Elemental Analysys of metallic samples by nanopartiles-enhanced laser-ablation ICP-MS

This conventional method of Solid sample analysis is very dirty and produces a lot of chemical waste. Conversely, laser ablation is a green technology because it does not require acid dissolution and does not generate chemical wastes. Moreover, LA-ICPMS technique presents other interesting features such as high spatial resolution, extended linear dynamic range, low detection limits, extremely small sample quantities required for analysis. We propose an analytical strategy to enhance the sensitivity of LA- ICPMS by the deposition of gold nanoparticles (AuNPs) on the surface of investigated samples. The undoubted strengths of this approach are represented by simplicity, low-cost budget and fast performance. The commercial LA-ICPMS set-up has not been changed in any way and laser parameters, type and flow of gas carrier is not modified to improve the ablation of the sample [1]. The sample surfaces have been altered by depositing metallic nanoparticle (NPs) colloidal dispersions, thus increasing their response to laser, but preserving their chemical properties. A consistent lowering of the breakdown threshold and a remarkable increase in the measured signal intensity have been observed. This has allowed to determine traces and ultratraces in many areas (environmental, forensic, clinical, cultural heritage, food analysis, ecc.). In the method developed, the drops of NPs can be put in a controlled manner on the sample surfaces and completely removed before the analysis by laser ablation. This represents a further advantage compared to the classical methods of sample analysis. The first results obtained with this technique in the analysis of metal matrices show enhancement of the signal of one order of magnitude for most of the analyzed metals. [1] Z. Wang, B. Hattendorf and D. Günther, J. Am. Soc. Mass Spectrom. 17 (2006) 641-651

Mapping Apulian Red Figure Pottery by a multitechnique approach

Apulian red-figured pottery, one of the most important examples of ceramic handcraft production in Magna Graecia, dating back to the 5th and 4th centuries BCE and coming from the most relevant sites in Apulia (Southern Italy), has been extensively characterized by our group for several years [1-5]. Our main goals are various and quite ambitious: highlighting technological differences between Apulian red-figured pottery and the most famous Attic one, obtaining valuable knowledge about pottery workshops and painters and defining the nature of coatings and decorations. We have investigated ceramic body, black gloss and overpainting areas of items by different techniques according to issues to be solved and samples availability. The ceramic bodies’ elemental composition has been investigated by inductively coupled plasma mass spectrometry (ICPMS), the mineralogical composition of pastes by polarized-light optical and electron microscopies (OM and SEM-EDS), and X-ray powder diffraction (PXRD). The fruitful combination of results driven from multivariate statistical treatment of compositional data and mineralogical arrangement of pastes allows us to formulate hypotheses about the provenance of items and manufacturing tradition of workshops, starting to make it possible to comprehend the connections among ceramic technology, artistic expression, and workshop practice in the samples analyzed. Also, with regard to the material brought to light during the 19th century, it is known that “antiquarian type” of restoration was the most used (i.e. reconstruction and repainting, following the mimetic taste of the time). From this point of view, our archaeometric investigations have also provide detailed guidelines on the 19th century restoration techniques [6]. All 5th century objects analyzed up to know, nevertheless sites of provenance, show the same features: fine texture of the ceramic body, red figures saved from the ceramic paste and black gloss painted directly on the ceramic body. Regarding the 4th century objects, some highlight features similar to the 5th century ones, whereas others are characterized by a ceramic body with a coarser texture and a layer of ingobbio rosso. This intermediate layer entirely covered the external part of the vase and was reddish than the ceramic body -visually better to obtain red decorations- and the black gloss -when present- was painted on it. The chemical and minero-petrographic results make it possible to discriminate different production technologies of red figured Apulian vases used in Apulia during the 4th century BCE. This technology seems to take shape of a distinctive characteristic of Late Apulian production regardless of sites of provenance. Finally, we selected a consistent number of items to be analyzed by LA-ICPMS (Laser Ablation ICPMS). We compared Apulian samples and Attic ones, obtaining info on major, minor and trace elements. From an archaeometric point of view, the results showed differences both in the black gloss and in the ceramic body raw materials used in Apulia with respect to Attic ones, so providing an objective parameter of regional production discrimination. The comparison carried on leads us to exclude imports of black gloss from Greece, as hypothesized by some scholars [7]. Nevertheless, in order to accomplish conclusive observations, sampling has to be extended, both in terms of numbers and provenance of samples

A FORS (Fiber Optics Reflectance Spectroscopy) database for the re-evalutation of a historic pattern books collection: the case of the Cassella Color Company

The Cassella Color Company was founded at Frankfurt am Main (Germany) by Leopold Cassella in 1789 and started towards the end of the 19th century a dyestuff manufacture, rapidly becoming one of the worldwide major synthetic dyes producers. In particular, the firm specialized in the patenting and production of “Diamine Colors”, azo dyes with the general structure of a diamine (benzidine, tolidine, methoxy tolidine or ethoxy tolidine) linked to two terminal alike or different groups [1]. Their pattern books describe the developing of these dyes and the various dyeing processes of silk, cotton, linen, wool, straw and chips: they contain also fragments of fabrics colored with the synthesized dyes, thoroughly supplied with the description and percentage of each dye, applied individually or in a mixture. The precious collection of the Commodity Science Museum of the University Aldo Moro of Bari (Italy) includes rare pattern books of yarns and textiles dated to the end of the 19th – beginning of the 20th century, among which an important corpus of the Cassella Color Company editions. This work is included in a wider project aimed to the re-evaluation of the Commodity Science Museum collection, starting with the scientific cataloguing by means of reflectance spectroscopy data of the dyestuff production from the above-mentioned firm. Fiber Optics Reflectance Spectroscopy (FORS), much used for the identification of dyes and pigments, has scarcely been employed in the study of textile dyestuff [2], for which the main applications were directed to the revelation of natural/traditional dyes in fabrics prior to the era of synthetic colors [3, 4]. The FORS technique was employed with the aim of generating a reference database for the future characterizations of 20th century dyestuff. Up to now, silk cotton blend, wool cotton blend, straw and chips dyed with Diamine Colors and finally color lakes precipitated in different ways were analyzed

Shining like gold and soft like silk. The case of byssus samples coming from the Commodity Science Museum of the University of Bari

The word byssus is the zoological term used to call the fine but strong filaments of fibre beard produced by the mollusc Pinna nobilis. Byssus was the basic raw material used to make sea-silk, but, given that this species, endemic in the Mediterranean, is protected since 1992 [1], a renewed production of the beautiful iridescent amber-golden textile is essentially impossible. It is proved that the use of sea-silk dates back at least to the Roman age. In the modern times, up to the middle 20th century, Sardinia and Apulia (especially Taranto), were production centers of sea-silk and keep their importance still nowadays in the transmission of the knowledge of the ancient expertise, concerning the procedures of cutting, washing, drying, combing, spinning and -much rarely- waving of the fibre. The oral handing down of the know-how must be protected as part of our immaterial demoethno-anthropological heritage, because it is unfortunately gradually disappearing, like the concept of cultural heritage linked to the precious and rare textile that it produced. Only recently some effort has been made to draw attention on this subject with projects and exhibitions [2]. We studied samples of sea-silk stored at Commodity Science Museum of University of Bari “Aldo Moro” (Fig.1), where one valve, some pearls and all the different phases of crafting of this textile are represented, starting from the raw byssal threads up to the woven textile. The aim is to characterize morphologically and chemically the threads, especially the evolution and changing throughout the different working phases. In this way, there will be a scientific trace of what started as an oral tradition and is not yet nowadays widespread and well-known. We used different techniques like optical microscopy (OM), Scanning Electron Microscopy coupled with Energy Dispersive Spectroscopy (SEM-EDS) and Inductively Coupled-Mass Spectrometry (ICP-MS). The results obtained show how the fiber of the Sea-silk changes until the achievement of the golden “soul of the sea” [3]

Chemical-phisical and morpho-mineralogical methodologies as tools for a fresh viewpoint on medieval graffita pottery

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-styl

. Oxidative Potential Characterization of water-soluble fraction of PM and PM in an urban background site in Southern Italy: influence of the carbon content.

Oxidative potential (OP) of ambient particulate matter (PM) is a measure of the ability of PM to produces remarkable concentrations of reactive oxygen species (ROS) that could lead to oxidative stress in humans. Therefore, OP is a possible measure of PM biological reactivity. When the amount of ROS exceeds the neutralizing capacity of antioxidant compounds, other cellular components can be involved in the oxidation process, which finally could result in health issues. Indeed, the harmful process can be activated, although human body is capable of react to ROS, in case defence mechanisms are debilitated by diseases. The aim of this study was to investigate the seasonal trends of OP measured in two size fractions and how this is influenced by carbon content. Daily (November 2016-November 2017) PM2.5 and PM10 samples were simultaneously collected, on quartz substrates, using a dual channel low-volume (2.3 m3 /h) sampler (SWAM, Fai Instruments). Sampling was carried out at the Environmental-Climate Observatory of Lecce (Italy), a regional station being part of the Global Atmosphere Watch (GAW-WMO) network (Fig. 1). It is basically an urban background station, being placed at 4 km from the town of Lecce and between 30 km and 80 km from large industrial sites of Brindisi and Taranto (Cesari et al., 2017). Roughly one sample every three was selected for carbon content analysis and OP determinatio

Synergic analytical strategy to follow the technological evolution of campanian medieval glazed pottery

Three classes of medieval lead-tin-glazed ceramics (protomajolica, transition enamel pottery and white enamel pottery), from the archaeological site of Castello del Monte in Montella (Avellino, southern Italy), were investigated. Inductively coupled plasma–mass spectrometry (ICP-MS), optical and scanning electron microscopy with energydispersive X-ray spectroscopy (OM and SEM-EDS) and Xray powder diffraction (XRPD) were carried out on ceramic bodies, coatings and decorations in order to outline the technological features and define the nature of glazes and pigments. The aim of this work, in addition to delineating the features of production, is to confirm the archaeological hypothesis that transition enamel pottery produced between the fourteenth and fifteenth centuries, although having much in common with the protomajolica, is in fact a version of white enamel pottery, characterised by morphological and ornamental diversity. Our results show that both ceramic bodies and coatings feature different structural and compositional characteristics, linking the three ceramic classes and making it possible to confirm the archaeological hypothesis that transition enamel pottery can be defined as a ceramic class with transitional features between protomajolica and white enamel pottery