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.     

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.     

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.     

中国大陆新生代典型火山区温室气体释放的规模及其成因

火山活动能够将地球深部的碳输送到大气圈,是地质碳排放和深部碳循环的重要形式.火山作用不仅在喷发期能够释放大量温室气体,而且在休眠期也能释放巨量的温室气体.在全球变暖的背景下,定量化地研究火山活动对大气圈温室气体含量增加的贡献具有至关重要的意义.本文利用密闭气室法等该领域国际先进的测试技术,测量并计算了长白山、腾冲、五大连池及青藏高原南部的羊八井等典型火山区的温室气体释放规模.结果显示,我国大陆新生代典型火山区向大气圈输送的温室气体总通量约为8.13×10⁶t·a^-1,接近10⁷t·a^-1级别,相当于全球火山活动导致的温室气体(主要为CO₂)释放总量的6%左右.太平洋构造域火山区的温室气体在释放通量与总量方面均低于特提斯构造域,并且太平洋构造域火山气体的地壳混染程度较低,显示出大洋俯冲带与大陆俯冲带火山区温室气体释放的成因差异.     

Gas flux to the atmosphere from mud volcanoes in eastern Romania

Gas flux measurements have for the first time been taken from vents and soil of eastern Romania mud volcanoes, the largest geological structures in Europe releasing methane into the atmosphere. In the quiescent phase, the methane emission from single vents is up to 28 t yr^?1. Diffuse soil microseepage is of the order of 10²?10⁵ mg m^?2 day^?1. A total output of at least 1200 tonnes of CH₄ per year can be conservatively estimated over the area investigated alone (～ 2.3 km²). Helium fluxes are up to five orders of magnitude higher than the average flux in a stable continental area, pointing to a close link between mud volcanoes and crustal degassing through faults crossing the deep hydrocarbon reservoirs. These data represent a key contribution towards refining global CH₄‐emission estimates, which indicate mud volcanoes as a significant and unavoidable source of greenhouse gases for the atmosphere.     

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.     

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.     

Magmatic fluids of Tatun volcanic group,Taiwan

Two distinctive magmatic fluids were recognized in the Tatun volcanic group (TVG), Taiwan. One is a relatively reduced fluid represented by the fumarolic gases at Hsiao-you-ken (HYK) geothermal field. Another is an oxidized fluid containing high concentrations of HCl represented by the fumarolic gases at Da-you-ken (DYK). An intermediate gas was recognized at Gung-tze-ping (GTP) and She-hung-ping (SHP). The fumarolic gases at HYK and GTP possess the features of so-called primary steam generated on mixing of magmatic gas and meteoric groundwater. The fumarolic gases at DYK are a simple mixture between magmatic gas and water vapor of meteoric origin. The CO₂/H₂O molar ratio of the magmatic component in the fumarolic gases at DYK was estimated to be 0.018, meanwhile it was estimated to be 0.027 for the fumarolic gases at HYK and GTP, suggesting the magma beneath DYK is depleted in volatiles relative to the magma beneath HYK and GTP. The estimated CO₂/H₂O ratio for the magmatic component is comparable to that of some active volcanoes in Japan, suggesting the enrichment of volatiles in the magmas beneath TVG.     

长白山火山区温泉温室气体排放通量研究

温泉是深部岩浆活动在地表的直接表现,并且向大气圈排放大量的温室气体.然而,国内尚无火山区温泉排放的温室气体通量研究报道.我国长白山火山区水热活动强烈,主要有湖滨温泉带、聚龙温泉群、锦江温泉以及火山口外围的十八道沟温泉.本文利用数字皂膜流量计测量温泉气体排放通量,并结合前人对长白山火山区温泉气体成分的研究成果,估算了研究区温泉所排放的温室气体通量.结果表明,长白山火山区温泉排放的CO2通量为6.9×104t·a-1,CH4排放通量为428.44t·a-1,与意大利Pantelleria Island火山区温泉排放的温室气体通量规模相当.本文的测试结果表明:数字皂膜流量计在火山区温室气体排放通量估算研究中的应用是可行的.     

Chemical monitoring of volcanic gas using remote FT-IR spectroscopy at several active volcanoes in Japan

Chemical compositions of volcanic gases of several Japanese active volcanoes have been monitored from distant safe places since the beginning of the 1990s using an FT-IR spectral radiometer. For absorption measurements, an infrared light source behind volcanic gas emissions is necessary in a volcanic environment. In the early observations, infrared radiation from hot lava domes (Unzen volcano) and hot ground heated by high-temperature fumaroles (Usu, Aso, and Satsuma-Iwojima volcanoes) were used as infrared light sources. However, these sources were not available in many cases. This remote FT-IR method became more commonly applied to chemical monitoring of volcanic gases emitted from the summit or slopes of active volcanoes using scattered solar infrared light as infrared light sources (Sakurajima, Miyakejima, and Asama volcanoes). To date, eight species have been measured using this method: SO₂, HCl, HF, CO, CO₂, COS, SiF₄, and H₂O. The observations indicate that volcanic gases for each volcano have different chemical composition on a SO₂–HCl–HF ternary diagram in spite of similar tectonic settings, suggesting that vapor/melt volume ratios during volcanic gas formation differ among volcanoes. During more than 15 years of monitoring, chemical changes in volcanic gases attributable to ascent of magma were observed only at Asama, where HCl/SO₂ and HF/HCl ratios in the eruptive period were higher than those in non-eruptive period because of scrubbing of more soluble components in surface hydrothermal systems in the non-eruptive stage or solubility-controlled fractionation processes. Results show that these parameters are the most prospective ones among the various parameters measured using the remote FT-IR method to monitor volcanic activities.     

Isotopic-geochemical peculiarities of gases in mud volcanoes of eastern Georgia

Isotopic-geochemical study revealed the presence of mantle He (³He/⁴He up to 223 × 10^?8) in gases from mud volcanoes of eastern Georgia. This fact confirms that the Middle Kura basin fill encloses an intrusive body previously distinguished from geophysical data. Wide variations in the carbon isotopic composition δ¹³C of CH₄ and CO₂ and the chemical composition of gas and water at a temporally constant ³He/⁴He ratio indicate their relation with crustal processes. Unusual direct correlations of the ³He/⁴He ratio with the contents of He and CH₄ and the ⁴⁰Ar/³⁶Ar ratio can be explained by the generation of gas in the Cenozoic sequence of the Middle Kura basin.     

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。     

长岭凹陷深层天然气藏中CO_2及CH_4充注次序的流体包裹体证据

对长岭凹陷深层天然气藏储层——营城组火山岩中发育的流体包裹体进行了详细研究,结果表明在火山岩发育的石英、方解石细网脉中均存在较多的碳质流体包裹体,单个包裹体激光拉曼光谱分析结果表明其主要为CO2及CH4两种类型的碳质包裹体。其中方解石细网脉体中发育有原生及次生CH4包裹体,而含CO2包裹体多以原生包裹体产于石英细网脉中。很多含CO2包裹体的石英细脉中发现了含CH4包裹体的方解石脉体的角砾,这就表明石英细脉形成晚于方解石细脉。营城组火山岩储层中CO2及CH4包裹体的产状特征研究表明,松辽盆地深层天然气藏的形成系火山岩成岩后CO2及CH4等气体不同期次充注的结果,CH4气的充注时间早于CO2气,火山岩中发育的原生孔隙及次生裂隙为上述气体的充注和聚集提供了重要通道。     

Gases of mud volcanoes in the Copper River Basin,Alaska

The gases emitted from mud volcanoes in the Copper River Basin of Alaska fall into two distinct types which are not mixed during vertical migration. The gases in the eastern volcanoes are nearly pure carbon dioxide, whereas the western ones contain methane and nitrogen and almost no carbon dioxide. Chemical and carbon isotopic compositions suggest the carbon dioxide rich gases originated by solution of limestones and that methane rich gases probably formed by thermal decomposition of coals.Permafrost may be a strong factor in separating the Copper River Basin gases. Extending downward for several hundred feet, the permafrost would prevent shallow lateral migration and focus the energy of the gas into occasional mud volcano vents. Soil gas analyses show rapidly decreasing amounts of the methane to about 150 m and of carbon dioxide to about 20–40 m away from the mud volcano pools. Isotopic variations of these natural methane and carbon dioxide gases, which are not intermixed, indicate that calculations of formation temperatures based on δ¹³C ratios cannot be used generally.     

Origin of light volatile hydrocarbon gases in mud volcano fluids, Gulf of Cadiz — Evidence for multiple sources and transport mechanisms in active sedimentary wedges

Widespread mud volcanism across the thick (≤ 14 km) seismically active sedimentary prism of the Gulf of Cadiz is driven by tectonic activity along extensive strike–slip faults and thrusts associated with the accommodation of the Africa–Eurasia convergence and building of the Arc of Gibraltar, respectively. An investigation of eleven active sites located on the Moroccan Margin and in deeper waters across the wedge showed that light volatile hydrocarbon gases vented at the mud volcanoes (MVs) have distinct, mainly thermogenic, origins. Gases of higher and lower thermal maturities are mixed at Ginsburg and Mercator MVs on the Moroccan Margin, probably because high maturity gases that are trapped beneath evaporite deposits are transported upwards at the MVs and mixed with shallower, less mature, thermogenic gases during migration. At all other sites except for the westernmost Porto MV, δ¹³C–CH₄ and δ²H–CH₄ values of ~ − 50‰ and − 200‰, respectively, suggest a common origin for methane; however, the ratio of CH₄/(C₂H₆ + C₃H₈) varies from ~ 10 to > 7000 between sites. Mixing of shallow biogenic and deep thermogenic gases cannot account for the observed compositions which instead result mainly from extensive migration of thermogenic gases in the deeply-buried sediments, possibly associated with biodegradation of C₂₊ homologues and secondary methane production at Captain Arutyunov and Carlos Ribeiro MVs. At the deep-water Bonjardim, Olenin and Carlos Ribeiro MVs, generation of C₂₊-enriched gases is probably promoted by high heat flux anomalies which have been measured in the western area of the wedge. At Porto MV, gases are highly enriched in CH₄ having δ¹³C–CH₄ ~ − 50‰, as at most sites, but markedly lower δ²H–CH₄ values < − 250‰, suggesting that it is not generated by thermal cracking of n-alkanes but rather that it has a deep Archaeal origin. The presence of petroleum-type hydrocarbons is consistent with a thermogenic origin, and at sites where CH₄ is predominant support the suggestion that gases have experienced extensive transport during which they mobilized oil from sediments ~ 2–4 km deep. These fluids then migrate into shallower, thermally immature muds, driving their mobilization and extrusion at the seafloor. At Porto MV, the limited presence of petroleum in mud breccia sediments further supports the hypothesis of a predominantly deep microbial origin of CH₄.     

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.     

Carbon and hydrogen isotopic evidence for the origin of combustible gases in water-supply wells in north-central Pennsylvania

The origin of the combustible gases in groundwater from glacial-outwash and fractured-bedrock aquifers was investigated in northern Tioga County, Pennsylvania. Thermogenic methane (CH₄) and ethane (C₂H₆) and microbial CH₄ were found. Microbial CH₄ is from natural in situ processes in the shale bedrock and occurs chiefly in the bedrock aquifer. The δ¹³C values of CH₄ and C₂H₆ for the majority of thermogenic gases from water wells either matched or were between values for the samples of non-native storage-field gas from injection wells and the samples of gas from storage-field observation wells. Traces of C₂H₆ with microbial CH₄ and a range of C and H isotopic compositions of CH₄ indicate gases of different origins are mixing in sub-surface pathways; gas mixtures are present in groundwater. Pathways for gas migration and a specific source of the gases were not identified. Processes responsible for the presence of microbial gases in groundwater could be elucidated with further geochemical study.     

Computer modeling of methanotrophic oxidation of hydrocarbons in the unsaturated zone from an enhanced oil recovery/sequestration project, Rangely, Colorado, USA

One of the proposals for large-scale sequestration of fossil fuel-derived CO₂ is deep geologic disposal in depleted oil/gas reservoirs or deep aquifers. Previously published scenarios for this inadequately proven technology have either ignored or dismissed the possibility of vertical migration of gases caused by overpressure. Overpressuring of a reservoir or aquifer will be necessary in order to have acceptable rates for dispersal of injected CO₂. This research describes methodology and the results of measurement of microseepage of CO₂ and CH₄ at a large-scale CO₂-enhanced oil recovery (EOR) operation at Rangely, Colorado, USA. Shallow and deep soil gas concentrations, and direct transport of CO₂ and CH₄ into the atmosphere were measured. The interpretation of the measurements was complemented by both stable and radiogenic isotopic measurements of C. The results have demonstrated an estimated microseepage to the atmosphere of approximately 400 metric tonnes of CH₄/a from the 78 km² area of the Rangely field. Preliminary estimates of deep-sourced CO₂ losses are <3800 tonnes/a, based on stable isotope measurements of soil gases. Several holes up to 10 m deep were drilled on, and off the field for nested gas sampling of composition and stable C isotopic ratios for CO₂ and CH₄. Carbon-14 measurements on CO₂ from these holes indicate that deep-sourced CO₂ microseepage losses were approximately 170 tonnes/a.     

Rate measurements and detection of gas microseepage to the atmosphere from an enhanced oil recovery/sequestration project,Rangely, Colorado,USA

One of the proposals for large-scale sequestration of fossil fuel-derived CO₂ is deep geologic disposal in depleted oil/gas reservoirs or deep aquifers. Previously published scenarios for this inadequately proven technology have either ignored or dismissed the possibility of vertical migration of gases caused by overpressure. Overpressuring of a reservoir or aquifer will be necessary in order to have acceptable rates for dispersal of injected CO₂. This research describes methodology and the results of measurement of microseepage of CO₂ and CH₄ at a large-scale CO₂-enhanced oil recovery (EOR) operation at Rangely, Colorado, USA. Shallow and deep soil gas concentrations, and direct transport of CO₂ and CH₄ into the atmosphere were measured. The interpretation of the measurements was complemented by both stable and radiogenic isotopic measurements of C. The results have demonstrated an estimated microseepage to the atmosphere of approximately 400 metric tonnes of CH₄/a from the 78 km² area of the Rangely field. Preliminary estimates of deep-sourced CO₂ losses are <3800 tonnes/a, based on stable isotope measurements of soil gases. Several holes up to 10 m deep were drilled on, and off the field for nested gas sampling of composition and stable C isotopic ratios for CO₂ and CH₄. Carbon-14 measurements on CO₂ from these holes indicate that deep-sourced CO₂ microseepage losses were approximately 170 tonnes/a.     

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.