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

How future surgery will benefit from SARS-COV-2-related measures: a SPIGC survey conveying the perspective of Italian surgeons

COVID-19 negatively affected surgical activity, but the potential benefits resulting from adopted measures remain unclear. The aim of this study was to evaluate the change in surgical activity and potential benefit from COVID-19 measures in perspective of Italian surgeons on behalf of SPIGC. A nationwide online survey on surgical practice before, during, and after COVID-19 pandemic was conducted in March-April 2022 (NCT:05323851). Effects of COVID-19 hospital-related measures on surgical patients' management and personal professional development across surgical specialties were explored. Data on demographics, pre-operative/peri-operative/post-operative management, and professional development were collected. Outcomes were matched with the corresponding volume. Four hundred and seventy-three respondents were included in final analysis across 14 surgical specialties. Since SARS-CoV-2 pandemic, application of telematic consultations (4.1% vs. 21.6%; p < 0.0001) and diagnostic evaluations (16.4% vs. 42.2%; p < 0.0001) increased. Elective surgical activities significantly reduced and surgeons opted more frequently for conservative management with a possible indication for elective (26.3% vs. 35.7%; p < 0.0001) or urgent (20.4% vs. 38.5%; p < 0.0001) surgery. All new COVID-related measures are perceived to be maintained in the future. Surgeons' personal education online increased from 12.6% (pre-COVID) to 86.6% (post-COVID; p < 0.0001). Online educational activities are considered a beneficial effect from COVID pandemic (56.4%). COVID-19 had a great impact on surgical specialties, with significant reduction of operation volume. However, some forced changes turned out to be benefits. Isolation measures pushed the use of telemedicine and telemetric devices for outpatient practice and favored communication for educational purposes and surgeon-patient/family communication. From the Italian surgeons' perspective, COVID-related measures will continue to influence future surgical clinical practice

Archaeometric study on orichalcum coins

metalli, puri o in lega, hanno sempre giocato un ruolo fondamentale nella storia dell’uomo: la produzione regolare di oggetti in rame, ferro, bronzo e oricalco in antichità è infatti attestata dai numerosi ritrovamenti archeologici. In particolare, l’oricalco è una lega a base di rame e zinco, simile al moderno ottone, considerata dagli antichi un’invenzione degli dei. L’antica tecnica utilizzata per la produzione dell’oricalco era la cementazione, diffusa sia in Oriente che tra i popoli del bacino mediterraneo. Usato sin dal primo millennio a.C. in Asia Minore, l’oricalco fu introdotto come lega per la monetazione nel secondo secolo a.C. in Anatolia e solo successivamente nella penisola italica. Qui, Giulio Cesare per primo produsse monete in oricalco, come emissione sperimentale. Ottaviano Augusto, nel 23 a.C., promulgò una riforma monetaria in cui introdusse l’emissione di due nominali in oricalco. Successivamente, con la riforma monetaria di Nerone nel 63-64 d.C. furono introdotti altri tre nominali in oricalco. La tesi di dottorato di seguito presentata ha lo scopo di caratterizzare la lega di oricalco e valutarne il degrado, attraverso uno studio archeometrico di monete antiche emesse tra il primo secolo a.C. e la fine del primo secolo d.C. Allo scopo, sono state impiegate tecniche non distruttive, nano-invasive e distruttive. In particolare, metodologie superficiali (XRF, FTIR-ATR, VIMP) hanno permesso una prima caratterizzazione delle monete in oricalco e degli strati superficiali della patina. Con tecniche di microscopia (SEM-EDS, FIB-FESEM-EDS, HR-FESEM-EDS) è stato possibile studiare le microstrutture tipiche della lega oricalco, il pattern corrosivo delle patine e il loro sviluppo all’interno dei campioni. L’analisi quantitativa (attraverso l’EMPA) dei nuclei non corrosi e delle patine dei campioni ha consentito la caratterizzazione dell’oricalco e la descrizione del processo di dezincificazione. Attraverso l’approccio multianalitico è stato possibile identificare caratteri di autenticità dei campioni, differenziare le monete per emissione e riesaminare le precedenti teorie utilizzate per la datazione di campioni in oricalco. Per tanto, con questa tesi di dottorato si è voluto contribuire alle attuali conoscenze sulla coniazione romana in oricalco e si è tentato di approfondire i meccanismi dei processi corrosivi a carico delle leghe antiche.Metals, pure or in alloy, have always played a fundamental role in human history. Indeed, the regular roduction in antiquity of objects in copper, iron, bronze and orichalcum is attested by the numerous archaeological findings. In particular, the orichalcum is a copper-zinc based alloy, similar to the modern brass, considered by the ancient populations an invention of the gods. The cementation was the ancient technique used for the production of the orichalcum, common both in the East and in the Mediterranean basin. Used since the first millennium BC in Asia Minor, the orichalcum was introduced as alloy for coinage in Anatolia in the second century BC and only later was adopted in the Italian peninsula. Here, Julius Caesar first produced coins in orichalcum, as an experimental emission. Octavianus Augustus, in the 23 BC, promulgated a monetary reform, introducing two denominations in orichalcum. Subsequently, with the monetary reform of Nero in 63-64 AD three other denominations in orichalcum were introduced. The PhD thesis presented below aims to characterise the orichalcum alloy and to evaluate its degradation, through an archaeometric study of ancient coins issued between the first century BC and the end of the first century AD. For this purpose, non-destructive, nano-invasive and destructive techniques were used. In particular, surface methodologies (XRF, FTIR-ATR, VIMP) allowed a first characterization of the orichalcum coins and the superficial investigation of the patinas. With microscopy techniques (SEM-EDS, FIBFESEM-EDS, HR-FESEM-EDS) it was possible to study the typical microstructures of the orichalcum alloy, the corrosive pattern of the patinas and their development within the samples. The quantitative analysis (through the EMPA) of non-corroded cores and patinas of the samples allowed the characterization of the ancient orichalcum and the description of the dezincification process. Therefore, using a multi-analytical approach it was possible to define the authenticity of the samples, to grouping the coins by emission and to review the previous theories used for dating samples in orichalcum. This PhD thesis wanted to contribute to the current knowledge on Roman coinage in orichalcum and to attempt investigating the mechanisms of corrosive processes affecting ancient alloys

Multi-analytical approach for an archaeometric study on orichalcum coins

Orichalcum is a Cu-Zn based alloy known since the 1st millennium BC. The cementation was the ancient technique used for its production. The PhD project here presented aimed to characterise this alloy and to evaluate its degradation: for this purpose, non-destructive, nano-invasive and destructive techniques were used on a collection of ancient coins issued from the 1st century BC to the end of the 1st century AD. In particular, a multi-analytical approach was used: to investigate the patinas and their corrosive patterns, to study the alloy microstructures and their degradation, to describe the dezincification process and grouping the coins by emission. In addition, quantitative analyses allowed a complete characterization of this ancient alloy. The multi-analytical approach allowed to review the previous theories used for dating samples in orichalcum. This project wanted to contribute to the current knowledge on Roman coinage and to attempt to investigate the mechanisms of corrosive processes affecting ancient alloys

Polisaccaridi di microalghe per un restauro sostenibile

La forte richiesta di materiali, innovativi e sostenibili, per la conservazione/restauro di opere d’arte rappresenta un punto centrale nell’attuale ricerca nell’ambito dei beni culturali. In tale contesto, nasce il progetto NYMPHA, basato sull’idea di proporre una nuova soluzione per il restauro/protezione di superfici polimateriche attraverso l’utilizzo di una miscela di polisaccaridi estratti da cellule microalghe. A tal fine, è stato messo a punto e sviluppato un protocollo sostenibile per l’estrazione e purificazione dei polisaccaridi utilizzando l’alga unicellulare Chlamydomonas reinhardtii. Il prodotto così ottenuto è stato caratterizzato dal punto di vista chimico (FT-IR, GC-MS, Raman e saggi quantitativi quali il test del fenolo/acido solforico e test del cloruro di Bario) e biologico (test antiossidanti e analisi della resistenza all’attacco biologico). La composizione del contenuto in polisaccaridi è stata invece determinata tramite derivatizzazione ed analisi GC-MS. Da queste prime analisi è stato possibile comparare la composizione dei polisaccaridi e la concentrazione totale in zuccheri presente all’interno della miscela polisaccaridica estratta da Chlamydomonas reinhardtii rispetto ad altri prodotti commerciali largamente utilizzati nel settore del restauro come: Funori e JunFunori. Sono stati eseguiti i primi esperimenti di applicazione e valutazione dell’efficacia degli estratti polisaccaridici su substrati organici ed inorganici. In particolare, per valutare l’efficacia dell’estratto su materiale organico, sono state eseguite prove di stesura su materiale cartaceo (carta Whatman), selezionata per le sue caratteristiche di purezza e omogeneità. L’estratto polisaccaridico a diverse concentrazioni è stato applicato sia sulla superficie tal quale che su pellicola pittorica, al fine di testarne le proprietà colorimetriche e valutarne le capacità coesive. Per quanto concerne invece il materiale inorganico, è stato selezionato il marmo bianco, essendo un litotipo metamorfico di estremo interesse e di largo uso nel campo artistico sia antico che contemporaneo. Le proprietà fisiche dei campioni sono state testate sia prima che dopo l’applicazione dei polisaccaridi per valutare l’efficacia del trattamento e il rispetto delle caratteristiche estetiche delle superfici originali. Ringraziamenti Questo progetto è stato supportato da fondi regionali POR FESR Progetti Gruppi di Ricerca Lazio Innova NYMPHA Project A0375-2020-36489

A multi-analytical approach for the characterization of ancient Roman coins in orichalcum

A selected number of Roman orichalcum coins, from private collections, have been studied. Numismatic analysis indicates that (Crawford, 1974; Sutherland, 1984) they are asses, sestertius and dupondium, minted by Julius Caesar, Augustus and Claudius. The aim of this study was to disclose the chemical composition of the orichalcum alloy, the nature of the patina and corrosion products; orichalcum is an ancient copper based alloy with a variable percentage of zinc (Craddock, 1978). With this aim a multi-analytical approach was involved, i.e. X-ray fluorescence (XRF), scanning electron microscope (SEM-EDS), electron micro probe analyser (EMPA). In particular, XRF analysis was performed on different spots of coins’ surfaces to have information about the chemical composition of the external layers. SEM-EDS analysis allowed to investigate alloy’s microtexture (e.g. segregation micro-domains) and to obtain morphological information. In addition, X-ray maps, acquired across section of coins, give information about elemental distribution inside the alloy; whereas EMPA analysis permits a quantitative chemical composition of major, minor and trace elements composing this ancient alloy. All these techniques confirmed that copper and zinc are the main components of the coins. Other metals, i.e. Fe, Pb, Sn, Co, Ni, As, Sn, Sb and Bi, were also found in the alloy. These elements can provide information about sourcing raw materials sites. Si, S, Cl, K and Ca were found on the surfaces, being contaminant from the soil. Quantitative analysis with microprobe permitted to evaluate the different percentage of Cu and Zn in all the samples. The use of invasive technique (EMPA) was necessary to quantify the abundances of each elements composing the original alloy, thus eliminating soil contaminants and alteration product of the layers developed through time on surfaces. These results, could contribute to fill the lack of knowledge about the orichalcum alloy

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

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

HR-FESEM-EDS study of corrosion pattern in Cu-Zn based alloy

Corrosion phenomena are processes that can create several problems in archaeological materials. Nanoscale studies of the corrosion mechanism of ancient alloys and the distribution of the damage both on the patina and in the core of metal object represent one of the major challenges that must be implemented to protect archaeological metal findings. In this research, the corrosion pattern of Cu-Zn-based Roman coins was investigated from micro to nanoscale using SEM-EDS and HR-FESEM-EDS (high resolution field emission scanning electron microscope). Both the patinas and the uncorroded cores of the samples were analysed, exploring the nature of the alloy, structures and complex patterns of the external layers. The high magnification imaging highlighted signs of selective corrosion, depending of the Cu-Zn ratio, as well as marks of cold-working of coins. The X-ray maps showed the distribution of the elements that compose the samples, helping to understand the evolution of the dezincification processes. Nanoscale investigation highlighted a heterogeneous composition within the strain lines structures, induced by selective de-alloying. The corroded micro and nanodomains were explored in depth to study the structural constrains which control altered areas inside orichalcum coins. We evaluated also all the parameters that induced corrosion and dealloying. The results suggested that mechanical stressed-areas could be the trigger zone of corrosion processes. Moreover, this research aimed to fill the scientific gap about this ancient alloy and to improve the knowledge on the mechanisms involved in orichalcum degradation