Geochemical analysis of steranes in source rocks from the Western Canada Basin has allowed the identification of several C 21 and C 22 short-chain sterane isomers. The principal compounds in carbonates from the U. Jurassic Nordegg Formation have been identified as diginane and homodiginane, more thermodynamically-stable isomers of the compounds pregnane and homopregnane that have 5α, 14β, 17β(H) stereochemistry. The Triassic Doig formation also contains two compounds tentatively identified on the basis of geologic and geochemical data as diapregnane and diahomopregnane, rearranged isomers of pregnane and homopregnane with methyl substitution at the 5- and 14-carbon positions. The distribution of these compounds parallels that of the higher molecular weight diasteranes. A well-defined relationship is evident between the ratio Fe/S and short-chain diasterane content: samples with Fe/S approximately <0.90 exhibit low diasterane contents, while those with Fe/S approximately >0.90 exhibit high diasterane content. This threshold Fe/S value is nearly equal to the value associated with stoichiometric pyrite (0.87) and suggests that the abundance of short-chain diasteranes is related to excess iron associated with detrital clays. This is consistent with the accepted mechanism of sterane rearrangement, which is thought to proceed via catalysis of clay minerals. In contrast to the higher molecular-weight diasteranes, which increase in abundance relative to other sterane isomers with increasing thermal maturation, the abundance of the rearranged short-chain compounds varies little relative to diginane or homodiginane in a maturity suite from the U. Devonian Duvernay Formation. Predicted stabilities based on computational chemistry agree with the observed distributions; diginane/diapregnane and homodiginane/homodiapregnane represent compound pairs with similar thermal stabilities. The relative invariance of short-chain sterane distributions with maturity suggest that these compounds may be better suited for estimating the clastic content (i.e., Fe/S ratio) of source rocks than the higher molecular-weight steranes, which are both maturity and facies dependent. Copyright © 1997 Elsevier Science Ltd.