[1] Over the last 30 years, geochemical research has demonstrated that abiotic methane (CH 4 ), formed by chemical reactions which do not directly involve organic matter, occurs on Earth in several specific geologic environments. It can be produced by either high-temperature magmatic processes in volcanic and geothermal areas, or via low-temperature (<100 C) gas-water-rock reactions in continental settings, even at shallow depths. The isotopic composition of C and H is a first step in distinguishing abiotic from biotic (including either microbial or thermogenic) CH 4 . Herein we demonstrate that integrated geochemical diagnostic techniques, based on molecular composition of associated gases, noble gas isotopes, mixing models, and a detailed knowledge of the geologic and hydrogeologic context are necessary to confirm the occurrence of abiotic CH 4 in natural gases, which are frequently mixtures of multiple sources. Although it has been traditionally assumed that abiotic CH 4 is mainly related to mantle-derived or magmatic processes, a new generation of data is showing that low-temperature synthesis related to gas-water-rock reactions is more common than previously thought. This paper reviews the major sources of abiotic CH 4 and the primary approaches for differentiating abiotic from biotic CH 4, including novel potential tools such as clumped isotope geochemistry. A diagnostic approach for differentiation is proposed.

What controls clumped isotopes? Stable isotopes of a molecule can clump together in several combinations, depending on their mass. Even for simple molecules such as O 2 , which can contain 16 O, 17 O, and 18 O in various combinations, clumped isotopes can potentially reveal the temperatures at which molecules form. Away from equilibrium, however, the pattern of clumped isotopes may reflect a complex array of processes. Using high-resolution gas-phase mass spectrometry, Yeung et al. found that biological factors influence the clumped isotope signature of oxygen produced during photosynthesis (see the Perspective by Passey). Similarly, Wang et al. showed that away from equilibrium, kinetic effects causing isotope clumping can lead to overestimation of the temperature at which microbially produced methane forms. Science , this issue p. 431; p. 428; see also p. 394

Injecting CO(2) into deep geological strata is proposed as a safe and economically favourable means of storing CO(2) captured from industrial point sources. It is difficult, however, to assess the long-term consequences of CO(2) flooding in the subsurface from decadal observations of existing disposal sites. Both the site design and long-term safety modelling critically depend on how and where CO(2) will be stored in the site over its lifetime. Within a geological storage site, the injected CO(2) can dissolve in solution or precipitate as carbonate minerals. Here we identify and quantify the principal mechanism of CO(2) fluid phase removal in nine natural gas fields in North America, China and Europe, using noble gas and carbon isotope tracers. The natural gas fields investigated in our study are dominated by a CO(2) phase and provide a natural analogue for assessing the geological storage of anthropogenic CO(2) over millennial timescales. We find that in seven gas fields with siliciclastic or carbonate-dominated reservoir lithologies, dissolution in formation water at a pH of 5-5.8 is the sole major sink for CO(2). In two fields with siliciclastic reservoir lithologies, some CO(2) loss through precipitation as carbonate minerals cannot be ruled out, but can account for a maximum of 18 per cent of the loss of emplaced CO(2). In view of our findings that geological mineral fixation is a minor CO(2) trapping mechanism in natural gas fields, we suggest that long-term anthropogenic CO(2) storage models in similar geological systems should focus on the potential mobility of CO(2) dissolved in water.

Geochemical, microbiological, and molecular analyses of alkaline saline groundwater at 2.8 kilometers depth in Archaean metabasalt revealed a microbial biome dominated by a single phylotype affiliated with thermophilic sulfate reducers belonging to Firmicutes . These sulfate reducers were sustained by geologically produced sulfate and hydrogen at concentrations sufficient to maintain activities for millions of years with no apparent reliance on photosynthetically derived substrates.