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25th International Meeting on Organic Geochemistry IMOG 2011

25th International Meeting on Organic Geochemistry IMOG 2011

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P-204<br />

Are poriferan biomarkers preserved in the geological record? A<br />

study <strong>on</strong> sp<strong>on</strong>ge fossils and sp<strong>on</strong>ge-rich sediments of various<br />

ages<br />

Juliane Germer, Martin Blumenberg, Joachim Reitner, Volker Thiel<br />

Georg-August-University, Göttingen, Germany (corresp<strong>on</strong>ding author:jgermer@gwdg.de)<br />

Sp<strong>on</strong>ges are c<strong>on</strong>sidered to be the most ancient<br />

metazoans. 14 fossilized sp<strong>on</strong>ges and sediments<br />

c<strong>on</strong>taining abundant sp<strong>on</strong>ge remains were extracted<br />

to test the preservati<strong>on</strong> potential of four classes of<br />

sp<strong>on</strong>ge-derived lipid biomarkers in the bitumen<br />

fracti<strong>on</strong>s of geological samples (mid-chain branched<br />

fatty acids, demosp<strong>on</strong>gic acids, sterols and<br />

brominated sec<strong>on</strong>dary metabolites). Modern sp<strong>on</strong>ges<br />

and sp<strong>on</strong>ge-microbial carb<strong>on</strong>ate crusts were used as<br />

reference materials.<br />

The recent samples c<strong>on</strong>tain large amounts of midchain<br />

branched fatty acids (MBFA) characterized by a<br />

remarkable variety of structural isomers in the C16 to<br />

C26 range. Specific, yet unknown sp<strong>on</strong>ge-associated<br />

bacteria are suggested to be the producers of shortchain<br />

MBFA (C16 – C19) which are subsequently<br />

el<strong>on</strong>gated by the sp<strong>on</strong>ge cells to l<strong>on</strong>g-chain MBFA [1].<br />

M<strong>on</strong>omethylated mid-chain branched alkanes,<br />

potential diagenetic derivatives of MBFA, occurred in<br />

small amounts in some of the ancient samples<br />

studied. These compounds showed, as well as the<br />

MBFA, a great variety of structural isomers in the C16<br />

– C20 range. Comparis<strong>on</strong>s with the hydrocarb<strong>on</strong><br />

compositi<strong>on</strong>s of ancient carb<strong>on</strong>ates and the fatty acid<br />

and desulphurized hydrocarb<strong>on</strong> patterns of a recent<br />

demosp<strong>on</strong>ge suggested that MBFA represent<br />

plausible biological precursors of mid-chain branched<br />

alkanes found in the ancient materials. However,<br />

interpretati<strong>on</strong>s should be drawn with cauti<strong>on</strong>, since<br />

other n<strong>on</strong>-sp<strong>on</strong>ge sources may also account for midchain<br />

branched alkanes in ancient sediments.<br />

L<strong>on</strong>g-chain demosp<strong>on</strong>gic acids (Δ 5,9 unsaturated,<br />

≥C24) are widespread in members of the sp<strong>on</strong>ge<br />

classes Demosp<strong>on</strong>giae and Hexactinellida. However,<br />

no plausible geological derivatives could be<br />

recognized in ancient sp<strong>on</strong>ge-derived sediments,<br />

suggesting that these compounds do not provide<br />

suitable biomarkers for the c<strong>on</strong>tributi<strong>on</strong> of sp<strong>on</strong>gederived<br />

organic matter in the bitumen fracti<strong>on</strong>s of<br />

ancient sediments.<br />

Using MS/MS, the samples were carefully examined<br />

for 24-isopropycholesterol and its geological<br />

counterpart, 24-isopropylcholestane (24-ipc), whose<br />

presence in ancient sediments and oils has been<br />

proposed to record the first occurrence of metazoans<br />

in the geological biomarker record [2][3]. However, no<br />

24-ipc was detected in the ancient sp<strong>on</strong>ge-derived<br />

samples.<br />

Brominated organic compounds, potentially derived<br />

from sec<strong>on</strong>dary metabolites, were observed as trace<br />

compounds in the majority of the ancient samples<br />

studied. These structures, however could not be<br />

unambiguously assigned to biogenetic sources, but<br />

may also be due to anthropogenic c<strong>on</strong>taminati<strong>on</strong>,<br />

which argues against an applicati<strong>on</strong> of brominated<br />

sec<strong>on</strong>dary compounds as sp<strong>on</strong>ge-derived<br />

biomarkers.<br />

Additi<strong>on</strong>ally, two methane-seep derived carb<strong>on</strong>ates<br />

c<strong>on</strong>taining ample sp<strong>on</strong>ge fossils were investigated for<br />

their potential to preserve poriferan biomarkers under<br />

c<strong>on</strong>diti<strong>on</strong>s of early and rapid lithificati<strong>on</strong>. It was found<br />

that signals from the microbial anaerobic oxidati<strong>on</strong> of<br />

methane were preserved remarkably well in these<br />

seep carb<strong>on</strong>ates, but again, no distinctive sp<strong>on</strong>ge<br />

biomarkers were detected.<br />

Summarizing, this study did not reveal a preservati<strong>on</strong><br />

of sp<strong>on</strong>ge-cell derived biomarkers in the bitumen<br />

fracti<strong>on</strong>s of ancient samples.<br />

1. Pape, T., Lipidbiomarker<br />

schwammassoziierter Bakterien und<br />

Archaeen, in Institute of Biogeochemistry<br />

and Marine Chemistry. 2003, University of<br />

Hamburg: Hamburg. p. 164.<br />

2. McCaffrey, M.A., et al., Paleoenvir<strong>on</strong>mental<br />

implicati<strong>on</strong>s of novel C30 steranes in<br />

Precambrian to Cenozoic age petroleum and<br />

bitumen. Geochimica et Cosmochimica Acta,<br />

1994. 58: p. 529-532.<br />

3. Love, G.D., et al., Fossil steroids record the<br />

appearance of Demosp<strong>on</strong>giae during the<br />

Cryogenian period. Nature, 2009. 457(7230):<br />

p. 718-721.<br />

343

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