Novel carotenol chlorin esters in marine sediments and water column particulate matter

Novel esters of carotenols and chlorins (carotenol chlorin esters, CCEs) were found in recent sediments from the California Borderlands, Monterey Bay, and the Peru and Oman margins. The chlorins associated with CCEs were pheophorbide a and pyropheophorbide a, degradation products of chlorophyll a. Isofucoxanthin-dehydrate and isofucoxanthinol-dehydrate and possibly their isomers, degradation products of fucoxanthin, were the only carotenols associated with CCEs. This result is surprising, considering that at least 8 major degradation products of fucoxanthin are present in organic-rich marine sediments. The carotenols of CCEs are likely derived from diatoms as these are the primary source for fucoxanthin in the marine environment. In sediments studied by us, CCEs contributed approximately 10% to total solvent extractable chlorins. The high relative concentrations of CCEs in these sediments suggest that CCEs are an important degradation product of chlorophyll a in some marine environments; a pathway hitherto unrecognized. Off Oman and Southern California we found CCEs in water column suspended particulate matter when diatoms dominated the phytoplankton community. By analogy with sterol chlorin esters, we suggest that CCEs are primarily produced by enzymatically mediated transesterifications in crustaceans grazing on diatoms. We are currently studying if CCEs are biomarkers for the grazing of crustaceans on diatoms, an important pathway of carbon remineralization in the marine environment. (C) 1999 Elsevier Science Ltd.