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25th International Meeting on Organic Geochemistry IMOG 2011

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O-22<br />

New insights into the sources and applicati<strong>on</strong> of biohopanoid<br />

molecular proxies in diverse settings<br />

Helen Talbot<br />

School of Civil Engineering and Geosciences, Newcastle University, Newcastle up<strong>on</strong> Tyne, United Kingdom<br />

(corresp<strong>on</strong>ding author:h.m.talbot@ncl.ac.uk)<br />

Microbially-mediated processes at the Earth‘s<br />

surface and in the subsurface are fundamental<br />

c<strong>on</strong>trols <strong>on</strong> the global carb<strong>on</strong> and climate cycle. One<br />

way to trace these processes in the geological record<br />

is to through the applicati<strong>on</strong> of bacteriohopanepolyols<br />

(BHPs) 1 , membrane lipids biosynthesised by many,<br />

but not all bacteria. These complex molecules<br />

c<strong>on</strong>sisting of a stable pentacyclic hydrocarb<strong>on</strong><br />

skelet<strong>on</strong> with an extended, highly functi<strong>on</strong>alised side<br />

chain c<strong>on</strong>taining at least 4 functi<strong>on</strong>al groups, are<br />

widely recognised as being significant comp<strong>on</strong>ents in<br />

soils and sediments, both terrestrial and marine.<br />

Some BHPs have a diverse range of biological<br />

source organisms 1 whilst others have more restricted<br />

origins making them highly diagnostic markers. New<br />

correlati<strong>on</strong>s to envir<strong>on</strong>ment are emerging as BHP<br />

inventories are obtained from an ever broader range<br />

of settings. For example, recent studies have<br />

covered locati<strong>on</strong>s from the Arctic 2 to the Tropics 3 and<br />

from geothermal cyanobacterial mats and silica<br />

sinters to peat bogs and anoxic lakes (Table 1).<br />

As expected, tetrafuncti<strong>on</strong>alised BHPs (with<br />

functi<strong>on</strong>al groups at C32,33,34 and 35) are comm<strong>on</strong><br />

in all settings but are typically the least diagnostic<br />

with the widest range of sources; however, other<br />

groups have emerged with potential as tracers for<br />

specific processes.<br />

The prevalence of adenosylhopane (and related<br />

structures) in soils combined with their (near) total<br />

absence in marine samples far removed from any<br />

significant terrestrial source, has prompted the<br />

proposal that the relative c<strong>on</strong>tributi<strong>on</strong> of this group of<br />

compounds to the sedimentary BHP pool may be a<br />

useful proxy for soil organic matter input. As a<br />

foundati<strong>on</strong> to this potential applicati<strong>on</strong>, we have<br />

surveyed the BHP compositi<strong>on</strong> of over 600 soil<br />

samples from around the world and the comparis<strong>on</strong><br />

of these terrestrial BHP fingerprints to those from a<br />

range of aquatic sediments of different ages reveals<br />

significant differences.<br />

More recently it has been observed that<br />

unsaturated BHPs, which are <strong>on</strong>ly present in trace<br />

amounts (if at all) in most settings including soils, are<br />

highly abundant in surface peat layers and may<br />

reflect the activity of nitrogen-fixing bacteria.<br />

In geothermal settings with significant<br />

cyanobacterial biomass, a suite of novel C-2<br />

methylated and n<strong>on</strong>-methylated structures are<br />

comm<strong>on</strong> at diverse locati<strong>on</strong>s from North America,<br />

Chile and New Zealand. 4 However, BHPs methylated<br />

at the C-3 positi<strong>on</strong> are rarely observed in any setting<br />

in stark c<strong>on</strong>trast with observati<strong>on</strong>s of 3methylhopanes<br />

in older systems.<br />

Finally, recent data have highlighted the<br />

significance and potential of aminoBHPs (and<br />

aminobacteriohopanepentol in particular) as tracers<br />

for aerobic methane oxidati<strong>on</strong> in both terrestrial and<br />

marine systems with these compounds observed in<br />

samples up to 55Ma.<br />

Table 1. Characteristic envir<strong>on</strong>mental BHP<br />

compositi<strong>on</strong>s<br />

Sample type BHP groups a<br />

No. BHPs b<br />

Soil T> A >> P and H 18-22<br />

Peat (oxic) UT � T >> A, P and H > P and H > A 20-22<br />

Lakes (small) T � P � H >> A 10-12<br />

Lakes (large) T, A >> P and H 8-10<br />

Rivers T, A >> P and H 10-15<br />

Estuary T, A, H > P 8-12<br />

Deep Sea Fan T, H>> A, P and An 8-12<br />

Open Marine T, An 0-4<br />

Silica Sinters T > P 10-15<br />

Mats T, MT, P, MP 6-8<br />

a<br />

Key: A = adenosylhopane and related structures; An<br />

= 32,35-anhydrobacteriohopanetetrol; M= methylated;<br />

T, P and H = tetra-, penta- and hexafuncti<strong>on</strong>alised<br />

BHPs respectively; U = unsaturated (� 6 and/or 11 )<br />

b<br />

Number of BHPs observed; indicated values are<br />

typical but not exclusive<br />

References<br />

[1] Talbot H.M. & Farrim<strong>on</strong>d P., 2007. <strong>Organic</strong><br />

<strong>Geochemistry</strong> 38, 1212-1225.<br />

[2] Rethemeyer, J. et al. 2010. <strong>Organic</strong> <strong>Geochemistry</strong><br />

41, 1130-1145.<br />

[3] Handley, L., et al., 2010. <strong>Organic</strong> <strong>Geochemistry</strong><br />

41, 910-914.<br />

81

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