On the vertical distribution of carbon monoxide and methane in the stratosphere

The vertical distribution of the methane concentration in the stratosphere is related to its dissociation by two simultaneous daytime reactions with excited oxygen atoms O(¹D) and with OH radicals and depends on the stratospheric eddy diffusion coefficient.Dissociation of CH₄ in the lower stratosphere leads to the production of CO molecules while in the upper stratosphere thepphotodissociation of CO₂ molecules is an additional process to the CO production.In the upper stratosphere (40±10 km) there is an equilibrium between the formation and destruction processes of carbon monoxide which leads to a minimum of its mixing ratio. There is an increase of the CO mixing ratio in the troposphere and mesosphere compared with that of the stratosphere.The vertical distribution of the CO mixing ratio is closely related to the eddy diffusion coefficient in the whole stratosphere but the absolute values of the hydroxyl radical concentration also determine the values of the CO mixing ratio.     

The concentration of molecular H2 and CH4 in the stratosphere

Stratospheric profiles of CH₄ and H₂ over eastern Texas have been derived up to 31 km altitude from air samples collected aboard a balloon and analyzed by gas chromatography. For H₂, contamination during flight and measurement presented a problem which has been resolved only recently. The earlier profiles require corrections which are rather large for the highest altitudes.The three profiles indicate an increase of the H₂ concentration in the lower stratosphere from about 0.5 p.p.m. per volume at the tropopause to about 0.8 p.p.m. at around 27 km altitude. Above that altitude the H₂ concentration decreases again. An air sample collected between 44 and 62 km by a rocket-borne cryogenic sampler had an H₂ concentration of 0.4 p.p.m.The five CH₄ profiles showed a decrease in CH₄ concentration with altitude generally with a steeper gradient directly above the tropopause and a weaker gradient at higher altitudes reaching 0.9 p.p.m. at 30 km altitude. The CH₄ concentration in the rocket sample was 0.25 p.p.m., in good agreement with the gradient obtained from the balloon samples.The National Center for Atmospheric Research is sponsored by the National Science Foundation.     

Sources and sinks of atmospheric methane

In 1972 average mixing ratio of methane in the troposphere was 1.41 ppm and 1.3 ppmv for the northern and southern hemisphere, respectively, which corresponds to a total amount of 4×10¹⁵ g of CH₄ present in the atmosphere. Most is of recent biologic origin.¹⁴C analyses show that no more than 20 percent is released by fossil sources. The various ecosystems producing CH₄ are discussed and the total annual production is estimated to lie between 5.5×10¹⁴ g/yr and 11×10¹⁴ g/yr. The corresponding turnover times for atmospheric CH₄ range from 4 to 7 yrs. The destruction of CH₄ takes place mainly in the troposphere, most probably through the reaction of CH₄ + OH CH₃ + H₂O. About 10 percent of the CH₄ is destroyed in the stratosphere. The CH₄ cycle contributes on the order of 1 percent to the atmospheric carbon cycle.     

Assessing Methane in Shallow Groundwater in Unconventional Oil and Gas Play Areas,Eastern Kentucky

The expanding use of horizontal drilling and hydraulic fracturing technology to produce oil and gas from tight rock formations has increased public concern about potential impacts on the environment, especially on shallow drinking water aquifers. In eastern Kentucky, horizontal drilling and hydraulic fracturing have been used to develop the Berea Sandstone and the Rogersville Shale. To assess baseline groundwater chemistry and evaluate methane detected in groundwater overlying the Berea and Rogersville plays, we sampled 51 water wells and analyzed the samples for concentrations of major cations and anions, metals, dissolved methane, and other light hydrocarbon gases. In addition, the stable carbon and hydrogen isotopic composition of methane (δ¹³C‐CH₄ and δ²H‐CH₄) was analyzed for samples with methane concentration exceeding 1 mg/L. Our study indicates that methane is a relatively common constituent in shallow groundwater in eastern Kentucky, where methane was detected in 78% of the sampled wells (40 of 51 wells) with 51% of wells (26 of 51 wells) exhibiting methane concentrations above 1 mg/L. The δ¹³C‐CH₄ and δ²H‐CH₄ ranged from ?84.0‰ to ?58.3‰ and from ?246.5‰ to ?146.0‰, respectively. Isotopic analysis indicated that dissolved methane was primarily microbial in origin formed through CO₂ reduction pathway. Results from this study provide a first assessment of methane in the shallow aquifers in the Berea and Rogersville play areas and can be used as a reference to evaluate potential impacts of future horizontal drilling and hydraulic fracturing activities on groundwater quality in the region.     

Greenhouse gas emissions (CO2, CH4, and N2O) from several perialpine and alpine hydropower reservoirs by diffusion and loss in turbines

We investigated greenhouse gas emissions (CO₂, CH₄, and N₂O) from reservoirs located across an altitude gradient in Switzerland. These are the first results of greenhouse gas emissions from reservoirs at high elevations in the Alps. Depth profiles were taken in 11 reservoirs located at different altitudes between the years 2003 and 2006. Diffusive trace gas emissions were calculated using surface gas concentrations, wind speeds and transfer velocities. Additionally, methane entering with the inflowing water and methane loss at the turbine was assessed for a subset of the reservoirs. All reservoirs were emitters of carbon dioxide and methane with an average of 970?±?340?mg?m^?2?day^?1 (results only from four lowland and one subalpine reservoir) and 0.20?±?0.15?mg?m^?2?day^?1, respectively. One reservoir (Lake Wohlen) emitted methane at a much higher rate (1.8?±?0.9?mg?m^?2?day^?1) than the other investigated reservoirs. There was no significant difference in methane emissions across the altitude gradient, but average dissolved methane concentrations decreased with increasing elevation. Only lowland reservoirs were sources for N₂O (72?±?22???g?m^?2?day^?1), while the subalpine and alpine reservoirs were in equilibrium with atmospheric concentrations. These results indicate reservoirs from subalpine/alpine regions to be only minor contributors of greenhouse gases to the atmosphere compared to other reservoirs.     

Geochemical monitoring of the 2002–2003 eruption at Stromboli volcano (Italy): precursory changes in the carbon and helium isotopic composition of fumarole gases and thermal waters

Significant changes in the helium and carbon isotopic composition of shallow thermal waters vs. gas and a crater fumarolic gas have been recorded at Stromboli prior and during the 2002–2003 eruption. The³He/⁴He ratios corrected for air contamination (Rc/Ra), and δ¹³C of fumarolic gases gradually increased from May to November 2002 before the eruption onset. These variations imply early degassing of a gas-rich magma at depth that likely fed both the intense Strombolian activity and small lava overflows recorded during that period. The lava effusion of late December 2002 was shortly preceded by a marked Rc/Ra decrease both in water and fumarolic gases. Comparison of He/CO₂ and CH₄/CO₂ ratios in dissolved gas and with values rules out the Rc/Ra decrease due to an increasing input of radiogenic⁴He. The Rc/Ra decrease is attributed to the He isotope fractionation during rapid magma ascent and degassing. A new uprising of ³He-rich magma probably occurred in January to February 2003, when Rc/Ra ratios displayed the highest values in dissolved gases ever measured before (4.56 Rc/Ra). The increase in He/CO₂ and CH₄/CO₂ ratios and decrease in δ¹³C of dissolved CO₂ was recorded after the 5 April 2003 explosive paroxysm, likely caused by enhanced gas-water interaction inducing CO₂ dissolution. No anomalous Rc/Ra values were recorded in the same period, when usual Strombolian activity gradually resumed.Editorial responsibility: H Shinohara     

Carbon monoxide on the primitive earth

The reaction of CO + OH^? in aqueous solution to give formate was studied as a carbon monoxide sink on the primitive earth and in the present ocean. The reaction is first order in OH^? and first order in the molar CO concentration. The second order rate constant is given by log k(M^?1hr^?1) = 15.83?4886/T between 25°C and 60°C. Using the solubility of CO in sea water, and assuming a pH of 8 for a primitive ocean of the present size, the halflife of CO in the atmosphere is calculated to be 12 × 10⁶ yr at 0°C and 5.5 × 10⁴ yr at 25°C.Three other CO sinks would have been important in the primitive atmosphere: CO + H₂ → H₂CO driven by various energy sources, CO + OH → CO₂ + H, and the Fischer-Tropsch reaction of CO + H₂ → hydrocarbons, etc. It is concluded that the lifetime of a CO atmosphere would have been very short on the geological time scale although the relative importance of these four CO sinks is difficult to estimate.The CO + OH^? reaction to give formate is a very minor CO sink on the earth at the present time.     

Winter methane dynamics beneath ice and in snow in a temperate poor fen

The influence of winter on methane (CH₄) stored in pore water and emitted through snow was investigated in a temperate poor fen in New Hampshire over two winters. Methane accumulated beneath ice layers (1 cm) deposited by freezing rain, resulting in snow-pore air mixing ratios as high as 140 ppmv during the first winter and 600 ppmv during the second. An early winter snow crust of 300 kg m^?3 caused no discontinuity in a linear mixing ratio profile and therefore was not observed to retard snowpack emissions. Methane concentration-depth profiles in pore water steepened and concentrations increased by as much as 400 μM at the 10 and 20 cm depths as the ice cover formed. This suggests that the peat-ice cover plays an important part in CH₄ build-up in pore water by limiting the transport of gases between the peat and the atmosphere. Pore water concentrations gradually declined through late winter. The seasonality of dissolved CH₄ in pore water over two winters and one summer showed an average annual amplitude of 1.3 gCH₄m^?2 (25–75cm depth range), with a winter maximum of 4.7gCH₄m^?2. Emissions during the winter with average snowfall accounted for a larger percentage (9.2% in 1993–1994) of total annual emission than the winter with below-average snowfall and warmer air temperature (2% in 1994–1995). Emissions averaged 56 and 26mg m^?2 day^?1 during the first and second winter (December, January and February), respectively.     

Quantification of seep-related methane gas emissions at Tommeliten,North Sea

Tommeliten is a prominent methane seep area in the Central North Sea. Previous surveys revealed shallow gas-bearing sediments and methane gas ebullition into the water column. In this study, the in situ methane flux at Tommeliten is re-assessed and the potential methane transport to the atmosphere is discussed, with regards to the hydrographic setting and gas bubble modeling. We have compiled previous data, acquired new video and acoustic evidence of gas bubble release, and have measured the methane concentration, and its C-isotopic composition in the water column. Parametric subbottom sonar data reveal the three-dimensional extent of shallow gas and morphologic features relevant for gas migration. Five methane ebullition areas are identified and the main seepage area appears to be 21 times larger than previously estimated. Our video, hydroacoustic, subbottom, and chemical data suggest that ～1.5×10⁶ mol CH₄/yr (～26 tons CH₄/yr) of methane gas is being released from the seepage area of Tommeliten. Methane concentration profiles in the vicinity of the gas seeps show values of up to 268 nM (～100 times background) close to the seafloor. A decrease in δ¹³C-CH₄ values at 40 m water depth indicates an unknown additional biogenic methane source within the well oxygenated thermocline between 30 and 40 m water depth. Numerical modeling of the methane bubbles due to their migration and dissolution was performed to estimate the bubble-derived vertical methane transport, the fate of this methane in the water column, and finally the flux to the atmosphere. Modeling indicates that less than ～4% of the gas initially released at the seafloor is transported via bubbles into the mixed layer and, ultimately, to the atmosphere. However, because of the strong seasonality of mixing in the North Sea, this flux is expected to increase as mixing increases, and almost all of the methane released at the seafloor could be transferred into the atmosphere in the stormy fall and winter time.     

Methanogenesis in the sediment of the acidic Lake Caviahue in Argentina

The biogeochemistry of methane in the sediments of Lake Caviahue was examined by geochemical analysis, microbial activity assays and isotopic analysis. The pH in the water column was 2.6 and increased up to a pH of 6 in the deeper sediment pore waters. The carbon isotope composition of CH₄ was between − 65 and − 70‰ which is indicative for the biological origin of the methane. The enrichment factor ε increased from − 46‰ in the upper sediment column to more than − 80 in the deeper sediment section suggesting a transition from acetoclastic methanogenesis to CO₂ reduction with depth. In the most acidic surface layer of the sediment (pH < 4) methanogenesis is inhibited as suggested by a linear CH₄ concentration profile, activity assays and MPN analysis. The CH₄ activity assays and the CH₄ profile indicate that methanogenesis in the sediment of Lake Caviahue was active below 40 cm depth. At that depth the pH was above 4 and sulfate reduction was sulfate limited. Methane was diffusing with a flux of 0.9 mmol m^− 2 d^− 1 to the sediment surface where it was probably oxidized. Methanogenesis contributed little to the sediments carbon budget and had no significant impact on lake water quality. The high biomass content of the sediment, which was probably caused by the last eruption of Copahue Volcano, supported high rates of sulfate reduction which probably raised the pH and created favorable conditions for methanogens in deeper sediment layers.     

Vertical distribution of chlorofluoromethanes in the upper troposphere and lower stratosphere

Vertical profiles of CCl₄, CFCl₃, and CF₂Cl₂ mixing ratios in the upper troposphere and lower stratosphere have been measured on four flights with chartered aircraft, type HS 125. The flights were carried out in November and December 1976 over Europe at latitudes between 50 and 60°N. At least eight air samples were taken during each ascent and descent of the aircraft at altitudes between 7 and 12.5 km. The samples were analysed in the laboratory using gaschromatographic procedures. The results indicate a decrease of the CCl₄, CFCl₃, and CF₂Cl₂ mixing ratios above the tropopause. The observed average gradients in the stratosphere are 14 pptv/km for CCl₄, 12 pptv/km for CFCl₃ and 27.8 pptv/km for CF₂Cl₂. With exception of CFCl₃ these gradients are higher than those predicted by model calculations. Apparently, further sink mechanisms for CCl₄ and CF₂Cl₂ exist in the lower stratosphere not yet included in the models.     

Investigating Correlations and Variations of Air Pollutant Concentrations under Conditions of Rapid Industrialization – Kocaeli (1987–2009)

In this study, it was aimed to characterize temporal variations of air pollutants for determining contribution to pollution episodes and to obtain correlations between these pollutants. With this aim we used data analysis for measured sulfur dioxide (SO₂), particulate matter (PM, black fume and PM10), nitrogen oxides (NO_x), ozone (O₃), carbon monoxide (CO), methane (CH₄), and non‐methane hydrocarbons (NMHC) recorded in Kocaeli, one of the most industrilizated cities of Turkey. Pollutant concentrations were the results of continuous and semi‐automatic measurements. Semi‐automatic measurements of SO₂ and PM (black fume) were enclosing period from 1987 to 2008 whereas continuous monitoring of all pollutants included years of 2007–2009. In the first stage of the study daily, monthly, annual, and seasonal variations of pollution were researched. Annual average concentrations were compared with limits set by Air Quality Protection Regulation (AQPR), Air Quality Evaluation and Management Regulation (AQEMR), World Health Organization (WHO), European Union (EU), and National Ambient Air Quality Standards (USEPA). In the following stage relationships between pollutants such as NO₂–O₃, NO_x–CO, NO_x–NMHC, and NO_x–SO₂ were investigated and correlation coefficients were determined as 0.87, 0.56, 0.51, and 0.69, respectively. R² values of regression models developed from these correlations were 0.78, 0.56, 0.34, and 0.72, respectively. Vehicle density of the traffic was evaluated with NO_x–O₃ emissions and decrease was seen in NO_x emissions due to decreasing vehicle density at weekends whereas O₃ concentrations increased. These correlations enable prediction of the parameters that cannot be measured which is important for providing improvement in early warning systems.     

Inhibition by nitrite ion in the process of methane anaerobic oxidation by microorganisms and fractionation dynamics of stable carbon and hydrogen isotopes

In the process of methane oxidation by nitrite ion, the latter, when in high concentration, inhibits the oxidation process. The effect of inhibition is incorporated in the proposed model, describing the dynamics of anaerobic oxidation of methane and its heavy fractions δ¹³CH₄ and δC²H¹H₃ by nitrite ion. Two substrates—methane and nitrite—are considered in a modified Monod function, describing the oxidation rate. The model is calibrated against experimental data given in [8]. The dynamic behavior of the system under a deficiency of methane or nitrite ion is described. The dynamics of δ¹³CH₄ and δC²H¹H₃ are shown to be governed by the oxidation dynamics of total methane CH₄. By contrast to the conventional opinion that Rayleigh equation corresponds to 1st-order kinetics in terms of substrate concentration, this study shows that Rayleigh equation can be derived from dynamic equations for methane with heavy isotopes (¹³C and ²H), whatever the kinetic type of total methane oxidation.     

Fluid mixing as the mechanism of formation of the Dajing Cu-Sn-Ag-Pb-Zn ore deposit,Inner Mongolia

Dajing Cu-Sn-Ag-Pb-Zn ore deposit, in the Inner Mongolia Autonomous Region of China, is a fissure-filling hydrothermal ore deposit. The δD values of quartz-hosted inclusion water are centered at −100%.– −130%.. The δ³⁴S values of sulfide ore minerals and δ¹³ C values of carbonate gangue minerals vary from −0.3%. to 2.6%. and from −2.9%. to −7.0%., respectively. Integrated isotopic data point to two major contributions to the mineralizing fluid that include a dominant meteoric-derived groundwater, and sulfur and carbon species from hypogene magma. Linear trends are exhibited on the gaseous H₂O versus CO₂ plot, and plots of CO, N₂, CH₄, and C₂H₆. It is shown by quantitative simulation that magma degassing cannot explain the linear trends. Hence, these linear trends are interpreted in terms of mixing of CO₂-rich magmatic fluid with meteoric-derived groundwater. The groundwater circulated in Paleozoic sedimentary rocks and absorbed CO, N₂, CH₄, C₂H₆ and radiogenic Ar from organic matter. Cooling effects resulting from mixing have caused the precipitation of ore minerals.     

Methane in shallow cold seeps at Mocha Island off central Chile

We studied for the first time the intertidal and subtidal gas seepage system in Mocha Island off Central Chile. Four main seepage sites were investigated (of which one site included about 150 bubbling points) that release from 150 to 240 tonnes CH₄ into the atmosphere per year. The total amount of methane emitted into the atmosphere is estimated in the order of 800 tonnes per year. The gases emanated from the seeps contain 70% methane, and the stable carbon isotopic composition of methane, δ¹³C-CH₄ averaged −44.4±1.4‰ which indicates a major contribution of thermogenic gas. Adjacent to one of the subtidal seeps, rocky substrates support a diverse community of microbial filaments, macroalgae, and benthic organisms. While stable carbon isotopic compositions of marine benthic organisms indicate a dominant photosynthesis-based food web, those of some hard-substrate invertebrates were in the range −48.8‰ to −36.8‰, suggesting assimilation of methane-derived carbon by some selected taxa. This work highlights the potential subsidy of the trophic web by CH₄-C, and that its emission to the atmosphere justifies the need of evaluating the use of methane to support the energy requirements of the local community.     

Excess of bottom-released methane in an Arctic shelf sea polynya in winter

Latent heat polynyas are regions generating strong ice formation, convection and extensive water mass formation. Here we report on the effects of these processes on resuspension of sediments and subsequent methane release from the seafloor and on the resulting excess methane concentration in surface water on a polar shelf during winter. The study is based on measurements of concentration and δ¹³C values of methane, water temperature, salinity, light transmission and sea ice data collected in March 2003 in Storfjorden, southern Svalbard. In winter, strong and persistent northeasterly winds create polynyas in eastern Storfjorden and cause ice formation. The resulting brine-enriched water cascades from the Storfjordbanken into the central depression thereby enhancing the turbulence near the seafloor. A distinct benthic nepheloid layer was observed reflecting the resuspension of sediments by the cascading dense bottom water. High concentrations of ¹³C-depleted methane suggest submarine discharge of methane with the resuspended sediments. As the source of the submarine methane, we propose recent bacterial methanogenesis near the sediment surface because of extremely high accumulation rates of organic carbon in Storfjorden. Convective mixing transports newly released methane from the bottom to the sea surface. This eventually results in an excess concentration in surface water with respect to the atmospheric equilibrium, and a sea-air flux of methane during periods of open water. When a new ice cover is formed, methane becomes trapped in the water column and subsequently oxidized. Thus, the residual methane is strongly enriched in ¹³C in relation to the δ¹³_CCH4${\delta }^{13}{\mathrm{C}}_{{\mathrm{CH}}_4}$ signature of atmospheric methane. Our results show that latent heat polynyas may induce a direct pathway for biogases like methane from sediments to the atmosphere through coupling of biogeochemical and oceanographic processes. Extrapolating these processes to all Arctic ocean polynyas, we estimate a transfer of CH₄ between 0.005 and 0.02 Tg yr⁻¹. This is not a large contribution but the fluxes from the polynyas are 20–200 times larger than the ocean average and the methane evasion process in polynyas is certainly one that can be altered under climate change.     

Oxidation and emission of methane in a monomictic lake (Rotsee, Switzerland)

The build-up of methane in the hypolimnion of the eutrophic Lake Rotsee (Lucerne, Switzerland) was monitored over a full year. Sources and sinks of methane in the water column were characterized by measuring concentrations and carbon isotopic composition. In fall, high methane concentrations (up to 1 mM) were measured in the anoxic water layer. In the oxic layer, methane concentrations were much lower and the isotopic composition shifted towards heavy carbon isotopes. Methane oxidation rates peaked at the interface between oxic and anoxic water layers at around 8–10 m depth. The electron balance between the oxidants oxygen, sulphate, and nitrate, and the reductants methane, sulphide and ammonium, matched very well in the chemocline during the stratified season. The profile of carbon isotopic composition of methane showed strong indications for methane oxidation at the chemocline (including the oxycline). Aerobic methane oxidizing bacteria were detected at the interface using fluorescence in situ hybridization. Sequencing the responsible organisms from DGGE bands revealed that aerobic methanotrophs type I closely related to Methylomonas were present. Sulphate consumption occurred at the sediment surface and, only towards the end of the stagnation period, matched with a zone of methane consumption. In any case, the flux of sulphate below the chemocline was not sufficient to oxidize all the methane and other oxidants like nitrate, iron or manganese are necessary for the observed methane oxidation. Although most of the methane was oxidized either aerobically or anaerobically, Lake Rotsee was still a source of methane to the atmosphere with emission rates between 0.2 mg CH₄ m^?2 day^?1 in February and 7 mg CH₄ m^?2 day^?1 in November.     

No evidence for thermogenic methane release in coal from the Karoo-Ferrar large igneous province

The Early Jurassic Toarcian oceanic anoxic event (T-OAE) and concurrent negative carbon-isotope (δ¹³C) excursion have recently been attributed to either the release of methane (CH₄) clathrates or thermogenic CH₄ gas associated with the Karoo-Ferrar large igneous province (LIP) into coals and organic-rich shales. ¹²C-enriched thermogenic CH₄ production associated with the Karoo-Ferrar would result in residual material being ¹²C-depleted nearer the intrusions. In this study, geochemical analyses (carbon isotopes, volatile matter (VM), vitrinite reflectance (R_o)) are reported for two coal transects associated with dykes intruding the No. 4L coal in the Highveld Coalfield, Karoo Basin, South Africa. VM decreases from over 35% to around 15% in one transect, and the second transect shows a less pronounced decrease (from > 25% to ~ 16%). Accompanying the decrease in VM content is an increase in R_o from background levels of around 0.7% to over 4% adjacent to the dyke; used as a palaeo-geothermometer, R_o values indicate background temperatures of ~ 100 °C increasing to > 300 °C close to the contact. Despite changes in VM and R_o, there are no significant changes in δ¹³C, certainly not of the magnitude that would be expected associated with large-scale thermogenic CH₄ generation. These and other Gondwanan coals have low vitrinite and liptinite contents (components more prone to CH₄ generation), in part explaining the modest decreases in VM adjacent to the dykes. This, combined with the relatively narrow metamorphic aureole surrounding the intrusions and the likelihood that at least some of the volatiles generated by the intrusion were trapped as coalbed CH₄ or condensed as pyrolytic carbon, suggests only limited CH₄ release. In addition, based on original estimates of moisture contents in these coals and the depth at time of intrusion (1,000–2,000 m) the dykes would have lost most of their energy heating and evaporating water, thus having very little remaining energy to generate thermogenic CH₄.     

Hydrothermal vent waters at 13°N on the East Pacific Rise: isotopic composition and gas concentration

Gas concentrations and isotopic compositions of water have been measured in hydrothermal waters from 13°N on the East Pacific Rise. In the most Mg-depleted samples ( 5 × 10⁻³ moles/kg) the gas concentrations are: 3–4.5 × 10⁻⁵ cm³ STP/kg helium, 0.62–1.24 cm³ STP/kg CH₄, 10.80–16.71 × 10⁻³ moles/kg CO₂. The samples contain large quantities (95–126 cm³/kg) of H₂ and some carbon monoxide (0.26–0.36 cm³/kg) which result from reaction with the titanium sampling bottles. δ¹³C in methane and CO₂ (−16.6 to −19.5 and −4.1 to −5.5 respectively) indicate temperatures between 475 and 550°C, whereas δ¹³C_CO is compatible with formation by reduction of CO₂ on Ti at 350°C close to the sampling temperature.³He/⁴He are very homogeneous at (7.5 ± 0.1)R_A(³He/⁴He = 1.0 × 10⁻⁵) and very similar to already published data as well as CH₄/³He ratios between 1.4 and 2.1 × 10⁶.¹⁸O and D in water show enrichments from 0.39 to 0.69‰ and from 0.62 to 1.49‰ respectively. These values correspond to W/R ratios of 0.4–7. The distinct¹⁸O enrichments indicate that the isotopic composition of the oceans is not completely buffered by the hydrothermal circulations. The³He-enthalpy relationship is discussed in terms of both hydrothermal heat flux and³He mantle flux.     

Hydrocarbon‐Rich Groundwater above Shale‐Gas Formations: A Karoo Basin Case Study

Horizontal drilling and hydraulic fracturing have enhanced unconventional hydrocarbon recovery but raised environmental concerns related to water quality. Because most basins targeted for shale‐gas development in the USA have histories of both active and legacy petroleum extraction, confusion about the hydrogeological context of naturally occurring methane in shallow aquifers overlying shales remains. The Karoo Basin, located in South Africa, provides a near‐pristine setting to evaluate these processes, without a history of conventional or unconventional energy extraction. We conducted a comprehensive pre‐industrial evaluation of water quality and gas geochemistry in 22 groundwater samples across the Karoo Basin, including dissolved ions, water isotopes, hydrocarbon molecular and isotopic composition, and noble gases. Methane‐rich samples were associated with high‐salinity, NaCl‐type groundwater and elevated levels of ethane, ⁴He, and other noble gases produced by radioactive decay. This endmember displayed less negative δ¹³C‐CH₄ and evidence of mixing between thermogenic natural gases and hydrogenotrophic methane. Atmospheric noble gases in the methane‐rich samples record a history of fractionation during gas‐phase migration from source rocks to shallow aquifers. Conversely, methane‐poor samples have a paucity of ethane and ⁴He, near saturation levels of atmospheric noble gases, and more negative δ¹³C‐CH₄; methane in these samples is biogenic and produced by a mixture of hydrogenotrophic and acetoclastic sources. These geochemical observations are consistent with other basins targeted for unconventional energy extraction in the USA and contribute to a growing data base of naturally occurring methane in shallow aquifers globally, which provide a framework for evaluating environmental concerns related to unconventional energy development (e.g., stray gas).