Differential effects of clay mineralogy on thermal maturation of sedimentary n-alkanes

Clay minerals serve as important catalysts for the degradation of a range of biomolecules during diagenesis, yet their effects are seldom considered when interpreting organic molecular and isotopic data in the context of paleoenvironmental reconstruction. We investigated the thermal maturation of immature sedimentary organic matter in the presence of two clay minerals (kaolinite and montmorillonite) using a series of laboratory-based anhydrous pyrolysis experiments. Organic matter was extracted from a modern terrestrial sediment, mixed with each clay mineral, and heated at 100–300 °C for up to 30 days – in this way, initial organic matter was identical in each system. Abundances, molecular distributions, and paired compound-specific stable isotopic compositions (δDn-alkane and δ13Cn-alkane) of n-alkanes were measured as a function of heating time. For both kaolinite and montmorillonite amended experiments, the shifts in molecular distributions are highly controlled by significant secondary production of n-alkanes from molecularly large lipid precursors, as evidenced by significant increases in the total amount of n-alkanes accompanying increased thermal maturation. Significant decreases in carbon preference index (CPI) are observed before minor decreases in average chain length (ACL), leading to behavior in CPI-ACL space that is fundamentally different from identical systems free of clay minerals. Furthermore, distinct distributions of secondary n-alkanes between the clay mineral systems indicate differential mechanisms and sites of precursor degradation. In the presence of clay minerals, δ13Cn-alkane of immature bituminous organics initially decreases with increasing thermal maturation, opposite most data reported from experimental alteration of relatively mature sedimentary matter. This shift is similarly driven by secondary production of n-alkanes, arising from kinetic fractionation associated with preferential cleavage of 12C12C bonds from parent molecules – the kinetics of this process vary per clay mineralogy but are controlled by the same process. Conversely, we see an enrichment in δDn-alkane with increasing maturation, indicating control of the two isotopic systems by separate mechanisms. Moreover, kaolinite and montmorillonite exhibit differential control on δDn-alkane, leading to separate domains in dual isotopic space. Overall, the changes in δ13Cn-alkane and δDn-alkane are relatively small over the timescales studied, even at temperatures as high as 300 °C (less than ∼0.6–1‰ for δ13Cn-alkane and ∼8–15‰ for δDn-alkane). Considering these factors on a geological timescale, variations in clay mineralogy through a buried sedimentary sequence may impart matrix effects on molecular and isotopic signatures that can bias interpretation of paleoenvironmental conditions.