Millennial-scale changes in the molecular composition of Posidonia australis seagrass deposits: Implications for Blue Carbon sequestration.

• Molecular analysis of 3200 yr Posidonia australis seagrass soil record (Australia). • Tracing diagenetic effects on sheaths and root/rhizome detritus. • Ageing-induced selective degradation of polysaccharides and enrichment of lignin. • Minor constituents cutin, suberin and tannin also preferentially depleted. • Overall C storage capacity associated with lignocellulose chemical recalcitrance. Seagrass ecosystems are recognised for their role in climate change mitigation, due to their capacity to form organic-rich sediments. The chemical recalcitrance of seagrass organs is one characteristic driving carbon storage, but the molecular background of this feature is poorly understood. We assessed molecular composition changes of Posidonia australis sheaths (SH) and roots plus rhizomes (RR) along a sediment core, encompassing 3200 cal. yr BP, by means of nuclear magnetic resonance spectroscopy (13C NMR), conventional analytical pyrolysis (Py-GC–MS) and thermally assisted hydrolysis and methylation (THM-GC–MS). Significant trends with depth (age) in the composition of both SH and RR remains of P. australis were observed from all methods. In general terms, polysaccharides become depleted (degraded) and lignin enriched (selectively preserved) as age increases, and the minor constituents cutin, suberin and condensed tannin are also preferentially depleted during ageing in both fractions. Molecular changes with ageing were smaller in SH, especially regarding polysaccharides, indicative of a superior stability compared to RR. The molecular changes observed are most pronounced within the first 75 cm of the record, which reflects the recalcitrance of P. australis detritus once it is buried below that depth (corresponding to approximately 700 cal. yr BP). The capacity of P. australis to act as a long-term carbon sink seems to be mainly related to the resistance of buried lignocellulose materials to decomposition. The results on diagenetic effects on the molecular fingerprint of seagrass detritus contribute to our understanding of carbon sequestration in Blue Carbon ecosystems. Furthermore, data comparison of the methods applied using principal component analysis (PCA) allowed us to identify consistencies, discrepancies and complementarities. [ABSTRACT FROM AUTHOR]