Seagrass contributes substantially to the sedimentary lignin pool in an estuarine seagrass meadow.

Shallow coastal ecosystems are reservoirs of carbon derived from allochthonous organic matter and autochthonous organic matter produced by microalgae and macrophytes. Carbon stored in vegetated coastal ecosystems has attracted broad attention as an important component of carbon sinks. Characterizing the source of carbon in sediments is essential for quantifying the carbon-sequestration function of shallow coastal ecosystems. In this study, we investigated the origins of organic matter using organic biomarkers (lignin phenols, fatty acids, cutin acids, diacids, and ω-hydroxy acids) in surface sediments in a seagrass-dominated lagoon (Furen Lagoon, Japan). Biomarkers derived from allochthonous vascular plants, such as long-chain fatty acids, showed higher concentrations near river mouths. Furthermore, biomarker signals indicated that sedimentary organic carbon originated in large part from degraded allochthonous vascular plants including roots. A Bayesian mixing model using the ratios of syringyl phenols to vanillyl phenols and cinnamyl phenols to vanillyl phenols indicated that up to about 65% of lignin in the sediments was derived from seagrass. This result indicates a substantial contribution of seagrass to the sedimentary lignin pool in an estuarine seagrass meadow. However, the percent contribution of seagrass to the lignin pool varied, with higher values near a tidal inlet and relatively low values near river mouths. Vertical profiles of organic biomarkers varied with the differences in degradability of organic compounds. Specifically, long-chain fatty acids decreased with increasing depth more than the other compounds, suggesting that they degraded more easily. Conversely, we observed a tendency for lignin phenols to be selectively preserved in the vertical sediment profiles. Our results show that sediment organic biomarkers can provide diverse information such as the composition and origins of organic carbon, the contribution of seagrass derived lignin, and the varying degrees of decomposition. This approach should bring new insights to the estimation of carbon in future blue carbon studies.

Methyl Ether-Derivatized Sterols and Coprostanol Produced via Thermochemolysis Using Tetramethylammonium Hydroxide (TMAH).

Sterols are widely distributed in nature from lipids in organisms to sediments. As a conventional method, extraction and derivatization with TMS have been applied for sterol analysis, requiring a long preparation time for gas chromatography-mass spectrometry analysis. In this study, for sterol analysis, thermochemolysis using tetramethylammonium hydroxide (TMAH) was applied. This method performs hydrolysis and methylation simultaneously; thus, free and ether-bonding sterols can be analyzed as sterol methyl ethers in a relatively short time period. A sediment sample from a tideland (the Yatsu tideland, Japan) was analyzed using the TMAH method, and we detected more than 10 sterols, which include cholest-5-en-3ß-ol (cholesterol), 24-ethylcholest-5-en-3ß-ol (sitosterol), 24-methylcholesta-5,22E-3ß-ol (brassicasterol), 24-ethylcholesta-5,24(28)Z-dien-3ß-ol (isofucosterol), 4α,23,24-trimethyl-5α(H)-cholest-22E-en-3ß- ol (dinosterol), and 5ß(H)-cholestan-3ß-ol (coprostanol). The detection of the various sterols can be attributed to multiple natural and artificial sources around the Yatsu tideland. In this paper, the mass spectra of these sterols are provided together with an interpretation of their fragmentation patterns. Additionally, the fecal pollution in the Yatsu tideland is discussed in the context of the detection of coprostanol.