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This talk will outline how the immediate impact of climatic events on societies of the past can be identified and quantified more robustly by archaeological research using mollusc shell records.Advances in data acquisition regarding speed and resolution promise improved access to this high-resolution climate archive, and thus an improved interdisciplinary palaeo-perspective. Different to most long-term climate archives, mollusc shells are often found on site and record temperature changes on a seasonal scale, allowing us to measure weather extremes on a resolution that a) would have been immediately noticeable by individuals and b) is essential to subsistence strategies. In particular, we hope to provide a better environmental backdrop to the question of the climatic impact on the Neolithic Dispersal along the Mediterranean coasts and verify extreme short-term events on site, should they have occurred.We are employing an innovative way of acquiring sea surface temperature (SST) data using a combined approach of stable oxygen isotopes (δ18O) and LIBS-screening (Laser Induced Breakdown Spectroscopy), resulting in a lower quantity of δ18O values required per shell and, as a result, a higher quantity of sampled shells. Our improved data acquisition process enables us to use a high resolution (i.e. +1000 data points per shell record) as well as a high sample quantity (100s of shells) approach, that provides extensive coverage across entire site stratigraphies. By sourcing our climate data from shell remains found in archaeological layers, we are able to directly compare archaeological information of that layer with the individual climate records, side-stepping the need of radiocarbon-dating either dataset extensively and instead using the shared stratigraphic position to infer temporal concurrence.This high quantity and high resolution approach produces a combined natural and societal archive, that because of its size can more easily and robustly reveal links between society and the immediate climate change, extreme events and natural hazards it experienced.

This document outlines aspects of innovation considered relevant for HS and proposes general actions for an Exploitation plan. Innovation is an essential component of the strategic objectives of E-RIHS. It encompasses novel research actions, offer of unique access services and provision of smart tools. Exploiting innovation, for the benefit of the E-RIHS ecosystem and the society, requires a number of actions along the innovation chain, including the presence of an efficient monitoring and evaluation system, appropriate knowledge and technology transfer channels, proper IPR protection and efficient communication with key stakeholders both in the public and the private sectors. An overall systematic approach to the above will ensure success and sustainability of ERIHS as an innovator and as a leader in the global HS landscape. This document is Deliverable 6.2, elaborated in the context of project IPERION HS, WP-06: Innovation and Exploitation, Task 6.4: Exploitation Plan. The analysis for the work presented herein was based on extensive interactions between the co-authors and builds upon a number of documents produced in the context of IPERION HS and E-RIHS PP (in particular Deliverable 9.4: Innovation Agenda).

International audience; Reaction control by laser light is a unique method of the reaction dynamics mastery in the molecular chemistry. We provide evidence of phase control processing with femtosecond lasers in macroscopic solids. Rutile TiO2 monocrystals with (001) and (100) surface orientations were irradiated with repetitive pulses of femtosecond KrF laser of variable fluences and a temporal delay between two superimposed linearly polarized beams. The appearance of three types of surface morphology was thoroughly analyzed: low-spatial frequency laser-induced periodic surface structures (LSFL), grooves and unusual featureless flat area (FFA). The interaction of light with the excited surface led to the onset or suppression of the subwavelength LSFL, depending on whether the temporal delay between laser beams is larger or smaller than the critical value of ~6 ps. By contrast, the suprawavelength grooves and FFA appeared at longer temporal delays. A strong decrease of the grooves onset energy was observed on the (001) oriented crystal after the delay of ~8 ps; the decrease of onset energy was also observed on the (100) oriented crystal, where FFA appeared instead of grooves. The critical delay is discussed in framework of a phenomenological model describing the energy evolution of excited transient states along the "reaction" coordinate.

A simple and straightforward methodology, based on laser-induced fluorescence (LIF) spectroscopy, is introduced as a real-time monitoring tool to follow laser ablation thinning of degraded varnish films in the context of paintings conservation. The proposed methodology defines a simple spectral indicator which monitors the removal of varnish and signals when a critical point has been reached beyond which interaction of the laser beam with the underlying paint layers might take place. The methodology has been developed upon a series of UV laser (KrF excimer laser, λ = 248 nm) ablation experiments, carried out on model, artificially aged, dammar films of varying thickness. It is based on measuring LIF emission spectra during cleaning, and the evolution of the process is quantified by means of the fluorescence ratio (R), which represents the fluorescence emission signal loss in ablated areas relative to the non-irradiated varnish. A graphical representation of R versus the number of ablative laser pulses, traces closely the thinning of the varnish layer defining clear-cut regimes indicative of partial, critical and complete varnish removal. In the critical regime an abrupt change of the value of R is observed and this is of great importance because it determines the limit above which further varnish removal may place the underlying paint-layers at risk. Moreover, the ratio of the varnish thickness over the optical penetration depth is significant for the discrimination of the different regimes for varnish thinning and the adjustment of the methodology for optically transparent or opaque films. All the experimental results are consistent with a simple theoretical description of R, based on the Beer-Lambert law.

Elemental analysis of biogeochemical archives is an established technique used to study climate in a range of applications, including ocean circulation, glacial/interglacial climates, and anthropogenic climate change. Data from mollusc archives are especially important because of their global abundance and sub-annual resolution. Despite this potential, they are underrepresented among palaeoclimate studies, due to enigmatic physiological influences skewing the elemental record. Understanding the patterns behind these influences will improve data interpretation and lead to the development of new climate proxies. Here, we show for the first time that extensive spatial mapping of multiple mollusc specimens using Laser Induced Breakdown Spectroscopy (LIBS) across a wider region can resolve enigmatic patterns within the elemental record caused by physiological influences. 2D elemental (Mg/Ca) maps of whole limpet shells (Patella caerulea) from across the Mediterranean revealed patterns of variability within individual mollusc records as well as within isochronous parts of specimens. By registering and quantifying these patterns, we established previously uninterpretable correlations with temperature (R2 > 0.8, p

The potential of laser induced breakdown spectroscopy (LIBS) as a non-contact probe, for characterizing organic photovoltaic devices during selective laser scribing, was investigated. Samples from organic solar cells were studied, which consisted of several layers of materials including a top electrode (Al, Mg or Mo), organic layer, bottom electrode (indium tin oxide), silicon nitride barrier layer and substrate layer situated from the top consecutively. The thickness of individual layers varies from 115 to 250 nm. LIBS measurements were performed by use of a 40 femtosecond Ti:Sapphire laser operated at very low pulse energy (

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.

Records of past environmental conditions in shell carbonate are usually derived from compositional analysis (i.e. trace elements, stable oxygen, carbon, and nitrogen isotopes) performed along the direction of the shell’s growth and thus through time. However, compositional variations within isochronous parts of the shell can distort the environmental record and are difficult to assess without extensively mapping the whole shell. Here we apply Laser Induced Breakdown Spectroscopy (LIBS) to efficiently map the elemental change throughout the growth increments of three mollusc shells (Conomurex fasciatus, Ostrea edulis, Anomalocardia flexuosa). We employ an automated LIBS setup to map the Mg/Ca composition of whole shell sections with over 2,000 data points per hour. By assessing the spatial variability of Mg/Ca intensity ratios this method has the potential to mitigate distorted results while increasing the resolution of derived palaeoenvironmental information.

Laser-induced breakdown spectroscopy (LIBS) is a versatile analytical technique that can be used to probe the elemental composition of materials in diverse types of heritage samples, objects or monuments. The main physical principles underlying LIBS are presented along with analytical figures of merit and technical details concerning instrumentation. In practice, LIBS analysis does not require any sample preparation and the technique is nearly non-invasive, offering close to microscopic spatial resolution and the possibility for depth profile analysis. These features are, at present, available in a number of compact or transportable instruments that offer versatility and enable the use of LIBS for the analysis of a broad variety of objects/samples at diverse locations and this can be highly valuable at several stages of archaeological investigations and conservation campaigns. Representative examples are presented indicating how LIBS has been used to obtain compositional information for materials in the context of archaeological science, art history and conservation.

Elemental analysis of biogeochemical archives is an established technique used to study climate in a range of applications, including ocean circulation, glacial/interglacial climates, and anthropogenic climate change. Data from mollusc archives are especially important because of their global abundance and sub-annual resolution. Despite this potential, they are underrepresented among palaeoclimate studies, due to enigmatic physiological influences skewing the elemental record. Understanding the patterns behind these influences will improve data interpretation and lead to the development of new climate proxies. Here, we show for the first time that extensive spatial mapping of multiple mollusc specimens using Laser Induced Breakdown Spectroscopy (LIBS) across a wider region can resolve enigmatic patterns within the elemental record caused by physiological influences. 2D elemental (Mg/Ca) maps of whole limpet shells (Patella caerulea) from across the Mediterranean revealed patterns of variability within individual mollusc records as well as within isochronous parts of specimens. By registering and quantifying these patterns, we established previously uninterpretable correlations with temperature (R2 > 0.8, p < 0.01). This outcome redefines the possibilities of accessing sub-annual climate proxies and presents the means to assess annual temperature ranges using oxygen isotope analysis requiring only 2 samples per shell.

Detailed analytical work based on mobile Raman microspectroscopy has been performed on a mortuary assemblage, comprising a group of 59 stone artifacts (vessels, implements and figurines) excavated in one of the richest burial sites in south-central Crete, Tholos tomb P at the Minoan site of Porti (ca. 2700–1700 BCE). Mineral identification was possible for over half of the objects examined and the results expand our understanding, originally obtained on the basis of visual and microscopic characterization of the objects. Patterns of variability in the stones investigated are correlated with the typological repertoire of the final products and compared with data from the neighboring site of Apesokari; further inferences on craft specialization issues are finally drawn. In all, the data obtained lead us to suggest that stone vessel manufacture at Porti was predominantly focused on the exploitation of local softstone outcrops. This hypothesis agrees with the current knowledge concerning the geological formation of the Asterousia area, on the northern fringes of which the site of Porti is located. In parallel, the capacity of mobile Raman microspectrometry to contribute to stone object characterization as regards their mineral composition is discussed along with advantages and limitations of the methodology followed. Raman analysis is preformed quickly, non-invasively, directly on the object and over several spots across its surface for probing heterogeneous mineral distributions. The mobile spectrometer permits measurements to be conducted on location, namely within the museum study facilities. A major limitation with respect to obtaining clean analytical information resulted from strong fluorescence emission observed in some of the measurements, which interfered with the Raman scattering signal. These emissions were attributed to organic materials present on the stone surface either as environmental contamination or as a result of previous, often undocumented, conservation treatments. Finally, the need to collect and thoroughly characterize local stone outcrops as well as archaeological stone objects has become evident and building a representative Raman spectral database will certainly facilitate future studies.

Fluorescence excitation–emission spectroscopy and Surface-Enhanced Raman Spectroscopy (SERS) are applied in the analysis of model proteinaceous compounds with the aim to develop versatile methodologies so as to aid analytical investigations of organic and bio-organic archaeological residue materials. A compact mobile Raman spectrometer was employed and SER spectra were collected from thin film samples of natural amino acids (L-Trp, L-Tyr, L-Cys) and egg white, properly mixed with silver colloidal nanoparticles. In parallel the fluorescence behavior of egg white, egg yolk and milk films was investigated on a laboratory spectrofluorimeter. Comparison of 2D-fluorescence excitation-emission maps collected from fresh and aged films, revealed the formation of new fluorophores, indicative of chemical alteration and degradation process of the proteins taking place during aging.

The use of composite polymeric insulators in overhead high voltage (HV) power transmission lines and in substations has been rapidly growing, as a result of their excellent operational performance, even under environmental pollution conditions. However, it has been observed that the insulation capacity of the composites deteriorates gradually for in-service insulators as a result of ageing, caused by several processes arising because of environmental, electrical and mechanical stresses. For these reasons, development of non-destructive diagnostic techniques for real-time, on-site inspection of the insulators' condition is required for ensuring high reliability of power transmission networks. To this end, laser-induced breakdown spectroscopy (LIBS) is found to offer an effective and reliable method for assessing the state of polymeric insulators, primarily silicone rubber (SIR) ones, that have been in service for up to 20 years on the HV power network of Crete, Greece. Determining the type of composite and furthermore the chemical integrity of the insulator is based on simple spectral indicators, which reflect the extent of chemical modifications induced on the insulator surface, as found in both standard and remote LIBS measurements performed in the laboratory. As a result, a stepwise diagnostic procedure was proposed and tested in an outdoors campaign, demonstrating that LIBS can become a field deployable technique for the efficient and reliable assessment of the performance of HV outdoor insulators in service.

Nanohybrids, composed of luminescent zinc oxide (ZnO) nanoparticles dispersed in an inert polydimethylsiloxane (PDMS) matrix, exhibit an excellent ability to follow changes in the type and composition of their surrounding atmosphere. These changes are found to affect the UV photoluminescence (PL) emission of the ZnO-PDMS hybrids measured at room temperature. The influence of irradiation parameters, such as excitation intensity and wavelength, on the response of the ZnO-PDMS sensor against ethanol and oxygen, have been systematically investigated in a comparative study performed employing pulsed excitation at 248 and 355 nm. This study represents the first demonstration that the sensing performance of the PL-based ZnO sensors can be optimized by tuning the excitation parameters and it particularly illustrates that maintaining a low pump energy density is crucial for enhancing the sensitivity of the sensor achieving response values approaching 100%.

Laser-based surface patterning of rutile TiO2 monocrystals with (001) and (100) surface orientation is investigated following irradiation by a femtosecond KrF laser (248 nm) with variable fluences and multiple linearly polarized beams. Different types of structures were observed: volcano-like craters, nanoparticle-covered structures, ripples, and grooves. Furthermore, two kinds of distinct laser-induced periodic structures, 1D and 2D patterns, were observed. Morphological maps of characteristic surface morphologies were produced for each crystalline orientation, which indicate the significant influence of the crystalline anisotropy.

Pollution of insulators is one of the most significant problems that can affect the reliability of power systems. Several practices have been employed to improve the insulation performance under polluted conditions such as extending the creepage distance, using specially designed profiles, washing of insulators and using hydrophobic materials to manufacture insulators or to coat their surfaces. Depending on the pollution type and severity as well as the local climatic conditions at the site of installation, different maintenance procedures against pollution should be employed. In this study, the insulators' pollution problem in the transmission system of Crete is described based on a statistical analysis of the insulators' faults since 1969. Also, the practices employed against insulators' pollution as well as their effectiveness are presented. Among them, the most efficient practice has been evinced the use of polymeric coatings and composite insulators. However, after about 2 decades of their large scale installation, without any faults, their performance becomes questionable due to the ageing of the polymeric materials. In order to prevent the risk of the in-service insulators failures, a fruitful collaboration of power network operator with local academia and research institutes has led to the investigation of new diagnostic procedures aiming at the assessment of the condition of field-aged insulators. To this end, the use of laser-induced breakdown spectroscopy (LIBS) technique is proposed for the remote and real-time diagnosis of the condition of in-service composite insulators.

A new optical gas sensor platform based on highly luminescent ZnO-polymer nanohybrids is demonstrated. The nanohybrids consist of ZnO nanoparticles, typically 125 (±25) nm in size, dispersed in an inert cross-linked polydimethylsiloxane (PDMS) matrix. Upon exposure to ethanol-enriched air at room temperature, the nanocomposites exhibit a clear increase in their photoluminescence (PL) emission, which shows a nearly Langmuir dependence on the alcohol vapor pressure. The response time is on the order of 50 s, particularly at low ethanol concentrations. The limit of ethanol vapor detection (LOD) is as low as 0.4 Torr, while the sensor remains unaffected by the presence of water vapor, demonstrating the potential of the ZnO–PDMS system as an optical gas sensing device. The interaction of the ZnO nanoparticles with molecular oxygen plays an essential role on the overall performance of the sensor, as shown in comparative experiments performed in the presence and absence of atmospheric air. Notably, O2 was found ...

NMR spectroscopy is a powerful analytical tool for the identification and quantitative analysis of organic materials in a cultural heritage context. In this report, we present an analytical NMR protocol for the identification and semiquantification of egg yolk binders and mixed binding media that also contain a drying oil, namely linseed oil. The samples studied have been artificially and/or naturally aged in order to simulate the composition of organic materials in paintings. Analysis of the 1D and 2D NMR spectra showed that egg yolk can be identified even in binding media of considerable age via signals originating from cholesterol and/or cholesterol oxidation products present in the aged binding medium. Based on cholesterol-related and other lipid signals in the NMR spectra of egg yolk binders, a molecular marker (R/F) that suggests the presence of egg yolk in paint binders is proposed. Via this marker, the presence of egg yolk in the organic material obtained from an early 18th century Greek icon is confirmed, and this is further verified by 2D NMR spectroscopy. It is demonstrated that NMR molecular markers developed to estimate the hydrolysis/oxidation state of oil paintings are also suitable for the analysis of egg yolk and mixed medium (egg yolk–linseed oil) binders, indicating the generality of the NMR methodological approach in the analysis of organic materials in a cultural heritage context. Copyright © 2014 John Wiley & Sons, Ltd.

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.

A novel, portable spectrometer, combining two analytical techniques, laser-induced breakdown spectroscopy (LIBS) and diffuse reflectance spectroscopy, was developed with the aim to provide an enhanced instrumental and methodological approach with regard to the analysis of pigments in objects of cultural heritage. Technical details about the hybrid spectrometer and its operation are presented and examples are given relevant to the analysis of paint materials. Both LIBS and diffuse reflectance spectra in the visible and part of the near infrared, corresponding to several neat mineral pigment samples, were recorded and the complementary information was used to effectively distinguish different types of pigments even if they had similar colour or elemental composition. The spectrometer was also employed in the analysis of different paints on the surface of an ancient pottery sherd demonstrating the capabilities of the proposed hybrid diagnostic approach. Despite its instrumental simplicity and compact size, the spectrometer is capable of supporting analytical campaigns relevant to archaeological, historical or art historical investigations, particularly when quick data acquisition is required in the context of surveys of large numbers of objects and samples.

A novel methodology is proposed that combines sonic spray ionization (SSI) mass spectrometry (MS) with laser induced breakdown spectroscopy (LIBS) for analyzing metal-containing biomolecules and complexes. Focusing pulses from a nanosecond laser (Nd:YAG, λ=1064 nm) in the microdroplet ensemble produced by a pneumatic nebulizer yielded LIBS spectra that enabled highly sensitive detection of several metal ions in aqueous and aqueous methanolic solutions. Based on the calibration curve method, LOD values at the ng/mL level were achieved for Ca (15 ng/mL), Ba (27 ng/mL), Cu (67 ng/mL) and Fe (650 ng/mL) with accuracy N90%. LIBS measurements were performed for the first time on aerosols of solutions of known biomolecules such as superoxide dismutase and alpha-lactalbumin, which led to the reliable determination of the concentration of Cu and Ca, respectively, both in the range of a few μg/mL. In parallel, the relative molecular mass of the metalloproteins was determined by separate SSI-MS measurements performed using an identical pneumatic nebulizer based sample introduction system. This is a first step towards the ultimate aim of integrating the two analytical techniques by use of a single pneumatic nebulization system for simultaneous sample introduction for both LIBS and SSI-MS. Such a system is expected to greatly enhance our capabilities to simultaneously acquire molecular and atomic data.

Laser-induced breakdown spectroscopy (LIBS) was used to determine the mineral composition of various industrial scale samples. The aim of the study has been to investigate the capacity of LIBS to provide a fast, reliable analytical tool for carrying out routine analysis of inorganic scales, potentially on site, as a means to facilitate decision making concerning scale removal procedures. LIBS spectra collected in the range of 200–660 nm conveyed information about the metal content of the minerals. Via a straightforward analysis based on linear correlation of LIBS spectra it was possible to successfully discriminate scale samples into three main groups, Fe-rich, Ca-rich and Ba-rich, on the basis of correlation coefficients. By combining correlation coefficients with spectral data collected in the NIR, 860–960 nm, where sulfur emissions are detected, it became further possible to discriminate sulfates from carbonates as confirmed by independent analysis based on Raman spectroscopy. It is emphasized that the proposed LIBS-based method successfully identifies the major mineral or minerals present in the samples classifying the scales into relevant groups hence enabling process engineers to select appropriate scale dissolution strategies.

A detailed feasibility study on the combined use of laser-induced breakdown spectroscopy with optical coherence tomography (LIBS/OCT), aiming at a realistic depth-resolved elemental analysis of multilayer stratigraphies in paintings, is presented. Merging a high spectral resolution LIBS system with a high spatial resolution spectral OCT instrument significantly enhances the quality and accuracy of stratigraphic analysis. First, OCT mapping is employed prior to LIBS analysis in order to assist the selection of specific areas of interest on the painting surface to be examined in detail. Then, intertwined with LIBS, the OCT instrument is used as a precise profilometer for the online determination of the depth of the ablation crater formed by individual laser pulses during LIBS depth-profile analysis. This approach is novel and enables (i) the precise in-depth scaling of elemental concentration profiles, and (ii) the recognition of layer boundaries by estimating the corresponding differences in material ablation rate. Additionally, the latter is supported, within the transparency of the object, by analysis of the OCT cross-sectional views. The potential of this method is illustrated by presenting results on the detailed analysis of the structure of an historic painting on canvas performed to aid planned restoration of the artwork.

Analysis by laser-induced breakdown spectroscopy (LIBS) is compared, on the basis of a hybrid experimental set-up, with laser ablation time-of-flight mass spectrometry (LA-TOF-MS) for the characterization of materials relevant to cultural heritage. The present study focuses on the analysis of selected paint materials such as lithopone, a white inorganic pigment, and two synthetic organic paint formulations, lemon yellow and phthalocyanine blue. Optical emission spectra, obtained by LIBS, lead to rapid, straightforward identification of the elemental content of the paint samples while mass spectra yield, additionally to elemental analysis, complementary isotopic analysis and, more importantly, enable detection of molecules and molecular fragments, permitting a more complete structural and compositional characterization of composite materials. Mass spectra were recorded either simultaneously with the optical emission ones, or sequentially. The latter was preferred for materials having significantly lower fluence threshold for desorption/ionization relative to plasma formation resulting to optimum mass resolution and minimal surface damage. In all, the results of this study demonstrate the advantages of instrumentally complementing LIBS with TOF-MS in relation to applications in cultural heritage materials analysis, with exciting prospects when laser ablation sampling can be carried out under ambient atmosphere.

In this work, the results of a study on the influence of buffer gas and pressure on the LIBS spectrum characteristics are reported. Ultraviolet femtosecond pulses were employed in the analysis of several solid samples including brass, copper, aluminum and silicon under different buffer gasses: air, argon and helium. Given a buffer gas, ambient pressure was varied and its effect on the intensity and broadening of the spectral emission lines and on the background of the spectra was evaluated. A maximum emission intensity of the lines was observed at 500 hPa in helium or argon and at 30 hPa in air. Line broadening, attributed to the Stark effect, was found to be negligible in spectra acquired with helium as a buffer gas compared to spectra recorded under air or argon atmosphere, which showed noticeable line broadening particularly at high ambient pressure.

In this work, the potential of plume imaging was investigated as a real-time monitoring technique for the control of the laser cleaning process in cultural heritage objects with emphasis on encrusted stonework. Optical pulses generated by Nd:YAG laser were used to remove a high absorbing layer of crust from the surface of a lower absorbing marble substrate. Two regimes of operation have been employed for laser cleaning test, Q-switched ns mode, and short free running μs mode. Laser induced breakdown spectroscopy (LIBS) was also employed to study the stratigraphy of the cleaned surfaces, and thus to confirm the validity of the suggested monitoring technique. The tests proved the prospective of introducing plume imaging techniques as a straightforward and inexpensive tool for the real-time monitoring of laser ablation and the determination of the critical point for a safe surface cleaning intervention.

Double-pulse femtosecond laser ablation has been shown to lead to significant increase of the intensity and reproducibility of the optical emission signal compared to single-pulse ablation particularly when an appropriate interpulse delay is selected, that is typically in the range of 50–1000 ps. This effect can be especially advantageous in the context of femtosecond laser-induced breakdown spectroscopy analysis of materials. A detailed comparative study of collinear double- over single-pulse femtosecond laser-induced breakdown spectroscopy has been carried out, based on measurements of emission lifetime, temperature and electronic density of plasmas, produced during laser ablation of brass with 450 fs laser pulses at 248 nm. The results obtained show a distinct increase of plasma temperature and electronic density as well as a longer decay time in the double-pulse case. The plasma temperature increase is in agreement with the observed dependence of the emission intensity enhancement on the upper energy level of the corresponding spectral line. Namely, intensity enhancement of emission lines originating from higher lying levels is more profound compared to that of lines arising from lower energy levels. Finally, a substantial decrease of the plasma threshold fluence was observed in the double-pulse arrangement; this enables sensitive analysis with minimal damage on the sample surface.

This article reviews laser-based analytical techniques, which find applications in the field of cultural heritage diagnostics, providing information about the chemical composition of materials, at the atomic or molecular level. Lasers are intense sources of light featuring unique characteristics that have been exploited in order to enhance the performance of certain spectroscopic techniques such as Raman or fluorescence spectroscopy, or even produce new schemes of analysis, including, for instance, non-linear or remote sensing spectroscopy as well as laser ablative sampling and excitation. In parallel, with advances in laser and detector technology, compact, mobile instrumentation is becoming available that permits broader use of such laser-based techniques for analysis of materials in works of art and archaeological findings.

This paper reports on the effects of LIBS experimental conditions on the measurement of the surface hardness of calcified tissues. The technique mainly depends on a previously demonstrated correlation between the intensity ratio of ionic to atomic spectral lines and the hardness of the target material. Three types of calcified tissues have been examined, namely enamel of human teeth, shells, and eggshells. Laser-induced breakdown spectra were obtained under two different experimental conditions. In the first nano and picoseconds, laser pulses were used in a single-pulse arrangement, while in the second, single- and double-pulse regimes with nanosecond laser excitation were utilized. The results show that the ionic to atomic spectral line intensity ratios are higher in the case of picosecond laser pulse for both Ca and Mg spectral lines. This effect has been justified in view of the repulsive force of the laser-induced shock waves which depends clearly on the target surface hardness and on the laser irradiance. The electron densities ratio (pico/nano) is shown to be strongly depending on the laser irradiance too. In the case of calcium, single-pulse ratios are higher than the double-pulse ratios, while there is no appreciable difference between both in the case of magnesium. The results obtained herein suggest that double-pulse nanosecond arrangement and the choice of a minor element such as Mg furnishes the best experimental conditions for estimating the surface hardness via LIBS spectra. To validate this method, it has been applied on two previously measured groups of teeth enamel, the first is of ancient Egyptians, and the second from Nubians and Ugandans. The results support the usefulness of this method for similar real-life applications.

We present LIBS experimental results that demonstrate the use of a newly developed, compact, versatile pulsed laser source in material analysis related to art and archaeological applications in view of research aiming at the development of portable LIBS instrumentation. LIBS qualitative analysis measurements were performed on various samples and objects, and the spectra were recorded in gated and non-gated modes. The latter is important because of advantages arising from size and cost reduction when using simple, compact spectrograph-CCD detection systems over the standard ICCD-based configurations. The new laser source exhibited a very reliable performance in terms of laser pulse repeatability, autonomy and interface. Having the ability to work in double pulse mode it provided versatility in the measurements leading to increased LIBS signal intensities, improved the signal-to-noise ratio and the RSD of the spectra. The first test results are encouraging and demonstrate that this new laser is suitable for integration in compact, portable LIBS sensors with a wide spectrum of materials analysis applications.

This paper presents results obtained in a study of collinear geometry double pulse femtosecond LIBS analysis of solids in ambient environment. LIBS signal enhancement of 3–10 fold, accompanied by significant improvement of signal reproducibility, in comparison with the single pulse case, has been found in different samples such as brass, iron, silicon, barium sulfate and aluminum when an optimum temporal separation between the two ablating pulses is used. The influence of the delay between pulses in the LIBS signal intensity was investigated and two intervals of interaction were established. A first transient regime from 0 to 50 ps, in which the LIBS signal increases until reaching a maximum, and a second regime that ranges from 50 to 1000 ps (maximum inter-pulse delay investigated) in which the signal enhancement remains constant. Emissions from both ionized and neutral atoms show the same pattern of enhancement with a clear tendency of lines arising from higher energy emissive states to exhibit higher enhancement factors.

Selected pottery sherds coming from the Ayanis, Dilkaya and Karagunduz excavations in eastern Turkey and dated from the Early to Middle Iron Age were examined as regards their composition by using laser-induced breakdown spectroscopy (LIBS). The objective of the study was first to investigate the potential of the LIBS technique in the compositional analysis of pottery and further to explore correlations in spectral data, by using chemometrics methods that would possibly enable discrimination among different sherds. This work is part of a broader study aiming to examine clay variability both before and during the Urartian State period and to explore possible relationships and differences among pottery objects from fortresses and settlements or settlements and cemeteries on the basis of the clay composition of sherds. Preliminary results demonstrate that by using the LIBS technique it is possible to analyse pottery sherds in qualitative and semi-quantitative ways, providing information on the clay and slip composition. Furthermore, encouraging results have been obtained by carrying out principal component analysis (PCA) on the LIBS spectra, which suggest that in certain cases, it is possible to directly correlate spectral information with the origin of pottery sherds.

Graphite fluoride has been generally considered chemically inert against strong alkalis under ambient conditions. In the present study we demonstrate that treatment of graphite fluoride with eutectic NaOH–KOH mixture at 250 °C induces dramatic structural and textural changes in the solid as evidenced by XRD, FT-IR, Raman, UV–vis absorption and fluorescence and microscopy techniques (TEM, AFM). The reaction proceeds in the molten state leading to water-soluble, graphitized carbon particles which unlike graphite fluoride, adopt a variety of morphologies, like platy, tetragonal, triangular, discoid and spherical. The resulting carbon particles are dispersible in water and fluoresce under UV excitation.

The analysis of protein-based paint media used in paintings is presented using micro-Raman spectroscopy, carried out with a diode laser emitting at a wavelength of 785 nm. Following a contextualisation of the analysis and ageing of protein-based binding media, a consideration of the effects of artificial ageing using visible light on the Raman spectra of binding media is given and the interpretation of changes to the Raman spectra of selected binding media is presented. Bands associated with aromatic amino acids are most affected by ageing, but spectra retain diagnostic information for the identification of proteins. Specific changes to the spectra of dairy and collagen-based binding media are described and explained with reference to the oxidation of amino acids. A multivariate approach using Principal Component Analysis has been chosen for the assessment of the bands in CH stretching region for which a large set of over 150 spectra were recorded from artificially and naturally aged binding media which included egg white, egg yolk, milk and casein, and collagen-based glues from rabbit skin, ox bone, parchment and sturgeon bladder. Raman spectroscopy has been used for an assessment of the effects of ageing and the detection of degradation due to exposure of light. Multivariate analysis has allowed the differentiation between a large data set of spectra of naturally and artificially aged binding media. Copyright © 2008 John Wiley & Sons, Ltd.

The spectrofluorimetric analysis of protein-based binding media, which are commonly found as painting materials, is based on the detection of emissions from amino acids, as well as fluorescent degradation products that develop with aging. Laser-induced fluorescence spectroscopy, fluorescence excitation emission spectroscopy, and time-resolved fluorescence spectroscopy have all been employed in efforts to discriminate between commonly found proteinaceous binding media, including egg white, egg yolk, milk, and casein, as well as collagen-based glues from rabbit skin, ox bone, parchment, and fish. However, synchronous fluorescence spectroscopy (SFS), a rapid means of recording fluorescence properties of samples, has not been reported for the differentiation between binding media. This work focuses on the analysis of a large set of naturally aged films of different protein-based binding media using SFS with a range of different offsets between excitation and emission monochromators between 30–60 nm. An interpretation of synchronous fluorescence spectra of binding media is presented and is followed by an assessment and classification of a database of recorded spectra using multivariate analysis. Importantly, following SFS analysis of films of binding media, principal component analysis is used to differentiate among all the proteinaceous media considered on the basis of clustering of data. This application is thus a novel and nondestructive means for differentiation between protein-based binding media.

In the present work we are studying the influence of pulse duration (nanosecond (ns) and femtosecond (fs)) at λ = 248 nm on the laser-induced plasma parameters and the quantitative analysis results for elements such as Sn, Zn and Pb, in different types of bronze alloys adopting LIBS in ambient atmosphere. Binary (Sn–Cu), ternary (Sn–Zn–Cu or Sn–Pb–Cu) and quaternary (Sn–Zn–Pb–Cu) reference alloys characterized by a chemical composition and metallurgical features similar to those used in Roman times, were employed in the study. Calibration curves, featuring linear regression coefficients over 98%, were obtained for tin, lead and zinc, the minor elements in the bronze alloys (using the internal standardization method) as well as for copper, the major element. The effects of laser pulse duration and energy on laser-induced plasma parameters, namely the excitation temperature and the electron density have been studied in our effort to optimize the analysis. Finally, LIBS analysis was carried on three real metal objects and the spectra obtained have been used to estimate the type and elemental composition of the alloys based on the calibration curves produced with the reference alloys. The results obtained are very useful in the future use of portable LIBS systems for in situ qualitative and quantitative elemental analysis of bronze artifacts in museums and archaeological sites.

Spectrofluorimetric analysis of proteinaceous binding media is particularly promising because proteins employed in paintings are often fluorescent and media from different sources have significantly different fluorescence spectral profiles. Protein-based binding media derived from eggs, milk and animal tissue have been used for painting and for conservation, but their analysis using non-destructive techniques is complicated by interferences with pigments, their degradation and their low concentration. Changes in the fluorescence excitation emission spectra of films of binding media following artificial ageing to an equivalent of 50 and 100 years of museum lighting include the reduction of bands ascribed to tyrosine, tryptophan and Maillard reaction products and an increase in fluorescent photodegradation. Fluorescence of naturally aged paint is dependent on the nature of the pigment present and, with egg-based media, in comparison with un-pigmented films, emissions ascribed to amino acids are more pronounced.

Quantum dots are semiconductor nanocrystals that inherently fluoresce at specific wavelengths in the visible, enabling a number of potential applications to be realized. However, conventional quantum dots are based on metallic elements, which has raised concerns over toxicity, stability and high cost. As a result, the search for more benign substitutes is a worthwhile yet challenging undertaking. Recently a new type of visible emitters has been reported exclusively based on functionalized carbon nanoparticles. The carbon dots were 5 nm in diameter and were produced via laser ablation of graphite. Surface oxidation with nitric acid and subsequent covalent grafting of organic moieties afforded light-emitting derivatives. Notably, the light emitted by these dots depends on the wavelength of light used for excitation. It was suggested that the tethered modifier stabilizes the surface of the carbon nanoparticles helping to generate energy traps that emit light when stimulated, an effect described as emission from passivated surfaces. Because of its origin the emission is size-dependent, i.e., the smaller the size of the dots the better their photoluminescence efficiency. In another intriguing approach, photoluminescent carbon dots 3 nm in size were directly fabricated by electrochemical shocking of multi-wall carbon nanotubes. The demonstrated photoluminescence adds another dimension to the versatility of carbon-based

In this work, non-destructive techniques were employed for the spectrofluorimetric and micro-Raman differentiation of solid films of egg yolk and egg white as a function of exposure to light. Using both techniques it is possible to discriminate between the samples on the basis of composition and follow some chemical changes involved during the light-ageing of egg proteins and fatty acid esters. In egg white, fluorescence emission spectra highlighted the presence of multiple fluorophores, with an effective broadening of the fluorescence emissions following light exposure, ascribed to the partial oxidation and depletion of tryptophan; in the Raman spectrum of dark-aged egg white a peak at 758 cm −1 is ascribed to the vibrational mode of tryptophan, which is completely absent in the spectrum of samples exposed to light. Changes in the fluorescence of egg yolk following exposure to light are ascribed to the degradation of amino acids, cross-linking between amino acids and the formation of oxygenated triacylglycerides. These results are corroborated with Raman spectra of the light-exposed samples, which are associated with wavenumber shifts with respect to the dark-aged sample for the Amide I and for the characteristic carbonyl vibration at 1744 cm −1 ascribed to the oxidation of fatty acid esters. Copyright  2008 John Wiley & Sons, Ltd.

This work presents Raman spectra obtained from thin films of protein materials which are commonly used as binding media in painted works of art. Spectra were recorded over the spectral range of 3250-250 cm(-1), using an excitation wavelength of 785 nm, and several bands have been identified in the fingerprint region that correspond to the various proteins examined. Differences in the C-H vibrations located between 3200 and 2700 cm(-1) can be accounted for with reference to the amino acid composition of the protein-based binding media as well as the presence of fatty acid esters, in the case of egg yolk. In addition, the discrimination of different proteins on the basis of variations in spectra between 3200 and 2700 cm(-1) can be achieved following multivariate analysis of a large data set of spectra, providing a novel and nondestructive alternative based on Raman spectroscopy to other methods commonly used for the analysis of proteins.

The study of materials in cultural heritage artifacts and micro-samples benefits from diagnostic techniques based on intense radiation sources, such as synchrotrons, ion-beam accelerators and lasers. While most of the corresponding techniques are classified as non-destructive, investigation with photons or charged particles entails a number of fundamental processes that may induce changes in materials. These changes depend on irradiation parameters, properties of materials and environmental factors. In some cases, radiation-induced damage may be detected by visual inspection. When it is not, irradiation may still lead to atomic and molecular changes resulting in immediate or delayed alteration and bias of future analyses. Here we review the effects of radiation reported on a variety of cultural heritage materials and describe the usual practice for assessing short-term and long-term effects. This review aims to raise awareness and encourage subsequent research activities to limit radiation side effects.

Laser-induced fluorescence (LIF) spectroscopy can provide nondestructive, qualitative analysis of protein-based binding media found in artworks. Fluorescence emissions from proteins in egg yolk and egg white are due to autofluorescent aromatic amino acids as well as other native and age-related fluorophores, but the potential of fluorescence spectroscopy for the differentiation between binding media is dependent on the choice of a suitable excitation wavelength and limited by problems in interpretation. However, a better understanding of emission spectra associated with LIF can be achieved following comparisons with total emission fluorescence spectra where a series of consecutive emission spectra are recorded over a specific range. Results using nanosecond UV laser sources for LIF of egg-based binding media are presented which are rationalised following comparisons with total emission spectra. Specifically, fluorescence is assigned to tryptophan and oxidation products of amino acids; in the case of egg yolk, fatty-acid polymerisation and age-related degradation products account for the formation of fluorophores.

We present results from preliminary laser cleaning studies performed on a 20th century modern painting, in which laser-induced breakdown spectroscopy (LIBS) was employed for monitoring the progress of material removal. This synergistic approach, that combines laser ablation cleaning with spectroscopic control, is of obvious importance as it offers a reliable means of ensuring proper conservation and could be the basis of a standard protocol for laser-based restoration procedures.

Laser-Induced Breakdown Spectroscopy (LIBS) was used in the examination of Bronze Age painted plaster samples from several sites in the Aegean and Eastern Mediterranean. The elemental content of paint materials was determined in most cases leading to the identification of the pigment used in agreement with data from analyses of the same samples with other established techniques. The analyses demonstrate that a virtually non-destructive technique such as LIBS provides sufficient data for the elemental characterisation of painting materials while in parallel has the capability for routine, rapid analysis of archaeological objects enabling the quick characterisation or screening of different types of artefacts. This certainly shows an important way forward in technological studies of fragile and scarce archaeological material.

Pulse shaping introduces the method that makes possible the production of tunable arbitrary shaped pulses. We extend this method to control the prevalent growth of cubic SiC films on Si (1 0 0) substrates by pulsed laser deposition at temperatures around 973 K from a SiC target in vacuum. We used a laser system generating 200 fs pulses duration at 800 nm with 600 μJ at 1 kHz. The obtained structures are investigated by electron microscopy, X-ray diffraction and profilometry. We observed grains embedded in an amorphous texture, characteristic in our opinion to the depositions obtained with very short pulses. We present a comparison of deposited films with and without pulse shaping. Pulse shaping promotes increased crystallization and results in the deposition of thin structures of cubic SiC with a strongly reduced density of particulates, under similar deposition conditions.