A major DCO instrumentation objective is to measure ratios of methane molecules with doubly isotope-substituted rare isotopes (13CH3D vs. 12CH2D2) that might provide information on methane formation temperature and may help resolve questions related to abiotic versus microbial origins - one of DCO's decadal goals. In addition to providing support for the Panorama High-Resolution Mass Spectrometer, the DCO encouraged a second science team, who proposed a radically different concept for clumped isotope measurements based on quantum adsorption spectroscopy. With highly leveraged start-up funds from the DCO, a high-risk, high-reward alternative instrument - the Tunable Infrared Laser Direct Absorption Spectrometer (TILDAS) was developed by Shuhei Ono, MIT, at a low cost and with potential for mobilization and miniaturization for field applications.

Shuhei Ono and labmates with TILDAS

Principal Investigator Ono purchased key equipment in late 2012 and, as reported at the DCO International Science Meeting in March 2013, made rapid progress in building a prototype system for quantum cascade laser absorption spectroscopy. Preliminary test results are excellent and the initial DCO/Sloan investment will be leveraged by support from the U.S. National Science Foundation, which has recommended funding for the PI’s proposal for further research. 

The research lead by the team confirmed earlier measurements by mass-spectrometer that most geologic methane follows expected thermodynamic abundance.  They also demonstrated that methane samples from sites supporting active microbial methanogenesis (such as wetlands and cow rumens) and laboratory methanogen cultures carry unique non-statistical 13CH3D abundance. Currently the science team is applying the technique to test the origin of methane in various environments, including sites of serpentinization and marine hydrates.

Principal Investigator


Gruen DS, Wang DT, Könneke M, Topçuoğlud BD, Stewart LC, Goldhammer T, Holden JF, Hinrichs K, Ono S (2018) Experimental investigation on the controls of clumped isotopologue and hydrogen isotope ratios in microbial methane. Geochimica et Cosmochimica Acta 237:339-356    

Wang DT, Reeves EP, McDermott JM, Seewald JS, Ono S (2018) Clumped isotopologue constraints on the origin of methane at seafloor hot springs. Geochimica et Cosmochimica Acta 223:141-158

Ijiri A, Inagaki F, Kubo Y, Adhikari RR, Hattori S, Hoshino T, Imachi H, Kawagucci S, Morono Y, Ohtomo Y, Ono S, Sakai S, Takai K, Toki T, Wang DT, Yoshinaga MT, Arnold GL, Ashi J, Case DH, Feseker T, Hinrichs K, Ikegawa Y, Ikehara M, Kallmeyer J, Kumagai H, Lever MA, Morita S, Nakamura K, Nakamura Y, Nishizawa M, Orphan VJ, Røy H, Schmidt F, Tani A, Tanikawa W, Terada T, Tomaru H, Tsuji T, Tsunogai U, Yamaguchi YT, Yoshida N (2018) Deep-biosphere methane production stimulated by geofluids in the Nankai accretionary complex. Science Advances EAAO4631

Whitehill AR, Joelsson LMT, Schmidt JA, Wang DT, Johnson MS, Ono S (2017) Clumped isotope effects during OH and Cl oxidation of methane. Geochimica et Cosmochimica Acta 196:307-325

Wang DT, Welander PV, Ono S (2016)  Fractionation of the methane isotopologues 13CH412CH3D, and 13CH3D during aerobic oxidation of methane by Methylococcus capsulatus (Bath). Geochimica et Cosmochimica Acta192:186–202

Joelsson LMT, Schmidt JA, Nilsson EJK, Blunier T, Griffith DWT, Ono S, Johnson MS (2016) Kinetic isotope effects of 12CH3D  + OH and 13CH3D  + OH from 278 to 313 K. Atmoshere Chemistry and Physics 16: 4439-4449

Wang DT, Gruen DS, Sherwood Lollar B, Hinrichs K-U, Stewart LC, Holden JF, Hristov AN, Pohlman JW, Morrill PL, Könneke M, Delwiche KB, Reeves EP, Sutcliffe CN, DJ Ritter, Seewald JS, McIntosh JC, Hemond HF, Kubo MD, Cardace D, Hoehler TM, Ono S (2015) Nonequilibrium clumped isotope signals in microbial methane. Science 348:428-431

Inagaki, F, Hinrichs KU, Kubo Y, Bowles MW, Heuer VB, Hong WL, Hoshino T, Ijiri A, Imachi H, Ito M, Kaneko M, Lever MA, Lin YS, Methé BA, Morita S, Morono Y, Tanikawa W, Bihan M, Bowden SA, Elvert M, Glombitza C, Gross D, Harrington GJ, Hori T, Li K, Limmer D, Liu CH, Murayama M, Ohkouchi N, Ono S, Park YS, Phillips SC, Prieto-Mollar X, Purkey M, Riedinger N, Sanada Y, Sauvage J, Snyder G, Susilawati R, Takano Y, Tasumi E, Terada T, Tomaru H, Trembath-Reichert E, Wang DT Yamada Y (2015) Exploring deep microbial life in coal-bearing sediment down to ~2.5 km below the ocean floor. Science 349:420-424

Ono S, Wang DT, Gruen DS, Sherwood Lollar B, Zahniser MS, McManus BJ, Nelson DD (2014) Measurement of a Doubly Substitued Methane Isotopologue, 13CH3D, by Tunable Infrared Laser Direct Absorption Spectroscopy. Analytical Chemistry 86:6487-6494

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