Environmental Chemistry Letters

, Volume 12, Issue 3, pp 455–460 | Cite as

Identification of a novel di-unsaturated C25 highly branched isoprenoid in the marine tube-dwelling diatom Berkeleya rutilans

  • T. A. BrownEmail author
  • S. T. Belt
  • P. Cabedo-Sanz
Original Paper


Highly branched isoprenoids (HBIs) are known to be biosynthesised by diatoms and are a common component of many marine and freshwater environments. However, the ability to produce these unusual hydrocarbons appears to be restricted to a few diatom species that are represented by just four genera (Haslea, Pleurosigma, Rhizosolenia and Navicula). Despite this, we routinely observe some HBIs in the natural environment that are absent from cultures of known HBI-producing diatoms, indicating the possibility of further sources. Having identified one commonly observed, yet unknown HBI isomer in estuarine sediments, we isolated and cultured diatoms in the laboratory to identify the source of this novel di-unsaturated C25 HBI. Here, we show that analysis of purified extracts obtained from a laboratory culture of the tube-dwelling diatom Berkeleya rutilans enabled determination of the structure of this new compound by combined NMR spectroscopic and mass spectrometric analysis. This represents the first identification of an HBI alkene within the Berkeleya genus and adds to the growing number of reports of genera that produce these unusual hydrocarbons. The newly characterised HBI diene appears to be common in marine sediments and has also been reported in a range of marine biota, thus making it a potential tracer of source organic matter, as has been found for other HBI alkenes.


Highly branched isoprenoid Diatom Lipids Biomarkers 



We thank the University of Plymouth for a Fellowship to TB. We are grateful for the taxonomic assistance of Michel Poulin (Canadian Museum of Nature) and to Peter Bond at the University of Plymouth Electron Microscopy Centre for assistance with SEM. We are also grateful to two anonymous reviewers for their feedback and advice.


  1. Allard WG, Belt ST, Massé G, Naumann R, Robert J-M, Rowland S (2001) Tetra-unsaturated sesterterpenoids (Haslenes) from Haslea ostrearia and related species. Phytochemistry 56:795–800CrossRefGoogle Scholar
  2. Belt ST, Müller J (2013) The Arctic sea ice biomarker IP25: a review of current understanding, recommendations for future research and applications in palaeo sea ice reconstructions. Quat Sci Rev 79:9–25CrossRefGoogle Scholar
  3. Belt ST, Cooke DA, Hird SJ, Rowland S (1994) Structural determination of a highly branched C25 sedimentary isoprenoid biomarker by NMR spectroscopy and mass spectrometry. J Chem Soc Chem Commun, 2077–2078Google Scholar
  4. Belt ST, Cooke DA, Robert JM, Rowland S (1996) Structural characterisation of widespread polyunsaturated isoprenoid biomarkers: a C25 triene, tetraene and pentaene from the diatom Haslea ostrearia simonsen. Tetrahedron Lett 37:4755CrossRefGoogle Scholar
  5. Belt ST, Allard WG, Massé G, Robert JM, Rowland SJ (2000a) Highly branched isoprenoids (HBIs): identification of the most common and abundant sedimentary isomers. Geochim Cosmochim Ac 64:3839–3851CrossRefGoogle Scholar
  6. Belt ST, Allard WG, Massé G, Robert JM, Rowland SJ (2000b) Important sedimentary sesterterpenoids from the diatom Pleurosigma intermedium. Chem Commun 501–502Google Scholar
  7. Belt ST, Allard WG, Massé G, Robert JM, Rowland SJ (2001a) Structural characterisation of C30 highly branched isoprenoid alkenes (rhizenes) in the marine diatom Rhizosolenia setigera. Tetrahedron Lett 42:5583–5585CrossRefGoogle Scholar
  8. Belt ST, Massé G, Allard WG, Robert JM, Rowland SJ (2001b) Identification of a C25 highly branched isoprenoid triene in the freshwater diatom Navicula sclesvicensis. Org Geochem 32:1169–1172CrossRefGoogle Scholar
  9. Belt ST, Massé G, Allard WG, Robert JM, Rowland SJ (2001c) C25 highly branched isoprenoid alkenes in planktonic diatoms of the Pleurosigma genus. Org Geochem 32:1271–1275CrossRefGoogle Scholar
  10. Belt ST, Massé G, Allard WG, Robert J-M, Rowland SJ (2003) Novel monocyclic sester- and triterpenoids from the marine diatom, Rhizosolenia setigera. Tetrahedron Lett 44:9103–9106CrossRefGoogle Scholar
  11. Belt ST, Masse G, Rowland SJ, Rohmer M (2006) Highly branched isoprenoid alcohols and epoxides in the diatom Haslea ostrearia Simonsen. Org Geochem 37:133–145CrossRefGoogle Scholar
  12. Belt ST, Massé G, Vare LL, Rowland SJ, Poulin M, Sicre M-A, Sampei M, Fortier L (2008) Distinctive 13C isotopic signature distinguishes a novel sea ice biomarker in Arctic sediments and sediment traps. Mar Chem 112:158–167CrossRefGoogle Scholar
  13. Belt ST, Brown TA, Cabedo Sanz P, Navarro Rodriguez A (2012a) Structural confirmation of the sea ice biomarker IP25 found in Arctic marine sediments. Environ Chem Lett 10:189–192CrossRefGoogle Scholar
  14. Belt ST, Brown TA, Navarro-Rodriguez A, Cabedo-Sanz P, Tonkin A, Ingle R (2012b) A reproducible method for the extraction, identification and quantification of the Arctic sea ice proxy IP25 from marine sediments. Anal Methods 4:705–713CrossRefGoogle Scholar
  15. Brown TA (2011) Production and preservation of the Arctic sea ice diatom biomarker IP25. PhD Thesis. University of Plymouth, PlymouthGoogle Scholar
  16. Brown TA, Belt ST (2012a) Identification of the sea ice diatom biomarker IP25 in Arctic benthic macrofauna: direct evidence for a sea ice diatom diet in Arctic heterotrophs. Polar Biol 35:131–137CrossRefGoogle Scholar
  17. Brown TA, Belt ST (2012b) Closely linked sea ice–pelagic coupling in the Amundsen Gulf revealed by the sea ice diatom biomarker IP25. J Plankton Res 34:647–654CrossRefGoogle Scholar
  18. Brown TA, Belt ST, Piepenburg D (2012) Evidence for a pan-Arctic sea-ice diatom diet in Strongylocentrotus spp. Polar Biol 35:1281–1287CrossRefGoogle Scholar
  19. Brown TA, Belt ST, Ferguson SH, Yurkowski DJ, Davison NJ, Barnett JEF, Jepson PD (2013a) Identification of the sea ice diatom biomarker IP25 and related lipids in marine mammals: a potential method for investigating regional variations in dietary sources within higher trophic level marine systems. J Exp Mar Biol Ecol 441:99–104CrossRefGoogle Scholar
  20. Brown TA, Bicknell AWJ, Votier SC, Belt ST (2013b) Novel molecular fingerprinting of marine avian diet provides a tool for gaining insights into feeding ecology. Environ Chem Lett 11:283–288CrossRefGoogle Scholar
  21. Brown TA, Hegseth EN, Belt ST (in press) A biomarker-based investigation of the mid-winter ecosystem in Rijpfjorden, Svalbard. Polar BiolGoogle Scholar
  22. Cox EJ (1975) Further studies on the genus Berkeleya Grev. Brit Phycol J 10:205–217CrossRefGoogle Scholar
  23. Goutte A, Cherel Y, Houssais M-N, Klein V, Ozouf-Costaz C, Raccurt M, Robineau C, Massé G (2013) Diatom-specific highly branched isoprenoids as biomarkers in Antarctic consumers. PLoS ONE 8:e56504CrossRefGoogle Scholar
  24. Grossi V, Beker B, Geenevasen JAJ, Schouten S, Raphel D, Fontaine M-F, Sinninghe Damsté JS (2004) C25 highly branched isoprenoid alkene from the marine benthic diatom Pleurosigma strigosum. Phytochemistry 65:3049–3055CrossRefGoogle Scholar
  25. Guiry MD, Guiry GM (2013) AlgaeBase. World-wide electronic publication, National University of Ireland, Galway. Accessed 18th Dec 2013
  26. Hird SJ (1992) Origins and short-term sedimentary fate of globally distributed biological marker hydrocarbons: PhD thesis. University of PlymouthGoogle Scholar
  27. Johns L, Wraige EJ, Belt ST, Lewis CA, Massé G, Robert JM, Rowland SJ (1999) Identification of a C25 highly branched isoprenoid (HBI) diene in Antarctic sediments, Antarctic sea-ice diatoms and cultured diatoms. Org Geochem 30:1471–1475CrossRefGoogle Scholar
  28. Johns L, Belt ST, Lewis CA, Rowland SJ, Massé G, Robert JM, König WA (2000) Configurations of polyunsaturated sesterterpenoids from the diatom, Haslea ostrearia. Phytochemistry 53:607–611CrossRefGoogle Scholar
  29. Lobban CS (1984) Marine tube-dwelling diatoms of eastern Canada: descriptions, checklist, and illustrated key. Can J Bot 62:778–794CrossRefGoogle Scholar
  30. Makato M (1989) Autecological studies of the marine tube–dwelling diatom Berkeleya obtusa (Grev) Grunow. Scientific papers of the Institute of Algological Research, Faculty of Science, Hokkaido University 8:63–115Google Scholar
  31. Mangoni O, Saggiomo M, Modigh M, Catalano G, Zingone A, Saggiomo V (2009) The role of platelet ice microalgae in seeding phytoplankton blooms in Terra Nova Bay (Ross Sea, Antarctica): a mesocosm experiment. Polar Biol 32:311–323CrossRefGoogle Scholar
  32. Massé G (2003) Highly branched isoprenoid alkenes from diatoms: a biosynthetic and life cycle investigation. Ph. D thesis. University of Plymouth, PlymouthGoogle Scholar
  33. Massé G, Belt ST, Allard GW, Lewis CA, Wakeham SG, Rowland SJ (2004a) Occurrence of novel monocyclic alkenes from diatoms in marine particulate matter and sediments. Org Geochem 35:813–822CrossRefGoogle Scholar
  34. Massé G, Belt ST, Rowland SJ (2004b) Biosynthesis of unusual monocyclic alkenes by the diatom Rhizosolenia setigera (Brightwell). Phytochemistry 65:1101–1106CrossRefGoogle Scholar
  35. Massé G, Belt ST, Rowland SJ, Rohmer M (2004c) Isoprenoid biosynthesis in the diatoms Rhizosolenia setigera (Brightwell) and Haslea ostrearia (Simonsen). Proc Natl Acad Sci 101:4413–4418CrossRefGoogle Scholar
  36. Medlin LK (1990) Berkeleya spp. from Antarctic waters, including Berkeleya adeliensis, sp. nov., a new tube dwelling diatom. Beihefte zur Nova Hedwigia 100:77–89Google Scholar
  37. Müller J, Massé G, Stein R, Belt ST (2009) Variability of sea–ice conditions in the Fram Strait over the past 30,000 years. Nat Geosci 2:772–776CrossRefGoogle Scholar
  38. Riaux-Gobin C, Poulin M, Dieckmann G, Labrune C, Vétion G (2011) Spring phytoplankton onset after the ice break-up and sea-ice signature (Adélie Land, East Antarctica). Polar Research 30:5910. doi: 10.3402/polar.v30i0.5910
  39. Round FE, Brooks ME (1973) A new species of Amphipleura from Togo, W. Africa. Bot Mar 16. doi: 10.1515/botm.1973.16.2.77
  40. Round FE, Crawford RM, Mann DG (1990) The diatoms, biology and morphology of the genera. Cambridge University Press, CambridgeGoogle Scholar
  41. Sinninghe Damsté JS, Rijpstra WI, Schouten S, Peletier H, van der Maarel MJEC, Gieskes WWC (1999) A C25 highly branched isoprenoid alkene and C25 and C27 n-polyenes in the marine diatom Rhizosolenia setigera. Org Geochem 30:95–100CrossRefGoogle Scholar
  42. Stein R, Fahl K (2013) Biomarker proxy shows potential for studying the entire Quaternary Arctic sea ice history. Org Geochem 55:98CrossRefGoogle Scholar
  43. Volkman JK, Barrett SM, Dunstan GA (1994) C25 and C30 highly branched isoprenoid alkenes in laboratory cultures of two marine diatoms. Org Geochem 21:407–414CrossRefGoogle Scholar
  44. von Quillfeldt CH (1997) Distribution of diatoms in the Northeast Water Polynya, Greenland. J Mar Syst 10:211–240CrossRefGoogle Scholar
  45. Wraige EJ, Belt ST, Lewis CA, Cooke DA, Robert JM, Massé G, Rowland SJ (1997) Variations in structures and distributions of C25 highly branched isoprenoid (HBI) alkenes in cultures of the diatom, Haslea ostrearia (Simonsen). Org Geochem 27:497–505CrossRefGoogle Scholar
  46. Wraige EJ, Johns L, Belt S, Massé G, Robert J-M, Rowland S (1999) Highly branched C25 isoprenoids in axenic cultures of Haslea ostrearia. Phytochemistry 51:69–73CrossRefGoogle Scholar

Copyright information

© Springer International Publishing Switzerland 2014

Authors and Affiliations

  1. 1.Biogeochemistry Research Centre, School of Geography, Earth and Environmental SciencesPlymouth UniversityPlymouthUK

Personalised recommendations