Glazed roman ceramic. A multi-analytical approach

A multi-analytical approach has been applied to characterize ancient glazed ceramics from the archaeological sites of Magna Mater temple and Domus Tiberiana on the Palatine Hill (Rome, Italy) dated between the 3rd and the early 5th century AD. The aim of this work is to investigate the production technologies of the ceramic body and the glazed coating and to explore the nature and the provenance of the raw materials. Optical microscopy (OM), Fourier transform infrared spectroscopy (FTIR) and X-ray powder diffraction (XRPD) results showed that the ceramic body is composed by quartz, K-feldspar and plagioclase, fragments of igneous and sedimentary rocks. The firing temperature was estimated at about 900-1000 °C, in uncontrolled atmosphere conditions. The mineralogical assemblage of the ceramic body is consistent with a local source of the raw materials. The results of electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS) showed that the glazes contain different Si/ Pb ratios. In addition, X-ray fluorescence (XRF) detected the presence of Sn although its concentration does not allow defining the studied samples as tin-glazed ceramics. However, the occurrence of this element indicates an atypical Roman production, never recognized before in coeval samples from other archaeological sites

The phoenician red slip ware: a multi-analytical study of a technological marker among the shores of the Mediterranean Sea

La presente tesi di dottorato riporta i risultati dell’indagine archeometrica condotta su ceramiche fenicie in Red Slip Ware (RSW), datati tra il secolo IX a.C. e l'inizio del V secolo a.C. I campioni provengono da Mozia (Sicilia-Italia), Sulky (Sardegna-Italia), Cadice (Spagna), Mogador (Marocco), Ramat-Rahel (Israele), Tas Silg (Malta) e Pantelleria (Italia). La caratteristica principale di questa classe ceramica è l'aspetto esterno, simile in tutti i contesti archeologici, caratterizzato da una decorazione rossa lucida. Lo scopo di questa tesi è di individuare parametri mineralogici, chimici e microstrutturali che possano essere utili per discriminare tra campioni di diversa origine, nonostante il loro aspetto esterno simile. Al fine di ricostruire il background tecnologico e identificare le materie prime utilizzate, il corpo ceramico e la decorazione sono stati studiati mediante Microscopia Ottica (OM), Diffrazione di Raggi X su Polveri (XRPD), Microscopia Elettronica a Scansione abbinata al sistema EDS (SEM-EDS), Analisi in Microsonda Elettronica (EMPA) e Voltammetria di Microparticelle Immobilizzate (VIMP), una tecnica micro invasiva. Sono stati studiati quaranta campioni di Motya. I risultati suggeriscono un'attenta selezione delle materie prime (ovvero, argilla carbonica illitica e inclusioni), cotte a temperature comprese nell'intervallo >800 e <900 °C, in condizioni ossidanti. Il confronto della composizione mineralogica e chimica tra i depositi di argilla locale ed i campioni ceramici, unitamente alle differenze produttive, hanno permesso di distinguere i prodotti locali (due fabric che contano 36 campioni) dai quelli importati (tre fabric, che contano 4 campioni). La decorazione Red Slip è costituita da un rivestimento ricco di argilla, arricchito in Fe, ne sono state identificate tre tipologie differenti. Gli otto campioni di Sulky sono divisi in un fabric principale più un campione loner. I dati suggeriscono temperature di cottura comprese tra 800 e 900 °C e l'uso di materie prime, povere in Ca, simili per corpo ceramico e decorazione. I dati XRPD consentono di identificare l’associazione quarzo + cristobalite + tridimite, tipica delle ignimbriti del distretto vulcanico del Sulcis. Le analisi sottolineano inoltre che due diverse miscele ricche di Fe sono state utilizzate per decorare i campioni del fabric e del campione loner. I trenta campioni di Cadice provengono da due siti archeologici fenici (Cánovas del Castillo del VIII secolo a.C. e la Necropoli del VI secolo a.C.). I campioni di entrambi i contesti sono raggruppabili in due fabric, inoltre è stato identificato un campione loner. I microfossili di origine marina sono molto comuni in tutti i campioni, ma mentre nei due fabric prevalgono gli organismi bentonici, nel loner sono presenti quasi esclusivamente esemplari planctonici. I campioni, composti da argilla illitica ricca di Ca, sono stati cotti nell'intervallo di temperatura 700-850 °C in condizioni ossidanti. Il contenuto di microfossili, la presenza di monazite e framboidi di ossidi di Fe, sono compatibili con i sedimenti rinvenuti nell'area della baia di Cadice; solo il loner, realizzato con materie prime totalmente diverse, è stato probabilmente importato. Infine, le analisi elettrochimiche hanno permesso di discriminare i manufatti provenienti dallo stesso sito e da siti diversi. Le considerazioni finali sembrano supportare l’ipotesi che i Fenici preferissero produrre la RSW utilizzando materiale locale ma tramandando il loro know-how nelle colonie e commercializzando/importando solo pochissimi manufatti.The present PhD thesis reports the results of the archaeometric investigation on the Phoenician Red Slip Ware (RSW) artefacts dated back between the 9th century BC and the early 5th century BC. The studied samples come from Motya (Sicily-Italy), Sulky (Sardinia-Italy), Cádiz (Spain), Mogador (Morocco), Ramat-Rahel (Israel), Tas Silg (Malta), and Pantelleria (Italy). The main feature of this ceramic class is the external macroscopic appearance, similar in all archaeological contexts, characterized by a shiny red decoration. The aim of this thesis is to individuate compositional and technological parameters, which can be useful to discriminate among samples of different provenance, despite their similar external appearance. In order to reconstruct the technological background and to identify the nature of the raw materials, the body and decoration have been investigated using Optical Microscopy (OM), X-ray Powder Diffraction (XRPD), Scanning Electron Microscopy coupled with EDS system (SEM-EDS), Electron Microprobe Analysis (EMPA) and Voltammetry of Immobilized Microparticles (VIMP). The results on forty samples from Motya suggest a careful selection of the raw materials (i.e., illitic carbonate clay and inclusions) and firing temperature in the range >800 and <900 °C, under oxidizing conditions. The comparison of the mineralogical and chemical composition of local clay deposits with that of the ceramic products and differences in the manufacture allowed to distinguishing local (two fabrics, counting 36 samples) from imported vessels (three fabrics, counting 4 samples). The Red Slip decoration consists of clay-rich coating, enriched in Fe. Three different typologies of slips have been identified. The eight samples from Sulky are divided in one main fabric and one loner sample. The data suggest firing temperature in the range 800 – 900 °C and the use of similar Ca-poor raw materials for both the body and decoration. XRPD data, acquired in transmission mode along with Rietveld refinements, permit to identify the unusual quartz + cristobalite + tridymite association, typical of the ignimbrites of the volcanic district of Sulcis. This analysis outlines that two different Fe-rich mixtures have been used to decorate the samples of the fabric and the loner. The thirty samples from Cádiz come from two Phoenician archaeological site, one of the 8th century B.C. (Cánovas del Castillo) and the other from the 6th century BC (the Necropolis). The samples are divided in two fabrics (unimodal and bimodal) moreover a loner sample has been identified. Microfossils of marine origin are very common in all samples but in both the two fabrics benthic organisms prevail, while in the loner almost only planktonic specimens occur. The analysis permits to identify the use of Ca-rich illitic clay, fired in the range of 700-850 °C. The microfossils content, the presence of Fe oxides framboidal microstructures and monazite, are compatible with the sedimentary rocks of the area of the bay of Cádiz; probably only the loner sample, made with totally different raw materials, has a foreign origin. Finally, the electrochemical fingerprints discriminate between different vessels of pottery among that recovered in the same site, and between equivalent potteries from different sites. Considering all these data it is possible to hypothesize that the Phoenicians preferred to produce the RSW on site, handing down the technological knowledge in the colonies, using local raw materials, and marketing/importing only very few artefacts

Phoenician Red Slip Ware from Sulcis (Italy): a preliminary report

Phoenician expansion spread all over the Mediterranean coast and came together with the foundation of new colonies. Red Slip Ware, a ceramic class characterized by a shiny deep red surface, seems to be a good marker to identify and to date the early Phoenician presence on the territory. Indeed, Red Slip Ware is found in every Phoenician site, from the motherland to the colonies. Representative fragments of Red Slip Ware from the Phoenician-Punic site of Sulcis (Sant'Antioco, Sardinia) have been studied. These artifacts were unearthed in the area called Cronicario. The site has been dated employing the stratigraphy between the 750 and the 650 BC and it represents the oldest colonial settlement on the island (Campanella, 2005). The purpose of this work is to explore the technological background and the provenance of raw materials in order to discriminate imported or local ceramic productions. With this aim, X-ray powder diffraction (XRPD), optical (OM) and electron microscopy (SEM) were used. The external coating is a very thin clayish and non-vitrified layer with a very few inclusions of small size. Mineral assemblage is predominantly composed by quartz, K-feldspar and plagioclase feldspar, with minor amount of hematite, mica and rare calcite. The occurrence of hematite suggests an oxidizing firing environment. These results support the hypothesis that the samples were made with local raw materials and probably fired at temperature below 850°C (Riccardi et al., 1999) as supported by the high optical activity of the internal body. Electron microprobe analysis (EMPA) was also used to provide quantitative analysis on the outer surface, ceramic bulk and inclusions (Riccardi et al., 1999; Shoval, 2017). These Sardinian ceramics present similarities with other Red Slip Ware from Motya (Sicily), particularly in the external appearance and minerals assemblage. Thus, suggesting a selection of a similar raw material. Nevertheless, some peculiar differences such as the nature of accessory minerals and the content of CaO can be used to distinguish between artefacts of these two Phoenician-Punic sites (De Vito et al., 2013)

Following Phoenician technology through red slip ware artefacts

Following Phoenician technology through Red Slip Ware artifacts L. Fabrizi,1 A. Doménech-Carbó,2 L. Nigro,3 F. Spagnoli,3 F. Cappella,3 and C. De Vito1 1Department of Earth Sciences, Sapienza University of Rome, P.le Aldo Moro 5, 00185 Rome, Italy 2 Department de Química Analítica, Universitat de València. Dr. Moliner, 50, 46100 Burjassot, Valencia, Spain 3 Department of Oriental Studies, Sapienza University of Rome, P.le Aldo Moro 5, 00185 Rome, Italy Keywords:Firing conditions, Technology, Voltammetry of microparticles, Phoenician Red Slip, pottery The Red Slip Ware is a Phoenician prestigious ceramic production, characterized by a shiny red surface and manufactured in the Levant since the 11th century BCE [1]. This production had social and commercial value, occurring in different Phoenician archeological contexts from the Levantine motherland to the colonized territories of central and western Mediterranean [1]. In this panorama, to reconstruct the technological skills achieved in different archaeological sites could provide interesting historical and archaeometric information [1-2]. The samples, dated between the 8th and the early 6th century BCE, come from the motherland (i.e. Ramat–Rahel – Israel/Palestine) and from colonies, i.e. Motya, Sulky and Pantelleria in Italy, Tas Silg in Malta, Cádiz in Spain and Mogador in Morocco. Optical microscopy and X-ray diffraction analysis have been performed on representative samples of Red Slip Ware to investigate the mineralogical assemblage, temperature of firing and fO2, thus exploring the technological level of production [2]. Moreover, Voltammetry of Microparticles, a micro-invasive technique, has been applied to obtain electrochemical fingerprints [3]. Based on petrographic features (i.e. porosity, aplastic inclusion distribution and matrix microstructure), the pottery sherds are divided in five groups, that reflect differences in the forming methods employed by potters. The artifacts are decorated by a Fe-enriched claysh coating with a fine-grain structure. Three different ways of application have been identified. The mineralogical assemblage and the presence of neoformation phases, as hematite and gehlenite, along with the absence of vitrification of the matrix, allow estimating the firing temperature below 900 °C, in controlled oxidizing conditions. The results, compared with geological data, permit to identify the nature of the raw materials used and to distinguish imported vessels from those local manufactured. Finally, electrochemical results highlight a grouping by different production centers and suggest discrimination between shapes and age of vessels of the same archaeological site. [1] L. Nigro, Vicino Oriente, 18 (2013) 39 - 74. [2] C. De Vito, L. Medeghini, S. Mignardi, D. Orlandi, L. Nigro, F. Spagnoli; P.P. Lottici, D. Bersani, Applied Clay Science, 88-89 (2014) 202 - 213. [3] F. Di Turo, N. Montoya, J. Piquero-Cilla, C. De Vito, F. Coletti, I. De Luca, A. Doménech-Carbó, Applied Clay Science,162 (2018) 305 - 31

Deoxysphingolipids as candidate biomarkers for a novel SPTLC1 mutation associated with HSAN-I

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The application of non-destructive techniques for the study of corrosion patinas of ten Roman silver coins. The case of the medieval Grosso Romanino

This work focuses on the study of ten Grosso Romanino, a silver medieval coin, minted in Rome during the 13th century CE. As the coinage of this denomination occurred during a tumultuous period of the history of Rome, the official documentation from Mint was lost. For this reason, archaeometric investigations were necessary to have an overall knowledge of the Grosso Romanino. This work represents the first attempt of archaeometric study performed on this interesting denomination. The coins were characterized by a combination of non-destructive techniques, i.e., X-ray diffraction (XRD), Scanning Electron Microscopy (SEM-EDAX), micro-Raman spectroscopy and Voltammetry of Microparticles (VIMP), aiming to investigate the external surface and its microstructure and to explore the nature of the alloy and corrosion products. The results show an Ag- rich alloy with minor amount of copper (2.1–3.1 wt%), lead (0.7–3.2 wt%) and other elements. Moreover, the rare corrosion products on the surfaces indicate the presence of a random distributed patina composed by oxides, sulfides and chlorides

New insights on medieval Provisini silver coins by a combination of non-destructive and micro-invasive techniques

The aim of this research was to characterize ten Provisini, one of the most common silver coins in the Middle Age, dating back to the 13th century A.D. These coins are composed by Ag-Cu alloy and were coined in the Roman mint. A non-destructive, micro-destructive and multi-analytical approach was used, aiming to preserve the surfaces of the coins. The results of XRD and micro-Raman spectroscopy allow defining the alloy composition and the mineralogical nature of the alteration products (e.g. cuprite, tenorite, chlorargyrite, stromeyerite). X-ray maps provided information on major elements distribution on the surface. Finally, Electrochemical Impedance Spectroscopy (EIS) and Voltammetry of Immobilized Micro-Particles (VIMP) permitted to reconstruct the possible scheme of the multi-layering of the patina on the coins. Then, the conservation status was monitored