The unsaturation patterns of molecular fossils are critical in distinguishing their biological precursors and diagenetic processes. However, questions regarding the determination of double-bond positions of unsaturated dialkyl glycerol ethers (DAGEs) in submarine hydrocarbon seep ecosystems remain unsolved. To address this problem, a protocol for dimethyl disulfide (DMDS) derivative analysis using gas chromatography (GC)-mass spectrometry was optimised. Herein, the double-bond positions of monounsaturated short-chain alcohols, monoalkyl glycerol ethers (MAGEs), and DAGEs in seep carbonates were analysed. Among these compounds, the double-bond positions of trimethylsilyl (TMS) derivatives of the monounsaturated DAGE-DMDS adducts were determined for the first time, with mass spectra characterized by molecular ions (M+·) and two major diagnostic ions (ω+ and Δ+) cleaved at the double bonds. For both the MAGEs and DAGEs, the double-bond positions of the monounsaturated n-C16:1-alkyl moieties were identified at ω5 and ω7. Compared to monounsaturated short-chain alcohols and MAGEs, both ionization efficiency and relative sensitivity for the TMS derivatives of DAGE-DMDS adducts were low as indicated by the high limit of detection at a signal-to-noise ratio of 3. In addition, the appropriate injection parameters and oven temperature program during GC analyses may be crucial in determining the double-bond positions within monounsaturated DAGEs.
Keywords: Dimethyl disulfide (DMDS); Double-bond position; Gas chromatography-mass spectrometry (GC-MS); Monounsaturated alkyl glycerol ether lipids; Seep carbonate.
Copyright © 2022 Elsevier B.V. All rights reserved.