For Archaeological Samples

From the analysis of several archaeological samples by micro-PIXE, Neff and Dillmann (2001) have shown that ores containing important amount of phosphorus were used in ancient Europe to obtain iron by two different processes called the direct one and the indirect one. Phosphorus content was quantified as the heterogeneous phosphorus distribution was observed in the samples. The results confirm the fact that refining of phosphorus pig iron was possible with ancient refining processes. Moreover it seems that the phosphorus distribution ratio could be a discriminating factor to identify the iron making process. 

Kumar (2002) has analyzed the pottery samples of Harrapan period collected from Sanghol (Dist. Ludhiana, Punjab, India). The absolute elemental concentration measurements were made by EDXRF measurements using Mon-tanasoil and Brick clay as standards. The typical spectrum of pottery samples is shown in Fig. 1.31. 

On the other hand, a typical PIXE spectrum of 13th century Iranian bowl taken in air using external beam is presented in Fig. 1.32. The two peaks each corresponding to Fe and Cu are their Ka and K(3 peaks, while the three peaks corresponding to Pb are its La, L(3, and Ly peaks. The presence of Argon peak in the spectrum is noteworthy. 

Using a portable beam stability-controlled XRF spectrometer, Romano et al. (2005) have determined the concentrations of Rb, Sr, Y, Zr, and Nb in 50 fine potsherds from the votive deposit of San Francesco in Catania (Italy) by using a multilinear regression method in their bid for quantitative nondestructive determination of trace elements in archaeological pottery. A small portion of a few potsherds was even powdered in order to test the homogeneity of the material composing the fine pottery samples and the XRF data were compared with those obtained by chemical analysis of the powdered samples. 

---

Table 7.1. Collagen yield, carbon and nitrogen composition for archaeological samples. Layers are labeled O = outer, M = middle. 1 = inner,...

The factors affecting Rf include the quality of the stationary and mobile phases, the thickness and activity of the layer, and the amount of sample. Although standards may have the same Rf value as the sample, this does not uniquely identify the compound. For archaeological samples, the best identification achievable is only at a general class level (e.g., triacylglycerols, fatty acids, aromatic, or aliphatic) and not to individual molecular components. 

In Chapter 22, Herr et al. describe a monoclonal antibody used to test for human albumin in body fluids. The development of this monoclonal antibody was aimed at forensic evidence, but if (and it must be tested) degradation processes do not destroy the antigenic site that this antibody recognizes, it could be used for archaeological samples. Certainly as these techniques are developed they will prove valuable in the studies of objects that are suspected of containing blood. For example, these newer methods could help further define an artifact like the Shroud of Turin, which is described in Chapter 23. 

Romanian amber (Colti, Buzau County) 389 3200 OH frequencies, alcoholic (phenolic free OH and bound intramolecular OH) from hydro -acids observed wavenumbers shifte characteristic of amorphous structures. Less intense signals in this region for archaeological samples and slight shifts... 

Protocols for mass spectrometric peptide analysis are common to modern and archaeological samples. The only significant difference in the analytical protocol used for archaeological samples is the need for careful sample extraction and preparation. In addition, the usefulness of archaeological proteomics requires the development of a database for archaeological peptide data, which will expand and increase over time but is currently relatively small. 

For archaeological samples, CO2 extracted with 0-plasmas were sent to AMS laboratories for analyses. Radiocarbon dates were determined for three... 

A novel technique for dating archaeological samples called ammo acid racemiza tion (AAR) IS based on the stereochemistry of ammo acids Over time the configuration at the a carbon atom of a protein s ammo acids is lost m a reaction that follows first order kinetics When the a carbon is the only chirality center this process corresponds to racemization For an ammo acid with two chirality centers changing the configuration of the a carbon from L to D gives a diastereomer In the case of isoleucme for example the diastereomer is an ammo acid not normally present m proteins called alloisoleucme... 

Some solid materials are very intractable to analysis by standard methods and cannot be easily vaporized or dissolved in common solvents. Glass, bone, dried paint, and archaeological samples are common examples. These materials would now be examined by laser ablation, a technique that produces an aerosol of particulate matter. The laser can be used in its defocused mode for surface profiling or in its focused mode for depth profiling. Interestingly, lasers can be used to vaporize even thermally labile materials through use of the matrix-assisted laser desorption ionization (MALDI) method variant. 

Tabic 7.2. Comparison o[ paLlern profiles for the different layers of partitioned archaeological samples. 

The many possible errors, as well as the difficulties inherent to the radiocarbon dating method itself, serve to emphasize the need for a close collaboration between archaeologists and natural scientists when dating archaeological samples by the radiocarbon method. 

However, in many archaeological samples pimarane diterpenoids are often absent, and of the abietane compounds only dehydroabietic acid remains. In fact, dehydroabietic acid is present as a minor component in the fresh resins, but its abundance increases on ageing at the expense of the abietadienic acids since the latter undergo oxidative dehydrogenation to the more stable aromatic triene, dehydroabietic acid [2,18]. If oxygen is available, dehydroabietic acid can be oxidized to 7-oxodehydroabietic acid and 15-hydroxy-7-oxodehydroabietic acid. Since these diterpenoid compounds are often the dominant components in archaeological samples [95,97], they are considered characteristic for the presence of Pinaceae resins. 

The survival of a-boswellic acid, p-boswellic acid and their O-acetates, which have been isolated only from frankincense, has been demonstrated in archaeological samples [99,107,113]. These compounds are considered as very useful specific chemical markers for the identification of frankincense in resinous archaeological materials. 

S. Hamm, J. Bleton, A. Tchapla, Headspace solid phase microextraction for screening for the presence of resins in Egyptian archaeological samples, Journal of Separation Science, 27,235 243 (2004). 

To summarise, a fractionation step allows the isolation of the compounds of interest from the other molecular constituents, particularly from the fatty acids that are well-ionised. To compensate for the low ionisation yield of some compounds, such as TAGs, the solutions may be doped with a cation. Samples are then directly infused into the ion electrospray source of the mass spectrometer. A first spectrum provides an overview of the main molecular compounds present in the solution based on the peaks related to molecular cations. The MS/MS experiment is then performed to elucidate the structure of each high molecular compound. Table 4.2 shows the different methods of sample preparation and analysis of nonvolatile compounds as esters and TAGs from reference beeswax, animal fats and archaeological samples. 

T.J. Wess, M. Drakopoulos, A. Snigirev, J. Wounters, O. Paris, P. Fratzl, M. Collins, J. Hiller, K. Nielsen, The Use of Small Angle X Ray Diffraction Studies for the Analysis of Structural Features in Archaeological Samples, Archaeometry, 43, 117 129 (2001). 

Table 10.1 Compounds trapped by headspace SPME from different resins, gum resins and archaeological samples, presented by Increasing retention indices, with the corresponding relative peak areas (%) for each substance... 

SPME/GC/MS is an efficient technique to reveal the presence of resinic substances in archaeological samples. Indeed, volatile terpenes are still present in very old archaeological samples (4000 years old), particularly in the case of compact matrixes, and can be trapped by the SPME fibre. In comparison with methylene chloride extraction, SPME is very specific and allows the direct analysis of the volatile terpenes content in complex mixtures including oils, fats or waxes. For this reason, headspace SPME is the first method to use when analysing an archaeological sample it will either allow the identification of the resin or indicate further sample treatment in order to detect characteristic triterpenes. The method is not really nondestructive because it uses a little of the sample but the same sample can be used for several SPME extractions and then for other chemical treatments. 

The groups are not exhaustive in representing all possible clay procurement and manufacturing localities for pottery sampled in the archaeological survey. Approximately one-third of the initially considered sherds - those characterized by medium to fine quartz sand - were not amenable to independent grouping or to membership in the established reference units. 

PCR) and compared with sequences in other individuals and modern specimens. However, ancient DNA is severely damaged and fragmented. Contamination of aged samples and extracts with modern DNA is a serious problem and, whilst the study of DNA in archaeological samples will constitute a major area of future activity in the discipline, current research will continue to focus on the authentication of samples of ancient DNA advances have been so rapid that perusal of the appropriate scientific journals is essential. For somewhat more recent views of the state of ancient DNA research, see Willerslev and Cooper (2005). 

---