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.     

Geochemical and isotopic characteristics of fluids in the Niutuozhen geothermal field,North China

Niutuozhen geothermal field is located in the Jizhong graben, belonging to the northern part of Bohai Bay Basin in North China. Chemical and isotopic analyses were carried out on 14 samples of the geothermal fluids discharged from Neogene Minghuazhen (Nm), Guantao (Ng), and Jixianian Wumishan (Jxw) formations. The δ²H and δ¹⁸O in water, δ¹³C in CH₄, δ¹³C in CO₂, and ³He/⁴He ratio in the gases were analyzed in combination with chemical analyses on the fluids in the Niutuozhen geothermal field. The chemical and isotopic compositions indicate a meteoric origin of the thermal waters. The reservoir temperatures estimated by chemical geothermometry are in the range between 60 and 108 °C. The results show that the gases are made up mainly by N₂ (18.20–97.42 vol%), CH₄ (0.02–60.95 vol%), and CO₂ (0.17–25.14 vol%), with relatively high He composition (up to 0.52 vol%). The chemical and isotopic compositions of the gas samples suggest the meteoric origin of N₂, predominant crustal origins of CH₄, CO₂, and He. The mantle-derived He contributions are calculated to be from 5 to 8% based on a crust–mantle binary mixing model. The deep temperatures in the Jxw reservoir were evaluated based on gas isotope geothermometry to be in the range from 141 to 165 °C. The mantle-derived heat fraction in the surface heat flow is estimated to be in the range of 48–51% based on ³He/⁴He ratios.     

Diurnal Variations of Carbon Dioxide, Methane, and Nitrous Oxide Vertical Fluxes in a Subtropical Estuarine Marsh on Neap and Spring Tide Days

Measuring fluxes of greenhouse gases (GHGs) is fundamental to estimating their impact on global warming. We examined diurnal variations of carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O) vertical fluxes in a tidal marsh ecosystem. Measurements were recorded on neap and spring tide days in April and September 2010 in the Shanyutan wetland of the Min River estuary, southeast China. Here, we define a positive flux as directing into the atmosphere. CH₄ fluxes on the diurnal scale were positive throughout, and CH₄ emissions into the atmosphere on neap tide days were higher than on spring tide days. CH₄ releases from the marsh ecosystem on neap tide days were higher in the daytime; however, on spring tide days, daily variations of CH₄ emissions were more complex. The marsh ecosystem plays a twofold role in both releasing and assimilating CO₂ and N₂O gases on the diurnal scale. Average CO₂ fluxes were positive on the daily scale both on neap and spring days and were greater on the neap tide days than on spring tide days. Diurnal variations of N₂O fluxes fluctuated more. Over the diurnal period, soil temperature markedly controlled variations of CH₄ emissions compared to other soil factors, such as salinity and redox potential. Tidal water height was a key factor influencing GHGs fluxes at the water–air interface. Compared with N₂O, the diurnal course of CO₂ and CH₄ fluxes in the marsh ecosystem appeared to be directly controlled by marsh plants. These results have implications for sampling and scaling strategies for estimating GHGs fluxes in tidal marsh ecosystems.     

Soil temperature and moisture controls on surface fluxes and profile concentrations of greenhouse gases in karst area in central part of Guizhou Province, southwest China

In order to better understand the spatiotemporal variations and interrelationships of greenhouse gases (GHG), monthly surface fluxes and profile concentrations of GHG (CO₂, N₂O and CH₄) in karst areas in the Guizhou Province, southwest China, were measured from June 2006 to May 2007. GHG fluxes showed high variability, with a range of 460.9?C1,281.2?mg?m^?2?h^?1 for CO₂, ?25.4 to 81.5???g?m^?2?h^?1 for N₂O and ?28.7 to ?274.9???g?m^?2?h^?1 for CH₄, but no obvious seasonal change trends of the fluxes existed. Profile concentrations of CO₂, N₂O and CH₄ varied between 0.5 and 31.5?mL?L^?1, 0.273 and 0.734, and 0.1 and 3.5???L?L^?1, respectively. In general, concentrations of CO₂ and N₂O increased with depth, while CH₄ had an inverse trend. However, in October, November and January, the reversal of depth patterns of GHG concentrations took place below 15?cm, close to the soil?Crock interface. The spatiotemporal distribution of CO₂ in soil profile was significantly positively correlated with that of N₂O (p?<?0.05?C0.01) and negatively correlated with that of CH₄ (p?<?0.01). The correlation analysis showed that soil temperature and moisture may be responsible for GHG dynamics in the soils, rather than the exchange of GHG between land and atmosphere.     

Effects of water table changes on soil CO2, CH4 and N2O fluxes during the growing season in freshwater marsh of Northeast China

A field control experiment was carried out to determine the influence of water table changes on soil CO₂, CH₄, and N₂O emissions in Calamagrostis angustifolia freshwater marsh in Northeast of China. The results showed that the water depth of 5 cm below the ground surface increased soil CO₂ emission, but there was no significant influence of deeper water table on gas emission. CH₄ emission was accelerated by deep standing water and approached the peak in the plant booming time. This suggests that root activity has influence on CH₄ production. The result also demonstrated that both low water table level and inundated environment would inhibit N₂O emission. Comparing the total global warming potential of three gases under different conditions, it can be concluded that maintaining a comparatively steady water table near the soil surface can benefit soil carbon sequestration in the C. angustifolia marsh, and decrease of the greenhouse gases emissions to the atmosphere.     

Adsorption kinetics of CO2, CH4, and their equimolar mixture on coal from the Black Warrior Basin,West-Central Alabama

Laboratory experiments were conducted to investigate the adsorption kinetic behavior of pure and mixed gases (CO_2, CH₄, approximately equimolar CO₂ + CH₄ mixtures, and He) on a coal sample obtained from the Black Warrior Basin at the Littleton Mine (Twin Pine Coal Company), Jefferson County, west-central Alabama. The sample was from the Mary Lee coal zone of the Pottsville Formation (Lower Pennsylvanian). Experiments with three size fractions (45–150 µm, 1–2 mm, and 5–10 mm) of crushed coal were performed at 40 °C and 35 °C over a pressure range of 1.4–6.9 MPa to simulate coalbed methane reservoir conditions in the Black Warrior Basin and provide data relevant for enhanced coalbed methane recovery operations. The following key observations were made: (1) CO₂ adsorption on both dry and water-saturated coal is much more rapid than CH₄ adsorption; (2) water saturation decreases the rates of CO₂ and CH₄ adsorption on coal surfaces, but it appears to have minimal effects on the final magnitude of CO₂ or CH₄ adsorption if the coal is not previously exposed to CO₂; (3) retention of adsorbed CO₂ on coal surfaces is significant even with extreme pressure cycling; and (4) adsorption is significantly faster for the 45–150 μm size fraction compared to the two coarser fractions.     

Fugacities of gases and some mineralogical reactions at very high pressures and temperatures (an extrapolation)

Fugacities of H₂, N₂, O₂, CH₄, H₂O, H₂S, NH₃, CO, and CO₂ are calculated on the basis of the extrapolation of the caloric properties, and those of the compressibility of substances into the region of pressures up to 2 Mbar and of temperatures up to 4000K. Several equilibrium mineralogical reactions are calculated. The most probable sequence of decreasing the magnitudes of the equilibrium molar fractions (masses) of these gases in the lower mantle of the earth is predicted.     

Mesothermal Gold Vein Mineralization of the Seolhwa Mine,Asan Mining District,Korea

Gold mineralization of the Seolhwa mine occurs in a single stage of massive quartz veins which filled the north‐east‐trending fault shear zones in the Jurassic granitoid of 161 Ma within the Gyeonggi Massif. The vein quartz contains three main types of fluid inclusions at 25°C: (i) aqueous type I inclusions (0–15 wt.% NaCl) containing small amounts of CO₂; (ii) gas‐rich (more than 70 vol. %), vapor‐homogenizing, aqueous type II inclusions; and (iii) low‐salinity (less than 5 wt.% NaCl), liquid CO₂‐bearing, type III inclusions. The H₂O‐CO₂‐CH₄‐N₂‐NaCl inclusions represent immiscible fluids trapped earlier along the solvus curve in the temperature range 250–430°C at pressures of ～1 kb. Detailed fluid inclusion chronologies suggest a progressive decrease in pressure during the mineralization. Aqueous inclusion fluids represent either later fluids evolved through extensive fluid unmixing from a homogeneous H₂O‐CO₂‐CH₄‐N₂‐NaCl fluid due to decreases in temperature and pressure, or the influence of deep circulated meteoric waters. Initial fluids were homogeneous H₂O‐CO₂‐CH₄‐N₂‐NaCl fluids as follows: 250° to 430°C, 16–62 mol% CO₂, 5–14 mol% CH₄, 0.06–0.31 mol% N₂ and salinities of 0.4–4.9 wt.% NaCl. The T‐X data for the Seolhwa mine suggest that the hydrothermal system has been probably located nearer to the granitic melt, which facilitated the CH₄ formation and resulted in a reduced fluid state indicated by the predominance of pyrrhotite. Measured and calculated isotopic compositions of the hydrothermal fluids [δ¹⁸O = 5.3–6.5‰; δD =?69 to ?84‰] provide evidence of the CH₄‐H₂O equilibria and further indicate that the auriferous fluids were magmatically derived. Both the dominance of δ³⁴S values of sulfides close to the meteoric reference (?0.6–1.4‰; δ³⁴S_ΣS values of 0.3–1.1‰) and the available δ¹³C data (?4‰) are consistent with their deep igneous source. The Seolhwa mine was probably formed by extensive fracturing and veining due to the thermal expansion of water derived from the Jurassic granitoid melt.     

A study on gas inclusions in minerals. Analysis of the gases from micro-inclusions in allanite

In order to determine the chemical composition of the gases from micro-inclusions in allanite a comparative study, using the methods of heating to decrepitation and grinding in vacuum was undertaken. The dependence of gas composition on the grain size was studied, too. The analysis of gases was carried out in a vacuum apparatus for micro-analysis; the measurement was volumetric. The experiments using the decrepitation method were made in the temperature interval 200–1100°C. CO₂, H₂, CO, CH₄, N₂, He, and water were identified and determined. However, a considerable part of these gases is probably due to chemical reactions. By grinding in a vacuum ball mill, only small amounts of H₂, N₂, and He were evolved. Some experiments showed that CO₂ and H₂O are strongly adsorbed on the ground material, thus being lost for the analysis.The results obtained from these two methods were supplemented with data obtained from a new method for studying the composition of gas inclusions, by tracing the gas composition as a function of the sample grain size. Using an approximate model it was shown that this dependence should be non-linear (hyperbolic). The amount of gases, due to inclusions, decreases parallel to the decrease in size of the mineral grains down to a certain limiting size. This dependence could not be observed if the grains are smaller than this limiting value. The method offers a possibility for taking into account the amounts of gases having another origin (desorption, chemical interactions, etc.), using the experimental plots. The results from the three series of experiments showed that the gas phase of inclusions in examined allanite consists mainly of CO₂. The other gases which were found by the decrepitation method could not be unambiguously ascribed to inclusions.     

Observations of trace gases and aerosols over the Indian Ocean during the monsoon transition period

Characteristics of trace gases (O₃, CO, CO₂, CH₄ and N₂O) and aerosols (particle size of 2.5 micron) were studied over the Arabian Sea, equatorial Indian Ocean and southwest part of the Bay of Bengal during the monsoon transition period (October–November, 2004). Flow of pollutants is expected from south and southeast Asia during the monsoonal transition period due to the patterns of wind flow which are different from the monsoon period. This is the first detailed report on aerosols and trace gases during the sampled period as the earlier Bay of Bengal Experiment (BOBMEX), Arabian Sea Monsoon Experiment (ARMEX) and Indian Ocean Experiments (INDOEX) were during monsoon seasons. The significant observations during the transition period include: (i) low ozone concentration of the order of 5 ppbv around the equator, (ii) high concentrations of CO₂, CH₄ and N₂O and (iii) variations in PM2.5 of 5–20μg/m³.     

Factors Controlling Precipitation of Barite and Witherite and Genesis of the Ankang–Xunyang Barium Deposits, Shaanxi, China

The barium deposits in Ankang and Xunyang counties,Shaanxi Province,China,occur in the northernmost part of the world-class barium metallogenic belt in south Qinling.The deposits are hosted by the Lower Silurian carbonaceous siliceous rocks,with a unique combination of barite and witherite.The homogenization temperatures of fluid inclusions in the barite are mainly concentrated between 135 and 155 ℃,whereas those from the witherite have two peaks of 165-175 ℃,and 215-225℃,respectively.Laser Raman analysis of fluid inclusions indicates that the vapor phase of fluid inclusions in barite is dominated by H_2O,although some contains N_2,H_2S,and CH_4.The compositions of the vapor and liquid phases of fluid inclusions in witherite can be divided into two end-members,one dominated by H_2O without other volatiles,and the other containing CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6 in addition to H_2O.CO_2,H_2S,and some CH_4 are interpreted as products of chemical reactions during mineralization.Organic gases(CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6) in the fluids were critical in the formation of barium sulfate versus carbonate.The δ~(34)S values of barite range from 38.26‰ to54.23‰(CDT),the δ~(34)S values of sulfides coexisting with barium minerals vary from 22.44‰ to25.11‰(CDT),and those in the wall rock from 11.60‰ to 19.06‰(CDT).We propose that the SO_4~(2-)generally experienced bacterial sulfate reduction in seawater before mineralization,and some SO_4~(2-)also experienced thermochemical sulfate reduction in hydrothermal system during mineralization.The δ~(13)C values of witherite range from-27.30‰ to-11.80‰(PDB),suggesting that carbon was sourced from organic substances(like CH_4,C_2H_4,and C_2H_6).The formation of witherite was possibly associated with thermochemical sulfate reduction,which caused the consumption of the organic gases and SO_4~(2-) in the hydrothermal solutions,consequently inhibiting barite formation.The important conditions for forming witherite include high fluid temperatures,high Ba~(2+) concentrations,CO_2 in the fluids,low HS~- concentrations,and the subsequent rapid diffusion of H_2S during thermochemical sulfate reduction of the fluids.     

Composition and origin of coalbed gases in the Lower Silesian basin,southwest Poland

Coalbed gases in the Lower Silesian Coal Basin (LSCB) of Poland are highly variable in both their molecular and stable isotope compositions. Geochemical indices and stable isotope ratios vary within the following ranges: hydrocarbon (C_HC) index C_HC=CH₄/(C₂H₆₊ C₃H₈) from 1.1 to 5825, wet gas (C₂₊) index C₂₊=(C₂H₆₊ C₃H₈₊ C₄H₁₀₊ C₅H₁₂) / (CH₄₊ C₂H₆₊ C₃H₈₊ C₄H₁₀₊ C₅H₁₂) 100 (%) from 0.0 to 48.3%, CO₂–CH₄ (CDMI) index CDMI=CO₂/(CO₂₊ CH₄) 100 (%) from 0.1 to 99.9%, δ¹³C(CH₄) from −66.1 to −24.6‰, δD(CH₄) from −266 to −117‰, δ¹³C(C₂H₆) from −27.8 to −22.8‰, and δ¹³C(CO₂) from −26.6 to 16.8‰. Isotopic studies reveal the presence of 3 genetic types of natural gases: thermogenic (CH₄, higher gaseous hydrocarbons, and CO₂), endogenic CO₂, and microbial CH₄ and CO₂. Thermogenic gases resulted from coalification processes, which were probably completed by Late Carboniferous and Early Permian time. Endogenic CO₂ migrated along the deep-seated faults from upper mantle and/or magma chambers. Minor volumes of microbial CH₄ and CO₂ occur at shallow depths close to the abandoned mine workings. “Late-stage” microbial processes have commenced in the Upper Cretaceous and are probably active at present. However, depth-related isotopic fractionation which has resulted from physical and physicochemical (e.g. diffusion and adsorption/desorption) processes during gas migration cannot be neglected. The strongest rock and gas outbursts occur only in those parts of coal deposits of the LSCB which are dominated by large amounts of endogenic CO₂.     

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.     

Geochemistry of shallow aquifers and soil gas surveys in a feasibility study at the Rivara natural gas storage site (Po Plain,Northern Italy)

A geochemical survey, in shallow aquifers and soils, has been carried out to evaluate the feasibility of natural gas (CH₄) storage in a deep saline aquifer at Rivara (MO), Northern Italy. This paper discusses the areal distribution of CO₂ and CH₄ fluxes and CO₂, CH₄, Rn, He, H₂ concentrations both in soils and shallow aquifers above the proposed storage reservoir. The distribution of pathfinder elements such as ²²²Rn, He and H₂ has been studied in order to identify potential faults and/or fractures related to preferential migration pathways and the possible interactions between the reservoir and surface. A geochemical and isotopic characterization of the ground waters circulating in the first 200 m has allowed to investigation of (i) the origin of the circulating fluids, (ii) the gas–water–rock interaction processes, (iii) the amount of dissolved gases and/or their saturation status. In the first 200 m, the presence of CH₄-rich reducing waters are probably related to organic matter (peat) bearing strata which generate shallow-derived CH₄, as elsewhere in the Po Plain. On the basis of isotopic analysis, no hints of thermogenic CH₄ gas leakage from a deeper reservoir have been shown. The δ¹³C(CO₂) both in ground waters and free gases suggests a prevalent shallow origin of CO₂ (i.e. organic and/or soil-derived). The acquisition of pre-injection data is strategic for the natural gas storage development project and as a baseline for future monitoring during the gas injection/withdrawing period. Such a geochemical approach is considered as a methodological reference model for future CO₂/CH₄ storage projects.     

Chemical and isotopic equilibrium between CO2 and CH4 in fumarolic gas discharges: Generation of CH4 in arc magmatic-hydrothermal systems

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH₄) within two subduction-related magmatic-hydrothermal environments.Apparent temperatures derived from carbon isotope partitioning between CH₄ and CO₂ of around 340°C for Nisyros and 470°C for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H₂O-H₂-CO₂-CO-CH₄ geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH₄, CO₂ and H₂O implying that carbon isotope partitioning between CO₂ and CH₄ in both systems is controlled by aquifer temperature.N₂/³He and CH₄/³He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH₄ may have been primarily generated through the reduction of CO₂ by H₂ in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH₄ and subsequent re-equilibration with co-existing CO₂ cannot be ruled out entirely. CO₂/³He ratios and δ¹³C_CO2 values imply that the evolved CO₂ either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH₄ during thermometamorphism.     

Effects of nitrogen on the ecosystem respiration,CH<Subscript>4</Subscript> and N<Subscript>2</Subscript>O emissions to the atmosphere from the freshwater marshes in northeast China

Freshwater marshes could be a source of greenhouse gases emission because they contain large amounts of soil carbon and nitrogen. These emissions are strongly influenced by exogenous nitrogen. We investigate the effects of exogenous nitrogen on ecosystem respiration (CO₂), CH₄ and N₂O emissions from freshwater marshes in situ in the Sanjiang Plain Northeast of China during the growing seasons of 2004 and 2005, using a field fertilizer experiment and the static opaque chamber/GC techniques. The results show that there were no significant differences in patterns of seasonal variations of CO₂ and CH₄ among the fertilizer and non-fertilizer treatments, but the seasonal patterns of N₂O emission were significantly influenced by the exogenous nitrogen. Seasonal averages of the CO₂ flux from non-fertilizer and fertilizer were 987.74 and 1,344.35 mg m ⁻² h ⁻¹, respectively, in 2004, and 898.59 and 2,154.17 mg m ⁻² h ⁻¹, respectively, in 2005. And the CH₄ from the control and fertilizer treatments were 6.05 and 13.56 mg m ⁻² h ⁻¹ and 0.72 and 1.88 mg m ⁻² h ⁻¹, respectively, in 2004 and 2005. The difference of N₂O flux between the fertilizer and non-fertilizer treatments is also significant either in 2004 and 2005. On the time scale of 20-, 100-, and 500-year periods, the integrated global warming potential (GWP) of CO₂ + CH₄ + N₂O released during the two growing seasons for the treatment of fertilizer was 97, 94 and 89%, respectively, higher than that for the control, which suggested that the nitrogen fertilizer can enhance the GWP of the CH₄ and N₂O either in long time or short time scale.     

Geochemistry and episodic accumulation of natural gases from the Ledong gas field in the Yinggehai Basin, offshore South China Sea

The Ledong gas field, consisting of three gas pools in a shale diapir structure zone, is the largest gas discovery in the Yinggehai Basin. The gases produced from the Pliocene and Quaternary marine sandstone reservoirs show a considerable variation in chemical composition, with 5.4–88% CH₄, 0–93% CO₂, and 1–23.7% N₂. The CO₂-enriched gases often display heavier methane δ¹³C values than those with low CO₂ contents. The δ¹⁵N values of the gases range from −8 to −2‰, and the N₂ content correlates negatively with the CO₂ content. The high geothermal gradient associated with a relatively great burial depth in this area has led to the generation of hydrocarbon and nitrogen gases from the Lower–Middle Miocene source rocks and the formation of abundant CO₂ from the Tertiary calcareous-shales and pre-Tertiary carbonates. The compositional heterogeneities and stable carbon isotope data of the produced gases indicate that the formation of the LD221 gas field is attributed to three phases of gas migration: initially biogenic gas, followed by thermogenic hydrocarbon gas, and then CO₂-rich gas. The filling processes occurred within a short period approximately from 1.2 to 0.1 Ma based on the results of the kinetics modeling. Geophysical and geochemical data show that the diapiric faults that cut through Miocene sediments act as the main pathways for upward gas migration from the deep overpressured system into the shallow normal pressure reservoirs, and that the deep overpressure is the main driving force for vertical and lateral migration of the gases. This gas migration pattern implies that the transitional pressure zone around the shale diapir structures was on the pathway of upward migrating gases, and is also a favorable place for gas accumulation. The proposed multiple sources and multiple phases of gas migration and accumulation model for the Ledong gas field potentially provide useful information for the future exploration efforts in this area.     

汶川M_s 8.0地震破裂带CO_2、CH_4、Rn和Hg脱气强度

地震活动断裂带能够向大气释放大量的温室气体、放射性气体和有毒气体(CO_2、CH_4、Rn和Hg),并对大气环境的影响产生复杂的影响。利用静态暗箱法,对汶川M_s8.0地震破裂带CO_2、Rn和Hg脱气强度进行实地测量,并计算了CO_2和Hg脱气对大气的年贡献量。结果表明:(1)破裂带土壤气中CO_2、CH_4、Rn和Hg异常浓度最大值分别可以达到7.98%、2.38%、524.30k Bq/m~3和161.00ng/m~3;破裂带CO_2、Rn和Hg脱气平均通量是34.95g·m~(-2)d~(-1)、36.11m Bq·m~(-2)s~(-1)和26.56ng·m~(-2)h~(-1),最大值分别达到259.23g·m~(-2)d~(-1)、580.35m Bq·m~(-2)s~(-1)和387.67ng·m~(-2)h~(-1);(2)汶川Ms8.0地震破裂带向大气脱气的CO_2年贡献量是0.95Mt,Hg的年贡献量是15.94kg。汶川Ms8.0地震破裂带破裂CO_2、CH_4、Rn和Hg等的脱气强度,不仅与破裂带渗透率有关,还与断裂带浅部存在的气藏、煤层以及磷矿层等气体源有重要的联系。     

Chemical and isotopic characteristics of fluids along the Cameroon Volcanic Line, Cameroon

Results of the chemical and isotopic analysis of the water and gases discharged from volcanic crater lakes and soda springs located along the Cameroon Volcanic Line were used to characterize and infer their genetic relationships. Variations in the solute compositions of the waters indicate the dominant influence of silicate hydrolysis. Na⁺ (40–95%) constitutes the major cation in the springs while Fe²⁺ + Mg²⁺ (70%) dominate in the CO₂-rich lakes. The principal anion is HCO₃ (>90%), except in the coastal springs where Cl-predominates. Lakes Nyos and Monoun have FeMgCaHCO₃⁻ type signatures; the soda springs are essentially NaHCO₃⁻ type, while all other lakes show similar ionic compositions to dilute surface waters. Dissolved gases show essentially CO₂ (>90%), with small amounts of Ar and N₂, while CH₄ constitutes the principal component in the non-gassy lakes. Active volcanic gases are generally absent, except in the Lobe spring with detectable H₂S. Stable isotope ratio evidence indicates that the bicarbonate waters are essentially of meteoric origin. CO₂ (δ¹³C = −2 to −8%₀ and He (³He/⁴He = 1 to 5.6R_a) infer a mantle contribution to the total CO₂. CH₄ has a biogenic source, while Ar and N₂ are essentially atmospheric in origin, but mixing is quite common.     

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.