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25th International Meeting on Organic Geochemistry IMOG 2011

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P-468<br />

Carb<strong>on</strong> isotopic compositi<strong>on</strong> of Thaumarchaeotal ether-bound<br />

biphytanes during the early Eocene carb<strong>on</strong> isotope excursi<strong>on</strong>s<br />

Petra Scho<strong>on</strong> 1 , Appy Sluijs 2 , Henk Brinkhuis 2 , Claus Heilmann-Clausen 3 , Bo Pagh<br />

Schultz 4 , Jaap Sinninghe Damsté 1 , Stefan Schouten 1<br />

1 NIOZ Royal Netherlands Institute for Sea Research, Department of <strong>Organic</strong> Biogeochemistry, 't Horntje,<br />

Texel, Netherlands, 2 Biomarine Sciences, Institute of Envir<strong>on</strong>mental Biology, Faculty of Science, Utrecht<br />

University, Utrecht, Netherlands, 3 Aarhus Universitet, Geologisk Institut, Aarhus, Denmark, 4 Fur Museum,<br />

Fur, Denmark (corresp<strong>on</strong>ding author:petra.scho<strong>on</strong>@nioz.nl)<br />

Marine n<strong>on</strong>-thermophilic archaea (recently<br />

reclassified within the new phylum Thaumarchaeota<br />

[1]) are important organisms am<strong>on</strong>g present day<br />

marine microbes. Their membrane lipids, analyzed as<br />

glycerol dialkyl glycerol tetraethers (GDGTs) by<br />

means of HPLC, or as biphytane moieties after<br />

laboratory ether-b<strong>on</strong>d cleavage with HI/LIAlH4, are<br />

ubiquitous, and are found in recent and ancient<br />

sediments [2]. Crenarchaeol is thought to be a<br />

specific GDGT for Thaumarchaeota and c<strong>on</strong>sists of<br />

two biphytanes, <strong>on</strong>e with two cyclopentyl moieties and<br />

the other with an additi<strong>on</strong>al cyclohexyl moiety (c and<br />

d; Fig. 1A). Stable carb<strong>on</strong> isotopic measurements of<br />

these bihytanes have revealed a remarkably<br />

c<strong>on</strong>sistent � 13 C value of ca. 20-22 ‰ [2]. As archaea<br />

utilize dissolved bicarb<strong>on</strong>ate as carb<strong>on</strong> source [3],<br />

variati<strong>on</strong>s in � 13 C of the biphytanes may thus reflect<br />

variati<strong>on</strong>s in � 13 C of DIC. Indeed, this can probably<br />

explain the enrichment in biphytane 13 C c<strong>on</strong>tent<br />

during the Cretaceous anoxic event 1b [3]. However,<br />

the c<strong>on</strong>trolling factors <strong>on</strong> the stable carb<strong>on</strong> isotopic<br />

compositi<strong>on</strong> of crenarchaeol are not well known.<br />

Here we report the results of � 13 C analyses of<br />

biphytanes from crenarchaeol, and other GDGTs, in<br />

sediments deposited during two Eocene<br />

hyperthermals. The Paleocene-Eocene Thermal<br />

Maximum (PETM; ~55 Ma) and Eocene Thermal<br />

Maximum 2 (ETM2; ~53 Ma) are geological short<br />

episodes of extreme global warming and<br />

envir<strong>on</strong>mental change. Furthermore, both events are<br />

characterized by a negative carb<strong>on</strong> isotope excursi<strong>on</strong><br />

(CIE) of several ‰, induced by the injecti<strong>on</strong> of 13 Cdepleted<br />

carb<strong>on</strong> in the ocean-atmosphere system.<br />

However, am<strong>on</strong>g the various carb<strong>on</strong> reservoirs, such<br />

as marine and terrestrial carb<strong>on</strong>ates, the magnitude<br />

of the CIEs vary, making it difficult to c<strong>on</strong>strain the<br />

actual CIE and thereby the amount of carb<strong>on</strong> that was<br />

involved during these hyperthermals. Our � 13 C results<br />

of sediments deposited in the Arctic Ocean showed<br />

that at maximum of the CIE of ETM2, crenarchaeol<br />

was ~2.5 ‰ more negative than prior to the event.<br />

However, this � 13 C negative shift of the biphytanes<br />

coincided with peak c<strong>on</strong>centrati<strong>on</strong>s of derivatives of<br />

the specific biomarker isorenieratene and during<br />

cooler sea water temperatures inferred from TEX86.<br />

This may imply that the Thaumarchaeota resp<strong>on</strong>ded<br />

to the arising euxinic c<strong>on</strong>diti<strong>on</strong>s at this locati<strong>on</strong> by<br />

migrating to below the chemocline. It is therefore not<br />

certain whether this 2.5 ‰ truly reflects the CIE in<br />

DIC. In additi<strong>on</strong>, changing climate and oceanography<br />

may have altered the � 13 C of DIC differently in this<br />

relatively restricted basin than in the global ocean.<br />

Currently we are analyzing the � 13 C compositi<strong>on</strong> of<br />

GDGTs in sediments deposited during the PETM, at<br />

three off-shore secti<strong>on</strong>s in Denmark. This may<br />

provide the first c<strong>on</strong>tinuous � 13 C DIC record across an<br />

Eocene hyperthermal and may provide knowledge <strong>on</strong><br />

the CIE in the DIC pool during the PETM.<br />

Fig. 1. Structure of acyclic and cyclic biphytanes (A) and<br />

their distributi<strong>on</strong> (B) in a sediment deposited during ETM2<br />

with their corresp<strong>on</strong>ding � 13 C values.<br />

References<br />

[1] Spang et al. (2010), Trends Microbiol 18, pp. 331–340.<br />

[2] Schouten et al. (1998), Org. Geochem. 29, pp. 1305-<br />

1319.<br />

[3] Kuypers et al. (2001), Science 293, pp. 92-94.<br />

593

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