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GC-MS method for determining faecal sterols as biomarkers of human and pastoral animal presence in freshwater sediments

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Abstract

In order to determine sterols and stanols in freshwater sediments to reconstruct the past presence of humans and pastoral animals, we developed an analytical method based on pressurised liquid extraction (PLE), clean-up performed using solid phase extraction (SPE) and sterol determination using gas chromatography–mass spectrometry (GC-MS) analysis. PLE extraction conditions were optimised using dichloromethane (DCM) and DCM/methanol mixtures. Clean-up was performed with 2 g silica SPE cartridges, and the concentrated extracts were eluted with 70 mL DCM. Extraction yield was evaluated using an in-house reference material spiked with 13C-labelled cholesterol and aged for 10 days. In comparison with pre-extraction, where the sediment is extracted and then spiked with a known analyte concentration, this approach preserves the original composition of the sediment. DCM and DCM/methanol mixtures resulted in high extraction yields ranging from 86 to 92 % with good reproducibility (relative standard deviation (RSD) 5–8 %). PLE extraction yields obtained with DCM as the extracting solvent were about 1.5 times higher than extractions using an ultrasonic bath. The solvent extraction mixture and matrix composition strongly affected the solvent extraction composition where higher overall recoveries (70–80 %) for each compound were obtained with DCM. The extraction mixture and matrix composition also affected the analyte concentrations, resulting in a method precision ranging from 1 to 18 %. Diatomaceous earth spiked with 10 to 100 ng of sterols, and environmental samples fortified with suitable amounts of sterols provided apparent recovery values ranging from 90 to 110 %. We applied the method to environmental samples both close to and upstream from sewage discharge zones, resulting in substantially higher faecal sterol (FeSt) concentrations near the sewage. In addition, we also applied the method to a 37-cm freshwater sediment core in order to evaluate its applicability for obtaining vertical sterol profiles.

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Acknowledgments

This work was financially supported by the Early Human Impact ERC Advance Grant of the European Commission’s VII Framework Programme, grant number 267696, contribution no. 14. We would also like to thank Dr. Daniela Almansi and Dr. Natalie M. Kehrwald for the revision of our manuscript.

Conflict of interest

The authors declare that they have no competing interests.

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Authors and Affiliations

  1. Department of Environmental Science, Informatics and Statistics, University Ca’ Foscari of Venice, Via Torino, 155, 30172, Venezia Mestre, Venice, Italy

    Dario Battistel, Rossano Piazza, Elena Argiriadis, Enrico Marchiori & Carlo Barbante

  2. Institute for the Dynamics of Environmental Processes, IDPA/CNR, Via Torino, 155, 30172, Venezia Mestre, Venice, Italy

    Dario Battistel, Rossano Piazza, Marta Radaelli & Carlo Barbante

Authors
  1. Dario Battistel
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  2. Rossano Piazza
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  3. Elena Argiriadis
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  5. Marta Radaelli
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  6. Carlo Barbante
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Correspondence to Dario Battistel.

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Battistel, D., Piazza, R., Argiriadis, E. et al. GC-MS method for determining faecal sterols as biomarkers of human and pastoral animal presence in freshwater sediments. Anal Bioanal Chem 407, 8505–8514 (2015). https://doi.org/10.1007/s00216-015-8998-2

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  • DOI: https://doi.org/10.1007/s00216-015-8998-2

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