title: Fully automated, high-throughput instrumentation for measuring the δ13C value of methane and application of the instrumentation to rice paddy samples.
abstract: BACKGROUND
  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.
authors.affiliation: Carbon and Nutrient Cycles Division, National Institute for Agro-Environmental Sciences, Tsukuba, 305-8604, Japan.
authors.forename: Takeshi
authors.initials: T
authors.lastname: Tokida
authors.forename: Yasuhiro
authors.initials: Y
authors.lastname: Nakajima
authors.forename: Kentaro
authors.initials: K
authors.lastname: Hayashi
authors.forename: Yasuhiro
authors.initials: Y
authors.lastname: Usui
authors.forename: Nobuko
authors.initials: N
authors.lastname: Katayanagi
authors.forename: Masako
authors.initials: M
authors.lastname: Kajiura
authors.forename: Hirofumi
authors.initials: H
authors.lastname: Nakamura
authors.forename: Toshihiro
authors.initials: T
authors.lastname: Hasegawa