title: An ultrahigh-resolution mass spectrometry index to estimate natural organic matter lability.
abstract: BACKGROUND
  Determining the chemical constituents of natural organic matter (NOM) by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICRMS) remains the ultimate measure for probing its source material, evolution, and transport; however, lability and the fate of organic matter (OM) in the environment remain controversial. FTICRMS-derived elemental compositions are presented in this study to validate a new interpretative method to determine the extent of NOM lability from various environments.
  
  
  METHODS
  FTICRMS data collected over the last decade from the same 9.4 tesla instrument using negative electrospray ionization at the National High Magnetic Field Laboratory in Tallahassee, Florida, was used to validate the application of a NOM lability index. Solid-phase extraction cartridges were used to isolate the NOM prior to FTICRMS; mass spectral peaks were calibrated internally by commonly identified NOM homologous series, and molecular formulae were determined for NOM composition and lability analysis.
  
  
  RESULTS
  A molecular lability boundary (MLB) was developed from the FTICRMS molecular data, visualized from van Krevelen diagrams, dividing the data into more and less labile constituents. NOM constituents above the MLB at H/C ≥1.5 correspond to more labile material, whereas NOM constituents below the MLB, H/C <1.5, exhibit less labile, more recalcitrant character. Of all marine, freshwater, and glacial environments considered for this study, glacial ecosystems were calculated to contain the most labile OM.
  
  
  CONCLUSIONS
  The MLB extends our interpretation of FTICRMS NOM molecular data to include a metric of lability, and generally ranked the OM environments from most to least labile as glacial > marine > freshwater. Applying the MLB is useful not only for individual NOM FTICRMS studies, but also provides a lability threshold to compare and contrast molecular data with other FTICRMS instruments that survey NOM from around the world.
authors.affiliation: Department of Chemical and Biological Engineering, Montana State University, Bozeman, MT, 59717, USA.|Center for Biofilm Engineering, Montana State University, Bozeman, MT, 59717, USA.
authors.forename: Juliana
authors.identifier: http://orcid.org/0000-0002-3352-2564
authors.initials: J
authors.lastname: D'Andrilli
authors.affiliation: Department of Chemistry & Biochemistry, Florida State University, Tallahassee, FL, 32306, USA.
authors.forename: William T
authors.initials: WT
authors.lastname: Cooper
authors.affiliation: Department of Chemical and Biological Engineering, Montana State University, Bozeman, MT, 59717, USA.|Center for Biofilm Engineering, Montana State University, Bozeman, MT, 59717, USA.
authors.forename: Christine M
authors.initials: CM
authors.lastname: Foreman
authors.affiliation: Department of Chemistry & Biochemistry, Florida State University, Tallahassee, FL, 32306, USA.|Ion Cyclotron Resonance Program, National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL, 32310, USA.
authors.forename: Alan G
authors.initials: AG
authors.lastname: Marshall
mesh_terms: D000864:Antarctic Regions; D045424:Complex Mixtures / Q000032:analysis* / Q000737:chemistry*; D005618:Fresh Water / Q000737:chemistry; D012623:Seawater / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods*
chemical_list: D045424:Complex Mixtures