Energy & Fuels 1990,4, 653-657
653
Novel Chlorophyll-RelatedCompounds in Marine Phytoplankton: Distributions and Geochemical Implications R. R. Bidigare,**tM. C. Kennicutt, 11, and M. E. Ondrusek Geochemical & Environmental Research Group, 833 Graham Rd., Texas A&M University, College Station, Texas 77845
M. D. Keller and R. R. L. Guillard Bigelow Laboratory for Ocean Sciences, McKown Point, West Boothbay Harbor, Maine 04575 Received June 11, 1990. Revised Manuscript Received September 4, 1990
The distributions of chlorophyll-related pigments in marine phytoplankton are surveyed to document their occurrence, reevaluate their use as biological markers, and suggest precursor-geoporphyrin relationships. Newly identified chlorophyll c related pigments were widely distributed among the marine phytoplankton clones examined in this study. Two of the recently described chlorophyll c like pigments (chlorophyll c3 and a phytylchlorophyll c derivative) were found to be associated with common bloom-producing chromophytes, thus having potential for preservation in the sedimentary record. The taxonomic specificity and apparent geological stability of chlorophyll pigments suggest that geoporphyrins are excellent candidates as indicators of paleooceanographic/depositional environments. The high structural diversity observed among geoporphyrins may be explained by the complexity of precursor pigments found in marine phytoplankton and bacterioplankton and not by extensive diagenetic transformations. The introduction of methods providing greater resolution (liquid chromatography/mass spectrometry and supercritical fluid chromatography/mass spectrometry) of complex chlorophyll mixtures and specific detection should lead to the discovery of an even more diverse collection of chlorophyll pigments.
Introduction Historically, the tetrapyrrole-based accessory photosynthetic pigments (i.e., chlorophylls b and c and the phycobilins) have been used as one of the most crucial elements in delineation of the major groups of oxygenevolving photosynthetic organisms.' The same is true for certain carotenoids, notably fucoxanthin (and its 19' derivatives), peridinin, zeaxanthin, cryptoxanthin, myxoxanthophyll, oscillaxanthin, prasinoxanthin, and alloxanthin.24 Similarily, photosynthetic bacteria are distinguished by the unique suites of bacteriochlorophylls and bacteriocarotenoids they p o s s e s ~ . ~ *In ~ athe past decade, improvements in chromatographicelo and culture techniques" have led to the description of several novel chlorophyll-related pigments found in marine phytoplankton and bacterioplankton. These include a suite of ~ J ~ divinylchlorophyll c related c o m p o ~ n d s , ' ~ J two chlorophyll-like pigment~,'~J~ geranyl-44sobutylbacteriochlorophyll e,'6 and a phytylchlorophyll c like derivative.17 Concurrent advances in isolation (preparative-scale high-performance liquid chromatography) and spectroscopic (mass spectrometry and nuclear magnetic resonance) techniques have resulted in the structural characterization of parent pigments16J8and their diagenetic alteration products, the geoporphyrins.1"26 On the basis of structural and isotopic evidence, a number of precursor-product relationships for these compounds have been p r o p o ~ e d . ~ ~ However, * ~ ~ - ~ ~these proposed precursorproduct relationships necessarily imply that the parent pigments were widely distributed in nature, abundant in source organisms, and relatively stable over geologic time. Present address: Department of Oceanography, lo00 Pope Rd., University of Hawaii, Honolulu, H I 96822.
In the present paper, the distributions of novel chlorophyll-related pigments in marine phytoplankton are sur(1)Jeffrey, S. W. In Primary Productivity in the Sea; Falkowski, P. G., Ed.; Plenum Press: New York, 1980; pp 33-58. (2)Liaaen-Jensen, S.Pure Appl. Chem. 1979,51,661-675. (3) Liaaen-Jensen, S. Pure Appl. Chem. 1985,57,649-658. (4)Liaaen-Jensen, S.Pure Appl. Chem. 1989,61,369-372. (5)Rudiger, W.; Schoch, S. In Plant Pigments; Goodwin, T. W., Ed.; Academic Press: London, 1988; pp 1-59. (6)Gieakes, W. W.; Kraay, G. W. Limnol. Oceanogr. 1983,28,757-766. (7)Gieskes, W. W.; Kraay, G. W. Mar. Biol. 1986,92,45-52. (8) Mantoura, R. F. C.; Llewellyn, C. A. Anal. Chim. Acta 1983,151, 297-314. (9)Bidigare, R. R. In Novel Phytoplankton Bloom; Cwper, E. M., Bricelj, V. M., Carpenter, E. J., Eds.; Springer-Verlag: Berlin, 1989; pp 57-75. (10)Jeffrey, S.W. In The Chromophyte Algae: Problem and Perspectiues; Green, J. C., Lendbeater, B. S. C., Diver, W. L., Eds.;Clarendon Press: Oxford, 1989; pp 13-36. (11)Keller, M. D.; Selvin, R. C.; Claus, W.; Guillard, R. R. L. J. Phycol. 1987,23,633-638. (12)Jeffrey, S.W.; Wright, S. W. Biochim. Biophys. Acta 1987,894, 180-188. (13)Fawley, M. W. Plant Physiol. 1989,91, 727-732. (14)Chisholm, S. W.; Olson, R. J.; Zettler, E. R.; Goericke, R.; Waterbury, J. B.; Welschmeyer, N. A. Nature 1988,334,34&343. (15)Goericke, R. Pigmenta as Ecological Tracers for the Study of the Abundance and Growth of Marine Phytoplankton. Ph.D. Dissertation, Harvard University, Cambridge, MA, 1990, 419 pages. (16)Repeta, D.J.; Simpson, D. J.; Jorgensen, B. B.; Jannasch, H. W. Nature 1989,342,69-72. (17)Nelson, J. R.; Wakeham, S. G. J. Phycol. 1989,25,761-766. (18)Fookes, C. J. R.; Jeffrey, S. W. J. Chem. Soc., Chem. Commun. 1989,1827-1828. (19)Fookes, C. J. R. J. Chem. Soc., Chem. Commun.1983,1474-1476. (20)Ocampo, R.; Callot, H.J.; Albrecht, P.; Kintzinger, J. P. Tetrahedron Lett. 1984,25,2589-2592. (21)Ocampo, R.; Callot, H. J.; Albrecht, P. In Metal Complexes in Fossil Fuek, Filby, R. H., Branthaver, F., Eds.; ACS Symposium Series 344, American Chemical Society: Washington, DC, 1987;pp 68-73. (22)Kaur, S.;Chicarelli, M. I.; Maxwell, J. R. J. Am. Chem. Soe. 1986, 108,1347-1348.
0887-0624/90/2504-0653$02.50/00 1990 American Chemical Society
Bidigare et al.
654 Energy & Fuels, Vol. 4, No. 6,1990 Table I. List of Algal Cultures Used for the Pigment Survey
