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25th International Meeting on Organic Geochemistry IMOG 2011

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P-512<br />

The effect of fire intensity <strong>on</strong> alkane compositi<strong>on</strong> of plant<br />

organic matter and soils affected by fire<br />

Guido Wiesenberg 1 , Andreas Nestler 1,2 , Stefanie Birkner 1 , Ulrich Hambach 2<br />

1 Department for Agroecosystem Research, University of Bayreuth, Bayreuth, Germany, 2 Geomorphology<br />

Department, University of Bayreuth, Bayreuth, Germany (corresp<strong>on</strong>ding author:guido.wiesenberg@unibayreuth.de)<br />

Plant-derived biomass entering soil comm<strong>on</strong>ly leads<br />

to a typical chemical compositi<strong>on</strong> of soil organic<br />

matter (SOM), whereas alterati<strong>on</strong> of biomass during<br />

microbial and thermal degradati<strong>on</strong> results in chemical<br />

changes of plant-derived SOM. On a molecular level<br />

plant-derived SOM is characterized by a<br />

predominance of l<strong>on</strong>g-chain alkanes, fatty acids and<br />

alcohols within the lipid fracti<strong>on</strong> with a str<strong>on</strong>g relative<br />

predominance of odd or even carb<strong>on</strong>-numbered<br />

homologues depending <strong>on</strong> the lipid fracti<strong>on</strong>. E.g.<br />

plant-derived alkanes as typical epiculticular wax<br />

comp<strong>on</strong>ents and degradati<strong>on</strong> products of<br />

functi<strong>on</strong>alized lipids are dominated by odd l<strong>on</strong>g-chain<br />

alkanes. C<strong>on</strong>trastingly, a progressive increase in<br />

short-chain even-numbered alkanes was found in<br />

charred biomass with increasing temperature<br />

associated by a decrease in chain-length and a<br />

decrease in the predominance of odd n-alkanes [1].<br />

Thermal degradati<strong>on</strong> of plant biomass during a fire<br />

results in a modificati<strong>on</strong> of lipid distributi<strong>on</strong> patterns<br />

that differs from microbial degradati<strong>on</strong>. Not <strong>on</strong>ly the<br />

compositi<strong>on</strong>, but also the total amount of lipidic<br />

comp<strong>on</strong>ents changes. The aim of the current study<br />

was to assess effects of temperature oxygen<br />

availability and source biomass <strong>on</strong> amount and<br />

compositi<strong>on</strong> of thermal degradati<strong>on</strong> products.<br />

Additi<strong>on</strong>ally, we compared results from laboratory<br />

experiments with soil and archaeological samples of<br />

well known burning history.<br />

During charring at low temperatures (400°C) a decrease in abundance of the all lipidic<br />

fracti<strong>on</strong>s occurs including aromatic hydrocarb<strong>on</strong>s with<br />

a str<strong>on</strong>ger depleti<strong>on</strong> in aliphatic than in aromatic<br />

comp<strong>on</strong>ents. At higher temperatures (>350°C) even<br />

carb<strong>on</strong> numbered m<strong>on</strong>oalkenes increase in<br />

abundance presumably due to degradati<strong>on</strong> of ester<br />

bound lipids c<strong>on</strong>taining side chains with 14-18<br />

carb<strong>on</strong>s. In general this is in agreement with NMR<br />

spectra [2], indicating a higher aromaticity at higher<br />

charring temperatures.<br />

The effect of oxygen availability improved degradati<strong>on</strong><br />

of alkanes, whereas under nitrogen atmosphere<br />

degradati<strong>on</strong> was limited and resulted in larger<br />

amounts of alkanes, alkenes and PAHs.<br />

All these observati<strong>on</strong>s indicate that incomplete<br />

burning results in large amounts of complex organic<br />

remains in soil, where with increasing temperature<br />

burning gets more complete leaving less burning<br />

residues. Recent investigati<strong>on</strong>s indicate a structural<br />

re-arrangement of lipidic comp<strong>on</strong>ents in burned plant<br />

biomass not <strong>on</strong>ly as a functi<strong>on</strong> of temperature,<br />

durati<strong>on</strong> of thermal degradati<strong>on</strong>, and oxygen<br />

availability, but also as a functi<strong>on</strong> of the initial plant<br />

biomass compositi<strong>on</strong>.<br />

Additi<strong>on</strong>ally, we compared burning residues from the<br />

laboratory experiment, where thermal degradati<strong>on</strong><br />

was carried out from 200-700°C, the Roman Furnace<br />

Project at Velzeke (Belgium) with furnaces managed<br />

at 550°C and 1070°C, respectively, recent burnt<br />

agricultural residues derived from agricultural plots in<br />

Russia, material from ancient anthropogenic pits as<br />

well as fire places from different ancient settlements.<br />

The alkane distributi<strong>on</strong> patterns clearly correlated with<br />

proposed temperatures. Therefore, alkanes and<br />

alkenes as molecular marker might be useful to trace<br />

not <strong>on</strong>ly fire in recent and ancient soils, but also the<br />

burning c<strong>on</strong>diti<strong>on</strong>s and potentially the initial biomass.<br />

References<br />

[1] Wiesenberg GLB, Lehndorff E, Schwark L 2009.<br />

Org Geochem 40, 167.<br />

[2] Baldock JA, Smernik RJ 2002. Org Geochem 33,<br />

1093.<br />

633

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