Protocols for the Quantification of Dimethyl Sulfide (DMS) and Other Volatile Organic Compounds in Aquatic Environments

  • Filippo Franchini
  • Michael SteinkeEmail author
Part of the Springer Protocols Handbooks book series (SPH)


Aquatic environments produce a range of volatile organic compounds (VOCs) that can transfer into the atmosphere and affect climate. Much of our understanding on the biogeochemistry of volatiles in seawater stems from research on the biogenic trace gas dimethyl sulfide (DMS). Here, we describe four protocols for the quantification of DMS and other VOCs in aqueous samples that utilise direct injection or cryogenic enrichment techniques before separation and quantification using gas chromatography with flame photometric detection (GC-FPD). With few adjustments, the protocols can be customised to quantify a range of other gases including hydrocarbons such as isoprene and ethene, or halocarbons such as methyl chloride or bromoform. The limit of quantification for DMS is 1.5 pmol and the protocols range in sensitivities for DMS from 0.2 to 20 μM (direct injection of 200 μL headspace), 50 to 250 nM (headspace purging of 1.92 mL gaseous phase), 0.5 to 350 nM (in-vial purging of 3 mL aqueous phase), and the sub-nanomolar range for in-tube purging of sample volumes up to 200 mL. Two additional adaptations of the protocol include quantification of the biological DMS-precursor dimethylsulfoniopropionate (DMSP) and the DMS-oxidation product dimethyl sulfoxide (DMSO).


Biogenic trace gases Cryogenic enrichment Dimethyl sulfide (DMS) Dimethyl sulfoxide (DMSO) Dimethylsulfoniopropionate (DMSP) Flame photometric detection Gas chromatography VOC 



We thank two anonymous reviewers for their comments and suggestions. Data for the ethene calibration in Fig. 5 were kindly provided by Dr Ina Plettner. We are grateful for the technical support provided by Sue Corbett, Tania Cresswell-Maynard and John Green.


  1. 1.
    WMO (1994) Scientific assessment of ozone depletion: World Meteorological Organization (WMO) global ozone research and monitoring project. GenevaGoogle Scholar
  2. 2.
    Guenther A et al (1995) A global model of natural volatile organic compound emissions. J Geophys Res Atmos 100:8873–8892CrossRefGoogle Scholar
  3. 3.
    Graedel TE (1978) Chemical compounds in the atmosphere. Academic Press, New YorkGoogle Scholar
  4. 4.
    Graedel TE, Hawkins DT, Claxton LD (1986) Atmospheric chemical compounds. Sources, occurrence and bioassay. Academic Press, OrlandoGoogle Scholar
  5. 5.
    Goldstein AH, Galbally IE (2007) Known and unexplored organic constituents in the earth’s atmosphere. Environ Sci Technol 41:1514–1521CrossRefPubMedGoogle Scholar
  6. 6.
    Fehsenfeld F et al (1992) Emissions of volatile organic compounds from vegetation and the implications for atmospheric chemistry. Glob Biogeochem Cycles 6:389–430CrossRefGoogle Scholar
  7. 7.
    Buszewski B et al (2007) Human exhaled air analytics: biomarkers of diseases. Biomed Chromatogr 21:553–566CrossRefPubMedGoogle Scholar
  8. 8.
    Huybrechts T, Dewulf J, Van Langenhove H (2005) Priority volatile organic compounds in surface waters of the southern North Sea. Environ Pollut 133:255–264CrossRefPubMedGoogle Scholar
  9. 9.
    Bravo-Linares CM, Mudge SM (2009) Temporal trends and identification of the sources of volatile organic compounds in coastal seawater. J Environ Monit 11:628–641CrossRefPubMedGoogle Scholar
  10. 10.
    Simó R (2001) Production of atmospheric sulfur by oceanic plankton: biogeochemical, ecological and evolutionary links. Trends Ecol Evol 16:287–294CrossRefPubMedGoogle Scholar
  11. 11.
    Lana A et al (2011) An updated climatology of surface dimethylsulfide concentrations and emission fluxes in the global ocean. Glob Biogeochem Cycles 25, GB1004Google Scholar
  12. 12.
    Jones G et al (2007) Factors affecting the cycling of dimethylsulfide and dimethylsulfoniopropionate in coral reef waters of the Great Barrier Reef. Environ Chem 4:310–322Google Scholar
  13. 13.
    Malin G et al (1993) Dimethylsulphide and dimethylsulphoniopropionate in the northeast Atlantic during the summer coccolithophore bloom. Deep-Sea Res I 40:1487–1508CrossRefGoogle Scholar
  14. 14.
    Levasseur M (2013) Impact of Arctic meltdown on the microbial cycling of sulphur. Nat Geosci 6:691–700CrossRefGoogle Scholar
  15. 15.
    Asher EC et al (2011) High concentrations and turnover rates of DMS, DMSP and DMSO in Antarctic sea ice. Geophys Res Lett 38, L23609CrossRefGoogle Scholar
  16. 16.
    Bell TG et al (2013) Air-sea dimethylsulfide (DMS) gas transfer in the North Atlantic: evidence for limited interfacial gas exchange at high wind speed. Atmos Chem Phys 13:11073–11087CrossRefGoogle Scholar
  17. 17.
    Vogt M et al (2008) Laboratory inter-comparison of dissolved dimethyl sulphide (DMS) measurements using purge-and-trap and solid-phase microextraction techniques during a mesocosm experiment. Mar Chem 108:32–39CrossRefGoogle Scholar
  18. 18.
    Chambers ST et al (1987) Dimethylthetin can substitute for glycine betaine as an osmoprotectant molecule for Escherichia coli. J Bacteriol 169:4845–4847CrossRefPubMedPubMedCentralGoogle Scholar
  19. 19.
    Steinke M et al (2007) Substrate kinetics of DMSP-lyases in axenic cultures and mesocosm populations of Emiliania huxleyi. Aquat Sci 69:352–359CrossRefGoogle Scholar
  20. 20.
    Steinke M et al (2000) Determinations of dimethylsulphoniopropionate (DMSP) lyase activity using headspace analysis of dimethylsulphide (DMS). J Sea Res 43:233–244CrossRefGoogle Scholar
  21. 21.
    Steinke M et al (2011) Concentrations of dimethylsulfoniopropionate and dimethyl sulfide are strain-specific in symbiotic dinoflagellates (Symbiodinium sp., Dinophyceae). J Phycol 47:775–783CrossRefPubMedGoogle Scholar
  22. 22.
    Shrivastava A, Gupta VB (2011) Methods for the determination of limit of detection and limit of quantitation of the analytical methods. Chron Young Sci 2:21CrossRefGoogle Scholar
  23. 23.
    Andreae MO (1980) Determination of trace quantities of dimethylsulfoxide in aqueous solutions. Anal Chem 52:150–153CrossRefGoogle Scholar
  24. 24.
    Simó R, Grimalt JO, Albaiges J (1997) Dissolved dimethylsulphide, dimethylsulphoniopropionate and dimethylsulphoxide in western Mediterranean waters. Deep-Sea Res II 44:929–950CrossRefGoogle Scholar
  25. 25.
    Sander R (2015) Compilation of Henry’s law constants (version 4.0) for water as solvent. Atmos Chem Phys 15:4399–4981CrossRefGoogle Scholar
  26. 26.
    Klee MS (2012) Detectors. In: Poole CF (ed) Gas chromatography. Elsevier, AmsterdamGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  1. 1.University of EssexColchesterUK

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