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Mass spectrometric screening and identification of acidic metabolites in fulvic acid fractions of contaminated groundwater

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An Erratum to this article was published on 04 July 2014

Abstract

The anaerobic microbial degradation of aromatic and heterocyclic compounds is a prevalent process in contaminated groundwater systems. The introduction of functional groups into the contaminant molecules often results in aromatic and heterocyclic and succinic acids. These metabolites can be used as indicators for prevailing degradation processes. Therefore, there is a strong interest in developing analytical methods for screening and identification of these metabolites. In this study, neutral loss scans (NLS) by liquid chromatography-electrospray ionization/tandem mass spectrometry with losses of CO2 (NL ∆m/z = 44) and C2H4(CO2)2 (NL ∆m/z = 116) were applied for the first time successfully to screen selectively for acidic and succinic metabolites of aromatic and heterocyclic contaminants in two fulvic acid fractions from a contaminated site and a downstream region of a tar oil-polluted groundwater. Identification of these preselected signals was performed by high-resolution mass spectrometry with a liquid chromatography-electrospray ionization quadrupole time-of-flight mass spectrometry instrument. High-resolution mass and mass fragmentation data were then compared with a list of known metabolites from a literature search or matched with chemical databases supported with in silico fragmentation. Based on authentic analytical standards, several compounds from NLS were identified (e.g., 4-hydroxy-3-methylbenzoic acid, benzylsuccinic acid, naphthyl-2-methylsuccinic acid, 2-carboxyindane, and 2-carboxybenzothiophene) and tentatively identified (e.g., benzofuranmethylsuccinic acid and dihydrocarboxybenzothiophene) as aromatic, phenolic, heterocyclic, and succinic acids. The acidic metabolites were found exclusively in the contaminated region of the aquifer which indicates active biodegradation processes and no relevant occurrence of acidic metabolites in the downstream region.

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Acknowledgments

This study was funded by the German Research Foundation (DFG) as part of the research group “Electron Transfer Processes in Anoxic Aquifers” (FOR 580). We thank Prof. Meckenstock for the availability of the synthesized standard naphthy-2-methylsuccinic acid and three anonymous reviewers for their helpful comments.

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Authors and Affiliations

  1. Water Chemistry, Engler-Bunte-Institut, Karlsruhe Institute of Technology (KIT), 76131, Karlsruhe, Germany

    Carsten Jobelius & Fritz H. Frimmel

  2. Environmental Analytical Chemistry, Center for Applied Geosciences (ZAG), Eberhard Karls Universität Tübingen, 72074, Tübingen, Germany

    Christian Zwiener

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  1. Carsten Jobelius
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  2. Fritz H. Frimmel
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Correspondence to Christian Zwiener.

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Jobelius, C., Frimmel, F.H. & Zwiener, C. Mass spectrometric screening and identification of acidic metabolites in fulvic acid fractions of contaminated groundwater. Anal Bioanal Chem 406, 3415–3429 (2014). https://doi.org/10.1007/s00216-014-7783-y

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