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25th International Meeting on Organic Geochemistry IMOG 2011

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P-134<br />

Biomarkers preserved in cave sediments and their use as<br />

indicators of envir<strong>on</strong>mental change in Trang An, Vietnam<br />

Natalie F. Ludgate 1 , Thomas A. Griffiths 2 , Alis<strong>on</strong> J. Blyth 1 , William D. Gosling 1 , Iain<br />

Gilmour 1<br />

1 The Open University, Milt<strong>on</strong> Keynes, United Kingdom, 2 University College L<strong>on</strong>d<strong>on</strong>, L<strong>on</strong>d<strong>on</strong>, United<br />

Kingdom (corresp<strong>on</strong>ding author:n.f.ludgate@open.ac.uk)<br />

The aim of the Trang An archeological project is to<br />

understand hunter-gatherer mobility at the end of the<br />

last glacial maximum (LGM) [1]. Research into<br />

terrestrial flora since the LGM is of key importance in<br />

understanding hominid movement and cultural<br />

development. Floral rec<strong>on</strong>structi<strong>on</strong>s can then be<br />

integrated with cultural and dietary informati<strong>on</strong><br />

deduced from archaeological finds [1]. Clastic cave<br />

sediments may thus provide an important terrestrial<br />

record. Here we propose a novel technique using<br />

biological markers found in clastic cave sediments.<br />

The focus of this study is the use of lipids, including nalkanes,<br />

and n-fatty acids, derived from higher plants<br />

and molluscs from cave sediments in Vietnam.<br />

Previous studies have shown that lipid biomarkers are<br />

a valuable palaeoenvir<strong>on</strong>mental resource in soils,<br />

sediments and chemically precipitated speleothems<br />

[e.g. 2,3,4]. Caves can provide an ideal envir<strong>on</strong>ment<br />

for lipid biomarker preservati<strong>on</strong>. Within caves,<br />

sediments are accumulated by aeolian or fluvial<br />

depositi<strong>on</strong>, with relatively little further digenesis or<br />

post-depositi<strong>on</strong>al alterati<strong>on</strong>. Lipid biomarkers from<br />

local flora will therefore be transported into caves and<br />

preserved.<br />

Two caves in Vietnam (Ninh Bình province); Hang<br />

Boi, and Hang Tr<strong>on</strong>g have been chosen as study<br />

sites. Bulk sediment samples were taken from<br />

stratigraphic layers within each archeological trench:<br />

where strata were not determinable samples were<br />

taken in 10 cm spits. Hang Boi is an open cave<br />

situated at 78 m a.s.l. charcoal radiocarb<strong>on</strong> dates<br />

indicate c.20 cm of sediment was deposited between<br />

c. 12,400 and 12,100. The sec<strong>on</strong>d site, Hang Tr<strong>on</strong>g,<br />

is situated 142 m a.s.l. formed with openings <strong>on</strong> each<br />

sides of a karst tower, allows detailed investigati<strong>on</strong> of<br />

airborne depositi<strong>on</strong>. Radiocarb<strong>on</strong> dates, from<br />

charcoal, indicate the immediate sub-surface<br />

sediment is recent whilst at approximately 1.5 m from<br />

the surface it dates to 18,500 yrs. b.p. The sites are<br />

dominated by anthropogenic shell middens<br />

interspersed with aeolian sediments and bed-rock<br />

break down. For each stratum, freeze dried subsamples,<br />

were Soxhlet extracted with 93:7<br />

CH2Cl2/CH3OH. After evaporati<strong>on</strong> of the excess<br />

solvent, the samples were derivitised with bor<strong>on</strong><br />

triflouride methanol in additi<strong>on</strong> to BSTFA + TMCS.<br />

Sample analysis is completed <strong>on</strong> a GC-MS; Agilent<br />

Technology gas chromatograph coupled with a 5973<br />

mass spectrometer. Separati<strong>on</strong> was performed <strong>on</strong> a<br />

J&W Scientific HP-5MS capillary column the He<br />

carrier gas at a c<strong>on</strong>stant flow rate of 1.1 ml min -1 . The<br />

GC oven temperature was held for 2 min at 50°C and<br />

ramped to 300°C at 5°C min -1 and then held for 9 min.<br />

A wide range of lipids in the extracted fracti<strong>on</strong><br />

including: alkanes, alcohols, fatty acids, sterols, and<br />

triterpenoids. The c<strong>on</strong>tent of total extractable organic<br />

matter in the sediment ranges from 110-880 µg/g of<br />

dry sediment. Normal alkane homologues in the<br />

extracts range from C26 to C34 with an average<br />

maxima at C31. There is distinct odd-over-even carb<strong>on</strong><br />

predominance, indicating a vegetati<strong>on</strong>al source.<br />

Normal fatty acids and alkanol range from C24 to C34<br />

with average maxima at C30 and a str<strong>on</strong>g even-overodd<br />

carb<strong>on</strong> predominance.<br />

This is first comprehensive investigati<strong>on</strong> of lipid<br />

biomarkers from plants preserved in clastic cave<br />

sediments. The study will rec<strong>on</strong>struct the local<br />

vegetati<strong>on</strong>al history using both palynological and lipid<br />

biomarker analyses. The lipid biomarker time series<br />

can then be compared with the palynological record to<br />

determine the effectiveness of the method, providing<br />

key insights into the local palaeoenvir<strong>on</strong>mental<br />

c<strong>on</strong>diti<strong>on</strong>s and ecological impact <strong>on</strong> hominids. The<br />

lipid analysis technique developed during this project<br />

will support established methods and provide<br />

informati<strong>on</strong> from sites where existing techniques are<br />

unsuitable.<br />

[1] Rabett, R., et al., (2010). Quaternary <str<strong>on</strong>g>Internati<strong>on</strong>al</str<strong>on</strong>g>, Article in Press<br />

[2] Blyth, A.J., et al., (2007). Quaternary Research, 68(3), 314-324.<br />

[3] Bull, I.D. et al (2000). <strong>Organic</strong> Chemistry, 31, 389-408.<br />

[4] Meyers, P.A. et al., (2003). <strong>Organic</strong> Chemistry, 34, 261-289.<br />

276

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