Energy & Fuels 1990,4, 653-657 Novel Chlorophyll-Related Compounds in Marine Phytoplankton: Distributions and Geochemical Implications 653 R. R. Bidigare,**t M. 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 en- vironments. 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 photo- synthetic 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 oxygen- evolving photosynthetic organisms.' The same is true for certain carotenoids, notably fucoxanthin (and its 19' de- rivatives), peridinin, zeaxanthin, cryptoxanthin, myxo- xanthophyll, oscillaxanthin, prasinoxanthin, and allo- xanthin.24 Similarily, photosynthetic bacteria are dis- tinguished by the unique suites of bacteriochlorophylls and bacteriocarotenoids they posses~.~*~a In the past decade, improvements in chromatographicelo and culture tech- niques" have led to the description of several novel chlorophyll-related pigments found in marine phyto- plankton and bacterioplankton. These include a suite of chlorophyll c related compo~nds,'~J~J~ two divinyl- chlorophyll-like pigment~,'~J~ geranyl-44sobutylbacterio- chlorophyll e,'6 and a phytylchlorophyll c like derivative.17 Concurrent advances in isolation (preparative-scale high-performance liquid chromatography) and spectro- scopic (mass spectrometry and nuclear magnetic reso- nance) techniques have resulted in the structural charac- terization of parent pigments16J8and their diagenetic al- teration products, the geoporphyrins.1"26 On the basis of structural and isotopic evidence, a number of precur- sor-product relationships for these compounds have been propo~ed.~~*~~-~~ However, these proposed precursor- product 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, HI 96822. 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