We have developed a mid‐infrared continuous‐wave quantum cascade laser direct‐absorption spectrometer (QCLS) capable of high frequency (≥1 Hz) measurements of 12CH4 and 13CH4 isotopologues of methane (CH4) with in situ 1‐s RMS image precision of 1.5 ‰ and Allan‐minimum precision of 0.2 ‰. We deployed this QCLS in a well‐studied New Hampshire fen to compare measurements of CH4 isoflux by eddy covariance (EC) to Keeling regressions of data from automated flux chamber sampling. Mean CH4 fluxes of 6.5 ± 0.7 mg CH4 m−2 hr−1 over two days of EC sampling in July, 2009 were indistinguishable from mean autochamber CH4 fluxes (6.6 ± 0.8 mgCH4 m−2 hr−1) over the same period. Mean image composition of emitted CH4 calculated using EC isoflux methods was −71 ± 8 ‰ (95% C.I.) while Keeling regressions of 332 chamber closing events over 8 days yielded a corresponding value of −64.5 ± 0.8 ‰. Ebullitive fluxes, representing ∼10% of total CH4 fluxes at this site, were on average 1.2 ‰ enriched in 13C compared to diffusive fluxes. CH4 isoflux time series have the potential to improve process‐based understanding of methanogenesis, fully characterize source isotopic distributions, and serve as additional constraints for both regional and global CH4 modeling analysis.
Journal of Geophysical Research: Atmospheres
American Geophysical Union (AGU)
Digital Object Identifier (DOI)
Santoni, G.W., °B.H. Lee, °J.P. Goodrich, R.K. Varner, P.M. Crill, J.B. McManus, D.D. Nelson, M.S. Zahniser, and S.C. Wofsy (2012) Methane isofluxes by eddy covariance, Keeling regressions of autochamber sampling, and the resulting isotopic composition of methane from a New Hampshire fen using a novel 13CH4 and 12CH4 continuous wave quantum cascade laser spectrometer, J. Geophys. Res. Biogeosciences,117, D10301, 15 PP., doi:10.1029/2011JD016960.
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