Seawater sulfate reduction and sulfur isotope fractionation in basaltic systems: Interaction of seawater with fayalite and magnetite at 200–350°C

Sulfate reduction during seawater reaction with fayalite and with magnetite was rapid at 350°C, producing equilibrium assemblages of talc-pyrite-hematite-magnetite at low water/rock ratios and talc-pyrite-hematite-anhydrite at higher water/rock ratios. At 250°C, seawater reacting with fayalite produced detectable amounts of dissolved H₂S, but extent of reaction of solid phases was minor after 150 days. At 200°C, dissolved H₂S was not detected, even after 219 days, but mass balance calculations suggest a small amount of pyrite may have formed. Reaction stoichiometry indicates that sulfate reduction requires large amounts of H⁺, which, in subseafloor hydrothermal systems is provided by Mg metasomatism. Seawater contains sufficient Mg to supply all the H⁺ necessary for quantitative reduction of seawater sulfate.Systematics of sulfur isotopes in the 250 and 350°C experiments indicate that isotopic equilibrium is reached, and can be modeled as a Rayleigh distillation process. Isotopic composition of hydrothermally produced H₂S in natural systems is strongly dependent upon the seawater/basalt ratio in the geothermal system, which controls the relative sulfide contributions from the two important sulfur sources, seawater sulfate and sulfide phases in basalt. Anhydrite precipitation during geothermal heating severely limits sulfate ingress into high temperature interaction zones. Quantitative sulfate reduction can thus be accomplished without producing strongly oxidized rocks and resultant sulfide sulfur isotope values represent a mixture of seawater and basaltic sulfur.     

Simultaneous removal and measurement of sulfide on the basis of turn-on fluorimetry

Hydrogen sulfide is a flammable and poisonous gas pollutant often emitted to air as a by-product of water supply, chemical, petroleum and coal industries. It can be transferred into sulfur dioxide in the air under some meteorologic conditions. Herein, a novel functional copper complex is reported which can selectively absorb hydrogen sulfide and subsequently release a highly fluorescent molecule. The copper complex is functionalized with a benzoxadiazole moiety as a fluorescence reporter, and the copper center serves as the recognition and binding site for sulfide. The application of the copper complex has been demonstrated for sensitive and selective measurement of hydrogen sulfide on the basis of “turn-on” fluorescence method, and the limit of detection is determined to be 0.1 μM. Other relevant anionic ions such as bisulfite, sulfate and mercapto compounds showed no interference for the detection of sulfide. These results suggest that the compound and method can be potentially applied for on-site measurement and effective removal of sulfide from environment.     

The use of sulfur to extract hydrogen from coal

The world's recoverable coal reserves contain about 3 × 10¹⁰ tons of hydrogen. The reaction of sulfur vapor with medium-volatile bituminous coal produces hydrogen sulfide in yields up to 97% (based on sulfur), and utilizes 70–75% of the hydrogen from the coal. The conversion of hydrogen sulfide to hydrogen can be effected through commercially proven processes; several laboratory-scale processes could also be scaled up for future use. The solid by-product of the coal–sulfur reaction meets or exceeds specifications for fixed carbon, ash, and friability of conventional metallurgical coke, though produced at lower temperatures than typical by-product coke ovens. A conceptual process is presented in which sulfur is converted to hydrogen sulfide by reaction with coal, the hydrogen sulfide in turn is converted to the desired hydrogen and to sulfur, and the sulfur is recycled through the reactor. The by-product is a good quality coke, but may also have other applications as a carbon material.     

Changes in hydrocarbon maturity indices with coal rank and type,Buller Coalfield,New Zealand

The Buller Coalfield (South Island, New Zealand) is an inverted late Paleogene Basin that contains middle Eocene bituminous coals which exhibit considerable variation in both coal rank (across-basin), and coal type (in-seam). Twenty-two fractionated bitumen extracts of Brunner Coal Measures coal samples from 12 drillholes were analyzed by GC and GC–MS to characterize the effect of coal rank and type on conventional hydrocarbon maturity indices at the beginning and end of the oil window (0.56–1.26% Ro_max).The Carbon Preference Index, pristane/phytane and isoprenoid/n-alkane ratios evolve throughout the high volatile bituminous B rank stage, while other biomarker ratios [18α(H)-22,29,30-trisnorneohopane/17α(H)-22,29,30-trisnorhopane (Ts/Tm), 18α(H),21β(H)-30-norneohopane (C₂₉ Ts)/17α(H),21β(H)-30-norhopane and C₃₀ diahopane/hopane] do not show appreciable change in value until medium volatile bituminous rank. Various aromatic based ratios appear to be more effective in delineating rank throughout the entire oil window; in particular the Methylphenanthrene Index and vitrinite reflectance are positively correlated over the entire bituminous rank range. However, subtle changes in depositional conditions (variable coal type) complicate these rank estimates. Within a given coal seam, variation in CPI, isoprenoid/n-alkane and hopane/sterane ratios appear to be related to the hydrogen content of the coal, while the homohopane index and the oleanane/hopane ratio covary with sulfur content. As with depressed vitrinite reflectance values, MPI is similarly lowered in the perhydrous samples. The mechanisms that control these hydrocarbon parameters during deposition and diagenesis are complex and convoluted, however, changes in bacterial activity and community (with marine incursion) appear to play an important role. Due to these anomalies, none of the hydrocarbon maturity indices calculated can be singularly used to constrain coal rank.     

Hydrocarbon—Generating Characteristics of Barkinite—Rich Colas from Late Permian Longtan Formation ,South China

Leping coal (including barkinite-rich coal) is a unique kind of coal,which is widely distrbuted in the Late Permian Longan Formation,South China,In this paper,ROck-Eval,Py-GC and simulation experiment via an open-system were used to study the hydrocarbon-generating potential,hydrocarbon composition.and hydrocarbon-generating model of barkiniterich coals from the shuicheng coal field of Guizhou Province,Southwest China.The results show that barkinite-rich coals have high hydrocarbon-generating potential,with S1 S2 being 211-311mg/g,and can produce large amounts of hydrocorbon at the high-maturity stage,mostly within the temperature range of 420-450℃(corresponding to VR0 1.1-1.5%);barkinite-rich coal is one of the better oil sources and light hydrocarbon and wet gas are the major hydrocarbon components,which account for 45% and 33% of the total hydrocarbons.respectively.These characteristics are of importance for exploring oil and gas resources in the Late permian Longtan Formation coals,southwest China.     

Ore metal redistribution by hydrocarbon–brine and hydrocarbon–halide melt phases, North Range footwall of the Sudbury Igneous Complex, Ontario, Canada

We report methane-dominant hydrocarbon (fluid) inclusions (CH₄±C₂H₆–C₂H₂, C₃H₈) coexisting with primary brine inclusions and secondary halide melt (solid NaCl) inclusions in Au–Pt-rich quartz-sulfide-epidote alteration veins associated with the footwall-style Cu–PGE (platinum-group element)–Au deposits at the Fraser Mine (North Range of the Sudbury Igneous Complex). Evidence for coentrapment of immiscible hydrocarbon–brine, and hydrocarbon–halide melt mixtures is demonstrated. A primary CH₄–brine assemblage was trapped during quartz growth at relatively low T (min. T _trapping∼145–315°C) and P (max. P _trapping∼500 bar), prior to the crystallization of sulfide minerals in the veins. Secondary inclusions contain solid halite and a mixture of CH₄, C₂H₆–C₂H₂ and C₃H₈ and were trapped at a minimum T of ∼710°C. The halite inclusions may represent halide melt that exsolved from crystallizing sulfide ores that texturally postdate (by replacement) early alteration quartz hosting the primary, lower T brine–CH₄ assemblage. Laser ablation ICP-MS analyses show that the brine, hydrocarbon and halide melt inclusions contain significant concentrations of Cu (0.1–1 wt% range), Au, Bi, Ag and Pt (all 0.1–10 ppm range). Cu:Pt and Cu:Au ratios in the inclusions are significantly (up to 4 log units) lower than in the host alteration veins and adjacent massive sulfide ore veins, suggesting either (1) early Cu loss from the volatiles by chalcopyrite precipitation or (2) enhanced Au and Pt solubilities relative to Cu at the temperatures of entrapment. Concentration ratios between coexisting brine and CH₄ inclusions are lower for Cu, Au, Bi and Ag than for other elements (Na, Ca, Fe, Mn, Zn, Pb) indicating that during interaction with the brine, the hydrocarbon phase was enriched in ore metals. The high concentrations of ore metals in hydrocarbon, brine and halide melt phases confirm that both aqueous and non-aqueous volatiles were carriers of precious metals in the Sudbury environment over a wide range of temperatures. Volatile evolution and magmatic sulfide differentiation were clearly part of a single, continuous process in the Sudbury footwall. The exsolution of H₂O-poor volatiles from fractionated sulfide liquid may have been a principal mechanism controlling the final distribution of PGE and Au in the footwall ore systems. The study reports the first measurements of precious metal concentrations in fluid inclusions from a magmatic Ni–Cu–PGE environment (the Sudbury district). Electronic Supplementary Material Supplementary material is available for this article at     

Petrology, rank and evidence for petroleum generation, Upper Triassic to Middle Jurassic coals, Central Alborz Region, Northern Iran

Upper Triassic to Middle Jurassic coals from the Alborz region of northern Iran were analyzed by reflected light-fluorescence microscopy and Rock Eval 6® pyrolysis to evaluate their regional rank variation, degree of hydrothermal alteration, and petroleum generative potential. The coal ranks in the region range from a low of 0.69%Ro_R in the Glanddeh-Rud area to a high of 1.02%Ro_R in the Gajereh area. T_max (°C) values (Rock Eval 6 pyrolysis) also increase progressively with increasing vitrinite %Ro values, however T_max is suppressed lower than would be expected for each rank ranging from 428 °C for the Glandeeh coal to 438 °C for the Gajereh coal. T_max suppression may be caused by maceral composition and soluble organics within the coal. Moderately high hydrogen indices, persistent and oily exudations from the coals during UV exposure, and traces of hydrocarbon fluid inclusions suggest that liquid petroleum was likely generated within some of the coals.     

Geochemically induced shifts in catabolic energy yields explain past ecological changes of diffuse vents in the East Pacific Rise 9°50'N area

The East Pacific Rise (EPR) at 9°50'N hosts a hydrothermal vent field (Bio9) where the change in fluid chemistry is believed to have caused the demise of a tubeworm colony. We test this hypothesis and expand on it by providing a thermodynamic perspective in calculating free energies for a range of catabolic reactions from published compositional data. The energy calculations show that there was excess H₂S in the fluids and that oxygen was the limiting reactant from 1991 to 1997. Energy levels are generally high, although they declined in that time span. In 1997, sulfide availability decreased substantially and H₂S was the limiting reactant. Energy availability dropped by a factor of 10 to 20 from what it had been between 1991 and 1995. The perishing of the tubeworm colonies began in 1995 and coincided with the timing of energy decrease for sulfide oxidizers. In the same time interval, energy availability for iron oxidizers increased by a factor of 6 to 8, and, in 1997, there was 25 times more energy per transferred electron in iron oxidation than in sulfide oxidation. This change coincides with a massive spread of red staining (putative colonization by Fe-oxidizing bacteria) between 1995 and 1997. For a different cluster of vents from the EPR 9°50'N area (Tube Worm Pillar), thermodynamic modeling is used to examine changes in subseafloor catabolic metabolism between 1992 and 2000. These reactions are deduced from deviations in diffuse fluid compositions from conservative behavior of redox-sensitive species. We show that hydrogen is significantly reduced relative to values expected from conservative mixing. While H₂ concentrations of the hydrothermal endmember fluids were constant between 1992 and 1995, the affinities for hydrogenotrophic reactions in the diffuse fluids decreased by a factor of 15 and then remained constant between 1995 and 2000. Previously, these fluids have been shown to support subseafloor methanogenesis. Our calculation results corroborate these findings and indicate that the 1992-1995 period was one of active growth of hydrogenotrophic communities, while the system was more or less at steady state between 1995 and 2000.     

Experimental study of mechanisms of fixation and reduction of uranium by sedimentary organic matter under diagenetic or hydrothermal conditions

Interactions between lignite and soluble uranyl species have been investigated experimentally at different temperatures from 20° to 400°C. Fixation of uranyl species by lignite (45° to 250°C) and their reduction to uraninite (120° to 400°C) were observed. The fixation of uranyl species by lignite results in the formation of stable organo-uranyl compounds. The reduction of uranyl species by lignite results in a stoichiometric liberation of H⁺ in the solution medium and in a dehydrogenation of lignite. This dehydrogenation can be attributed to two different processes. The first is an oxidation of alcohol functional groups into aldehyde or ketone functions accompanied by a simultaneous reduction of uranyl species. The second is a dehydrogenation of hydrocarbonaceous aliphatic moieties induced by the uranium species. The molecular hydrogen produced during this process is subsequently used for an additional reduction of uranyl species.     

Stable hydrogen isotopes in iron oxides—isotope effects associated with the dehydration of a natural goethite

The dehydration of a natural goethite to hematite is accompanied by a systematic hydrogen isotope fractionation. Closed system dehydration at, and below, 250°C results in a significantly greater degree of isotopic fractionation than does open system dehydration. This relationship is apparently reversed at 300°C. Both processes produce a progressive decrease in the $\text{D}\text{H}$ ratio of the mineral hydrogen with increasing degree of dehydration. At temperatures of 160°C to 250°C the closed system mineralvapor fractionation factor is independent of temperature, while above 250°C, it varies strongly with temperature. The mineral-vapor fractionation factor associated with open system dehydration appears to be independent of temperature over the interval 160°C to 300°C. The closed system $\text{D}\text{H}$ fractionation suggests that natural goethite undergoing dehydration in the presence of water can isotopically exchange with that water.CO₂ loss from goethite during dehydration is correlated with the loss of H₂O. The CO₃ is thought to be present in carbonates which exist as impurities in the goethite. Loss of both H₂O and CO₂ appears to be diffusion-controlled.     

Hydrocarbons generation potential of the Jurassic–Lower Cretaceous Formation, Ajeel field, Iraq

Organic geochemical analysis and palynological studies of the organic matters of subsurface Jurassic and Lower Cretaceous Formations for two wells in Ajeel oil field, north Iraq showed evidences for hydrocarbon generation potential especially for the most prolific source rocks Chia Gara and Sargelu Formations. These analyses include age assessment of Upper Jurassic (Tithonian) to Lower Cretaceous (Berriasian) age and Middle Jurassic (Bathonian–Tithonian) age for Chia Gara and Sargelu Formations, respectively, based on assemblages of mainly dinoflagellate cyst constituents. Rock-Eval pyrolysis have indicated high total organic carbon (TOC) content of up to 18.5 wt%, kerogen type II with hydrogen index of up to 415 mg HC/g TOC, petroleum potential of 0.70–55.56 kg hydrocarbon from each ton of rocks and mature organic matter of maximum temperature reached (T_max) range between 430 and 440 °C for Chia Gara Formation, while Sargelu Formation are of TOC up to 16 wt% TOC, Kerogen type II with hydrogen index of 386 mg HC/g TOC, petroleum potential of 1.0–50.90 kg hydrocarbon from each ton of rocks, and mature organic matter of T_max range between 430 and 450 °C. Qualitative studies are done in this study by textural microscopy used in assessing amorphous organic matter for palynofacies type belonging to kerogen type A which contain brazinophyte algae, Tasmanites, and foraminifera test linings, as well as the dinoflagellate cysts and spores, deposited in dysoxic–anoxic environment for Chia Gara Formation and similar organic constituents deposited in distal suboxic–anoxic environment for Sargelu Formation. The palynomorphs are of dark orange and light brown, on the spore species Cyathidites australis, that indicate mature organic matters with thermal alteration index of 2.7–3.0 for the Chia Gara Formation and 2.9–3.1 for the Sargelu Formation by Staplin's scale. These characters have rated the succession as a source rock for very high efficiency for generation and expulsion of oil with ordinate gas that charged mainly oil fields of Baghdad, Dyala (B?aquba), and Salahuddin (Tikrit) Governorates. Oil charge the Cretaceous-Tertiary total petroleum system (TPS) are mainly from Chia Gara Formation, because most oil from Sargelu Formation was prevented passing to this TPS by the regional seal Gotnia Formation. This case study of mainly Chia Gara oil source is confirmed by gas chromatography–mass spectrometry analysis for oil from reservoirs lying stratigraphically above the Chia Gara Formation in Ajeel and Hamrine oil fields, while oil toward the north with no Gotnia seal could be of mainly Sargelu Formation source.     

Characterization of hydrocarbon-bearing fluid inclusion in sandstones of Jaisalmer basin, Rajasthan: A preliminary approach

The quartz grains from the sandstone of Jaisalmer, Pariwar and Goru Formations of the Jaisalmer basin, Rajasthan, India, exhibits a variety of primary and secondary fluid inclusions. Most of them are hydrocarbon bearing fluid inclusions. Laser Raman studies indicate that the primary fluid inclusions were mostly having aliphatic hydrocarbons with lower degree of maturity, while the secondary fluid inclusions were generally with aliphatic as well as aromatic hydrocarbons with higher degree of maturity. This inference was consistent with their fluorescence characteristics. The homogenization temperatures of primary monophase CH₄ rich fluid inclusions varied from ?80°C to ?100°C, whereas the primary biphase fluid inclusions (CH₄-CO₂) homogenized between +80°C and +150°C. The secondary petroleum rich monophase fluid inclusions were having homogenization temperature between ?80°C to ?90°C, whereas the secondary biphase fluid inclusions homogenized between +130°C and +180°C. Most of the secondary biphase fluid inclusions were having the mixtures of H₂O-CO₂-NaCl, and were identified on the basis clathrate formation and they got homogenized between +140°C and + 250 °C. The three past events of migration of petroleum inferred in the host rock which were marked by the presence of characteristic secondary fluid inclusions. They were identified on the basis of cross-cutting relationships of different trails of fluid inclusions in the quartz. The cement generation in the basin might have been occurred in two stages as per the fluid inclusion petrography.     

Separation of H<Subscript>2</Subscript>S from CH<Subscript>4</Subscript> by polymeric membranes at different H<Subscript>2</Subscript>S concentrations

In this work, permeation of mixed gases H₂S/CH₄ through commercial polyphenylene oxide (PPO) hollow fiber and poly (ester urethane) urea (PEUU) flat membranes was studied at pressures of 345–689 kPa, at ambient temperature and at 313.15 K. Various H₂S concentrations of about 100–5000 ppm in CH₄ binary synthetic gas mixtures as well as a real natural gas sample obtained from a gas refinery containing 0.3360 mol.% H₂S (equivalent to 3360 ppm) were tested. It was observed that the permeance of components was affected by the balance between competitive sorption and plasticization effects. Separation factors of H₂S/CH₄ were in the range of 1.3–2.9, 1.8–3.1 and 2.2–4.3 at pressures of 345, 517 and 689 kPa, respectively. In the range of 101–5008 ppm of H₂S in CH₄, the effect of temperature on the separation factor was nearly negligible; however, permeances of both components of the mixtures increased with temperature. Additionally, the results obtained by PEUU membrane indicated that it was a better choice for hydrogen sulfide separation from H₂S/CH₄ mixtures than PPO. For PPO membrane, removal of hydrogen sulfide from high-concentration (up to 5008 ppm) binary mixtures of H₂S/CH₄ was compared with that of low concentration (as low as 101 ppm) through PPO. At concentrations of 101–968 ppm, plasticization was dominant compared with the competitive sorption, while for the H₂S feed concentrations of 3048 ppm, the competitive sorption effect was dominant. For H₂S concentration of 5008 ppm, the balance between these two effects played an important role for explanation of its trend.     

Secondary mineral-forming processes in natural—anthropogenic hydrogeological systems at sulfide deposits. Simulation of the origin of the phase (Fe,Mg)SO4 · 7H2O in the course of sulfide oxidation at the Degtyarka copper sulfide deposit

Data on the decommissioned Degtyarka Cu sulfide deposit, Urals, confirm the hypothesis that the flooding of abandoned mine workings is associated with the synthesis of secondary sulfates. Numerical simulation of hydrogeochemical processes in the rock—water system imitating the flooding of an underground void makes it possible to evaluate the conditions under which kirovite (Fe,Mg)SO₄ · 7H₂O and melanterite are formed at the oxidation of ore sulfides. Secondary sulfates are formed when the redox potential of the system is transformed from reducing to oxidizing within the stability field of Fe(II) species. The Fe/Mg ratio of the kirovite (Fe,Mg)SO₄ · 7H₂O is controlled first of all by the percentage of sulfides in the rock—water system, the rock/water ratio, the openness of the system with respect to atmospheric gases, and the temperature.     

GEOCHEMICAL AND MINEROLOGIC STUDY OF A STONY METEORITE FROM THE VICINITY OF THE VILLAGE OF SEVRYUKOVO

In studying the conditions of formation of stony meteorites, we assume that 1) they are fragments of asteroids fallen to the surface of the earth. During their flight through the atmosphere, the meteorites develop a melted surface layer but their texture and mineralogic composition remain unchanged. 2) According to V. M. Goldschmidt, stone meteorites crystallize in a lesser gravity field than that of the earth, which is the reason for their chondritic texture and high porosity (about 4%). 3) Meteorites were formed in a medium with a deficiency of free oxygen. As a result, part of their iron and nickel was segregated as native metal; in addition, lawrencite and oldhamite, sulfides typical of meteorites, were formed.

We identify three stages of meteorite formation: magmatic, pneumatolytic, and hydrothermal. The interval 1450-850°C. corresponds to the magmatic stage at which a silicate phase and native iron with nickel were formed. As a result of thermal dissociation of water and because of the deficiency of oxygen required for a complete oxidation of metals and carbon, in the gaseous phase, free oxygen and H₂O were absent and the phase consisted probably of H₂, CH₄, CO₂, and CO.

The temperature interval 750-500°C. corresponds to the pneumatolytic phase. Here, H₂S, CH₄, CO₂, and CO were the principal agents of the gaseous phase. CH₄ was formed in a high temperature reaction between hydrogen and elementary carbon. As the temperature dropped to 750°C., electrolytic dissociation of H₂O rendered possible the formation of sulfides, especially of troilite.

Mineralization at the hydrothermal stage with a temperature interval of 400 to 300°C. has been observed only in carbon meteorites with a considerable graphitic carbon content. Here, a small portion of the ferrous iron is oxidized to the ferric, in the presence of CO₂ and at a temperature of 450° to 500°C.; the iron sulfide so formed is represented by pyrrhotite. Simultaneously, colored silicates are chloritized, with a separation of CaCO₃.—Auth. English summ.     

Reducing leachable petroleum hydrocarbon concentration in weathered fuel oil contaminated soil by chemical oxidation with hydrogen peroxide

Number 6 fuel oil is one of the most used energy sources for electricity generation. However, leaks can contaminate soil and also groundwater due to leaching. At old sites, the oil may have low toxicity but still contaminate groundwater with foul-tasting compounds even at low concentrations. The purpose of this study was to evaluate the feasibility of applying H₂O₂ to reduce the leaching potential of a fuel oil contaminated soil. A silt-loam soil was collected from a contaminated thermal-electric plant with a hydrocarbon concentration of 3.2% in soil producing 4.3 mg/l in leachate. Hydrogen peroxide was applied (0.1, 0.2, 0.3, 0.6, 1.2% dry weight basis), and petroleum hydrocarbons were measured in soil and leachate pre- and post-treatment (72 h). At first, the soil and leachate concentrations diminished linearly (24.4 and 27.3% in soil and leachate, respectively). This was followed by a phase in which the concentration in leachate diminished greatly (75.8%) although the concentration in soil was reduced only moderately (15.1%). Overall, hydrocarbons in leachates were reduced 82.4% even though concentrations in soil were only reduced 35.8%. Correlation analysis showed that at only 1.0% w/w H₂O₂ a concentration of petroleum hydrocarbons in leachate safe for human consumption (≤ 1 mg/l) could be obtained even with a final hydrocarbon concentration in soil > 2%. Thus, this study presents an alternative strategy for remediation of fuel oil contaminated soils in urban environments that protects water sources by focusing on contamination in leachates, without spending extra financial resources to reduce the hydrocarbon concentration in low-toxicity soil.     

A model of the diagenetic evolution of coaly sedimentary organic matter

Elemental composition was used to calculate the amounts of compounds produced during the diagenetic evolution of a coal series from the Mahakam delta (Kalimantan, Indonesia). These calculations were based on the following hypotheses: organic nitrogen does not take part in reactions and remains unchanged in the residual organic matter, the only compounds produced are water, carbon dioxide and hydrocarbons.This approach shows that carbon loss during diagenesis is mainly as CO₂, and hydrogen loss is mainly as H₂O. Hydrocarbon production is negligible, in accordance with absence of bacterial methane accumulations in the Mahakam delta.The δ¹³C of coals in the sequence becomes about 2 per mil more positive over the diagenetic depth range of coal evolution. Accounting for the coal δ¹³C change in terms of CO₂ loss requires that the CO₂ given off have δ¹³C of about ?40%.. Such negative CO₂ has not been observed in natural systems, except when CH₄ is undergoing oxidation. Several plausible causes for this effect are discussed.     

Spectroscopic and bond-topological investigation of interstitial volatiles in beryl from Slovakia

Nine beryl samples from Western Carpathians, Slovakia, were investigated by infrared and Raman spectroscopy and differential thermal analysis. Two types of water H₂O I and H₂O II were detected. Infrared spectroscopy proved the presence of water type I and II in the presence of alkali cations with several bands: (1) symmetric stretching vibration—ν₁; (2) antisymmetric stretching mode—ν₃; (3) bending vibration—ν₂. The presence of singly and doubly coordinated type II water (IIs and IId) was confirmed by single-crystal IR spectroscopy. From Raman spectra a band at 3606 cm^?1 was assigned to ν₁ of water type I and the range of 3597–3600 cm^?1 to water type II. The presence of doubly coordinating water indicates a relatively highly hydrated environment with the presence of alkali ions including Na as the dominant cation coordinated by H₂O II. CO₂ bands were detected only by single-crystal IR spectroscopy. Thermal analysis proved total water loss in the range of 1.4–2.0 wt% and three main dehydration events. Based on the study of bond-topological arrangements two molecules of H₂O IId are each bound with two H···O1 bonds and one Na–O_W bond with an angular distortion, and by releasing one H₂O molecule more stable H₂O IIs is produced. The H₂O I molecule is bound only by two equivalent hydrogen bonds. The H₂O IIs molecule with a Na–O_W bond strength of 0.28 vu and two H···O1 bonds of 0.14 vu without any forced angular distortion is the most stable of all.     

Diffusion compensation in natural silicates

The temperature dependence of diffusion is usually found to follow the Arrhenius law: D = D₀e^?E/RT Winchell (1969) showed that there is commonly an inter-dependence between D₀ and E (for diffusion in silicate glasses), such that diffusion of different species show a positive correlation on a log D₀ vs E plot. A similar effect was noted by Hofmann (1980) for cation diffusion in basalt. This implies that diffusion rates of different species tend to converge at a particular temperature; this effect is known as the ‘compensation effect’. I will show that this effect is also present for diffusion in feldspars and olivines. The equations for the compensation lines (with E given in kcal/mol) are: basalt—E = 50 + 7.5 log D₀ feldspar—E = 50.7 + 3.4 log D₀ olivine—E = 78.0 + 7.5 log D₀ The convergence, or crossover, temperatures for diffusion in various materials are: obsidian—3400°C basalt—1370°C olivine—1360°C feldspar—460°C Compensation plots are useful for evaluating and comparing experimental diffusion data (though of limited usefulness in a predictive sense) and for understanding ‘closure temperatures’ for diffusion in petrogenetic processes (since closure temperature, the temperature at which natural diffusion processes are frozen in, is dependent on E, log d₀, and cooling rate). I show that most diffusing species in feldspar have a closure-temperature close to the crossover or convergence temperature, implying that all species in feldspars can be expected to ‘freeze-in’ simultaneously at temperatures in the range 400–600°C (for cooling rates in the range 10¹–10⁵°C/myr). Closure temperatures of various species in olivine, on the other hand, span a much larger range (800°C) for a similar range in cooling rates, implying that different elements in olivine will record different time-temperature stages in petrogenetic processes.     

沉积有机质的成烃热模拟实验研究

作者采用小玻管热模拟方法研究了煤及碳质泥岩中藻类体、基质镜质体、沥青质体、运移沥青、角质体、树脂体、孢子体、现代栓皮栎的木栓层,水生植物蓝藻(粘球藻)和水生动物虾蛄的成烃规律。并根据有机组分的荧光特性和显微傅利叶红外光谱特征初步建立了我国煤系源岩生油组分及现代海生生物蓝藻和虾蛄的生油模式。研究结果表明:结构藻类体生油晚,结束晚;不同类型的基质镜质体和沥青质体的成烃过程存在差异,且基质镜质体可早期生油;现代木栓组织的成烃模拟支持了木栓质体早期生油的观点;角质体、基质镜质体B的成烃具多阶段性的特点;现代粘球藻具生油晚,结束晚,且成烃范围宽;水生动物虾蛄具成烃早,结束早,且成烃范围窄的特点。