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25th International Meeting on Organic Geochemistry IMOG 2011

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0 - 69.99<br />

P-052<br />

Incorporati<strong>on</strong> of archaeal and bacterial lipids into<br />

geomacromolecules: implicati<strong>on</strong>s for organic matter<br />

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

Lidia Chaves Torres, Katie L. H. Lim, Paul S. M<strong>on</strong>aghan, Richard P. Evershed, Richard<br />

D. Pancost<br />

<strong>Organic</strong> <strong>Geochemistry</strong> Unit, University of Bristol, Bristol, United Kingdom (corresp<strong>on</strong>ding<br />

author:chylc@bristol.ac.uk)<br />

The incorporati<strong>on</strong> of organic matter into<br />

geomacromolecules during diagenesis c<strong>on</strong>tributes to<br />

their formati<strong>on</strong> and compositi<strong>on</strong>. These<br />

geomacromolecules are generally resistant to<br />

degradati<strong>on</strong>, and thus, their formati<strong>on</strong> is a crucial<br />

aspect of understanding the bioavailability of organic<br />

carb<strong>on</strong> in the geosphere, the carb<strong>on</strong> cycle and its role<br />

in climate regulati<strong>on</strong>, and the formati<strong>on</strong> of source<br />

rocks. However, the mechanisms by which<br />

geomacromolecules are formed, including the<br />

incorporati<strong>on</strong> of lipids, remains poorly understood.<br />

Sulfurisati<strong>on</strong> processes have been shown to be<br />

important in S-rich marine c<strong>on</strong>texts, but in other<br />

settings, oxidative cross linking appears to be<br />

extensive (e.g. Versteegh et al., 2004 [1]).<br />

In order to better understand geomacromolecule<br />

formati<strong>on</strong>, we are examining the nature and timing of<br />

the incorporati<strong>on</strong> pathways of archaeal and bacterial<br />

lipids, as they have diagnostic structures that act as<br />

robust tracers am<strong>on</strong>g the different organic matter<br />

fracti<strong>on</strong>s. Furthermore, the wide range of different<br />

functi<strong>on</strong>alities of these compounds allow us to<br />

examine which chemical moieties might be most<br />

pr<strong>on</strong>e to cross-linking reacti<strong>on</strong>s. Thus, the purpose of<br />

the research is analyzing the fate of structurally<br />

diagnostic archaeal and bacterial membrane lipids<br />

through the comparis<strong>on</strong> of free biomarkers (free;<br />

those that are extractable with organic solvents,<br />

including core lipids and intact polar lipids) with their<br />

structural equivalents released from<br />

geomacromolecular fracti<strong>on</strong>s via sequential chemical<br />

degradati<strong>on</strong> (incorporated).<br />

In the first instance we have focused <strong>on</strong> a core with<br />

significant methanogenic activity, whose redox<br />

gradient across the water table enables the<br />

explorati<strong>on</strong> of both aerobic and anaerobic c<strong>on</strong>diti<strong>on</strong>s.<br />

In such a terrestrial setting sulfur does not play a<br />

predominant role, and instead oxidative<br />

polymerizati<strong>on</strong> may be the key pathway resp<strong>on</strong>sible<br />

for the geomacromolecule formati<strong>on</strong>. We have started<br />

by characterizing the free archaeal and bacterial<br />

membrane lipids, archaeol and branched fatty acids,<br />

respectively, and their occurrence as either core<br />

lipids, phospholipids or glycolipids. Selected secti<strong>on</strong>s<br />

Relative Abundance<br />

of the core were analyzed and the results show that<br />

archaeol c<strong>on</strong>centrati<strong>on</strong>s increased with depth,<br />

especially below the water table, whereas bacterial<br />

phospholipid fatty acid c<strong>on</strong>centrati<strong>on</strong>s decreased.<br />

These observati<strong>on</strong>s collectively show a shift in the<br />

populati<strong>on</strong> towards a relatively smaller bacterial<br />

community and larger archaeal community.<br />

Ongoing work is now focussed <strong>on</strong> the incorporati<strong>on</strong><br />

of these different compounds into the n<strong>on</strong>-extractable<br />

fracti<strong>on</strong>. Initially, we have hydrolysed the peat residue<br />

under basic and then acidic c<strong>on</strong>diti<strong>on</strong>s releasing<br />

bacterial and archaeal biomarkers. Given the age of<br />

the core (

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