Thanks to its analytical versatility, speed of analysis and relatively low cost, laser-induced breakdown spectroscopy (LIBS) is having a steadily increasing global impact in cultural heritage diagnostics. This book introduces LIBS to technicians, students and practising conservation scientists needing a hands-on approach to the technique. The book opens with the physical and chemical background of LIBS from the perspective of practical applications relevant to cultural heritage. Further discussions address the wider context of extant challenges, highlighting the technique’s strengths and weaknesses and the opportunities it offers, alone or in combination with other analytical methodologies. Readers are provided with a selection of case studies to familiarise themselves with the practical aspects necessary to design and successfully carry out analyses of different materials, with both benchtop and portable equipment. A tutorial section on instrumental set-up and LIBS data analysis and interpretation is also included, to support users and provide a comprehensive troubleshooting guide. Conceived as an introductory manual and an essential tool for heritage science practitioners interested in including LIBS in their skillset, the guide also has a broader appeal for LIBS beginners in any field.

This study investigates a high-purity calcite deposit from Bela Vista city, Mato Grosso do Sul state, Brazil, using X-ray diffraction (XRD), Raman spectroscopy, and Calibration-free Laser-induced Breakdown Spectroscopy (CF-LIBS). Rietveld refinement identified calcite as the dominant phase (77%) with substantial vaterite content (15.2%), with minor phases including monohydrocalcite (2.0%) and organic iron compounds (3%). Raman spectroscopy confirmed carbonate mineralogy through vibrational modes at 1086 cm⁻¹ and 731 cm⁻¹, while detecting iron oxide phases at 577 cm⁻¹. CF-LIBS revealed trace magnesium (0.09%, Mg/Ca = 0.31%) that correlates with metastable phase assemblages, as Mg²⁺ ions inhibit calcite nucleation and promote vaterite stabilization. CF-LIBS analytical reliability was validated through elemental ratio comparisons, where Fe/Ca molar ratios from CF-LIBS (2.93%) and XRD stoichiometric calculations (2.13%) showed good concordance within a factor of 1.38. The good agreement between carbon (70.41% observed vs. 60-65% expected) and calcium (28.67% observed vs. 29-30% expected) quantifications demonstrate that iterative plasma parameter optimization effectively minimizes systematic biases including carbon volatilization and calcium self-absorption effects in LIBS analysis. The integration of structural, molecular, and elemental data provides quantitative constraints on depositional conditions and establishes CF-LIBS as a valuable complement to crystallographic methods for industrial mineral characterization. Results demonstrate that trace element geochemistry controls carbonate polymorph stability, with implications for predicting material properties and optimizing industrial applications.​

The study of ancient sculptural polychromy increasingly relies on non-invasive analytical approaches capable of identifying pigments and reconstructing original decorative schemes while preserving the integrity of archaeological objects. This paper presents the investigation of the polychromy, extraordinarily preserved, on two Roman marble statues discovered in the forum of Formia (southern Latium) and currently housed in the National Archaeological Museum of Formia: a togate statue (inv. 147614) and a headless draped female figure (inv. 147680). Both sculptures retain exceptionally well-preserved traces of pigments, offering a rare opportunity to investigate materials and painting techniques applied to Roman marble statuary. The analytical protocol combined multiband imaging (Visible-Induced Luminescence and Ultraviolet Luminescence), optical microscopy, Fiber Optic Reflectance Spectroscopy (FORS), portable X-ray Fluorescence (XRF), and Surface Enhanced Raman Spectroscopy (Raman-SERS) applied to two micro-samples. The analyses allowed the identification of Egyptian blue, iron-based pigments, gilding, and an organic red lake on the palettes used for the statues. Raman-SERS measurements provided additional information on the composition of the organic lake detected on the female statue’s himation, supporting its attribution to a natural vegetal-derived dye, as madder lake. The results highlight the success of integrated non-destructive methodologies for the study of Roman sculptural polychromy and contribute to the reconstruction of complex decorative schemes on marble statuary.

Jewelled crosses containing relics of the True Cross occupy a central position in the devotional, artistic and symbolic traditions of Christianity. Beyond their liturgical function, the selection and arrangement of gemstones has layered meanings associated with protection, sanctity and divine renewal. This study examines three exceptional examples of jewelled crosses-the Crux Vaticana (6th century; Treasury Museum of St Peter's Basilica, Vatican City), the Enkolpion of Constantine (10th-11th century, Treasury Museum of St Peter's Basilica, Vatican City) and the Holy Cross of Castiglion Fiorentino (13th century; Municipal Art Gallery, Castiglion Fiorentino, Arezzo, Italy)-with particular emphasis on the coloured gems adoring the reliquaries and the archaeogemological questions they raise.A noninvasive, in situ analytical approach was employed, based on gemological observations and portable Raman spectroscopy, supported by portable x-ray fluorescence (XRF). Among the identified gems, the characteristic Raman doublet at approximately 822 and 855 cm-1, allowed secure identification of several green stones as peridots [(Mg,Fe)2SiO4], constituting the first analytical confirmation of peridots on these three important reliquaries and enable a coherent gemological mapping of their decorative schemes. In addition, comparative gemological observations suggest a probable provenance from the island of Zabargad (St John's Island, Red Sea), the principal historical source of high-quality peridot in antiquity. In addition to peridots, further gemological and Raman analyses enabled the characterization of several other gemstones. The combined spectroscopic and gemological evidence indicates that while a number of stones are original, others represent later substitutions, attesting a complex histories of maintenance, repair and restoration. The presence of non crystalline materials such as coloured glass further reflects changing material choices over time.Beyond mineralogical identification, this study contributes to the broader debate on materiality and symbolic meaning in devotional ancient jewellery. By integrating Raman spectroscopic analysis with art-historical perspectives, it demonstrates how gemstone choice-particularly the preference for green stones-played an active role in shaping the spiritual and symbolic meaning of True Cross reliquaries.

LIBS is emerging as a powerful technique for phosphorus analysis in agricultural, environmental and industrial applications. This review critically discusses recent advances, current limitations and future strategies for robust quantitative analysis.

This work responds to the objective of recovering, preserving and valorising ancient documents, with particular reference to those in Arabic, both manuscripts and small objects with Arabic inscriptions of significant historical-cultural interest, preserved in libraries and historical archives. The proposed approach aims to scientifically analyse both the form and content of the selected material in order to provide input for its conservation, digitisation, archiving, annotation and large-scale exploitation. To this end, the most advanced diagnostic and digital technologies will be adopted, integrated and tested with the aim of valorising and translating the uniqueness of the material objects into a format suitable for management and manipulation in innovative digital environments, while preserving all their complexity as objects of scientific analysis in the field of historical-cultural studies. The study presented here concerns the preliminary analysis of a copy of sacred texts in Arabic, Ms 566, dating from around the 15th century and currently held at the Biblioteca Nazionale of Pisa. The manuscript was chosen because it is representative of the material typology, state of preservation and content of the ancient manuscript, epigraphic and book heritage of the Arab world.

In 1900, Francis Herbert Jennison’s book The Manufacture of Lake Pigments from Artificial Colours was published in London. In the early 20th century, the technical literature focussing on synthetic dyes mainly dealt with their use for dyeing. Conversely, the literature on lake pigment manufacture is less comprehensive, and Jennison’s publication was the first monograph on this topic. His book comprises descriptions of the dyes, substrates, and various methods for lake making. Practical examples complete the work: sixteen colour plates with original samples of lake pigments showcase the practical effect on colour of the different dyes and preparation methods. Herein, we present an overview of the context of Jennison’s research and delve into a selection of formulations. Green lake pigment plates were sampled and analysed by liquid chromatography coupled with spectroscopic and spectrometric detectors and by X-ray fluorescence spectroscopy to correlate the chemical composition with the recipes reported in the book. Seldom or no longer used and unexplored historical dyes were detected, along with polyphenolic compounds possibly used as precipitating agents in lake pigment formulations. Moreover, the examination of two different editions of the Jennison manuscript (i.e., the English and German books) revealed different chemical profiles corresponding to the same lake pigment formulation. This emphasizes the significance of Jennison’s book, confirming how understanding of early formulations is needed to elucidate the later ones.

Street art murals are increasingly recognized as valuable contemporary artworks, often attaining significant artistic, historical, and social importance. As these murals become integral parts of cultural heritage, finding efficient strategies for their conservation is crucial. However, their typical large surface areas, heterogeneous materials, and high variability in exposure to environmental and pollution factors pose significant challenges in establishing appropriate analytical strategies to obtain the necessary information. This study proposes a multiscale and multitechnique noninvasive approach to investigate and monitor street art murals in situ. By combining portable point techniques-such as external reflection Fourier transform infrared spectroscopy, Raman spectroscopy, visible, near infrared, and short-wave infrared reflectance spectroscopy, and X-ray fluorescence spectroscopy-with visible and near infrared hyperspectral imaging, the mural's composition across a square meter surface could be analyzed. Additionally, multispectral imaging mounted on a drone provided a global reconstruction and characterization of the overall mural. This method was complemented by microdestructive laboratory analyses of selected samples, using pyrolysis gas chromatography-mass spectrometry and liquid chromatography coupled with diode array detector and tandem mass spectrometry, to further investigate selected samples and support noninvasive results. The approach was applied to the iconic mural "Musica Popolare" (2017) by Orticanoodles in Milan, Italy, revealing detailed information about its pigments, binders, fillers, and degradation. The findings demonstrate the potential of this integrated methodology for the effective material identification, conservation assessment, and short-and long-term monitoring of urban heritage.

This work consists of a scientific documentation of the eighteenth-century Chiadma carpet, currently on display at the Dar Si Said Museum in Marrakech. It is the earliest known carpet in Morocco, an example of Morocco’s tangible cultural heritage, commonly known as “Zarbia”. The study included scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) measurements, optical reflectance, 3D fluorescence, surface-enhanced Raman spectroscopy (SERS), and confocal µ-Raman spectroscopy. Since the few studies carried out on the Moroccan antique carpet heritage have focussed exclusively on the artistic aspects, the aim of the present work is to apply an integrated and non-destructive analytical approach to characterise the dyes used and then provide response elements on the dyeing protocol adopted. The wool fibres analysed by electron microscopy showed a certain degree of degradation/tearing and the presence of some impurities, while EDS allowed the detection of mordants in red and yellow fibres. In terms of dyes, the analyses highlighted carminic acid from cochineal extract in pinkish red shades, flavonoids from weld or Daphne gnidium in yellow shades, and natural indigo from Isatis or Indigofera tinctoria in blue shades. Mixtures of yellow dye plants with either madder or indigo were present in orange-yellow and green colours, respectively. The non-invasive techniques allowed rapid and real-time analysis, but their specificity was limited in terms of tracing the dyes to their botanical origin, i.e. the yellow-dyeing plants on aged fibres. On the other hand, the study highlighted the mastery of natural dye processing and provided relevant data to support any restoration of this prestigious carpet, which has suffered from ancient, non-controlled indoor conditions.

Enrico Van Lint (Pisa, 1808–1884) was a very prolific photographer, active in Pisa in the 19th century where he had a prominent photographic atelier. He was a meticulous experimenter, investigating the evolving photographic activity of his historical period. While his early works included calotypes using Fox Talbot’s methods, he rapidly adopted the collodion processes, becoming one of the most important Italian photographers that used this technique. At the present time, a vast number of examples of the works from Van Lint’s ateliers are preserved and archived in Pisa, under the supervision of the Italian Ministry of Culture in the Photographic Archive of the “Soprintendenza Archeologia, Belle Arti e Paesaggio per le provincie di Pisa e Livorno” (SABAP). This collection is composed of positive prints as well as glass plate negatives, from both Van Lint himself and his colleagues. To this day, Van Lint’s collection has not been studied using analytical techniques, and the identification of the photographic processes involved in the preparation of the positive prints has relied exclusively on thorough observation by historians and conservators. This provides a unique occasion for a first study of Van Lint’s collection, using multiple non-invasive and non-destructive techniques (multispectral imaging, XRF, and FTIR) that can identify the photographic process used to make the positives, as well as highlight significant differences or degradation phenomena. In this preliminary work, we investigated a selection of ten positive prints, attributed to both Van Lint himself and later reproductions from the original glass negatives. The selected samples include prints previously classified as albumen prints and gelatin prints, displaying slight differences in conservation status as well as in print finish. This analytical approach allowed for a proper characterization of these Van Lint’s prints, improving the historical and conservation knowledge to implement the best preventive preservation actions in the near future.

Although approximately half of global lithium consumption is used in the rechargeable battery industry, lithium is also in demand for other specialized applications, such as high-temperature lubricants, ceramics, glass, and pharmaceuticals. The growing need for efficient lithium recovery and recycling underscores the importance of fast and accurate analytical tools for determining lithium concentrations in non-compliant and waste materials generated by industrial processes. In this paper, we present a machine learning-based procedure utilizing Laser-Induced Breakdown Spectroscopy (LIBS) to accurately quantify lithium concentrations in lithium-rich non-compliant materials derived from the industrial production of enamels used for coating metallic surfaces. This procedure addresses challenges such as strong self-absorption and matrix effects, which limit the effectiveness of conventional univariate calibration methods. By employing a multivariate approach, we developed a single model capable of quantifying lithium content across a wide concentration range. A comparison of the LIBS results with those obtained using conventional laboratory analysis (Inductively Coupled Plasma–Optical Emission Spectrometry, ICP-OES) confirms that LIBS can deliver the speed, precision, and reliability required for potential routine applications in the lithium recovery and recycling industry.

Lithium has emerged as a pivotal material for the global energy transition, yet its supply security is challenged by limited geographical availability and growing demand. These constraints highlight the need for analytical methods that are not only accurate but also sustainable and deployable across the entire lithium value chain. In this context, Laser-Induced Breakdown Spectroscopy (LIBS) offers distinctive advantages, including minimal sample preparation, real-time and in situ analysis and the potential for portable and automated implementation. Such features make LIBS a valuable tool for monitoring and optimizing lithium extraction, refining and recycling processes. This review critically examines the recent progress in the use of LIBS for lithium detection and quantification in geological, industrial, biological and extraterrestrial matrices. It also discusses emerging applications in closed-loop recycling and highlights future prospects related to the integration of LIBS with artificial intelligence and machine learning to enhance analytical accuracy and material classification.

The Pace di Siena is a unique en ronde bosse enamel, with few comparable pieces in Europe. The enamel, preserved and exhibited in the Arezzo Diocesan Museum (Italy), is surrounded by a frame decorated with thirty blue and pink gems whose identity has never been explored through analytical studies. The historical art literature has traditionally described these gems as tourmaline, aquamarine, beryl, and quartz, without delving into their provenance. Only a few hypotheses exist regarding the manufacture of the precious frame. Gemological analysis, in situ Raman spectroscopy, and energy-dispersive portable x-ray fluorescence (ED-pXRF) analysis have, for the first time, revealed the true nature of the gems, identifying them as fourteen natural blue corundum (sapphires) and sixteen natural pink spinels. The analysis of the inclusions also supports the hypothesis of heat treatment in the natural sapphires while suggesting a possible reuse for the natural untreated spinels, as indicated by the presence of distinctive holes. Additionally, semiquantitative geochemical data obtained by ED-pXRF after calibration through particle-induced x-ray emission (PIXE) analysis on a set of reference gemstones has provided valuable insights into the possible origins of the sapphires (which seems to have a metamorphic origin consistent with a possible Sri Lankan origin) and the pink spinels (which may have originated be come from Myanmar or Tajikistan). The study highlights the intersections between the materiality of the object, the concept of object biography, the provenance of their gems, and its cha & icirc;ne op & eacute;ratoire.

The recent restoration of the painting "Enthroned Virgin Mary with Child, St. John the Baptist, St. Francis, St. Bartholomew and St. Jerome" (also known as "Madonna delle Grazie"- Oil on wood , 235 x 194 cm) carried out by the restorers of the Opera del Duomo in Pisa (2020-2021) provided the occasion for a multi-analytical study of this sixteenth-century masterpiece. We learn from Vasari's Lives of the Artists that the panel was commissioned to Andrea del Sarto (Andrea d'Agnolo, Florence 1486 - Florence 1530) by the friars of the Monastery of St. Francis in Pisa. The painting was left unfinished by Andrea del Sarto due to his sudden death during the plague in Florence in 1530 and was completed eight years later by Giovanni Antonio Sogliani (Florence, 1492 - Florence, 1544). The division of work between Andrea del Sarto and Sogliani in the painting remains a subject of debate. Art historians have largely agreed on the hypothesis that almost the entire painted surface, should be attributed to Sogliani. However, the attribution of the composition is still controversial; it is unclear whether the design is entirely by Andrea del Sarto, or if certain parts were reinterpreted by Giovanni Antonio Sogliani. To contribute analytical data to this debate, a novel multispectral approach incorporating the Interesting Feature Finding (IFF) method was utilized to examine the painting. Additionally, energy-dispersive Xray fluorescence (ED-XRF) and micro-Raman analyses were conducted to characterise the pigments used by the artist(s) in different parts of the masterpiece. The multispectral analysis revealed significant differences between the underdrawings - potentially attributable to Andrea del Sarto - and the painted surface. The ED-XRF and micro-Raman results do not exclude the possibility that parts of the painting were executed by del Sarto. The IFF method also uncovered several "pentimenti ", including a small (human?) figure, which opened intriguing comparisons with other works by Andrea del Sarto. (c) 2024 The Author(s). Published by Elsevier Masson SAS. This is an open access article under the CC BY license ( http://creativecommons.org/licenses/by/4.0/ )

Codex 462 of the Fondo Hortus Pisanus of the Biblioteca Universitaria of Pisa is a precious example of a 16th century illustrated herbal, Icones variarum plantarum, containing 35 tempera paintings by the German soldier Georg Dyckman, an amateur but highly talented artist. The manuscript was recently restored on the occasion of an international exhibition; the necessary preliminary studies for the restoration included a series of in situ diagnostic studies using contactless techniques (digital microscope, multispectral imaging, XRF, Raman and ER-FTIR). These analyses proved useful in deepening the knowledge of the materials and the execution technique of this type of illustrated herbals and in choosing the most appropriate solutions during the restoration phase. In view of the growing interest in this type of historical evidence, which involves both art history and the history of science, this study offers an interesting new perspective on the subject, useful both from a technical point of view for future conservation and for analytical and historical artistic studies.

Combining oxidative plasma pre-treatment of carbon fibers (CFs) with subsequent functionalization with branched polyethyleneimine (b-PEI) resulted in b-PEI-modified CFs. First, CFs were oxidized by plasma treatment, dipped into a water solution of b-PEI, and finally heated to promote reactions between the amine functionalities of b-PEI and carboxyl groups generated by plasma activation. By ajusting the operational parameters of the low-pressure oxygen plasma treatment, the b-PEI concentration, and the reaction time, we could modulate the content of grafted b-PEI. The extent of the modification was assessed by infrared and Raman spectroscopies, scanning electron microscopy, and thermogravimetric analyses. Interestingly, the described functionalization process is cost-effective and simple and offers a sustainable and environmentally friendly alternative to traditional industrial methods, as it does not require dangerous reactants and solvents. The latter part of the paper delves into the curing kinetics of an epoxy/anhydride system in the presence of 20 wt% of carbon fibers modified with b-PEI at two different concentrations, evidencing the role of grafted b-PEI in the curing process.

The chemical investigation of modern art materials and synthetic paint materials has been a major focus of research in cultural heritage science over the past decade. Since the 1970s, street art has become an influential cultural movement with significant artistic and social impact in modern cities, and the conservation of relevant artworks related to urban neo-muralism has been increasingly recognized. Understanding these materials is critical to developing conservation strategies, as their composition continues to change with industrial innovation and regulatory changes. This study presents the application of an analytical approach that integrates chemical mapping based on spectroscopic approaches together with analytical pyrolysis, chromatography, and mass spectrometry to investigate two key case studies and provide insights into the evolution of street art materials over the past 30 years. This comprehensive approach provides a deeper understanding of the composition and transformation of urban art materials over time, overcoming the limitations of individual methods and revealing both organic and inorganic materials. This combined approach represents the state of the art in the study of synthetic paints used in modern art and provides new insights into the evolution of the formulation of materials used by street artists.

Pharmacologically active compounds can be dispersed in nature during their manufacture, consumption, and disposal. In this study three pharmaceutical ingredients (acetaminophen, indomethacin and acetazolamide), commonly found in wastewaters, were studied in aqueous environment by Raman spectroscopy. Their spectroscopic properties were computed using density functional theory methods, and a combined atomistic/continuum description of the aqueous solution. The theoretical study allowed to explore the potential energy surface, to identify stable structures, and to accurately predict their Raman response in solution. Given the relevance of the determination of these compounds, their spectral information were related to their concentration level in water and synthetic wastewater by Raman multivariate regression models (partial least squares and Gaussian process regression), reaching limit of detection down to millimolar (investigated range 2.5 - 40 mM, 1.25 - 5 mM, and 0.25 - 5 mM for acetaminophen, indomethacin and acetazolamide, respectively). However, since in real samples pharmaceutical ingredients are usually found at trace level, the suitability of a more performing techniques such as surface-enhanced Raman spectroscopy was evaluated, which enabled us to lower the detection limit of one order on magnitude at least. The quality of the obtained surface-enhanced Raman spectra for the selected molecules should also be highlighted respect to those currently available in the literature. Surface-enhanced Raman analysis of acetazolamide, especially, shows promising features for the development of a sensitive (down to nanomolar) and highly specific analytical method.