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25th International Meeting on Organic Geochemistry IMOG 2011

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P-443<br />

Hopanoids in silica sinters: identificati<strong>on</strong> of an unusual pathway<br />

in hopanoid diagenesis with implicati<strong>on</strong>s for the sedimentary<br />

biomarker record<br />

Robert Gibs<strong>on</strong> 1,2 , Gurpreet Kaur 3 , Bruce Mountain 4 , Richard Pancost 3 , Helen Talbot 2<br />

1 NIOZ Royal Netherlands Institute for Sea Research, 't Horntje, Netherlands, 2 Newcastle University,<br />

Newcastle, United Kingdom, 3 Bristol University, Bristol, United Kingdom, 4 GNS Science, Taupo, New<br />

Zealand (corresp<strong>on</strong>ding author:Robert.gibs<strong>on</strong>@nioz.nl)<br />

Geohopanoids, i.e. geohopanols, hopanes,<br />

hopenes and hopanoic acids, are the molecular<br />

fossils of bacteriohopanepolyols (BHPs) that are<br />

produced by a diverse array of bacteria and are<br />

widespread throughout modern and ancient<br />

sedimentary depositi<strong>on</strong>s. Previously, we have shown<br />

that BHPs are produced by bacteria that col<strong>on</strong>ise<br />

terrestrial geothermal vents and BHPs are well<br />

preserved in silica sinters collected from the Taupo<br />

Volcanic Z<strong>on</strong>e, North Island, New Zealand (TVZ)[1].<br />

In this study we have analysed the geohopanoid<br />

compositi<strong>on</strong> of geothermal silica sinters from the TVZ<br />

with a view to understanding mechanisms of<br />

diagenesis affecting preserved BHPs and to assess<br />

the potential of geohopanoids as biomarkers in<br />

ancient geothermal siliceous deposits.<br />

Throughout our investigati<strong>on</strong>s, a high proporti<strong>on</strong> of<br />

C31 �� hopanol relative to C32 or C30 �� hopanols was<br />

observed. This is in stark c<strong>on</strong>trast to studies of the<br />

distributi<strong>on</strong> of geohopanoids from other depositi<strong>on</strong>al<br />

settings where C32 hopanol tends to predominate.<br />

Previously, it has been suggested that the formati<strong>on</strong><br />

of homohopanols is directly related to the degree of<br />

functi<strong>on</strong>alisati<strong>on</strong> in precursor BHPs [2]. However, in<br />

our study this is not the case as C31 �� hopanol,<br />

which would be expected to derive from<br />

pentafuncti<strong>on</strong>alised BHPs, is the most abundant<br />

geohopanol but pentafuncti<strong>on</strong>alised BHPs do not<br />

dominate the BHP distributi<strong>on</strong> to the same extent,<br />

(Figure 1).<br />

Hopanoic acids dominate distributi<strong>on</strong>s in older<br />

sinters and were found to closely-mirror BHP<br />

distributi<strong>on</strong>s. However, hopanoic acids were less<br />

prevalent in sinters deposited under acidic c<strong>on</strong>diti<strong>on</strong>s.<br />

This may reflect reducti<strong>on</strong> of the acid functi<strong>on</strong>ality to a<br />

terminal hydroxyl group leading to the observed<br />

predominance of geohopanols in sinters from acidic<br />

vents.<br />

This investigati<strong>on</strong> has highlighted a unique<br />

mechanism of BHP diagenesis that is significantly<br />

c<strong>on</strong>trolled by envir<strong>on</strong>mental setting and not, as<br />

previously assumed, entirely based <strong>on</strong> biological<br />

input. Furthermore, geohopanoids appear to be well<br />

preserved in older sinters suggesting that hopanoids<br />

may be useful biomarkers in ancient siliceous sinter<br />

material.<br />

1<br />

0.8<br />

0.6<br />

0.4<br />

0.2<br />

0<br />

1<br />

0.8<br />

0.6<br />

0.4<br />

0.2<br />

0<br />

‘Active’ C 31/(C31+C32) hopanol index<br />

P/(T+P) BHP index<br />

‘N<strong>on</strong>-active, older’<br />

Figure 1. Relative distributi<strong>on</strong>s of bio- and<br />

geohopanoids observed in active sinters (above) and<br />

n<strong>on</strong>-active sinters (below). Sample codes: CP -<br />

Champagne Pool; LR - Loop Road; OP - Opaheke<br />

Pool. C31/ C31+C32 hopanol index = ∑C31 ��+��+��<br />

hopanol/(∑ C31 ��+��+�� hopanol + ∑ C32 ��+��+��<br />

hopanol); P/(P+T) BHP index =[∑ pentafuncti<strong>on</strong>alised<br />

BHPs/(∑ tetrafuncti<strong>on</strong>alised BHPs + ∑<br />

pentafuncti<strong>on</strong>alised BHPs)].<br />

[1] Gibs<strong>on</strong> R.A., Talbot, H.M., Kaur, G., Pancost,<br />

R.D., Mountain, B.W., 2008. <strong>Organic</strong> geochemistry<br />

39, 1020, 1023<br />

[2] Farrim<strong>on</strong>d, P., Head, I.M., Innes, H.E., 2000.<br />

Geochimica et Cosmochimica Acta 64, 2985 – 2992.<br />

569

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