The paper presents the results of a study on Daunian ceramics, which were widespread in Apulia from the 7th to the 4th century B.C.E. with the main objective of identifying the raw materials and manufacturing techniques used by the Daunian population before the Greek influence. The ceramic bodies and surfaces were analyzed using a multi-technique approach that employed non-destructive or micro-destructive analytical methods-LA-ICP-MS, Raman spectroscopy, PXRD, SEM-EDS-. The results suggest the existence of local production at both sites-Canne della Battaglia and Ordona-which are considered among the most important centers for Daunian ceramic manufacturing. Moreover, the compositional homogeneity observed within each site across different chronological phases-Protogeometric, Geometric, and Subgeometric-indicates a remarkable consistency in raw material procurement strategies over several centuries. The analysis of surface treatments and pigments indicates a sophisticated use of local raw materials, such as calcium sulfate-based compounds or kaolinite for surface whitening. Red decorations were made with local terre rosse rich in hematite, while iron-manganese oxide mixtures produced dark brown pigments, with charcoal added to obtain black tones. All materials were applied before vessel firing. Overall, the results indicate that potters in northern Apulia from at least the Archaic period (7th century BCE) had advanced ceramic knowledge and made informed choices in raw materials and production techniques, pointing to a mature and well-organized ceramic industry.

Recent archaeological research on the emergence of red figure pottery in Sicily in the late fifth and early fourth century BCE reveals a fragmented yet dynamic artisanal landscape, with workshops catering to different sub-regional markets and exhibiting notable mobility. Red figure pottery from three of the most significant archaeological sites in Sicily – namely Himera, Lipari, and Syracuse – has been examined by optical and electron microscopy and atomic spectroscopy (ICP-OES and LA-ICP-MS) to broaden the documentary framework with the archaeometric evidence, in order to strengthen the foundations upon which to base interpretative proposals for new insights into South Italian figurative productions. The results allow us to distinguish between imported Greek and locally produced vases and to shed light on the production activities of key workshops, including the Chequer Painter, the Painter of Louvre K236, and the Locri Group. By highlighting the compositional and micromorphological features of artefacts from the same archaeological site, it has also been possible to confirm the existence of multiple production centres in Sicily, improving the framework for characterization and identification of certain local productions and their technological procedures. Moreover, it is also possible to consider this historical and archaeological framework from the perspective of the movement of painters, workshops and vases between Sicily, the Tyrrhenian region and Southern Calabria. Although the number of samples limits the possibility of drawing general conclusions, the research shows the merits of an integrated approach to better understand the complexities of this artistic and cultural tradition.

The Bilsk archaeological complex comprises the remains of many structures associated with an impressive Iron Age fortified site and extends over a vast area in central-east Ukraine. Its importance is marked by the presence of apparently imported objects, including some vitreous ones (represented mainly by glass and faience beads), which provide researchers with materials for studying past trade in the area. A representative set of vitreous fragments was subjected to an analytical study with several instrumental techniques (namely: scanning electron microscopy coupled with energy dispersive spectrometry, laser ablation inductively coupled plasma mass spectrometry, micro-Raman spectroscopy and micro-X-ray diffraction) in order to characterise the beads on compositional basis. The complementary data from different techniques revealed a complex picture for the raw materials, identifying several sources of silica and, consequently, several production centres for the items included in the analysed set. This information in turn led to a better understanding of the trade networks that operated in the region between the 7th and 4th century BCE. Colouring and opacifying agents are also discussed. (c) 2024 The Authors. Published by Elsevier Masson SAS on behalf of Consiglio Nazionale delle Ricerche (CNR). This is an open access article under the CC BY license ( http://creativecommons.org/licenses/by/4.0/ )

This research focuses on analyzing wool samples dyed with synthetic dyes from the early 20th century. A methodology to identify and distinguish wool fibers dyed with azo, triphenylmethane, and xanthene dyes, which are no longer in use, using the ATR-FTIR spectra, is presented. Firstly, the dataset was subjected to PCA, which revealed the similarities and differences among the samples, illustrating a distribution pattern based on dye classes. MCR-ALS was employed to extract the spectral profiles of the dyed fibers, thereby enhancing the efficacy of the analytical techniques and extracting the comprehensive information from a single instrument. The combination of ATR-FTIR spectroscopy with chemometric methods, such as PCA and MCR-ALS, has proven to be an effective strategy for identifying and differentiating wool fibers dyed with early azo, triphenylmethane, and xanthene dyes. This approach has demonstrated particular effectiveness in enabling rapid analysis without requiring sampling or pretreatment. Moreover, the analysis is supported by thorough bibliographic research on these no longer used colorants. In order to maximize the potential of non-destructive spectroscopic techniques, such as ATR-FTIR, the approach used has proven to be crucial. This study underscores how chemometric techniques expand the capabilities of spectroscopy, extracting extensive information from a single instrument and aligning with the goals of cultural heritage analysis.

An assemblage of black-appearing glass objects (predominantly beads) that is dated to the 9th–7th centuries BCE and found in Iron Age contexts of Southern Etruria and Latium (central Italy) was analysed using portable X-ray fluorescence spectrometry, laser ablation – inductively coupled plasma – mass spectrometry and micro-Raman spectroscopy. The analytical approach allowed us to discuss the technology of glass-making in a period of relevant technological changes. It resulted that the glass that reached the Italian peninsula was somewhat different, from a compositional point of view, from both earlier and later periods. The data collected showed that iron – the main colouring agent for these glasses – was obtained from several sources as was silica – the main component of glass. Lime, one of the main constituents of many types of glass, plays a modest role in this assemblage, which places these samples in a special position because of the peculiar batch formula. At least three centres of raw glass production are suggested by the compositional data, but in each case the glass was imported to the Italian peninsula.

The Iron Age was a period of change, with many innovations in the glass-making technology. The chemical composition of the set of objects considered in the present study demonstrates the diversity of the raw materials used and the depth of knowledge about the manipulation of glass appearance in the eighth-sixth centuries BCE. The study was carried out using fibre optics reflection spectroscopy and portable X-ray fluorescence spectrometry at the museums’ premises to examine a large number of glass beads and preliminarily group them on the basis of their composition and spectral characteristics. In addition, a smaller set of selected samples was analysed by laser ablation inductively coupled plasma mass spectrometry to provide a comprehensive chemical characterisation of the material. The compositional data indicated that the samples belonged to the high magnesium and low magnesium glass compositional types. Only one sample was recognised as low magnesium medium potassium glass. Glasses within each group were made from different sands, suggesting different provenances. Some of the samples were suggested to be of local origin, while the others were interpreted as imported glass. Evidence of glass colouring, decolouring and recycling are also discussed.

This study presents the petrographic and chemical characterization of the frescoes in the Church of San Panfilo in Tornimparte (AQ, Italy) by Saturnino Gatti, a prominent painter of the late 15th–early 16th century, known for his exquisite technique, composition, and use of color. The characterization of the frescoes is essential for understanding the materials and techniques used by Gatti, as well as for identifying the stratigraphy and painting phases. Eighteen samples were collected from the original paint layers, later additions (17th century), and restored surfaces, and analyzed by optical microscopy, cathodoluminescence microscopy, scanning electron microscopy (SEM-EDS), μ-Raman, and electron paramagnetic resonance (EPR). The analyses revealed a microstratigraphy often made of three main layers: (1) preparation, consisting of lime plaster and sand; (2) pigmented lime, applied by the fresco technique; and (3) additional pigmented layer on the surface. The most often recurring pigments are black, red, yellow (all generally linked with the fresco technique), and blue (applied “a secco”). The presence of two painting phases was also noted in one sample, probably resulting from a rethinking or restoration. These findings contribute to the understanding of the history and past restoration works of this cultural heritage site, providing important insights not only for conservators and restorers, but also for a broader understanding of Italian fresco painting and art history of the late 15th and early 16th centuries.

The wall paintings of five Hellenistic tombs in Apulia were analysed using a multi-technique approach to discern the painting techniques used and contextualise them within the phenomenon of Hellenistic tomb painting in Southern Italy. In particular, the question was asked whether technical knowledge played a role in the reception of Hellenistic artistic models and whether this knowledge was present locally. Raman and IR spectroscopies were used to identify pigments, colourants, and binders; light and electron microscopy were used to determine the structural characteristics of the paint layers and recognise the manufacturing technique. Analyses identified a fresco application for the Tomba dei Cavalieri (Arpi) and a dry application for the Canosian hypogea. The palette—typical for Hellenistic tomb painting in Southern Italy, Etruria and Macedonia—was composed of lime (white), charcoal (black), hematite (red), goethite (yellow), and Egyptian blue (blue). In the Tomba della Nike (Arpi), meanwhile, two particularly refined preparatory layers were observed. The palette was enriched with precious cinnabar and madder lake. The colouring components of the root were mixed with clay and K-alum applied on an additional layer of lime. The use of madder lake and a pink background link the painting to the polychrome Daunian pottery, and the contribution of a local workshop to the decoration of this tomb thus seems plausible.

The tomato (Solanum lycopersicum L.) is one of the most cultivated and sold fruit, growing worldwide and used in cuisines worldwide. Nutritionally it is rich in key substances, such as carotenoids, flavonoids and vitamins, fundamental in human diet.In this study, 201 Apulian date tomato samples, the so-called datterino, obtained by three different cultivation techniques (organic, conventional and hydroponics), have been analyzed using Raman spectroscopy, as spectroscopic fingerprint technique.Aim of the paper is to investigate whether Raman spectroscopy combined with chemometrics can be used as a rapid, robust and accurate method for the discrimination of tomatoes according to the different cultivation techniques.A Partial Least Square Discriminant Analysis (PLS-DA) was applied to create classification models and the obtained results showed that this approach provides an excellent ability to classify sample coming from different agricultural techniques, both in calibration that in validation.Moreover, permutations test demonstrates the reliability of the models built.The presented approach could be used as a screening tool to assess the authenticity and to ensure the traceability of the tomatoes

Several types of (mostly) blue-green glass beads from Iron-Age archaeological sites in Central Italy were studied using a range of spectroscopic techniques: portable X-Ray Fluorescence spectrometry, Fibre Optics Reflectance Spectroscopy, Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectrometry, micro-Raman spectroscopy and Laser Ablation Inductively Coupled Plasma Mass Spectrometry. Complementary information was gathered from each technique and discussed in the frame of the archaeological typology of the objects. The systematic evaluation of the results allowed us to draw some conclusions on the raw materials employed for primary production and to highlight some provenance indicators in the glass. Some of the beads found in the Iron Age (IA) contexts were preliminarily attributed to the Final Bronze Age (FBA) production based on their typology, and the compositional data obtained in this work confirmed that they were low magnesium high potassium (LMHK) glass, typical of FBA in the Italian peninsula. Other beads were assigned to low magnesium glass (LMG) or high magnesium glass (HMG), thus giving further information on the fluxing agents employed in the Early Iron Age (EIA) and beyond. Colour variations among the beads reflected their chemical composition, with different bead typologies coloured in a specific way. In some instances, it was possible to establish different origins for the colouring raw materials. The provenance of the samples was difficult to place, but the chemical evidence suggested a subdivision within the raw glass used to produce the beads: for one set of samples, a local origin of the glass could be hypothesised, whereas several production sites in the Near East were suggested for most of the beads considered in this study. Some preliminary clues for the local working of imported glass were also highlighted for one typological group.

The blue color of glass and ceramic glazes produced in Apulia and Basilicata (Southern Italy) between the 13th and 14th centuries and connected to the Norman-Swabian Emperor Frederick II, has been, for a long time, under archaeometric investigation. On the one hand, it has usually been associated with lapis lazuli, due to the finding of the polysulphide blue chromophores typical of lazurite. Moreover, the observation that the mineral haüyne, which belongs to the sodalite group as well as lazurite, can be blue and/or can gain a blue color after heating, due to the same chromophores, has caused this automatic attribution to be questioned, and also considering that the mineral is characteristic of the rock haüynophyre of Melfi (Potenza, Southern Italy), a location of interest for glass and pottery findings. In this paper, for the first time, several haüyne crystals were found in the blue glaze of a ceramic dish found at Melfi Castle, leading to the hypothesis that, in this case, the local haüyne-bearing source could have been used as the coloring raw material. The discovery was possible thanks to SEM-EDS and Raman analyses that, respectively, highlighted the typical numerous presence of very fine sulphur-based inclusions in the crystals and the characteristic Raman signal of blue haüyne. This study was also focused on the composition of the crystals inclusions, aided by SEM-EDS and Raman maps, since the original very fine pyrrhotite was transformed into Cu and Pb phases (copper sulphates, copper sulphides, and lead oxide) due to reactions with cations that had mobilized from the glaze, while the migration of Si from the glass allowed the transformation of the rim of the haüyne, a silica-undersaturated mineral, into a corona of small euhedral and neomorphic Pb-rich feldspars, a silica-saturated phase.

Sea-silk is made from the byssus threads of Pinna nobilis, an endemic species found in the Mediterranean.The fibers are carefully harvested by cutting them off the mussel, after which they undergo a series of processes including washing, drying, combing, and spinning.The end result is an exceptionally fine, distinctive, and highly valuable fabric.Pinna nobilis byssus is non-collagenous-based, and the fiber's nanostructure is still poorly understood.In this study, we present an investigation into Pinna nobilis byssus samples collected from the Commodity Science Museum of the University of Bari Aldo Moro (Italy) at various stages of the textile manufacturing process.Through scanning electron microscopy (SEM), we reveal a distinctive elliptical cross-section of the Pinna nobilis byssus fibers.Additionally, by using wide-angle X-ray diffraction (WAXRD) and infrared (IR) spectroscopy, we discover hydroxyapatite adsorbed onto the initial fibers.This finding provides intriguing insights into the composition and potential functional properties of the byssus threads.Furthermore, using a WAXRD-based method, we observe a decrease in the crystalline/amorphous ratio during the byssus treatment process.This finding suggests the occurrence of structural modifications as the fibers undergo manufacturing steps, potentially influencing the properties of the final sea-silk fabric.

Imaging studies by laser ablation–inductively coupled plasma mass spectrometry have been successfully developed to obtain qualitative and quantitative information on the presence/distribution of titanium (ionic titanium and/or titanium dioxide nanoparticles) in sea bream tissues (kidney, liver, and muscle) after exposure assays with 45-nm citrate-coated titanium dioxide nanoparticles. Laboratory-produced gelatine standards containing ionic titanium were used as a calibration strategy for obtaining laser ablation–based images using quantitative (titanium concentrations) data. The best calibration strategy consisted of using gelatine-based titanium standards (from 0.1 to 2.0 μg g−1) by placing 5.0-μL drops of the liquid gelatine standards onto microscope glass sample holders. After air drying at room temperature good homogeneity of the placed drops was obtained, which led to good repeatability of measurements (calibration slope of 4.21 × 104 ± 0.39 × 104, n = 3) and good linearity (coefficient of determination higher than 0.990). Under the optimised conditions, a limit of detection of 0.087 μg g−1 titanium was assessed. This strategy allowed to locate prominent areas of titanium in the tissues as well as to quantify the bioaccumulated titanium and a better understanding of titanium dioxide nanoparticle spatial distribution in sea bream tissues.

This work aims at studying the manufacturing and technology peculiarities of Apulian red figure (4th − 3rd century BCE) production from Arpi. In particular, the relationship between the red figure production from Arpi with coeval pottery of different classes retrieved in the same contexts in Arpi is investigated, as well as the connection between the red figure production from Arpi and same class vases from different Apulian sites. This goal has been achieved through widening the archaeometrical studies so far performed to red figures finds from two more tomb complexes in Arpi – i.e. tomb of the Niobids vase and 4/2004 tomb – and also organically reorganizing the so far obtained experimental data on Arpi findings of various ceramic classes. The systematic characterization of red figure vases was obtained by Inductively Coupled Plasma Mass Spectrometry (ICP-MS), Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Spectroscopy (EDS), Powder X-ray diffraction (PXRD) and Raman Spectroscopy. Analytical data allow to define the elemental and mineralogical composition of ceramic pastes and identify pigments and coatings. The results allow to validate the archaeological hypotheses that Arpi red figure production is different from the one from other Apulian areas and that pictorial experiences were shared among tombs, domus and ceramic production in Arpi.

The electrocatalytic effect exerted by hematite, a ubiquitous component of clay bodies, on the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) can be used to acquire information on archaeological ceramics. The solid-state voltammetric response of different hematite and ochre specimens, accompanied by SECM analysis in contact with 0.10 M HCl aqueous solution, is described. In air-saturated solutions, catalytic effects on the ORR and OER are accompanied by Fe(III)/Fe(II) and Fe(IV)/Fe(III) redox reactions. Such processes are conditioned by a variety of factors, the hydroxylation degree of the mineral surfaces being particularly influential, and exhibit significant variations upon heating the specimens between 300 and 900 degrees C. Voltammetric measurements carried out on a set of archaeological samples of Apulian red-figured pottery dated back within 5(th) and 4(th) centuries BCE permit to obtain site-characteristic voltammetric profiles.

Mussel-forming fibers manifest fascinating properties due to the numerous reactive functional groups present in their primary structure besides their secondary structures. Humans adopted these protein-based fibers to produce an extremely fine and valuable fabric, named byssus. Byssus is the bundle of filaments secreted by Pinna nobilis species employed to colonize the marine substrates. The byssus fibers coming from other species, such as Mytilus edulis , have been widely investigated in particular for their self-healing properties attributed to the collagen presence and their core-shell structure. Surprisingly, the Pinna nobilis byssus is non-collagenous based and the fibers nanostructure is still poorly understood. Here, we are reporting an investigation on the Pinna nobilis byssus samples retrieved intact in each stage of treatment. The scanning electron microscope (SEM) provides a peculiar feature of Pinna nobilis byssus, i.e. the elliptical cross-section of the fibers. Wide-angle X-ray scattering (WAXS), as well as infrared spectroscopy (IR), reveal the presence of hydroxyapatite adsorbed at the surface of the initial fibers and the presence of crystalline beta-sheet domains within the fibers. Finally, a WAXS-based method reveals a decrease in the crystalline/amorphous ratio during byssus treatment.

Voltammetry of immobilized particles (VIMP) and scanning electrochemical microscopy techniques are combined to study nanosamples from 60 Apulian red-figured pottery objects from six Apulian archaeological sites (Altamura, Arpi, Conversano, Egnazia, Monte Sannace, Taranto) and three Attic samples from Pella. The VIMP signatures corresponding to the electrocatalytic effect of microparticulate deposits of the clay body and the black gloss on the oxygen evolution reaction and the oxygen reduction reaction are obtained. These signatures provide information on the reducing/oxidizing conditions of firing. The combination of the above voltammetric data permits us to distinguish between Apulian production and Attic importations as well as to discriminate the productions from different archaeological sites or even within different technologies in samples from the same site.

A remarkable number of early 20th century azo synthetic textile dyes was characterized by Fiber Optics Reflectance Spectroscopy (FORS). Items are part of silk-cotton and wool-cotton blends pattern books of Leopold Cassella & Co., a leading firm at that time. Focusing on early dyes from this privileged point of view, meant for us providing our own scientific contribution to restore luster to a historical period that represented the keystone from upmarket natural dyes to synthetic ones on a large scale. A selection of spectra on silk-cotton blend with the same dye concentration was compared color by color. In the case of wool-cotton blend textiles, two concentrations were available for each dye. Therefore, spectra comparisons between the same dyes used in silk-cotton and wool-cotton blends were carried out, as well as between the same dyes in different concentration in the case of wool-cotton textiles, simulating possible fading conditions. In addition, almost each analyzed dye was linked to its molecular structure. Finally, the obtained set of data has been statistically treated. The complete dataset was subjected to an exploratory analysis using PCA that exhibited an organization of the samples based on brightness and colors. The generation and validation of a PLS-DA model confirmed the recognizability of the samples based on color and pointed out the excellent conservation conditions implemented. The method provides a non-invasive, fast and low-cost approach for the recognition of azo dyes, based on the combined application of FORS, colorimetric parameters and chemometrics and lays the foundation for a reference database.

In this paper, 4th century BC Apulian red vases, from sites among the most relevant in Apulia (Italy), are studied by means of Raman spectroscopy. The effectiveness of this technique in the archaeometric research is emphasized, particularly regarding the manufacturing procedures and raw materials of black and red surfaces. Scanning Electron Microscopy and Energy Dispersive X-ray Spectroscopy (SEM-EDS) analyses are carried out jointly with Raman spectroscopy in order to complete the morphological and chemical information. The results show that two different clays have been employed for black gloss and ceramic body. The black gloss proves composed of the finest fraction of terre rosse-very common all over Apulia-with no organic material added to its clayey suspension. Traces of carbon found on the surfaces can be ascribed to fly ash deposited during the firing process. This research highlights that two more methods besides red engobe were used by Apulian potters to color red the surface of whitish/grayish vases realized with local raw materials, namely, the addition of either "miltos" or a clayey layer enriched in Fe oxides. A multi-step firing (ox-red-ox), reaching the maximum temperature of about 900 degrees C, can be deduced from the different mineralogical phases identified through Raman. The possibility of gaining information on the hematite particles size from the position of its characteristic Raman bands is successfully investigated, allowing to get clues on the presence of a surface layer in a nondestructive manner by comparing the particle size there and in the ceramic body.