Natural product biomarkers as indicators of sources and transport of sedimentary organic matter in a subtropical river

The sources and transformations of sedimentary organic matter along the Harney River, a representative subtropical river of the Florida Everglades, were assessed using a natural product biomarker approach. Sediment samples were collected from the headwaters to the Continental Shelf, with characteristic vegetation dominated by freshwater marsh species, mangrove (middle to lower estuary), and seagrass as the marine end-member. A peat sample was collected inland. All sample extracts were analyzed by GC–MS as underivatized and as silylated compounds. With these total extract analyses, major compound classes can be defined: n-alkanols, n-alkanoic acids, methyl alkanoates, methyl - and ω-hydroxyalkanoates, triterpenoids, phytosterols and saccharides, with traces of hydrocarbons. In general, the peat sample extract has a different overall composition compared to the sediment extracts. The major differences include distinct carbon number maxima for the lipid series (e.g., C_max = 28 for n-alkanols) probably from sawgrass and periphyton biomass, and predominance of phytosterols (sitosterol and stigmasterol) from higher plant detritus. In contrast, river sediment extracts contain biomarkers predominantly from mangrove-derived organic matter, such as the triterpenoids taraxerol and myricadiol. Significant amounts of saccharides and ω-hydroxyalkanoates are also found. Generally, compound concentrations decrease downstream due to dilution, and alteration of organic compounds from plant waxes and coastal vegetation is obvious in both peat and sediment samples. This is confirmed by the significant low abundance of n-alkanes and n-alkenoic acids due to biodegradation, oxidation of -tocopherol to homophytanic acid γ-lactone, and presence of traces of dihydrolacunosic acid, a photochemical alteration product of taraxerol.