The origin and fate of 4-methyl steroids—II. Dehydration of stanols and occurrence of c30 4-methyl steranes

Certain features of the distributions of sedimentary 4-methyl steroid hydrocarbons have been investigated: (i) competitive dehydration experiments with stanols adsorbed on a shale suggests a possible explanation for the low abundance of 4-methyl sterenes relative to their desmethyl counterparts in immature sediments, (ii) a 4-methyl spirostene which is a minor product of the backbone rearrangement of 4-methylcholest-4-ene in the laboratory has been tentatively assigned; its presence in a Toarcian black shale with a second isomer provides further evidence that the sedimentary backbone rearrangement of 4-methyl sterenes is analogous to that of their desmethyl counterparts and (iii) the major C₃₀ 4-methyl steranes in Semécourt shale (Toarcian, Paris Basin) differ from those in an Eocene lacustrine shale from China; this indicates the potential complexity of C₃₀ steroidal alkanes (both 4-methyl and desmethyl) which can occur in sedimentary organic matter and shows that care must be taken in using m/z 217 mass chromatograms alone for routine input and maturity assessment using steroidal alkanes.