling fluid system, which solves the problems of wellbore instability and considerable friction in horizontal shale sections and provides a new idea and method for efficient shale gas drilling.

Genetic model for Jurassic shale-hosted Zn-Pb deposits of the Arak Mining District, Malayer-Esfahan metallogenic belt: Insight from sedimentological, textural, and stable isotope characteristics

The genetic model, including conditions under which mineralization formed, and relative timing of mineralization are critical questions for SEDEX (or shale-hosted massive sulfide, SHMS) deposits. There is increasing awareness that sub-seafloor replacement is an important process in the formation of some SEDEX deposits. We have studied the Hossein-Abad and Western Haft-Savaran Zn-Pb SEDEX deposits located in the Arak basin of the Malayer-Esfahan Metallogenic Belt, Iran, to address these questions of genesis. This metallotect formed in a back-arc paleotectonic setting as a result of the subduction of the Neo-Tethys oceanic plate beneath the Sanandaj-Sirjan Zone. The rocks that host the mineralization are Jurassic organic matter-bearing, fine-grained sandstones, siltstones, and shales. Asymmetric lenticular bedding, unidirectional flow (based on oblique silt lamination direction relative to horizontal bedding), graded bedding, and clay-rich interbeds indicate sediments were deposited from turbidity currents in a low-energy basin environment.There are three ore facies in the Hossein-Abad and Western Haft-Savaran Zn-Pb deposits: 1) bedded ore; 2) massive ore; 3) feeder zone. Bedded ore contains pyrite framboids and polyframboidal clusters. The size range of the pyrite framboids (3 to 6 µm in diameter) indicates they formed in the water column and not in the subsurface. Characteristic structures in bedded ore are: 1) sulfide-bearing silt injections into clay-filled burrows, 2) injection of sulfide-bearing silt into flame structures of claystone laminae, and 3) organic matter in claystone oriented obliquely relative to bedding. These structures are the result of seismic deformation induced by synsedimentary earthquakes, whereby sulfides that formed in permeable unconsolidated sediment were injected into the organic matter-bearing claystone unit.The δ18O and δ13C values of siderite, calcite and dolomite in veins from the feeder zone and massive ore range from 12.2 to 23.8‰ and −16.7 to 1.7‰, respectively. These values indicate that formational water, seawater and organic matter oxidation-decomposition all played a role in hydrothermal carbonate formation. Melting and homogenization temperatures for CO2 for CO2-bearing fluid inclusions range from −57.5 to −60 °C and 6.6 to 29.5 °C, respectively, and indicate the presence of < 15 mol percent CH4. The CO2 homogenization temperature range suggests the CO2-rich phase is a CO2-CH4 mixture. The CH4 and CO2 in the H2S-bearing fluid were likely generated by biodegradation and oxidation of organic matter via BSR and methanogenesis.The sulfur isotope compositions of pyrite, galena, sphalerite and chalcopyrite from the feeder zone and the massive ores range from δ34S −4.3 to + 7.2‰ and display equilibrium fractionations, indicating that the sulfur originated from two processes: (a) bacterial reduction of seawater sulfate (BSR) (distal from mineralization site), and (b) thermochemical reduction of seawater sulfate (TSR) (in both massive ore and feeder zone). Sulfur isotope geothermometric calculations (Δgalena-sphalerite) for two samples give temperatures in the range 209–224 °C for the massive ore facies. Such high temperatures negate a contribution of sulfur from BSR. However, BSR likely occurred in sediments distal to the feeder zone, where seawater sulfate was bacterially reduced to H2S, and this H2S migrated to the mineralization site during diagenesis. Collectively, the stable isotope data indicate mineralization formed in response to mixing occurred between ascending hot metalliferous hydrothermal fluid that rose up the fault and fracture network, with H2S-bearing fluid and sulfate-bearing percolating seawater, triggering sulfide deposition.

Biomarker Geochemical Evaluation of Organic Rich Shales in Mamfe Basin, Cameroon

The Mamfe Basin is an intra-continental basin in southwestern Cameroon. Shale from Cretaceous strata in the Mamfe Formation has been poorly characterized in terms of their palaeo-environmental conditions and origin of the organic matter. Also, the thermal maturity of the shale has not been well established. The aim of this study is to determine the origin of the organic matter, evaluate the thermal maturity, palaeo-environmental conditions, and thereby deduce their hydrocarbon generative potential. Biomarker geochemical analyses was carried out on the organic matter extracts of some selected shale samples from Mamfe Formation having total organic carbon content ranging from 0.69 and 4.50 wt. % (av. =1.82 wt. %). Base on the total organic carbon content, the shales are described to have good hydrocarbon generative potentials. Thermal maturity parameters base on 20S/(20S +20R), and ββ/(ββ + αα) C29 sterane ratios along with CPI and OED indicate that the analysed samples from Mamfe Formation sit at mature oil window generation. The origin of the organic matter have been deduced to be mainly of terrestrial plant source with minor lacustrine and marine influences. Palaeo-environmental conditions were decipher to be of sub-oxic to anoxic conditions that have preserved the organic matter. This study have highlight valuable insight based on the biomarker geochemistry of the shales of the Mamfe Basin thereby reducing petroleum exploration risk.

Sedimentary Evolution Characteristics of Fine-Grained Lithofacies under the High-Resolution Isochronous Shelf System: Insights from the Wufeng-Longmaxi Shales in the Sichuan Basin

Abstract The deposition and evolution of fine-grained sediments is a hot topic in fine-grained sedimentary rock studies and is important for accurately evaluating shale gas sweet spots. In this paper, the fine-grained deposition and evolution characteristics of the Wufeng-Longmaxi shales, major targets for Chinese shale gas exploration, were studied by using core observations, thin section analyses, scanning electron microscopy, geochemical analysis, and fossil identification. This work accurately identified six typical lithofacies; among them, the organic matter-rich siliceous shale facies (OMRSSF), the high-organic matter siliceous argillaceous shale facies (HOMSASF), and the medium-high organic matter low calcareous siliceous shale facies (M-HOMLCSASF) are favorable facies for shale gas exploration. The high-resolution isochronous unit in the shelf fine-grained sedimentary system was established, and the differential evolution of lithofacies in the system tract was discussed. The lithofacies deposition and differentiation in the transgressive system tract were controlled by the transgressive scale and tectonics under increasingly shallow water conditions. The lithofacies deposition and differentiation in the regressive system tract were controlled by tectonics and the preexisting lithofacies. The lithofacies in the regressive system tract had more frequent facies transitions and greater differentiation than those in the transgressive system tract, and they exhibited significant spatiotemporal inheritance. Sequential differential sedimentary sequences and symmetric differential sedimentary sequences were distinguished in the continental shelf sedimentary system. The lithofacies depocenters and subsidence centers were consistent in the transgressive system tract, while the tectonically active paleocontinent was important in the regression system tract. This study is of great significance for further high-resolution exploration of marine shale and improvement of the theory of shelf fine-grained sedimentary systems.

Gold in the Farallones Block of the Shale-Hosted, Clastic-Dominated Castellanos Zinc-Lead Deposit (Northwest Cuba)

The Zn-Pb ores of the Castellanos shale-hosted, clastic-dominated deposit in northwest Cuba average nearly 1 g/t Au, with local maximum concentrations up to 34 g/t Au. This deposit is stratiform with respect to the bedding in the host black shales and shows a bottom to top zoning of ore assemblages made up of a stockwork underlying the main orebody, a basal pyrite-rich zone and a disseminated to massive Zn-Pb ore zone capped by a discontinuous, thin barite-rich zone. Petrographic data and textural relations allow distinguishing five textural types of pyrite (framboidal Py I, colloform Py IIa, euhedral Py IIb, massive Py IIc and banded colloform Py III) successively formed during ore deposition. The main Zn-Pb ore formed after the crystallization of disseminated, sedimentary framboidal pyrite (Py I) in black shales by the superimposition of several crystallization events. The crystallization sequence of the main ore-forming stage evolved from the precipitation of colloform sphalerite and pyrite (Py IIa) with skeletal galena and interstitial dolomite-ankerite to similar ore assemblages but showing subhedral to euhedral crystal habits (Py IIb) and interstitial calcite-rich carbonates. This stage ended with the development of massive pyrite (Py IIc), mainly occurring at the base of the stratiform orebody. A late fracturing stage gave way to the development of a new generation of colloform banded pyrite (Py III) just preceding the crystallization of early barite. Au is mainly concentrated in pyrite showing variable contents in the different textural types of pyrite and a bottom to top enrichment trend. Minimum contents occur in massive pyrite (Py IIc) from the basal pyrite-rich zone (0.18 ppm Au average), increasing in pyrite IIa (from 0.29 to 2.86 ppm Au average) and in euhedral pyrite (Py IIb) (from 0.82 to 9.02 ppm Au average), reaching maxima in colloform banded pyrite (Py III) formed just before the crystallization of early barite at the top of the orebody. Au enrichment in pyrite correlates with that of Sb (0.08–4420 ppm), As (0.7–35,000 ppm), Ag (0.03–1560 ppm) and to a lesser extent Cu (3–25,000 ppm), Ni (0.02–1600 ppm) and Mn (0.6–5030 ppm). Au deposition should have taken place by oxidation and, probably cooling, of reduced (H2S-dominated) fluids buffered by organic matter-rich black shales of the host sedimentary sequence. The input of such reduced fluids in the ore-forming environment most probably occurred alternating with that of the main oxidized fluids which leached Zn and Pb from the large volume of sandstones and siltstones making up the enclosing sequence, thus being responsible for the precipitation of the majority Zn-Pb ore. Supply of Au-carrying reduced fluids might progressively increase over the course of ore formation, reaching a maximum at the beginning of the late fracturing stage. This evolution of Au supply is consistent with the early crystallization of barite since Ba can also only be transported at low temperature by highly reduced fluids. These results highlight the potential of medium-sized, shale-hosted, clastic-dominated deposits to contain economic (by product) Au amounts and show that ore-forming fluids can change from oxidized (SO42+ dominated) to reduced (H2S-dominated), and vice versa, throughout the evolutionary history of a single deposit.

Study on the damage characteristics and damage model of organic rock oil shale under the temperature effect

Thermal damage is of great importance to oil shale in situ mining. In this study, the relationship between the P-wave velocity, peak strength, and elastic modulus of samples from Nong’an County, Jilin Province, China, and temperature is analysed (at temperatures of 25–700 °C), and damage factors are defined to evaluate the damage degree. The effect of organic matter pyrolysis on the damage degree is investigated, and thermal damage is explained at the microscale according to scanning electron microscopy (SEM) images. Under the assumption that the strength of a micro-element obeys the power function distribution and micro-element failure follows the Mohr-Coulomb (M-C) strength criterion, a thermal damage constitutive model is established. It is found that when the temperature threshold is exceeded, organic matter pyrolysis becomes the main driver of the increase in thermal damage. The thermal damage rapidly increases, which is notably different from the damage process below the temperature threshold. This difference is clearly reflected in the physical and mechanical properties, damage factors, microstructure, and determined model parameters. The relationship between the mass loss rate, which can directly reflect the pyrolysis degree, and damage degree is notable. The research results have a certain theoretical significance that can help to better understand the thermal damage process of oil shale and the thermal damage difference between organic and inorganic rocks and can provide a reference for relevant engineering practices.

Metamorphic graphite from Szendr\u0151l\xe1d (Szendr\u0151 Mts., NE-Hungary) detected by simultaneous DTA-TG

Graphite, one of the polymorphic forms of carbon, has become a versatile industrial material of nowadays due to its particular attributes. It is used mainly in the automobile industry, metal extractive industry and in the high-tech industry. Moreover, it is also included in the list of critical raw materials for the EU. Our aim was to prove the presence of graphite by thermal analysis beyond X-ray powder diffraction (XRD) and Raman spectroscopy. Thermogravimetry yields comparable results with quantitative XRD. The formation conditions are described by Raman spectrometry and microscopy examinations of drill core samples from Szendrőlád (Szendrő Mts, NE-Hungary; (Szendrőlád Limestone Formation, middle-late Devonian, shelf-basin facies). Polished rock slabs were made for optical microscopy, scanning electron microscopy with energy dispersive spectrometry (SEM–EDS) and Raman spectroscopy. X-ray powder diffraction (XRD) and thermal analysis (DTA-TG) measurements were made on powders. Based on our results, the graphite is epigenetic; its quantity varies between 1.5–3 mass% in the samples. It was developed in 20–50 μm sized flakes, which are often arranged in > 300 μm sized aggregates. Graphite was formed during regional metamorphism from the organic matter-rich shales. The average formation temperature, calculated from the results of Raman spectroscopy, is around 410 °C (± 30 °C). The Raman measurements also indicated the presence of a partially graphitized (disordered graphite) material beside graphite.

Pore characteristics and pore structure deformation evolution of ductile deformed shales in the Wufeng-Longmaxi Formation, southern China

Marine shales in southern China experiences multiple complex tectonic movements, which highly affects shale pore characteristics and pore evolution. The effects of tectonic deformation on nanopore structure and petrophysical properties of organic shales remain unclear. Three ductile deformed shale samples were collected and analyzed through an integrated experiment procedure for a comparative research against undeformed shale samples. Field emission-Scanning electron microscopy (FE-SEM), low pressure N2 and CO2 adsorption and mercury injection porosimetry (MIP) analyses were performed to characterize pore structure of the shales. The results reveal that the mineral compositions of these shale samples are controlled by sedimentary environment and source and exhibits no obvious relationship with tectonic deformation. With increasing deformation degree, the micropore proportion gradually decreases (from 17% to 6%), and the macropore proportion increases from 16% to more than 20%. Micropore volumes and proportion in the fold core samples are the smallest (4.2 × 10−3 cm3/g and 6.3%) and account for only one-third of the undeformed shale values, while the meso- and macropore values are larger-1.2 times those of the undeformed shale values. The evolution characteristics and deformation modes of organic matter (OM), interparticle (interP) and intraparticle (intraP) pores and microfractures under ductile deformation were examined. All pore types become interconnected during deformation and form microfractures ranging from a few nanometers to tens of microns, which is the main reason for the enhanced shale connectivity caused by deformation. Under the same porosity conditions, the deformed shale permeability is much higher than the undeformed shale permeability, and stronger deformation corresponds to higher permeability. The fold core permeability is generally higher than the limb permeability and exceeds 30 times. The different ductile deformation positions were divided into five levels, and the corresponding reservoir quality was evaluated. This study is of great significance to better understand the pore structure evolution process for shale exploration and development under tectonic deformation.