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We present precise measurements of doubly deuterated methane ( 12 CH 2 D 2 ) in natural methane samples using tunable infrared laser direct absorption spectroscopy (TILDAS). Using a 413 m optical path length astigmatic Herriott cell and two quantum cascade lasers (QCLs) scanning the spectral regions of 1090.46 ± 0.1 and 1200.23 ± 0.1 cm -1 , the instrument simultaneously measures the five main isotopologues of methane. The ratios 13 CH 3 D/ 12 CH 4 and 12 CH 2 D 2 / 12 CH 4 are measured at 0.01‰ and 0.5‰ (1σ) instrumental precision, respectively. The instrumental accuracy was assessed by measuring a series of methane gases with a range of δ 13 C and δD values but with the abundances of all isotopologues driven to thermal equilibrium at 250 °C. The estimated accuracy of Δ 12 CH 2 D 2 is 1‰ (1σ) on the basis of the results of the heated methane samples. This new TILDAS instrument provides a simple and rapid technique to explore the sources of methane in the environment.

Precise Measurements of 12CH2D2 by Tunable Infrared Laser Direct Absorption Spectroscopy

Precise Measurements of ¹²CH₂D₂ by Tunable Infrared Laser Direct Absorption Spectroscopy