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25th International Meeting on Organic Geochemistry IMOG 2011

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O-53<br />

Biomarkers and stable isotopes of euxinia and their role in fossil<br />

preservati<strong>on</strong><br />

Ines Melendez 1 , Kliti Grice 1 , Kate Trinajstic 1 , Katherine Thomps<strong>on</strong> 1 , Mojgan Ladjaverdi 1 ,<br />

Arndt Schimmelmann 2 , Paul Greenwood 3<br />

1 WA <strong>Organic</strong> and Isotope <strong>Geochemistry</strong> Centre, Department of Chemistry, Curtin University of Technology,<br />

Perth, Australia, 2 Indiana University, Dept. of Geological Sciences, Bloomingt<strong>on</strong>, United States of America,<br />

3 University of Western Australia, Perth, Australia (corresp<strong>on</strong>ding author:ines.melendez@curtin.edu.au)<br />

The Gogo Formati<strong>on</strong>, located in the Canning Basin,<br />

north-western Western Australia, shows remarkable<br />

preservati<strong>on</strong> of a Late Dev<strong>on</strong>ian (380 MYA) reef<br />

fauna. The excepti<strong>on</strong>al preservati<strong>on</strong>, including original<br />

b<strong>on</strong>e and mineralized soft tissues, has resulted from a<br />

combinati<strong>on</strong> of rapid burial and cementati<strong>on</strong> within a<br />

relatively tect<strong>on</strong>ically stable envir<strong>on</strong>ment. Soft-tissues,<br />

including muscle bundles, nerve cells, and umbilical<br />

structures, have been identified and described in the<br />

vertebrate fauna (1, 2, 3). Through improved sampling<br />

and preparati<strong>on</strong> techniques extensive areas of soft<br />

tissue have now been recovered from the Gogo<br />

Formati<strong>on</strong>. However, the exact mode of preservati<strong>on</strong><br />

is yet to be determined.<br />

To determine the palaeoenvir<strong>on</strong>mental c<strong>on</strong>diti<strong>on</strong>s that<br />

resulted in the excepti<strong>on</strong>al preservati<strong>on</strong> of the ―Gogo‖<br />

Formati<strong>on</strong> an invertebrate fossil, c<strong>on</strong>taining soft<br />

tissue, and the carb<strong>on</strong>ate nodule were investigated<br />

for the presence of biomarkers.<br />

The nodule was divided in two with <strong>on</strong>ly <strong>on</strong>e half used<br />

for the experiments described below. The fossil was<br />

extracted and separated into different fracti<strong>on</strong>s.<br />

Dominant n-alkanes ranging from C15 to C32<br />

(maximizing at n-C18 and n-C25) were identified. Their<br />

� 13 C (-34 ‰ to -40 ‰) and �D values c<strong>on</strong>sidering Denrichment<br />

produced by thermal maturity (-230 ‰ to<br />

270 ‰) are c<strong>on</strong>sistent with a source from<br />

chemotrophic sulfate reducing bacteria (4, 5, 6). In<br />

additi<strong>on</strong>, the fossilised matrix was dominated by<br />

cholestane (with a � 13 C value of -30.5 ‰) �bearing the<br />

22R isomer (biological stereoisomer, reflecting an<br />

immature signal) and high relative amounts of<br />

phytane (� 13 C value of -34 ‰) probably derived from<br />

sterols and chlorophyll of phytoplankt<strong>on</strong>, respectively<br />

in the upper water column <strong>on</strong> which the crustacean<br />

used for its diet (7).<br />

The desulfurised polar fracti<strong>on</strong> (using Raney Nickel)<br />

yielded a similar distributi<strong>on</strong> of biomarkers to those<br />

found in the free bitumen fracti<strong>on</strong>. This observati<strong>on</strong> is<br />

remarkable for a sample 380 milli<strong>on</strong> years old. This<br />

data supports rapid burial and preservati<strong>on</strong> through<br />

sulfurisati<strong>on</strong> during the early stages of diagenesis.<br />

C<strong>on</strong>sistent with this hypothesis is the presence of<br />

abundant Chlorobi biomarkers present in both the free<br />

bitumen and sulfurised polar fracti<strong>on</strong>. Markers of<br />

Chlorobi, like isorenieratane and derivatives<br />

therefrom, globally identified across Permian/Triassic<br />

mass extincti<strong>on</strong> boundary, have also been identified<br />

here also supporting photic z<strong>on</strong>e euxinic c<strong>on</strong>diti<strong>on</strong>s<br />

(H2S and light) in the water column (8, 9).These<br />

results also support a recent study (10) which has<br />

dem<strong>on</strong>strated that the Gogo Formati<strong>on</strong>, Western<br />

Australia, and the equivalent aged - Duvernay<br />

Formati<strong>on</strong>, western Canada (and their associated<br />

oils) were deposited under highly euxinic c<strong>on</strong>diti<strong>on</strong>s<br />

based <strong>on</strong> the presence of biomarkers associated with<br />

Chlorobi.<br />

In marked c<strong>on</strong>trast to the immaturity reflected by the<br />

sterane distributi<strong>on</strong>s, the Ts/Tm ratio (0.62) of the<br />

sample supports late thermal maturity. In order to<br />

investigate the variati<strong>on</strong>s in maturity reflected by<br />

these different biomarkers the sec<strong>on</strong>d bitumen (after<br />

isolati<strong>on</strong> of kerogen) through heavy mineral<br />

separati<strong>on</strong> has been performed and compared with<br />

the other fracti<strong>on</strong>s from the free bitumen (cf. work<br />

carried out by 11).<br />

(1) K. Trinajstic et al., Biology Letters 3(2),197-200 (2007)<br />

(2) J. A. L<strong>on</strong>g et al., Nature 453:650–652 (2008)<br />

(3) J. A. L<strong>on</strong>g and K. Trinajstic, Annual Reviews of Earth and<br />

Planetary Sciences 38, 255- 270 (2010)<br />

(4) K. L<strong>on</strong>dry and D. Des Marais. Appl. Envir<strong>on</strong>. Microbiol.<br />

69:2942–2949 (2003)<br />

(5) K. L<strong>on</strong>dry et al., Appl. Envir<strong>on</strong>. Microbiol. 70:745–751 (2004)<br />

(6) X. Zhang et al., PNAS 106(31):12580-12586 (2009)<br />

(7) K. Grice et al., Paleoceanography 13, 686-693 (1998)<br />

(8) K, Grice et al., (2005) Science 307, 706-709.<br />

(9) B. Nabbefeld et al., Earth and Planetary Science Letters 291,<br />

84–96 (2010a)<br />

(10) E. Maslen et al., <strong>Organic</strong> <strong>Geochemistry</strong> 49, 1–17 (2009)<br />

(11) B. Nabbefeld et al., <strong>Organic</strong> <strong>Geochemistry</strong> 41, 78–87 (2010b)<br />

113

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