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25th International Meeting on Organic Geochemistry IMOG 2011

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P-431<br />

Carbohydrate dynamics in Cariaco Basin pore water and<br />

sediments<br />

Melesio Quijada 1 , Armelle Riboulleau 1 , Yann Guerardel 2<br />

1 FRE 3298 CNRS Géosystèmes, UFR des Sciences de la Terre, Université de Lille 1, Villeneuve d'Ascq,<br />

France, 2 UMR 8576 CNRS Laboratoire de Glycobiologie Structurale et F<strong>on</strong>cti<strong>on</strong>nelle, Université de Lille 1,<br />

Villeneuve d'Ascq, France (corresp<strong>on</strong>ding author:ma.quijada-hermoso@gmail.com)<br />

Carbohydrates are <strong>on</strong>e of the major c<strong>on</strong>stituents of<br />

the biomass, and account for a substantial amount of<br />

the total organic carb<strong>on</strong> (TOC) in water and<br />

sediments in marine envir<strong>on</strong>ments.<br />

It is often accepted that structural carbohydrates are<br />

rapidly re-mineralized during early diagenesis and do<br />

not make substantial c<strong>on</strong>tributi<strong>on</strong> to total organic<br />

carb<strong>on</strong> in ancient sediments and kerogens.<br />

However some studies has shown that structural<br />

carbohydrates may escape decompositi<strong>on</strong> and<br />

remineralizati<strong>on</strong> depending <strong>on</strong> different factors, such<br />

as paleoproductivity, presence of oxygen in water and<br />

sediments and sedimentati<strong>on</strong> rate (Moers et al. 1994).<br />

Even more, some studies report that <strong>on</strong>ce particulate<br />

carbohydrates escape water column in n<strong>on</strong><br />

oxygenated envir<strong>on</strong>ments, they may be preserved<br />

within the organic matrix (Cowie and Hedges, 1984).<br />

In our study we investigated the neutral<br />

carbohydrates (NCHO) variati<strong>on</strong> in sediments from<br />

Cariaco Basin, covering a period of time of 135ky.<br />

For that, 15 sediment samples were obtained from<br />

sediment cores 1002 D & E collected <strong>on</strong> the central<br />

saddle of the Cariaco Basin during the ODP Leg 165.<br />

The NCHO where determined quantitatively after (i)<br />

water extracti<strong>on</strong> to explore pore water carbohydrates<br />

(PNCHO) and (ii) acid hydrolysis to investigate<br />

structural and sediment-attached m<strong>on</strong>omers<br />

(HNCHO).<br />

M<strong>on</strong>osaccharides were analyzed by GC-FID and<br />

GC/MS after derivatizati<strong>on</strong> of aldoses to their<br />

corresp<strong>on</strong>ding alditol acetates as described in Eder et<br />

al. (2010).<br />

Sequential hydrolysis (2N, 4N and 6N trifluoroacetic<br />

acid) was used to avoid amino-acids and<br />

carbohydrates glycosidic reacti<strong>on</strong> to form melanoidins<br />

(Quijada et al. 2008). Variati<strong>on</strong>s in acid c<strong>on</strong>centrati<strong>on</strong><br />

during hydrolysis yielded different amounts of<br />

individual m<strong>on</strong>osaccharides for the same sample.<br />

These differences are related with differences in<br />

glycosidic b<strong>on</strong>ds behavior during hydrolysis (Mopper,<br />

1977).<br />

The total c<strong>on</strong>tent of carbohydrates ranged from 0,66<br />

to 2,25 wt% of the TOC in PNCHO and from 5,3 to<br />

11,36 wt% of the TOC in HNCHO. Hydrolysates were<br />

dominated by hexoses in both fracti<strong>on</strong>s, and no<br />

correlati<strong>on</strong> with TOC was found.<br />

Nine m<strong>on</strong>osaccharides were identified in the 15<br />

samples. Deoxysugars (fucose and rhamnose) are<br />

apparently more susceptible to 2N TFA hydrolysis.<br />

The c<strong>on</strong>tributi<strong>on</strong> of deoxysugars to the TOC (focusing<br />

<strong>on</strong> rhamnose) is c<strong>on</strong>sidered to be indicative for the<br />

presence of bacteria.<br />

Hexoses (galactose, manose, glucose) yielded mostly<br />

in the 4N hydrolysis. The large c<strong>on</strong>tributi<strong>on</strong> of glucose<br />

is related with the presence of storage<br />

polysaccharides (cyanobacteria accumulate polyglucoses<br />

in certain c<strong>on</strong>diti<strong>on</strong>s. Lehmann and Wöber,<br />

1976). Manose and galactose present a large<br />

c<strong>on</strong>tributi<strong>on</strong> to the total NCHO budget, corresp<strong>on</strong>ding<br />

to structural sugars of microorganisms.<br />

Xylose was more susceptible to 6N hydrolysis in all<br />

samples suggesting to be a building block<br />

carbohydrate, like previously reported for microbial<br />

resistant sheath material (Klok et al. 1984).<br />

We used the hexose to pentose ratio (Oades, 1984)<br />

to investigate the origin of sugars and its variati<strong>on</strong><br />

with depth. The (galactose + manose) / (arabinose +<br />

xylose) ratio>2 indicated an algae and zooplankt<strong>on</strong><br />

origin for NCHO during the all period studied.<br />

The NCHO profile present individual variati<strong>on</strong>s with<br />

depth depending <strong>on</strong> their individual reactivity and<br />

resistance to degradati<strong>on</strong>. Some sedimentary facies<br />

are characterized by a rather increase in NCHO<br />

c<strong>on</strong>tent reflecting envir<strong>on</strong>mental c<strong>on</strong>trol. Globally, the<br />

NCHO c<strong>on</strong>tent decrease with depth reflecting<br />

heterotrophic degradati<strong>on</strong> and/or preservati<strong>on</strong> via<br />

natural sulfurizati<strong>on</strong> (van D<strong>on</strong>gen et al. 2006).<br />

References:<br />

- Cowie and Hedges (1984). Geochim. Cosmochim.<br />

Acta 48, pp. 2075-2087.<br />

- Eder et al. (2010). Org. Geochem. 41, pp. 580-585.<br />

- Lehmann and Wöber (1976) Arch. Microbiol. 111,<br />

93-97<br />

- Klok et al. (1984). Org. Geochem. 7, pp. 73-84.<br />

- Mopper (1977). Mar. Chem. 5, pp. 585-603.<br />

- Oades et al. (1984). Plant Soil 76, pp. 319–337.<br />

- Quijada et al. (2009) 24 th <strong>IMOG</strong>. Poster.<br />

- van D<strong>on</strong>gen et al. (2006) Org. Geochem. 37, pp.<br />

1052-1073.<br />

557

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