title: From Spill to Sequestration: The Molecular Journey of Contamination via Comprehensive Multiphase NMR.
abstract: Comprehensive multiphase NMR is a novel NMR technique that permits all components (solutions, gels, and solids) to be studied in unaltered natural samples. In this study a wide range of CMP-NMR interaction and editing-based experiments are combined to follow contaminants (pentafluorophenol (PFP) and perfluorooctanoic acid (PFOA)) from the solution state (after a spill) through the gel-state and finally into the true solid-state (sequestered) in an intact water-swollen soil. Kinetics experiments monitoring each phase illustrate PFOA rapidly transfers from solution to the solid phase while for PFP the process is slower with longer residence times in the solution and gel phase. Interaction-based experiments reveal that PFOA enters the soil via its hydrophobic tails and selectively binds to soil microbial protein. PFP sorption shows less specificity exhibiting interactions with a range of gel and solid soil components with a preference toward aromatics (mainly lignin). The results indicate that in addition to more traditional measurements such as Koc, other factors including the influence of the contaminant on the soil-water interface, specific biological interactions, soil composition (content of lignin, protein, etc.) and physical accessibility/swellability of soil organic components will likely be central to better explaining and predicting the true behavior of contaminants in soil.
authors.affiliation: Department of Chemistry, University of Toronto , Toronto, Ontario Canada , M1C 1A4.
authors.forename: Hussain
authors.initials: H
authors.lastname: Masoom
authors.affiliation: Department of Chemistry, University of Toronto , Toronto, Ontario Canada , M1C 1A4.
authors.forename: Denis
authors.initials: D
authors.lastname: Courtier-Murias
authors.affiliation: Department of Chemistry, University of Toronto , Toronto, Ontario Canada , M1C 1A4.
authors.forename: Ronald
authors.initials: R
authors.lastname: Soong
authors.affiliation: Bruker BioSpin Corp., Billerica, Massachusetts 01821-3991, United States.
authors.forename: Werner E
authors.initials: WE
authors.lastname: Maas
authors.affiliation: Bruker BioSpin Corp., Billerica, Massachusetts 01821-3991, United States.
authors.forename: Michael
authors.initials: M
authors.lastname: Fey
authors.affiliation: Bruker BioSpin Canada, Milton, Ontario Canada , L9T 1Y6.
authors.forename: Rajeev
authors.initials: R
authors.lastname: Kumar
authors.affiliation: Bruker BioSpin Canada, Milton, Ontario Canada , L9T 1Y6.
authors.forename: Martine
authors.initials: M
authors.lastname: Monette
authors.affiliation: Bruker BioSpin Canada, Milton, Ontario Canada , L9T 1Y6.
authors.forename: Henry J
authors.initials: HJ
authors.lastname: Stronks
authors.affiliation: Department of Chemistry, University of Toronto , Toronto, Ontario Canada , M1C 1A4.
authors.forename: Myrna J
authors.initials: MJ
authors.lastname: Simpson
authors.affiliation: Department of Chemistry, University of Toronto , Toronto, Ontario Canada , M1C 1A4.
authors.forename: André J
authors.initials: AJ
authors.lastname: Simpson
mesh_terms: D002210:Caprylates / Q000032:analysis / Q000737:chemistry; D005461:Fluorine / Q000032:analysis; D005464:Fluorobenzenes / Q000032:analysis / Q000737:chemistry; D005466:Fluorocarbons / Q000032:analysis / Q000737:chemistry; D005782:Gels; D057927:Hydrophobic and Hydrophilic Interactions; D007700:Kinetics; D008031:Lignin / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D010636:Phenols / Q000032:analysis / Q000737:chemistry; D012987:Soil / Q000737:chemistry; D012988:Soil Microbiology; D012989:Soil Pollutants / Q000032:analysis* / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D002210:Caprylates; D005464:Fluorobenzenes; D005466:Fluorocarbons; D005782:Gels; D010636:Phenols; D012987:Soil; D012989:Soil Pollutants; D014867:Water; D005461:Fluorine; D008031:Lignin; C023036:perfluorooctanoic acid; C085539:2,3,4,5,6-pentafluorophenol