Isotopic signatures of CH4 and higher hydrocarbon gases from Precambrian Shield sites: A model for abiogenic polymerization of hydrocarbons

Lollar, Barbara Sherwood; Lacrampe-Couloume, Georges; Voglesonger, K.; Onstott, Tullis C.; Pratt, Lisa M.; Slater, G. F.

doi:10.1016/j.gca.2008.07.004

Cited by 176 publications

(104 citation statements)

References 71 publications

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“…In subsurface mines in the Canadian Shield, exploration boreholes intersecting extensive fracture networks release waters rich in reduced gases (H 2 , CH 4 , C 2+ ) and noble gases, which exsolve upon depressurization. Sampling and characterization of fracture fluids from Kidd Creek have been described in previous studies (Sherwood et al, 1988;Sherwood Lollar et al, 2002;Sherwood Lollar et al, 2007;Sherwood Lollar et al, 2008;Holland et al, 2013). We analyzed methane sampled from boreholes at the 7850 ′ -and 9500 ′ -levels (Table 2.1).…”

Section: Field Site Descriptions and Sampling Methodsmentioning

confidence: 99%

“…Carbon ( 13 C/ 12 C) and hydrogen (D/H) isotope ratios of methane are widely applied for distinguishing microbial from thermogenic methane in the environment (Welhan and Lupton, 1987;Whiticar, 1990;Sherwood Lollar et al, 2002;Flores et al, 2008;Sherwood Lollar et al, 2008;Pohlman et al, 2009;Baldassare et al, 2014) as well as for apportioning pathways of microbial methane production (Whiticar et al, 1986;Burke et al, 1988;McCalley et al, 2014). This bulk isotope approach, however, is largely based on empirical observations, and different origins of methane often yield overlapping characteristic isotope signals (Schoell, 1988;Whiticar, 1990; Whiticar, 1999;Pohlman et al, 2009;Etiope and Sherwood Lollar, 2013).…”

Section: Main Textmentioning

confidence: 99%

“…Apparent temperatures derived from D/H equilibria in the systems H 2 -H 2 O and H 2 -CH 4 were first used as geothermometers in studies of geothermal or volcanic gases and waters (Árnason and Sigurgeirsson, 1968;Gunter and Musgrave, 1971;Arnason, 1977;Kiyosu, 1983;Lyon and Hulston, 1984), and later examined with respect to data from seafloor hydrothermal fluids (Welhan and Craig, 1983;Horibe and Craig, 1995;Proskurowski et al, 2006;Bradley and Summons, 2010;Kawagucci et al, 2010;Kawagucci et al, 2011;Kawagucci et al, 2013), shieldhosted groundwaters (Sherwood Lollar et al, 1993;Sherwood Lollar et al, 2007;Sherwood Lollar et al, 2008), and continental springs, seeps, and well fluids influenced by serpentinization (Neal and Stanger, 1983;Coveney et al, 1987;Abrajano et al, 1988;Fritz et al, 1992;Etiope et al, 2011a;Suda et al, 2014). Temperatures returned from H 2 -H 2 O and H 2 -CH 4 equilibria often agree with each other and with realistic geologic and hydrologic scenarios for geothermal fluids exiting at high temperatures, but these relationships do not necessarily hold for lower-temperature fluids.…”

Section: Hydrogen Exchange and The Origin Of Hydrogen In Chmentioning

confidence: 99%

“…[4] Dissolved [H 2 ] for Kidd Creek fluids was estimated using gas/water flow rate data from Holland et al (2013) and gas-phase H 2 concentrations from Sherwood Lollar et al (2008), and assuming that all dissolved H 2 had completely partitioned into the gas phase prior to sampling. The C 1 /C 2 data are from Sherwood Lollar et al (2002).…”

Section: Model Of Isotopologue Systematics During Microbial Methanogementioning

confidence: 99%

“…The Kidd Creek methane occupies a distinct region in the ∆ 13 CH 3 D vs. ε methane/water diagram ( Fig. 2.2), due to strong D/H disequilibria between methane and water (Sherwood Lollar et al, 2008) and low ∆ 13 CH 3 D temperature signals of 56-90°C that are consistent with other temperature estimates for these groundwaters (Sherwood Lollar et al, 2008). Although the specific mechanisms by which the proposed abiotic hydrocarbons at Kidd Creek are generated remain under investigation (Sherwood Lollar et al, 2002;Sherwood Lollar et al, 2014) enables the differentiation of methane that has been formed at extremely low rates in the subsurface (Pohlman et al, 2009;Bates et al, 2011;Holler et al, 2011) from methane formed in cattle and surface environments in which methanogenesis proceeds at comparatively high rates (Johnson and Johnson, 1995;Varadharajan and Hemond, 2012).…”

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The geochemistry of methane isotopologues

Wang¹

2017

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This thesis documents the origin, distribution, and fate of methane and several of its isotopic forms on Earth. Using observational, experimental, and theoretical approaches, I illustrate how the relative abundances of 12 CH 4 , 13 CH 4 , 12 CH 3 D, and 13 CH 3 D record the formation, transport, and breakdown of methane in selected settings.Chapter 2 reports precise determinations of 13 CH 3 D, a "clumped" isotopologue of methane, in samples collected from various settings representing many of the major sources and reservoirs of methane on Earth. The results show that the information encoded by the abundance of 13 CH 3 D enables differentiation of methane generated by microbial, thermogenic, and abiogenic processes. A strong correlation between clumped-and hydrogen-isotope signatures in microbial methane is identified and quantitatively linked to the availability of H 2 and the reversibility of microbially-mediated methanogenesis in the environment. Determination of 13 CH 3 D in combination with hydrogen-isotope ratios of methane and water provides a sensitive indicator of the extent of C-H bond equilibration, enables fingerprinting of methane-generating mechanisms, and in some cases, supplies direct constraints for locating the waters from which migrated gases were sourced. Chapter 3 applies this concept to constrain the origin of methane in hydrothermal fluids from sediment-poor vent fields hosted in mafic and ultramafic rocks on slow-and ultraslow-spreading mid-ocean ridges. The data support a hypogene model whereby methane forms abiotically within plutonic rocks of the oceanic crust at temperatures above ca. 300• C during respeciation of magmatic volatiles, and is subsequently extracted during active, convective hydrothermal circulation. Chapter 4 presents the results of culture experiments in which methane is oxidized in the presence of O 2 by the bacterium Methylococcus capsulatus strain Bath. The results show that the clumped isotopologue abundances of partially-oxidized methane can be predicted from knowledge of 13 C/ 12 C and D/H isotope fractionation factors alone.: Shuhei Ono, Ph.D. Acknowledgments I fear that this section will not do justice to the people I have not the space to thank individually. Alas, here goes. To those whose names are not specifically listed here, thank you too. I wish first to thank Shuhei Ono. The work this thesis represents could not have happened without his bold vision and the license to explore and question that working in his lab afforded. His unbridled optimism, breadth of scientific curiosity, personal integrity, and accessibility to his personnel are traits I one day hope to emulate. I thank him for his nonjudgmental yet appropriately measured support of many of my ideas-even those that led nowhere-, for believing in me even when I found it difficult to do so myself, and for teaching me to change pump oil, build vacuum lines, and drink Icelandic vodka.I also wish to thank my thesis committee members Jeff Seewald, Roger Summons, and John Pohlman, for their in...

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Section: Field Site Descriptions and Sampling Methodsmentioning

confidence: 99%

Section: Main Textmentioning

confidence: 99%

Section: Hydrogen Exchange and The Origin Of Hydrogen In Chmentioning

confidence: 99%

Section: Model Of Isotopologue Systematics During Microbial Methanogementioning

confidence: 99%

mentioning

confidence: 99%

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The geochemistry of methane isotopologues

Wang¹

2017

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Natural H₂ in Kansas: Deep or shallow origin?

Guélard

Beaumont

Rouchon

et al. 2017

Geochem Geophys Geosyst

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Key Points: A new well provide the opportunity of a reappraisal of a persistent regional H 2 production in intracontiental settings, in Kansas. Two different origins are suggested for H 2 production in intra-cratonic context: a crustal origin, a surficial origin. Hypotheses of two H 2 are supported by geochemical properties of associated gases, by water associated and completion story of the well.2 AbstractA geochemical study of gas coming from three wells in northeastern Kansas supplements previous studies from the 1980s and points to a persistent regional phenomenon of H 2 production. In 2008, a new well showed, just after drilling, a dry gas phase with more than 80 mole % of H 2 , followed by a water production associated with gas. This gas is mainly composed of N 2 , He, H 2 and occasionally CH 4 , with changing proportions through time. A drastic decrease in H 2 at the well was observed since the aquifer is produced, along with occasional recharges in H 2 evidenced notably in the early phases of gas sampling. We demonstrate that this evolution of gas composition is closely associated to the well completion story. Accordingly, two distinct origins of H 2 are proposed: (1) water reduction associated to iron oxidation in the Precambrian basement (deep crustal H 2 ); (2) reactions occurring in the tubing, primarily attributed to a high Fe 2+ content and organic carbon (DOC=4.1 mg.L -1 ) dissolved in the water. The low δD values averaging -760 ‰ are attributed to low temperature processes, in agreement with both the hypothesis. Furthermore, the suggested origins are supported by the observed gas associations: (a) deep crustal H 2 with radiogenic gases ( 4 He and 40 Ar) and metamorphic N 2 ( 15 N averaging +2.5‰); (b) surficial H 2 with methane produced in the sedimentary aquifer and the tubing by methanogenic organisms.

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References

2018

Hydrogeochemistry Fundamentals and Advances

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Isotopic signatures of CH4 and higher hydrocarbon gases from Precambrian Shield sites: A model for abiogenic polymerization of hydrocarbons

Cited by 176 publications

References 71 publications

The geochemistry of methane isotopologues

The geochemistry of methane isotopologues

Natural H₂ in Kansas: Deep or shallow origin?

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Isotopic signatures of CH4 and higher hydrocarbon gases from Precambrian Shield sites: A model for abiogenic polymerization of hydrocarbons

Cited by 176 publications

References 71 publications

The geochemistry of methane isotopologues

The geochemistry of methane isotopologues

Natural H2 in Kansas: Deep or shallow origin?

References

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Product

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Natural H₂ in Kansas: Deep or shallow origin?