title: A novel high-temperature combustion based system for stable isotope analysis of dissolved organic carbon in aqueous samples. I: development and validation.
abstract: BACKGROUND
  Traditionally, dissolved organic carbon (DOC) stable isotope analysis (SIA) is performed using either offline sample preparation followed by elemental analyzer/isotope ratio mass spectrometry (EA/IRMS) or a wet chemical oxidation (WCO)-based device coupled to an isotope ratio mass spectrometer. The first method is time-consuming and laborious. The second involves the risks of underestimation of DOC concentration and isotopic fractionation due to incomplete oxidation. The development of an analytical method for accurate and sensitive DOC SIA is described in this study.
  
  
  METHODS
  A high-temperature combustion (HTC) system improves upon traditional methods. A novel total organic carbon (TOC) system, specially designed for SIA, was coupled to an isotope ratio mass spectrometer. An integrated purge and trap technique (peak focusing), flexible injection volume (0.05-3 mL), favorable carrier gas flow, modified ash crucible, new design of combustion tube and optimized drying system were used to achieve the necessary performance.
  
  
  RESULTS
  The system can reliably measure concentrations up to 1000 mgC/L. Compounds resistant to oxidation, such as barbituric acid, melamine and humic acid, were analyzed with recovery rates of 100 ± 1% proving complete oxidation. In this initial testing, the δ(13) C values of these compounds were determined with precision and trueness of ≤ 0.2‰ even with 3.5% salinity. Further tests with samples with low DOC concentrations resulted in LOQSIA method values of 0.5 mgC/L and 0.2 mgC/L for LOQSIA instr , considering an accuracy of ± 0.5‰ as acceptable.
  
  
  CONCLUSIONS
  The novel HTC system coupled to an isotope ratio mass spectrometer resulted in significantly improved sensitivity. The system is suitable for salt-containing liquids and compounds that are resistant to oxidation, and it offers a large concentration range. A second paper (which follows this one in this issue) will present a more comprehensive assessment of the analytical performance with a broad set of solutions and real samples. This highly efficient TOC stable isotopic analyzer will probably open up new possibilities in biogeochemical carbon cycle research.
authors.affiliation: Instrumental Analytical Chemistry, University of Duisburg-Essen, Universitätsstr. 5, 45141, Essen, Germany; Research and Innovation, Elementar Analysensysteme GmbH, Donaustr. 7, 63452, Hanau, Germany.
authors.forename: E
authors.initials: E
authors.lastname: Federherr
authors.forename: C
authors.initials: C
authors.lastname: Cerli
authors.forename: F M S A
authors.initials: FM
authors.lastname: Kirkels
authors.forename: K
authors.initials: K
authors.lastname: Kalbitz
authors.forename: H J
authors.initials: HJ
authors.lastname: Kupka
authors.forename: R
authors.initials: R
authors.lastname: Dunsbach
authors.forename: L
authors.initials: L
authors.lastname: Lange
authors.forename: T C
authors.initials: TC
authors.lastname: Schmidt
mesh_terms: D002247:Carbon Isotopes / Q000032:analysis*; D004867:Equipment Design; D006358:Hot Temperature; D006812:Humic Substances / Q000032:analysis*; D013058:Mass Spectrometry / Q000379:methods*; D015203:Reproducibility of Results; D045483:Rivers / Q000737:chemistry*; D012623:Seawater / Q000737:chemistry*; D012680:Sensitivity and Specificity
chemical_list: D002247:Carbon Isotopes; D006812:Humic Substances