Early diagenetic transformation of higher-plant triterpenoids in deep-sea sediments from Baffin Bay

Abstract

A sediment sequence of early Miocene to Holocene from Ocean Drilling Program Site 645 in central Baffin Bay was found to contain abundant triterpenoids of higher-plant origin including monodesmethyl derivatives and other oxidative degradation products. 24-nor-triterpenoids of the oleanene, ursene, and lupane series were found in the nonaromatic hydrocarbon and alcohol fractions of the sediment extracts. Other diagenetic transformation products included 24,28- dinor-olean-17-ene and 24- nor-urs-12-en-1 1-one as well as their tentatively identified des-A counterparts. The identification of these novel degradation products was confirmed by synthesis of a suite of reference compounds. The simple reaction sequence applied to obtain 24- nor-urs-12-ene from 3α-acetoxyurs-12-en-24-oic acid is likely to happen in a similar manner during early diagenesis of organic matter in nature. These results have implications for the understanding of the diagenetic reaction sequence leading to the formation of other demethylated triterpenoids of terrigenous origin (e.g., 24,28- dinor-lupanes). 28,30- dinor-17α-hopane is sometimes the dominant hydrocarbon in the most deeply buried samples. Its co-occurrence with higher plant triterpenoids and the low abundance of other regular hopanoids is not considered an indication, however, that 28,30 dinor-17α-hopane is derived from a higher plant precursor molecule. It is suggested that two independent sedimentary processes are responsible for the presence of the two types of demethylated triterpenoids observed in Baffin Bay sediments.