Rationale: The stable carbon isotope ratio ((13)C/(12)C or δ(13)C value) of methane (CH4) produced in methanogenic environments contains information about primary source material, CH4 production pathways, degree of oxidation, and transport. However, the availability of δ(13)C-CH4 data is severely limited because isotope analysis methods are low throughput, owing primarily to the need for manual processing steps. High-throughput, fully automated measurement is necessary to facilitate the use of the δ(13)C signature in understanding CH4 biogeochemistry.
Methods: We modified a conventional continuous-flow (CF) gas chromatography/combustion/isotope ratio mass spectrometry (IRMS) instrument system by incorporating (i) automated sample injection, (ii) a newly developed temperature-control unit for preconcentration and cryofocus traps, and (iii) an automatic system for liquid-nitrogen refilling. The system, which could run unattended for 1 day, was used to obtain δ(13)C-CH4 data for CH4 samples collected from an irrigated rice paddy with an automated closed-chamber system.
Results: Using the fully automated CF-IRMS system, we measured δ(13)C-CH4 data for 77 samples during a 21.5-h continuous run (17 min per sample) with high precision (1σ = 0.11‰, reproducibility) and moderate consumption of liquid nitrogen (11 L). Application of the system to CH4 samples obtained from the rice paddy revealed distinct seasonal and diurnal variations in δ(13)C values with the highest temporal resolution ever reported.
Conclusions: A fully automated, high-throughput system for the measurement of δ(13)C-CH4 values was developed and used to analyze air samples obtained from a rice paddy. Our results demonstrate the high potential of this system for obtaining δ(13)C data useful for process-level understanding of CH4 biogeochemistry with respect to spatiotemporal variation of CH4 sources and how that variation is affected by environmental and management factors.
Copyright © 2014 John Wiley & Sons, Ltd.