Isotopic Composition Of CH4 Research Articles

Application of concentration and 2-dimensional stable isotope measurements of methane to constrain sources and sinks in a seasonally stratified freshwater lake

Methane (CH4) emissions from aquatic systems have recently been comprised to account for up to 50% of global CH4 emissions, with lakes representing one of the largest CH4 sources within this pool. However, there is large uncertainty associated with CH4 emissions from freshwater environments to the atmosphere, because of a lack of understanding in the spatial and temporal dynamics of CH4 sources and sinks, as well as underlying mechanisms and processes. In this study, we investigated the concentrations and stable carbon (δ13C-CH4) and hydrogen (δ2H-CH4) isotope composition of CH4 in a small eutrophic lake (Lake Willersinnweiher) with seasonal stratification and its spatial and temporal variation. We found that while supersaturation of CH4 in the entire water column was present throughout the whole year, the isotopic composition of CH4 in sediment and water column varied depending on lake stratification, physiochemical conditions, and lake depth. During the stratification period, isotopic characteristics of pelagic surface water CH4 differed from littoral and sedimentary CH4, suggesting likely mixing of CH4 from different sources including vertical and lateral input as well as groundwater input and potentially oxic methane production in the mixed surface water layer. Aerobic CH4 oxidation indicated by a strong increase in both δ13C-CH4 and δ2H-CH4 values at the bottom of the oxycline was found to significantly reduce upward migrating CH4 released at the sediment-water interface. In the sediment, stable isotope characteristics of CH4 showed an increasing dominance of the acetoclastic CH4 formation pathway from the pelagic towards the littoral area. Furthermore, the occurrence of sulfate-dependent anaerobic methane oxidation in the sediment was suggested by an increase in δ13C-CH4 and δ2H-CH4 values. During the mixing period, the isotopic CH4 composition of the water column was distinctively less negative than during the stratification period potentially resulting from a greater impact of groundwater CH4 input compared to the stratification period. Our findings implicate that the application of concentrations and dual isotope measurements of CH4 is a promising approach for constraining CH4 sinks and sources in Lake Willersinnweiher and potentially other small lakes to clearly disentangle the complex CH4 dynamics in lakes both spatially and seasonally.

Sources and migration pathways of methane and light hydrocarbons in the subsurface of the Southern Po River Basin (Northern Italy)

This paper presents new chemical and isotopic data on gases from deep oil and gas fields, bubbling gases, dissolved gases in groundwaters and dry seeps of the Southern Po River Basin (Emilia-Romagna, Italy), aiming to (i) characterize and differentiate the various types of deep natural gases; (ii) identify the source(s) of methane and light hydrocarbons in shallow aquifers and surface gas-rich emissions; (iii) propose a conceptual model of natural fluid migration pathways in the sedimentary prism of the Southern Po River Basin. Based on the isotopic composition of CH4 and C2–C4 n-alkanes, CH4/(C2H6+C3H8) ratio, relative proportion of the C7 hydrocarbons and relative concentration of cyclic compounds with respect to the total cyclic abundance, three main deep reservoirs of hydrocarbons are identified in the subsurface of the Southern Po River Basin: (1) microbial gas hosted in Pliocene-Pleistocene marine sediments, (2) thermogenic gas hosted in Miocene deposits and (3) thermogenic gas produced in Triassic carbonates. Helium isotopes of these deep fluids indicate an almost pure crustal origin (Rc/Ra values = 0.014–0.04), with negligible contributions from mantle-derived helium. A variable contribution of atmosphere-derived fluids is highlighted by low 4He/20Ne (down to 5.42) and 40Ar/36Ar (≤319.5) values. Comparison of chemical and isotopic signatures of deep and surficial hydrocarbon occurrences suggests that methane in shallow groundwaters or gas seeps is sourced by microbial gas migrating upward from deep Plio-Pleistocene reservoirs, with no detectable contributions of Triassic or Miocene thermogenic hydrocarbons. At shallow depths (roughly around 20–50 m.b.g.l.), Plio-Pleistocene microbial methane appears to be mainly stored in anoxic aquifers. However, where CH4 further migrates upwards and reaches aerobic environments (e.g., aquifers or soils), it readily undergoes a process of exothermic microbial oxidation mediated by methanotrophic bacteria. Where the structural architecture of the sedimentary sequence favors the migration of fluids, the methanotrophic biofilter is bypassed and CH4 is discharged through soil diffuse degassing or gas bubbling at water wells. We argue that microbial consumption might be able to bio-sequester significant amounts of Plio-Pleistocene deep-sourced methane in the form of CO2 and biomass. Such process might be widespread in the subsurface of the Southern Po River Basin and, possibly, in other foreland basins worldwide.

Experimental determination of hydrogen isotope exchange rates between methane and water under hydrothermal conditions

The hydrogen isotopic composition of methane (CH4) is used as a fingerprint of gas origins. Exchange of hydrogen isotopes between CH4 and liquid water has been proposed to occur in both low- and high-temperature settings. However, despite environmental evidence for hydrogen isotope exchange between CH4 and liquid water, there are few experimental constraints on the kinetics of this process. We present results from hydrothermal experiments conducted to constrain the kinetics of hydrogen isotope exchange between CH4 and supercritical water. Seven isothermal experiments were performed over a temperature range of 376–420 °C in which deuterium-enriched water and CH4 were reacted in flexible gold reaction cell systems. Rates of exchange were determined by measuring the change in the δD of CH4 over the time course of an experiment. Regression of derived second order rate constants (kr) vs. 1000/T (i.e., an Arrhenius plot) yields the following equation: ln(kr) = −17.32 (±4.08, 1 s.e.) × 1000/T + 3.19 (±6.01, 1 s.e.) (units of kr of sec−1 [mol/L]−1), equivalent to an activation energy of 144.0 ± 33.9 kJ/mol (1 s.e.). These results indicate that without catalysts, CH4 will not exchange hydrogen isotopes with liquid water on a timescale shorter than the age of the Earth (i.e., billions of years) at temperatures below 100–125 °C. Exchange at or below these temperatures is thought to occur due to the activity of life, and thus hydrogen isotopic equilibrium between methane and water may be a biosignature at low temperatures on Earth (in the present or the past) and on other planetary bodies. At temperatures ranging from 125 to 200 °C, hydrogen isotope exchange between CH4 and liquid water can occur on timescales of millions to hundreds of thousands of years, indicating that in thermogenic natural gas systems CH4 may isotopically equilibrate with water and achieve equilibrium isotopic compositions. Finally, the kinetics indicate that in deep-sea hydrothermal systems, the hydrogen (and thus clumped) isotopic composition of CH4 is likely set by formation and/or storage conditions isolated from the active flow regime. The determined kinetics indicate that once methane is entrained in circulating fluids, the expected time-temperature pathways are insufficient for measurable hydrogen isotope exchange between CH4 and water to occur.

Seasonal Variation of Methane Microseepage in the Dawanqi Oilfield (China): A Possible Climatic Control

AbstractNatural gas microseepage in petroleum‐bearing sedimentary basins is an important complement to geophysical methods in oil‐gas exploration and a natural source of methane (CH4) for the atmosphere. Microseepage, typically occurring in correspondence with petroleum fields throughout the world, is generally lower in summer, due to temperature‐driven methanotrophic consumption, and higher in winter. The global estimates of microseepage methane emission have, however, relatively high uncertainties because of limited amounts of flux data, leading to poor knowledge of the spatial distribution and temporal variability of the gas emission factors. We studied the seasonal variation of microseepage flux to the atmosphere from a petroleum field in China (the Dawanqi oilfield), through methane flux measurements performed in summer 2014, winter 2015, and summer 2019. Winter data refer to frozen soil conditions, with snow cover and ice thickness in the soil exceeding 60 cm. Gas concentration (CH4, CO2, C2+ alkanes) and stable C isotopic composition of CH4 and CO2 in shallow (4 m deep) boreholes confirmed the existence of thermogenic gas seepage. Methane microseepage is higher in summer and lower or nil in winter. This seasonal trend is opposite to what was observed in areas where winter soil is not or poorly frozen. Our data suggest that seasonal microseepage variation may not be univocal worldwide, being strongly dependent on the presence of ice and snow cover in winter. The regional increase of temperature due to climate change, already demonstrated for the Tarim Basin over the last 50 years, could, in the future, reduce winter ice and enhance annual methane emission to the atmosphere.

In situ observations of greenhouse gases over Europe during the CoMet 1.0 campaign aboard the HALO aircraft

Abstract. The intensive measurement campaign CoMet 1.0 (Carbon Dioxide and Methane Mission) took place during May and June 2018, with a focus on greenhouse gases over Europe. CoMet 1.0 aimed at characterising the distribution of CH4 and CO2 over significant regional sources with the use of a fleet of research aircraft as well as validating remote sensing measurements from state-of-the-art instrumentation installed on board against a set of independent in situ observations. Here we present the results of over 55 h of accurate and precise in situ measurements of CO2, CH4 and CO mole fractions made during CoMet 1.0 flights with a cavity ring-down spectrometer aboard the German research aircraft HALO (High Altitude and LOng Range Research Aircraft), together with results from analyses of 96 discrete air samples collected aboard the same platform. A careful in-flight calibration strategy together with post-flight quality assessment made it possible to determine both the single-measurement precision as well as biases against respective World Meteorological Organization (WMO) scales. We compare the result of greenhouse gas observations against two of the available global modelling systems, namely Jena CarboScope and CAMS (Copernicus Atmosphere Monitoring Service). We find overall good agreement between the global models and the observed mole fractions in the free tropospheric range, characterised by very low bias values for the CAMS CH4 and the CarboScope CO2 products, with a mean free tropospheric offset of 0 (14) nmol mol−1 and 0.8 (1.3) µmol mol−1 respectively, with the numbers in parentheses giving the standard uncertainty in the final digits for the numerical value. Higher bias is observed for CAMS CO2 (equal to 3.7 (1.5) µmol mol−1), and for CO the model–observation mismatch is variable with height (with offset equal to −1.0 (8.8) nmol mol−1). We also present laboratory analyses of air samples collected throughout the flights, which include information on the isotopic composition of CH4, and we demonstrate the potential of simultaneously measuring δ13C−CH4 and δ2H−CH4 from air to determine the sources of enhanced methane signals using even a limited number of discrete samples. Using flasks collected during two flights over the Upper Silesian Coal Basin (USCB, southern Poland), one of the strongest methane-emitting regions in the European Union, we were able to use the Miller–Tans approach to derive the isotopic signature of the measured source, with values of δ2H equal to −224.7 (6.6) ‰ and δ13C to −50.9 (1.1) ‰, giving significantly lower δ2H values compared to previous studies in the area.

Methane and nitrous oxide temporal and spatial variability in two midwestern USA streams containing high nitrate concentrations

Concentrations and emissions of greenhouse gases CO2, CH4, and N2O commonly are examined individually in aquatic environments in which each is expected to be relatively important; however, their co-occurrence and dynamic interactions in fluvial settings could provide important information about their controlling biogeochemical processes and potential contributions to global climate change. Spatial and temporal variability of CH4, N2O, and CO2 concentrations were measured from June 1999 to September 2003 in two nitrate-rich (40–1200 μM) streams draining agricultural land in the midwestern USA that differed ~13-fold in flow. Seasonal (biweekly), diel (hourly), and transport-oriented (reach-scale) sampling approaches were compared. Dissolved gas concentrations exceeded atmospheric equilibrium values up to 700- and 16-fold, for CH4 and N2O, respectively. Mean concentrations were higher in the larger stream than in the smaller stream. In both streams, CH4 emissions were generally higher in summer-fall and negatively correlated with flow and NO3− concentration while N2O emissions were generally higher in winter/spring and positively correlated with flow and NO3−. In the small stream, diel variations in the concentrations, emissions, and isotopic compositions of CH4, N2O, and NO2− resulted from diel variations in sources, sinks, and air-water gas exchange velocities. Seasonal mean total (CH4 + N2O) area-normalized emission rates, expressed as CO2 warming potential equivalents, were similar for the two streams, but the total reach-scale emission rate for the larger stream, including CO2, was about 2.9 times that of the smaller stream (131.6 vs 46.0 kg CO2 equivalents km−1 day−1, respectively). The CH4 contribution to this flux was 9–28%, despite the relatively high NO3− and O2 concentrations in the streams, indicating contributions from upwelling groundwater or reactions in streambed sediment.

Shallow submarine seep of abiotic methane from serpentinized peridotite off the Island of Elba, Italy

Abiotic methane (CH4) is today widely reported in gas seeps and hyperalkaline springs in ophiolites and peridotite massifs characterized by low temperature continental serpentinization. Origin and distribution of this gas have far reaching implications in microbiology, astrobiology and carbon cycle. We report an in-depth study of a recently described abiotic CH4 seep occurring in shallow seafloor along the western coast of Elba Island, Tyrrhenian Sea (Italy). The gas is characterized by stable C and H isotopic compositions of CH4 (δ13C ∼ −18‰; δ2H ∼ −141‰) and a very low CO2 content that are typical of abiotic gas in continental ultramafic rock systems. Based on local geothermal gradients, the temperature of methane production is estimated to be below 100 °C. The isotope signature of methane is similar to that occurring in the Liguria region, about 200 km north of Elba Island, where the same ophiolite unit exposed. A mantle CO2 component, suggested by relatively high 3He/4He ratios, has likely acted as CH4 precursor. The reconstruction of the geological-structural setting of Elba ophiolite sequence highlighted that the seep occurs in correspondence with a faulted reverse limb of the antiform of the ophiolite unit. The gas bearing fault forms a contact between mafic and ultramafic serpentinized rocks, as typically observed in other continental seeps and springs related to ophiolites. Magmatic intrusions in the island may have contributed to the C feedstock of methane.

Methane transport in agricultural soil after injection of isotopically-enriched methane in the sub-surface

Small quantities of radioactive methane (14CH4) may be released over prolonged periods from geological disposal facilities for radioactive waste. The impact of this release depends on the capacity of soil to oxidise 14CH4 to 14CO2 during transport from the sub-surface to the atmosphere. We investigated this capacity by pulse-injecting isotopically-enriched methane 50 cm below the surface of an agricultural soil in central England. Three sequential injections were made during growth of a spring wheat crop. Samples of gas were taken from the pore space throughout the soil profile at predetermined time points after injection, accompanied by samples of the atmosphere above the soil collected in sampling chambers, deployed at scheduled intervals. Methane and CO2 were measured in soil and above-ground gas using gas chromatography; the isotopic composition of CH4 and CO2 was determined using gas chromatography with isotopic ratio mass spectrometry. Supporting measurements of environmental variables were made during the experiment. The data can be used to test mathematical models describing CH4 and CO2 transport and fate in temperate agricultural soils.

Carbon stable isotopes as indicators of the origin and evolution of CO2 and CH4 in urban solid waste disposal sites and nearby areas

Isotopic compositions of CH4 and CO2 surface and subsurface gases and groundwater from an urban solid waste disposal site from Gualeguaychu city (Argentina) were measured to detect origin, depth distribution, migration lateral, CH4 oxidation, and dissolution in groundwater. The highest CH4 concentrations (60–88 %) with δ13C-CH4 (between −60 and −45 ‰) and δ2H-CH4 (between −350 and −260 ‰) were attributed to CH4 originated by microbial sources, v. gr. acetate fermentation. The δ13C-CO2 related to this CH4 (between −15 and −5.9 ‰) were compatible with this process. Also, the increase of DIC associated to an increase in δ13C-DIC values (−12.4, −6.4, −5.8, −1.5, +0.1 and +4 ‰) indicated the transport of dissolved gases (from methanogenesis) in the groundwater flow system. High excess deuterium in 3 piezometers suggests that there were hydrogen isotope exchange between CH4 and water too. Evidences for CH4 oxidation were decrease in CH4 concentrations, shift in C and H isotope ratios of CH4 to more enriched in the remaining CH4 (in both, δ13C-CH4 >−50 ‰ and δ2H >−260 ‰) and depletion in 13C of the associated CO2 (<−20 ‰). Since surface CH4 and CO2 concentrations over the covering layer were very low, and the major CH4 concentrations were found between 60m and 90 cm depth, it is very probable USW has been compacted with low permeability materials (e.g., clay) avoiding large emissions to the atmosphere and creating horizontal barriers within the waste that enable lateral gas migration. Horizontally, it can be seen that these gases migrated outside the disposal site following the topography and that CH4 disappeared leading to anomalous concentrations of CO2 whose values are greater than those produced by normal soil respiration. The isotopic value (δ13C) of this CO2 was also different from that of normal soil respiration (~−25 ‰) and reflected effects that generated isotopic depletion by diffusion (~−25 to −32 ‰). The analysis of C isotopes as the main tracer, together H isotopes, has allowed the effective detection of the origin and those secondary processes.

Tiber delta CO2‐CH4 degassing: A possible hybrid, tectonically active Sediment‐Hosted Geothermal System near Rome

AbstractFiumicino town in the Tiber River delta, near Rome International Airport (Italy), is historically affected by large amounts of carbon dioxide (CO2) in the ground and gas eruptions triggered by shallow drilling. While it is known that CO2 originates from carbonate thermometamorphism and/or mantle degassing, the origin of methane (CH4) associated with CO2 is uncertain and the outgassing spatial distribution is unknown. Combining isotope gas geochemistry, soil gas, and structural‐stratigraphic analyses, we provide evidence for a hybrid fluid source system, classifiable as Sediment‐Hosted Geothermal System (SHGS), where biotic CH4 from sedimentary rocks is carried by deep geothermic CO2 through active segments of a half‐graben. Molecular and isotopic composition of CH4 and concentration of heavier alkanes (ethane and propane), obtained from gas vents and soil gas throughout the delta area, reveal that thermogenic CH4 (up to 3.7 vol% in soil gas; δ13CCH4: −37 to −40‰ VPDB‐Vienna Peedee Belemnite, and δ2HCH4: −162 to −203‰ VSMOW ‐ Vienna Standard Mean Ocean Water in gas vents) prevails over possible microbial and abiotic components. The hydrocarbons likely result from known Meso‐Cenozoic petroleum systems of the Latium Tyrrhenian coast. Overmaturation of source rocks or molecular fractionation induced by gas migration are likely responsible for increased C1/C2+ ratios. CO2 and CH4 soil gas anomalies are scattered along NW‐SE and W‐E alignments, which, based on borehole, geomorphologic, and structural‐stratigraphic analyses, coincide with active faults of a half‐graben that seems to have controlled the recent evolution of the Tiber delta. This SHGS can be a source of considerable greenhouse gas emissions to the atmosphere and hazards for humans and buildings.

Methane oxidation pathways and associated methanotrophic communities in the water column of a tropical lake

We examined methane (CH4) oxidation pathways and associated methanotrophic communities in the water column of Lake Kivu using abundance and isotopic compositions of CH4 and phospholipid fatty acids (PLFA), distributions of glycerol dialkyl glycerol tetraethers, and catalyzed reporter deposition fluorescence in situ hybridization (CARD–FISH) analysis. The carbon isotopic data of CH4 indicate that aerobic CH4 oxidation is the predominant pathway of microbial CH4 consumption with an isotopic fractionation factor (α) of 1.022–1.038. A small amount of CH4 is oxidized anaerobically, with an α of 1.002–1.006. Aerobic CH4 oxidation is mediated by type II methane–oxidizing bacteria (type II MOB) based on the 13C depletion (δ13C of −40.5‰ to −43.7‰) of diagnostic C18:1ω7 fatty acids in the surface waters. CARD–FISH images and PLFA components C16:1ω7 and C16:1ω5 indicate the presence of type I MOB in the methane and nutrient–rich deep–water region. 13C depletion of C16:1ω7 and C16:1ω5 (δ13C, ∼ −40‰ to −50.6‰) in the lake water below 52 m suggests the involvement of type I MOB in methane oxidation in the anoxic deep–water regions of the lake. A novel cluster of anaerobic methane–oxidizing archaea (ANME) rather than the known ANME–1 and ANME–2 appear to be involved in anaerobic oxidation of methane (AOM). Sulfate reducing bacteria are associated with AOM in the lake based on the 13C depletion (δ13C, −38.2‰ to −45.0‰) of anteiso–methyl–C15:0 fatty acid. Methane constitutes an important carbon and energy source (up to 38%) for the heterotrophic and autotrophic communities in the lake.

Dissolved hydrogen and methane in the oceanic basaltic biosphere

The oceanic basaltic crust is the largest aquifer on Earth and has the potential to harbor substantial subsurface microbial ecosystems, which hitherto remains largely uncharacterized and is analogous to extraterrestrial subsurface habitats. Within the sediment-buried 3.5 Myr old basaltic crust of the eastern Juan de Fuca Ridge flank, the circulating basement fluids have moderate temperature (∼65 °C) and low to undetectable dissolved oxygen and nitrate concentrations. Sulfate, present in high concentrations, is therefore expected to serve as the major electron acceptor in this subsurface environment. This study focused on the availability and potential sources of two important electron donors, methane (CH4) and hydrogen (H2), for the subseafloor biosphere. High integrity basement fluids were collected via fluid delivery lines associated with Integrated Ocean Drilling Program (IODP) Circulation Obviation Retrofit Kits (CORKs) that extend from basement depths to outlet ports at the seafloor. Two new CORKs installed during IODP 327 in 2010, 1362A and 1362B, were sampled in 2011 and 2013. The two CORKs are superior than earlier style CORKs in that they are equipped with coated casing and polytetrafluoroethylene fluid delivery lines, reducing the interaction between casing materials with the environment. Additional samples were collected from an earlier style CORK at Borehole 1301A.The basement fluids are enriched in H2 (0.05–1.8 μmol/kg), suggesting that the ocean basaltic aquifer can support H2-driven metabolism. The basement fluids also contain significant amount of CH4 (5–32 μmol/kg), revealing CH4 as an available substrate for subseafloor basaltic habitats. The δ13C values of CH4 from the three boreholes ranged from −22.5 to −58‰, while the δ2H values ranged from −316 to 57‰. The isotopic compositions of CH4 and the molecular compositions of hydrocarbons suggest that CH4 in the basement fluids is of both biogenic and abiotic origins, varying among sites and sampling times. The δ2H values of CH4 in CORK 1301A fluid samples are much more positive than found in all other marine environments investigated to date and are best explained by the partial microbial oxidation of biogenic CH4. In conclusion, our study shows that CH4 and H2 are persistently available to fuel the deep biosphere and that CH4 is both produced and potentially consumed by microorganisms in the oceanic basement.

Fluid geochemistry and geothermometry in the unexploited geothermal field of the Vicano–Cimino Volcanic District (Central Italy)

The Vicano–Cimino Volcanic District (VCVD) is related to the post-orogenic magmatic activity of the peri-Tyrrhenian sector of Central Italy. The chemical and isotopic compositions of 333 water discharges and 25 gas emissions indicate the occurrence of two main sources: 1) cold Ca-HCO3 to Ca(Na, K)-HCO3 type waters from relatively shallow aquifers hosted in volcanic and sedimentary formations; and 2) thermal Ca-SO4(HCO3) type waters located in a deep CO2-pressurized reservoir, hosted in carbonate–evaporite rocks and separated from the shallow aquifers by thick sequences of low-permeability formations. Carbon dioxide is mainly produced by thermal metamorphic decarbonation within the deepest and hottest parts of the carbonate–evaporite reservoir (δ13C–CO2 from −3.1 to +2.2‰ vs. VPDB), likely affected by a mantle-rooted CO2. Release of CO2-rich gases from the deep aquifer into the overlying shallow aquifers produces high-CO2 springs and bubbling pools. The spatial distribution of thermal waters and CO2-rich cold discharges is strongly controlled by fractures and faults located in correspondence with buried structural highs. Stable isotopes (δD and δ18O) suggest that meteoric water feeds both the shallow and deep reservoirs. The relatively low R/Ra values (0.27–1.19) indicate that He is mainly deriving from a crustal source, with minor component from the mantle affected by crustal contamination related to the subduction of the Adriatic plate. Consistently, relatively high N2/Ar and N2/3He ratios and positive δ15N–N2 values (from 0.91 to 5.7‰ vs. air) characterize the VCVD gas discharges, suggesting the occurrence of a significant “excess” nitrogen. Isotopic compositions of CH4 (δ13C–CH4 and δD–CH4 values from −28.9 to −22.1‰ vs. VPDB and from −176 to −138‰ vs. VSMOW, respectively), and composition of light alkanes are indicative of prevalent thermogenic CH4, although the occurrence of abiogenic CH4 production cannot be excluded. The δ34S–H2S values (from +9.3 to +11.4‰ vs. VCDT) are consistent with the hypothesis of H2S production from thermogenic reduction of Triassic anhydrites. Gas geothermometry in the H2O–H2–Ar–H2S system suggests that the VCVD gases equilibrated in a liquid phase at redox conditions controlled by interactions of fluids with the local mineral assemblage at temperatures lower (<200°C) than that and measured in deep (>2000m) geothermal wells. This confirms that secondary processes, i.e. steam condensation, gas dissolution in shallow aquifers, re-equilibration at lower temperature, and microbial activity, significantly affect the chemistry of the uprising fluids. Thermal water chemistry supports the occurrence in this area of an anomalous heat flow that, coupled with the recent demographic growth, makes this site suitable for direct and indirect exploitation of the geothermal resource, in agreement with the preliminary surveys carried out in the 1970's–1990's for geothermal exploration purposes.

Methane in serpentinized ultramafic rocks in mainland Portugal

We report a new case of methane (CH4) of apparent abiotic origin in continental serpentinized ultramafic rocks. Multiple analytical techniques, on-site and in the laboratory, revealed methane and ethane degassing from hyperalkaline (pH > 11) Ca2+–OH− mineral waters in boreholes drilled in the Alter-do-Chão igneous intrusion, at Cabeço de Vide, in mainland Portugal. The C and H isotopic composition of CH4 (δ13C ∼ −20‰; δ2H: −283‰) suggests a dominant abiotic origin, although minor thermogenic contributions cannot be excluded. Similarly, low methane-to-ethane ratios suggest a predominantly non-microbial source, consistent with previous microbiological data showing the lack of methanogenic archaea in these waters. Heavier hydrocarbons, CO2 and H2 are below detection limits. This case study confirms that CH4 from serpentinized ultramafic rocks can be transported by hyperalkaline fluids linked to deep circulation of meteoric waters. Maximum depth of Cabeço de Vide serpentinized rocks is less than 1 km, and present temperatures are likely lower than 50 °C. Serpentinization and related gas formation may have occurred at any time during thermal evolution of the igneous intrusion, so gas formation temperature cannot be easily determined. This case is an opportunity to test thermometry provided by CH4 isotopologue analyses. The existence of methane in continental serpentinized igneous rocks is more widespread than previously thought and petroleum systems with similar serpentinized ultramafics in reservoir rocks may have traces of the observed 13C-enriched CH4.

Potential of microbial methane formation in a high-temperature hydrocarbon seep

Abstract Hydrocarbon seepage is a surface expression where fluids mixed with sediments and hydrocarbons are expelled through fracture systems that potentially tap into gas–petroleum reservoirs. Hydrocarbons released from most seeps appear to be thermogenic on the basis of their relative abundance and isotopic composition. The potential for subsurface microbial processes modifying these geochemical fingerprints remains poorly constrained. In this study, microcosm incubations were conducted on mud slurries supplied with/without various methanogenic precursors at temperatures ranging from ambient conditions to 90 °C, in order to assess microbial CH4 formation in the subsurface beneath hydrocarbon seeps. The analyses indicated that CH4 production was positive at ⩽80 °C, regardless of whether or not or which precursors were added. However, the pattern of CH4 production rates varied with the precursor and temperature. In general, the optimum CH4 production from H2/CO2 and formate occurred over a wide range of temperatures (⩾40 °C), whereas that from acetate, methanol and methylamine was restricted to relatively lower temperatures (40–50 °C). The CH4 recoveries, together with the C isotopic compositions of CH4, further indicated that the quantities of CH4 produced could not completely account for the quantities of precursor consumed, suggesting that a complex metabolic network was involved in the transformation of the added precursor and organic C inherited from inoculated sediments. Microbial CH4 was estimated to constitute 7–61% of the CH4 observed using experimentally-derived apparent isotope fractionations as the end member compositions. This illustrates the possibility that microbial CH4 produced at shallower depths could quantitatively and isotopically alter deeply-sourced thermogenic CH4 in hydrocarbon seep environments.

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.

The isotopic composition of methane in the stratosphere: high-altitude balloon sample measurements

Abstract. The isotopic composition of stratospheric methane has been determined on a large suite of air samples from stratospheric balloon flights covering subtropical to polar latitudes and a time period of 16 yr. 154 samples were analyzed for δ13C and 119 samples for δD, increasing the previously published dataset for balloon borne samples by an order of magnitude, and more than doubling the total available stratospheric data (including aircraft samples) published to date. The samples also cover a large range in mixing ratio from tropospheric values near 1800 ppb down to only 250 ppb, and the strong isotope fractionation processes accordingly increase the isotopic composition up to δ13C = −14‰ and δD = +190‰, the largest enrichments observed for atmospheric CH4 so far. When analyzing and comparing kinetic isotope effects (KIEs) derived from single balloon profiles, it is necessary to take into account the residence time in the stratosphere in combination with the observed mixing ratio and isotope trends in the troposphere, and the range of isotope values covered by the individual profile. The isotopic composition of CH4 in the stratosphere is affected by both chemical and dynamical processes. This severely hampers interpretation of the data in terms of the relative fractions of the three important sink mechanisms (reaction with OH, O(1D) and Cl). It is shown that a formal sink partitioning using the measured data severely underestimates the fraction removed by OH, which is likely due to the insensitivity of the measurements to the kinetic fractionation in the lower stratosphere. Full quantitative interpretation of the CH4 isotope data in terms of the three sink reactions requires a global model.

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.

The influence of CO on the carbon isotopic composition of CH4 in closed pyrolysis experiment with coal

A low-mature coal (R(subscript o)=0.4%, from the Manjia'er depression, Tarim Basin, China) was subjected to closed system pyrolysis, in sealed gold tubes, under isothermal temperature conditions. The carbon isotopic compositions of the pyrolyst fractions (hydrocarbon, CO2, CO, etc.) at two temperature points (350℃ and 550℃) were measured. The results showed that δ 13C(subscript CH4) value is generally heavier at 350℃ than that at 550℃, because the high abundance of CO generated at low temperature would greatly influence δ 13C(subscript CH4) value, and the retention time of CO in gas chromatograph is close to that of CH4. But CO is formed through chemical reaction of the oxygen-containing functional group -C=0, e. g. lactones, ketones, ether, etc. at low temperature, while CO2 comes mainly from decarboxylization. The carbon isotopic composition of coal gas from Lanzhou Coal Gas Works was definitely different from that of thermally pyrolysed products from coal. The 6 1311 value of coal gas was abnormally heavier than δ 13(subscript CO) At the same time, the reversed sequence (δ 13C1＞δ 13C2) of δ 13C1 and δ 13C2 happened. The bond energy of free ions generally decides the sequence of generation of hydrocarbon fractions according to the chemical structure, whereas the stability of pyrolysate fractions and their carbon isotope fractionation are affected by the C-C bond energy.

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The persodic, 1.16 Ga old Ilímaussaq intrusion consists of alkali granites, syenites, and agpaitic nepheline syenites. These rocks are cut by late-magmatic veins and lenses consisting of albite, aegirine, ussingite (Na2AlSi3O8(OH)), fluorite, and occasionally quartz. Oxygen-isotope compositions of quartz indicates both orthomagmatic (δ18Oqtz = 8.5‰) and country rock-influenced (δ18Oqtz ~ 10‰) origin. While albite and aegirine do not contain fluid inclusions suitable for investigations, ussingite contains secondary hydrocarbon fluid inclusions, fluorite contains brine inclusions of primary and secondary origin with up to 26.3 wt.% NaClequiv., and quartz contains predominantly secondary brine inclusions with up to 29.7 wt.% NaClequiv. or CH4–H2O–NaCl mixtures. These fluids are interpreted to reflect fluids in equilibrium with late-stage melts at Ilímaussaq at ≤ 450 °C.The carbon- and hydrogen-isotope composition of CH4 in ussingite (δ13C = − 6 to − 3‰, δD = ~− 121‰) is indicative of a magmatic abiogenic origin. However, the isotopic composition of CH4 in fluid inclusions in quartz veins resembles the signature of thermogenic CH4 (δ13C = − 43 to − 23‰, δD = − 176 to − 121‰), but the higher hydrocarbons are mostly 13C-depleted in relation to CH4 (up to 7.3‰), which is typical of abiogenically-derived hydrocarbons.Ion-chromatography of fluid inclusion leachates from the late-stage veins reveals Cl/Br ratios of ~ 100. As such values seem to be typical of peralkaline magmatic rocks, at least in the Gardar Province of South Greenland, it is suggested that this ratio is typical of Gardar magmatic fluids and may be characteristic of the Cl/Br ratio of the lithospheric mantle from which these alkaline melts are derived.