Portable LIBS; Micro-invasive investigation; Pyrotechnological materials; Late bronze age workshop contexts; Tiryns-Greece;PIGMENT ANALYSIS; PAINTED PLASTER; COPPER; ABLATION; IRON; ENVIRONMENT; INSTRUMENT; ARTWORKS; BRONZES; GLASSES

Laser-Induced Breakdown Spectroscopy (LIBS) was used in the investigation of pyrotechnological materials (metal and ceramic items, glass-based objects, plaster-based materials) from several Late Bronze Age workshop and activity area contexts at Tiryns, Greece. The use of a portable instrument, which could be brought into the study place where all objects were housed, was crucial in order to establish the elemental content or verify the material composition of almost all materials analysed. In almost all cases, the LIBS analyses led to the preliminary identification of the materials investigated. In most cases, the results sufficed to confirm earlier research carried out or was in agreement with similar analyses published in the literature. The analyses demonstrate that the micro-invasive LIBS technique provides useful preliminary elemental characterization of most of the pyrotechnological materials while for some, additional work needs to be conducted for securing conclusive results. Essentially, the portability and compactness of the instrumentation enable its use in any workspace with a solid desk, light and electricity access which makes this technique very attractive for obtaining preliminary elementary results. While the technique remains limited by spot analyses it does open up an immense array of possibilities for routine characterization or speedy screening of different types of artefacts in any storage or museum context. These important methodological and scientific findings are considered prerequisite steps leading towards and aiding in responsible sampling strategies for further analyses. (C) 2017 Elsevier Ltd. All rights reserved.

Laser-induced breakdown spectroscopy; LIBS; laser spectroscopy; paleoclimate;MYTILUS-EDULIS; PECTEN-MAXIMUS; DA COSTA; ICP-MS; SCLEROCHRONOLOGY; TEMPERATURE; SEASONALITY; CHALLENGES; CHEMISTRY; BIVALVIA

The chemical composition of mollusk shells offers information about environmental conditions present during the lifespan of the organism. Shells found in geological deposits and in many archeological sites can help to reconstruct past climatic conditions. For example, a correlation has been found between seawater temperature and the amount of some substituent elements (e.g., magnesium, strontium) in the biogenerated calcium carbonate matrix of the shell, although it is very species-specific. Here we propose the use laser-induced breakdown spectroscopy (LIBS) to estimate Mg/Ca ratios in modern specimens of the common limpet Patella vulgata. An automated setup was used to obtain a sequence of Mg/Ca ratios across a sampling path that could be compared with the seawater temperatures recorded during the organism's lifespan. Results using four shells collected in different months of the year showed a direct relationship between the Mg/Ca ratios and the seawater temperature, although the sequences also revealed small-scale (short-term) variability and an irregular growth rate. Nevertheless, it was possible to infer the season of capture and the minimum and maximum seawater temperatures from the LIBS sequences. This fact, along with the reduction in sampling and measurement time compared with other spectrometric techniques (such as inductively coupled plasma mass spectrometry [ICP-MS]), makes LIBS useful in paleoclimatic studies.

The years 1289-1313 witnessed particularly prolific minting activities at different southern and central Greek mints on behalf of different polities. The coin issues are of great economic and political relevance, and therefore of interest to modern historians. Our understanding of these is based on traditional sources, either numismatic (types and finds), or historical. This paper aims to investigate the possibilities of adding further details to the picture through archaeometry. Specifically, tournois pennies of the three main mints of the region (Clarentza, Thebes, Naupaktos) excavated at Ancient Corinth were analysed according to two different non-destructive methods, X-ray fluorescence spectrometry (XRF) and laser-induced breakdown spectroscopy (LIBS). The resulting relative silver percentages and the fingerprints of the trace elements have supported our attempts to put the different coin types in chronological order and to add detail to the context and intent for each one of these. A vivid picture of monetary production emerges. The different issuing authorities were usually intent on maintaining a decent standard while variously trying to put pressure on rivals or to harmonise their productions with their allies. All the analysed mints were commercial in character, though they were subject to the great political changes affecting Greece in this period, the ambitions of the Angevin dynasty, the various challenges which it faced in Athens, the Peloponnese and the western Mainland, and finally the destructive arrival of the Catalans. In times of need, specifically military, these same mints could therefore rely on further bullion which reached them through internal or external political channels.

LIBS; prehistorical pigments; caves; calcite layer; climatic conditions;INDUCED BREAKDOWN SPECTROSCOPY

Painted caves are a specific environment which preservation needs multidisciplinary studies carried out within the different actors. The actions set-up must follow national and European ethics and treaties and be as less invasive as possible to preserve the integrity of the site. Studying colorants in caves should meet these expectations and take into account on-field conditions: high humidity rate, reduced access to electricity, etc. Therefore, non-invasive analyses should be preferred. However, their limits restrict the field of application and sometimes sampling and laboratory analyses must be used to answer the problematic. It is especially true when the pigment is covered by calcite. For this purpose, the Laser-Induced Breakdown Spectroscopy (LIBS) has been assessed to identify the composition with stratigraphic analyses. This study carries out in-depth profile on laboratory samples in conditions close to the ones meet in caves. Samples were prepared on a calcareous substrate using three pigments: red ochre, manganese black and carbon black and two binding media: water and saliva. All samples have been covered by calcite. Four sets of measurements have then been done using the LIBS instrument. The in-depth profiles were obtained using the Standard Normal Variate (SNV) normalization. For all the samples, the pigment layer was identified in the second or third shot, the calcite layer being quite thin. However, the results remain promising with the carbon black pigment but not really conclusive, the carbon being generally quite difficult to quantify.

Archeological objects; ceramics; laser-induced breakdown spectroscopy; LIBS; pottery;PIGMENT IDENTIFICATION; RAMAN MICROSCOPY; PAINTED ARTWORKS; LIBS

In recent decades, numerous analytical techniques have been used for the analysis of archeological samples. Laser-induced breakdown spectroscopy (LIBS) is a promising technique due to its practically nondestructive nature and minimal sample preparation. In this work, LIBS was used for the qualitative and quantitative elemental analyses of pottery manufactured in ancient settlements of Rome. The qualitative study showed that the ceramics were composed of Fe, Ca, and Mg. For quantitative analysis, calibration curves of Fe, Ca, and Mg were constructed with reference samples of each element in a KBr matrix with zinc as an internal standard. The results obtained by LIBS were compared with values obtained by atomic absorption.

LIBS; Laser-induced breakdown spectroscopy; Speleothems; Alterations; Ornated cave; Conservation;NEEDLE-FIBER CALCITE; MOONMILK DEPOSITS; TRACE-ELEMENTS; SPELEOTHEMS; ORIGIN; SPECTROMETRY; MORPHOLOGY; RESOLUTION; PROFILES; LIBS

Cave walls are affected by different kinds of alterations involving preservative issues in the case of ornate caves, in particular regarding the rock art covering the walls. In this context, coralloids correspond to a facies with popcorn-like aspect belonging to the speleothem family, mostly composed of calcium carbonate. The elemental characterization indicates the presence of elements that might be linked to the diagenesis and the expansion of the alterations as demonstrated by prior analyses on stalagmites. In this study, we report the use of laserinduced breakdown spectroscopy (LIBS) to characterize the elemental composition of one coralloid sample with a portable instrument allowing punctual measurements and a laboratory mapping setup delivering elemental images with spatial resolution at the micrometric scale, being particularly attentive to Mg, Sr, and Si identified as elements of interest. The complementarity of both instruments allows the determination of the internal structure of the coralloid. Although a validation based on a reference technique is necessary, LIBS data reveal that the external layer of the coralloid is composed of laminations correlated to variations of the LIBS signal of Si. In addition, an interstitial layer showing high LIBS signals for Fe, Al, and Si is interpreted to be a detrital clay interface between the external and the internal part of the coralloid. These preliminary results sustain a possible formation scenario of the coralloid by migration of the elements from the bedrock.

Laser Induced Breakdown Spectroscopy (LIBS); qualitative and quantitative analysis; metal artefacts;ABLATION

In the present work, we report on the analysis of archaeological metal artefacts from Late Bronze Age, performed by means of Laser Induced BreakdownSpectroscopy (LIBS). The experiment was carried out at ambient air and at 1064 nm of a Nd:YAG laser with pulse durations of 10 ns and energy of 10 mJ. The analytical information obtained by LIBS spectra was used for qualitative determination of the elements in the material used for manufacturing of the investigated objects. Quantitative estimation of the elemental concentration of tin and lead in the bulk of the samples was done after generating calibration curves for a set of four standard samples with a wide range of tin and lead concentrations and with similar matrix composition. The preliminary results of the qualitative and the quantitative analyses gave indications about the manufacturing process of the investigated objects and for their provenance as well.