Novel methyl-branched alkenones with up to five double bonds in saline lakes

Abstract

Long-chain alkenones, a class of highly specific and widely used lipid biomarkers found in ocean and lake sediments, have been so far found as straight-chain alkyl ketones with 2 to 4 double bonds. Jaraula et al. (2010) reported assignments of a series of tri- to penta-unsaturated alkenones as straight-chain C38 methyl (C38Me) and C39 ethyl (C39Et) alkenones in Lake Fryxell, Antarctica. The same series of compounds were later found in sediments from Lake Van (Randlett et al., 2014). The structure assignments by Jaraula et al (2010) were primarily based on strong ions at [M−43]+ for C38 alkenones and [M−57]+ for C39 alkenones, which were interpreted as a loss of CH3CO and CH3CH2CO groups. However, such fragmentation is atypical for common straight-chain methyl and ethyl alkenones. In this study, we reanalyzed Lake Van sediment samples. We show these new C38 and C39 alkenones elute earlier than the common straight-chain C38Me and C39Et alkenones on a mid-polarity GC column. After hydrogenation, mass spectra of these new alkenones show distinct peaks at m/z 72 or 86 caused by McLafferty rearrangement, indicating a methyl substitution at the α position of the carbonyl group in these C38 and C39 alkenones (i.e., α-methyl-branched C38Me and C39Et). Our new assignments as methyl-branched alkenones are further confirmed by the synthesis of an analog α-methyl C25 methyl ketone and comparison of mass spectra. Double bond positions for branched C38:5Me (brC38:5Me) are found to be Δ4, Δ7, Δ14, Δ21 and Δ28 based on the mass spectrum of corresponding dimethyl disulfide adducts. Analysis of Lake Van alkenone data reveals that Ubr38MeK∗ based on brC38Me shows a trend similar to U37K for the past 270 ka, suggesting that the degree of unsaturation of branched alkenones is also sensitive to temperature.