title: Advanced solvent based methods for molecular characterization of soil organic matter by high-resolution mass spectrometry.
abstract: Soil organic matter (SOM), a complex, heterogeneous mixture of above and belowground plant litter and animal and microbial residues at various degrees of decomposition, is a key reservoir for carbon (C) and nutrient biogeochemical cycling in soil based ecosystems. A limited understanding of the molecular composition of SOM limits the ability to routinely decipher chemical processes within soil and accurately predict how terrestrial carbon fluxes will respond to changing climatic conditions and land use. To elucidate the molecular-level structure of SOM, we selectively extracted a broad range of intact SOM compounds by a combination of different organic solvents from soils with a wide range of C content. Our use of electrospray ionization (ESI) coupled with Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) and a suite of solvents with varying polarity significantly expands the inventory of the types of organic molecules present in soils. Specifically, we found that hexane is selective for lipid-like compounds with very low O/C ratios (<0.1); water (H2O) was selective for carbohydrates with high O/C ratios; acetonitrile (ACN) preferentially extracts lignin, condensed structures, and tannin polyphenolic compounds with O/C > 0.5; methanol (MeOH) has higher selectivity toward compounds characterized with low O/C < 0.5; and hexane, MeOH, ACN, and H2O solvents increase the number and types of organic molecules extracted from soil for a broader range of chemically diverse soil types. Our study of SOM molecules by ESI FTICR MS revealed new insight into the molecular-level complexity of organics contained in soils. We present the first comparative study of the molecular composition of SOM from different ecosystems using ultra high-resolution mass spectrometry.
authors.affiliation: †Environmental Molecular Sciences Laboratory and Biological Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99354, United States.
authors.forename: Malak M
authors.initials: MM
authors.lastname: Tfaily
authors.affiliation: †Environmental Molecular Sciences Laboratory and Biological Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99354, United States.
authors.forename: Rosalie K
authors.initials: RK
authors.lastname: Chu
authors.affiliation: †Environmental Molecular Sciences Laboratory and Biological Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99354, United States.
authors.forename: Nikola
authors.initials: N
authors.lastname: Tolić
authors.affiliation: †Environmental Molecular Sciences Laboratory and Biological Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99354, United States.
authors.forename: Kristyn M
authors.initials: KM
authors.lastname: Roscioli
authors.affiliation: †Environmental Molecular Sciences Laboratory and Biological Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99354, United States.
authors.forename: Christopher R
authors.initials: CR
authors.lastname: Anderton
authors.affiliation: †Environmental Molecular Sciences Laboratory and Biological Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99354, United States.
authors.forename: Ljiljana
authors.initials: L
authors.lastname: Paša-Tolić
authors.affiliation: †Environmental Molecular Sciences Laboratory and Biological Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99354, United States.
authors.forename: Errol W
authors.initials: EW
authors.lastname: Robinson
authors.affiliation: †Environmental Molecular Sciences Laboratory and Biological Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99354, United States.
authors.forename: Nancy J
authors.initials: NJ
authors.lastname: Hess
mesh_terms: D017753:Ecosystem; D005583:Fourier Analysis; D009930:Organic Chemicals / Q000032:analysis* / Q000737:chemistry; D012987:Soil / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D014867:Water / Q000737:chemistry
chemical_list: D009930:Organic Chemicals; D012987:Soil; D012997:Solvents; D014867:Water