Light hydrocarbons geochemistry of surface sediments from Pranhita-Godavari Basin,Andhra Pradesh

A geochemical study of surface sediments from Pranhita-Godavari Basin, Andhra Pradesh, India was carried out using light hydrocarbon compounds to assess the hydrocarbon potential of the basin. Suite of 80 soil samples were collected from the depth of 2.5 m and analyzed for adsorbed light gaseous hydrocarbons namely methane (CH₄), ethane (C₂H₆) and propane (C₃H₈) in Gas chromatograph. Compound specific Carbon isotope ratios for CH₄ and C₂H₆ were also determined using GC-C IRMS (Gas Chromatograph Combustion Isotope Mass Spectrometer). The presence of moderate to low concentrations of methane (C_CH4 C_{CH_4 } : 1 to 138 ppb), ethane (H₄{H_4 }: 1 to 35 ppb) and propane (C_{C3 H8} C_{C_3 H_8 } : 1 to 20 ppb) was measured in the soil samples. Carbon isotopic composition of d¹³ C_CH4 \delta ^{13} C_{CH_4 } ranges between −27.9 to −47.1 ‰ and d¹³ C_{C2 H6} \delta ^{13} C_{C_2 H_6 } ranged between −36.9 to −37.2 ‰ (V-PDB) indicating that these gases are of thermogenic origin. Study of soil samples suggests the area has good potential for hydrocarbon.     

Authigenic carbonates in methane seeps from the Norwegian sea: Mineralogy, geochemistry, and genesis

Authigenic carbonates in the caldera of an Arctic (72°N) submarine mud volcano with active CH₄bearing fluid discharge are formed at the bottom surface during anaerobic microbial methane oxidation. The microbial community consists of specific methane-producing bacteria, which act as methanetrophic ones in conditions of excess methane, and sulfate reducers developing on hydrogen, which is an intermediate product of microbial CH₄ oxidation. Isotopically light carbon (δ¹³C_av =−28.9%0) of carbon dioxide produced during CH₄ oxidation is the main carbonate carbon source. Heavy oxygen isotope ratio (δ¹⁸O_av = 5%0) in carbonates is inherited from seawater sulfate. A rapid sulfate reduction (up to 12 mg S dm⁻³ day⁻¹) results in total exhausting of sulfate ion in the upper sediment layer (10 cm). Because of this, carbonates can only be formed in surface sediments near the water-bottom interface. Authigenic carbonates occurring within sediments occur do notin situ. Salinity, as well as CO ₃ ²⁻ /Ca and Mg/Ca ratios, correspond to the field of nonmagnesian calcium carbonate precipitation. Calcite is the dominant carbonate mineral in the methane seep caldera, where it occurs in the paragenetic association with barite. The radiocarbon age of carbonates is about 10000 yr.     

Origin,distribution and hydrogeochemical controls on methane occurrences in shallow aquifers,southwestern Ontario,Canada

Natural gas reservoirs in organic-rich shales in the Appalachian and Michigan basins in the United States are currently being produced via hydraulic fracturing. Stratigraphically-equivalent shales occur in the Canadian portion of the basins in southwestern Ontario with anecdotal evidence of gas shows, yet there has been no commercial shale gas production to date. To provide baseline data in the case of future environmental issues related to hydraulic fracturing and shale gas production, such as leakage of natural gas, saline water, and/or hydraulic fracturing fluids, and to evaluate hydrogeochemical controls on natural gas accumulations in shallow groundwater in general, this study investigates the origin and distribution of natural gas and brine in shallow aquifers across southwestern Ontario. An extensive geochemical database of major ion and trace metal chemistry and methane concentrations of 1010 groundwater samples from shallow, domestic wells in bedrock and overburden aquifers throughout southwestern Ontario was utilized. In addition, select wells (n = 36) were resampled for detailed dissolved gas composition, δ¹³C of CH₄, C₂, C₃, and CO₂, and δD of CH₄. Dissolved gases in groundwater from bedrock and overburden wells were composed primarily of CH₄ (29.7–98.6 mol% of total gas volume), N₂ (0.8–66.2 mol%), Ar + O₂ (0.2–3.4 mol%), and CO₂ (0–1.2 mol%). Ethane was detected, but only in low concentrations (<0.041 mol%), and no other higher chain hydrocarbons were present, except for one well in overburden overlying the Dundee Formation, which contained 0.81 mol% ethane and 0.21 mol% propane. The highest methane concentrations (30 to >100 in situ % saturation) were found in bedrock wells completed in the Upper Devonian Kettle Point Formation, Middle Devonian Hamilton Group and Dundee Formation, and in surficial aquifers overlying these organic-rich shale-bearing formations, indicating that bedrock geology is the primary control on methane occurrences. A few (n = 40) samples showed Na–Cl–Br evidence of brine mixing with dilute groundwater, however only one of these samples contained high (>60 in situ % saturation) CH₄. The relatively low δ¹³C values of CH₄ (−89.9‰ to −57.3‰), covariance of δD values of CH₄ and H₂O, positive correlation between δ¹³C values of CH₄ and CO₂, and lack of higher chain hydrocarbons (C₃₊) in all but one dissolved gas sample indicates that the methane in groundwater throughout the study area is primarily microbial in origin. The presence or absence of alternative electron acceptors (e.g. dissolved oxygen, Fe, NO₃, SO₄), in addition to organic substrates, controls the occurrence of microbial CH₄ in shallow aquifers. Microbial methane has likely been accumulating in the study area, since at least the Late Pleistocene to the present, as indicated by the co-variance and range of δD values of CH₄ (−314‰ to −263‰) and associated groundwater (−19‰ to −6‰ δD-H₂O).     

Gases in Taiwan mud volcanoes: Chemical composition,methane carbon isotopes,and gas fluxes

Mud volcanoes are important pathways for CH₄ emission from deep buried sediments; however, the importance of gas fluxes have hitherto been neglected in atmospheric source budget considerations. In this study, gas fluxes have been monitored to examine the stability of their chemical compositions and fluxes spatially, and stable C isotopic ratios of CH₄ were determined, for several mud volcanoes on land in Taiwan. The major gas components are CH₄ (>90%), “air” (i.e. N₂ + O₂ + Ar, 1–5%) and CO₂ (1–5%) and these associated gas fluxes varied slightly at different mud volcanoes in southwestern Taiwan. The Hsiao-kun-shui (HKS) mud volcano emits the highest CH₄ concentration (CH₄ > 97%). On the other hand, the Chung-lun mud volcano (CL) shows CO₂ up to 85%, and much lower CH₄ content (<37%). High CH₄ content (>90%) with low CO₂ (<0.2%) are detected in the mud volcano gases collected in eastern Taiwan. It is suggestive that these gases are mostly of thermogenic origin based on C₁ (methane)/C₂ (ethane) + C₃ (propane) and δ¹³C_CH4 results, with the exception of mud volcanoes situated along the Gu-ting-keng (GTK) anticline axis showing unique biogenic characteristics. Only small CH₄ concentration variations, <2%, were detected in four on-site short term field-monitoring experiments, at Yue-shi-jie A, B, Kun-shui-ping and Lo-shan A. Preliminary estimation of CH₄ emission fluxes for mud volcanoes on land in Taiwan fall in a range between 980 and 2010 tons annually. If soil diffusion were taken into account, the total amount of mud volcano CH₄ could contribute up to 10% of total natural CH₄ emissions in Taiwan.     

Infrared spectroscopic characterization of dehydration and accompanying phase transition behaviors in NAT-topology zeolites

Relative humidity ( P_{\textH 2 \textO} P_{{{\text{H}}_{ 2} {\text{O}}}} , partial pressure of water)-dependent dehydration and accompanying phase transitions in NAT-topology zeolites (natrolite, scolecite, and mesolite) were studied under controlled temperature and known P_{\textH 2 \textO} P_{{{\text{H}}_{ 2} {\text{O}}}} conditions by in situ diffuse-reflectance infrared Fourier transform spectroscopy and parallel X-ray powder diffraction. Dehydration was characterized by the disappearance of internal H₂O vibrational modes. The loss of H₂O molecules caused a sequence of structural transitions in which the host framework transformation path was coupled primarily via the thermal motion of guest Na⁺/Ca²⁺ cations and H₂O molecules. The observation of different interactions of H₂O molecules and Na⁺/Ca²⁺ cations with host aluminosilicate frameworks under high- and low- P_{\textH 2 \textO} P_{{{\text{H}}_{ 2} {\text{O}}}} conditions indicated the development of different local strain fields, arising from cation–H₂O interactions in NAT-type channels. These strain fields influence the Si–O/Al–O bond strength and tilting angles within and between tetrahedra as the dehydration temperature is approached. The newly observed infrared bands (at 2,139 cm⁻¹ in natrolite, 2,276 cm⁻¹ in scolecite, and 2,176 and 2,259 cm⁻¹ in mesolite) result from strong cation–H₂O–Al–Si framework interactions in NAT-type channels, and these bands can be used to evaluate the energetic evolution of Na⁺/Ca²⁺ cations before and after phase transitions, especially for scolecite and mesolite. The 2,176 and 2,259 cm⁻¹ absorption bands in mesolite also appear to be related to Na⁺/Ca²⁺ order–disorder that occur when mesolite loses its Ow4 H₂O molecules.     

Enrichment of nitrogen and 13C of methane in natural gases from the Khuff Formation,Saudi Arabia,caused by thermochemical sulfate reduction

Permian Khuff reservoirs along the east coast of Saudi Arabia and in the Arabian Gulf produce dry sour gas with highly variable nitrogen concentrations. Rough correlations between N₂/CH₄, CO₂/CH₄ and H₂S/CH₄ suggest that non-hydrocarbon gas abundances are controlled by thermochemical sulfate reduction (TSR). In Khuff gases judged to be unaltered by TSR, methane δ¹³C generally falls between −40‰ and −35‰ VPDB and carbon dioxide δ¹³C between −3‰ and 0‰ VPDB. As H₂S/CH₄ increases, methane δ¹³C increases to as much as −3‰ and carbon dioxide δ¹³C decreases to as little as −28‰. These changes are interpreted to reflect the oxidation of methane to carbon dioxide.Khuff reservoir temperatures, which locally exceed 150 °C, appear high enough to drive the reduction of sulfate by methane. Anhydrite is abundant in the Khuff and fine grained nodules are commonly rimmed with secondary calcite cement. Some cores contain abundant pyrite, sphalerite and galena. Assuming that nitrogen is inert, loss of methane by TSR should increase N₂/CH₄ of the residual gas and leave δ¹⁵N unaltered. δ¹⁵N of Paleozoic gases in Saudi Arabia varies from −7‰ to 1‰ vs. air and supports the TSR hypothesis. N₂/CH₄ in gases from stacked Khuff reservoirs varies by a factor of 19 yet the variation in δ¹⁵N (0.3–0.5‰) is trivial.Because the relative abundance of hydrogen sulfide is not a fully reliable extent of reaction parameter, we have attempted to assess the extent of TSR using plots of methane δ¹³C versus log(N₂/CH₄). Observed variations in these parameters can be fitted using simple Rayleigh models with kinetic carbon isotope fractionation factors between 0.98 and 0.99. We calculate that TSR may have destroyed more than 90% of the original methane charge in the most extreme instance. The possibility that methane may be completely destroyed by TSR has important implications for deep gas exploration and the origin of gases rich in nitrogen as well as hydrogen sulfide.     

Superdense CO2 inclusions in Cretaceous quartz–stibnite veins hosted in low-grade Variscan basement of the Western Carpathians, Slovakia

CO₂ inclusions with density up to 1,197 kg m⁻³ occur in quartz–stibnite veins hosted in the low-grade Palaeozoic basement of the Gemericum tectonic unit in the Western Carpathians. Raman microanalysis corroborated CO₂ as dominant gas species accompanied by small amounts of nitrogen (<7.3 mol%) and methane (<2.5 mol%). The superdense CO₂ phase exsolved from an aqueous bulk fluid at temperatures of 183–237°C and pressures between 1.6 and 3.5 kbar, possibly up to 4.5 kbar. Low thermal gradients (∼12–13°C km⁻¹) and the CO₂–CH₄–N₂ fluid composition rule out a genetic link with the subjacent Permian granites and indicate an external, either metamorphogenic (oxidation of siderite, dedolomitization) or lower crustal/mantle, source of the ore-forming fluids.According to microprobe U–Pb–Th dating of monazite, the stibnite-bearing veins formed during early Cretaceous thrusting of the Gemeric basement over the adjacent Veporic unit. The 15- to 18-km depth of burial estimated from the fluid inclusion trapping PT parameters indicates a 8- to 11-km-thick Upper Palaeozoic–Jurassic accretionary complex overlying the Gemeric basement and its Permo-Triassic autochthonous cover.     

Raman spectra of methane hydrate up to 86 GPa

High-pressure Raman studies of methane hydrate were performed using a diamond anvil cell in the pressure range of 0.1–86 GPa at room temperature. Raman spectra of the methane molecules revealed that new softened intramolecular vibration mode of ν ₁ appeared at 17 GPa and that the splitting of vibration mode of ν ₃ occurred at 15 GPa. The appearance of these two modes indicates that an intermolecular attractive interaction increases between the methane molecules and the host water molecules and between the neighboring methane molecules. These interactions might result in the exceptional stability of a high-pressure structure, a filled ice Ih structure (FIIhS) for methane hydrate, up to 40 GPa. At 40 GPa, a clear change in the slope of the Raman shift versus pressure occurred, and above 40 GPa the Raman shift of the vibration modes increased monotonously up to 86 GPa. A previous XRD study showed that the FIIhS transformed into another new high-pressure structure at 40 GPa. The change in the Raman spectra at 40 GPa may be induced by the transition of the structure.     

Sources and flux of natural gases from Mono Lake,California

The ability to identify a formation mechanism for natural gas in a particular environment requires consideration of several geochemical factors when there are multiple sources present. Four primary sources of methane have been identified in Mono Lake. Two of these sources were associated with numerous natural gas seeps which occur at various locations in the lake and extend beyond its present boundary; the two other gas sources result from current microbiological processes. In the natural gas seeps, we observed flow rates as high as 160 moles CH₄ day⁻¹, and estimate total lakewide annual seep flux to be 2.1 × 10⁶ moles CH₄. Geochemical parameters (δ¹³CH₄,δDCH₄,CH₄/[C₂H₆+ C₃H₈]) andδ¹⁴CH₄measurements revealed that most of the seeps originate from a paleo-biogenic (δ¹³CH₄ = about −70%.). natural gas deposit of Pleistocene age which underlies the current and former lakebed. Gas seeps in the vicinity of hot springs had, in combination with the biogenic gas, a prominent thermogenic gas component resulting from hydrothermal alteration of buried organic matter.Current microbiological processes responsible for sources of natural gas in the lake included pelagic meth- anogenesis and decomposition of terrestrial grasses in the littoral zone. Methanogenesis in the pelagic sediments resulted in methane saturation (2–3 mM at 50 cm; δ₁₃CH₄ = about −85%.). Interstitial sulfate decreased from 133 mM at the surface to 35 mM by 110 cm depth, indicating that sulfate-reduction and methanogenesis operated concurrently. Methane diffused out of the sediments resulting in concentrations of about 50 μM in the anoxic bottom waters. Methane oxidation in the oxic/anoxic boundry lowered the concentration by >98%, but values in surface waters (0.1–1.3μM) were supersaturated with respect to the atmosphere. The δ¹³CH₄ (range = −21.8 to −71.8%.) of this unoxidized residual methane was enriched in ¹³C relative to methane in the bottom water and sediments. Average outward flux of this methane was 2.77 × 10⁷ moles yr⁻¹. A fourth, but minor source of methane (δ¹³CH₄ = −55.2%.) was associated with the decomposition of terrestrial grasses taking place in the lake's recently expanded littoral zone.     

Chemical composition of nyerereite and gregoryite from natrocarbonatites of Oldoinyo Lengai volcano,Tanzania

Alkali carbonates nyerereite, ideally Na₂Ca(CO₃)₂ and gregoryite, ideally Na₂CO₃, are the major minerals in natrocarbonatite lavas from Oldoinyo Lengai volcano, northern Tanzania. They occur as pheno- and microphenocrysts in groundmass consisting of fluorite and sylvite; nyerereite typically forms prismatic crystals and gregoryite occurs as round, oval crystals. Both minerals are characterized by relatively high contents of various minor elements. Raman spectroscopy data indicate the presence of sulfur and phosphorous as (SO₄)²⁻ and (PO₄)³⁻ groups. Microprobe analyses show variable composition of both nyerereite and gregoryite. Nyerereite contains 6.1–8.7 wt % K₂O, with subordinate amounts of SrO (1.7–3.3 wt %), BaO (0.3–1.6 wt %), SO₃ (0.8–1.5 wt %), P₂O₅ (0.2–0.8 wt %) and Cl (0.1–0.35 wt %). Gregoryite contains 5.0–11.9 wt % CaO, 3.4–5.8 wt % SO₃, 1.3–4.6 wt % P₂O₅, 0.6–1.0 wt % SrO, 0.1–0.6 wt % BaO and 0.3–0.7 wt % Cl. The content of F is below detection limits in nyerereite and gregoryite. Laser ablation ICP-MS analyses show that REE, Mn, Mg, Rb and Li are typical trace elements in these minerals. Nyerereite is enriched in REE (up to 1080 ppm) and Rb (up to 140 ppm), while gregoryite contains more Mg (up to 367 ppm) and Li (up to 241 ppm) as compared with nyerereite.     

Ammonium in aqueous fluids to 600 °C, 1.3 GPa: A spectroscopic study on the effects on fluid properties, silica solubility, and K-feldspar to muscovite reactions

The behavior of ammonium, NH₄⁺, in aqueous systems was studied based on Raman spectroscopic experiments to 600 °C and about 1.3 GPa. Spectra obtained at ambient conditions revealed a strong reduction of the dynamic three-dimensional network of water with addition of ammonium chloride, particularly at small solute concentrations. The differential scattering cross section of the ν₁-NH₄⁺ Raman band in these solutions was found to be similar to that of salammoniac.The Raman band of silica monomers at ∼780 cm⁻¹ was present in all spectra of the fluid at high temperatures in hydrothermal diamond-anvil cell experiments with H₂O ± NH₄Cl and quartz or the assemblage quartz + kyanite + K-feldspar ± muscovite/tobelite. However, these spectra indicated that dissolved silica is less polymerized in ammonium chloride solutions than in comparable experiments with water. Quantification based on the normalized integrated intensity of the H₄SiO₄⁰ band showed that the silica solubility in experiments with H₂O + NH₄Cl was significantly lower than that in equimolal NaCl solutions. This suggests that ammonium causes a stronger decrease in the activity of water in chloridic solutions than sodium.The Raman spectra of the fluid also showed that a significant fraction of ammonium was converted to ammonia, NH₃, in all experiments at temperatures above 300 °C. This indicates a shift towards acidic conditions for experiments without a buffering mineral assemblage. The estimated pH of the fluid was ∼2 at 600 °C, 0.26 GPa, 6.6 m initial NH₄Cl, based on the ratio of the integrated ν₁-NH₃ and ν₁-NH₄⁺ intensities and the HCl⁰ dissociation constant. The NH₃/NH₄⁺ ratio increased with temperature and decreased with pressure. This implies that more ammonium should be retained in K-bearing minerals coexisting with chloridic fluids upon high-P low-T metamorphism. At 500 °C, 0.73 GPa, ammonium partitions preferentially into the fluid, as constrained from infrared spectroscopy on the muscovite and from mass balance.The conversion of K-feldspar to muscovite proceeded much faster in experiments with NH₄Cl solutions than in comparable experiments with water. This is interpreted as being caused by enhancement of the rate-limiting alumina solubility, suggesting complexation of Al with NH₄. Nucleation and growth of mica at the expense of K-feldspar and NH₄⁺/K⁺ exchange between fluid and K-feldspar occurred simultaneously, but incorporation of NH₄⁺ into K-feldspar was distinctly faster than K-feldspar consumption.     

Anaerobic oxidation of methane in coastal sediment from Guishan Island (Pearl River Estuary), South China Sea

The concentrations of CH₄, SO₄²⁻, σCO₂ and the carbon isotope compositions of ΣCO₂ and CH₄ in the pore-water of the GS sedimentary core collected from Guishan Island (Pearl River Estuary), South China Sea, were determined. The methane concentration in the pore-water shows dramatic changes and sulfate concentration gradients are linear at the base of the sulfate reduction zone for the station. The carbon isotope of methane becomes heavier at the sulfate-methane transition (SMT) likely because of the Raleigh distillation effect; ¹²CH₄ was oxidized faster than ¹³CH₄, and this caused the enrichment of residual methane δ ¹³C and δ ¹³C-ΣCO₂ minimum. The geochemical profiles of the pore-water support the existence of anaerobic oxidation of methane (AOM), which is mainly controlled by the quality and quantity of the sedimentary organic matter. As inferred from the index of δ ¹³C-TOC value and TOC/TN ratio, the organic matter is a mix of mainly refractory terrestrial component plus some labile alga marine-derived in the study area. A large amount of labile organic matter (mainly labile alga marine-derived) is consumed via the process of sedimentary organic matter diagenesis, and this reduces the amount of labile organic matter incorporated into the base of the sulfate reduction zone. Due to the scarcity of labile organic matter, the sulfate will in turn be consumed by its reaction with methane and therefore AOM takes place. Based on a diffussion model, the portion of pore-water sulfate reduction via AOM is 58.6%, and the percentage of ΣCO₂ in the pore-water derived from AOM is 41.4%. Thus, AOM plays an important role in the carbon and sulfur cycling in the marine sediments of Pearl River Estuary.     

Preliminary reservoir model of enhanced coalbed methane (ECBM) in a subbituminous coal seam,Huntly Coalfield,New Zealand

The Huntly coalfield has significant coal deposits that contain biogenically-sourced methane. The coals are subbituminous in rank and Eocene in age and have been previously characterised with relatively low to moderate measured gas (CH₄) contents (2–4 m³/ton). The CO₂ holding capacity is relatively high (18.0 m³/ton) compared with that of CH₄ (2.6 m³/ton) and N₂ (0.7 m³/ton) at the same pressure (4 MPa; all as received basis). The geothermal gradient is also quite high at 55 °C/km.A study has been conducted which simulates enhancement of methane recovery (ECBM) from these deposits using a new version of the TOUGH2 (version 2) reservoir simulator (ECBM-TOUGH2) that can handle non-isothermal, multi-phase flows of mixtures of water, CH₄, CO₂ and N₂. The initial phase of the simulation is CH₄ production for the first 5 years of the field history. The model indicates that methane production can be significantly improved (from less than 80% recovery to nearly 90%) through injection of CO₂. However, although an increase in the rate of CO₂ injection increases the amount of CO₂ sequestered, the methane recovery (because of earlier breakthrough with increasing injection rate) decreases. Modeling of pure N₂ injection produced little enhanced CH₄ production. The injection of a hypothetical flue gas mixture (CO₂ and N₂) also produced little increase in CH₄ production. This is related to the low adsorption capacity of the Huntly coal to N₂ which results in almost instantaneous breakthrough into the production well.     

Channel constituents in synthetic beryl: ammonium

 The infrared spectra and electron paramagnetic resonance (EPR) of channel constituents in beryls synthesized hydrothermally in the presence of NH₄Cl were investigated. Two forms of ammonium ion were observed to be incorporated into the c -channel. IR-spectra show the double band at 3295 and 3232 cm⁻¹ and two broad bands between 2600 and 3000 cm⁻¹ which were assigned to the NH₃ molecule and NH₄ ⁺ ion, respectively. Similar N–H stretching vibrations are also observed in Regency hydrothermal synthetic beryls and can be used to separate these synthetic beryls from their natural counterparts. After γ-irradiation of hydrothermally grown samples at 77 K, the EPR of the NH₃ ⁺(I) radical was observed. The NH₃ ⁺(II) radical replaces the NH₃ ⁺(I) radical when the sample is heated to room temperature. Both the NH₃ molecule and the NH₃ ⁺ radical have their C₃ symmetry axes perpendicular to the crystal c-axis. The spin Hamiltonian parameters of the NH₃ ⁺(I) are axial-symmetric due to the rapid rotation of the radical about the c-axis. The NH₃ ⁺(II) radical has a low symmetry and shows a hindered rotation because of its shift from the c-axis position and an interaction with the proton in the near neighbourhood. Possible models for the paramagnetic centres are discussed. Received: 16 May 2000 / Accepted: 5 July 2001     

Fluid evolution of rare-element and muscovite granitic pegmatites from central Galicia, NW Spain

Fluid inclusions have been studied in three pegmatite fields in Galicia, NW Iberian Peninsula. Based on microthermometry and Raman spectroscopy, eight fluid systems have been recognized. The first fluid may be considered to be a pegmatitic fluid which is represented by daughter mineral (silicates)-rich aqueous inclusions. These inclusions are primary and formed above 500 °C (dissolution of daughter minerals). During pegmatite crystallization, this fluid evolved to a low-density, volatile-rich aqueous fluid with low salinity (93% H₂O; 5% CO₂; 0.5% CH₄; 0.2% N₂; 1.3% NaCl) at minimum P–T conditions around 3 ± 0.5 kbar and 420 °C. This fluid is related to rare-metal mineralization. The volatile enrichment may be due to mixing of magmatic fluids and fluids equilibrated with the host rock. A drop in pressure from 3 ± 0.5 to 1 kbar at a temperature above 420 °C, which may be due to the transition from predominantly lithostatic to hydrostatic pressure, is recorded by two-phase, water-rich inclusions with a low-density vapour phase (CO₂, CH₄ and N₂). Another inclusion type is represented by two-phase, vapour-rich inclusions with a low-density vapour phase (CO₂, CH₄ and N₂), indicating a last stage of decreasing temperature (360 °C) and pressure (around 0.5 kbar), probably due to progressive exhumation. Finally, volatile (CO₂)-rich aqueous inclusions, aqueous inclusions (H₂O-NaCl) and mixed-salt aqueous inclusions with low Th, are secondary in charac- ter and represent independent episodes of hydrothermal fluid circulation below 310 °C and 0.5 kbar. Received: 14 October 1999 / Accepted: 5 October 1999     

A unified equation for calculating methane vapor pressures in the CH4-H2O system with measured Raman shifts

A unified equation has been derived by using all available data for calculating methane vapor pressures with measured Raman shifts of C-H symmetric stretching band (υ₁) in the vapor phase of sample fluids near room temperature. This equation eliminates discrepancies among the existing data sets and can be applied at any Raman laboratory. Raman shifts of C-H symmetric stretching band of methane in the vapor phase of CH₄-H₂O mixtures prepared in a high-pressure optical cell were also measured at temperatures between room temperature and 200 °C, and pressures up to 37 MPa. The results show that the CH₄υ₁ band position shifts to higher wavenumber as temperature increases. We also demonstrated that this Raman band shift is a simple function of methane vapor density, and, therefore, when combined with equation of state of methane, methane vapor pressures in the sample fluids at elevated temperatures can be calculated from measured Raman peak positions. This method can be applied to determine the pressure of CH₄-bearing systems, such as methane-rich fluid inclusions from sedimentary basins or experimental fluids in hydrothermal diamond-anvil cell or other types of optical cell.     

Reduction of nitrogen compounds in oceanic basement and its implications for HCN formation and abiotic organic synthesis

Hydrogen cyanide is an excellent organic reagent and is central to most of the reaction pathways leading to abiotic formation of simple organic compounds containing nitrogen, such as amino acids, purines and pyrimidines. Reduced carbon and nitrogen precursor compounds for the synthesis of HCN may be formed under off-axis hydrothermal conditions in oceanic lithosphere in the presence of native Fe and Ni and are adsorbed on authigenic layer silicates and zeolites. The native metals as well as the molecular hydrogen reducing CO₂ to CO/CH₄ and NO₃ ^-/NO₂ ^- to NH₃/NH₄ ⁺ are a result of serpentinization of mafic rocks. Oceanic plates are conveyor belts of reduced carbon and nitrogen compounds from the off-axis hydrothermal environments to the subduction zones, where compaction, dehydration, desiccation and diagenetic reactions affect the organic precursors. CO/CH₄ and NH₃/NH₄ ⁺ in fluids distilled out of layer silicates and zeolites in the subducting plate at an early stage of subduction will react upon heating and form HCN, which is then available for further organic reactions to, for instance, carbohydrates, nucleosides or even nucleotides, under alkaline conditions in hydrated mantle rocks of the overriding plate. Convergent margins in the initial phase of subduction must, therefore, be considered the most potent sites for prebiotic reactions on Earth. This means that origin of life processes are, perhaps, only possible on planets where some kind of plate tectonics occur.     

Displacement behavior of CH4 adsorbed on coals by injecting pure CO2, N2, and CO2–N2 mixture

Gas adsorption isotherms of Akabira coals were established for pure carbon dioxide (CO₂), methane (CH₄), and nitrogen (N₂). Experimental data fit well into the Langmuir model. The ratio of sorption capacity of CO₂, CH₄, and N₂ is 8.5:3.5:1 at a lower pressure (1.2 MPa) regime and becomes 5.5:2:1 when gas pressure increases to 6.0 MPa. The difference in sorption capacity of these three gases is explained by differences in the density of the three gases with increasing pressure. A coal–methane system partially saturated with CH₄ at 2.4 MPa adsorption pressure was experimentally studied. Desorption behavior of CH₄ by injecting pure CO₂ (at 3.0, 4.0, 5.0, and 6.0 MPa), and by injecting the CO₂–N₂ mixture and pure N₂ (at 3.0 and 6.0 MPa) were evaluated. Results indicate that the preferential sorption property of coal for CO₂ is significantly higher than that for CH₄ or N₂. CO₂ injection can displace almost all of the CH₄ adsorbed on coal. When modeling the CH₄–CO₂ binary and CH₂–CO₂–N₂ ternary adsorption system by using the extended Langmuir (EL) equation, the EL model always over-predicted the sorbed CO₂ value with a lower error, while under-predicting the sorbed CH₄ with a higher error. A part of CO₂ may dissolve into the solid organic structure of coal, besides its competitive adsorption with other gases. According to this explanation, the EL coefficients of CO₂ in EL equation were revised. The revised EL model proved to be very accurate in predicting sorbed ratio of multi-component gases on coals.     

Formation and abundance of doubly-substituted methane isotopologues (CH3D) in natural gas systems

Formation of the Carbon-13 (¹³C) and deuterium (D) doubly-substituted methane isotopologues (¹³CH₃D) in natural gases is studied utilizing both first-principle quantum mechanism molecular calculation and direct FTIR laboratorial measurements of specifically synthesized high isotope concentration methane gas. For ¹³CH₃D, the symmetrically breathing mode A₀ emerges as IR-detectable attributed to the molecular symmetry lowering to C_3v from T_d of the non-isotopic methane (CH₄), along with a large vibrational frequency shift from ∼3000 to ∼2250 cm⁻¹. Our studies also indicate that the concentration of ¹³CH₃D is dependent on the environmental temperature through isotope exchanges among methane isotopologues; and the Gibbs’ Free Energy difference due to Quantum Mechanics Zero-Point vibrational motions has the major contribution to this temperature dependency. Potential geologic applications of the ¹³CH₃D measurement to natural gas exploration and assessments are also discussed. In order to detect the ¹³CH₃D concentration change of each 50 °C in the natural gas system, a 10⁻⁹ resolution is desirable. Such a measurement could provide important add-on information to distinguish natural gas origin and distribution.     

Electron density distributions and bonded interactions for the fibrous zeolites natrolite, mesolite and scolecite and related materials

 For the fibrous zeolites natrolite, Na₂[Al₂Si₃O₁₀]·2H₂O, mesolite, Na₂Ca₂[Al₂Si₃O₁₀]₃·8H₂O, and scolecite, Ca[Al₂Si₃O₁₀]·3H₂O, with topologically identical aluminosilicate framework structures, accurate single-crystal X-ray diffraction data have been analyzed by least-squares refinements using generalized scattering factor (GSF) models. The final agreement indices were R(F ) = 0.0061, 0.0165, and 0.0073, respectively. Ensuing calculations of static deformation [Δρ(r)], and total, [ρ(r)], model electron density distributions served to study chemical bonding, in particular by topological electron density analyses yielding bond critical point (bcp) properties and in situ cation electronegativities. The results for 32 SiO, 24 AlO, 14 CaO, and 12 NaO unique bonds are compiled and analyzed in terms of both mean values and correlations between bond lengths, bonded oxygen radii, bcp densities, curvatures at the bcps, and electronegativities. Comparison with recent literature data obtained from both experimental electron density studies on minerals and model calculations for geometry-optimized molecules shows that the majority of the present findings conforms well with chemical expectation and with the trends observed from molecular modeling. For the SiO bond, the shared interaction is indicated to increase with decreasing bond length, whereas the AlO bond is of distinctly more polar nature, as is the NaO bond compared to CaO. Also, the observed ranges of the Si and Al in situ electronegativities and their mean electronegativities agree well with both Pauling's values and model calculation results, and statistically significant correlations are obtained which are consistent with trends described for oxide and nitride molecules. Received: 10 May 1999 / Revised, accepted: 14 September 1999