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Quantification of dimethylsulfoniopropionate (DMSP) in Acropora spp. of reef-building coral using mass spectrometry with deuterated internal standard

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Abstract

Dimethylsulfoniopropionate (DMSP) in scleractinian coral is usually analysed indirectly as dimethylsulfide (DMS) using gas chromatography (GC) with a sulfur-specific detector. We developed a headspace GC method for mass spectral analysis of DMSP in branching coral where hexa-deuterated DMSP (d 6 -DMSP) was added to samples and standards to optimise the analytical precision and quantitative accuracy. Using this indirect HS-GC-MS method, we show that common coral sample handling techniques did not alter DMSP concentrations in Acropora aspera and that endogenous DMS was insignificant compared to the store of DMSP in A. aspera. Field application of the indirect HS-GC-MS method in all seasons over a 5-year period at Heron Island in the southern Great Barrier Reef indicated that healthy colonies of A. aspera ordinarily seasonally conserve their branch tip store of DMSP; however, this store increased to a higher concentration under extended thermal stress conditions driven by a strong El Niño Southern Oscillation event. A liquid chromatography mass spectral method (LC-MS) was subsequently developed for direct analysis of DMSP in branching coral, also utilising the d 6 -DMSP internal standard. The quantitative comparison of DMSP in four species of Acropora coral by indirect HS-GC-MS and direct LC-MS analyses gave equivalent concentrations in A. aspera only; in the other three species, HS-GC-MS gave consistently higher concentrations, indicating that indirect analysis of DMSP may lead to artificially high values for some coral species.

Dimethylsulfoniopropionate (DMSP) was quantified in Acropora spp. of branching coral using deuterated stable isotope dilution mass spectrometry

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Acknowledgments

This research was partly funded by grants awarded to GBJ from the Marine Ecology Research Centre, Southern Cross University (SCU), and the Australian Research Council Discovery Program (ARCDP) DP140100681. Additional funding was provided from ARCDP grants DP110103638 and DP150102092 awarded to BDE. HBS would like to thank the National Measurement Institute (NMI) and Agrifor Scientific (Sydney, Australia) for use of analytical equipment, and Dr. Mahiuddin Alamgir (NMI) for synthesis of the DMSP.HCl and d 6 -DMSP.HCl chemical standards used in this study. All the authors thank the staff of the Heron Island Research Station for assistance with their experimental needs, the Great Barrier Reef Marine Park Authority for provision of permits to collect coral, and Prof. Peter Harrison (SCU) for coral species identification.

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Authors and Affiliations

  1. School of Environment, Science and Engineering, Southern Cross University, Military Road, Lismore, New South Wales, 2480, Australia

    Hilton B. Swan, Elisabeth S. M. Deschaseaux, Graham B. Jones & Bradley D. Eyre

  2. Marine Ecology Research Centre, Southern Cross University, Military Road, Lismore, New South Wales, 2480, Australia

    Hilton B. Swan, Elisabeth S. M. Deschaseaux & Graham B. Jones

  3. Centre for Coastal Biogeochemistry, Southern Cross University, Military Road, Lismore, New South Wales, 2480, Australia

    Hilton B. Swan, Elisabeth S. M. Deschaseaux & Bradley D. Eyre

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  1. Hilton B. Swan
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Correspondence to Hilton B. Swan.

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Swan, H.B., Deschaseaux, E.S.M., Jones, G.B. et al. Quantification of dimethylsulfoniopropionate (DMSP) in Acropora spp. of reef-building coral using mass spectrometry with deuterated internal standard. Anal Bioanal Chem 409, 1929–1942 (2017). https://doi.org/10.1007/s00216-016-0141-5

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