title: Geochemistry of Dissolved Organic Matter in a Spatially Highly Resolved Groundwater Petroleum Hydrocarbon Plume Cross-Section.
abstract: At numerous groundwater sites worldwide, natural dissolved organic matter (DOM) is quantitatively complemented with petroleum hydrocarbons. To date, research has been focused almost exclusively on the contaminants, but detailed insights of the interaction of contaminant biodegradation, dominant redox processes, and interactions with natural DOM are missing. This study linked on-site high resolution spatial sampling of groundwater with high resolution molecular characterization of DOM and its relation to groundwater geochemistry across a petroleum hydrocarbon plume cross-section. Electrospray- and atmospheric pressure photoionization (ESI, APPI) ultrahigh resolution mass spectrometry (FT-ICR-MS) revealed a strong interaction between DOM and reactive sulfur species linked to microbial sulfate reduction, i.e., the key redox process involved in contaminant biodegradation. Excitation emission matrix (EEM) fluorescence spectroscopy in combination with Parallel Factor Analysis (PARAFAC) modeling attributed DOM samples to specific contamination traits. Nuclear magnetic resonance (NMR) spectroscopy evaluated the aromatic compounds and their degradation products in samples influenced by the petroleum contamination and its biodegradation. Our orthogonal high resolution analytical approach enabled a comprehensive molecular level understanding of the DOM with respect to in situ petroleum hydrocarbon biodegradation and microbial sulfate reduction. The role of natural DOM as potential cosubstrate and detoxification reactant may improve future bioremediation strategies.
authors.affiliation: Helmholtz Zentrum München-German Research Center for Environmental Health , Research Unit Analytical BioGeoChemistry, D-85764 Neuherberg, Germany.
authors.forename: Sabine E-M
authors.initials: SE
authors.lastname: Dvorski
authors.affiliation: University of Maryland Center for Environmental Science , Chesapeake Biological Laboratory, Solomons, Maryland 20688, United States.
authors.forename: Michael
authors.initials: M
authors.lastname: Gonsior
authors.affiliation: Helmholtz Zentrum München-German Research Center for Environmental Health , Research Unit Analytical BioGeoChemistry, D-85764 Neuherberg, Germany.
authors.forename: Norbert
authors.initials: N
authors.lastname: Hertkorn
authors.affiliation: Helmholtz Zentrum München-German Research Center for Environmental Health , Research Unit Analytical BioGeoChemistry, D-85764 Neuherberg, Germany.
authors.forename: Jenny
authors.initials: J
authors.lastname: Uhl
authors.affiliation: Helmholtz Zentrum München-German Research Center for Environmental Health , Institute of Groundwater Ecology, D-85764 Neuherberg, Germany.
authors.forename: Hubert
authors.initials: H
authors.lastname: Müller
authors.affiliation: Helmholtz Zentrum München-German Research Center for Environmental Health , Institute of Groundwater Ecology, D-85764 Neuherberg, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Griebler
authors.affiliation: Helmholtz Zentrum München-German Research Center for Environmental Health , Research Unit Analytical BioGeoChemistry, D-85764 Neuherberg, Germany.|Technische Universität München , Chair of Analytical Food Chemistry, D-85354 Freising-Weihenstephan, Germany.
authors.forename: Philippe
authors.initials: P
authors.lastname: Schmitt-Kopplin
mesh_terms: D001673:Biodegradation, Environmental; D060587:Groundwater; D006838:Hydrocarbons; D010578:Petroleum / Q000378:metabolism*; D014874:Water Pollutants, Chemical
chemical_list: D006838:Hydrocarbons; D010578:Petroleum; D014874:Water Pollutants, Chemical