Search

Highlights • Molecular composition of Posidonia oceanica and P. australis seagrasses compared. • Lignin of P. oceanica has an extraordinary abundance of p -hydroxybenzoic acid. • p -hydroxybenzoates attach to the γ-OH of the lignin side-chains. • Lignin composition may explain higher carbon storage capacity of P. oceanica. Abstract There is considerable variability in the ability of seagrass ecosystems to sequester organic carbon (C org) in their sediments, which act as natural carbon sinks contributing to climate change mitigation. In this work, we studied the chemistry of two Posidonia seagrass species aiming to elucidate whether differences in chemical composition might explain differences in their C org sequestration capacity. Pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) and Thermally assisted Hydrolysis and Methylation (THM) GC-MS data showed a remarkable difference in phenolic compound patterns between P. oceanica and P. australis bulk plants and individual organs (leaves, sheaths, roots and rhizomes). The lignin of P. australis generates a series of p -hydroxyphenyl (H), guaiacyl (G) and syringyl (S) products that are typical of herbaceous plants, whereas P. oceanica is particularly rich in p -hydroxybenzoic acid (p BA) derivatives. The structural characteristics of the lignins were further investigated by two-dimensional Nuclear Magnetic Resonance (2D-NMR) spectroscopy and Derivatization Followed by Reductive Cleavage (DFRC), focusing on sheath tissues. The analyses confirmed important differences in the lignin content (19.8% in P. australis and 29.5% in P. oceanica) and composition between the two species; intriguingly, the cell-walls of P. oceanica sheaths were highly enriched in p BA, a component that was completely absent in P. australis. 2D-NMR and DFRC data further revealed that p BA was esterified to the lignin, acylating the γ-OH of the lignin side-chain. Interestingly, P. oceanica lignin presented an extremely high degree of p -hydroxybenzoylation in both guaiacyl (73%) and syringyl (61%) lignin units; the highest p -hydroxybenzoylation degree reported in plant lignins to date. It is tempting to conclude that the higher C org storage capacity of P. oceanica ecosystems might be related to the higher abundance of p BA-rich lignin and its recalcitrant nature. [ABSTRACT FROM AUTHOR]

• 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]