Abundance of sulfur in Eocene coal beds from Bapung, Northeast India

At 625°C the percentage of sulfur in the non-volatile portion of the Bapung coal beds ranges from 1.08 to 3.10 wt.%, with the pyritic sulfur ranging from 0.02 to 0.32 wt.%, the sulfate sulfur ranges from 0.02 to 0.30 wt.%, and the organic sulfur from 0.88 to 2.49 wt.%. The total sulfur in the Bapung coal ranges from 2.50 to 12.44%. Organic sulfur appears to be more abundant among the different sulfur species. However, the pyritic sulfur increases quickly as the total sulfur content increases at 925°C, the percentage of sulfur in non-volatile portion ranges from 1.27 to 2.54 wt.%, with pyritic sulfur ranging from 0.02 to 0.56 wt.%, sulfate sulfur ranges from 0.04 to 0.16 wt.%, and the organic sulfur from 1.15 to 2.03 wt.%.     

Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH₂ and HI/LiAlH₄) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis–GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260°C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak carbon–heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220°C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.     

In situ and laboratory investigation of the alteration of Boom Clay (Oligocene) at the air–geological barrier interface within the Mol underground facility (Belgium): Consequences on kerogen and bitumen compositions

The Boom Clay formation (Oligocene) is studied as a reference host rock for methodological studies on deep geological disposal of radioactive waste. During excavation of galleries within the Clay formation (HADES underground research facility, Mol, Belgium), the physico-chemical conditions are significantly modified as an air–clay interface is created. In order to study the long-term impact of the air–clay contact on the organic matter contained in the Boom Clay, two types of samples were studied: (1) a reference series of clay samples having been in contact with the atmosphere of the HADES gallery for increasing times up to several years and (2) unaltered clay samples submitted to artificial oxidation in a ventilated oven at 80 °C. The evolution of geochemical data of the two series was compared using Rock-Eval pyrolysis, GC–MS and size exclusion chromatography. The organic matter of the unaltered clays sampled in the HADES galleries is dominated by type III kerogen (terrestrial) with some contribution of type II (marine) and is thermally immature. The evolution of geochemical parameters during air alteration for the two series are very similar. They show progressive oxidation of kerogen accompanied by the release of bitumen enriched in low molecular weight constituents. Molecular analysis evidences the presence of a complex mixture of aliphatic and aromatic O-bearing compounds, inherited from the degradation of kerogen as well as from the clay catalyzed oxidation of the bitumen. These results show that (1) air oxidation is a major process in the in situ alteration of the organic matter of Boom Clay within the HADES galleries, (2) laboratory oxidation experiments at 80 °C yield similar results as in situ air alteration of Boom Clay and (3) artificial air oxidation may be used to assess the long term exposure of the organic matter to air.     

Role of water in hydrocarbon generation from Type-I kerogen in Mahogany oil shale of the Green River Formation

Hydrous and anhydrous closed-system pyrolysis experiments were conducted on a sample of Mahogany oil shale (Eocene Green River Formation) containing Type-I kerogen to determine whether the role of water had the same effect on petroleum generation as reported for Type-II kerogen in the Woodford Shale. The experiments were conducted at 330 and 350 °C for 72 h to determine the effects of water during kerogen decomposition to polar-rich bitumen and subsequent bitumen decomposition to hydrocarbon-rich oil. The results showed that the role of water was more significant in bitumen decomposition to oil at 350 °C than in kerogen decomposition to bitumen at 330 °C. At 350 °C, the hydrous experiment generated 29% more total hydrocarbon product and 33% more C₁₅₊ hydrocarbons than the anhydrous experiment. This is attributed to water dissolved in the bitumen serving as a source of hydrogen to enhance thermal cracking and facilitate the expulsion of immiscible oil. In the absence of water, cross linking is enhanced in the confines of the rock, resulting in formation of pyrobitumen and molecular hydrogen. These differences are also reflected in the color and texture of the recovered rock. Despite confining liquid-water pressure being 7-9 times greater in the hydrous experiments than the confining vapor pressure in the anhydrous experiments, recovered rock from the former had a lighter color and expansion fractures parallel to the bedding fabric of the rock. The absence of these open tensile fractures in the recovered rock from the anhydrous experiments indicates that water promotes net-volume increase reactions like thermal cracking over net-volume decrease reactions like cross linking, which results in pyrobitumen. The results indicate the role of water in hydrocarbon and petroleum formation from Type-I kerogen is significant, as reported for Type-II kerogen.     

Kerogen-mineral reactions at raised temperatures in the presence of water

Kerogen has been artificially matured under “hydrous pyrolysis” conditions in the presence of various minerals in order to investigate the influence of the latter on the organic products. In addition to three clay minerals (montmorillonite, illite, kaolinite), calcium carbonate and limonite were also employed as inorganic substrates. Kerogen (Type II) isolated from the Kimmeridge Blackstone band was heated in the presence of water and a 20-fold excess of mineral phase at two different temperatures (280 and 330°C) for 72 hr. Control experiments were also carried out using kerogen and water only and kerogen under anhydrous conditions. This preliminary study describes the bulk composition of the pyrolysates with detailed analyses of the aliphatic hydrocarbon distributions being provided by gas chromatography and combined gas chromatography-mass spectrometry.In the 280°C experiments, considerably more organic-soluble pyrolysate (15% by weight of original kerogen) was produced when calcium carbonate was the inorganic phase. At 330°C, all samples generated much greater amounts of organic-soluble products with calcium carbonate again producing a large yield (40% wt/wt). Biomarker epimerisation reactions have also proceeded further in the 330°C pyrolysate formed in the presence of calcium carbonate than with other inorganic phases. Implications of these and other observations are discussed.     

Geochemistry and petrogenesis of placer nephrite from Hetian, Xinjiang, Northwest China

The Yurungkash and Karakash rivers, also known respectively as the White Jade and Black Jade rivers, located in Hetian, Xinjiang Province, Northwest China, are the two main sources in China of white, green, and black placer nephrite, with a long history (~ 5000 years) of exploration and mining. The twenty-nine placer nephrite samples collected from both rivers and analyzed in the present study possess fine-grained and compact microstructures. The mineral assemblages in the samples provide clues to the metamorphic/metasomatic processes that formed the nephrite, which was the result of one of the following reactions: dolomitic marble → tremolite, or dolomitic marble → diopside → tremolite. White nephrite from the Yurungkash River and green nephrite from the Karakash River are predominantly tremolite. Based on electron probe microanalytical data, backscattered electron images, and Raman spectra, two kinds of black nephrite from the Karakash River are identified: one dominated by actinolite aggregates, and another consisting of tremolite aggregates with graphite crystals up to 2 mm in length. Compared with black nephrite, white and green nephrites contain fewer mineral inclusions and have lower FeO and MnO contents. All the amphiboles in the nephrites have very low contents of Cr₂O₃ (0.00–0.07 wt.%) and NiO (0.00–0.05 wt.%) relative to serpentinite-related nephrite (0.07–0.43 wt.% Cr₂O₃, 0.08–0.36 wt.% NiO). Most of the nephrite samples have low total rare earth element (ΣREE) contents, ranging from 12.22 to 49.40 ppm. In two nephrite samples, relatively high ΣREE concentrations (161 and 190 ppm) are related to the presence of REE-bearing minerals. Whole-rock REE chondrite-normalized patterns of all samples are characterized by strong negative Eu anomalies (0.16–0.48), moderate light-REE enrichment (La/Nd_N = 1.8–5.0), and nearly flat heavy-REE distributions (Gd/Yb_N = 0.3–1.7). Nephrite samples from both river locations have δ¹⁸O and δD isotope compositions ranging from 1.1‰ to 5.6‰ and − 55.7‰ to − 72.4‰, respectively. These values are closer to those recorded in dolomite-related nephrites than those in serpentinite-related deposits. Importantly, δ¹⁸O and δD values correspond to fluid isotope compositions of δ¹⁸O = 1.6‰ to 6.1‰ (330 °C), 1.8‰ to 6.3‰ (350 °C), and 2.5‰ to 7.0‰ (430 °C), and δD = − 34.9‰ to − 52.5‰ (350 °C to 650 °C). These values are close to or within the field of magmatic water. Geochemical and petrographic characteristics point to a dolomite-related metamorphic/metasomatic origin for nephrite at both locations. The placer nephrite is likely to have been derived from primary nephrite deposits in the Kunlun Mountains around Hetian, based on the geological occurrence of the deposits.     

Investigations on the extraction of molybdenum and vanadium from ammonia leaching residue of spent catalyst

Extraction of molybdenum and vanadium from ammonia leaching residue (main chemical composition: 2.05% Mo, 0.42% V, 65.6% Al₂O₃ and 10.7% SiO₂) of spent catalyst was investigated by roasting the residue with soda carbonate, followed by hydrometallurgical treatment of the roasted products. In the roasting process, over 91.3% of molybdenum and 90.1% of vanadium could be extracted when a charge containing a sodium carbonate to spent catalyst ratio of 0.15 was roasted at 750 °C for 45 min and the roasted mass was leached with water (liquid to solid ratio of 2) at 80–90 °C for 15 min. After the purification of leach liquor, an extraction solvent consisting of 20 vol.% trialkylamine (N₂₃₅, commercialized in China) and 10 vol.% secondary octyl alcohol (phase modifier) dissolved in sulfonated kerosene was used to extract molybdenum and vanadium in leach liquor. 10 wt.% ammonia water was used as stripping agent. Adding 30 g/l NH₄NO₃ to the stripping solution and adjusting the pH to 7–8.5, over 99% of vanadium can be crystallized as ammonium metavanadate. Over 98% of molybdenum can be crystallized as ammonium polymolybdate when pH is between 1.5 and 2.5 (pH is adjusted by HNO₃). Ammonium metavanadate and ammonium polymolybdate were calcinated at 500–550 °C, the purity of MoO₃ and V₂O₅ was 99.08% and 98.06% respectively. In the whole process, 88.2% of molybdenum and 87.1% of vanadium could be achieved. The proposed roasting, leaching and separation steps give a feasible alternative for the processing of ammonia leaching residue of spent catalyst and can be applied in the comprehensive utilization of low grade molybdenum ores.     

Enhanced late gas generation potential of petroleum source rocks via recombination reactions: Evidence from the Norwegian North Sea

Gas generation in the deep reaches of sedimentary basins is usually considered to take place via the primary cracking of short alkyl groups from overmature kerogen or the secondary cracking of petroleum. Here, we show that recombination reactions ultimately play the dominant role in controlling the timing of late gas generation in source rocks which contain mixtures of terrigeneous and marine organic matter. These reactions, taking place at low levels of maturation, result in the formation of a thermally stable bitumen, which is the major source of methane at very high maturities. The inferences come from pyrolysis experiments performed on samples of the Draupne Formation (liptinitic Type II kerogen) and Heather Formation (mixed marine-terrigeneous Type III kerogen), both Upper Jurassic source rocks stemming from the Norwegian northern North Sea Viking Graben system. Non-isothermal closed system micro scale sealed vessel (MSSV) pyrolysis, non-isothermal open system pyrolysis and Rock Eval type pyrolysis were performed on the solvent extracted, concentrated kerogens of the two immature samples. The decrease of C₆₊ products in the closed system MSSV pyrolysis provided the basis for the calculation of secondary gas (C_1-5) formation. Subtraction of the calculated secondary gas from the total observed gas yields a “remaining” gas. In the case of the Draupne Formation this is equivalent to primary gas cracked directly from the kerogen, as detected by a comparison with multistep open pyrolysis data. For the Heather Formation the calculated remaining gas formation profile is initially attributable to primary gas but there is a second major gas pulse at very high temperature (>550 °C at 5.0 K min⁻¹) that is not primary. This has been explained by a recondensation process where first formed high molecular weight compounds in the closed system yield a macromolecular material that undergoes secondary cracking at elevated temperatures. The experiments provided the input for determination of kinetic parameters of the different gas generation types, which were used for extrapolations to a linear geological heating rate of 10⁻¹¹ K min⁻¹. Peak generation temperatures for the primary gas generation were found to be higher for Heather Formation (T_max = 190 °C, equivalent to R_o appr. 1.7%) compared to Draupne Formation (T_max = 175 °C, equivalent to appr. R_o 1.3%). Secondary gas peak generation temperatures were calculated to be 220 °C for the Heather Formation and 205 to 215 °C for the Draupne Formation, respectively, with equivalent vitrinite reflectance values (R_o) between 2.4% and 2.0%. The high temperature secondary gas formation from cracking of the recombination residue as detected for the Heather Formation is quantitatively important and is suggested to occur at very high temperatures (T_max approx. 250 °C) for geological heating rates. The prediction of a significant charge of dry gas from the Heather Formation at very high maturity levels has important implications for petroleum exploration in the region, especially to the north of the Viking Graben where Upper Jurassic sediments are sufficiently deep buried to have experienced such a process.     

Fluid evolution of the Chalukou giant Mo deposit in the northern Great Xing'an Range,NE China

The Chalukou giant Mo deposit in the Heilongjiang Province, northeastern China, is a porphyry deposit hosted in an intermediate‐felsic complex surrounded by Mesozoic volcano–sedimentary rocks. The mineralization process is composed of four stages, including quartz + K‐feldspar (Stage I), quartz + molybdenite (Stage II), pyrite + chalcopyrite + quartz ± other sulphides (Stage III) and carbonate ± fluorite ± quartz (Stage IV). The mineralization is generally associated with intense K‐feldspar‐, fluorite‐, phyllic‐ and propylitic alteration. Primary fluid inclusions (FIs) in quartz include four compositional types, i.e. pure carbonic (PC‐type), aqueous‐carbonic (C‐type), daughter mineral‐bearing (S‐type) and aqueous (W‐type) inclusions. Halite, sylvite and hematite are recognized as the daughter minerals in Stage I S‐type FIs, whereas molybdenite and chalcopyrite occur as daughter minerals in Stage II S‐type FIs. High‐salinity and high pressure (>220 MPa) FIs exist in Stage I quartz veins, characterized by homogenization through halite dissolution at temperatures of 324 to 517 °C. The paucity of coexisting vapour‐rich FIs with similar homogenization temperatures at this stage indicates that the initial S‐type inclusions have directly exsolved from the magma rather than boiling off of a low‐salinity vapour. Stage I quartz has captured the C‐ and W‐type FIs, which have totally homogenized at 270–530 °C with salinities of 1.6–17.0 wt.% NaCl equiv. At Stage II, the coexistence of all FI types were only observed at pressures of 150–218 MPa and temperatures of 352–375 °C, with two salinity clusters of 0.9–16.6 wt.% NaCl equiv. and 37–56 wt.% NaCl equiv. Stage III quartz contains W‐type FIs with homogenization temperatures of 158–365 °C, salinities of 0.5–9.0 wt.% NaCl equiv., and minimum pressures of 12–116 MPa; whilst Stage IV fluorite or calcite only contains W‐type FIs with homogenization temperatures of 121–287 °C, salinities of 0.5–5.3 wt.% NaCl equiv., and minimum pressures of 10–98 MPa. The estimated trapping pressure from Stages II to III suggests an alternating lithostatic–hydrostatic fluid‐system caused by fluid boiling. Ore fluids at the Chalukou Mo deposit may have been evolved from a CO₂‐rich, high‐salinity, and high‐oxygen fugacity (fO₂) magma system, to a CO₂‐poor, low‐salinity, and low‐fO₂ epithermal system. Two key points may have contributed to the formation of the Chalukou giant Mo deposit: The magmatic origin and fluid boiling that has resulted in decompression and rapid precipitation of metals. Copyright © 2014 John Wiley & Sons, Ltd.     

Environmental impact of mineral transformations undergone during coal combustion

The mineral transformations undergone by high sulfur coal ash were studied. An X-ray diffraction (XRD) experiment was carried out to reproduce experimentally the mineral transformations produced during coal combustion in coal-fired power stations. We have verified that the anhydrite is the main crystalline phase that contains sulfur in the solid combustion waste from 500°C until its decomposition at 1060±10°C. Thus, this calcium sulfate is the main crystalline phase involved in the sulfur retention in the combustion wastes at high temperatures. Therefore, a considerable proportion of the sulfur would not be emitted into the atmosphere at temperatures lower than 1060°C. Taking as a reference the annual coal consumption of the Teruel Mining District (6 million tons), the mean sulfur content and the anhydrite content at 900°C, it was shown that the SO₂ emissions could be reduced by approximately 13 percent (83,000 ton/yr) provided that the combustion temperature was 900°C.     

Characterization of Bulgarian oil shale kerogen revealed by oxidative degradation

A 13-step alkaline permanganate degradation of Bulgarian oil shale kerogen concentrate at ambient temperature was carried out. A high yield of oxidation products (90.1%) and a low yield of gaseous products (2.79%) were obtained. IR and ¹H NMR spectroscopic studies have shown that two significantly different types of high molecular products are present in kerogen. Further oxidation of these structures leads to the formation of low molecular aliphatic and aromatic acids, proven by gas chromotography (GC) and gas chromatography-mass spectrometry (GC-MS). The data obtained at these mild conditions allow us to acquire detailed information about the aromatic structures and polymethylene chain lengths in kerogen.The 5-step oxidation of the kerogen at 90 °C provides information about stable aromatic structures. Soluble and insoluble polyfunctional acids in acid medium have close molecular masses and spectral characteristics. The amount of benzene and naphthalene carboxylic acids is 11.3% of the organic matter of the oil shale.     

Progressive oxidation of pyrite in five bituminous coal samples: An As XANES and Fe Mössbauer spectroscopic study

Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period of 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32–1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26–0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O₂ atmosphere; (3) room atmosphere (relative humidity ∼20–60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and ⁵⁷Fe Mössbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. ⁵⁷Fe Mössbauer spectroscopy also shows a much greater proportion of Fe³⁺ forms (jarosite, Fe³⁺ sulfate, FeOOH) for samples stored under wet conditions, but much less difference among samples stored under dry conditions in different atmospheres. The air-wet experiments show evidence of pyrite re-precipitation from soluble ferric sulfates, with As retention in the jarosite phase. Extents of As and Fe oxidation were similar for samples having differing As substitution in pyrite, suggesting that environmental conditions outweigh the composition and amount of pyrite as factors influencing the oxidation rate of Fe sulfides in coal.     

Study of petroleum generation by pyrolysis—I. Pyrolysis experiments by Rock-Eval and assumption of molecular structural change of kerogen using13C-NMR

Green River shale (Type I kerogen), Yaamba shale (Type II kerogen) and Sarufutsu coal (Type III kerogen) were heated to various temperatures using Rock-Eval. The amount of hydrocarbons generated and weight loss by pyrolysis were measured to obtain a better understanding of petroleum generation. After the pyrolysis experiments, elemental analysis (C, H), vitrinite reflectance (%R_o) measurement, maceral observation, infrared spectroscopy (IR) and¹³C-NMR spectroscopy were carried out on the coal samples. Changes in H/C atomic ratio, IR and NMR spectra indicate that experiments by Rock-Eval resemble those of the natural evolution of kerogen. However, the petrographic changes of the coal show more similarity to coal liquefaction and coking than to natural coalification. Changes in the amount of generated hydrocarbons with increasing maturation show that Type II kerogen produces more hydrocarbons than does Type I when R_o does not exceed 1.1%. Petroleum generation curves for the three samples were concordant with trends in natural systems, and a conceptual model of petroleum generation curve classified into three types is proposed, namely (1) curve of total amount enerated, (2) curve of generation rate, and (3) curve of fluid composition. Changes of IR and NMR spectra after pyrolysis imply that generated hydrocarbons are derived from aliphatic C structures of kerogen macromolecules. Moreover, the difference in genetic potential between Type I and Type III reflects different amounts of aliphatic structures. Type I is assumed to have a simple assemblage (mainly polymethylene carbons), and Type III is assumed to have a more complex variety of structures that are responsible for the difference in generation rates between the two kerogen Types. A quantitative analysis of C species of various bond structure by¹³C-NMR confirms that petroleum generation is the process of bond cleavage of kerogen macromolecules; lower-energy bonds decrease at an earlier stage of reaction, while aromatic carbons with higher bond energies survive to form graphitic structure at postmature stages. Emphasis is placed on the idea that the most important and direct factor in petroleum generation is a change in the molecular structure of kerogen with increasing maturation. NMR and other methods providing information about molecular structures of kerogen will become strong tools for evaluating source rocks and sedimentary basins in the future.     

Dike intrusions into bituminous coal, Illinois Basin: H, C, N, O isotopic responses to rapid and brief heating

Unlike long-term heating in subsiding sedimentary basins, the near-instantaneous thermal maturation of sedimentary organic matter near magmatic intrusions is comparable to artificial thermal maturation in the laboratory in terms of short duration and limited extent. This study investigates chemical and H, C, N, O isotopic changes in high volatile bituminous coal near two Illinois dike contacts and compares observed patterns and trends with data from other published studies and from artificial maturation experiments. Our study pioneers in quantifying isotopically exchangeable hydrogen and measuring the D/H (i.e., ²H/¹H) ratio of isotopically non-exchangeable organic hydrogen in kerogen near magmatic contacts. Thermal stress in coal caused a reduction of isotopically exchangeable hydrogen in kerogen from 5% to 6% in unaltered coal to 2-3% at contacts, mostly due to elimination of functional groups (e.g., OH, COOH, NH₂). In contrast to all previously published data on D/H in thermally matured organic matter, the more mature kerogen near the two dike contacts is D-depleted, which is attributed to (i) thermal elimination of D-enriched functional groups, and (ii) thermal drying of hydrologically isolated coal prior to the onset of cracking reactions, thereby precluding D-transfer from relatively D-enriched water into kerogen. Maxima in organic nitrogen concentration and in the atomic N/C ratio of kerogen at a distance of ∼2.5 to ∼3.5 m from the thicker dike indicate that reactive N-compounds had been pyrolytically liberated at high temperature closer to the contact, migrated through the coal seam, and recombined with coal kerogen in a zone of lower temperature. The same principle extends to organic carbon, because a strong δ¹³C_kerogen vs. δ¹⁵N_kerogen correlation across 5.5 m of coal adjacent to the thicker dike indicates that coal was functioning as a flow-through reactor along a dynamic thermal gradient facilitating back-reactions between mobile pyrolysis products from the hot zone as they encounter less hot kerogen. Vein and cell filling carbonate is most abundant in highest rank coals where carbonate δ¹³C_VPDB and δ¹⁸O_VSMOW values are consistent with thermal generation of ¹³C-depleted and ¹⁸O-enriched CO₂ from decarboxylation and pyrolysis of organic matter. Lower background concentrations of ¹³C-enriched carbonate in thermally unaffected coal may be linked to ¹³C-enrichment in residual CO₂ in the process of CO₂ reduction via microbial methanogenesis.Our compilation and comparison of available organic H, C, N isotopic findings on magmatic intrusions result in re-assessments of majors factors influencing isotopic shifts in kerogen during magmatic heating. (i) Thermally induced shifts in organic δD values of kerogen are primarily driven by the availability of water or steam. Hydrologic isolation (e.g., near Illinois dikes) results in organic D-depletion in kerogen, whereas more common hydrologic connectivity results in organic D-enrichment. (ii) Shifts in kerogen (or coal) δ¹³C and δ¹⁵N values are typically small and may follow sinusoidal patterns over short distances from magmatic contacts. Laterally limited sampling strategies may thus result in misleading and non-representative data. (iii) Fluid transport of chemically active, mobile carbon and nitrogen species and recombination reactions with kerogen result in isotopic changes in kerogen that are unrelated to the original, autochthonous part of kerogen.     

A chemical and thermodynamic model of oil generation in hydrocarbon source rocks

Thermodynamic calculations and Gibbs free energy minimization computer experiments strongly support the hypothesis that kerogen maturation and oil generation are inevitable consequences of oxidation/reduction disproportionation reactions caused by prograde metamorphism of hydrocarbon source rocks with increasing depth of burial.These experiments indicate that oxygen and hydrogen are conserved in the process.Accordingly, if water is stable and present in the source rock at temperatures ?25 but ?100 °C along a typical US Gulf Coast geotherm, immature (reduced) kerogen with a given atomic hydrogen to carbon ratio (H/C) melts incongruently with increasing temperature and depth of burial to produce a metastable equilibrium phase assemblage consisting of naphthenic/biomarker-rich crude oil, a type-II/III kerogen with an atomic hydrogen/carbon ratio (H/C) of ∼1, and water. Hence, this incongruent melting process promotes diagenetic reaction of detritus in the source rock to form authigenic mineral assemblages.However, in the water-absent region of the system CHO (which is extensive), any water initially present or subsequently entering the source rock is consumed by reaction with the most mature kerogen with the lowest H/C it encounters to form CO₂ gas and a new kerogen with higher H/C and O/C, both of which are in metastable equilibrium with one another.This hydrolytic disproportionation process progressively increases both the concentration of the solute in the aqueous phase, and the oil generation potential of the source rock; i.e., the new kerogen can then produce more crude oil.Petroleum is generated with increasing temperature and depth of burial of hydrocarbon source rocks in which water is not stable in the system CHO by a series of irreversible disproportionation reactions in which kerogens with higher (H/C)s melt incongruently to produce metastable equilibrium assemblages consisting of crude oil, CO₂ gas, and a more mature (oxidized) kerogen with a lower H/C which in turn melts incongruently with further burial to produce more crude oil, CO₂ gas, and a kerogen with a lower H/C and so forth.The petroleum generated in the process progresses from heavy naphthenic crude oils at low temperatures to mature petroleum at ∼150 °C. For example, the results of Computer Experiment 27 (see below) indicate that the overall incongruent melting reaction in the water-absent region of the system C-H-O at 150 °C and a depth of ∼4.3 km of an immature type-II/III kerogen with a bulk composition represented by C₂₉₂H₂₈₈O_12(c) to produce a mature (oxidized) kerogen represented by C₁₂₈H₆₈O_7(c), together with a typical crude oil with an average metastable equilibrium composition corresponding to C_8.8H_16.9 (C_8.8H_16.9(l)) and CO₂ gas (CO_2(g)) can be described by writing

(A)     

An absarokite from a phlogopite lherzolite source

An absarokite (SiO₂ 47.72 wt %, K₂O 3.41 wt %) occurs in the Katamata volcano, SW Japan. The rock carries phenocrysts of olivine, phlogopite, clinopyroxene, and hornblende. Chemical compositions of bulk rock (FeO^*/ MgO 0.73) and minerals (Mg-rich olivine and phlogopite, Cr-rich chromite) suggest that the absarokite is not differentiated. Melting experiments at high pressures on the Katamata absarokite have been conducted. The completely anhydrous absarokite melt coexists with olivine, orthopyroxene, and clinopyroxene at 1310° C and 1.0 GPa. The melt with 3.29 wt % of H₂O also coexists with the above three phases at 1230° C and 1.4 GPa; phlogopite appears at temperatures more than 80° C below the liquidus. On the other hand, the melt is not saturated with lherzolite minerals in the presence of 5.13 wt % of H₂O and crystallizes olivine and phlogopite as liquidus phases; the stability limit of phlogopite is little affected at least by the present variation of H₂O content in the absarokite melt. It is suggested that the absarokite magma was segregated from the upper mantle at 1170° C and 1.7 GPa leaving a phlogopite lherzolite as a residual material on the basis of the above experimental results and the petrographical observation that olivine and phlogopite crystallize at an earlier stage of crystallization sequence than clinopyroxene. The contribution of phlogopite at the stage of melting processes is also suggested by the geochemical characteristics that the absarokite is more enriched in Rb, K, and Ba and depleted in Ca and Na than a typical alkali olivine basalt from the same volcanic field.     

The geology, petrology, palynology and geochemistry of Permian coal basins in Tanzania: 2. Songwe-Kiwira Coalfield

This study provides coal quality, petrological, palynological and geochemical (Rock Eval) data on Permian coal seams and associated shales and mudstones of the Karoo Supergroup of the Songwe-Kiwira Coalfield, Tanzania. The coal seams, which have a cumulative thickness of 6.80 m, occur in the shale–coal–sandstone facies of the Mchuchuma Formation of Artinskian to Kungurian(?) age.Coal quality data (calorific values, volatile matter contents) and vitrinite reflectances indicate high volatile C bituminous to high volatile A bituminous coals, having relatively high ash yields (22–49 wt.%) and highly variable sulphur contents (0.17–9.2 wt.%). They could be used to fuel small-scale power generation units thereby providing electricity to nearby towns and villages. Also, the coals could be used as a substitute for wood, which is becoming increasingly scarce. In rural Tanzania, charcoal is still the main energy source for cooking, and wood is used extensively in brick kilns and for making roofing tiles.Petrological analysis indicated that the coals are dominated by dull to banded dull lithotypes, with seams at the base of the Mchuchuma Formation enriched in inertinite macerals (up to 83 vol.%), whereas up-section vitrinite contents increase. Palynological analyses indicated that the assemblage in the lower Mchuchuma Formation (Scheuringipollenites assemblage) is dominated by trilete spores, whereas in the remainder of the section, non-taeniate disaccates dominate (Scheuringipollenites–Protohaploxypinus assemblage). Facies critical macerals suggest for most seams a marsh/wet forest swamp depositional setting, which is consistent with the palynological data.Rock Eval analyses indicate type II/III kerogen, with Tmax (°C) values ranging from 426 to 440, corresponding to the early stage of hydrocarbon generation. Thermal Alteration Indices (2 to 2+) and vitrinite reflectance levels (0.60–0.83 Ro (%) support the Rock Eval maturity assessment, and despite the predominance of terrestrial-derived organic matter, there is evidence of oil generation and expulsion in the form of cavity and fracture filling exsudatinite.     

Porphyry to epithermal transition in the Agua Rica polymetallic deposit, Catamarca, Argentina: An integrated petrologic analysis of ore and alteration parageneses

Agua Rica (27°26′S–66°16′O) is a world class Cu–Au–Mo deposit located in Catamarca, Argentina. In the E–W 6969400 section examined, the Seca Norte and the Trampeadero porphyries that have intruded the metasedimentary rock are cut by interfingered igneous and hydrothermal heterolithic and monolithic breccias, and sandy dikes. Relic biotite and K-feldspar of the early potassic alteration (370° to > 550 °C) with Cu (Mo–Au) mineralization are locally preserved and encapsulated in a widespread, white mica + quartz + rutile or anatase halo (phyllic alteration) with pyrite + covellite that suggests fluids with temperatures ≤ 360 °C and high f(S₂). The Trampeadero porphyry and the surrounding metasedimentary rock with phyllic alteration have molybdenite in stringers and B-type quartz veinlets and the highest Mo grades (> 1000 ppm).Multistage advanced argillic alteration overprinted the earlier stages. Early andalusite ± pyrite ± quartz is preserved in the roots of the argillic halo rimmed by an alumina–silica material and white micas. This alteration assemblage is considered to have been formed at temperatures ≥ 375 °C from condensed magmatic vapor. At higher levels, pyrophyllite replaces muscovite and illite in clasts of hydrothermal breccias in the center and east sector of the study section, suggesting temperatures of 280 to 360 °C. Clasts of vuggy silica in the uppermost levels of the central breccia, indicates that at lower temperatures (< 250 °C), fluids reached very low pH (pH < 2). In this early stage of the advanced argillic alteration, hydrothermal fluids seem to have not precipitated sulfides or sulfosalts.Hydrothermal brecciation was concurrent with fluid exsolution (↑? V), which precipitated intermediate-temperature advanced argillic alunite (svanbergite + woodhouseite) ± diaspore ± zunyite as breccia cement along with abundant covellite + pyrite + enargite ± native sulfur ± kuramite at intermediate depths and in lateral transitional zones to unbrecciated rocks. This mineral assemblage indicates temperatures near 300 °C, oxidized and silica-undersaturated hydrothermal fluids with high sulfur fugacity to prevent gold precipitation. Multiple generations of pyrite, emplectite, colusite, Pb- and Bi-bearing sulfosalts, and native sulfur with Au and Ag, accompanied by alunite introduction in the upper level breccias, probably occurred at lower temperatures, but still high sulfur and oxygen activity. An independent Zn and Pb (as galena) mineralization stage locally coincides with Au–Ag and sulfosalts, and advanced at depth, controlled by fractures and overprinting much of the previous mineralization. A later paragenesis of veinlets of alunite + woodhouseite + svanvergite + pyrite ± enargite that cut the phyllic halo suggests temperatures ~ 250 °C and without woodhouseite + svanvergite, temperatures ~ 200 °C. Kaolinite occurs in the phyllic halo as a late mineral in clots and in veinlets thus, in this zone, the fluid had cooled enough for its formation.     

Inverse methods and kinetic models of hydrocarbon generation. IV. Sensitivity analysis, synthetic tests, and application of a residual kerogen analysis model to geological conditions

An investigation is given of sensitivity analysis, synthetic tests, and application to geological conditions of an inverse kinetic model for residual kerogen analysis. Using kinetic parameters derived from different experimental data a sensitivity analysis study allows a discussion of the discrepancies in predictions of kerogen degradation rates and cumulative amounts of kerogen degraded with temperature, time, and depth of sediments. The synthetic tests and the application examine the applicability to different geological conditions and the uncertainty in predictions of hydrocarbon generation. The study shows that when average values of the kinetic parameters derived from different experimental conditions and samples are used under geological conditions, the modeled kerogen degradation rates and cumulative amount of kerogen degraded are uncertain by about 25°C in temperature, 12.5 My in time and 600 m in depth.     

Experimental study of the influence of sulfur on gold sorption by bitumen at 200–400°C and 1 kbar Pressure

The effect of sulfur on the sorption of gold by carbonaceous matter (CM) was investigated under hydrothermal conditions (200–400°C and 1 kbar) using the autoclave-ampoule method. The model CM was represented by asphaltenes fractionated from the lignite of the Pavlovskoe coal field. The source of gold was the walls of the Au container, which were dissolved in water under the experimental conditions. Sulfur was added as finely ground pyrite (C-S-Fe-O-H-Au system) or elemental sulfur powder (C-S-O-H-Au system). The contents of Au were measured by atomic absorption spectrometry with electrothermal atomization in quenched aqueous solutions (WF), soluble organic fraction (SF), and insoluble residue (kerogen). The lowest Au concentration was detected in the WF, −8.96 < logmAu < −6.32. The Au concentration is higher in the SF (−5.02 < logmAu < −4.34) and increases by more then an order of magnitude in the kerogen, −3.94 < logmAu < −2.33. The IR spectra of the experimental products showed that sulfur was accumulated in the kerogen, whereas no C-S functional groups were observed in the SF. This is the reason for the negligible influence of sulfur in this system on Au concentration in the SF. The maximum Au concentration was detected in the kerogen in the presence of pyrite, which was transformed into pyrrhotite at 400°C. Thus, iron sulfides promote Au uptake by kerogen from ore-bearing hydrothermal fluids.