Detection of multiply deuterated methane in the atmosphere

Mroz, E. J.; Alei, Mohammed; Cappis, J.H.; Guthals, P.R.; Mason, Allen S.; Rokop, D.J.

doi:10.1029/gl016i007p00677

Cited by 20 publications

(11 citation statements)

References 4 publications

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“…Noting that the precision requirement of 10 À9 is based on the measurement of highly concentration of CH 4 level, a higher resolution will be required in order to distinguish lowconcentration of methane in atmosphere. For instance, since the approximated methane concentration in air is of the order of 10 À6 , more sensitive detection methods with at least a 10 À15 resolution of the measured atmospheric [ 13 CH 3 D] concentration will be required (Mroz et al, 1989;Kaye et al, 1990).…”

Section: Geologic Implications Of the 13 Ch 3 D Concentration Measurementioning

confidence: 99%

Formation and abundance of doubly-substituted methane isotopologues (13CH3D) in natural gas systems

Ma¹,

Wu²,

Tang³

2008

Geochimica et Cosmochimica Acta

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Section: Geologic Implications Of the 13 Ch 3 D Concentration Measurementioning

confidence: 99%

Formation and abundance of doubly-substituted methane isotopologues (13CH3D) in natural gas systems

Ma¹,

Wu²,

Tang³

2008

Geochimica et Cosmochimica Acta

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“…One previous study reports data for 12 CD 4 and/or 13 CD 3 H concentrations in air (suggesting Ն500-fold enrichments relative to those expected for a random distribution of stable C and H isotopes among all methane isotopologues; Mroz et al, 1989), and two previous studies have attempted to predict atmospheric abundances of multiply substituted methane (Kaye and Jackman, 1990) and N 2 O (Kaiser et al, 2003). However, to the best of our knowledge, this is the first report of precise (sub-per mil level) measurements of abundances of multiply substituted species in nature.…”

Section: Introductionmentioning

confidence: 96%

18O13C16O in Earth’s atmosphere

Eiler

Schauble

2004

Geochimica et Cosmochimica Acta

321

280

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“…At least 10 volumes of CO 2 -rich gas was flowed through the slip-stream section during each cycle of tracer addition, prior to repeating the depressurisation step, to reduce the likelihood of the presence of tracers being released from the slip-stream and contaminating the near-site Boreham et al (2008). c Mroz et al (1989). d IPCS Inchem MSDS (http://www.inchem.org).…”

Section: Tracer Injection Methods -The Slip-stream Loopmentioning

confidence: 99%

Application of tracers to measure, monitor and verify breakthrough of sequestered CO2 at the CO2CRC Otway Project, Victoria, Australia

et al. 2015

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At the Cooperative Research Centre for Greenhouse Gas Technology's (CO2CRC) field site in the Otway Basin of Victoria, Australia, investigations into the storage of CO 2 -rich gas in a depleted hydrocarbon gas field have been conducted in the Waarre C reservoir. The injected gas from the nearby Buttress field contained 75 mol% CO 2 , 21 mol% CH 4 with the remaining balance being a mixture of wet hydrocarbons, condensate and nitrogen. Chemical tracers (sulphur hexafluoride, SF 6 ; krypton, Kr; perdeuterated methane, CD 4 ) were added on the basis of literature surveys and small volume trials at the Frio II Brine experiment in Texas. The aim of the project was to measure, monitor and verify the presence of injected CO 2 in a depleted gas field and that the arrival of tracers was a major component of demonstrating breakthrough of CO 2 at the monitoring well, Naylor-1. The paper focuses on methods developed for the injection, recovery and analysis of samples collected at the Naylor-1 well. Results of tracer analysis compare well with other data collected (including pH and density measurements) to demonstrate breakthrough. A slip-stream injection system was designed to deliver the tracers mixed with the CO 2 -rich gas into the subsurface at the CRC-1 well. The tracers were added to the gas stream 17 days after the start of injection (CO 2 injection commenced 18th March, 2008) into the depleted natural gas field at Naylor. A U-tube system was used to retrieve the samples from the Naylor-1 monitoring well. Collected gas and formation water samples were analysed in detail for gas composition, tracers, isotopes ( 13 C CO 2 mainly) and inorganic geochemistry for the broader project. The tracer results confirm that CO 2 breakthrough at the monitoring well occurred within the predicted times. However the interval between samples taken from the U-tubes was too coarse to resolve detailed differences in arrival times between the CO 2 and tracers. Of the three tracers used, SF 6 provided the clearest evidence of breakthrough at U-tube 2. Kr, because of its abundance in air, and its potential to be present in the subsurface, was more prone to contamination and had higher background levels prior to breakthrough. CD 4 was expected to provide some more unique data based on the presence of abundant CH 4 in the reservoir interval. With hindsight, larger volumes should have been injected to facilitate comparisons with the other tracers and add value to the data set. The test of CD 4 however acted as a suitable proof of concept that CD 4 could be used in such a high background of CH 4 . Further work is ongoing to generate data for partition coefficients between supercritical CO 2 , CH 4 and water under the injection conditions.

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Detection of multiply deuterated methane in the atmosphere

Cited by 20 publications

References 4 publications

Formation and abundance of doubly-substituted methane isotopologues (13CH3D) in natural gas systems

Formation and abundance of doubly-substituted methane isotopologues (13CH3D) in natural gas systems

18O13C16O in Earth’s atmosphere

Application of tracers to measure, monitor and verify breakthrough of sequestered CO2 at the CO2CRC Otway Project, Victoria, Australia

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