Diagenesis of plant biopolymers: Decay and macromolecular preservation of Metasequoia

Analysis of modern Metasequoia leaves revealed the presence of the structural polyester cutin, guaiacyl lignin units and polysaccharides. Analysis of environmentally decayed Metasequoia leaves revealed that guaiacyl lignin units and cellulose were degraded more than vinyl phenol (the last being the primary pyrolysis product of cutin and plant cuticles) suggesting that cutin is more stable than lignin and cellulose during degradation, contrary to some previous studies. This observation is supported by electron microscopy showing changes in the cellular structure and cuticle of modern, decayed and fossil Metasequoia leaves. Metasequoia fossils from the Eocene of Republic (Washington State) showed a significant aliphatic component, but biopolymeric lignin and polysaccharides were not detected. Fossils from the Eocene of Axel Heiberg revealed the presence of lignin and an aliphatic polymer up to C29 with cellulose, and fossils from the Miocene Clarkia deposit (Idaho) revealed lignin and an aliphatic polymer up to C27 without any polysaccharides. Modern Metasequoia needles heated experimentally in confined conditions generated a macromolecular composition with an aliphatic polymer up to C32 and additional phenolic compounds similar to those present in the fossils. Experimental heating of cutin is known to generate an aliphatic polymer with carbon chain length units <C20. Thus, the n-alkyl component with chain length units >C20 in the heated Metasequoia needles is a product of incorporation of longer chain plant waxes, indicated by the odd/even predominance of the >C27 n-alkanes. The resistant nature of cutin compared to lignin and polysaccharides explains the presence of an n-alkyl component (<C20) in fossil leaves even when polysaccharides are absent and lignin has decayed; cutin and its diagenetically altered products contribute significantly to the presence of aliphatic components in terrestrially derived sedimentary organic matter.