Gas seepage from Tokamachi mud volcanoes, onshore Niigata Basin (Japan): Origin, post-genetic alterations and CH4-CO2 fluxes

Methane and CO₂ emissions from the two most active mud volcanoes in central Japan, Murono and Kamou (Tokamachi City, Niigata Basin), were measured in from both craters or vents (macro-seepage) and invisible exhalation from the soil (mini- and microseepage). Molecular and isotopic compositions of the released gases were also determined. Gas is thermogenic (δ¹³C_CH4 from −32.9‰ to −36.2‰), likely associated with oil, and enrichments of ¹³C in CO₂ (δ¹³C_CO2 up to +28.3‰) and propane (δ¹³C_C3H8 up to −8.6‰) suggest subsurface petroleum biodegradation. Gas source and post-genetic alteration processes did not change from 2004 to 2010. Methane flux ranged within the orders of magnitude of 10¹-10⁴ g m⁻² d⁻¹ in macro-seeps, and up to 446 g m⁻² d⁻¹ from diffuse seepage. Positive CH₄ fluxes from dry soil were widespread throughout the investigated areas. Total CH₄ emission from Murono and Kamou were estimated to be at least 20 and 3.7 ton a⁻¹, respectively, of which more than half was from invisible seepage surrounding the mud volcano vents. At the macro-seeps, CO₂ fluxes were directly proportional to CH₄ fluxes, and the volumetric ratios between CH₄ flux and CO₂ flux were similar to the compositional CH₄/CO₂ volume ratio. Macro-seep flux data, in addition to those of other 13 mud volcanoes, supported the hypothesis that molecular fractionation (increase of the “Bernard ratio” C₁/(C₂ + C₃)) is inversely proportional to gas migration fluxes. The CH₄ “emission factor” (total measured output divided by investigated seepage area) was similar to that derived in other mud volcanoes of the same size and activity. The updated global “emission-factor” data-set, now including 27 mud volcanoes from different countries, suggests that previous estimates of global CH₄ emission from mud volcanoes may be significantly underestimated.     

A geochemical study on mud volcanoes in the Junggar Basin, China

A comprehensive study was performed to characterize, for the first time, the mud, water, and gases released from onshore mud volcanoes located in the southern margin of the Junggar Basin, northwestern China. Chemical compositions of mud, along with the geology of the basin, suggest that a source of the mud is Mesozoic or Cenozoic shale. Oxygen and H isotope compositions of the released water suggest a local meteoric origin. Combined with the positive Eu anomalies of the water, a large ¹⁸O shift of the water suggests extensive interaction with rocks. Gases discharged from the mud volcanoes are predominantly thermogenic hydrocarbons, and the high δ¹³C values (>+20‰ VPDB) for CO₂ gases and dissolved carbonate in muddy water suggest secondary methanogenesis with CO₂ reduction after oil biodegradation.The enrichments of Eu and ¹⁸O in water and the low thermal gradient of the area suggest that the water-rock interactions possibly occur deeper than 3670 ± 200 m. On the other hand, considering the relationship to the petroleum reservoir around the mud volcanoes, the depth of the gases can be derived from about 3600 m, a depth that is greater than that generally estimated for reservoirs whose gas is characterized by ¹³C-enriched CO₂. Oil biodegradation with CO₂ reduction likely occurs at a shallower depth along the seepage system of the mud volcano. The results contribute to the worldwide data set of gas genesis in mud volcanoes. Moreover, they further support the concept that most terrestrial mud volcanoes release thermogenic gas produced in very deep sediments and may be early indicators of oil biodegradation, an important problem in the petroleum industry.     

Composition and exhalation flux of gases from mud volcanoes in Taiwan

Many mud volcanoes are distributed along the tectonic sutures in southern Taiwan and can be divided into five zones based on their relative positions in different tectonic domains. Most active mud volcanoes are exhaling methane-dominated gases. Nevertheless, some gases show unusual carbon dioxide-dominated and/or nitrogen-excess compositions. This implies that there are multiple sources for the gas compositions of mud volcanoes in Taiwan.For better understanding the total amount of exhalation gases and its flux, the gas flow and compositions were continuously measured in the interval of two minutes at Chung-lun (CL) bubbling mud pool for a few months. The major compositions of gases exhaling from this site were 75~90% of CO₂ and 5~12% of CH₄. The amount of gases exhaling from the mud pool can be estimated to be about 1.4 ton/year for CH₄ and 28 ton/year for CO₂, respectively. The preliminary results of exhaling gas flux from the major vents of representative active mud volcanoes, yielded an estimated total CH₄ output of the mud volcanoes in Taiwan of ca. 29 ton/year during quiescent period.     

Methane and sulfide fluxes in permanent anoxia: In situ studies at the Dvurechenskii mud volcano (Sorokin Trough, Black Sea)

The Dvurechenskii mud volcano (DMV) is located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea). The DMV was studied during the RV Meteor expedition M72/2 as an example of an active mud volcano system, to investigate the significance of submarine mud volcanism for the methane and sulfide budget of the anoxic Black Sea hydrosphere. Our studies included benthic fluxes of methane and sulfide, as well as the factors controlling transport, consumption and production of both compounds within the sediment. The pie-shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at its summit north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was repressed in this zone due to the upward flow of sulfate-depleted fluids through recently deposited subsurface muds, apparently limiting microbial methanotrophic activity. Consequently, the emission of dissolved methane into the water column was high, with an estimated rate of 0.46 mol m⁻² d⁻¹. On the wide plateau and edge of the mud volcano surrounding the summit, fluid flow and total methane flux were lower, allowing higher SR and AOM rates correlated with an increase in sulfate penetration into the sediment. Here, between 50% and 70% of the methane flux (0.07-0.1 mol m⁻² d⁻¹) was consumed within the upper 10 cm of the sediment. The overall amount of dissolved methane released from the entire mud volcano structure into the water column was significant with a discharge of 1.3 × 10⁷ mol yr⁻¹. The DMV maintains also high areal rates of methane-fueled sulfide production and emission of on average 0.05 mol m⁻² d⁻¹. This is a difference to mud volcanoes in oxic waters, which emit similar amounts of methane, but not sulfide. However, based on a comparison of this and other mud volcanoes of the Black Sea, we conclude that sulfide and methane emission into the hydrosphere from deep-water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea.     

Microbial methane turnover at mud volcanoes of the Gulf of Cadiz

The Gulf of Cadiz is a tectonically active area of the European continental margin and characterised by a high abundance of mud volcanoes, diapirs, pockmarks and carbonate chimneys. During the R/V SONNE expedition “GAP-Gibraltar Arc Processes (SO-175)” in December 2003, several mud volcanoes were surveyed for gas seepage and associated microbial methane turnover. Pore water analyses and methane oxidation measurements on sediment cores recovered from the centres of the mud volcanoes Captain Arutyunov, Bonjardim, Ginsburg, Gemini and a newly discovered, mud volcano-like structure called “No Name” show that thermogenic methane and associated higher hydrocarbons rising from deeper sediment strata are completely consumed within the seabed. The presence of a distinct sulphate-methane transition zone (SMT) overlapping with high sulphide concentrations suggests that methane oxidation is mediated under anaerobic conditions with sulphate as the electron acceptor. Anaerobic oxidation of methane (AOM) and sulphate reduction (SR) rates show maxima at the SMT, which was found between 20 and 200 cm below seafloor at the different mud volcanoes. In comparison to other methane seeps, AOM activity (<383 mmol m⁻² year⁻¹) and diffusive methane fluxes (<321 mmol m⁻² year⁻¹) in mud volcano sediments of the Gulf of Cadiz are low to mid range. Corresponding lipid biomarker and 16S rDNA clone library analysis give evidence that AOM is mediated by a mixed community of anaerobic methanotrophic archaea and associated sulphate reducing bacteria (SRB) in the studied mud volcanoes. Little is known about the variability of methane fluxes in this environment. Carbonate crusts littering the seafloor of mud volcanoes in the northern part of the Gulf of Cadiz had strongly ¹³C-depleted lipid signatures indicative of higher seepage activities in the past. However, actual seafloor video observations showed only scarce traces of methane seepage and associated biological processes at the seafloor. No active fluid or free gas escape to the hydrosphere was observed visually at any of the surveyed mud volcanoes, and biogeochemical measurements indicate a complete methane consumption in the seafloor. Our observations suggest that the emission of methane to the hydrosphere from the mud volcano structures studied here may be insignificant at present.     

Geochemistry of mud volcano fluids in the Taiwan accretionary prism

Taiwan is located at the collision boundary between the Philippine Sea Plate and the Asian Continental Plate and is one of the most active orogenic belts in the world. Fluids sampled from 9 sub-aerial mud volcanoes distributed along two major geological structures in southwestern Taiwan, the Chishan fault and the Gutingkeng anticline, were analyzed to evaluate possible sources of water and the degree of fluid-sediment interaction at depth in an accretionary prism. Overall, the Taiwanese mud volcano fluids are characterized by high Cl contents, up to 347 mM, suggesting a marine origin from actively de-watering sedimentary pore waters along major structures on land. The fluids obtained from the Gutingkeng anticline, as well as from the Coastal Plain area, show high Cl, Na, K, Ca, Mg and NH₄, but low SO₄ and B concentrations. In contrast, the Chishan fault fluids are much less saline (1/4 seawater value), but show much heavier O isotope compositions (δ¹⁸O=5.1–6.5 ‰). A simplified scenario of mixing between sedimentary pore fluids and waters affected by clay dehydration released at depth can explain several crucial observations including heavy O isotopes, radiogenic Sr contents (⁸⁷Sr/⁸⁶Sr=0.71136–0.71283), and relatively low salinities in the Chishan fluids. Gases isolated from the mud volcanoes are predominantly CH₄ and CO₂, where the CH₄–C isotopic compositions show a thermogenic component of δ¹³C=−38 ‰. These results demonstrate that active mud volcano de-watering in Taiwan is a direct product of intense sediment accretion and plate collision in the region.     

Soil gas composition above gas deposits and perspective structures of the Carpathian Foredeep,SE Poland

In 2001 a surface geochemical survey was carried out in the Carpathian Foredeep, in the area between Jaros?aw and Radymno (SE Poland) where multihorizon gas deposits were discovered. These deposits accumulate microbial CH₄ with small amounts of N₂ and higher molecular weight gaseous hydrocarbons. Soil–gas composition in the hydrocarbon fields in the study area is relatively different from the original composition of natural gas occurring in the subsurface reservoir. In 449 analyzed soil gas samples collected from 1.2 m depth relatively low concentrations were found for CH₄ (median value 2.2 ppm) and its homologues (median value of total alkanes C₂–C₄ – 0.02 ppm). Alkenes were encountered in 36.3% of the analyzed samples (mean value of total alkenes C₂–C₄ – 0.015 ppm) together with distinctly higher concentrations of H₂ (maximum value – 544 ppm, mean value – 42 ppm) and CO₂ (maximum value – 10.26 vol.%, mean value – 2.27 vol.%). Individual, very high concentrations of CH₄ (up to about 35 vol.%) resulted from sub-surface biochemical reactions whereas higher alkanes detected in soil gases (up to about 68 ppm) originated from deep gas accumulations. Both the H₂ and alkenes may be indirect indicators of deep hydrocarbon accumulations. Carbon dioxide may also be useful for hydrocarbon exploration, revealing increased concentrations in those sampling sites where CH₄ concentrations are strongly depleted, presumably due to bacterial oxidation. These relationships are valid only for the study area and should not be extended as an universal principle.     

Mud volcanic natural phenomena in the South Caspian Basin: geology,fluid dynamics and environmental impact

The South Caspian sedimentary basin is a unique area with thick Mesozoic-Cenozoic sediments (up to 30–32 km) characterized by an extremely high fluid generation potential. The large amount of active mud volcanoes and the volumes of their gas emissions prove the vast scale of fluid generation. Onshore and offshore mud volcanoes annually erupt more than 10⁹ cubic meters of gases consisting of CH₄ (79–98%), and a small admixture of C₂H₆, C₃H₈, C₄H₁₀, C₅H₁₂, CO₂, N, H₂S, Ar, He. Mud volcanism is closely connected to the processes occurring in the South Caspian depression, its seismicity, fluctuations of the Caspian Sea level, solar activity and hydrocarbon generation.The large accumulations of gas hydrates are confined to the bottom sediments of the Caspian Sea, mud volcanoes crater fields (interval 0–0.4 m, sea depth 480 m) and to the volcanoes body at the depth of 480–800 from the sea bottom. Resources of HC gases in hydrates saturated sediments up to a depth of 100 m and are estimated at 0.2×10¹⁵–8×10¹⁵ m³. The amount of HC gases concentrated in them is 10¹¹–10¹² m³.The Caspian Sea, being an inland closed basin is very sensitive to climatic and tectonic events expressed in sea level fluctuations. During regressive stages as a result of sea level fall and the reducing of hydrostatic pressure the decomposition of gas hydrates and the releasing of a great volume of HC gases consisting mainly of methane are observed.From the data of deep drilling, seismoacoustics, and deep seismic mud volcanic activity in the South Caspian Basin started in the Lower Miocene. Activity reached its highest intensity at the boundary between the Miocene and Pliocene and was associated with dramatic Caspian Sea level fall in the Lower Pliocene of up to 600 m, which led to the isolation of the PaleoCaspian from the Eastern ParaTethys. Catastrophic reduction of PaleoCaspian size combined with the increasing scale of mud volcanic activity caused the oversaturation and intoxication of water by methane and led to the mass extinction of mollusks, fishes and other groups of sea inhabitants. In the Upper Pliocene and Quaternary mud volcanism occurred under the conditions of a semi-closed sea periodically connected with the Pontian and Mediterranean Basins. Those stages of Caspian Sea history are characterized by the revival of the Caspian organic world.Monitoring of mud volcanoes onshore of the South Caspian demonstrated that any eruption is predicted by seismic activation in the region (South-Eastern Caucasus) and intensive fluid dynamics on the volcanoes.     

Carbon isotope effects in the open-system Fischer-Tropsch synthesis

Carbon isotopic composition was measured for products of the Fischer-Tropsch synthesis: catalytic reaction between CO and H₂ to produce CO, CO₂, light hydrocarbons C1-C4 and “oil” fraction. Hydrogen isotopes were also measured in the oil fraction and the produced water. Experimental runs were conducted in the flow-through reactor at 260-310 °C and 30 bar using the synthesis gas composed of 5N₂ + 3H₂ + 2CO, on Fe-catalyst mixed with ZSM-5 synthetic zeolite. In the two of seven runs a Fe + Co-catalyst was used that gives a lower yield of unsaturated hydrocarbons in reaction products. The isotopic effects depended on the conversion of the carbon monoxide. Under steady-state conditions (CO conversion more than 90%) a strong kinetic fractionation was observed between CO and CO₂ (∼−10‰) and CO and hydrocarbons (∼+38‰). At low conversion a clear “inverse” isotopic trend of the depletion in ¹³C of longer hydrocarbon chains was observed. On average, Δ₁₂ = δ¹³C(CH₄) − δ¹³C(C₂H₆) correlates well with the CO conversion: the C₂H₆ is ∼6‰ isotopically lighter than CH₄ at low conversion and ∼2‰ heavier at steady-state regime. Under steady-state conditions there almost no difference was observed in the isotopic composition of methane and ethane and higher hydrocarbons. The chemical composition of light hydrocarbons in the products of flow-through, dynamic FTS is different from that found in the static FTS-type experiments with Fe-catalyst, but isotopic effects are similar. Our results suggest that the isotopic distribution of carbon found in so-called “abiogenic” hydrocarbons from some natural gases (δ¹³C1 > δ¹³C2 > δ¹³C3  >?) is somewhat similar to that at low conversion of CO, but do not resemble the distribution characteristic for the high conversion products, at least, on Fe-catalyst. Other processes (a simple mixing of two or more endmembers) or other P-T conditions of the carbon reduction could be responsible for the “inverse” isotopic trend found in meteorites and some natural gases.     

Chemical and isotopic tracers of the contribution of microbial gas in Devonian organic-rich shales and reservoir sandstones,northern Appalachian Basin

In this study, the geochemistry and origin of natural gas and formation waters in Devonian age organic-rich shales and reservoir sandstones across the northern Appalachian Basin margin (western New York, eastern Ohio, northwestern Pennsylvania, and eastern Kentucky) were investigated. Additional samples were collected from Mississippian Berea Sandstone, Silurian Medina Sandstone and Ordovician Trenton/Black River Group oil and gas wells for comparison. Dissolved gases in shallow groundwaters in Devonian organic-rich shales along Lake Erie contain detectable CH₄ (0.01–50.55 mol%) with low δ¹³C–CH₄ values (−74.68 to −57.86‰) and no higher chain hydrocarbons, characteristics typical of microbial gas. Nevertheless, these groundwaters have only moderate alkalinity (1.14–8.72 meq/kg) and relatively low δ¹³C values of dissolved inorganic C (DIC) (−24.8 to −0.6‰), suggesting that microbial methanogenesis is limited. The majority of natural gases in Devonian organic-rich shales and sandstones at depth (>168 m) in the northern Appalachian Basin have a low CH₄ to ethane and propane ratios (3–35 mol%; C₁/C₂ + C₃) and high δ¹³C and δD values of CH₄ (−53.35 to −40.24‰, and −315.0 to −174.6‰, respectively), which increase in depth, reservoir age and thermal maturity; the molecular and isotopic signature of these gases show that CH₄ was generated via thermogenic processes. Despite this, the geochemistry of co-produced brines shows evidence for microbial activity. High δ¹³C values of DIC (>+10‰), slightly elevated alkalinity (up to 12.01 meq/kg) and low SO₄ values (<1 mmole/L) in select Devonian organic-rich shale and sandstone formation water samples suggest the presence of methanogenesis, while low δ¹³C–DIC values (<−22‰) and relatively high SO₄ concentrations (up to 12.31 mmole/L) in many brine samples point to SO₄ reduction, which likely limits microbial CH₄ generation in the Appalachian Basin. Together the formation water and gas results suggest that the vast majority of CH₄ in the Devonian organic-rich shales and sandstones across the northern Appalachian Basin margin is thermogenic in origin. Small accumulations of microbial CH₄ are present at shallow depths along Lake Erie and in western NY.     

Extreme methane deuterium,nitrogen and helium enrichment in natural gas from the Homorod seep (Romania)

Methane (CH₄) in terrestrial environments, whether microbial, thermogenic, or abiogenic, exhibits a large variance in C and H stable isotope ratios due to primary processes of formation. Isotopic variability can be broadened through secondary, post-genetic processes, such as mixing and isotopic fractionation by oxidation. The highest and lowest ¹³C and ²H (or D, deuterium) concentrations in CH₄ found in various geologic environments to date, are defined as “natural” terrestrial extremes. We have discovered a new extreme in a natural gas seep with values of deuterium concentrations, δD_CH4, up to + 124‰ that far exceed those reported for any terrestrial gas. The gas, seeping from the small Homorod mud volcano in Transylvania (Romania), also has extremely high concentrations of nitrogen (> 92 vol.%) and helium (up to 1.4 vol.%). Carbon isotopes in CH₄, C₂H₆ and CO₂, and nitrogen isotopes in N₂ indicate a primary organic sedimentary origin for the gas (a minor mantle component is suggested by the ³He/⁴He ratio, R/Ra ~ 0.39). Both thermogenic gas formation modeling and Rayleigh fractionation modeling suggest that the extreme deuterium enrichment could be explained by an oxidation process characterised by a δD_CH4 and δ¹³C_CH4 enrichment ratio (ΔH/ΔC) of about 20, and may be accounted for by abiogenic oxidation mediated by metal oxides. All favourable conditions for such a process exist in the Homorod area, where increased heat flow during Pliocene–Quaternary volcanism may have played a key role. Finally we observed rapid variations (within 1 h) in C and H isotope ratios of CH₄, and in the H₂S concentrations which are likely caused by mixing of the deep oxidized CH₄–N₂–H₂S–He rich gas with a microbial methane generated in the mud pool of one of the seeps.We hypothesize that the unusual features of Homorod gas can be the result of a rare combination of factors induced by the proximity of sedimentary organic matter, mafic, metal-rich volcanic rocks and salt diapirs, leading to the following processes: a) primary thermogenic generation of gas at temperatures between 130 and 175 °C; b) secondary alteration through abiogenic oxidation, likely triggered by the Neogene–Quaternary volcanism of the eastern Transylvanian margin; and c) mixing at the surface with microbial methane that formed through fermentation in the mud volcano water pool. The Homorod gas seep is a rare example that demonstrates how post-genetic processes can produce extreme gas isotope signatures (thus far only theorized), and that extremely positive δD_CH4 values cannot be used to unambiguously distinguish between biotic and abiotic origin.     

Evaluating the gas content of coals and isolated maceral concentrates from the Paleocene Guasare Coalfield,Venezuela

This work presents the results from evaluating the gases sorbed by coal samples extracted from the Paleocene Guasare Coalfield (Marcelina Formation, northwestern Venezuela), as well as by their distinct maceral concentrates. The aim of this work has been to obtain an initial experimental main value of the gas content per unit weight of high volatile bituminous A coal samples from the open-pit Paso Diablo mine. An additional goal was to study differences in the CH₄ storage ability of the distinct maceral groups forming part of the coal matrix. Both the coal samples and the maceral concentrates were studied by thermogravimetric analysis (TGA) in order to determine the temperature to be used in subsequent experiments. On-line analyses of hydrocarbons (C₁, C₂, C₃) and CO₂ yielded gas concentrations, plus δ¹³C values. Thermogenic gas is prevalent in the Guasare coals with vitrinite reflectance (%R_o) values from 0.65% to 0.88%. The amount of gas retained in the coals and maceral concentrates was measured with a special device that allows determination of the volume of gas sorbed by a solid sample subjected to controlled thermal treatment. The average coalbed gas concentration obtained was 0.51 cm³/g. The following list of maceral concentrates shows the relative capacity for the volume of sorbed gas per unit weight: inertinite > low-density vitrinite > liptinite ≈ high-density vitrinite. It is concluded that the gas volumes retained in the distinct maceral concentrates are not controlled by porosity but rather by their microscopic morphology.     

Geochemistry of volcanic and hydrothermal fluids and volatile budget of the Kamchatka-Kuril subduction zone

A data base for the composition and emission rates of more than 100 thermal manifestations including boiling geothermal systems and 23 volcanoes along the 1900 km long Kamchatka-Kuril (KK) arc is presented. These results were used to estimate mean fluxes of volatiles from the KK arc. The fluxes from the KK arc are compared with the fluxes from the best studied Central American (CA) arc and with the compiled literature data on global fluxes. The error ranges and the OUT/IN (in)balance calculations are also discussed. The estimated fluxes of volatiles from volcanic fumaroles and the observed, normalized to the Cl content, fluxes from hydrothermal systems are very close, with the higher hydrothermal flux from Kuril Islands due to a larger number of the acidic Cl-SO₄ springs on the Islands and their outflow rates. The total volcanic SO₂ flux from the whole KK arc is estimated to be higher than 3000 t/d. The measured S and C fluxes from hydrothermal systems are much lower than the volcanic output due to the loss of these components in the upper crust (mineral precipitation). The Cl/³He ratio is inferred to be a stable indicator of the arc setting for hydrothermal and volcanic fluids with a mean value of (2 ± 4) × 10⁹. Comparison of the obtained volcano-hydrothermal fluxes with fluxes calculated from the erupted solid volcanic products at Kamchatka and Kurils during Holocene time reveals that the total estimated volatile output from the KK arc is compatible with the total magmatic output if the intruded to erupted ratio is close to 7, i.e. almost the same as assumed for the Central American arc. Calculated fluxes as well as the ratios for OUT/IN fluxes (volcanic + hydrothermal output/slab + mantle input) for CO₂, S, H₂O, Cl, N₂, ⁴He and ³He from the KK arc normalized to the arc length are in general close to the global estimates. The fractions of CO₂ and S in the total volatile output at KK arc derived directly from the mantle wedge are 18% and 16% (mole basis), respectively. Fractions of mantle derived H₂O, N₂ and Cl are much lower, less that 5% of their output.     

Potential environmental issues of CO2 storage in deep saline aquifers: Geochemical results from the Frio-I Brine Pilot test,Texas, USA

Sedimentary basins in general, and deep saline aquifers in particular, are being investigated as possible repositories for large volumes of anthropogenic CO₂ that must be sequestered to mitigate global warming and related climate changes. To investigate the potential for the long-term storage of CO₂ in such aquifers, 1600 t of CO₂ were injected at 1500 m depth into a 24-m-thick “C” sandstone unit of the Frio Formation, a regional aquifer in the US Gulf Coast. Fluid samples obtained before CO₂ injection from the injection well and an observation well 30 m updip showed a Na–Ca–Cl type brine with ∼93,000 mg/L TDS at saturation with CH₄ at reservoir conditions; gas analyses showed that CH₄ comprised ∼95% of dissolved gas, but CO₂ was low at 0.3%. Following CO₂ breakthrough, 51 h after injection, samples showed sharp drops in pH (6.5–5.7), pronounced increases in alkalinity (100–3000 mg/L as HCO₃) and in Fe (30–1100 mg/L), a slug of very high DOC values, and significant shifts in the isotopic compositions of H₂O, DIC, and CH₄. These data, coupled with geochemical modeling, indicate corrosion of pipe and well casing as well as rapid dissolution of minerals, especially calcite and iron oxyhydroxides, both caused by lowered pH (initially ∼3.0 at subsurface conditions) of the brine in contact with supercritical CO₂.     

Methane and carbon dioxide flux from a macrotidal salt marsh,Bay of Fundy,New Brunswick

Fluxes of methane (CH₄) and carbon dioxide (CO₂) to the atmosphere at 52 sites within a salt marsh were measured by a dark static chamber technique from mid July to mid September. Mean CH₄ fluxes ranged from 0.2 mg m^?2 d^?1 to 11.0 mg m^?2 d^?1, with an overall average of 1.6 mg m^?2 d^?1. Flux of CH₄ was inversely correlated (r²=0.23, p = 0.001) with salinity of the upper porewater at the site, suggesting the dominant role of SO₄ ^2? in inhibiting methanogenesis in salt-marsh sediments. The combination of salinity and water table position was able to explain only 29% of the variance in CH₄ emission. Mean soil flux of CO₂ ranged from 0.3 g m^?2 d^?1 to 3.7 g m^?2 d^?1, with an overall average of 2.5 g m^?2 d^?1; it was correlated with aboveground biomass (positive, r²=0.38, p = 0.001) and position of the water table (negative, r² = 0.55, p = 0.001). The combination of biomass and water table position accounted for 63% of the variance in CO₂ flux. There were high variations in gas flux within the six plant communities. The sequences were CH₄: upland edge > panne > pool > middle marsh > low marsh > high marsh, and CO₂: middle marsh > low marsh > upland edge > high marsh > panne > pool. Compared to other salt-marsh systems, this Bay of Fundy marsh emits small amounts of CH₄ and CO₂.     

Isotopic evidence (He,B, C) for deep fluid and mud mobilization from mud volcanoes in the Caucasus continental collision zone

The Caucasian orogenic wedge formed as a consequence of the closure of the Tethyan Ocean, and numerous fields of active mud volcanoes pepper the area adjacent to the Black and Caspian Seas. Stable isotope ratios of boron, helium, and carbon have been measured for gas, fluid and sediment samples from active mud volcanoes of Taman Peninsula and Georgia to estimate the sources and mobilization depths of the fluid phase and mud. Boron concentrations in mud volcano fluids were found to be 5–35× higher than seawater. Fluid isotope ratios vary between ¹¹B=22 and 39, while isotope ratios of the smectite- and illite-rich extruded mud are considerably depleted in heavy ¹¹B (¹¹B=–8 to +7). B contents of these muds are ~8× higher than modern marine sediments. This suggests that liquefaction prior to mud volcanism was accompanied by both B enrichment and isotope fractionation, most likely at an intermediate depth mud reservoir at 2–4 km.The hydrocarbon-generating source beds to the mud volcanoes are located at 7 to >10 km depth in the folded Maikop Formation and are of proposed Oligocene–Miocene age. The most likely mechanism is re-hydration of these shales by both hydrocarbons and a geochemically mature fluid from greater depth within the orogenic wedge. Such a deep fluid source is supported by our results from gas analyses, which imply an admixture of minor amounts (less than 1%vol) of ³He (Georgia), thermogenic ¹³C in methane as well as "ultraheavy" ¹³C in CO₂ (both Taman and Georgia). The overall results attest active local flow of geochemically different fluids along deep-seated faults penetrating the two study areas in the Caucasian orogenic wedge, with the waters as well as the gases coming from below the Maikop Formation.     

Hazardous gas emissions from the flanks of the quiescent Colli Albani volcano (Rome,Italy)

Gas hazard was evaluated in the three most important cold gas emission zones on the flanks of the quiescent Colli Albani volcano. These zones are located above structural highs of the buried carbonate basement which represents the main regional aquifer and the main reservoir for gas rising from depth. All extensional faults affecting the limestone reservoir represent leaking pathways along which gas rises to the surface and locally accumulates in shallow permeable horizons forming pressurized pockets that may produce gas blowout when reached by wells. The gas, mainly composed of CO₂ (>90 vol.%), contains appreciable quantities of H₂S (0.35–6 vol.%), and both represent a potentially high local hazard. Both gases are denser than air and accumulate near ground where they may reach hazardous concentrations, and lethal accidents frequently occur to animals watering at local ponds. In order to evaluate the rate of degassing and the related hazard, CO₂ and H₂S diffuse soil flux surveys have been repeatedly carried out using an accumulation chamber. The viscous gas flux of some important discrete emissions has been evaluated and the CO₂ and H₂S air concentration measured by portable devices and by Tunable Diode Laser profiles. The minimum potential lethal concentration of the two gases (250 ppm for H₂S and 8 vol.% for CO₂) is 320 times higher for CO₂, whereas the CO₂/H₂S concentration ratio in the emitted natural gas is significantly lower (15–159). This explains why H₂S reaches hazardous, even lethal, concentrations more frequently than CO₂. A relevant hazard exists for both gases in the depressed zones (channels, excavations) particularly in the non-windy early hours of the day.     

Stable carbon isotope behaviour of natural seepage of deep underground C-rich methane detected along a fault zone and adsorbed in mudstone: Tokyo Bay area,Japan

Gas was sampled regionally, including by drilling into faults, in the South Kanto gas-field around Tokyo Bay, Japan. Gas samples were collected from cores in a gas sampling container immediately after drilling. A value of δ¹³C₁ = −44.3‰ was obtained for gas in the container and δ¹³C₁ = −36.3‰ for seeping gas in a fault zone. However, typical CH₄ in this dissolved-in-water gas-field is mainly depleted in ¹³C, and δ¹³C₁ values range from −66‰ to −68‰ owing to microbial degradation of organic material. ¹³C-rich CH₄ is so far uncommon in the South Kanto gas-field. Seepages were observed from the surface along the north–south fault zone. The natural gas is stored below the sandstone layer by impermeable mudstone underlying the boundary at a depth of 30 m. Gas seepages were not observed below a depth of 40 m. Gas rises along the fault zone dissolved-in-groundwater up to the shallow region and then separates from the groundwater. ¹³C-rich CH₄ (adsorbed CH₄) was found to have desorbed from drilled mudstone core samples taken at depths of 1400–1900 m in the main gas-production strata. Similarly, ¹³C-rich CH₄ was found in black shale overlying the oceanic crust forming part of a sedimentary accretionary prism underling the Tokyo region. It also appears in the spring-water of spa wells, originating at a depth of 1200–1500 m along a tectonic line. Methane generated by microbial degradation of organic material through CO₂ reduction in the South Kanto gas-field mainly originates as biogenic gas mixed with a small amount of ¹³C-rich CH₄, derived from thermogenic gas without oil components in strata. It is assumed that ¹²C-rich CH₄ is easily detached from core or pore water through gas production, whereas ¹³C-rich CH₄ is strongly adsorbed on the surfaces of particles. The ¹³C-rich CH₄ rises along the major tectonic line or up the 50 m wide normal fault zone from relatively deep sources in the Kanto region.     

Organic inclusions as an indicator of oil/gas potential assessment of carbonate reservoir beds

Organic inclusions could be formed at the stages of either primary or secondary migration of hydrocarbons so long as mineral crystallization or recrystallization takes place in the sediments, presenting a direct indicator of oil/gas evolution, migration and abundance. Based on the study of organic inclusions in carbonate-type reservoir beds of commercial importance from North China, Xingjing, North Jiangsu, Jianghan, Sichuan and Guizhou in China, many inclusion parameters for oil/gas potential assessment of carbonate reservoir beds are summarized in this paper, including: 1) Types of organic inclusion: Commercially important oil beds are characterized by inclusions consisting of either pure liquid hydrocarbons or liquid plus minor gaseous hydrocarbons, while commercially important gas reservoirs are characterized by inclusions consisting of either pure gaseous hydrocarbons or gas plus minor liquid hydrocarbons. 2) Quantity of organic inclusions: The number of organic inclusions in commercially important oil/gas reservoirs is over 60% of the total inclusion percentage. 3) Temperature of saline inclusions: The homogenization temperatures of contemporaneous saline inclusions in oil reservoirs range from 91–161 °C, while in gas reservoirs from 150–250 °C). 4) Inclusion composition: In commercially important oil reservoirs, C₁/C₂=2−10, C₁/C₃=2−4, C₁/C₄=2−21, (C₂−C₄)/(C₁−C₄)(%)>20, (CH₄+CO+H₂)/CO₂ (molecules/g)=0.5−1.0, and in C₂−C₃−nC₄ triangle diagram there should be an upside-down triangle with the apex within the ellipse, while in commercial gas reservoirs, C₁/C₂=10−35, C₁/C₃=14−82, C₁/C₄=21−200, (C₂−C₄)/(C₁−C₄)(%)<20, (CH₄+CO+H₂)/CO₂>1, and there would be an upright triangle with the apex within the ellipse. The above-mentioned parameters have been used to evaluate a number of other unknown wells or regions and the results are very satisfactory. It is valid to use organic inclusions as an indicator to assess the oil/gas potential during oil/gas exploration and prospecting. This approach is effective, economic, rapid, and easy to popularize.     

Methane microseepage from different sectors of the Yakela condensed gas field in Tarim Basin,Xinjiang, China

Methane microseepage is the result of natural gas migration from subsurface hydrocarbon accumulations to the Earth’s surface, and it is quite common in commercial petroleum fields. While the role of microseepage as a pathfinder in petroleum exploration has been known for about 80 a, its significance as an atmospheric CH₄ source has only recently been studied, and flux data are currently available only in the USA and Europe. With the aim of increasing the global data-set and better understanding flux magnitudes and variabilities, microseepage is now being extensively studied in China. A static flux chamber method was recently applied to study microseepage emissions into the atmosphere in four different sectors of the Yakela condensed gas field in Tarim Basin, Xinjiang, China, and specifically in: (a) a faulted sector, across the Luntai fault systems; (b) an oil–water interface sector, at the northern margin of the field; (c) an oil–gas interface sector, in the middle of the field; (d) an external area, outside the northern gas field boundaries. The results show that positive CH₄ fluxes are pervasive in all sectors and therefore, only part of the CH₄ migrating from the deep oil–gas reservoirs is consumed in the soil by methanotrophic oxidation. The intensity of gas seepage seems to be controlled by subsurface geologic settings and lateral variabilities of natural gas pressure in the condensed gas field. The highest CH₄ fluxes, up to ∼14 mg m⁻² d⁻¹ (mean of 7.55 mg m⁻² d⁻¹) with higher spatial variability (standard deviation, σ: 2.58 mg m⁻² d⁻¹), occur in the Luntai fault sector. Merhane flux was lower in the oil–water area (mean of 0.53 mg m⁻² d⁻¹) and the external area (mean of 1.55 mg m⁻² d⁻¹), and at the intermediate level in the gas–oil sector (mean of 2.89 mg m⁻² d⁻¹). These values are consistent with microseepage data reported for petroleum basins in the USA and Europe. The build-up of methane concentration in the flux chambers is always coupled with an enrichment of ¹³C, from δ¹³C₁ of −46‰ to −42.5‰ (VPDB), which demonstrates that seeping methane is thermogenic, as that occurring in the deep Yakela reservoir. Daily variations of microseepage are very low, with minima in the afternoon, corresponding to higher soil temperature (and higher methanotrophic consumption), and maxima in the early morning (when soil temperatures are lowest). A preliminary and rough estimate of the total amount of CH₄ exhaled from the Yakela field is in the order of 10² tonnes a⁻¹.