Increased need for non-destructive investigation methods in archaeology has become a major issue since sampling is in most cases restricted in view of the importance or uniqueness of the objects. For this reason, preliminary investigation using non-destructive techniques was performed on five samples of amber beads obtained from different excavation and archaeological sites. The use of FTIR and micro-Raman analysis revealed the presence of carboxyl, peroxide, hydroxyl, and complex ester functional groups as well as single and double bonds in the structure of the studied resin varieties. Further analysis of the amber samples from both archaeological and geological types by XPS, XRF, and SEM showed the presence of sulfur and a wide range of trace elements on the surface of the analysed samples. Our results proved that the combination of structural-molecular and surface elemental techniques for amber characterisation provides a very useful and simple methodology for the description of geological and archaeological amber samples from different regions of Europe.

The investigation was aimed at defining the compositional and structural characteristics of a group of monochrome blue faiences recovered in Pompeii to assess provenance on the basis of their technological features. Different complementary analytical techniques were used: Scanning Electron Microscopy (SEM) to investigate the morphological aspects of the samples and in particular of the interfaces, micro-Raman Spectroscopy and XRPD to identify crystalline phases and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) to assess the elemental composition due to its sensitivity to a wide range of elements and the adequate lateral resolution. Statistical data treatment of the elemental concentrations of both the ceramic bodies and the glazes allowed us to classify the objects into compositional groups and to verify the previously established archaeological hypothesis suggesting an Egyptian provenance for faience of Pompeii.

Fibulae from the archaeological site of Egnatia were examined with the aim of identifying types of alloys, the processes employed for their manufacturing, and outlining the corrosion products. The results obtained, by identifying the raw materials and the technological solutions used allowed us to provide convincing answers to most of the archaeological questions and confirmed the integration of Egnatia in a complex commercial network. In addition, investigations focused on the study of corrosion products, with a view to the planning of more suitable restoration and preservation strategies.

Painted Canosa ceramicswere examined to identify the nature of the pigments employed and theirmanufacturing technology. A multi-technique approach was used, comprising Raman microspectroscopy and laser ablation hyphenated to inductively coupled plasma-mass spectrometry (LA-ICP-MS). The analysed samples were mainly produced for burial in tombs and were not intended for everyday use. They belong to the period between the end of themid-7th century andthe first half of the 4th century BC, and were excavated from the Toppicelli archaeological district near the suburbs of Canosa (Puglia, Italy). Forty-eight pottery fragments were available for this study. No handling of the samples was required for the Raman study, and it was possible to excise the pigmented layer in such a way that the lacunae were not distinguishable to the naked eye due to the micrometric size of the laser spot as far as LA-ICP-MS is concerned. Their combination turned out to be quite useful for the investigation of these archaeological materials: the chemical nature of the white, red, brown and black pigments employed in the pottery manufacture was investigated. Iron and manganese compounds were identified as the red and brown/black main colouring substances, respectively; on the other hand, whites and engobes (whitish slips) were based on kaolinite. This set of colouring substances is of importance, as it enabled the artisan to obtain in one oxidising firing cycle brown, black and red paints. Finally, the finding of manganese black in these Canosa potsherds confirms that Canosa was an important centre connecting the near East to central Italy and Europe since the pre-Roman age.

Laser Induced Breakdown Spectroscopy can provide a useful contribution in mineralogical field in which the quantitative chemical analyses (including the evaluation of light elements) can play a key role in the studies on the origin of the emeralds. In particular, the chemical analyses permit to determine those trace elements, known as fingerprints, that can be useful to study their provenance. This technique, not requiring sample preparation results particularly suitable for gemstones, that obviously must be studied in non-destructive way. In this paper, the LIBS technique was applied to distinguish synthetic emeralds grown by Biron hydrothermal method from those grown by Chatham flux method. The analyses performed by collinear double-pulse LIBS give a signal enhancement useful for the quantitative chemical analyses while guaranteeing a minimal sample damage. In this way it was obtained a considerable improvement on the detection limit of the trace elements, whose determination is essential for determining the origin of emerald gemstone. The trace elements V, Cr, and Fe and their relative amounts allowed the correct attribution of the manufacturer. Two different methods for quantitative analyses were used for this study: the standard Calibration-Free LIBS (CF-LIBS) method and its recent evolution, the One Point Calibration LIBS (OPC-LIBS). This is the first approach to the evaluation of the emerald origin by means of the LIBS technique.

Abstract Glazed pottery with ‘‘negative decoration’’ samples, dating back to the twelfth to thirteenth century AD and coming from three sites along the Adriatic coast, Siponto, Egnatia and Trani (Southern Italy) were characterized from physical–chemical, mineralogical and morphological points of view. Optical microscopy, scanning electron microscopy with energy dispersive X-ray spectroscopy, inductively coupled plasma-mass spectroscopy, X-ray diffraction and micro-Raman spectroscopy investigations were carried out on ceramic bodies, pigments and glazes of the fragments. We aimed to outline the technological features, define the nature of decorations and coatings—glazes and engobes—and look for clues to hypothesize provenance. Results obtained show clear differences in raw materials and production technology between the impressed ceramic of Islamic tradition and the incised one of Byzantine tradition. Regarding the latter, evidences of a non-local origin can be found in the compositional diversity of raw materials used for the ceramic bodies of fragments decorated with spiral and pseudo-kufic motifs, which stressed the use of clays so far not recorded in Apulia. At the same time, at least in the case of Siponto, the compositional similarity of both ceramic bodies and materials used under the glaze for impressed ceramic and painted polychrome ceramics (RMR and protomaiolica), more likely local production, could suggest that both were produced in the same workshops.

Shards of medieval glazed pottery with negative decoration, usually called graffita, coming from three different archaeological sites in Apulia werw examined by OM, SEM, EDS, ICP-MS. The results obtained, based on similarities/differences of raw materials and technological features, allowed to enclose objects in two groups, reflecting the shared tendencies in taste in the medieval era across the Mediterranean area (11 th - 13 th centuries: Islamic style and Bizantine-style

A group of enamelled and gilded glass objects, coming from Melfi Castle (PZ - Italy) from an area dated to the period between the end of the 12th and the last quarter of the 13th century, offered the opportunity to closely investigate this technology with the aim of understanding the raw materials and the procedures employed to realize the objects and their precious decorations. Optical microscopy, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, Raman spectroscopy, laser ablation-inductively coupled plasma-mass spectrometry and X-Ray photoelectron spectroscopy were used to observe and analyze the glass, the enamels, the gildings and their mutual relations. The bulk of the objects resulted a soda-lime glass, while the enamels are lead-based 'soft' enamels or soda-lime glass; the palette of pigments employed to obtain their colours included iron III oxide and minium for red, lazurite and/or cobalt for blue, lead-tin-antimony pyrochlore solid solution oxide (yellow) plus cobalt for green, manganese oxides for black and calcium phosphate for white. Results obtained for gilding, in particular stratigraphy and morphology, suggest the use of the so called 'liquid gold'.

Late Apulian red figured pottery [1] from Egnatia (Fasano, Brindisi, ITALY) was studied in order to widen the view on this ceramic class in Southern Italy. Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) provided the samples elemental composition that allowed to make provenance hypotheses. Optical Microscopy (OM) and Scanning Electron Microscopy (SEM) with Energy Dispersive Spectrometry (EDS), supplied information about the minero-petrographic features of the objectsto better understand their production technology. The set of results highlighted the contemporary presence in the Apulian land in the late 4th century b.C. of both local and imported finds and showed the existence of two different kinds of local production, the "classic" Attic and a peculiar one, characterized by the application of an engobe layer before the black gloss. Our previous studies resulted in the discovery that an engobe layer, with similar chemical and minero-petrographic characteristics, was found in finds from another site in central Apulia (Monte Sannace). So the discovery of red engobe on fragments from Egnatia, proves that its use was not an isolated occurrence, but was quite common in the production of red figured in Apulia during the Late period, appearing as a peculiar technological mark of Apulian potters.

Su una vasta campionatura di frammenti compresi tra l'età tardoantica e il Medioevo lo studio archeologico e archeometrico hanno messo a fuoco aspetti relativi alla tecnologia e al degrado

Colouring materials of the Neolithic wall paintings at Santa Croce Caves (Bisceglie, Apulia) - Neolithic wall paintings of the Santa Croce caves (Bisceglie, Apulia) were analysed to define the painting technique through the analytical characterization of the pigments and binding media. Samples of red wall paintings film from two different areas of the caves have been examined by means of various analytical techniques. XRD, Raman and SEM–EDS analyses identified the red pigments as the local terra rossa sediments. They are silty-clayey continental sedimentary deposits, formed mainly by Fe-oxides/hydroxides (hematite and goethite), as colouring material, and clay minerals (mainly kaolinite), as inorganic binder.

At Gnatia, an important municipium, and then Late Antique civitas, along the Adriatic coast, since 2001 are held excavations and topographical survey (conducted under the ‘Progetto Egnazia. Dallo scavo alla valorizzazione’, directed by prof. Raffaella Cassano - University of Bari): these researches are proving the economic vitality and urban articulation. Among the pottery found, locally produced and imported, the lamps show a vast typological repertoire that expresses interesting diagnostic potential. The study presented was applied to specimens of Forms ‘Atlante’ X, XIII, XV, producted in North Africa and widely exported in the Mediterranean Sea, where there are phenomena of imitative manufacturing, at local and district. Archaeometric analysis conducted on 'local' and 'imported' lamps allowed to characterize the productions and to precise the classification. The results support the hypothesis – already advanced on a chronological kind – of different backgrounds and different technological chain of the finds. As for the 'imitation', it was possible to determine the production of Egnatia: nullifying appears the comparison with the contemporary amphoras like 'broad line ware', found within a furnace collapsed in the late sixth century AD. The mineralogical investigations have also identified in alluvial deposits, outcropping around Gnatia, the raw material used for the production of lamps and amphoras.

Il progetto archeometrico affrontato è stato rivolto alla caratterizzazione chimico-fisica di varie classi ceramiche, rinvenute nell’area del castello di Montella, con l'obiettivo di definirne i connotati tecnologici per una corretta classificazione e per identificarne la produzione: locale o di importazione. Oltre agli obiettivi indicati, l’indagine archeometrica è stata finalizzata a confermare l’ipotesi archeologica che le classi ceramiche con rivestimento vetroso piombo-stannifero (protomaioloica, smaltata di transizione, smaltata) siano il risultato di una evoluzione tecnologica. Gli aspetti più ampiamente indagati sono stati: - la composizione chimica e minero-petrografica dei corpi ceramici; - la natura e la composizione del rivestimento nelle classi ceramiche in cui esso è presente; - la natura dei pigmenti utilizzati nelle decorazioni

A modified version of the calibration-free (CF) method was applied to the analysis of a set of archaeological brooches made of various copper-based alloys and coming from the archaeological site of Egnatia (Apulia, Southern Italy). The developed methodology consists in determining the plasma temperature by reversing the set of equations employed in the usual CF algorithm, and it is thus referred to as "inverse method". The plasma temperature is determined for one certified standard, by using its known elemental composition as an input data, and then applied to the set of unknown samples to evaluate their composition in a CF mode. The feasibility of such an approach is demonstrated by comparing the results obtained with classical LIBS (drawing calibration lines with a series of matrix-matched certified standards) and with independent measurements performed with a conventional technique (LA-ICP-MS).

This study focuses on defining compositional and structural characteristics, identifying raw materials and production technology, and validating the archaeological hypothesis of a local production of thin-walled pottery (2nd cent. BC–3rd cent. AD) in the Vesuvian area. Samples investigated were analysed using OM, SEM-EDS, XRD and LA-ICPMS supported by a statistical multivariate treatment of the compositional data of the ceramic bodies. The results obtained show how an integrated approach of analytical techniques can provide answers to archaeological questions and also give a valuable insight into the exchange of raw materials and/or finished products between sites. The paper also discloses how a combined analytical methodology represents a positive step in answering the one question which remains unsolved concerning the entire ceramic production in the Vesuvian area: the provenance of the clayey raw materials used. Indeed, the massive pottery production in the Bay of Naples down the ages contrasts with the unavailability of the necessary clayey local resources.

Gilded and enamelled glasses of Islamic style, coming from a 13th century landfill in Melfi castle, a Swabian emperor Frederick II fortress, were subjected to a multi-techniques approach in order to explore the complex and very fascinating ancient production technology of gilding and enamelling on glass. Non-destructive μ-Raman spectroscopy was employed on the most important and well-preserved objects, optical (OM) and electron (SEM) microscopies were used to investigate the sections stratigraphy of tiny fragments sampled from the borders of the already damaged objects. In order to provide the chemical analyses of the bodies and the enamels, energy dispersive X-rays spectroscopy (EDS) and X-rays photoelectron spectroscopy (XPS) were also employed. The body of the objects proved to be made of silica-soda-lime glass, while the enamels of lead-rich glass (“soft enamels”) and coloured by lapis lazuli and cobalt for blue, hematite and minium for red, lead-tin yellow for green and calcium phosphate for white. The gilding was found to be applied on a red enamel basis. The presence of carbon inside the gildings and the detection of two different gold signals by XPS suggested the hypothesis of the use of the so-called “liquid gold”. This study gave thus an important contribution to the understanding of the production of this class of rare and precious objects, also confirming that the materials and technological procedures are consistent with the Islamic tradition, probably due to the presence of Islamic artisans at the court of Frederick II.

Fifty oil lamps from the catacombs of ‘Ponte della Lama’ (Canosa di Puglia, second to sixth centuries AD) were analysed to understand the correlations existing between types and fabrics and to determine their provenance. Petrographic and chemical analyses confirmed the archaeological hypothesis of local production of the oil lamps, using fluvial deposits. However, the three samples of oil lamps imitating the African ‘Atlante VIII’ are considered chemical outliers compared to the rest and are supposedly of foreign origin. The extensive and original repertory of lamp types characterizes Canusium as the production centre in the late Roman period.

Palladium nanoparticles have been electrochemically supported on zirconium oxide nanostructured powders and all the nanomaterials have been characterized by several analytical techniques. The Pd/ZrO2 nanocatalyst is demonstrated to be a very efficient catalyst in Heck, Ullmann, and Suzuki reactions of aryl halides in water. The catalyst efficiency is attributed to the stabilization of Pd nanophases provided by tetra(alkyl)- ammonium hydroxide, which behaves both as base and PTC (phase transfer catalyst) agent.

Samples of Mytilus galloprovincialis were examined to investigate the levels of polybrominated diphenyl ethers (PBDEs) in the Apulia's marine environment, a region in the South of Italy. The levels of nine PBDE congeners were measured in 40 mussel samples taken from the aquaculture farms in the South of Adriatic Sea and North Ionian Sea along the Apulia coast. While accelerated solvent extraction (ASE) was the extraction technique adopted using acetone/n-hexane (1:1, v/v), the content of PBDEs was evaluated by using gas chromatography coupled with high-resolution mass spectrometry (GC-HRMS) via electron ionization (EI) in the multiple ion monitoring (MIM) mode (two ions for each compound). The (13)C mass-labeled compounds were used to establish the levels of PBDEs in M. galloprovincialis samples. The total concentration of PBDEs (Sigma PBDEs) ranged from 0.2 to 6.9 ng/g dry mass, with the highest concentrations found around coastal areas of Salento. With regard to the composition of PBDE congeners, BDE-47, BDE-99 and BDE-100 were the predominant congeners in most of the samples. The present study is the first to report levels of PBDEs occurring in aquatic organisms living in aquaculture farms of Apulia region.

Procedimento per la realizzazione, o il ripristino, per via plasmochimica di un film (film barriera, eventualmente multistrato, che consente di effettuare in modo controllato, uniforme e duraturo il rilascio di sostanze di interesse da un substrato che include come micro/nano particelle la sostanza da rilasciare, oppure da uno strato depositato sul substrato che include come micro/nano particelle la sostanza da rilasciare, oppure da uno strato di sostanza da rilasciare depositata sul substrato, oppure da un substrato che è la sostanza da rilasciare eventualmente in forma di particelle, in cui la sostanza da rilasciare è scelta dal gruppo comprendente metalli e composti con proprietà antibatteriche e molecole biologicamente attive, quali farmaci, ormoni, estratti vegetali, oligopeptidi, lipidi, protidi e glicidi; lo strato con la sostanza da rilasciare (matrice) è ottenuto dal deposito di uno strato, inorganico o organico, eventualmente con struttura simile ai polimeri di polietilenossido (PEO-like); il film barriera è ottenuto dal deposito di almeno uno strato, inorganico o organico, eventualmente con struttura simile ai polimeri di polietilenossido (PEO-like); ed i substrati su cui vengono fatti i depositi sono dispositivi medicochirurgici, manufatti di uso comune, strutture note come scaffold e le sostanze da rilasciare stesse. L’invenzione ha anche per oggetto i dispositivi medicochirurgici, i manufatti di uso comune e gli scaffold rivestiti con substrato e strato barriera, come pure le sostanze biologicamente attive rivestite con almeno uno strato barriera.

Biological agents play an important role in the deterioration of cultural heritage causing aesthetic, biogeophysical and biogeochemical damages. Conservation is based on the use of preventive and remedial methods. The former aims at inhibiting biological attack, and the latter aims at eradicating the biological agents responsible for biodeterioration. Here, we propose the preparation and the analytical characterisation of copper-based nanocoating, capable of acting both as a remedy and to prevent microbial proliferation. Core–shell CuNPs are mixed with a siliconbased product, commonly used as a water-repellent/consolidant, to obtain a combined bioactive system to be applied on stone substrates. The resulting coatings exert a marked biological activity over a long period of time due to the continuous and controlled release of copper ions acting as biocides. To the best of our knowledge, this is the first time that a multifunctional material is proposed, combining the antimicrobial properties of nanostructured coatings with those of the formulations applied to the restoration of stone artworks. A complete characterisation based on a multitechnique analytical approach is presented.

The founding of lapis lazuli to give blue colour to glass and glazes is more and more coming out from the most recent studies of pottery and glassware of different epochs and provenances. The recent discovery in the south of Italy (Frederick II, Melfi castle) of enamelled glass pieces including blue enamels questioned the real nature of the blue colour raw materials because the castle is built over and not far from outcrops of two volcanic rocks – haüynophire and phonolite – that contain haüyne, mineral belonging to sodalite group as lazurite, that can be blue or become blue after heating. Raman microscopy and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy were tested in order to identify the rock used as raw material and to understand if the chromophore-bearing mineral in the artefacts could be other than lazurite. To do this, the two volcanic rocks, lapis lazuli and archaeological glass with blue enamels, were studied. In particular, temperature-dependent Raman measurements and Raman mappings both on single lazurite and haüyne crystals and on the rocks and the enamels were carried out also in order to investigate the colouration mechanism of haüyne. The results obtained allowed to make hypotheses about the transformations occurring in haüyne with heating and about the procedures of distinguishing the raw materials.

In order to improve the dispersion of multi-walled carbon nanotubes (MWCNTs) in aqueous media, their surface functionalization was carried out in O2-fed low-pressure plasmas. Differently from what can be found in the literature of this field, homogeneous functionalization was achieved by generating the plasma inside vials containing the nanotube powders properly stirred. Experimental parameters, such as input power, treatment time and pressure, were varied to investigate their influence on the process efficiency. A detailed characterization of the plasma treated nanotubes, dry and in aqueous suspension, was carried out with a multi-diagnostic analytical approach, to evaluate their surface chemical properties, morphology, structural integrity and stability in the colloidal state. The plasma grafting of polar ionizable (e.g. acid) groups has been proved to successfully limit the agglomeration of MWCNTs and to produce nanotubes suspensions that are stable for one month and more in water.

Organic functionalization of carbon nanotube sidewalls is a tool of primary importance in material science and nanotechnology, equally from a fundamental and an applicative point of view. In this paper, a mild and easily tunable approach to the sidewall decoration of single-walled carbon nanotubes (SWCNTs) with epoxides and their subsequent derivatization (ring opening) upon treatment with reactive nucleophiles is presented. The treatment of HiPco purified SWCNTs with dioxirane solutions results in highly oxidized CNTs, which are used as electrophilic platforms for their successive derivatization/functionalization. As a result of the choice of accessible, easy to handle and store dioxiranes, multiple oxidation cycles could be performed on the same sample, thus allowing for a final improvement in the extent of oxidation at the CNT sidewall.