title: In-situ molecular-level elucidation of organofluorine binding sites in a whole peat soil.
abstract: The chemical nature of xenobiotic binding sites in soils is of vital importance to environmental biogeochemistry. Interactions between xenobiotics and the naturally occurring organic constituents of soils are strongly correlated to environmental persistence, bioaccessibility, and ecotoxicity. Nevertheless, because of the complex structural and chemical heterogeneity of soils, studies of these interactions are most commonly performed indirectly, using correlative methods, fractionation, or chemical modification. Here we identify the organic components of an unmodified peat soil where some organofluorine xenobiotic compounds interact using direct molecular-level methods. Using (19)F→(1)H cross-polarization magic angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectroscopy, the (19)F nuclei of organofluorine compounds are used to induce observable transverse magnetization in the (1)H nuclei of organic components of the soil with which they interact after sorption. The observed (19)F→(1)H CP-MAS spectra and dynamics are compared to those produced using model soil organic compounds, lignin and albumin. It is found that lignin-like components can account for the interactions observed in this soil for heptafluoronaphthol (HFNap) while protein structures can account for the interactions observed for perfluorooctanoic acid (PFOA). This study employs novel comprehensive multi-phase (CMP) NMR technology that permits the application of solution-, gel-, and solid-state NMR experiments on intact soil samples in their swollen state.
authors.affiliation: Department of Chemistry, University of Toronto, 1265 Military Trail, Toronto, Ontario, Canada, M1C 1A4.
authors.forename: James G
authors.initials: JG
authors.lastname: Longstaffe
authors.forename: Denis
authors.initials: D
authors.lastname: Courtier-Murias
authors.forename: Ronald
authors.initials: R
authors.lastname: Soong
authors.forename: Myrna J
authors.initials: MJ
authors.lastname: Simpson
authors.forename: Werner E
authors.initials: WE
authors.lastname: Maas
authors.forename: Michael
authors.initials: M
authors.lastname: Fey
authors.forename: Howard
authors.initials: H
authors.lastname: Hutchins
authors.forename: Sridevi
authors.initials: S
authors.lastname: Krishnamurthy
authors.forename: Jochem
authors.initials: J
authors.lastname: Struppe
authors.forename: Mehran
authors.initials: M
authors.lastname: Alaee
authors.forename: Rajeev
authors.initials: R
authors.lastname: Kumar
authors.forename: Martine
authors.initials: M
authors.lastname: Monette
authors.forename: Henry J
authors.initials: HJ
authors.lastname: Stronks
authors.forename: André J
authors.initials: AJ
authors.lastname: Simpson
mesh_terms: D000418:Albumins / Q000737:chemistry / Q000378:metabolism; D001665:Binding Sites; D002210:Caprylates / Q000737:chemistry / Q000378:metabolism; D017611:Fluorine Compounds / Q000032:analysis / Q000737:chemistry* / Q000378:metabolism; D005462:Fluorine Radioisotopes; D005466:Fluorocarbons / Q000737:chemistry / Q000378:metabolism; D006812:Humic Substances / Q000032:analysis; D008031:Lignin / Q000737:chemistry / Q000378:metabolism; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D012987:Soil / Q000737:chemistry*
chemical_list: D000418:Albumins; D002210:Caprylates; D017611:Fluorine Compounds; D005462:Fluorine Radioisotopes; D005466:Fluorocarbons; D006812:Humic Substances; D012987:Soil; D008031:Lignin; C023036:perfluorooctanoic acid