# Analytical Pyrolysis and Mass Spectrometry to Characterise Lignin in Archaeological Wood
## 2 Case Studies and Archaeological Wood Samples
### Biskupin Archaeological Site (Poland)  
Found in 1933, Biskupin was a fortified settlement dating to the Bronze Age (around mid-8 th century BC). The site stretches across an area of about 2 ha. Between 1934 and 1974 several excavation campaigns were carried out [64; 65], at the end of which the findings included a sizeable amount of oak and pine wood. An _in-situ_ conservation strategy was adopted, based on keeping the wood remains in the environment where they were found, \begin{table}
\begin{tabular}{l l l l l l} \hline \hline
**Archaeological Site** & **Wood Fragment** & **Sample Description** & **Species** & **Analytical Techniques** & **Ref** \\ \hline \multirow{8}{*}{Biskupin (Poland)} & & 4 samples collected & & Direct Exposure Mass & \\  & & from two fragments & & Spectrometry (DE-MS) * & \\  & & of wooden parts & & Pyrolysis & \\  & Oak 4 & from the pavement & & (Hexamethyldisylazane)- & \\  & Oak 6 & of the ancient & & Gas & [7; 53] \\  & & settlement. Samples & & Chromatography/Mass & \\  & & & Oak 4, and one & & Spectrometry \\  & & sample from Oak 6. & & (Py(HMDS)-GC/MS) \({}^{\ddagger}\) & \\ \hline \multirow{8}{*}{Marmotta (Italy)} & & 7 samples collected & & & \\  & & from the external & & DE-MS * & \\  & & part to the core of & & Evolved Gas Analysis & \\  & & the pile, following its & & Mass Spectrometry & [33; 62] \\  & & annual growth rings & & (EGA-MS) \({}^{\ddagger}\) & \\  & & in groups of five and & & Py(HMDS)-GC/MS \({}^{\lx@sectionsign}\) & \\  & & labelled from A to G. & & & \\ \hline \multirow{8}{*}{Oseberg collection (Norway)} & & 6 samples from & & & \\  & & fragment 185 treated & & & \\  & & with album in 1905-12. & & & \\  & & & The object had & Diffuse porous & \\  & & broken up into 6 & ring & & \\  & & parts at some point & species—probably & & \\  & (Norway) & Fragment 185 & before or after the & birch (_Betula_ spp.) & Py(HMDS)-GC/MS \({}^{\lx@sectionsign}\) & [8; 63] \\  & & & treatment. Sample & or alter (_Almus_ & \\  & & & 185-1 had the best & spp.) & \\  & & & visual conditions, & & \\  & & & whereas 185-6 was in & & \\  & & & the worst condition. & & \\ \hline \multirow{2}{*}{San Rossore (Italy)} & \multirow{2}{*}{4 shipwcks} & 9 samples collected & & Beech (_Fagus_ spp.) & \\  & & from 4 different & Elm (_Ulamus_ spp.) & DE-MS * & [53; 54] \\  & & & shipwrecks. & Pine (Pinus spp.) & & \\ \hline \multirow{2}{*}{Zötte (Poland)} & & 5 samples collected & Alder (_Almus_ spp.) & & \\  & & from different & Beech (_Fagus_ spp.) & DE-MS * & [37; 53] \\  & & wooden objects. & Oak (_Quercus_ spp.) & & \\ \hline \multirow{2}{*}{Lyon (France)} & \multirow{2}{*}{Lyon2 ship} & 2 samples from the & & & \\  & & Lyon2 ship (2 nd & Oak (_Quercus_ spp.) & Single-shot and & \\  & & century AD) & Pine (_Pinus_ spp.) & double-shot & \\ \cline{1-1}  & & & & Py(HMDS)-GC/MS \({}^{\lx@sectionsign}\) & \\ \hline \hline \end{tabular}  
* Direct Exposure Probe, coupled with a Polaris Q ion trap external ionisation mass spectrometer (Thermo Electron Corporation, USA). The probe program: 0 mA for 20 s, from 0 to 1000 mA in 2 s and 60 s at 1000 mA. \({}^{\dagger}\) Pyrolyser 5150 CDS Pyroprobe 5000 Series coupled with a 6890 GC and 5973 Mass Selective Detector (Agilent Technologies). Pyrolysis T: 550 \({}^{\circ}\)C; HMDS silylating agent for the _in-situ_ derivatisation of pyrolysis products. \({}^{\ddagger}\) Multi-Shot Pyrolyzer EGA/Py-3030D (Frontier Lab) coupled with a 6890 GC and 5973 Mass Selective Detector (Agilent Technologies). Micro-furrance program temperature: Initial 70 \({}^{\circ}\)C; 20 \({}^{\circ}\)C min\({}^{-1}\) up to 200 \({}^{\circ}\)C; 8 \({}^{\circ}\)C min\({}^{-1}\) up to 500 \({}^{\circ}\)C; 20 \({}^{\circ}\)C min\({}^{-1}\) up to 700 \({}^{\circ}\)C. \({}^{\lx@sectionsign}\) Multi-Shot Pyrolyzer EGA/Py-303D (Frontier Lab) coupled with a 6890 GC and 5973 Mass Selective Detector (Agilent Technologies). Pyrolysis T: 550 \({}^{\circ}\)C; HMDS for the in situ silylation of pyrolysis products.  
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