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25th International Meeting on Organic Geochemistry IMOG 2011

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P-173<br />

Oxidati<strong>on</strong> and physical protecti<strong>on</strong> of organic matter by mineral<br />

matrix : their influence <strong>on</strong> the diagenesis of hopanoids<br />

Yann Hautevelle, Apolline Lefort, Pierre Faure, Raym<strong>on</strong>d Michels<br />

UMR7566 G2R, CNRS, Nancy Université, Vandoeuvre-lès-Nancy, France (corresp<strong>on</strong>ding<br />

author:yann.hautevelle@g2r.uhp-nancy.fr)<br />

Hopanoids are am<strong>on</strong>g the most abundant<br />

organic compounds in the geosphere. Their<br />

distributi<strong>on</strong> is classically studied in organic<br />

geochemistry for assessing the thermal history of<br />

sedimentary series. Indeed, it is now well known that<br />

hopanoids are biosynthesized under a<br />

thermodynamic unstable biological c<strong>on</strong>formati<strong>on</strong>.<br />

Furthermore, thermal immature sedimentary rocks are<br />

typically characterized by the presence of hopenes.<br />

During thermal stress, hopenes are hydrogenized into<br />

hopanes, the 22S isomer appears for each<br />

homohopanes and the biological c<strong>on</strong>formati<strong>on</strong> is<br />

transformed into the more stable geological<br />

c<strong>on</strong>formati<strong>on</strong>.<br />

However, some of our work suggests that the<br />

classical interpretati<strong>on</strong> of hopane distributi<strong>on</strong>s, based<br />

<strong>on</strong> the influence of heating, should be moderated due<br />

to the fact that other stresses, like oxidati<strong>on</strong>, have a<br />

similar incidence <strong>on</strong> the diagenesis of hopanoids.<br />

Indeed, experiments show that oxidati<strong>on</strong> of the<br />

thermally immature Callovian-Oxfordian clayst<strong>on</strong>es<br />

from the east of the Paris basin also induces a<br />

progressive decrease of hopenes, the appariti<strong>on</strong> of<br />

22S isomers as well as the transformati<strong>on</strong> of<br />

biological c<strong>on</strong>formati<strong>on</strong> into the geological.<br />

We also studied these Callovian-Oxfordian<br />

clayst<strong>on</strong>es as well as their Oxfordian surrounding<br />

limest<strong>on</strong>es. The clayst<strong>on</strong>es are characterized by a<br />

clearly immature distributi<strong>on</strong> of hopanoids<br />

(abundance of hopenes, hopanes in the biological<br />

c<strong>on</strong>formati<strong>on</strong> and the large predominance of the 22R<br />

epimers over the 22S). Surprisingly, a more mature<br />

distributi<strong>on</strong> was found in the limest<strong>on</strong>es (lower<br />

abundance of hopenes, the presence of higher<br />

proporti<strong>on</strong> of hopanes in the geological c<strong>on</strong>formati<strong>on</strong><br />

and the significant presence of 22S epimers). In this<br />

case, thermicity cannot be invoked to explain this<br />

discrepancy because the Oxfordian limest<strong>on</strong>es lie<br />

above the clayst<strong>on</strong>es and their temperature has not<br />

exceeded 50°C since depositi<strong>on</strong>. So, another<br />

explanati<strong>on</strong> must be advanced to account for this<br />

difference. As oxidati<strong>on</strong> seems to have a similar effect<br />

than thermicity <strong>on</strong> hopanoid distributi<strong>on</strong>s, we can<br />

expect that the ―mature‖ distributi<strong>on</strong> characterizing the<br />

limest<strong>on</strong>es can be related to a more intense post-<br />

depositi<strong>on</strong>al oxidati<strong>on</strong>. At the opposite, the hopane<br />

distributi<strong>on</strong> indicates that the organic matter of the<br />

clayst<strong>on</strong>es was not oxidized although the deposit<br />

c<strong>on</strong>diti<strong>on</strong>s were also oxic. This can be explained by a<br />

protective matrix effect of clay minerals.<br />

In the Cretaceous siltites of Marcoule, we show that<br />

hopanoids also underwent oxidati<strong>on</strong> but <strong>on</strong>ly in<br />

specific layers associated to bioturbati<strong>on</strong>. In this case,<br />

oxidati<strong>on</strong> seems to be favored by the disturbati<strong>on</strong> of<br />

the embedding sediment which lowers the protective<br />

matrix effect.<br />

More recently, we focused our investigati<strong>on</strong><br />

<strong>on</strong> the carb<strong>on</strong>ate Oxfordian-Kimmeridgian platform at<br />

Gudm<strong>on</strong>t-Villiers (Eastern Paris basin). These<br />

limest<strong>on</strong>es were deposited in a lago<strong>on</strong> & shallow<br />

marine envir<strong>on</strong>ments. They present an alternati<strong>on</strong> of<br />

carb<strong>on</strong>ate mudst<strong>on</strong>e and grainst<strong>on</strong>e beds. These<br />

deposits underwent a similar and very low thermicity<br />

after their depositi<strong>on</strong> since they are located above the<br />

Callovo-Oxfordian clayst<strong>on</strong>es. In this case, carb<strong>on</strong>ate<br />

mudst<strong>on</strong>e beds also present a typically ―immature‖<br />

distributi<strong>on</strong> of hopanes while the grainst<strong>on</strong>es show a<br />

more ―mature‖ distributi<strong>on</strong>. Once again, thermicity<br />

cannot be at the origin of this discrepancy. However,<br />

mudst<strong>on</strong>es are associated to a settling hydrodynamic<br />

regime and are rather impermeable, while grainst<strong>on</strong>es<br />

are related to more agitated c<strong>on</strong>diti<strong>on</strong>s and typically<br />

porous at depositi<strong>on</strong> time. In mudst<strong>on</strong>es organic<br />

matter is much more protected from oxidati<strong>on</strong> than in<br />

grainst<strong>on</strong>es.<br />

This work clearly shows that care must be<br />

taken when interpreting the distributi<strong>on</strong> of hopanoids<br />

in terms of thermicity. Yet, differences in hopanes<br />

distributi<strong>on</strong>s as a functi<strong>on</strong> of facies may be combined<br />

with other biomarkers to infer diagenetic/<br />

palaeoenvir<strong>on</strong>mental c<strong>on</strong>diti<strong>on</strong>s during depositi<strong>on</strong>.<br />

313

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