Unusual C35 to C38 alkenones in mid-Holocene sediments from a restricted estuary (Charlotte Harbor, Florida)

Abstract

Unusual C35 to C38 alkenones were identified in mid-Holocene (8–3.5kyr BP) sediments from a restricted estuary in southwest Florida (Charlotte Harbor). The distribution was dominated by a C36 diunsaturated (ω15,20) ethyl ketone, identical to the one present in Black Sea Unit 2 sediments. Other unusual alkenones were tentatively assigned as a C35:2 (ω15,20) methyl ketone, a C37:2 (ω17,22) methyl ketone and a C38:2 (ω17,22) ethyl ketone. In late Holocene sediments<3.5kyr BP, the common C37 to C39 alkenones were found. Compound-specific 14C, 13C, and D isotope measurements were used to constrain the possible origin of the alkenones. Conventional radiocarbon ages of alkenones and higher plant-derived long chain n-alcohols indicated no significant difference in age between mid-Holocene alkenones and higher plant n-alcohols. Both alcohols and alkenones were offset vs. calibrated ages of shell fragments in the same sediment core, which suggests they were pre-aged by 500–800yr, implying resuspension and redistribution of the fine-grained sedimentary particles with which they are associated. The hydrogen isotopic (δD) composition (−190‰ to −200‰) of the C37 and C38 alkenones in the late Holocene sediments is in line with values for coastal haptophytes in brackish water. However, the unusual C36 and C38 alkenones from the mid Holocene sediments were enriched in D (by ca. 100‰) vs. the late Holocene alkenones. Also, δ13C values of mid-Holocene alkenones were consistently offset compared with late Holocene alkenones (−21‰ to −22‰ and −22‰ to −23‰, respectively). We suggest that the alkenones in Charlotte Harbor were produced by unknown alkenone-producing haptophyte.