Alkenones are long-chain unsaturated methyl and ethyl n-ketones produced by a few phytoplankton species of the class Prymnesiophyceae.[1] Alkenones typically contain between 35 and 41 carbon atoms and with between two and four double bonds.[2] Uniquely for biolipids, alkenones have a spacing of five methylene groups between double bonds, which are of the less common E configuration. The biological function of alkenones remains under debate although it is likely that they are storage lipids.[3][4] Alkenones were first described in ocean sediments recovered from Walvis Ridge[5] and then shortly afterwards in cultures of the marine coccolithophore Gephyrocapsa huxleyi.[6] The earliest known occurrence of alkenones is during the Aptian 120 million years ago.[7] They are used in organic geochemistry as a proxy for past sea surface temperature.
The chemical structure of a 37:3 alkenone, (8E,15E,22E)-heptatriaconta-8,15,22-trien-2-one, C37H68O
Alkenone-producing species respond to changes in their environment — including to changes in water temperature — by altering the relative proportions of the different alkenones they produce. At higher temperatures more saturated alkenones are produced proportionally. This means that the relative degree of unsaturation of alkenones can be used to estimate the temperature of the water in which the alkenone-producing organisms grew.[8] The relative degree of unsaturation as first described (UK37) included the tetra unsaturated C37 alkenone:
UK37 = (C37:2 - C37:4)/(C37:2 + C37:3 + C37:4) [8]
However, a simplified Unsaturation Index (UK′37), generally more useful in marine settings, is based on di- versus tri- unsaturated C37 alkenones and defined as:
- UK′37 = C37:2/(C37:2 + C37:3) [9]
The UK′37 can then be used to estimate sea surface temperature according to an empirical relationship determined from core-top calibrations. The most commonly used calibration is that of Müller et al., 1998:
- UK′37 = 0.033T [°C] + 0.044 [10]
The Müller et al. (1998) calibration is not suitable for all environments and, in particular, different calibrations are required for high latitudes and lacustrine settings.
References
edit- ^ Marlowe, I.T.; Green, J.C.; Neal, A.C.; Brassell, S.C.; Eglinton, G.; Course, P.A. (1984). "Long chain ( n -C37–C39) alkenones in the Prymnesiophyceae. Distribution of alkenones and other lipids and their taxonomic significance". British Phycological Journal. 19 (3): 203–216. doi:10.1080/00071618400650221.
- ^ Rontani, Jean‐François; Prahl, Fredrick G.; Volkman, John K. (2006). "RE‐EXAMINATION OF THE DOUBLE BOND POSITIONS IN ALKENONES AND DERIVATIVES: BIOSYNTHETIC IMPLICATIONS". Journal of Phycology. 42 (4): 800–813. doi:10.1111/j.1529-8817.2006.00251.x. S2CID 84316762.
- ^ Epstein, B.L.; d'Hondt, S.; Hargraves, P.E. (2001). "The possible metabolic role of C37 alkenones in Emiliania huxleyi". Organic Geochemistry. 32 (6): 867–875. Bibcode:2001OrGeo..32..867E. doi:10.1016/S0146-6380(01)00026-2.
- ^ Eltgroth, Matthew L.; Watwood, Robin L.; Wolfe, Gordon V. (2005). "PRODUCTION AND CELLULAR LOCALIZATION OF NEUTRAL LONG‐CHAIN LIPIDS IN THE HAPTOPHYTE Algae ISOCHRYSIS GALBANA AND EMILIANIA HUXLEYI". Journal of Phycology. 41 (5): 1000–1009. doi:10.1111/j.1529-8817.2005.00128.x. S2CID 22092773.
- ^ De Leeuw, J.W.; v.d. Meer, F.W.; Rijpstra, W.I.C.; Schenck, P.A. (1980). "On the occurrence and structural identification of long chain unsaturated ketones and hydrocarbons in sediments". Physics and Chemistry of the Earth. 12: 211–217. Bibcode:1980PCE....12..211D. doi:10.1016/0079-1946(79)90105-8.
- ^ Volkman, J.K.; Eglinton, G.; Corner, E.D.S.; Sargent, J.R. (1980). "Novel unsaturated straight-chain C37C39 methyl and ethyl ketones in marine sediments and a coccolithophore Emiliania huxleyi". Physics and Chemistry of the Earth. 12: 219–227. Bibcode:1980PCE....12..219V. doi:10.1016/0079-1946(79)90106-X.
- ^ Brassell, Simon C.; Dumitrescu, Mirela (2004). "Recognition of alkenones in a lower Aptian porcellanite from the west-central Pacific". Organic Geochemistry. 35 (2): 181–188. doi:10.1016/j.orggeochem.2003.09.003.
- ^ a b Brassell, S. C.; Eglinton, G.; Marlowe, I. T.; Pflaumann, U.; Sarnthein, M. (1986). "Molecular stratigraphy: A new tool for climatic assessment". Nature. 320 (6058): 129–133. Bibcode:1986Natur.320..129B. doi:10.1038/320129a0. S2CID 4366905.
- ^ Prahl, F. G.; Wakeham, S. G. (1987). "Calibration of unsaturation patterns in long-chain ketone compositions for palaeotemperature assessment". Nature. 330 (6146): 367–369. Bibcode:1987Natur.330..367P. doi:10.1038/330367a0.
- ^ Müller, Peter J.; Kirst, Georg; Ruhland, Götz; von Storch, Isabel; Rosell-Melé, Antoni (1998). "Calibration of the alkenone paleotemperature index U37K′ based on core-tops from the eastern South Atlantic and the global ocean (60°N-60°S)". Geochimica et Cosmochimica Acta. 62 (10): 1757–1772. doi:10.1016/S0016-7037(98)00097-0.
Further reading
edit- Bradley, S R. (1999) Paleoclimatology: Reconstructing Climates of the Quaternary. Second edition. Academic Press
External links
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