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25th International Meeting on Organic Geochemistry IMOG 2011

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P-064<br />

Biodegradati<strong>on</strong> of Aromatic Hydrocarb<strong>on</strong>s at Basin and<br />

Laboratory Scales<br />

Frank Haeseler, Françoise Behar, Denis Blanchet, Mari<strong>on</strong> Courtiade<br />

IFP New Energy, Rueil Malmais<strong>on</strong>, France (corresp<strong>on</strong>ding author:frank.haeseler@ifpen.fr)<br />

Oil biodegradati<strong>on</strong> at Basin scale has been shown by<br />

Haeseler et al. 2010 to be a compositi<strong>on</strong>al process for<br />

which different classes of hydrocarb<strong>on</strong>s are degraded<br />

in parallel. These c<strong>on</strong>cepts are implemented in the<br />

BioClass 0D model which describes the compositi<strong>on</strong>al<br />

changes and determines the hydrocarb<strong>on</strong> losses. In<br />

this model the classes are subdivided according to<br />

chemical criteria (saturated and aromatic, light and<br />

heavy) and they are characterised by specific relative<br />

kinetics. The susceptibility to biodegradati<strong>on</strong> (Kbio<br />

factors) has been found very similar for two very<br />

different Basins: Potiguar and Willist<strong>on</strong>.<br />

The aim of the present study is to quantify the<br />

hydrocarb<strong>on</strong> loss in the aromatic fracti<strong>on</strong>. For that<br />

purpose we used a quantitative GC2D technique<br />

described by Vendeuvre et al. (2005) in which<br />

aromatics are characterized in both number of<br />

aromatic rings and length of site chain. C<strong>on</strong>sequently<br />

it is possible to quantify the loss of HC as a functi<strong>on</strong> of<br />

aromatic rings and carb<strong>on</strong> number of the alkyl chain.<br />

The Figure 1 illustrates the separati<strong>on</strong> and<br />

identificati<strong>on</strong> potential of this method for the<br />

phenanthrene / alkyl-phenanthrene regi<strong>on</strong> of the 2D-<br />

GC chromatogram. This procedure was applied to a<br />

natural series of reservoir biodegraded oil and to an<br />

oil that has been exposed under aerobic and<br />

anaerobic c<strong>on</strong>diti<strong>on</strong>s to specifically adapted<br />

hydrocarb<strong>on</strong> degrading microflora. So far a<br />

comparis<strong>on</strong> can be d<strong>on</strong>e between basin and aerobic<br />

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

C 1 -Phe<br />

0,170%<br />

Phe<br />

0,066%<br />

C 1 -Phe<br />

0,375%<br />

(-3,3%)<br />

Phe<br />

0,166%<br />

(-8,6%)<br />

C 3 -Phe<br />

0,189%<br />

C 2 -Phe<br />

0,211%<br />

C 3 -Phe<br />

0,0572%<br />

(-3,0%)<br />

C 2 -Phe<br />

0,603%<br />

(-2,7%)<br />

Figure 1: Zoom in a GCxGC chromatogram of an oil before<br />

biodegradati<strong>on</strong>.<br />

Figure 2a shows that the C1-m<strong>on</strong>oaromatic (e.g.<br />

toluene) behaves in a very similar way under lab and<br />

basin c<strong>on</strong>diti<strong>on</strong>s. The sum of the C6-m<strong>on</strong>oaromatic<br />

hydrocarb<strong>on</strong>s present a linear trend in the aerobic lab<br />

scale oil whereas its biodegradati<strong>on</strong> seems to start<br />

and to become very efficient at later times in basins<br />

(Fig. 2b). The C15-m<strong>on</strong>oaromatic hydrocarb<strong>on</strong> class<br />

shows another behaviour: linear loss for the aerobic<br />

process, no biodegradati<strong>on</strong> in basins (Fig. 2c). C2naphtenodiaromatics<br />

are recalcitrant in lab c<strong>on</strong>diti<strong>on</strong>s<br />

and become str<strong>on</strong>gly biodegraded in severely<br />

biodegraded oils at basin scale (Fig. 2d).<br />

Residual mass in <strong>on</strong>e T<strong>on</strong> [kg] aerobic<br />

Residual mass in <strong>on</strong>e T<strong>on</strong> [kg]<br />

20<br />

18<br />

15<br />

13<br />

10<br />

8<br />

5<br />

3<br />

Aerobic<br />

a<br />

Basin<br />

0,40<br />

0,30<br />

5<br />

4<br />

b<br />

0<br />

0,00<br />

0 10 20 30 40 50 60 70 80 90<br />

2,5<br />

2,0<br />

1,5<br />

1,0<br />

0,5<br />

Biodegradati<strong>on</strong> loss, oil [%]<br />

0,0<br />

0 10 20 30 40 50 60 70 80 90<br />

c<br />

Biodegradati<strong>on</strong> loss, oil [%]<br />

Aerobic<br />

Basin<br />

0,50<br />

0,20<br />

0,10<br />

Residual mass in <strong>on</strong>e T<strong>on</strong> [kg] Basin<br />

Residual mass in <strong>on</strong>e T<strong>on</strong> [kg]<br />

Residual mass in <strong>on</strong>e T<strong>on</strong> [kg]<br />

6<br />

3<br />

2<br />

1<br />

0<br />

0 10 20 30 40 50 60 70 80 90<br />

2,0<br />

1,8<br />

1,5<br />

1,3<br />

1,0<br />

0,8<br />

Biodegradati<strong>on</strong> loss, oil [%]<br />

Aerobic<br />

Basin<br />

0,5<br />

0 10 20 30 40 50 60 70 80 90<br />

Biodegradati<strong>on</strong> loss, oil [%]<br />

Figure 2: Residual mass of C1- (a), C6- (b) and C15-(c)<br />

m<strong>on</strong>oaromatic and C2- (d) napthenoaromatic hydrocarb<strong>on</strong>s.<br />

This work shows that aromatic hydrocarb<strong>on</strong>s with<br />

different number of carb<strong>on</strong> atoms (7, 12, 19 and 25)<br />

can behave very differently according to their<br />

chemical structure (ring numbers and chain length)<br />

and to the biological process they have been<br />

subjected to.<br />

Insight in their structure with GCxGC c<strong>on</strong>tributes to a<br />

far better understanding of the biodegradati<strong>on</strong> and<br />

may c<strong>on</strong>tribute in the future to determine the process<br />

(aerobic or anaerobic).<br />

Furthermore, GCxGC analyses also provide similar<br />

data for saturated hydrocarb<strong>on</strong>s and particularly<br />

napthenes. These data of course also c<strong>on</strong>tribute to a<br />

better understanding of the hydrocarb<strong>on</strong><br />

biodegradati<strong>on</strong> and will be presented during the<br />

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

References<br />

Haeseler et al, 2010, <strong>Organic</strong> <strong>Geochemistry</strong>, 41, 1156–1170.<br />

Vendoeuvre et al., 2005, Journal of Chromatography. 1090,<br />

116-25.<br />

Aerobic<br />

Basin<br />

d<br />

209

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