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25th International Meeting on Organic Geochemistry IMOG 2011

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P-184<br />

Have they lost their heads? Differential detecti<strong>on</strong> of archaeal<br />

IPLs and GDGTs<br />

Sara A. Lincoln, Edward F. DeL<strong>on</strong>g, Roger E. Summ<strong>on</strong>s<br />

Massachusetts Institute of Technology, Cambridge, MA, United States of America (corresp<strong>on</strong>ding<br />

author:slincoln@mit.edu)<br />

The use of intact polar lipids (IPLs) as tools for<br />

obtaining ecological and tax<strong>on</strong>omic informati<strong>on</strong> has<br />

burge<strong>on</strong>ed in the past decade. Notably, they have<br />

been used as markers for living biomass in the<br />

envir<strong>on</strong>ment. This applicati<strong>on</strong> is based <strong>on</strong> the<br />

assumpti<strong>on</strong> that hydrolysis of labile polar head<br />

groups, such as the cleavage of hexose from an<br />

archaeal tetraether IPL yielding a glycerol dialkyl<br />

glycerol tetraether (GDGT) core lipid, occurs shortly<br />

after cell death. C<strong>on</strong>sequently, the presence of intact<br />

archaeal IPLs in envir<strong>on</strong>mental samples can be<br />

viewed as evidence of an active archaeal community.<br />

As part of an effort to understand the ecology of<br />

modern marine archaea and the distributi<strong>on</strong> of their<br />

fossil lipids in the geologic record we have analyzed<br />

archaeal IPLs and GDGTs in suspended marine<br />

particulate matter from five sites. We report the<br />

striking, apparent absence of archaeal IPLs in our<br />

sample set, even in those samples in which abundant<br />

GDGTs have been detected. This absence is<br />

surprising for several reas<strong>on</strong>s: living archaea are<br />

nearly ubiquitous in the world‘s oceans; large volumes<br />

(600-1500L) of seawater were filtered; bacterial IPLs<br />

were detected in the same samples, indicating proper<br />

sample handling and extracti<strong>on</strong>; and synoptic<br />

microbiological studies have shown high archaeal cell<br />

counts and activity at a number of depths/sites.<br />

Following established protocols, IPLs were analyzed<br />

by high performance liquid chromatography mass<br />

spectrometry (HPLC-MS) using electrospray<br />

i<strong>on</strong>izati<strong>on</strong> (ESI), while GDGTs were analyzed using<br />

atmospheric pressure chemical i<strong>on</strong>izati<strong>on</strong> (APCI). We<br />

c<strong>on</strong>clude that the limits of detecti<strong>on</strong> (LOD) for IPLs<br />

and GDGTs analyzed using these two analytical<br />

techniques differ significantly.<br />

To determine the extent to which established IPL<br />

analysis may underestimate active archaeal<br />

communities several HPLC-MS experiments were<br />

c<strong>on</strong>ducted. A laboratory stock seawater extract, a<br />

commercially available intact GDGT mixture and acid<br />

hydrolyzed aliquots of both were analyzed at a range<br />

of c<strong>on</strong>centrati<strong>on</strong>s in order to determine limits of<br />

detecti<strong>on</strong> and to compare resp<strong>on</strong>se factors. We also<br />

compare LODs obtained using quadrupole-time-offlight,<br />

single quadrupole and i<strong>on</strong> trap instruments.<br />

Our results suggest that cauti<strong>on</strong> is warranted when<br />

drawing c<strong>on</strong>clusi<strong>on</strong>s about active archaeal<br />

communities from IPL analysis, particularly in lowbiomass<br />

envir<strong>on</strong>ments such as the oligotrophic open<br />

ocean.<br />

324

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