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Measuring dissolved organic carbon δ13C in freshwaters using total organic carbon cavity ring-down spectroscopy (TOC-CRDS)

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Abstract

This article reports the first application of coupled total organic carbon cavity ring-down spectroscopy (TOC-CRDS) for the analysis of the δ13C signature of dissolved organic carbon (DOC) in freshwater samples. DOC represents a major, dynamic component of the global carbon cycle. The export of DOC from soils into rivers and groundwaters may be highly climate sensitive, and much of this export may occur in ephemeral fluxes. Thus, a robust, simple and inexpensive method for the continuous determination of DOC concentration and quality is urgently needed. We detail recent advances made in the analysis of the δ13C signature of DOC using a TOC-CRDS system optimised for the analysis of DOC with natural abundances greater than 2.5 mg L−1 with no sample pre-concentration required and sample volumes of 40 mL. Precision between replicated samples was comparable to conventional analysis by gas-source isotope ratio mass spectrometry, yielding δ13C values with standard deviations of ± 0.5 ‰ for DOC concentrations higher than 1.5 mg L−1. The utility of this technique for the analysis of DOC in samples with a broad range of compositions and concentrations (2.5–25 mg L−1 DOC) is demonstrated. Since DOC δ13C can be measured continuously, ca. 45 min per measurement, this method enables the online monitoring of DOC in river water, water intakes and treated waters, allowing changes in DOC fluxes to be monitored in real time.

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Acknowledgments

This work was funded by the National Centre for Groundwater Research and Training, an Australian Government initiative supported by the Australian Research Council and the National Water Commission. The analytical equipment used in this study was funded through the Australian Government Groundwater Education Investment Fund. We also acknowledge funding to YS through ARC grant LP1002000259 and a scholarship from Water Quality Research Australia.

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Authors and Affiliations

  1. Connected Waters Initiative Research Centre, Water Research Laboratory, University of New South Wales, 110 King St., Manly Vale, NSW, 2093, Australia

    Adam Hartland, Andy Baker & Wendy Timms

  2. National Centre for Groundwater Research and Training, Australia http://www.groundwater.com.au/

    Adam Hartland, Andy Baker & Wendy Timms

  3. School of Civil and Environmental Engineering, University of New South Wales, Kensington, Sydney, NSW, 2052, Australia

    Adam Hartland & Yulia Shutova

  4. School of Mining Engineering, University of New South Wales, Kensington, Sydney, NSW, 2052, Australia

    Wendy Timms

  5. Mark Wainwright Analytical Centre, University of New South Wales, Kensington, Sydney, NSW, 2052, Australia

    Dorothy Yu

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  1. Adam Hartland
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  2. Andy Baker
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  3. Wendy Timms
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  4. Yulia Shutova
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  5. Dorothy Yu
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Correspondence to Adam Hartland.

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Hartland, A., Baker, A., Timms, W. et al. Measuring dissolved organic carbon δ13C in freshwaters using total organic carbon cavity ring-down spectroscopy (TOC-CRDS). Environ Chem Lett 10, 309–315 (2012). https://doi.org/10.1007/s10311-012-0377-z

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  • DOI: https://doi.org/10.1007/s10311-012-0377-z

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