Multifacetted study of a cretaceous coal with algal affinities—II. Composition of liquefaction products

Two hydrogen-rich lithobodies of highly alipathic character from a coal occurring in southwest Utah, have been studied. Bituminite (>50%), vitrinite (25–30%) and liptodetrinite (7–12%) are the principal macerals. The hexane-soluble products of hydrogenating the lithotypes at 400° with tetralin and hydrogen have been analyzed by GC-MS. Products identified include homologous series of alkylated naphthalenes, phenols, furans, cyclohexenones and hydroxy-pyridines. In the case of furans, the alkyl groups extend beyond C₃₀. Materials released by Soxhlet extraction with pyridine consist chiefly of homologous series of fatty acids and their methyl esters and of methyl alkyl ketones, which were not found in the hydrogenation products. The long alkyl chains in these substances can account for about 75% of the alkanes found in the hydrogenation products but not in the extracts. Most of the compounds mentioned in the foregoing are thought to be physically held or trapped in the coal, rather than chemically combined in its macromolecular network. Except for the fatty acids, the origins of these substances are difficult to identify.     

Composition,Structure, and Conditions of Formation of Fluorine-Bearing Sodalite: Experimental Evidence

Fluoro-sodalite was synthesized for the first time at temperatures of 400–800°C and H₂O pressures of 1–2 kbar in the Si–Al–Na–H–O–F system. X-ray diffraction and infrared spectroscopic investigations showed that fluorine is incorporated in the sodalite structure as anionic octahedral groups, [AlF₆]^3–, the number of which can vary from 0 to 1. Correspondingly, the end-members of the F-sodalite series are Na₇(H₂O)₈[Si₅Al₇O₂₄] and Na₈(AlF₆)(H₂O)₄[Si₇Al₅O₂₄]. Depending on the composition of the system, F-sodalite associates at 500–650°C with nepheline, albite, cryolite, and villiaumite, which are joined by analcime below 500°C and aluminosilicate melt above 650°C. Fluorine-bearing sulfate–chlorine-sodalite was found for the first time in a pegmatite sample from the Lovozero massif. The highest fraction of the fluorine end-member in natural sodalite is 0.2. The incorporation of F into the sodalite structure requires much more energy compared with Cl^– and SO ₄ ^2- , because it is accompanied by a structural rearrangement and a transition from tetrahedral Al to octahedral Al.     

Paleo-environment and reservoir evolution of the Middle Ordovician Kelimoli Formation in the northern Tianhuan area,Ordos Basin,China: implications for high-quality reservoir development

The Middle Ordovician Kelimoli Formation carbonate reservoirs in the northern Tianhuan area, Ordos Basin, China are main exploration targets. Subsurface core samples, logging, drilling and production data from the area were used to characterise the carbonate reservoir and to construct a genetic model for exploration. The sedimentary facies identified include trough–continental rise, upper–lower slope, platform margin reef-shoal, open platform and evaporation-restricted platform. The slope and platform margin facies are potential zones for high-quality reservoirs. Porosity in the study area comprises intergrain, intercrystal, intragrain and intracrystal pores, fractures and vughs. The Sr/Ba (0.40–4.87) and V/(V + Ni) (0.64–0.97) ratios indicate deposition in a brackish water-dominated environment under reducing conditions, associated with sea-level fluctuations during the deposition of the Kelimoli Formation. The Sr/Ba, V/(V + Ni), ⁸⁷Sr/⁸⁶Sr ratios, δ¹⁸O values and crystal texture of dolomite samples suggest that meteoric water was involved in the diagenetic fluid in the near-surface depositional environment. Isotopes (δ¹³C and δ¹⁸O) and trace elements (Fe and Mn) allowed the identification of seepage-reflux and mixed-water dolomitisation. The crystal textures of the samples consist of micritic, bioclastic and reefal limestones, and dolomite with gypsum, which were easily dissolved during the early diagenetic stage. The epidiagenetic stage was the key period for the development of high-quality reservoirs because of large-scale bedding-parallel karstification from meteoric water. The reservoir zones, dominated by partially filled and unfilled vughs, and fractures, are favourable exploration targets in the northern Tianhuan area.     

Petrophysical characterisation of tight sandstone gas reservoirs using nuclear magnetic resonance: a case study of the upper Paleozoic strata in the Kangning area,eastern margin of the Ordos Basin,China

Residual and movable porosity are significant parameters for characterising petrophysical properties, especially in tight reservoirs. Eight tight sandstone samples from the upper Paleozoic gas-bearing strata in the Kangning area, from the eastern margin of the Ordos Basin, were analysed using nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), petrography, and porosity and permeability tests. The lithology and pore types were identified and classified using petrography and SEM. The residual and movable porosity were obtained with NMR. In addition, NMR was used to visualise pore structure and pore size distribution. The results suggest that the upper Paleozoic sandstones in the study area mainly comprise feldspathic litharenite and litharenite. The sandstone porosity and permeability are low, with means of 5.9% and 0.549 mD, respectively. Four pore types exist in the tight sandstones: residual primary pores, grain dissolution pores, micropores (clay-dominated) and microfractures. The T₂ spectra under water-saturated conditions correlate with pore size and can be used to distinguish small and large pores based on the transverse relaxation time cutoff value of 10 ms, which corresponds to a pore diameter of 0.232 μm. Small pores account for 72% of the pores in the tight sandstones. The continuous bimodal T₂ spectra suggest good connectivity between small and large pores, despite the low porosity and permeability. In this study, the movable porosity of the major tight sandstone gas reservoirs is higher than the residual porosity, which confirms the effective evaluation of movable porosity to tight sandstone reservoirs, based on NMR experiments.     

Age and Provenance Areas of Terrigenous Rocks of the Dzhida Terrane: Results of U—Th—Pb (LA-ICP-MS) Geochronological Study of Detrital Zircons

The results of U—Th—Pb (LA-ICP-MS) geochronological studies of detrital zircons from terrigenous rocks of the Dzhida terrane of the Central Asian Fold Belt (CAFB) are presented. The data obtained allow us to distinguish the following age maxima (Ma): 578 and 634 (Vendian); 720, 823, and 919 (Late Riphean); 1922, 2090, 2225, and 2321 (Early Proterozoic). A number of zircons have Late Archean age in the interval of 2670–2980 Ma. Taking into account Late Cambrian age (504–506 Ma) of intrusive rocks that intruded the Dzhida terrane, a possible sedimentation period of sequences of this terrane is estimated to be in the interval of 580–510 Ma (from Vendian to Late Cambrian). The possible provenance areas of terrigenous sediments are proposed and the previously proposed models of geodynamic evolution of the Dzhida terrane are correlated with new geochronological data.     

Experimental Study of the SiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O–KF–KCl–NaF System at 700–800°C and 1–2 kbar Based on Synthetic Fluid Inclusions in Quartz

The phase state of the fluid in the H₂O–KF ± KCl ± NaF system is studied in the presence of quartz for an experimental assay of the mutual influence of various salts of the fluid-forming mixture on heterogeneous fluid equilibria. The fluid inclusions were synthesized in quartz by the fracture healing method from solutions with KF + KCl and KF + NaF mixtures at 1 or 2 kbar and 700, 750, or 800°C. The results of the fluid inclusion study indicate a heterogeneous state of the fluid and variation in the fluid composition during experiments as a result of its interaction with quartz. The increase in temperature and pressure, as well as variation in the proportions of the salt contents in the fluid-forming mixture, changed the course of chemical reactions. After all the experiments, a glassy phase was observed in some types of inclusions. It is known that aqueous KF or KCl solutions, the solubility of which increases during heating, are characterized by phase equilibria of systems of the first type (Valyashko, 1990), when liquid and vapor are equilibrated for a heterogeneous state of the fluid. In this case, some inclusions should homogenize to vapor. However, no similar inclusions were observed in contrast to denser fluid phases (liquids), which are typical of the upper heterogeneous area of systems of the second (P–Q) type. Some inclusions host solid phases, the solubility of which decreases as the temperature increases. The results of experiments in the presence of KF + NaF solutions showed that the amount of inclusions of heterogeneous entrapment increases at higher temperatures simultaneously with a decrease in the H₂O content of the glassy phase.     

The oldest (~ 1.9 Ga) metadolerites of the southern Siberian craton: age,petrogenesis, and tectonic setting

Geological, geochronological, and isotope-geochemical studies of the metadolerites of the Angaul complex, widespread in the Urik-Iya graben of the southern Siberian craton, were carried out. The metadolerites forming separate conformal bodies (sills) among the metasandstones of the Ingash Formation were studied in detail. U-Pb zircon (SHRIMP) dating of metadolerites yielded an age of 1913 ± 24 Ma, and U-Pb baddeleyite (ID-TIMS) dating of these rocks yielded an age of 1914.0 ± 1.7 Ma. Thus, the date of 1914 ± 2 Ma can be taken as the most precise age estimate for the studied rocks. The metadolerites of the Angaul complex correspond in chemical composition to the normal-alkaline tholeiitic basalts. Metadolerites are differentiated rocks with mg# of 36 to 58. They show fractionated REE patterns: (La/Yb)_n = 1.2-3.5. All metadolerites, independently of their mg# value, have low contents of Nb (1.6-10.2 ppm) and show well-pronounced negative Nb-Ta anomalies in multielement patterns (Nb/Nb* = 0.19-0.54). The metadolerites are characterized by positive ε_Nd(T) values ranging from 0.4 to 5.2, which correlate well with their SiO₂ content and mg# value. The isotope-geochemical parameters of the metadolerites of the Angaul complex indicate that fractional crystallization, along with the assimilation of the host rocks (AFC), might have been the main process during the formation of the most differentiated metadolerites. The geochemical characteristics of metadolerites with the maximum mg# values of 57-58 and ε_Nd(T) = 5.2 suggest that the parental mantle source of the metadolerites resulted from mixing of predominant depleted mantle material with the subcontinental-lithosphere material. Intrusion of the dolerites of the Angaul complex, as well as the deposition of the sedimentary strata of the Ingash Group, took place at the Paleoproterozoic stage of intracontinental extension caused by the collapse of the orogen resulted from the collision of the Biryusa block with the Tunguska superterrane in the southern Siberian craton.     

Mineralogy and geochemistry of sediments from Simbock Lake,Yaoundé area (southern Cameroon): provenance and environmental implications

Two cores of sediments, named NR and EB, were collected in the Simbock Lake (Mefou watershed, Yaoundé) to assess their provenance and the degree of heavy metal pollution based on mineralogical and geochemical data. The sediments are sandy, sand-clayey to clayey, and yellowish brown to greenish brown, and with high amounts of organic matter (average value of TOC is 1.95%). The sediments are mainly composed of quartz, kaolinite, accessory goethite, smectite, rutile, feldspars, illite, gibbsite, and interstratified illite-vermiculite. Fourier transform infrared (FT-IR) spectroscopy shows that kaolinite is less crystallized in the NR core than in the EB core. The Index of Compositional Variability (ICV), Chemical Index of Alteration (CIA), Plagioclase Index of Alteration (PIA), and the Rb/Sr and K₂O/Rb ratios indicate a high weathering intensity in the source area. These sediments have low contents in Al₂O₃, Fe₂O₃, Na₂O, K₂O, MgO, and CaO as well as high values in SiO₂, P₂O₅, TiO₂, and MnO relative to the upper continental crust. The concentrations of Cr, V, Ba, and Zr are higher in the NR core than those in EB. The total rare earth element (REE) content varies between 78 and 405 ppm. The light REE are abundant (LREE/HREE ~?18–59; avg.?=?25.61). The chondrite-normalized REE patterns exhibit (i) negative Eu anomaly (Eu/Eu^* ~?0.38–0.62; avg.?=?0.5), (ii) slight positive Ce anomaly (Ce/Ce^* ~?1.11–1.34; avg.?=?1.11), and (iii) high REE fractionation ((La/Yb)_N ~?12.3–51.75; avg.?=?25.61). The enrichment factor (EF) shows that the Mefou watershed through the Simbock Lake sediments is slightly polluted by the agricultural and urban activities.     

Zircon geochronology and geochemistry to constrain the youngest eruption events and magma evolution of the Mid-Miocene ignimbrite flare-up in the Pannonian Basin,eastern central Europe

A silicic ignimbrite flare-up episode occurred in the Pannonian Basin during the Miocene, coeval with the syn-extensional period in the region. It produced important correlation horizons in the regional stratigraphy; however, they lacked precise and accurate geochronology. Here, we used U–Pb (LA-ICP-MS and ID-TIMS) and (U–Th)/He dating of zircons to determine the eruption ages of the youngest stage of this volcanic activity and constrain the longevity of the magma storage in crustal reservoirs. Reliability of the U–Pb data is supported by (U–Th)/He zircon dating and magnetostratigraphic constraints. We distinguish four eruptive phases from 15.9 ± 0.3 to 14.1 ± 0.3 Ma, each of which possibly includes multiple eruptive events. Among these, at least two large volume eruptions (>10 km³) occurred at 14.8 ± 0.3 Ma (Demjén ignimbrite) and 14.1 ± 0.3 Ma (Harsány ignimbrite). The in situ U–Pb zircon dating shows wide age ranges (up to 700 kyr) in most of the crystal-poor pyroclastic units, containing few to no xenocrysts, which implies efficient recycling of antecrysts. We propose that long-lived silicic magma reservoirs, mostly kept as high-crystallinity mushes, have existed in the Pannonian Basin during the 16–14 Ma period. Small but significant differences in zircon, bulk rock and glass shard composition among units suggest the presence of spatially separated reservoirs, sometimes existing contemporaneously. Our results also better constrain the time frame of the main tectonic events that occurred in the Northern Pannonian Basin: We refined the upper temporal boundary (15 Ma) of the youngest counterclockwise block rotation and the beginning of a new deformation phase, which structurally characterized the onset of the youngest volcanic and sedimentary phase.