Ochre fingerprints: Distinguishing among Malawian mineral pigment sources with Homogenized Ochre Chip LA–ICPMS

In this study, we compared the effectiveness of instrumental neutron activation analysis (INAA) of bulk ochre to laser ablation‐inductively coupled plasma mass spectrometry of homogenized ochre chips (HOC LA–ICPMS) at distinguishing among three ochre sources in northern Malawi. Both techniques upheld the Provenance Postulate; however, HOC LA–ICPMS required less sample material than INAA and facilitated fast, inexpensive replicate observations that allowed for more robust statistical analysis. Our results indicated that HOC LA–ICPMS is a maturing technique that will be a valuable option for analysing artefacts that require minimally destructive sampling but are too large to fit into the laser cell for direct ablation. With regard to the statistical procedures used, stepwise canonical discriminant analysis was demonstrated to be a highly effective method for distinguishing among ochre sources, even in the presence of significant intra‐source and intra‐sample heterogeneity. Continued development of the HOC sample preparation technique will expand the range of archaeological ochre artefacts that can be included in provenance studies and prevent bias towards artefacts of convenient‐to‐analyse dimensions.     

A MULTI‐ANALYTICAL APPROACH FOR THE CHARACTERIZATION OF COMMODITIES IN A CERAMIC JAR FROM ANTINOE (EGYPT)*

This paper describes a multi‐analytical chemical study performed on the original, almost totally conserved, content of a small ceramic jar from the Antinoe archaeological site (fifth to seventh centuries ad, Roman Egypt) and now belonging to the archaeological collection of the Istituto Papirologico ‘Girolamo Vitelli’ (Florence, Italy). Scanning electron microscopy with an energy‐dispersive X‐ray spectrometer (SEM–EDX), Fourier transformed infrared spectroscopy (FTIR) and X‐ray diffraction (XRD) were all used to characterize the inorganic components of the archaeological material. The organic substances were analysed using FTIR, direct exposure mass spectrometry (DE–MS) and gas chromatography – mass spectrometry (GC–MS). The inorganic component essentially consisted of halite (NaCl). Among the NaCl crystals, lamellar elements were identified. They were chemically characterized by carbonato‐apatite and showed a concentric morphology typical of the scales of small fish. The most prevalent organic constituents of the sample were monocarboxylic acids, α,ω‐dicarboxylic acids, and cholesterol and its oxidation products. The organic material composition was consistent with the occurrence of lipids of animal origin. In addition, diterpenes related to pine pitch were also identified. The overall results suggest that the material recovered in the small ceramic jar found in Antinoe is a residue of fish‐based pickles such as garum, muria, allex and liquamen, which were commonly used in Roman times.     

The taphonomy of cooked bone: characterizing boiling and its physico–chemical effects

Cooking is perhaps the most common pre–burial taphonomic transformation that occurs to bone, yet it is still one of the least understood. Little progress has been made in determining a method of identifying cooked bone in the archaeological record, despite its import for various branches of archaeology. This paper attempts to describe boiling in terms of its physico–chemical effects on bone, and uses a suite of diagenetic indicators to do this. It is shown that cooking for brief periods of time has little distinguishable effect on bone in the short term, but that increased boiling times can mirror diagenetic effects observed in archaeological bone. The relationship between the loss of collagen and alterations to the bone mineral is explored through heating experiments, and the results compared with archaeological data.The possibility of boiling being used as an analogue for bone diagenesis in future studies is raised, and the key relationship between protein and mineral is once again highlighted as vital to our understanding of bone diagenesis.     

Collagen deamidation in archaeological bone as an assessment for relative decay rates

Attempts to extend methods for dating archaeological bones beyond that of radiocarbon dating, such as amino acid racemization, have met with limited success owing to the dependence on multiple environmental factors and controls. Despite facing similar challenges, deamidation of glutamine has recently been investigated as a potential indicator of ‘thermal age' in archaeological bones, as well as a measure of their preservation quality. In this study, we undertook a series of simulated diagenetic experiments to understand the various factors affecting deamidation. Further, we analysed bones from different Middle Palaeolithic layers from Grotte Mandrin (France), with the results suggesting potential use of deamidation for relative dating, but only in case of extremely well‐preserved layers. The results also suggested the possible use of attenuated total reflectance‐Fourier transform infrared (ATR‐FTIR) spectroscopy as a screening test for soluble collagen before proteomic analysis.     

THERMAL ALTERATIONS IN ARCHAEOLOGICAL BONES*

Archaeological bones, found close to Mexico City (Tlatelcomila), with alterations due to probable thermal exposure attributed to a possible case of cannibalism, have been characterized by XRD, SAXS and SEM. It is shown how these non‐destructive techniques, which are not conventionally used in archaeological research, may provide useful information. The deterioration degree of the bone structure is quantified through parameters such as gyration radius or fractal dimension. As some of the reported modifications could be attributed to diagenesis, a discussion is presented in terms of bone crystallinity and ionic exchange. Furthermore, the hydroxyapatite crystallite size increased depending on colour: this feature is not explained by diagenesis—it can only be attributed to temperature. We conclude that the samples were thermally treated. Indeed, thermal treatment alters the structure and morphology of bone at a very fine level (microscopic and nanometric), while morphology follows the structural modifications. It is determined that the studied human bones were treated at three different temperatures close to 100, 250 and 600°C. Therefore, they were either boiled (barbacoa) or grilled.     

NO STONE UNBURNED: A COMPOSITIONAL ANALYSIS OF OBSIDIAN MICRODEBITAGE BY LASER ABLATION TOF–ICP–MS

Obsidian is an effective material for the study of prehistoric raw material use and exchange, due to the high degree of homogeneity and redundancy of obsidian materials and manufactured objects in the archaeological record. The destructive nature of many analytical techniques often impedes compositional research because of the damage that may occur to priceless archaeological artefacts. The combination of time‐of‐flight (TOF) ICP–MS with a laser ablation sample introduction system provides a highly efficient means of chemically characterizing obsidian. This study shows that sample size limit capabilities of TOF–ICP–MS analysis of obsidian can reach less than 100 μm. Sampling and analysis of microartefacts enables researchers to overcome problems of sampling bias with very little damage to the valuable existing materials within the archaeological record and expands the potential for chemical compositional analyses in archaeology.     

Polarizing Microscopy Identification of Chemical Diagenesis in Archaeological Cementum

Cementum increment analysis can potentially retrieve relatively complete, high-precision seasonality and mortality profiles from archaeological mammalian tooth assemblages. However, cementum exhibits many similarities to bone in composition, histology, ultrastructure, and even microstructure. Consequently, the mineralized dental tissue may be prone to the same processes of post-depositional chemical alteration that affect bone. This article reviews the issues surrounding chemical diagenesis in cementum and presents a new application to archaeological ungulate cementum of a polarizing microscopy technique that has previously been utilized to identify the effects of chemical diagenesis in archaeological bone and human cementum (Geusa et al., 1999; Gilbert, 1989; Watson, 1975; Zeder, 1978). It is argued that the post mortem leaching of collagen and the diagenetic growth of apatite crystallites can develop into banded features that mimic seasonal cementum increments. This pattern of diagenesis is demonstrated in multiple locations on a macroscopically well-preserved Upper Pleistocene-age archaeological tooth, which was previously interpreted by the author to exhibit biogenic seasonal cementum increments (Stutz, 1993; Stutz et al., 1995). It is suggested that if researchers seek to retrieve seasonality and mortality data from archaeological cementum, the microscopy analysis protocol must include screening of a pilot sample for the frequency and extent of chemical diagenesis.     

NON‐DESTRUCTIVE ANALYTIC METHOD USING XRF FOR DETERMINATION OF PROVENANCE OF ARCHAEOLOGICAL OBSIDIANS FROM THE MEDITERRANEAN AREA: A COMPARISON WITH TRADITIONAL XRF METHODS*

A non‐destructive analytical method using wavelength‐dispersive X‐ray fluorescence (WDXRF) that allows the establishment of the provenance of archaeological obsidians was developed and a comparison with the classical XRF method on powders is discussed. Representative obsidian samples of all the geological outcrops of archaeological interest of the Mediterranean area (Lipari, Pantelleria, Sardinia, Palmarola and the Greek islands of Melos and Gyali), were analysed with the normal procedures used in rock analysis by XRF (crushing, powdering and pelletizing). The non‐destructive XRF analysis was instead conducted on splinters taken from the original geological pieces, with the shape deliberately worked to be similar to the refuse usually found at archaeological sites. Since the analysis was conducted on the raw geological fragment, intensity ratios of the suitably selected chemical elements were used, instead of their absolute concentrations, to avoid surface effects due to the irregular shape. The comparison between concentration ratios (obtained by traditional XRF methods) and the intensity ratios of the selected trace elements (obtained from the non‐destructive methodology) show that the different domains of the chemical composition, corresponding to the geological obsidians of the source areas, are perfectly equivalent. In the same way, together with the geological splinters, complete archaeological obsidians, from Neolithic sites, may be analysed and their provenance may be determined. The proposed non‐destructive method uses the XRF method. Due to its sensitivity, low cost and high speed, it is surely an extremely valid instrument for the attribution of the provenance of the archaeological obsidian from Neolithic sites.     

The application of a new method of Fourier Transform Infrared Spectroscopy to the analysis of burned bone

A new method of Fourier Transform Infrared Spectroscopy (FTIR) is applied to the analysis of burned bones. FTIR analyses were undertaken to examine changes in Crystallinity Index (CI), Ca/P and C/C ratios in bone experimentally burned to known, but varying, temperatures and durations. Three sample groups were used to assess the new FTIR method. Blind tests were performed to assess the use of the CI for predicting burning conditions. The results suggested that the new method of FTIR was preferable to the traditional approach, but that CI is affected by factors other than temperature of burning, including the method of FTIR used, and that predictions of burning conditions in archaeological material may not extend beyond that of ‘high’ or ‘low’ intensity of burning.     

A procedural guide to metacarpal radiogrammetry in archaeology

The technique of metacarpal radiogrammetry was devised in 1960 as a clinical method to aid in the identification of thinned cortical bone, which may help in diagnosis of osteoporosis. Through taking measurements from radiographs, calculations of the amount of cortical bone can be made. The technique is relatively simple and is not destructive. This paper examines the value of the application of this technique to archaeological remains. A standardized methodology of bone assessment is incorporated to enhance the comparability of future research. Statistical tests demonstrate that the technique is robust, as the position of the bone on the film, radiographic enlargement and use of either the left or right metacarpal will not affect the results obtained. However, differences in film type and measurement position can introduce unacceptable variance into the results. Therefore, guidance is given on future applications of the technique. The technique does have value as a widely available, non‐destructive technique for assessing cortical bone loss and the probable prevalence of osteoporosis in archaeological collections. Copyright © 2004 John Wiley & Sons, Ltd.     

Pick the Right Pocket. Sub‐sampling of Bone Sections to Investigate Diagenesis and DNA Preservation

Many archaeological bones display a heterogeneous degradation pattern. Highly degraded bones could contain pockets of well‐preserved bone, harbouring good quality DNA. This dichotomy may explain why the relationships between global bone preservation parameters such as histological integrity, bone mineral crystallinity or collagen yield, and bulk DNA preservation/amplification success rate have been found to be at best, weak to moderate. In this pilot study, we explore whether or not a more localised approach will highlight a stronger relationship between diagenetic parameters and DNA preservation. This study includes a detailed histological characterisation of bone diagenesis in sub‐areas of three bone samples. Regions of the same bone, which displayed differential degrees of preservation or type of diagenesis were sampled for further analysis and both genetic (small scale Illumina MiSeq sequencing) and chemical (Fourier‐transform infrared spectrometric analysis) analyses were performed. The aim was to investigate how bone diagenetic processes relate to DNA preservation at a higher resolution than in previous studies. This is key in order to improve DNA analytical success rates. The expected relationship between bone and DNA preservation (retrieved endogenous DNA) was observed and the results corroborate previous work that DNA preservation is linked to the integrity of bone collagen and mineral. The results further suggest that non‐biological diagenetic alterations such as etching and the presence of mineral infiltrations and inclusions have a negative effect on DNA preservation/extraction. Copyright © 2016 John Wiley & Sons, Ltd.     

The crystallinity of ancient bone and dentine: new insights by transmission electron microscopy

We studied various archaeological and palaeontological bones and dentines from different burial environments by Fourier transform infrared spectroscopy (FT–IR), X–ray diffraction (XRD) and transmission electron microscopy (TEM), in the framework of a general study of diagenesis. FT–IR and XRD were used to evaluate the global preservation state of the bone and dentine mineral phase by determining a splitting factor (SF) or a crystallinity index (CI), respectively. These data can be combined with studies on the nanometer scale made with TEM. This latter technique,coupled with electron microdiffraction, provides determination of dimensions and shapes of individual bone and dentine apatite nanocrystals as well as of secondary minerals formed during diagenesis. It enables us to distinguish between heat–induced recrystallization processes and crystal growth in solution occurring during diagenesis.     

Cooked Bones? Method and Practice for Identifying Bones Treated at Low Temperature

Is it possible to determine low‐temperature cooking in archaeological bones? The indirect exposure of bones to fire at low temperature (≤ 100 °C), linked to cooking, produces macroscopic modifications on these bones. These modifications have not been clearly or systematically described previously. Instead, physicochemical changes at nanometric level are only now beginning to be understood. In this paper, our principle aim is to explore new methods and techniques that correlate macroscopic features such as smoothness or light transparency with physicochemical characterization results that could aid towards detecting cooked bones in the archaeological record. This study then selected 11 archaeological samples, both human and non‐human. Bones were considered to be thermally treated or not, on the basis of macroscopic criteria. Complementary characterization techniques were used to study morphology (scanning electron microscopy and small angle X‐ray scattering), structure (X‐ray diffraction and transmission electron microscopy), local composition (energy‐dispersive X‐ray spectroscopy) and texture (gas adsorption). Indeed, fractal dimension, particle size, crystalline percentage or specific surface area may well explain some of the macroscopically observed modifications on these samples. The possibility that such apparent modifications may also be due to diagenesis is also considered. From an archaeological point of view, the results are promising. Our characterization of human and non‐human bones demonstrates that physicochemical techniques are complementary and provide good criteria against which to distinguish boiled from un‐boiled archaeological samples. Copyright © 2013 John Wiley & Sons, Ltd.     

REPRODUCIBILITY OF ELEMENTAL ANALYSES OF BASALTIC STONE ARTEFACTS BY QUADRUPLE ICP–MS USING DIFFERENT SAMPLE SIZES AND DIGESTION METHODS,WITH IMPLICATIONS FOR ARCHAEOLOGICAL RESEARCH

Using high‐precision inductively coupled plasma mass spectrometry (ICP–MS), we measured >40 elements in basalts sampled by diamond micro‐drills to evaluate the effectiveness of different digestion methods and the reproducibility of elemental analysis for different sample sizes from 5 mg to 100 mg. The results indicate that those elements that are most suitable for geochemical characterization, such as rare earth elements (REE), high‐field strength elements (HFSE) and certain mobile elements (Rb, Sr, Th, U), show excellent reproducibility with an average relative standard deviation (RSD) of 3% between open‐beaker and pressured ‘bomb’ digestion methods. This observation rules out the presence of refractory phases such as zircon, which can only dissolve in pressured ‘bombs’, and suggests that the results from open‐beaker digestion are reliable. The ICP–MS data for powders of different weights ranging from 10 to 100 mg collected from two fine‐grained basalt artefacts display excellent reproducibility, with a RSD of <5% for the most important elements. The reproducibility is reduced when including the 5 mg weight fraction (RSD of ～2–9%), which is still sufficient for archaeological applications. Our results demonstrate the usefulness of 10 mg samples for elemental measurement, which is valuable for geochemical characterization and sourcing of fine‐grained basalt artefacts from museum collections that require minimal destructive sampling.     

INDUCTIVELY COUPLED PLASMA-MASS SPECTROMETRY FOR THE ANALYSIS OF ANCIENT METALS*

Inductively coupled plasma-mass spectrometry (ICP-MS) is a relatively new analytical technique, growing in popularity, that offers many advantages over previously available instrumentation for the measurement of both the elemental and isotopic composition of metallic antiquities. The application of this method of analysis to archaeological metalwork is discussed and the technique compared with other methods of analysis commonly used in archaeometallurgy. Particular attention is drawn to the potential pitfalls and difficulties associated with ICP-MS and the need for extremely careful sample preparation and instrument operation.     

Assessing Ceramic Compositional Data: A Comparison of Total Reflection X‐ray Fluorescence and Instrumental Neutron Activation Analysis On Late Iron Age Spanish Celtiberian Ceramics

A solid‐phase, non‐chemical processing protocol was recently developed as a means of chemically characterizing archaeological ceramics by total reflection X‐ray fluorescence (TXRF). Following this methodology, TXRF can provide semi‐quantitative determinations for 18 elements with comparable levels of precision and accuracy for the majority of them in comparison with a clay reference material analysed by instrumental neutron activation (INAA). In order critically to assess the analytical capabilities of TXRF, a large sample set of Late Iron Age Spanish Celtiberian ceramics and modern clays was analysed both by TXRF and INAA. Semi‐quantitative chemical data provided by TXRF and quantitative data provided by INAA were subjected to commonly used multivariate statistical methods as a way of evaluating the ability of the new technique to discriminate among different compositional groups. The comparison of the two data sets shows no significant discrepancies, thereby allowing support for the same archaeological interpretation. These results suggest that TXRF has potential applicability for compositional characterization of archaeological ceramics, providing data that are useful for provenance studies.     

Skeletal Manifestations of Skin Ulcer in the Lower Leg

Skin ulcers of the lower leg are known to cause both destructive and, more commonly, bone‐forming lesions. Typically, bone‐forming lesions in this disorder have clearly defined margins although there may be extensive reactive bone formation involving much or all of the adjacent diaphysis. These lesions are best described in patients from tropical areas, and in these environmental contexts, these are known as tropical ulcers, but leg ulcers can be caused by a variety of diseases and conditions, of which vascular insufficiency plays an important role among the elderly. The lesions are important clinically because of the disability associated with the ulcer and because of complications that can develop including osteomyelitis and cancer. In most cases, the bone lesions caused by ulcer are easily diagnosed in archaeological human skeletal remains and provide some insight into the prevalence of this disorder in antiquity. In this paper, we review the gross and radiological manifestations of bone lesions resulting from overlying skin ulcer in tibiae of 13 cases including archaeological and modern medically documented skeletons. In two of the cases, there is medical documentation regarding the presence of a chronic ulcer on the lower leg. The objectives of this paper were to explore the diversity of bone lesions associated with ulcers of the tibia and to provide an improved basis for the diagnosis of this disorder in human skeletal remains. Copyright © 2011 John Wiley & Sons, Ltd.     

ARCHAEOLOGICAL AMBERS FROM NORTHERN ITALY: AN FTIR–DRIFT STUDY OF PROVENANCE BY COMPARISON WITH THE GEOLOGICAL AMBER DATABASE*

European geological ambers of five different localities and types, and Italian geological ambers from seven different deposits have been studied with Fourier transform infrared spectroscopy (FTIR) and diffuse‐reflectance infrared Fourier transform (DRIFT). Ambers from several localities have been characterized for the first time. The research aims to create a database of European ambers, containing both FTIR and DRIFT data. The FTIR spectra are easily comparable with the data commonly available in the literature, whereas DRIFT analyses are shown to be more useful to characterize the archaeological finds. The provenance of several archaeological ambers from northern and southern Italy, dating from the Middle Bronze Age to the Iron Age, is assessed on the basis of the developed database. Of the 35 analysed archaeological objects, all but five are composed of Baltic succinite amber.     

Isolation and Isotopic Analysis of Individual Amino Acids from Archaeological Bone Collagen: A New Method Using Rp‐hplc

This paper presents a new method for the isolation and isotopic analysis of some individual amino acids from proteins. The technique and its constituent steps are discussed; then isotopic analyses of amino acids from several samples of bone collagen from the Late Roman site of Poundbury, Dorset, UK are presented. The applications of the method are discussed, as well as some advantages of this technique relative to other methods. Although developed for use with archaeological bone collagen, the technique is equally applicable to other proteinaceous materials. The use of reversed‐phase HPLC avoids problems of isotopic fractionation inherent in using ion‐exchange HPLC. Amino acids are isolated preparatively, allowing both carbon and nitrogen isotopic values to be measured on a single sample using CF‐IRMS. Since amino acids are isotopically analysed in an underivatized form (unlike GC‐C‐IRMS), the method also presents the possibility of collecting the CO₂ generated during CF‐IRMS: this would allow the subsequent dating by ¹⁴C‐AMS of individual amino acids isolated from archaeological samples.     

Restrictions on fluorine depth profiling for exposure age dating in archaeological bones

Archaeological fragments of bone and teeth that are exposed to a humid environment take up fluorine from the surrounding soil. The fluorine ion replaces the hydroxyl group in the mineral phase of the bone, forming chemically more stable fluorapatite. In cortical parts of the long bone diaphysis a fluorine concentration profile can be observed, which decreases from the outer surface and the marrow cavity towards the inner parts of the bone matrix. Geological time spans are needed for this process to reach equilibrium and for the distribution to become uniform. As the shape of the profile, which can be described by a diffusion model, contains information on the exposure duration of the fossil object, several attempts to use fluorine profiling as a dating method have been undertaken. The distribution of fluorine in an archaeological sample however is strongly influenced by environmentally induced processes of bone diagenesis, i.e. alteration in the structure and composition of the mineral phase and degradation of organic components that may make the time information indistinct. The primary chemical composition of bones can thus be obscured by diagenesis within tens, hundreds or thousands of years. This depends more on the diagenetic environment than on the geological age. To observe the impact of environmental influence on the profile shape, samples from several burial sites featuring various soil conditions have been analyzed for their fluorine distribution and preservation state. This paper provides an overview on the restrictions that have to be considered when attempts are undertaken to relate a fluorine diffusion pattern to the archaeological age of a bone specimen.