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PIETRO BARALDI

PROFESSORE FUORI RUOLO Esterno
Dipartimento di Scienze Chimiche e Geologiche sede ex-Chimica

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Pubblicazioni

2019 - Archaeobotanical evidence of funerary rituals in roman necropolis of Mutina (Northern Italy): a multidisciplinary approach [Abstract in Atti di Convegno]
Riso, F. M.; Pellegrini, S.; Baraldi, P.; Bosi, G.
abstract

An interdisciplinary method involving different disciplines of archeology was carried out on the necropolis of Mutina, in order to have a complete view of the funerary rituals. Cremation graves coming from Mutina necropolis have been analysed (1st – 2th century AD). In addition to traditional methods, new technologies helped to study offerings presence. For what concerns Via Cesana necropolis, a computed tomography has been performed on 8 urns thanks to TEC-EUROLAB (Modena), in order to carry out a systematic microexcavation. Then soil has been sieved and then archaeobotanical (seeds/fruit) and archaeological findings were collected. Seeds/fruits found mostly belong to cultivated plants or, anyway, plants that can be used as food, as Cereals, Pulses and Fruit plants, even if the analysis are still an ongoing research. These remains of meals left on the graves and of the objects involved in the ceremonies, are evidence resulting from the attendance of the funeral space. It has been also decided to analyse the dust inside the balsamari found among the grave goods of the urns. Raman and XRF analysis have been carried out in order to verify the presence of cosme- tic dusts: hematite, cinnambar, malachite marks have been found. In tomb 15 a grape flower has been found and it could be a residue of the preparation of oenanthe or it could also be the evidence of omphacio, prepared with unripe grapes.

2019 - Archeometria della pittura parietale a Reggio Emilia: gli intonaci dipinti dello scavo di Palazzo Mogardini [Poster]
Capurso, Annalisa; Baraldi, Pietro; Zannini, Paolo; Baraldi, Cecilia; Lugli, Stefano; Tirelli, Giulia; Rossi, Andrea
abstract

A Reggio Emilia, durante lo scavo di un cortile di Palazzo Mongardini nel 2009, è stato rinvenuto un gruppo di circa 500 frammenti di intonaco dipinto di epoca romana sui quali, dal 2017, è stato intrapreso uno studio da parte di una équipe multidisciplinare. lacerti pittorici, per quanto in giacitura secondaria, appaiono di grande interesse sia in relazione al luogo di ritrovamento, sia per la tecnica di esecuzione. Le indagini XRF, Raman e IR-ATR hanno mostrato che la tavolozza dei pigmenti impiegata è ampia e fa uso di pigmenti stesi con latte di calce a formare uno strato di colore ad affresco. Ma anche la tecnica a mezzo fresco risulta applicata, come nel caso di ripresa di colori dopo la carbonatazione per coprire una stesura o per avere determinati effetti coloristici.

2019 - DA PLACENTIA AD ARIMINUM: TECNICHE E MATERIALI DELLA PITTURA MURALE ROMANA NELLE DOMUS DELLA OCTAVA REGIO Pitture frammentarie di epoca romana da Roma e dal Lazio: nuove ricerche [Articolo su rivista]
Baraldi, Pietro; Baraldi, Cecilia; Ferrari, Giorgia; Tassi, Lorenzo; Zannini, Paolo
abstract

The analyses of polychrome plaster from the Octava Regio of ancient Roman Italy have enabled the identification of the palette of pigments used, the pictorial techniques and the different ways of decorating painted surfaces. Despite the short distances between the towns founded along the Via Aemilia, the paintings exhibit differences relating to these important domus: the decorative motifs, pigments, intonachinos and plaster all vary. Some of the more unusual pigments may come from geological features found in the territory or from the nearby mountains.

2018 - Images and colors from the tombs of Paestum: a multidisciplinary study of the pigments in the flora and fauna iconography [Articolo su rivista]
Ferrari, G.; Bosi, G.; Ansaloni, I.; Sala, L.; Pederzoli, A.; Baraldi, P.; Mussi, L.; Nannini, Matteo; Zannini, P.; Bandini Mazzanti, M.
abstract

This work presents the results of a multidisciplinary study on iconographic elements and painting technique of painted tombstones from Paestum (Italy), dated from the end of the V century to the end of the IV century BC. The focus was a botanical and zoological analysis of the flora and fauna present in 33 tombs, from both the iconographic and chemical point of view. Pigments (red, yellow, orange, pink, blue, green, black, grey and brown) have been studied by XRF and Raman techniques. The animal and vegetal elements (the formers gen- erally represented with more accuracy and details) in Paestum funerary art are not simply decorations, but they have numerous meanings, in both decorative systems and figured scenes, related to the ideal image of the dead (the social status of the dead, victory, heroic transfigurations, the voyage to the afterlife, etc.). Their high fre- quency confirms their important symbolism in funeral rituals. The artists' palette is quite limited and coherent with the contemporary funerary art in the Mediterranean basin. The use of Egyptian blue and of a red ochre enriched in manganese is interesting and deeper studies on these materials could help to better clarify the commercial background of Paestum during the 4th century BC.

2018 - Indagine sui recipienti con pigmenti da domus pompeiane [Relazione in Atti di Convegno]
Baraldi, P.; Baraldi, C.; Trojsi, G.
abstract

Negli ultimi 250 anni di scavi eseguiti nei siti di Pompei ed Ercolano sono stati rinvenuti numerosi pigmenti che sono serviti a dipingere e adornare le numerose ville alle falde del Vesuvio. Tali colori sono arrivati a noi, spesso, accuratamente conservati in ciotole, vasi, balsamari e altri piccoli contenitori fittili, in vetro e bronzo trovati all'interno di botteghe e abitazioni. Secondo il"Giornale degli Scavi di Pompei" della Soprintendenza Archeologica di Pompei, il primo scavo nella Regio l, lnsula 9 (l 9, 9) ebbe luogo nel 1952. Vicino agli scheletri di quattro individui, vennero trovate circa 150 ciotole globulari, fritilla e olle. La presenza di materiale all'interno costituisce un'opportunità per la ricostruzione della storia e delle tecniche pittoriche di Pompei e del mondo romano. Sui contenuti sono stati applicati metodi molecolari di analisi, quali spettroscopia FT-lR e microscopia Raman, per l'identificazione della composizione. I risultati ottenuti consentono alcune considerazioni. Molti componenti quali quarzo, calcite, feldspati, diopside e pirite sono riferibili all'intonaco o ai prodotti dell'eruzione. L'aragonite presente massivamente puo' derivare da minerali bianchi, ma più probabilmente può essere dovuta alla macinazione di valve di molluschi. Ciò è importante per la comprensione dei decori bianchi su fondo colorato dei dipinti murali romani. ll pigmento blu è sempre a base di blu egiziano, mentre il verde può essere ottenuto mescolando un giallo e un blu; più frequentemente il verde è accertato come miscela di terra verde e blu egiziano. Malachite e azzurrile si ritrovano come prodotti di degrado di leghe metalliche a base di rame. Altri rari casi sono la cuprite, derivante da alterazione del rame e il litargirio, dall'alterazione di cerussite o piombo. La cerussite, identificata in alcuni contenitori, non è un pigmento per pitture murali: è noto da Plinio e da altri autori il suo uso come fondotinta, e questo può essere una prova della preparazione in I 9, 9 anche di contenitori per cosmetici.

2018 - Le pitture parietali delle ville di Stabia: materiali e degrado [Poster]
Baraldi, P.; Zannini, P.; Baraldi, C.; Tassi, L.; Rossi, A.; Troisi, G.
abstract

A partire dal 2009 con una serie di missioni in area stabiana, dopo il rilascio dei permessi da parte della Soprintendenza archeologica di Napoli e Pompei, sono state attuate indagini sulle pitture murali delle ville imperiali (Villa Arianna e Villa San lvlarco) per avere una descrizione dettagliata delle tecniche e dei materiali impiegati nelle pitture murali dei vari ambienti. Sono stati anche programmati controlli sul degrado dei materialj pittorici. Di concerto con archeologi e restauratori presenti sul sito, consapevoli delle operazioni di restauro attuate nel passato e tenendo conto dell'effetto degli eventi drammatici del 79 d.C., si è cercato di capire la situazione conservativa delle pitture per fornire indicazioni sulle operazioni di restauro. Nel corso delle missioni si sono osservate mediante microscopio digitale le superfici pittoriche divari ambienti e si sono effettuati dei microprelievi in posizioni marginali e rappresentative delle cromie presenti. Successivamente i campioni sono stati sottoposti ad analisi presso i laboratori universitari, ad analisi con varie tecniche analitiche e spettroscopìche di tipo atomico e molecolare, come la fluorescenza di raggi X (XRF). la spettroscopia FT-lR in trasmissione e in riflessione, la microscopia Raman con laser rosso e verde. Una considerevole massa di dati ottenuta con i vari tipi di analisi permette di tracciare una sinossi delle tavolozze pittoriche degli artisti al lavoro, dello stato di conservazione dello strato pittorico, del degrado di alcuni dei pigmenti utilizzati in antico, e della presenza di materiali impiegati per il restauro nel corso dei decenni. Sono state evidenziate opere di mani differenti, in base all'impiego di tonalità realizzate con miscele di pigmenti e con sovrapposizione di materiali diversì. ln alcune aree il cinabro risulta virato in nero con produzione di solfocloruri di mercurio. Le decorazioni a mezzo fresco risultano spesso alterate e soggette a caduta di parti dello strato pittorico.

2017 - Application of micro-Raman spectroscopy for conservation projects in art and archaeology with a case study on Cappadocia rock-hewn wall paintings [Articolo su rivista]
Baraldi, P.; Baraldi, C.; Pelosi, C.
abstract

This paper aims at reporting an overview of the principles and applications of micro-Raman spectroscopy in cultural heritage. Micro-Raman was used for characterizing painting pigments, inorganic binders, degradation materials in artworks with different goals: to know the materials and so the execution technique, to investigate the state of preservation, to establish the authenticity of the artefacts. The micro-Raman analyses were often performed on the occasion of conservative projects and they were able to supply valid and useful information to the conservators during their work. As case study, the project on the investigation of rock-hewn wall paintings in Cappadocia (Turkey) will be shortly presented as exemplificative of application of Raman techniques for the knowledge of the constituent materials, for supporting the conservation work and for detecting degradation products. Analysis were performed in the Interdepartmental instrument Center of Modena and Reggio Emilia University by a bench top system equipped with a microscope allowing for studying in non-destructive way different kinds of samples: powders, cross and thin sections, pre-treated samples.

2015 - A Raman investigation of ancient Colliria [Abstract in Atti di Convegno]
Gamberini, Maria Cristina; Baraldi, Pietro; Deviese, Tibaut; Baraldi, Cecilia; Tinti, Anna
abstract

In January 1884, in Atestino territory (PD-Este, northern of Italy), was discovered in Morlungo district, where is present the southern necropolis aged in pre-Roman and Roman period (Ateste), a tomb dated to the second half of the I sec d.C (Tomb civic IX) whose furnishings exhibition being a doctor-surgeon-apothecary (Simonetta Bonomi - "Medici in Este romana. 3. La tomba del medico” Aquileia nostra”, 55, 1984, p. 78-108.). Among the various finds is present a bronze box (capsula), several medicinal preparations in the solid state form were also found inside. They were collyria (from the greek = κολλύριον small pills solid elongated), not necessarily used in ophthalmologic practice (Celse V 28 G; Hippocrates, Mul. I 51). In bibliography, rare are the articles published regarding the discovery of these findings, but even more rare are articles on collyria chemical analysis. In this study, 17 collyria / fragments of collyria exposed in Este National Museum and other six fragments from the tomb of a physician and stored in warehouses, using non-invasive and non-destructive techniques were analyzed in-situ. Raman microscopy, FT-IR spectroscopy and X-ray Fluorescence techniques were chosen for the analysis using portable equipments. In this study we report the preliminary composition data of these remains. The analyzes performed, chemical charaterized several components already identified to the specific literature on these findings: calcite, indrocerussite, litharge, cuprite, tenorite, azzurite, realgar, pararealgar, orpiment. Moreover in this work some components, not analyzed in collyria forms yet, were also identified: pyrite and alumina. In the next future could be interesting study the remains with micro-invasive techniques, this in order to better investigate the organic component present and complete the knowledge of these rare and interesting archaeological finds, on which many questions still remain open and unanswered.

2015 - An approach to the identification of ambers from different archaeological sites (P1) [Abstract in Atti di Convegno]
Gamberini, Maria Cristina; Baraldi, Pietro; Deviese, Thibaut; Baraldi, Cecilia; Tinti, Anna; Pacciarelli, Marco
abstract

Chemical studies on resinous materials in archaeological remains are generally aimed at identifying the origin of the materials present, at studying the production and manufacturing techniques, and at improving techniques for their conservation and restoration. This is particularly true for ambers remains. This paper presents some significant results for a systematic characterisation of the chemical composition of ambers of different provenance. The study has been carried out by using spectroscopic techniques, Raman and FT-IR with the aim of creating or extend FT-IR, Raman, FT-Raman libraries of geological and archaeological ambers. The data could be used as references in provenance studies of archaeological amber finds. Based on this knowledge, archaeological resinous materials, recovered in a various sites, dating back from the ninth century BC to the second century AD, have been analysed and the relevant results discussed. Comparisons of analytical detailed results enable the recent and ancient history of the materials to be traced. It is shown that provenance can be ascertained, in addition to the classical Beck’s method of FT-IR spectra (based on the special shape of the infrared spectrum in the 1500- 1000 cm-1 region), also by using Raman spectra and XRF data. The alteration of Museum preserved samples are taken into consideration for a description of the rapid changes of the spectra recorded.

2015 - An approach to the identification of ambers from different archaeological sites (Part 2) [Abstract in Atti di Convegno]
Gamberini, Maria Cristina; Baraldi, Pietro; Deviese, Thibaut; Baraldi, Cecilia; Tinti, Anna; Pacciarelli, Marco
abstract

Chemical studies on resinous materials in archaeological remains are generally aimed at identifying the origin of the materials present, at studying the production and manufacturing techniques, and at improving techniques for their conservation and restoration. This is particularly true for ambers remains. This paper presents some significant results for a systematic characterisation of the chemical composition of ambers of different provenance. The study has been carried out by using spectroscopic techniques, Raman and FT-IR with the aim ofcreating or extend FT-IR, Raman, FT-Raman libraries of geological and archaeological ambers. The data could be used as references in provenance studies of archaeological amber finds. Based on this knowledge, archaeological resinous materials, recoveredin a various sites, dating back from the VI century BC to the second centuryAD, have been analysed and the relevant results discussed. Comparisons of analytical detailed results enable the recent and ancient history of the materials to be traced. It is shown that provenance can be ascertained, in addition to the classical Beck’s method of FT-IR spectra (based on the special shape of the infrared spectrum in the 1500- 1000 cm-1 region), also by using Raman spectra and XRF data. The alteration of Museum preserved samples are taken into consideration for a description of the rapid changes of the spectra recorded.

2015 - Indagine multidisciplinare sul codice “It. 1005 =α.R.9.24 – Raccolta di animali per lo più volatili miniati” della Biblioteca Estense Universitaria di Modena [Articolo su rivista]
Mareggini, Graziano; Ansaloni, Ivano; Baraldi, Pietro; Sala, Luigi
abstract

This paper presents the results of multidisciplinary research carried out on the code “It.1005 = α.R.9.24 – Collection of illuminated animals mostly birds”, kept in the Estense Library of Modena (Italy). The study addressed both the codicological and the scientific aspects, with the identification of the animal species represented and the analysis of the pigments and materials used.

2015 - Pigments and cosmetics from Regio I, Insula 9 (I,9,9): archaeometrical analyses [Relazione in Atti di Convegno]
Baraldi, Pietro; Baraldi, Cecilia; Trojsi, Giorgio
abstract

After a review of the color containers found in Pompeii, a group of them coming from the Officina Pigmentaria is considered. A large amount of data concerning the contents of bowls of different kinds found in a Pompeiian house is presented. Many materials are encountered that can be classified in many ways. Some distinctions could be based on the nature of the possible contents at the time of the Vesuvius eruption in 79 A. D. A statistical evaluation of the frequencies of attestation of different materials suggests some hypotheses. A possible interpretation of the house as being a shop for preparing pigments, cosmetics and drugs is advanced.

2014 - A study of some illuminated Armenian manuscripts [Abstract in Atti di Convegno]
Keheyan, Yeghis; Baraldi, Pietro; Zannini, Paolo; Eliazan, Gayane; Baraldi, Cecilia; Gamberini, Maria Cristina; Nunziante, Stella
abstract

Due to its early Christianization, Armenia has preserved a huge patrimony of religious figures in paintings, statues, icons and illuminated codices. Most of the latter are still conserved in Matenadaran Library in Yerevan and their chronology is widely represented from the Middle Ages to XIX century. Armenian manuscripts embrace also various humanities, such as history, philosophy, law, medicine and mathematics. A rich historiographic literature is also present. Therefore it was attractive to carry out an attempt to discover materials and techniques used in the past to prepare the manuscripts and to assemble the codices. Inks and gilding were also considered. Specific materials of Armenian culture will be emphasized. The samples were taken by some of us at the Matenadaran Library of Yerevan (Armenia) and some additional materials, such as Armenian bole and cochineal powder, were found in Yerevan too. The samples were taken with a lancet on deteriorated portions of some papers and parchments pertaining to Armenian codices. Only small fragments were used, since the spectroscopic techniques used need amount down to some micrograms. This is due to their high spatial resolution, enabling also the overlapping layers of pigments and preparation to be studied and their molecular identity to be ascertained in a non-destructive non –invasive way: the same samples could be subjected to other analyses with other techniques. The use of so small samples enabled the use of high performance instrumentation in the Centre of Great Instruments in Modena (CIGS) and to carry out additional experiments with silver nano-particles for Sers technique (surface enhanced Raman spectroscopy). Fourier-Transform infrared (FTIR) spectra were recorded using an Alpha FT-IR spectrometer (Bruker) equipped with the Diffuse Reflection Infrared Fourier Transform ( DRIFT) module in the spectral range 7500 – 375 cm-1 at a resolution of 2 cm-1 cumulating at least 200 scans. The use of SEM-EDX technique was important for characterization of papers and inks. Py/GS/MS was fundamental for organic binding media characterization. The methods of study were the application of atomic (XRF X-ray fluorescence spectroscopy), molecular (FT-IR and microRaman), SEM-EDX and pyrolisis GS/MS spectroscopic techniques to the samples in such a way to obtain the information useful for the understanding of the materials and art techniques applied. Particularly, the analysis of the different inks used in different times and the decoration with gilding on bole with a proper binder was taken into consideration. Experimental Results. Many materials were seen to be used through centuries in Armenian illumination. As already pointed out by Orna and co-workers [1, 2] many materials were identified and the execution techniques were clarified. According to recent investigation [3] other results on new materials and specific products coming from the territory have appeared based on Raman microscopy. A rich polychromy was often present and rare materials are shown to have been employed, such as the green antlerite, a basic copper sulfate mineral present in Caucasus and South of Iran. Lazurite, vermilion, azurite, orpiment, white lead, red lead, indigo, litharge, massicot, carbon were identified. Gilding was applied on an assisa. The Armenian bole is shown to be composed of white Kaolinite and Hematite. Forthcoming information is the application of Raman Sers technique for the identification of the materials and techniques used in Armenian illumination through times. The Armenian Cochineal (from Porphyrophora hamelii Brandt) is composed of carminic acid, that is highly fluorescent in Raman microscopy, unless Sers is used on a sample. With the application of simple atomic and molecular spectroscopy techniques available in many laboratories it was shown to be possible to obtain fundamental information on the specificity of Armenian illuminati

2014 - ARMENIAN ILLUMINATED MANUSCRIPTS, A COLOURFUL TESTIMONY OF RELIGIOUS ART EXAMINED BY MOLECULAR SPECTROSCOPY TECHNIQUES [Relazione in Atti di Convegno]
Baraldi, Pietro; Yeghis, Keheyan; Gayane, Eliazan; Andranik, Mkrtichian; Stella, Nunziante; Baraldi, Cecilia
abstract

Proceeding in the analysis of the painting materials and techniques of Armenian illuminated manuscripts we refer about a XIV century manuscript with colourful images that were under restoration. Some microsamples were analyzed with microRaman spectroscopy and showed that traditional pigments were used, but some products and mixtures are typical of Armenia illumination, such as vergaut a mixture of indigo and orpiment.

2014 - Archaeometric analysis of painted tombstones (IV century BC) from Paestum (Italy) [Poster]
Ferrari, Giorgia; Baraldi, Pietro; Cipriani, Marina; Nannini, Matteo; Zannini, Paolo
abstract

50 graves, painted by fresco technique, have been analyzed by micro-Raman Spectroscopy and X-Ray Fluorescence in order to identify the artists’ palettes and attempt to differentiate various workshops. Before sampling, points of interest were selected by a preliminary in situ XRF analysis. Then, samples were collected and analyzed in laboratory by micro-Raman Spectroscopy. We sampled from Green, Blue, Red, Yellow and Black areas, from every grave, and created a database where we put together analytical and historical data. Red and Yellow are obtained by Hematite and Goethite, respectively; Blue is always Egyptian Blue; Black contains Carbon or Magnetite, or a mix of them. Interesting data came from Green areas. We found 2 mixtures: Egyptian Blue and Yellow Ochre, or Yellow Ochre and Carbon. This peculiarity could be useful in the future for the discrimination of the different workshops.

2014 - Calibration and use of the heating microscope for indirect evaluation of the viscosity and meltability of archeological glasses [Articolo su rivista]
Montanari, F.; Miselli, P.; Leonelli, C.; Boschetti, C.; Henderson, J.; Baraldi, P.
abstract

The heating microscope is a widely used instrument in many industrial applications, especially in the ceramic field, to obtain information on the sintering behavior and, indirectly, on the viscosity curve of glass. It is therefore important for the study of glass technology. Usually, heating microscopes work by taking images of the sample outline, during a preset thermal cycle, which define five characteristic temperatures corresponding to particular shapes of the specimen. The first two characteristic temperatures can also be extracted from the sintering curves provided by the instrument. In agreement with three published models, the five temperatures are associated with five viscosity values, producing the two best-fitting plots (Log10(η) - T). In this work, the heating microscope was calibrated using a glass with known properties, to determine the most reliable model, so that it can be applied successfully in the field of archeological science. The selected methodologies were used to analyze two opacified Roman mosaic glass tesserae excavated in Pompeii, previously characterized chemically. A Pompeiian transparent glass, sampled from a large block of base (raw) glass, and its experimental reproduction were also studied. Finally, the relationship between the opacifiers and the thermal behavior of base glass was investigated. © 2013 The American Ceramic Society and Wiley Periodicals, Inc.

2013 - Application of heating microscopy on sintering and melting behaviour of natural sands of archaeological interest [Articolo su rivista]
Montanari, F.; Boschetti, C.; Miselli, P.; Hanuskova, M.; Baraldi, P.; Leonelli, C.
abstract

In antiquity, beach sand was one of the main raw materials for glass-making and for the production of other vitreous materials, like Egyptian blue and faience. During the 1st century AD, glass and pigments manufacturing industry was active along the Gulf of Naples, Italy, where we sampled four littoral sands. Samples were analyzed with different techniques: chemical analysis was performed by means of X-Ray Fluorescence (XRF) and mineralogical analyses with X-Ray Powder Diffraction (XRPD) and Raman Spectroscopy. The complete sintering to melting thermal behaviour of the four sands was studied by heating microscopy or hot-stage microscope (HSM) equipped with an high resolution camera capable to collect sample profile during heating. The effect of the grain size on the sintering curves, which were automatically elaborated by specimen profile transformation, was also investigated. Finally, some deductions about the granulometry effect and the presence of alkaline and alkaline-earth oxides on sintering and melting behaviour were drawn. All the four sands were found suitable for highly sintered manufacts rather than glasses, to reach complete amorphous materials the addition of fluxes was necessary.

2013 - Electropolymerization of ortho-phenylenediamine. Structural characterisation of the resulting polymer film and its interfacial capacitive behaviour [Articolo su rivista]
Vanossi, Davide; Pigani, Laura; Seeber, Renato; Paolo, Ferrarini; Baraldi, Pietro; Fontanesi, Claudio
abstract

The physico-chemical characteristics of thin poly-(orth o-phenylenediamine) (PPD) films, obtained by electrochemical oxidation of the relevant monomer, are investigated using electrochemical, morpholog-ical and spectroscopic techniques. In particular, cyclic voltammetry and electroche mical impedance spec-troscopy (EIS) techniques are used to collect information concerning the redox, conductivity and double layer capacitance properties of the PPD film. AFM imaging and Raman spectroscopy results are exploited to characterize the film structure. In this respect, Raman spectra of two possible PPD oligomers are cal-culated at the B3LYP/6-311G level of the theory.

2013 - Phoenicians preferred red pigments: micro-Raman investigation on some cosmetics found in Sicily archaeological sites [Abstract in Atti di Convegno]
Baraldi, Cecilia; Giada, Freguglia; Elsa Van, Elslande; Pamela, Toti; Baraldi, Pietro; Gamberini, Maria Cristina; Claudia, Pelosi
abstract

This research was undertaken in the aim of identifying and getting deeper knoowledge into materials and pigments used in cosmestics concerning the contest of the phoenician settlements in Sicilian territory. In fact, about the typologies of cosmetics in use among the Phoenicians, little is known. On this subject, generally references come from bibliographic latin sources: in antiquity, women preferred to paint white their face, red lips and cheeks, yellowish eyes and black to sorround their look (Pliny the Elder, Naturalis Historia; Ovidius, De medicamine faciei feminae). An interesting aspect of this research is that just one paper is known on Punic cosmetics.[1] In the Museo Archeologico Regionale “Antonino Salinas” (Palermo, Sicily) an important collection of unguentaries coming from the town of Selinunte is preserved. Some of them, finely crafted, come from the sanctuary of Demetra Malophoros, some unguentaries come from the acropolis and some more from the necropolis (dating from the 6th to the 5th century b. C). The sacred area, excavated by Cavallari (1818) and Salinas (1903-1905), have provided a great amount of archaeological materials. In the area where once the acropolis rose, the remains show a mixed village, Phoenician and Greek. In this study, the findings from Salinas were considered, as well as some others from the Museum Conte Agostino Pepoli (Trapani), from the Museum Baglio Anselmi (Marsala) and from the museum of Mozia. The number of glass and fictile unguentaries, pyxis and alabastra examined were large: 142 items from Salinas, 210 from Mozia, 14 from Pepoli and 117 from Baglio Anselmi. This research has completed the one carried out on 210 samples from the Museum of Whitaker Foundation from Mozia, a merely phoenician –punic settlement.[2,3] The samples were analyzed by spectroscopic techniques. The IR spectra were acquired with a spectrophotometer VERTEX 70 (Bruker) FT-IR, equipped with a detector deuterium triglycine sulphate (DTGS). The setting parameters were: resolution 4 cm-1, spectral range 4000-600 cm-1, number of scans 32. ATR spectra were recorded using an Elmer Golden-Gate accessory. The micro-Raman spectrometer used in this case was a Labram Model from the Jobin Yvon-Horiba with a spatial resolution of 1 µm and with quick detection ability as a result of the CCD detector 1024x256 pixels cooled to -70°C by the Peltier effect. The spectral resolution was 1 cm-1. The exciting wavelength was the 632.8 nm red line of a He-Ne laser. Generally the samples were presented as inorganic powders of different colors: white, black, blue and red. Though the samples came from different museums, they were considered togheter, since they belonged all to the Phoenician culture and coming from Trapani archaeological sites. The white samples were of two types. The first one was mainly composed of gypsum and anhydrite mixtures (e.g. Inv No 1680, 1663, 1753); the other type (e.g. pyxes Inv N° 1393, 1451) was composed of fully carbonated cerussite, gypsum and litharge. The second kind of cosmetic corresponded to the most famous Greek cosmetic, called psymition, used by women to white the skin. The first type suggested that, for the same use, alternative materials, cheaper and most readily available, could be employed in the past. The black powders, usually used to outline the eyes, were mostly given by carbon obtained from vegetable combustion (e.g. Inv. N° 1566, 2314, 4313) or, sometimes, from bone combustion (animal charcoal) as for the samples Inv. N° 3140, 1761. A single blue powder (Inv N° 42259) was consisted by the famous Egyptian blue (CaCuSi4O10). The love for the red color by Phoenician is evident from the great number of powders of this color, probably used to give color to the cheeks or lips. A wide variety of red minerals was found. In many cases the presence of hematite (e.g. Inv N° 2309, 2689, 4269) was detected. A large number of pink and r

2012 - A 15th Century Polychromatic Wooden Statue by Francesco of Valdambrino. The scientific investigation and preservation challenges. [Relazione in Atti di Convegno]
Baraldi, Pietro; V., Cuozzo; A., LO MONACO; C., Pelosi
abstract

The focus of this work is a polychrome wooden statue attributed to Francesco, a 15th century Italian sculptor, from Valdambrino. In this study, original and additional materials were examined in order to provide a deeper understanding of the technique utilised and a greater awareness of how well preserved the object is, as well as an analysis of previous preservation and conservation interventions. The component materials of the statue were analysed by: micro-Raman spectroscopy in order to identify the pigments, Fourier Transform Infrared spectrometry (FTIR) to study the binders and the restoration materials, optical microscopy to examine the technique utilised, scanning electron microscopy (SEM) to identify the type of wood used. Temperature (T) and relative humidity (RH) near the statue were recorded for a year using a digital data logger with the aim of evaluating the suitability of the environment for the preservation of the artefact.

2012 - ANALYSES OF ROMAN WALL PAINTINGS , BASILICA OF SANTA MARIA MAGGIORE, TRENTO. [Relazione in Atti di Convegno]
Minghelli, Silvia; Baraldi, Pietro; Zannini, Paolo; M. T., Guaitoli
abstract

Questo studio mira alla caratterizzazione chimico-fisica dei numerosi frammenti di pittura romana rinvenuti durante lo scavo archeologico della Basilica di Santa Maria Maggiore a Trento.L’obiettivo è quello di confermare la destinazione d’uso delle strutture di epoca romana riportate in luce, identificate dagli archeologi con i resti di un impianto termale pubblico risalente al I secolo d.C., attraverso l’identificazione dei pigmenti e delle tecniche pittoriche usate per la loro decorazione. Le principali tecniche analitiche utilizzate per determinare la composizione dei campioni sono state la spettrometria infrarossa a trasformata di Fourier (FT-IR), la microscopia Raman e la fluorescenza a raggi X (XRF).

2012 - Ampicillina: studio vibrazionale mediante FT-IR, micro-Raman e SERS di forme solvate e polimorfe [Abstract in Atti di Convegno]
Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; A., Tinti; Baraldi, Pietro
abstract

Dalla letteratura è noto che numerosi principi attivi farmaceutici (APIs) tendono a cristallizzare in differenti impaccamenti cristallini (polimorfi) oppure comprendendo molecole di solvente come parte della struttura cristallina (pseudopolimorfi). All’interno di una formulazione farmaceutica, l’identità o la possibilità di conversione del’API potrebbe alterare le caratteristiche e l’efficacia della forma farmaceutica, in particolare portando a differente biodisponibilità.L’ampicillina o α-aminobenzylpenicillina o 6-[D (-)-α aminophenylacetamido] penicillanic acid esiste come forma anidra (attestate 2 forme polimorfe) ed in altre forme idrate, in particolare triidrata e monoidrata. All’interno delle diverse formulazioni farmaceutiche in commercio, come polveri per uso iniettabile o orale, oppure come compresse o capsule, l’ampicillina è presente come forma triidrata, talora come anidra o come sale sodico.Dalla letteratura è noto che numerosi principi attivi farmaceutici (APIs) tendono a cristallizzare in differenti impaccamenti cristallini (polimorfi) oppure comprendendo molecole di solvente come parte della struttura cristallina (pseudopolimorfi). All’interno di una formulazione farmaceutica, l’identità o la possibilità di conversione del’API potrebbe alterare le caratteristiche e l’efficacia della forma farmaceutica, in particolare portando a differente biodisponibilità.L’ampicillina o α-aminobenzylpenicillina o 6-[D (-)-α aminophenylacetamido] penicillanic acid esiste come forma anidra (attestate 2 forme polimorfe) ed in altre forme idrate, in particolare triidrata e monoidrata [1-3]. All’interno delle diverse formulazioni farmaceutiche in commercio, come polveri per uso iniettabile o orale, oppure come compresse o capsule, l’ampicillina è presente come forma triidrata, talora come anidra o come sale sodico.Il presente studio ha compreso la cristallizzazione e la caratterizzazione delle varie forme polimorfe e solvate dell’ampicillina. La forma triidrata, la monoidrata (detta forma A) e la forma anidra γ (o forma B) sono state ottenute con tecniche riportate in letteratura [4]. Per la forma δ, meno nota e studiata (sono riportati XRPD e IR) si è seguito il metodo di cristallizzazione riportato da Parker et al. [5]. Tali metodi di cristallizzazione (forme A, B, δ) hanno portato ad un prodotto finale di colore giallo chiaro, che potrebbe indicare decomposizione dei campioni [1]. In questo lavoro viene riportato come le due forme anidre siano state cristallizzate da riscaldamento in un capillare sigillato: a seconda della velocità diriscaldamento si sono ottenute la forma y (riscaldamento lento) e δ (riscaldamento rapido) senza alcun cambiamento di colore della polvere (cristalli bianchi). Le forme ottenute allo stato solido sono poi state caratterizzate mediante differenti tecniche analitiche (FT-IR, XRPD e DSC) ed i dati sperimentali sono stati confrontati con la bibliografia [1,4,5]. Inoltre, le differenti forme sono state studiate anche mediante la microscopia Raman (laser 632 nm). Per la prima volta in questo studio viene riportato uno studio SERS della molecola di ampicillina, utilizzando una soluzione colloidale di nanoparticelle d’argento secondo Lee e Meisel [6]. L'uso della Hot Stage Raman Microscopy (HSRM) ha permesso di seguire il passaggio dalla forma triidrata ad ampicillina monoidrata amorfa. Inoltre, con la stessa tecnica si sono potute studiare le trasformazioni solido-solido dal triidrato alle due forme anidre.Bibliografia[1] E. Shefter et al., J. Pharm. Sci. 1973, 62/5 791.[2] M.N.J. James et al. Nature 1968, 220 168.[3] E. Ivashkiv, In: Analytical Profiles of Drug Substances, vol. 2., Academic Press, New York, K. Florey, (Ed.), 1973.[4] K.W.B. Austin et al., Nature 1965, 208, 999.[5] Parker et al., 1976, USP 3933796.[6] P.C. Lee and D. Meisel J. Phys. Chem. 1982, 86, 3391.

2012 - Analisi micro-Raman di polveri cosmetiche greche e puniche [Abstract in Atti di Convegno]
Freguglia, Giada; Baraldi, Cecilia; Gamberini, Maria Cristina; E., Van Elslande; Baraldi, Pietro
abstract

Presso il Museo Archeologico Regionale “Antonino Salinas” di Palermo è conservato un importante nucleo di balsamari provenienti da Selinunte. Taluni, di pregevole manifattura, provengono dal Santuario di Demetra Malophoros. Altri unguentari e balsamari provengono dall’acropoli, altri ancora dalle necropoli. Appartengono ad un periodo compreso tra la metà del VI e la metà del V secolo a. C. L’area sacra, messa in luce durante gli scavi effettuati da Cavallari nel 1818 e da Salinas nel 1903-1905, ha portato alla luce una quantità immensa di materiali archeologici. Nell'area dove prima sorgeva l'acropoli i resti presentano un abitato misto, punico e greco. Al fine di questo studio sono stati inoltre presi in esame anche altri campioni, conservati nei saloni espositivi e in magazzino, provenienti dall’isola di Mozia, insediamento prettamente fenicio-punico.Gli insediamenti da cui provengono i contenitori, Selinunte e Mozia, offrono una gamma di valenze culturali assai variegata che sta a confermare il loro carattere di insediamenti nati da e per lo scambio. Le analisi condotte nel presente lavoro fanno seguito a quelle relative ad un importante gruppo di contenitori cosmetici di età Punica, coevi a quelli qui studiati, conservati presso il Museo della Fondazione Withaker sull’isola di Mozia [1,2].Il nucleo di balsamari fittili e vitrei, pissidi e alabastra considerati è stato ispezionato e si sono raccolte polveri di vari colori.La microscopia Raman ha permesso di identificare e caratterizzare i residui. Campioni bianchi hanno rivelato essere composti prevalentemente da miscele di gesso e anidrite (n inv. 1680, 1663, 1753). Le pissidi n. 1393 e 1451 presentavano residui bianchi composti da cerussite completamente carbonatata, gesso e litargirio. Si tratta del cosmetico greco per eccellenza, denominato psymition, utilizzato dalle donne per conferire pallore all’incarnato.Polveri rosa contenute in balsamari figurati di origine greca hanno mostrato come componenti ematite, quarzo, calcite, anatasio e goetite oppure, nel caso dell’askos zoomorfo n. 610, calcite, ossido di piombo, ematite, carbone e residuo organico. Il contenitore in vetro policromo n. 34228 presentava un abbondante residuo rosso composto da magnetite, quarzo, silicati ed ematite. Una conchiglia del genere Pecten (n. 34396) mostrava residui rossi composti da ematite, magnetite, lepidocrocite, goetite e tracce di cinabro (HgS). Un’interessante polvere rossa, (HgS miscelato con anatasio) è stata rinvenuta all’interno dell’ alabstron n. 7317/7 proveniente dalla necropoli di Marsala (tomba n.34). Risultati simili si sono ottenuti nell’ambito delle precedenti indagini su Mozia relative a contenitori della stessa tipologia. Il rinvenimento di questi pigmenti in associazione ad alasbatra è interessante in quanto la letteratura generalmente indica l’uso dedicato di questi particolari contenitori ad unguenti e profumi. Le analisi del contenuto azzurro della coppetta fittile n. 42259 hanno rilevato la presenza del celebre blu egiziano (CaCuSi4O10).Bibliografia[1] G. Freguglia, C. Baraldi, M.C. Gamberini, P. Toti, P. Baraldi,; PRIN07- Colors and balms in antiquity: from the chemical study to the knowledge of technologies in cosmetics, painting and medicine. Aboca, Sansepolcro (Arezzo, Italy), 2-3th December 2010, p. 50-51[2] C. Baraldi, G. Freguglia, M.C. Gamberini, P. Baraldi, RAA2011 Parma 5-8th September 2011, pp. 103-104;

2012 - First analytical evidences of precious colourants on Mediterranean illuminated manuscripts [Articolo su rivista]
Aceto, M.; Agostino, A.; Fenoglio, G.; Baraldi, Pietro; Zannini, Paolo; Hofmann, C.; Gamillscheg, E.
abstract

Two Byzantine VI century manuscripts known as Vienna Dioskurides and Vienna Genesis, held in the Aus- trian National Library at Vienna, were analysed with in situ non-invasive techniques. Raman spectros- copy, UV-Vis diffuse reflectance spectrophotometry with optic fibres and X-ray fluorescence spectrometry were used to characterise the palette of these early Middle Ages manuscripts. The analyt- icaI study was performed to have a better knowledge on the colourants used by ancient miniature paint- ers, a subject known more on the basis of traditional sources (i.e. medieval treatises) than of analytical evidences. Indeed these illuminated manuscripts afe, to the authors' knowledge, among the oldest ever being analysed, so that the coIourants found in them can be considered among the oldest evidences of their use. The main feature of Vienna Dioskurides and Vienna Genesis palettes is their richness, exemplified by the simultaneous presence of gold and ultramarine blue: in Vienna Dioskurides cinnabar is al so presento Information regarding ultramarine blue is surprising, being the analytical evidence of the use of this pre- cious pigment at least three centuries before its use in Western manuscripts, a feature justified by the fact that the Byzantine Empire was the dominant culture in early Middle Ages in the Mediterranean World. Other colourants include azurite and indigo, red lead, orpiment, red and yellow ochres, while a mixture of blue and yellow colourants, known as vergaut, was used to render green hues. Organic colourants were also used, such as madder and Tyrian purple, the latter employed to dye the parchment of Vienna Genesis.

2012 - I codici purpurei: dal mito alla scienza. Analisi non invasive preliminari su tre codici. [Relazione in Atti di Convegno]
M., Aceto; A., Agostino; G., Fenoglio; Baraldi, Pietro
abstract

I codici purpurei sono tra le realizzazioni librarie più importanti e prestigiose dell’epoca tardoantica e medievale. Si tratta di testi delle Sacre Scritture scritti con inchiostro dorato o argentato su pergamena tinta in colore porpora. Secondo tradizione, il colore della pergamena era ottenuto immergendo il foglio in un bagno di tintura contenente la celeberrima porpora di Tiro.Dal punto di vista materiale, tuttavia, ben poco si sa delle sostanze realmente impiegate nella manifattura di questi manoscritti. Le informazioni di cui si dispone attualmente sono limitate alla trattatistica con poche evidenze diagnostiche, che peraltro non hanno confermato in alcun caso la presenza della porpora di Tiro. È evidente quindi la necessità di disporre di informazioni più numerose ed esaurienti per verificare ciò che ci proviene esclusivamente dalla tradizione letteraria. Nel presente studio sono illustrati risultati preliminari provenienti da indagini non invasive su codici purpurei del VI secolo: il Vienna Genesis (Vienna, Österreichische Nationalbibliothek), l’Evangeliario di Sarezzano (Tortona, Archivio Diocesano) e il Codice di Brescia (Brescia, Biblioteca Queriniana). Le analisi sono state effettuate mediante spettrometria XRF e spettrofotometria FORS e suggeriscono l’ipotesi che l’impiego della porpora di Tiro fosse parziale, ovvero in miscela con altri coloranti, tra cui il tornasole. I risultati andranno confrontati con altri codici coevi che saranno analizzati nel seguito del progetto.

2012 - IL PRESBITERIO DELL’ORATORIO DEI SANTI ANTONIO E ROCCOIN VARESE LIGURE (SP): RESTAURO E DIAGNOSTICA. [Relazione in Atti di Convegno]
S., Vassallo; P., Parodi; A., Sartori; Baraldi, Pietro; G., Firpo; U., Valbusa
abstract

La Confraternita dei Santi Antonio e Rocco in Varese Ligure (SP) si è costituita nel 1451, l‟oratorio attuale è stato eretto nel XVI secolo e presenta un complesso apparato in stucco dipinto e dorato realizzato tra XVII e XVIII secolo. Il recente restauro del presbiterio dell‟Oratorio ha consentito il recupero dei decori in stucco realizzati in due distinte fasi, la prima databile all‟inizio del XVIII secolo la seconda intorno alla metà del XVIII secolo. La diagnostica di cantiere ha documentato inoltre la presenza di uno strato pittorico originale degli stucchi dell‟inizio del “700” sotto ad un generale rifacimento con colore e dorature della policromia datato agli ultimi anni del medesimo secolo.Nel corso del restauro sono stati effettuati 35 microprelievi di colore su stucchi intonaci e manufatti lignei della chiesa. Su questi campioni è stata effettuata la spettroscopia infrarossa FTIR, la sezione stratigrafica, le indagini al SEM/EDX, e la spettroscopia MicroRaman. In cantiere sono state fatte delle ulteriori verifiche in microscopia ottica portatile e in spettroscopia visibile.

2012 - INDAGINI ARCHEOMETRICHE SU PITTURE MURALI DALL’INSEDIAMENTO DI MONTEGIBBIO. [Relazione in Atti di Convegno]
Baraldi, Pietro; Zannini, Paolo; F., Guandalini; Ferrari, Giorgia
abstract

Frammenti di pittura murale di epoca romana, provenienti dall'insediamento di Montegibbio (Modena), sono stati analizzati tramite Spettroscopia μ-Raman, FT-IR e XRF. I campioni provenienti dagli strati datati nel primo periodo imperiale sono stati confrontati con frammenti provenienti dagli strati tardo-antichi; è stata ricostruita una tavolozza piuttosto ampia,caratterizzata da particolari miscele di pigmenti per ottenere determinate tonalità.

2012 - Identification of colorants on XVIII century scientific hand-coloured print volumes [Articolo su rivista]
Zannini, Paolo; Baraldi, Pietro; Aceto, Maurizio; Agostino, Angelo; Fenoglio, Gaia; Bersani, Danilo; Canobbio, Eleonora; Schiavon, Elisabetta; Zanichelli, Giusi; De Pasquale, Andrea
abstract

Two series of printed volumes, respectively, created in Parma and in Vienna at the end of XVIII century, were analysed in arder to characterise the palettes used in the hand-coloured miniatures and to determine whether decoration had been carried out simultaneously to, or shortly after, the ti me of printing. The application of complementary non-invasive analytical techniques allowed to yield a thorough knowledge of the colorants present and to determine that artists used a mixing of ancient, traditional materials such as cinnabar, minium or indigo, and materials of recent introduction in late XVIII century such as gamboge, Prussian blue or blue verditer. There was no evidence of colorants created successively to the age of printing, so that it can be conduded that decoration could have been done at the ti me of printing. Interesting is the use of metal pigments in the Vienna volumes, either in powder form and in foil form as a basis to obtain iridescence effects, a due to evaluate the great skillfulness of the artist. Among the colorants identified, particularly relevant is the identification of gamboge, a colorant almost exdusively used among Far Eastern Asian painters according to the literature; this fact suggests that information on the use of pictorial materials can be strongly updated by diagnostic analyses.

2012 - Indagini Archeometriche su Lacerti di Pittura Murale da Cattolica (Rimini) [Relazione in Atti di Convegno]
M., Nannini; Baraldi, Pietro; Zannini, Paolo; L., Stoppioni
abstract

Il lavoro svolto ha avuto come oggetto lo studio di frammenti d’intonaco dipintiprovenienti da uno dei siti archeologici di epoca romana, rinvenuti a Cattolica. Mediante l’uso di tecniche spettroscopiche Raman ed FT-IR è stato possibile determinare i pigmenti utilizzati, ricostruire la tavolozza, discriminare contaminazioni accidentali e avvalorare l’ipotesi dell’esistenza del substrato romano cittadino.

2012 - L’IMPIEGO DEL MICROSCOPIO OTTICO PER LA VALUTAZIONE DELLA VISCOSITA’ DI VETRI ANTICHI. [Relazione in Atti di Convegno]
F., Montanari; C., Boschetti; Baraldi, Pietro; Leonelli, Cristina
abstract

La determinazione della viscosità è un fattore di fondamentale importanza per lo studio della tecnologia dei vetri antichi, ma tale valutazione implica grandi quantitativi di vetro, che spesso non sono disponibili in ambito archeometrico. In questo articolo presentiamo un metodo per determinare indirettamente la viscosità, attraverso l‟analisi al microscopio ottico riscaldante.L‟analisi viene effettuata su qualche milligrammo di vetro in polvere, che viene sottoposto a un ciclo di riscaldamento reimpostato, mentre lo strumento raccoglie immagini del profilo del campione. Dall‟andamento del profilo del campione in sinterizzazione è possibile ricavare alti punti di viscosità caratteristici del rammollimento. Il lavoro propone un confronto tra due vetri Pompeiani colorati ed opacizzati ed un vetro trasparente riprodotto in laboratorio.

2012 - NEW STUDIES ON LORENZO LOTTO’S PIGMENTS: NON-INVASIVE AND MICRO-INVASIVE ANALYSES. [Relazione in Atti di Convegno]
M. L., Amadori; Baraldi, Pietro; S., Barcelli; G., Poldi
abstract

In the frame of large research project, also related to the exhibition “Lorenzo Lotto” (Venezia, 1480 – Loreto, 1556-57) held at the Scuderie del Quirinale in Rome in spring 2011, more than 50 paintings of Lotto spanning from 1505 to around 1556 were studied by means of scientific examinations.The University of Bergamo coordinated and carried out non-invasive analyses using portable instruments: IR reflectography in different bands, false colour IR, reflectance spectrometry in the visible range (vis-RS), X-ray spectrometry (EDXRF), sometimes UV-induced fluorescence and X-ray radiography. On the basis of the obtained results some areas of four paintings undergoing restoration treatments were subjected to micro-sampling in order to be mounted in cross-sections and studied by optical microscopy (OM) and SEM/EDX by the University of Urbino e by micro- Raman spectroscopy by the University of Modena and Reggio Emilia.Non invasive exams allowed to know the evolution of Lotto’s palette during all the periods of his activity, as well as his underdrawing, the nature of painting changes and his pictorial technique.Among the most interesting results, the use of lapis lazuli and azurite in different combinations , and their mixture with red lakes. About these lakes, Lotto shows a peculiar use of madder, also alternated with carmine-type lake, according to desired effects. About yellows, he uses both lead-tin and lead-antimony (Naples yellow) pigments, the latter found by XRF in works starting from 1530 to the last years: it can be related to the “zalolin da vasarj” cited by Lotto in 1541 in his account book (Libro di spese diverse). Micro-invasive analyses (Raman and SEM/EDX) stated also the presence, among yellows, oflitharge, of a high tin content “giallorino” (lead-tin yellow) and of saffron, as well as the use of grinded transparent glass in the pictorial layers, the existence of coloured priming and – in one case – of an iron-oxides coloured ground, the complexity of some stratifications and mixtures.This kind of analyses were carried out on a few selected samples of four works painted during different periods of Lotto’s career, from 1508 (Recanati) to 1522 (Bergamo).

2012 - PIGMENTI E LEGANTI IN USO A POMPEI TRA LA FINE DEL II SEC.A.C. E IL 79 D.C. Casi studio: affresco “Scena di Mercato”, Casa de Bracciale D’Oro, Regio IX. [Relazione in Atti di Convegno]
A., Arpaia; G., Trojsi; Baraldi, Pietro; S., Vanacore
abstract

Le operazioni di restauro possono essere eseguite con cognizione di causa se affiancate ad indagini archeometriche che permettano di conoscere la composizione chimico-fisica del manufatto; perrmettendo di individuare i prodotti più idonei agli interventi. Sono state eseguite indagini archeometriche mediante spettroscopia Raman ed IR (FT-IR), diffrazione e fluorescenza ai raggi X (XRD, XRF) e microscopia ottica in sezione lucida su campioni di intonaco dipinto prelevati a Pompei, per lo studio dei pigmenti e dei leganti.. I risultati sono stati confrontati conquelli ottenuti dalle indagini svolte negli ultimi vent’anni a Pompei, confermando o meno quanto già conosciuto in letteratura.

2012 - UNA MAPPA RINASCIMENTALE INEDITA DELL'ARCHIVIO DI STATO DI MODENA. DALLO STUDIO INTERDISCIPLINARE ALLA DATAZIONE. [Relazione in Atti di Convegno]
Baraldi, Pietro; Badiali, Federica
abstract

Si presenta lo studio interdisciplinare di una mappa policroma rinascimentale inedita, proveniente dal Mappario estense, conservata presso l'Archivio di Stato di Modena e raffigurante l'alto Appennino Bolognese e Modenese.Gli autori stanno realizzando sulla mappa un complesso studio interdisciplinare, che coinvolge indagini archeometriche, geomorfologiche, cartografiche, paleografiche, topologiche, toponomastiche e storico/artistiche, che hanno dimostrato la ricchezza di informazioni che questo documento offre per lo studio e la ricostruzione dell'antico paesaggio dell'Appennino.Sono stati identificati i toponimi riportati sulla mappa e, sulla base di aspetti paleografici e stilistici, si suppone che il documento risalga alla II metà del XV secolo, probabilmente intorno al 1480. L'analisi dei pigmenti mediante microscopia Raman ha sostanzialmente confermato tale ipotesi, mentre sono tuttora in corso ricerche storico-archivistiche.

2012 - UTILIZZO DELLA SPETTROSCOPIA RAMAN E FT IR (ATR) SU UN DIPINTO SU TAVOLA DI SCUOLA NAPOLETANA DEL SECOLO XVII:ANALISI E RESTAURO DEL SAN GEROLAMO NEL DESERTO. [Relazione in Atti di Convegno]
A., Zaccaria; Baraldi, Pietro; G., Fatigati; G., Trojsi
abstract

La ricerca illustra l’importanza della collaborazione tra scienza e restauro. Come caso esplicativo si presenta l’analisi e il restauro del “San Gerolamo nel deserto”, un dipinto su tavola del XVII secolo di scuola napoletana. Si indica un percorso da leggere come una “stratigrafia” in cui, dal supporto alla vernice protettiva, si analizzano in successione le tipologie dei materiali artistici e le tecniche di esecuzione, il tutto costantemente supportato dalle indagini diagnostiche. Una volta terminata la fase conoscitiva del manufatto, ossia integrando le ricerche scientifiche con accurate ricerche storiche, storico-artistiche e archivistiche, si è proceduto con la stesura del progetto e la realizzazione dei restauri.

2011 - A multi-analytical approach for the characterization of powders from the Pompeii archaeological site [Articolo su rivista]
C., Canevali; P., Gentile; M., Orlandi; F., Modugno; J. J., Lucejko; M. P., Colombini; L., Brambilla; S., Goidanich; C., Riedo; O., Chiantore; Baraldi, Pietro; Baraldi, Cecilia; Gamberini, Maria Cristina
abstract

Nine black powders found in Pompeii housesin three different types of bronze vessels (cylindricaltheca atramentaria, unguentaries, and aryballoi) werecharacterized in order to assess a correspondence betweenthe composition and the type of vessel and,possibly, to verify if these powders were inks or not.For the compositional characterization, a multi-analyticalapproach was adopted, which involved the use ofscanning electron microscopy–energy dispersive X-ray,Fourier-transformed infrared spectroscopy, Raman, X-raydiffraction, electron paramagnetic resonance spectroscopy,thermogravimetric analysis, gas chromatographycoupled with mass spectrometry (GC/MS), and pyrolysis GC/MS. Powders contained in cylindrical theca atramentariaform a homogeneous group, and their organic andinorganic compositions suggest that they were writinginks, while powders contained in unguentaries andaryballoi could have had several different uses, includingwriting inks and cosmetics. Furthermore, the compositionprofile of the powders found in cylindrical cases showsthat, at 79AD, in Pompeii, carbon-based inks were stillused for writing, and iron gall inks had not beenintroduced yet.

2011 - Combined technique analysis on Punic cosmetic powders [Abstract in Atti di Convegno]
Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; Baraldi, Pietro
abstract

The Whitaker Museum in Mozia (Sicily) conserves some funerary vessels coming from the isle’s archaic necropolis. Greek, Phoenician and Etruscan amphorae, a rich collection of jars of Birgi necropolis and also materials coming from Mozia Tofet and houses are exposed. Also jewels and weapons, amulets, scarabs and objects with original inscriptions engraved are found, as well as cosmetic and surgical instruments and fragments of inscribed stones coming from the Lilibaeum necropolis. From the collection of the Mozia Museum 77 samples from an interesting variety of containers including Unguentaria, Balsamaria, Alabastra, pyxes and shell valves were taken. The powders found in this cosmetic vessels have been analyzed by using FT-IR, micro-Raman, SERS (Surface Enhanced Raman Spectroscopy) and XRF techniques and the results are reported in this work. The analyses carried out have shown the presence of a variety of compounds.The white powders, that are the more frequent ones, present in lead pyxes, were identified by micro-Raman as made of Cerussite PbCO3 coming from a complete carbonatation of hydrocerussite PbCO3*Pb(OH)2. This is compatible with the high chronology of the samples: instead, hydrocerussite has been identified in Pompeii samples. Its presence, confirmed by XRF measurements, can be a clear indication of cosmetic use, since it is well known that its use in mural painting is not advisable. At the time, cerussa (lead white) was employed as a foundation. Other white powders are mainly composed of calcite or aragonite: the first could come from the soil where the ancient founds were situated, the second one could derive from ground sea shells. Among white samples, but not only, TiO2 is frequently attested. Its presence should amount to the cosmetic use of ground rocks or could come from the Mozia soil, for example if ophiolites are available in the region.Litharge, an oxide present in many containers, could derive from the alteration of cerussa, or from a proper addition, whether the yellow colour had a special meaning for the population of the site. As to the yellow pigments a yellow ochre based on goethite was found together with lepidocrocite.Among the red pigments, beloved by Phoenician people, there are cinnabar and hematite: the latter can be found as a natural compound or as a thermodegradation product from goethite. The presence of red lead chromates crocoite and phoenicocroite, two rare minerals, in a particularly precious unguentary is a singular discovery.In one sample a trace of blue material was seen, that gave the spectrum of indigotine, a dye extracted in the past from many plants and used for dyeing tissues and in cosmesis.Among black materials carbon is one of the most frequently attested, alongside MnO2 (pyrolusite) and magnetite.Three samples analyzed exhibited red organic compounds, all fluorescent with normal Raman technique. By appliying a SERS technique it has been possible to record spectra relative to these red dyes, but till now, with a comparison of reference materials, it was only possible to exclude the common red such as madder, purple and kermes. Other comparisons are outstanding.In comparison with other sites, such as Pompeii, Herculaneum and Oplontis, this cosmetic powders showed a wider range of materials.

2011 - First chemical evidence of royal purple as a material used for funeral treatment discovered in a Gallo-Roman burial (Naintré, France, third century AD) [Articolo su rivista]
Devièse, Thibaut; Ribechini, Erika; Baraldi, Pietro; Farago Szekeres, Bernard; Duday, Henri; Regert, Martine; Colombini, Maria Perla
abstract

Violet-purple residues collected from a Gallo-Roman burial dated back to the second half of the third century A.D. and excavated at Naintré (France) were chemically investigated by multi-analytical methodology involving the use of Raman spectroscopy, direct exposure-mass spectrometry (DE-MS) and high-performance liquid chromatography (HPLC-UV-visible). Little is known about funeral treatment and rituals during Roman times. Retrieving valuable information on these by chemical analysis of organic residues was thus a key aspect of this work. Analyses demonstrated the presence of the very precious purple colorant obtained from shellfish glands commonly known as Tyrian or royal purple and its exceptional preservation. Chemical investigation and archaeological evidence have shown that purple was widely spread after the deposition of the body for burial. These results are the earliest chemical evidence of purple colorant used during funeral rituals (not as textile dye) and enabled us to highlight new aspects of funeral practices in Roman times

2011 - Spectral analysis of pharmaceutical formulations prepared according to ancient recipes in comparison with old museum remains [Articolo su rivista]
Gamberini, Maria Cristina; Baraldi, Cecilia; Freguglia, Giada; Baraldi, Pietro
abstract

A study of the composition of the remains ofancient ointments from museums was undertaken to enableunderstanding of the preparation techniques. Comparison ofancient recipes from different historical periods andspectroscopic characteristics of inorganic and/or organicremains recovered in museum vessels enabled preparationof ancient pharmaceutical–cosmetic formulations. FarmacopeaAugustana by Occo was one the most importantbooks studied for the 14 formulations prepared in thelaboratory. Three formulations are discussed in detail andraw materials and new preparations were proposed forozone ageing. The most important micro Raman results arediscussed. The spectra of the raw materials lipids, beeswax,and resins are discussed; beeswax and pig suet (axŭngia)Raman spectra were found to be similar, but different fromthose of the aged oils. SERS was applied to ancientointments and galbanum and the Raman spectra arereported and discussed for the first time.

2011 - The Officina Pigmentaria in Pompei: pigments and cosmetics [Relazione in Atti di Convegno]
Baraldi, Pietro; S., Petrullo; Baraldi, Cecilia; G., Trojsi; A., Varone
abstract

According to the “Giornale di Scavo” of the Archaeological Superintendance of Pompeii, the first excavation in the Regio I, Insula 9 (I,9,9) took place in 1952. In a building of seven rooms there was a stair in opus incertum with the floors in cocciopesto. Near the skeletons of four individuals, about 150 globular bowls, fritilla and ollae were found. They were assigned the numbers between 9389 and 9700. Due to the high number of containers and to the presence of material inside, they have a high importance for the history of materials in Pompeii and in the Roman world. In particular, they should be important for the reconstruction of the painting history and techniques of this period. An investigation with different techniques for the identification of the contents composition and subsequently for the understanding of the materials present was then undertaken. For the study two molecular techniques were used, that is FT-IR spectroscopy and Raman microscopy. The first is able to supply information about the general composition of the compound present in the samples at least in the concentration of about 1 %. The second techniques can inform on the composition of single grains as small as 1-2 micrometers. Therefore, the results of the two techniques must help each other to understand what the analyzed powder is. The analyses of all the bowl contents are summarized in a long table, of which we report only a section. By comparing the results obtained some considerations come to light. Many containers have quartz and calcite, that are the main component of plasters, to which feldspars and pyrite can be added. At the same time diopside can come from eruptive rocks or from silicate materials heated to high temperature. Aragonite is present, sometimes at high concentration, in many pigments, and its presence can be due to natural provenance from white minerals, but more probably can be due to the grinding of shells. This is an important testimony of what is identified in white lines on colored background in Roman wall paintings. The blue pigment is always based on Egyptian blue, at the time of Pompeii destruction coming from Puteoli or Liternum. Green can be obtained by mixing a yellow and a blue, and this is generally found on wall paintings; more frequently green is ascertained to be a mixture of green earth and some Egyptian blue. Malachite and azurite are encountered as degradation products of copper and brass containers. Other rare occurrence are cuprite, also coming from alterations of a metal, and litharge, from alteration of cerussite or lead objects. The case of cerussite or hydrocerussite is different. It can be identified in many recipients, but it is not a pigment for wall paintings. Since it is known from Pliny and other authors that it was used as a fard, this can be a proof of the production and filling also of cosmetics containers in I, 9, 9.

2010 - Auctoribus curae fuere lapides mortariorum quoque nec medicinalium tantum aut ad pigmenta pertinentium (Pliny 36, 43). Our authors are interested in stones, for making mortars, and not only in officinal mortars or those uded for colors. [Relazione in Atti di Convegno]
Baraldi, Pietro; Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina
abstract

A very important phase for reconstructing ancient technology and human activities is the analisys of artifacts. It can supply a lot of information, but sometimes the data obtained are not understandable. On the other hand an amount of written information is available since the classical antiquity. Some of the authors are considered not to be scientist and therefore their data are neither used nor interpreted. Beyond published texts some unpublished manuscripts are known that could be very interesting. Other documents include ancient translations from other languages, such as the Greek papyrii, and the Arabian documents from Spain, documents regarding trade and history of countries, icones in ancient paintings, tools used for paintings and other activities. In more recent time it is to recall, the "secreti", the books for treating diseases, where the subjects not only concern madicine, but include preparation of pigments, dyes, lakes, cosmetics, alloys inks...Their contents can be very old, some being composed much before Christ and re-written many times, and translated and sometimes erroneusly read. The transcription, understanding and interpretationof these recipes can help in understanding: the ancient paintings, decorations, alloys, textiles and cosmetics; the presence of some compounds as a consequence of past treatments and restorations; the survival of some compounds not necessary for the formulate, but added for somo forgotten reasons, such as folklore, superstition, faith, magic; the degradation of somo parts of artworks due to time and environment.These items have been followed in examining and unpublished miscellanea from the Biblioteca Estense Universitaria in Modena.

2010 - COSMETIC AND PHARMACEUTICAL FORMULATIONS: FROM PAST TO PRESENT [Relazione in Atti di Convegno]
Gamberini, Maria Cristina; Freguglia, Giada; Baraldi, Cecilia; Baraldi, Pietro
abstract

The interest devoted to the scientific treatment of analytical data obtained from ancient founds preserved in Italian and foreign institutions and Museums is nowadays relevant. However, till now the study of the composition and the understanding of the preparation technologies of ancient founds is scanty and fragmentary. Now, the progress of instrumental techniques enables the material composition to be cleared in details and to advance a possible re-proposition of the handiworks. On the basis of analytical data, the possibility to establish the nature of raw materials and the formulations, becomes even more concrete.In the framework of the PRIN project the unit of Modena has thrown the basis for the study of ancient cosmetic, medical and pictorial founds, in particular: 1)Identification and sampling of ancient remains in national and international Museums and of handiworks not purely cosmetic or medical.2)Spectroscopic studies (FT-IR, micro-Raman and XRF) for the characterisation of inorganic and/or organic remains recovered in unguentaries and in containers of ancient workshops.3)Identification and study of the ancient published and unpublished bibliographic sources: translation from Latin and vernacular followed by an interpretation of the function of raw materials. 4)Identification in the actual market of the materials used in antiquity.5)Preparation or acquirement of raw materials not available on the market.6)Reproduction in a modern perspective of ancient formulations on the basis of the ancient sources. The first step faced was the acquirement of ancient founds, that is the sampling on the spot of samples to be studied. Therefore, samples were taken at the Museum Aboca (Sansepolcro, Arezzo). At the Aboca Museum about 68 pots were inspected and 30 exhibited a fair amount of residue of which 9 were the object of the study.After sampling, the materials were analysed by Micro-Raman and FT-IR in order to have a first screening of them, that is to determine whether they were of organic or inorganic origin and which compounds were present. In this way we got a first idea of what the materials were. Thanks to the spectroscopic analyses and to the labels on the containers, we proceeded into the research of ancient similar formulations. Therefore, it was necessary to examine the recipe books starting from the classical age till to the beginning of scientific chemistry and pharmacology in order to critically compare the materials found, to understand their nature, their possible alteration undergone with time, the novelties in comparison with preceding versions, the technological acquirements of an age in comparison with the others. From the study of the inscriptions reported on the containers and the interpretations carried out, the period of actualisation of the formulation was hypothesised. The study of the same formulation in subsequent times has shown the evolution and the adaptation to the age.Many ancient books and manuscripts reporting recipes concerning the subject in the period between 1597 and 1872 have been considered, the most interesting of these was Farmacopea Augustana by Occo, 1597. For each source, the desired recipes were searched for and then, if necessary, translated and interpreted. In fact, some texts are in Latin or vernacular (Farmacopea Augustana by Occo), French (Abrégé de Matière médicale et de Thérapeutique by C. Binz) or Spanish (Farmacopea Hispanica), and the translation must be careful, since the meaning of the terms at the time was searched 1-7.The next step was to study the raw materials used in the recipes, that is to verify the persistence of the ingredients today and their availability in commerce. The ointments to be prepared were chosen as a function of the remains found in the containers, but mainly on the basis of the results of the spectroscopic analyses. Those reproduced in the laboratory were many, sometimes the preparations have been ma

2010 - Color traces and their identification in paintings, cosmetics, writings [Abstract in Atti di Convegno]
Baraldi, Pietro; Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; Ansaloni, Ivano
abstract

During the last years of research carried out on the basis of a financial support by MIUR, many samples have been encountered of different nature, colour, origin and physical state. In examining containers present in the Italian Archaeological depositories and Museums, we have found or we were adviced of interesting coloured materials and we were asked to identify them.The identification is sometimes rich of information about the ancient technology for preparing elaborated formulates, such as cosmetics, drugs, ointments, perfumes, pigments, lakes, dyes. Thereby, their analysis enables important passages of the production to be understood and some literary sourced to be interpreted. In examining some materials present on bones due to particular rituals of the first centuries after Christ in Aemilia, a particular identification of manganese based materials was encountered. The presence of manganese oxides can be related to the geology of the Aemilian territory. However, similar compounds are present in Etruscan tiles decorated with Egyptian blue and other pigments in Marzabotto. This fact supply information on the commerce of Egyptian blue far before Roman Empire times and the passage of manganese oxide treatment for painting to subsequent cicilizations.The necessity for ancient populations to paint testimonies of past religious or military chiefs lead to a search for materials coming from far centuries, such as Baltic amber, Egyptian blue, indigo… In places with an always more ancient chronology, such as Verucchio Aemilia, these materials are found in large amounts. It is not clear whether indigo was extracted from Isatis tinctoria or an Indigofera.Traces of saffron and indigotine on fictile antefissae in Cuma testifies the use of re-painting the artefacts every while, as a sign of respect for the temples. Ancient colored lipsticks contain pink ingredients, that may be purpurissum, but could be also the cheaper purpurissum puteolanum, as revealed by SERS analysis of Pompeiian samples.Residuals of precious materials are found also in small containers of the Roman ages. Smal traces of gold an a black preparation identify the knowledge of a gilding technique on alabaster, whit the black assisa applied on small spots. The ensemble of materials and their use enable an amount of knowledge to be supposed in ancient populations in order to make their life more comfortable and elegant.

2010 - Indagine sui colori delle pitture murali della torre Ghirlandina. Investigation on the colors of the wall paintings of the ghirlandina tower. [Capitolo/Saggio]
Baraldi, Pietro
abstract

Mediante microscopia Raman e spettroscopia IR si è proceduto all'analisi in loco e ex-situ delle pitture che decorano la torre Ghirlandina. I dati analitici mostrano che si tratta di pittura a calce condotta a fresco o in alcuni casi a secco. La calcite è fortemente solfatata in dipendenza dell'esposizione del monumento a gas presenti nell'atmosfera. La presenza di ossalati di calcio è ascrivibile a effetti ambientali di tipo biologico. Sulle pitture si è riscontrata la presenza di pigmenti recenti: baritina, bianco di anatasio, blu di ftalocianina di rame (entrato in uso verso il 1940). Tutto testimonia l'esecuzione di un intervento di restauro nel XX secolo. La tavolozza pittorica è costituita da ocre, terra verde, malachite, tracce di oltremare.

2010 - Indagini in microscopia Raman sul manoscritto 3632. [Capitolo/Saggio]
Baraldi, Pietro
abstract

Contestualmente al restauro del codice greco BUB 3632 si sono effettuate delle indagini scientifiche mediante microscopia Raman con strumento portatile dotato di laser rosso. Si sono anche raccolti microcampioni da analizzare con strumento Raman fisso. Si sono identificati tra i vari pigmenti usati: indigotina, minio, cinabro, litargirio, azzurrite...

2010 - MULTI ANALITYCAL APPROACH TO AGED COMPLEX MATRICES [Abstract in Atti di Convegno]
Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; Baraldi, Pietro; M. P., Colombini
abstract

Since a decade our research group deals with the analysis of ancient cosmetics and drugs, starting from the Roman founds. At present some founds from pharmacies of Italy (Genua, Sansepolcro) and Spain (Majorca) amounting to the XVII century and Egyptian ointments of the II millennium b.C. from the Turin Museum are under study.The analysis protocol provides firstly non-destructive analyses and then the more expensive and destructive analyses, such as gas-chromatography-mass spectrometry (GC-MS) methods. We report the results of the vibrational spectroscopy techniques, such as Raman microscopy (laser 632 nm), FT-Raman spectroscopy (laser 1064 nm) and FT-IR/ATR with a golden gate accessory, were identified as the most suitable techniques for a first approach to the analysis of the ancient samples. Raman microscopy is the most suitable technique in order to identify minor inorganic components and contaminants at the micrometric scale inside these complex matrices. This technique can easily identify compounds like lead oxide, vermillion, rare minerals, (etc.) that could give interesting informations about the provenance of the raw materials and the original composition of the formulate. In this study are reported some data about the composition of some ancient Egyptian samples. It can be observed that Titanite is present, a mineral possibly coming from mines in Southern Egypt.Concerning to organic materials, their possibility of identification, is very different from that of inorganic ones. Some compounds were rapidly degraded, some others persisted till to present day, often unchanged (e.g. wax). Historical samples give a chemical variability like the natural products, in addiction there are the ageing and the degradation process that make very difficult to recognize the raw material originally present. For understanding the possible changes undergone by materials in ageing, a specific database of spectra must be available.Some thirty raw materials were chosen among oils (e.g. olive, almond, and palm oil), gums (e.g. gum arabic, gum tragacanth), animal fats and waxes commonly employed in the ancient preparations. On the basis of the examination and critical interpretation of ancient literature sources (pharmacopoeias) fifteen samples based on pharmaceutical and cosmetic recipes were prepared as a reference samples. The raw materials and thereference formulations were artificially aged by using heating (in a oven at 60°C for 1 month), photo-oxidation (with ozone for 20 hours) and enzymatic degradation (by means of a pool of cellulase, lipase and laccase).Concerning the raw materials, only few showed fluorescence in Raman microscopy, but this decreases sharply with the artificial ageing process. This fact could be due to the loss of fluorophores.The artificial ageing produces different alterations according to the type of ageing. Among the first results we reported the analysis of Pompeii sample already identified as palm oil by GC-MS2. The comparison with our database showed correspondence with palm oil enzymatically degraded. This indicates that this database is interesting in recognising the organic materials into archaeological holders.

2010 - Multianalytical approach to aged complex matrices [Abstract in Atti di Convegno]
Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; Baraldi, Pietro
abstract

Since a decade our research group deals with the analysis of ancient cosmetics and drugs, starting from the Roman founds. At present some founds from pharmacies of Italy (Genua, Sansepolcro) and Spain (Majorca) amounting to the XVII century and Egyptian ointments of the II millennium b.C. from the Turin Museum are under study. The analysis protocol provides firstly non-destructive analyses and then the more expensive and destructive analyses, such as gas-chromatography-mass spectrometry (GC-MS) methods. These measurements involve other research groups of our project supported by a national Fund (PRIN: Colours and ointments in antiquity). We report the results of the vibrational spectroscopy techniques, such as Raman microscopy (laser 632 nm), FT-Raman spectroscopy (laser 1064 nm) and FT-IR/ATR with a golden gate accessory, were identified as the most suitable techniques for a first approach to the analysis of the ancient samples. Raman microscopy is the most suitable technique in order to identify minor inorganic components and contaminants at the micrometric scale inside these complex matrices. This technique can easily identify compounds like lead oxide, vermillion, rare minerals, (etc.) that could give interesting informations about the provenance of the raw materials and the original composition of the formulate. Concerning the organic materials, their possibility of identification, is very different from that of inorganic ones. Some compounds were rapidly degraded, some others persisted till to present day, often unchanged (e.g. wax). Historical samples give a chemical variability like the natural products, in addiction there are the ageing and the degradation process that make very difficult to recognize the raw material originally present. For understanding the possible changes undergone by materials in ageing, a specific database of spectra must be available.Some thirty raw materials were chosen among oils (e.g. olive, almond, and palm oil), gums (e.g. gum arabic, gum tragacanth), animal fats and waxes commonly employed in the ancient preparations. On the basis of the examination and critical interpretation of ancient literature sources (pharmacopoeias) fifteen samples based on pharmaceutical and cosmetic recipes were prepared as a reference samples. The raw materials and the reference formulations were artificially aged by using heating (in a oven at 60°C for 1 month), photo-oxidation (with ozone for 20 hours) and enzymatic degradation (by means of a pool of cellulase, lipase and laccase).Concerning the raw materials, only few showed fluorescence in Raman microscopy, but this decreases sharply with the artificial ageing process. This fact could be due to the loss of fluorophores. The artificial ageing produces different alterations according to the type of ageing. Among the first results we reported the analysis of Pompeii sample already identified as palm oil by GC-MS2. The comparison with our database showed correspondence with palm oil enzymatically degraded. This indicates that this database is interesting in recognising the organic materials associated to archaeological founds.

2010 - MultyAnalytical Approach to Aged complex Matrices [Abstract in Atti di Convegno]
Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; Baraldi, Pietro; M. P., Colombini
abstract

Since a decade our research group deals with the analysis of ancient cosmetics and drugs, starting from the Roman founds. At present some founds from pharmacies of Italy (Genua, Sansepolcro) and Spain (Majorca) amounting to the XVII century and Egyptian ointments of the II millennium b.C. from the Turin Museum are under study.The analysis protocol provides firstly non-destructive analyses and then the more expensive and destructive analyses, such as gas-chromatography-mass spectrometry (GC-MS) methods. These measurements involve other research groups of our project supported by a national Fund (PRIN: Colours and ointments in antiquity). We report the results of the vibrational spectroscopy techniques, such as Raman microscopy (laser 632 nm), FT-Raman spectroscopy (laser 1064 nm) and FT-IR/ATR with a golden gate accessory, were identified as the most suitable techniques for a first approach to the analysis of the ancient samples. Raman microscopy is the most suitable technique in order to identify minor inorganic components and contaminants at the micrometric scale inside these complex matrices4. This technique can easily identify compounds like lead oxide, vermillion, rare minerals, (etc.) that could give interesting informations about the provenance of the raw materials and the original composition of the formulate. In Tab.1 are reported some data about the composition of some ancient Egyptian samples. It can be observed that Titanite is present, a mineral possibly coming from mines in Southern Egypt. Concerning to organic materials, their possibility of identification, is very different from that of inorganic ones. Some compounds were rapidly degraded, some others persisted till to present day, often unchanged (e.g. wax). Historical samples give a chemical variability like the natural products, in addiction there are the ageing and the degradation process that make very difficult to recognize the raw material originally present. For understanding the possible changes undergone by materials in ageing, a specific database of spectra must be available.Some thirty raw materials were chosen among oils (e.g. olive, almond, and palm oil), gums (e.g. gum arabic, gum tragacanth), animal fats and waxes commonly employed in the ancient preparations. On the basis of the examination and critical interpretation of ancient literature sources (pharmacopoeias) fifteen samples based on pharmaceutical and cosmetic recipes were prepared as a reference samples. The raw materials and the reference formulations were artificially aged by using heating (in a oven at 60°C for 1 month), photo-oxidation (with ozone for 20 hours) and enzymatic degradation (by means of a pool of cellulase, lipase and laccase).Concerning the raw materials, only few showed fluorescence in Raman microscopy, but this decreases sharply with the artificial ageing process. This fact could be due to the loss of fluorophores. The artificial ageing produces different alterations according to the type of ageing. Among the first results we reported the analysis of Pompeii sample already identified as palm oil by GC-MS2. The comparison with our database showed correspondence with palm oil enzymatically degraded. This indicates that this database is interesting in recognising the organic materials into archaeological holders.

2010 - RAMAN TECHNIQUES APPLIED TO ANCIENT COSMETIC AND PHARMACEUTICAL PREPARATIONS [Relazione in Atti di Convegno]
Baraldi, Cecilia; Gamberini, Maria Cristina; Freguglia, Giada; Baraldi, Pietro
abstract

Complementary spectroscopic techniques, such as FT-IR and Micro-Raman spectroscopies are valuable means for maximizing the amount of information provided by complex matrices like the remains in archaeological containers. The difficulty in analyzing archaeological samples is due to their composition which generally involves a mixture of different inorganic and organic materials, some times degraded by the environmental conditions. We report the results of the vibrational spectroscopy techniques, such as Raman microscopy (laser 632 nm), FT-Raman spectroscopy (laser 1064 nm) and FT-IR/ATR with a golden gate accessory, of a first approach to the analysis of the ancient samples. The analytical results showed the importance of micro-Raman Spectroscopy in discriminating between inorganic and organic materials, thereby underlining the complexity of pharmaceutical and cosmetic matrices.Raman microscopy is the most suitable technique in order to identify minor inorganic components and contaminants at the micrometric scale inside these complex matrices. On the basis of the FT-IR and micro-Raman spectra, it was possible to identify some specific old cosmetic materials and some binders used in cosmetic preparations. In particular, Raman microscopy was able to identify the presence of constituents at the trace levels or compounds having vibrations at low wavenumbers within the sample examined, that it is not possible with normal FT-IR technique. This technique can easily identify compounds like lead oxide, red lead, cinnabar, rare minerals, (etc.) that could give interesting information about the original composition of the formulate and the provenance of the raw materials.Concerning the organic materials, their possibility of identification is very different from that of inorganic ones. Some compounds were rapidly degraded, some others persisted till to present day, often unchanged (e.g. wax). Historical samples are subjected to ageing and degradation process that make difficult to recognize the raw material originally present. For understanding the possible changes undergone by materials during ageing, a specific database of spectra must be available.In the project PRIN 2007 “Colours and balms in antiquity” some thirty raw materials were chosen among oils (e.g. olive, almond, and palm oil), gums (e.g. gumarabic), animal fats and waxes, commonly employed in the ancient preparations. The raw materials and the reference formulations prepared in the laboratory, were artificially aged. The reference Raman spectra have supplied an interesting database.The use of Surface-Enhanced Raman Spectroscopy (SERS) enabled to increase Raman signal and to decrease the background fluorescence for some samples. This techniques exhibits new perspectives for the study of organic and inorganic compounds in the field of cultural heritage.

2010 - STUDY AND PREPARATION OF ANCIENT COSMETIC AND PHARMACEUTICAL FORMULATIONS IN A PRESENT PRESPECTIVE [Abstract in Atti di Convegno]
Freguglia, Giada; Baraldi, Cecilia; Gamberini, Maria Cristina; Baraldi, Pietro
abstract

The study of ancient cosmetic and pharmaceutical formulations involved the examination of several recipe books starting from the classical age till to the beginning of scientific chemistry and pharmacology. The study of the same formulation in subsequent times has shown the evolution and the adaptation to the age. Many ancient books and manuscripts reporting recipes concerning the subject in the period between 1597 and 1872 have been considered. Study of the ancient remains found inside unguentaries and of the raw materials used in the recipes has been necessary. Not all the raw materials could be bought, some needed to be prepared in the laboratory, such as the rose-water and the turnip juice, two ingredients used in the preparation of many ointments.The ointments to be prepared were chosen as a function of the remains found in the containers, but mainly on the basis of the analytical results coming out from ancient remains analysis. Those reproduced in the laboratory were many, sometimes the preparations have been made in double or triple, according to the sources of different historical periods. The total number of the ointments reproduced was fourteen.

2010 - STUDY OF ANCIENT PHOENICIAN REMAINS [Abstract in Atti di Convegno]
Freguglia, Giada; Baraldi, Cecilia; Gamberini, Maria Cristina; P., Toti; Baraldi, Pietro
abstract

The Mozia Museum conserves some funerary vessels coming from the isle’s archaic necropolis, commercial Greek, Phoenician and Etruscan amphorae, a rich collection of black varnish jars with red images of Birgi necropolis and also materials coming from Mozia Tofet and houses. Also jewels and weapons, amulets, scarabs and objects with original captions engraved are found, as well as cosmetic and surgical instruments and fragments of inscribed stones coming from the Lilibeo necropolis. From the collection of the Mozia Museum about 200 samples from the Unguentaria and Balsamaria were taken, some having large amount of residue, others a very small one. A preliminary spectroscopic analysis was carried out on these samples by using Micro-Raman and SERS techniques and the results of a first series are reported in this study. The preliminary analyses carried out with the Raman techniques have shown the presence of a variety of compounds.The white powders, among the more abundant ones, present in lead pyxes, were made of Cerussite PbCO3 coming from a complete carbonatation of hydrocerussite PbCO3*Pb(OH)2. This is compatible with the high chronology of the samples: instead, hydrocerussite has been identified in Pompeii samples. Its presence can be a clear indicator of cosmesis, since it is well known that its use in mural painting is not advisable. At the time, cerussa (lead white) was employed as a foundation. Other white substances are calcite and aragonite: the first could come from the ground where the unguentaria were found, the second one could derive from ground sea shells.Litharge, an oxide present in many containers, could derive from the alteration of cerussa, or from a proper addition, whether the yellow colour had a special meaning for the population of the site.The container NI 3149 had a gray powder composed of Carbon mixed with calcium phosphate. This could have been a bone-black or could come from cinerary urn.Among the red pigments found there are cinnabar and hematite: the latter can be found as a natural compound or as a thermodegradation product from goethite. The presence of red lead chromates crocoite and phoenicocroite, two rare minerals, in a particularly precious unguentary is a singular discovery.With the SERS technique it has been possible to record spectra relative to red dyes. However, these spectra do not correpond to compounds coming from madder, purple and kermes. Other comparisons are outstanding. In comparison with other sites, such as Pompeii, Herculaneum and Oplontis, this cosmetic powders exhibit a wider range of materials.

2010 - Spectroscopic Characterization Of Ancient Matrices [Abstract in Atti di Convegno]
Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; Baraldi, Pietro; M. P., Colombini; O., Chiantore
abstract

Since a decade our research group deals with the analysis of ancient cosmetics and drugs, starting from the Roman founds 1-3. Actually, this kind of study involves other research groups supported by a national Fund (PRIN: Colours and ointments in antiquity). Firstly the analysis protocol provides non-destructive analyses and then the more expensive and destructive analyses, such as gas-chromatography-mass spectrometry (GC-MS) methods. The samples analyzed in this study were collected from the Egyptian Museum of Turin, Italy. The discovery of the studied archaeological finds was made by Ernesto Schiaparelli (1906 until 1913) and the archaeological founds were dated from the late III millenium b.C. to early II millenium b.C. The sites of finding were in Assiut (at about 400 Km from Cairo on the bank of the Nile) and Gebelein (south of Assiut), near the southern border with Nubia. In the sarcophagus usually it is possible to find weapons, like bows and arrows, textiles and also ointments. Here the results of the vibrational spectroscopy techniques, such as Raman microscopy (laser 632 nm), FT-Raman spectroscopy (laser 1064 nm) and FT-IR/ATR with a golden gate accessory are reported. These techniques are identified as the most suitable ones for the first approach to ancient samples analysis. Raman microscopy is in fact the most suitable technique in order to identify minor inorganic components and contaminants at the micrometric scale inside these complex matrices4. This technique can easily identify compounds like lead oxide, vermillion, rare minerals, (etc.) that could give interesting informations about the provenance of the raw materials and the original composition of the formulate. In the present study some data are reported concerning the composition of five ancient Egyptian samples. It can be observed that Titanite is present, a mineral possibly coming from mines in Southern Egypt5.Concerning to organic materials, their possibility of identification, is very different from that of inorganic ones. Some compounds were rapidly degraded, some others persisted till to present day, often unchanged (e.g. wax). Historical samples give a chemical variability due to the natural products, in addiction, ageing and degradation processes make very difficult to recognize raw materials originally present. For understanding the possible changes undergone by materials in ageing, a specific database of spectra must be available. Some thirty raw materials were chosen among oils, gums, animal fats and waxes commonly employed in the ancient preparations. The reference materials were in laboratory artificially aged by heating, photo-oxidation and enzymatic degradation. Some artificial materials aged produced different alterations according to the type of ageing. The comparison to one remain sample and our database spectrum showed a correspondence with the enzymatically degraded palm oil spectrum. This indicates the importance of this database in recognising the organic materials into archaeological holders.

2009 - A scientific and historical investigation on Italian scagliola [Articolo su rivista]
Baraldi, Pietro; L., Cannalire; M. P., Colombini
abstract

Fragments from works of art made of scagliola, a material typical of northern Italy imitating marble, were investigated. Thefragments are representative of art objects that were once widespread in the region centred on the town of Carpi. Vibrationalspectroscopic techniques were applied in order to identify the pigments used to tint the gypsum paste; in particular, Ramanmicroscopy was used for the identification of pigment particles. Pyrolysis gas chromatography combined with mass spectroscopy wasused to identify binding media. Several documents were examined, both ancient and recent, preserved in local archives, describingthe pigments and dyes and the techniques used in the preparation of scagliola. The information provided in these documents wascompared to results obtained from scientific analysis.

2009 - An investigation on the palette and techniques of some high medieval codices by Raman microscopy [Articolo su rivista]
Baraldi, Pietro; Moscardi, Giulia; P., Bensi; M., Aceto; Tassi, Lorenzo
abstract

a non-desctructive investigation of inks and pigments used in late antiquity and in medievasl codices. Inks from Pompeii and codices have been compared. A change in the use of pigments is observable between the 9th and the 12th centuries in the production of the scriptorium of Nonantola.

2009 - Caratterizzazione analitica della pittura murale "Madonna con bambino, San Martino ed offerente" ritrovata nel chiostro della Chiesa di San Biagio al Carmine in Modena [Articolo su rivista]
Baraldi, Pietro; Muscio, Alberto; Zannini, Paolo
abstract

Indagini analitico-strumentali sono state effettuate su di un dipinto murale del XIV secolo ritrovato fortuitamente nel 2005 durante i lavori di restauro del chiostro della Chiesa di San Biagio in Modena. Indagini in diffrattometria di raggi X, microscopia elettronica SEM-EDS, spettroscopia Raman, riflettografia UV e termografia IR sono state effettuate per stabilire la tecnica di realizzazione, la natura dei pigmenti e dei leganti, le problematiche di risalita capillare di umidità e per guidare i lavori di consolidamento e restauro.

2009 - Materiali e tecniche della pittura romana dei primi secoli in Italia [Relazione in Atti di Convegno]
Baraldi, Pietro
abstract

E' stato trattato un panorama delle tecniche e dei materiali impiegati nella pittura murale dei primi secolo in area Vesuviana. Emerge un quadro in certo senso uniforme, ma complesso, con alcune innovazioni nei materiali e nelle tecniche applicate.

2009 - Una procedura integrata per l'intervento sui materiali lapidei del recinto del Pontile del Duomo di Modena [Relazione in Atti di Convegno]
Baraldi, Pietro; P., Bensi; C., Bertorelli; D., Ferriani
abstract

Sono state considerate le pareti lapidee e i leoni del Pontile del Duomo di Modena. La diagnostica ha consentito di rilevare le parti improprie aggiunte durante le fasi di ricomposizione del monumenro. Il restauro ha riprinstinato la cromia dei lapidei

2008 - AN INTEGRATED ANALYTICAL APPROACH FOR CHARACTERIZING AN ORGANIC RESIDUE FROM AN ARCHAEOLOGICAL GLASS BOTTLE RECOVERED IN POMPEII (NAPLES, ITALY) [Articolo su rivista]
F., Modugno; E., Ribechini; Baraldi, Cecilia; Baraldi, Pietro; M. P., Colombini
abstract

Within the framework of an Italian research project aimed at studying organic residues found in archaeological objects from the Roman period, the chemical composition of the contents of several glass vessels recovered from archaeological sites from the Vesuvian area (Naples, Italy) was investigated.In particular, this paper deals with the study of an organic material found in a glass bottle from the archaeological site of Pompeii using a multi-analytical approach, including FT-IR, direct exposure mass spectrometry (DE-MS) and GC–MS techniques.The overall results suggest the occurrence of a lipid material of vegetable origin. The hypothesis that the native lipid material had been subjected to a chemical transformation procedure before being used is presented and discussed.

2008 - Analisi di vetri: alcuni risultati preliminari [Capitolo/Saggio]
Baraldi, Pietro; C., Giardino; Moscardi, Giulia; G., Trojsi
abstract

si discutono le analisi di alcuni frammenti vitrei rinvenuti in area capitolina e risalenti al periodo imperiale

2008 - Codici Miniati: incontro tra arte e scienzaParma 13 giugno 2008, Palazzo della Pilotta [Esposizione]
Baraldi, Pietro; D., Bersani; M., Aceto; G., Zanichelli; S., Scipioni
abstract

La giornata è stata dedicata allo Studio di codici miniati delle collezioni italiane, con particolare riguardo alle metodologie scientifiche di indagine. Sono presentate relazioni sulla classidicazione, identificazione di provenienza e di scrittorio, studio delle tecniche pittoriche e dei materiali impiegati per l'esecuzione delle miniature. Alcune relazioini riguardavano le ricette per la preparazione di colori, inchiostri, vernici, vetri.

2008 - Far infrared spectroscopy analysis of inorganic pigments [Articolo su rivista]
E., Kendix; G., Moscardi; R., Mazzeo; Baraldi, Pietro; S., Prati; E., Joseph; S., Capelli
abstract

Far IR and Raman spectra of the same pigment products are compared and the possibility of identifying some pigments are discussed.

2008 - I Taccuini dei Piranesi alla Biblioteca Estense Universitaria di Modena: studio no distruttivo dei materiali e delle tecniche e ipotesi per la conservazione [Relazione in Atti di Convegno]
Baraldi, Pietro; P., Bensi; A., Andreotti; P., di Pietro; Moscardi, Giulia; M., Ricci
abstract

Sono state analizzate molte carte dei due codici dei Piranesi conservati alla Estense Universitaria di Modena. Si sono identififati i materiali grafici e si suggeriscono ipotesi per la conservazione delle rubriche.

2008 - Indagini in microscopia Raman [Articolo su rivista]
Baraldi, Pietro
abstract

Indagine non distruttiva mediante mkicroscopia Raman sulla Bibbia di Borso d'Este. E' risultata una tavolozza quattrocentesca con dovizia di materiali.

2008 - Investigation on Palette and Techniques of Some High Middle-age Codices by Raman Microscopy [Abstract in Atti di Convegno]
Baraldi, Pietro; Moscardi, Giulia; Bensi, Paolo; Aceto, Maurizio; Tassi, Lorenzo
abstract

to be published in E-PRESERVATION SCIENCE, http//www.E-PRESERVATIONSCIENCE.ORG

2008 - Isotopic analysis of lead present in the cinnabar of Roman wall paintings from the Xth Regio "(Venetia et Histria)" by ICP-MS [Articolo su rivista]
G. A., Mazzocchin; Baraldi, Pietro; C., Barbante
abstract

some red sample containing cinnabar of Roman age have been examined by ICP-MS and differences were found among them that can be attributed to the provenance of the source materials

2008 - La diagnosticain "San Pietro in Banchi", Studi e Restauri [Capitolo/Saggio]
S., Vassallo; P., Calvini; Baraldi, Pietro; S., Sfrecola; L., Negretti; C., Carbone
abstract

sono state eseguite indagini diagnostiche non distruttive o microdistruttive per rilevare la struttura delle pitture di S. Pietro in Banchi di Genova. Si è identificata la tavolozza dei materiali pittorici, la tecnica esecutiva, la stratigrafia per la conoscenza delle fasi preparatorie.

2008 - Libro di Vari Secreti [Concordanza]
Baraldi, Cecilia; Baraldi, Pietro; F., Paccagnella
abstract

Il manoscritto cartaceo D/XI/20 a firma di Francesco Pinelli è una miscellanea di indicazioni per vari tipi di operazioni: contiene ricette tra le quali alcune sono indicate come copiate da qualche testo precedente. Le dimensioni sono di 175 x 140 mm. Pur essendo del primo Settecento, appare interessante in quanto contiene la descrizione di numerose modalità di esecuzione di dorature e argentature, di tempere di metalli, di saldature, di preparazione di smalti, specchi, colle, vernici e leghe. Sono da rilevare anche ricette per la preparazione di alcuni colori, inchiostri, sali, acquaforte. Un piccolo trattato di alchimia ad opera di un medico di nome Giovanni Filomani e inserito interamente riportando il linguaggio usuale della materia di quel tempo. Vengono ricordati tra l’altro Raimondo e Arnaldo che sono chiaramente da identificarsi in Raimondo Lullo e Arnaldo di Villanova, due celebri alchimisti. Un terzo nome riportato, Elmoncio, sembra quello di van Helmonth (1577-1644), lo scopritore dell’acido cloridrico, alchimista e medico.Numerosi simboli per gli elementi, metalli e composti sono rappresentati e riassunti in una tavola alla fine del testo che prende tre pagine successive (vedi foto sotto). Vengono citati anche tre termini di origine alchemica: devenec che può raffrontarsi al duhenec o duenech dei testi alchemici (G. Testi, Dizionario di Alchimia e di Chimica Antiquaria, Ed. Mediterranee Roma 1980), azoqueh, mercurio e alchaesth, preparato a base di mercurio.

2008 - MicroRaman and infrared spectroscopic characterization of ancient cosmetics [Articolo su rivista]
Gamberini, Maria Cristina; Baraldi, Cecilia; Palazzoli, Federica; E., Ribechini; Baraldi, Pietro
abstract

By FT-IR and microRaman spectrometry a large number of black to gray powders have been analysed. The studied remains were found inside Pompeiian unguentaries situated in depository of ‘‘Casa Bacco’’. By the analytical results it has been possible to understand the different nature and composition of the materials employed in preparation of ancient cosmetic powders. Dark black powders were essentially composed of amorphous carbon probably due to the carbonisation of vegetal or animal tissues. By using different starting materials or by adding different powders to the black carbon other hues could be also obtained. Particularly, this study enabled to gain a complete and unambiguous composition characterization of these old cosmetics.

2008 - Raman characterisation of painted mortar in Republican Roman mosaics [Articolo su rivista]
C., Boschetti; Corradi, Anna; Baraldi, Pietro
abstract

some Roman age mosaics reveal the presenco of some mortar. Its composition determined bu Raman spectroscopy shows that pigments like cinnabar and Egyptian blue were used

2008 - Raman spectroscopy in art and archaeology [Relazione in Atti di Convegno]
Baraldi, Pietro; A., Tinti
abstract

...

2007 - A Raman study of white cosmetics from the classic world [Abstract in Atti di Convegno]
Gamberini, Maria Cristina; Baraldi, Cecilia; Palazzoli, Federica; P., Walther; Baraldi, Pietro
abstract

Some samples coming from different regions of the ancient Mediterranean World have been studied by Raman microscopy. The powders were apparently white cosmetics used in female contexts. A detailed analysis of their FT-IR and Raman spectra revealed that many compounds were present.Fluorite, apatite, sodium nitrate; pyrolusite, lead white, quartz, indigo, black cuprite, gypsum, goethite, have been identified. The presence of so many different and coloured compounds can help in the description of the preparation method used at the time by the artisans and to understand the changes intervened due to chemical alterations and degradation in the course of time. Perhaps different technologies to obtain white cosmetics were used, depending on local availability of materials and social levels of buyers. Traces of binders are sometimes detectable by infrared spectroscopy.

2007 - A micro-Raman archaeometric approach to Roman wall paintings [Articolo su rivista]
Baraldi, Pietro; Baraldi, Cecilia; R., Curina; Tassi, Lorenzo; Zannini, Paolo
abstract

Infrared and Raman spectra have been recorded on the surface of plasters from Regium Lepidi (Reggio Emilia, Italy). A palette has been identified, that can be compared with the ones from the nearby towns of the Roman Empire, but some peculiarities can be outlined. Some of the pigments could come from the territory, even though the techniques could be ascribed to those usually present in the 1st century a.c.

2007 - Black eyeliners in ancient Rome: the case of Pompeii [Abstract in Atti di Convegno]
Gamberini, Maria Cristina; Baraldi, Cecilia; Palazzoli, Federica; E., Ribechini; Baraldi, Pietro; P., Walter
abstract

Many of the ancient black eye paints, the kohls, consisted of galena, stibine or antimony sulfide, cerussite and in addition laurionite and phosgenite as reported by other authors. The Roman civilization made of their own this type of Egyptian cosmetic, moreover the literature reports also the use of the simplest and cheapest fuligo (black smoke) used to mark the eyebrows and the contour of the eyelashes. A large number of black-to-grey powders found inside Pompeiian unguentaries have been analysed by infrared spectrometry and Raman microscopy. The analyses show that deep black powders are essentially amorphous carbon that can derive from the carbonisation of vegetal or, frequently, animal tissues. In fact, carbon is found to be associated with apatite, whose presence could be attributed to the carbonisation of animal bones in a controlled atmosphere. Concerning the gray powders it is also to underline the rare occurrence of some particular materials that have been detected in painting materials (“Casa dei Casti Amanti” and the “Officina pigmentaria”); among them it is to recall jarosite, a yellow basic iron sulphate already identified in Egyptian paintings.Other interesting findings are anglesite and epsomite, not ascribable to the existence on the site of minerals of this kind: they can be interpreted as degradation products of other materials, such as magnesite, dolomite and cerussa, in the presence of sulfur dioxide from the surges or from the modern acid rains.The rare occurrence of minium could be bound to the use as a pinkish material for fards or to a degradation due to heating of cerussa during the violent surges of the 79 a.C. The presence of the iron classes of compounds (hematite, goethite, lepidocrocite and magnetite) could derive in some cases from a proper addition of an ochre, in order to obtain a special nuance of fard. The occurrence of aragonite and dolomite is parallel to the analogous findings among the painting materials, whereas cerussite comes from a carbonatation of hydrocerussite, the proper component of cerussa, the preeminent ancient white cosmetic used as foundation cream.

2007 - Development of Complementary Microscopic Techniques in the Analisis of Cultural Heritage [Articolo su rivista]
Baraldi, Pietro; F., Paccagnella; Zannini, Paolo
abstract

Development of Complementary Microscopic Techniques in the Analisis of Cultural Heritage

2007 - I materiali pittoriciinLa Cappella Contrari nella Rocca di Vignola [Capitolo/Saggio]
Baraldi, Pietro; P., Bensi
abstract

Sono stati analizzati i pigmenti, le tecniche esecutive e lo stato di alterazione dei pigmenti impiegati per l'esecuzione degli affreschi di anonimo della Cappella Contrari. Si evidenzia un'ampia tavolozza, contenente pigmenti di prestigio, come l'oltremare, e altri che normalmente non sono idonei per la pittura murale. Segni di alterazione appaiono per alcuni pigmenti dovuti all'ambiente.

2007 - IV International Conference on the Application of Raman Spectroscopy in Art and ArchaeologyModena, Palazzo dell'Accademia, 5-8/9/2007 [Esposizione]
Baraldi, Pietro
abstract

Il Convegno internazionale è dedicato allo studio mediante la spettroscopia Raman di reperti artistici e archeologici in maniera non distruttiva, ai fini conservativi e per il restauro. La presenza di scienziati da tutto il mondo garantisce lo scambio di esperienze e la conoscenza delle ultime ricerche nel campo della diagnostica per i Beni Culturali.

2007 - Il Libellus di Chicago [Recensione in Rivista]
Baraldi, Pietro
abstract

2007 - Indagine su alcuni frammenti di pergamenacei da rilegature: materiali, tecniche, testi, problemi di recupero [Relazione in Atti di Convegno]
Baraldi, Pietro; Moscardi, Giulia; M., Ricci; P., di Pietro
abstract

Frammenti pergamenacei risalenti al tardo XIII sec. recuperate da imbottiture di coperte di libri a stampa sono stati recuperati e analizzati. Sono risultati presenti importanti pigmenti dell'epoca e in particolare la purpurina, di rara attestazione.

2007 - Indagini non distruttive sui materiali e le tecniche esecutive del breviario di Ercole d'Este [Relazione in Atti di Convegno]
Baraldi, Pietro; P., Bensi; P., di Pietro; M., Ricci
abstract

Sono state applicate solo metodologie non invasive per le in dagini sui materiali pertinenti il breviario di Ercole d'Este. Si è evidenziata la tavolozza dei pigmenti, che risulta meno estesa di quella della Bibbia di Borso. E' stata sviluppata una metodologia non distruttiva di recupero di microframmenti spontaneamente staccati dalle superfici.

2007 - La tavolozza dei pigmenti nelle pitture dell'Insula del Centenario [Capitolo/Saggio]
Baraldi, Pietro; Bonazzi, A; Fagnano, C.
abstract

Vengono descritti i più importanti ritrovamenti di pigmenti dell'Insula del Centenario, le loro alterazioni, l'effetto del fuoco, le tecniche impiegate nella pittura murale. Si rilevano alterazioni cromatiche e la formazione di nuovi composti. Vengono discusse le conoscenze cromatiche degli antichi artigiani e la presenza di tracce di sostanze organiche

2007 - Preparazioni alimentari tratte da un antico manoscritto [Articolo su rivista]
Baroni, Roberta; Sgarbi, Elisabetta; Baraldi, Pietro
abstract

Questo manoscritto cartaceo, inedito, conservato presso la Biblioteca Estense Universitaria fa parte della collezione Campori ed ha per titolo "Il libro è composto e raccolto da Gio(van)ni Villani c(irca) nel 1300". Il manoscritto contiene una miscellanea di più di 1000 ricette estremamente varie per tipologia, a volte molto fantasiose o con riferimenti a pratiche magiche e alchemiche.Sono state qui enucleate alcune ricette riguardanti soprattutto le modalità di conservazione dei cibi che prevedevano l'uso di zucchero, miele e spezie.

2007 - identificazione delle sostanze organiche nelle pitture murali dell'Insula del Centenario [Capitolo/Saggio]
Baraldi, Pietro; A., Bonazzi; A., Casoli; E., Mastrobattista; C., Violante
abstract

sono stati analizzati con varie tecniche analitiche e spettroscopiche i campioni prelevati sulle pareti dell?Insula del Centenario per identificare le tracce di leganti differenti dalla calcite dell'affresco. I risultati mostrano solo tracce di leganti.

2006 - Alterazioni delle materie coloranti nelle pitture murali prodotte dalle alte temperature: fonti storiche ed indagini scientifiche [Relazione in Atti di Convegno]
Baraldi, Pietro; Bensi, P.
abstract

Vengono riportati i risultati delle ricerche sull'effetto del fuoco sulle pitture murali. Vengono esaminati molti casi di pigmenti e coloranti e il loro comportamento al riscaldamento.

2006 - Analisi del contenuto di alcuni Unguentari Pompeiani [Articolo su rivista]
Baraldi, Pietro; C., Fagnano; Baraldi, Cecilia; Gamberini, Maria Cristina
abstract

Una ricerca svolta sul contenuto di un gruppo di balsamari di Pompei ha portato ad evidenziare una serie di composti organici di varia natura. Mediante tecniche di spettroscopia infrarossa, microRaman e di gascromatografia applicata alla spettrometria di massa si sono identificati vari componenti noti e alcuni finora incogniti. I composti inorganici identificati possono fornire indicazioni sulla provenienza di materiali o preferenze locali per prodotti disponibili, le sostanze organiche, le tecnologie di preparazione del cosmetico. In generale, dall'esame dei dati qui riportati, risulta una cosmesi di tipo economico, rispetto a siti contemporanei posti in zone limitrofe. Non mancano però alcune singolarità, come l'impiego dell' huntite e della jarosite, materiali di probabile provenienza egiziana.

2006 - Analytical characterization of Roman plasters of the 'Domus Farini' in Modena [Articolo su rivista]
Baraldi, Pietro; Bonazzi, A; Giordani, N; Paccagnella, Francesca; Zannini, Paolo
abstract

The paper refers to the analytical characterization of Roman painted plasters dating back to the second century AD. The following techniques were used: optical microscopy (OM), scanning electron microscopy (SEM-EDS), micro-Raman and Fourier transform infrared spectroscopies (mu-Raman and FT-IR), X-ray diffraction (XRPD), colorimetry and thermal analyses (TG/DTA). The investigation analysed the chemical composition and structure of the plasters, the chemical composition of the pigment layers, the use of binders and any chemical alteration of pigments as well as deterioration of the samples. Stratigraphic analysis of plasters allowed identification of their individual components, which proved helpful in finding out more about the mural painting technique employed.

2006 - Aragonite in Roman wall paintings of the VIIIa Regio, Aemilia, and Xa Regio, Venetia et Histria [Articolo su rivista]
Ga, Mazzocchin; Ef, Orsega; Baraldi, Pietro; Zannini, Paolo
abstract

In the Roman wall paintings different white colours were used, named Paraetonium, Melinum, Anularia, Eretria, Argentaria, etc. FTIR, Raman spectroscopy and X-Ray diffraction were applied to study different white pigments, such as calcite, aragonite, dolomite and huntite, white carbonates present in archaeological findings from roman walls in the Mediterranean region. This study showed that it is possible to distinguish and identify these components in white colours. About 450 samples of Roman wall paintings were analysed and it was observed that often aragonite is associated to precious coloured pigments. On the basis of the obtained results some considerations about the period in which the different kinds of white pigments were used are proposed.

2006 - Gli unguentari pompeiani e il loro contenuto -prima parte [Articolo su rivista]
Baraldi, Cecilia; Gamberini, Maria Cristina; Baraldi, Pietro; Mp, Colombini; E., Ribechini
abstract

Il gruppo di studio sulla cosmesi antica e moderna, costituito da ricercatori delle Università di Modena e Reggio Emilia e di Pisa, ha analizzato il contenuto di un gruppo di balsamari di area Campana. Mediante tecniche di spettroscopia infrarossa, microscopia Raman e di gascromatografia abbinata alla spettrometria di massa è stato possibile identificare componenti di varia natura tra i quali alcuni finora sconosciuti in questo campo. Una serie di composti inorganicipresenti fanno pensare alle preferenze delle matrone romane, altri alle vie commerciali diapprovvigionamento, altri ancora alle tecnologie per l’elaborazione del cosmetico. In generale, è possibile rilevare l’impiego di materiali di varia origine, di larga diffusione e di talora complessa preparazione. Non mancano però alcune singolarità,che si riferiscono all’uso di prodotti e tonalità particolari, di probabile provenienza extraitalica.

2006 - Gli unguentari pompeiani e il loro contenuto -seconda parte [Articolo su rivista]
Baraldi, Cecilia; Gamberini, Maria Cristina; Baraldi, Pietro; Mp, Colombini; E., Ribechini
abstract

Il gruppo di studio sulla cosmesi antica e moderna, costituito da ricercatori delle Università di Modena e Reggio Emilia e di Pisa, ha analizzato il contenuto di un gruppo di balsamari di area Campana. Mediante tecniche di spettroscopia infrarossa, microscopia Raman e di gascromatografia abbinata alla spettrometria di massa è stato possibile identificare componenti di varia natura tra i quali alcuni finora sconosciuti in questo campo. Una serie di composti inorganici presenti fanno pensare alle preferenze delle matrone romane, altri alle vie commerciali di approvvigionamento, altri ancora alle tecnologie per l’elaborazione del cosmetico. In generale, è possibile rilevare l’impiego di materiali di varia origine, di larga diffusione e di talora complessa preparazione. Non mancano però alcune singolarità, che si riferiscono all’uso di prodotti e tonalità particolari, di probabile provenienza extraitalica.

2006 - Indagini chimiche su resti antropici dalla Necropoli di casinalbo (Modena): aspetti paleonutrizionali [Articolo su rivista]
Baraldi, Pietro; A., Cardarelli; F., Scacchetti
abstract

Sono stati analizzati ossa incinerate dalla necropoli di Casinalbo. I microelementi presenti mostrano correlazioni con il sesso e la paleobotanica del territorio

2006 - Investigation on a Roman copper alloy artefact from Pompeii (Italy) [Articolo su rivista]
Baraldi, Pietro; Baraldi, Cecilia; Ferrari, Giorgia; Foca, Giorgia; Marchetti, Andrea; Tassi, Lorenzo
abstract

A selection of samples, obtained from a particular copper-alloy domestic artefact of Roman style from Pompeii, has been analysed by using different techniques (IR, Raman, SEM-EDX, FAAS), in order to investigate the chemical nature and composition of the metals utilised for such manufacturing pieces. The surface analysis of the bright red metallic microfragments conducted by different analytical techniques, emphasises the presence of pure unalloyed copper and confirms the absence of other metallic species on the upper layers. On the contrary, the mapping analysis of the section of the laminar metal of the investigated sample shows a consistent enrichment in tin content. Finally, destructive analysis by FAAS confirms that the artefact looks like a bronze metal alloy, with a medium Sn content of about 6.5%

2006 - Le piante tintorie nella storia dell'uomo [Relazione in Atti di Convegno]
Baroni, Roberta; Sgarbi, Elisabetta; Baraldi, Pietro
abstract

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2006 - Raman study of a 'Tabula Colorum Physiologica' in a 1686 printed journal [Articolo su rivista]
Baraldi, Pietro; Fagnano, C; Bensi, P.
abstract

A Table painted in 1686 with spots of colors on paper was investigated. It appears that the Table is composed of pure pigments, and their mixtures in a 1:1 proportion. However, there were some problems when analyzing the pure compounds and the mixtures, due to the interaction of some pigments, as degradation had occurred. Possible explanations of the nature of the compound are analyzed and discussed. Copyright (C) 2006 John Wiley & Sons, Ltd.

2006 - Scientific investigations of the Tokhung-Ri tomb mural paintings (408 AD) of the Koguryo era, Democratic People's Republic of Korea [Articolo su rivista]
Mazzeo, R; Joseph, E; Minguzzi, V; Grillini, G; Baraldi, Pietro; Prandstraller, D.
abstract

In the framework of the UNESCO workshops on the Conservation and Preservation of the Koguryo mural paintings, which were held in Pyongyang in 2004 and 2005, paint samples were collected from the Tokhung-Ri tomb located in suburban Pyongyang and analyzed by optical, polarized and FTIR microscopy, scanning electron microscopy coupled with energy-dispersive X-ray analysis (SEM-EDX), X-ray diffraction (XRD) as well as Raman spectroscopy, in order to characterize the composition of pigments, the execution technique adopted and the state of conservation of the murals. The first scientific results seem to confirm the suggestion of local conservators about the adoption of a fresco technique, even though it is not yet clear whether this was intentionally achieved by the North Korean painters. As regards this, analyses of more samples as well as confirmations from a survey of the historical literature are needed. Copyright (C) 2006 John Wiley & Sons, Ltd.

2006 - VIBRATIONAL SPECTRA OF SOME PIGMENTS FROM POMPEII [Articolo su rivista]
Baraldi, Pietro; C., Fagnano; A., LOSCHI GHITTONI; Tassi, Lorenzo; Zannini, Paolo
abstract

Some powder pigments found in bowls in the ruins of Pompeii were investigated. Their chemical and mineralogical compositions were obtained by using FT-IR spectroscopy, Raman microscopy, X-Ray diffraction and DSC. With FTIR spectroscopy and X-Ray diffraction the main components were ascertained and the pigments attributed to Plinius' names as far as possible. With Raman microscopy a detailed examination of minor components was carried out, thereby enabling some considerations on the pigment preparation techniques to be traced. Two unusual pigments were identified, namely jarosite and buntite, already detected in wall painting and ceramics elsewhere.

2005 - A MicroRaman study of some paintings from Tassili (Sahara) [Relazione in Atti di Convegno]
Baraldi, Pietro; Sighinolfi, G. P.
abstract

Some investigations on the composition of the powders found in the Egypt desert and used as pigments

2005 - A scientific and Archivistic investigation on Italian scagliola altar frontals [Relazione in Atti di Convegno]
Baraldi, Pietro; Cannalire, L.; Colombini, M. P.
abstract

analyses of some pigments found in fragments, many dyes and pigments have been identified and the technique clarified

2005 - Aragonite in Roman wall paintings of the VIII Regio, Aemilia and X Regio, Venetia et Histria [Relazione in Atti di Convegno]
Mazzocchin, G. A.; Baraldi, Pietro; Zannini, P.
abstract

Aragonite was found in white stripes painted on mural paintings of the Roman period. This is so in VIII and X Regio of Italy

2005 - Caratterizzazione morfo-anatomica e analisi chimiche di piante tintorie [Relazione in Atti di Convegno]
Baroni, Roberta; Sgarbi, Elisabetta; Baraldi, Pietro
abstract

.

2005 - Chemya Colorum Bibliae: La Bibbia di Borso d'Este indagata con nuove metodologie scientificheModena, Palazzo Ducale, 18 novembre 2005 [Esposizione]
Baraldi, Pietro; Sola, Marco; P., Di Pietro Lombardi
abstract

Una giornata di Studio sulle metodologie non distruttive per lo studio di opere preziose come i codici miniati presenti nelle nostre biblioteche. Sono state presentate relazioni sull'iconologia animale e vegetale, sulla storia della miniatura e dei materiali per l'arte, sull'analisi chimica non distruttiva dei materiali impiegati nell'esecuzione delle miniature della Bibbia più bella del mondo.

2005 - Conoscenza e proposta di Conservazione delle superfici murali decorate interne ed esterne di Villa Ansaldo in località Allou, Recco (GE) [Relazione in Atti di Convegno]
Baraldi, Pietro; Bensi, P.; Bocci, V.; Campodonico, A.; Gardella, C.; Jacopino, E.; Magnani, L. G.; Montiani, M. R.; Pittaluga, D.; Ricci, R.; Simonetti, F.
abstract

indagini archeometriche sui materiali della pittura murale di villa Ansaldo

2005 - Diagnostics on Scagliola Altar Frontals from the Area of Modena (Italy) [Abstract in Atti di Convegno]
Baraldi, Pietro; M. P., Colombini; Baraldi, Cecilia
abstract

Traditionally, the town of Carpi is considered the home of scagliola. The old attestations of scagliola masters starting from the 16th century and the presence on the spot of hundreds of altar frontals and other lithurgical and domestic objects testify this tradition, besides the presence of a Municipal Museum of Scagliola in the Castle of Pio family. The art of scagliola developed from the simple white-and-black artifacts to the polychrome altar frontals and tables whit elaborate workmanship, and spread beyond the Modena area, as it is testified by both the works in adjacet provinces and regions, and the propagation of schools whit the transfer of masters outside the Emilia region. Recent studies carryed out by means of non destructive techniques have put in evidence the correspondences among the techniques identified for the preparation of the artifacts and the literature sources. Some more manuscripts preserved in the Archivio Storico of Carpi and amounting to the age of the ruling by the Pio family, indicate a series of materials for preparing the support and the coloured dough. We report the results of a research carried out by means of different analytical methods for the identification of the materials employed in the execution of these artefacts. The research was carried out in order to identify some more correspondences between measurements and old sources and to ascertain possible differences among ateliers or schools. Whereas Raman microscopy enabled to find out the pigments and dyes used for the scagliola, Gas-Chromatografy coupled whit Mass Spectrometry gave micro-distructively information on the nature of binders and of the products for the surface finish. The application of these techniques to the study of some altar frontal samples from the area of Carpi, Modena and Reggio has led to the identification of pigments such as minium, vermillon, lazurite, orpiment, red and yellow ochres, lead white and lampblack, and of dyes such as indigo, saffron, and of a red dye with a clear spectrum, but unknown nature. The binder corresponds to an animal glue that is locally known as “colla garavella” or “german glue”, the preparation of which is reported in many medieval and Renaissance recipe-books.

2005 - Libro/per secreti varij/ 1793 - Prodotti minerali, vegetali e animali per l'arte, il restauro e la scagliola. [Monografia/Trattato scientifico]
Baraldi, Pietro; Baroni, Roberta; Sgarbi, Elisabetta
abstract

Il manoscritto, tratto dai "secreti" di Antonio Donelli e scritto da Carlo Caleffi, è conservato presso l'Archivio Capitolare di Modena. Riporta una raccolta di ricette di vari argomenti: metodiche per la purificazione di pigmenti, ricette per miniare, per tingere tessuti, per stendere vernici sui dipinti. Le materie coloranti hanno un'importanza significativa nel testo e spesso si tratta di sostenze di origine vegetale. Una parte considerevole è dedicata alla preparazione delle vernici e alla descrizione della procedura per fare "lavori di scagliola" e per la sua "ombreggiatura". Il testo è stato trascritto, commentato e corredato di note esplicative sui prodotti vegetali e minerali e sul loro utilizzo.

2005 - Materiali pittorici e pigmenti [Relazione in Atti di Convegno]
Baraldi, Pietro; Bonazzi, A.; Fagnano, C.; Tassi, Lorenzo; Zannini, Paolo
abstract

Le pitture di Pompei e le indagini scientifiche sui materiali e le tecniche, con i rinvenimenti più comuni e più insoliti

2005 - Osservazioni in Margine ai Pigmenti dei Romani [Articolo su rivista]
C., Seccaroni; Baraldi, Pietro
abstract

viene esaminata una serie di pigmenti identificati nella pittura murale romane e si prospetta lo studio di altri materiali di rara attestazione

2005 - Regole di miscelazione di pigmenti e coloranti in età Romana [Relazione in Atti di Convegno]
Baraldi, Pietro; Fagnano, C.
abstract

miscele e sovrapposizione di colori impiegate nel passato per l'esecuzione di pitture murali vengono discusse e legate alla conoscenza moderna sul colore

2005 - Ricetta per compor il vin medicato [Articolo su rivista]
R., Baroni Fornasiero; Sgarbi, Elisabetta; Baraldi, Pietro
abstract

si esaminano alcuni testi antichi per la decorazione e uso alimentare di estratti colorati da piante in epoca rinascimentale

2005 - Virtù d'alcune Erbe d'Horti - Archivio Pio di Savoia [Articolo su rivista]
Baroni, Roberta; Baraldi, Pietro; Sgarbi, Elisabetta
abstract

Il Manoscritto "Virtù d'alcune erbe d'Horti" è contenuto in un quadernetto collocato presso l'Archivio Storico di Carpi. Vengono qui presentate note di commento alle ricette riportate nella prima parte del manoscritto, che trattano delle caratteristiche terapeutiche di alcune piante orticole. Nelle note vengono riportati l'inquadramento sistematico, le caratteristiche etnobotaniche e i principi attivi presenti nelle specie utilizzate.

2005 - studio in spettrometria micro Raman della policromia di terrecotte campane dei musei di Capua e S. Maria Capua Vetere [Relazione in Atti di Convegno]
Baraldi, Pietro; P., Bensi; C., Fagnano; C., Rescigno; V., Sampaolo
abstract

Le analisi di una serie di frammenti di antefisse fittili di provenienza campana mediante indagini in spettrometria micro Raman ha mostrato la presenza di interessantyi pigmenti e coloranti. Mentre sono presenti pigmenti usuali, insoliti risultano alcuni coloranti come il giallo di zafferano e l'indaco, sulla cui persistenza esistono pochi dati.

2004 - Antichi coloranti alimentari: uso di estratti vegetali e polveri minerali per decorare [Articolo su rivista]
Baroni, Roberta; Sgarbi, Elisabetta; Baraldi, Pietro
abstract

Questo lavoro riguarda alcune ricette tratte da un lungo manoscritto anonimo dal titolo "Ricettario di cose mangerecce", datato tra i secoli XVI e XVII, collocato presso la Biblioteca Estense Universitaria di Modena. La parte enucleata consite nella descrizione di come approntare dolci per decorare le tavole nobiliari dell'epoca. Le ricette sono state trascritte , liberamente tradotte e corredate di note riguardanti gli estratti vegetali, le polveri minerali e alcune voci di significato incerto.

2004 - Characterization of mural painting pigments from the Thubchen Lakhang temple in Lo Manthang, Nepal [Articolo su rivista]
Mazzeo, R; Baraldi, Pietro; Lujan, R; Fagnano, C.
abstract

Very few publications are available on materials and techniques used by ancient Nepalese artists to paint mural decorations. This paper presents the first results of scientific examination aimed at characterizing the composition of the pigments present in paint samples collected from the south and east wall decorations of the 15th century Thubchen Lakhang monastery located in Lo Manthang, upper Mustang, Nepal. The temple was built in rammed mud and wood by order of King bKra.shis.mgon in 1470 and completed by 1472. Cross-sections of the 14 collected samples were prepared and the pigment composition was analysed stratigraphically. The same samples were also investigated, without preparation, for surface pigment characterization. The first results of the micro-Raman analyses showed that different blue pigments were used, sometimes alone, as in the case of azurite, and sometimes in combination with lazurite. The red and orange paint layers are constituted of orpiment and vermilion, both alone and in combination. A very interesting gilding technique that makes use as mordant of pararealgar with traces of orpiment and vermilion has been identified. Red ochre is present in the brown colour decorations. Malachite was used to paint the green decorations. Some samples also showed the presence of the copper sulfate hydrate brochantite, which may represent an alteration product of malachite. Further research will be needed in order to characterize the organic binding media composition that, in conjunction with these results, will guide restorers in the identification of the most appropriate restoration procedures to be adopted. Copyright

2004 - Ricerca sul contenuto dei Balsamari di Oplontis [Articolo su rivista]
Baraldi, Pietro; Baraldi, Cecilia; C., Fagnano; Ferioli, Valeria; Gamberini, Maria Cristina
abstract

Sono stati presi in considerazione i balsamari rinvenuti al momento dello scavo della villa B di Oplontis. Mediante moderne tecniche di analisicome la gascromatografia abbinata alla spettrometria di massa e la spettroscopia infrarossa sono stati identificati sia i componenti inorganici che organici. Il contenuto dei balsamari è risultato prevalentemente di origine organica e permette di ipotizzare dai residui individuati la presenza originaria di grassi e di essenze di provenienza anche extraeuropea. Questo permette da una parte di comprovare una abilità locale per l'estrazione per l'estrazione e la lavorazione di prodotti cosmetici e dall'altra l'esistenza di vie commerciali dall'Estremo Oriente nel I sec. d.C. Alcune delle presenze accertate sono indicative dell'elevato livello di vita degli abitanti della domus.

2003 - "Scienze e Archeologia" Le Scienze Chimico FisichePompei 19 Novembre 2003 [Esposizione]
A., Ciarallo; Baraldi, Pietro
abstract

Un libro edito a margine della giornata di Studi a Pompei sulle ricerche scientifiche di tipo chimico fisico: indagini sulle pitture murali, sui cosmetici e profumi antichi, sulla natura dei vetri, della composizione dei recipienti in rame e bronzo, sulla fabbricazione dei pigmenti.

2003 - Caratterizzazione chimica di un reperto bronzeo Romano [Relazione in Atti di Convegno]
Baraldi, Pietro; Tassi, Lorenzo; A., Varone
abstract

Ed fotolito Sicignano, Pompei

2003 - Characterization of mural painting pigments from the Thubchen Lhakhang temple in Lo Manthang, Nepal [Relazione in Atti di Convegno]
Mazzeo, R.; Baraldi, Pietro; Lujan, R.; Fagnano, C.
abstract

Ed P. Vandenabeele, L. Moens Ghent (Belgium)

2003 - La tavolozza dei Colori negli affreschi di Pompei [Capitolo/Saggio]
Fagnano, C.; Tinti, A.; Taddei, P.; Baraldi, Pietro
abstract

Sono riportati numerosi spettri raman registrati su campioni originari di Pompei. I pigmenti risultano talora puri, talora sono miscele con due o più componenti. Molti precursori vengono identificati nelle polveri delle ciotole e alcuni prodotti di degrado. Si dà una valutazione della frequenza di attestazione.

2003 - Le Pilae di Vitruvio e gli intonaci bolognesi di età imperiale [Relazione in Atti di Convegno]
Baraldi, Pietro; Pradelli, M.; Zannini, P.
abstract

Indagini sulla composizione di alcune palline di blu egiziano rinvenute nella città di Bologna

2003 - Racolta di varj Secreti si per far colori da miniare che di vernici di ogni sorte Et altri per varij mali, provati effica(ci)ssimi, come ancora, alcuni attenenti all’Arte degl’Orefici. [Monografia/Trattato scientifico]
Baraldi, Pietro; Baroni, Roberta; Sgarbi, Elisabetta
abstract

Il manoscritto, anonimo e risalente presumibilmente alla fine del XVII secolo, è collocato presso la Biblioteca di Discipline storiche dell'Università di Bologna. Riporta più di un centinaio di ricette riguardanti vari argomenti, tra i quali la preparazione di pigmenti per miniare, di inchiostri, di cere colorate e di vernici. Il manoscritto è stato trascritto, commentato e corredato di note riguardanti i prodotti di origine vegetale e minerale impiegati nelle ricette.

2002 - Antico ricettario modenese di mano femminile per miniare e dorare. Note sulle specie vegetali e sui composti chimici menzionati [Articolo su rivista]
Baraldi, Pietro; Baroni, Roberta; Baraldi, Cecilia; Sgarbi, Elisabetta
abstract

L'antico manoscritto, qui trascritto e commentato, consiste in una raccolta di Ricette per miniare, per applicare l'oro, per stemperare il cinabro, per ottenere l'acqua verde e il colore azzurro, per brunire ecc... e fa parte del vasto lascito del conte modenense G. Campori destinato alla Biblioteca Estense Universitaria. Nel breve manuale sono riportati composti diversi, minerali, succhi estratti da piante, terre di origine non italiana, utilizzati in tecniche particolari di pittura, scrittura con l'oro e soprattutto di brunitura.

2002 - Caratterizzazione dei contenuti cosmetici nei balsamari di Oplontis [Abstract in Atti di Convegno]
Baraldi, Pietro; Ferioli, Valeria; Benedetti, Adriano; Baraldi, Cecilia; Zannini, Paolo
abstract

Lo scavo, condotto secondo metodologie scientifiche avanzate, del sito di Oplontis rappresenta per l’archeologo e l’archeometra una possibilità nuova di indagine e comprensione di una somma di situazioni importanti. Una di queste è rappresentata certamente dal rinvenimento di 17 balsamari pressoché intatti contenenti una quantità considerevole di residuo. La collaborazione con la Soprintendenza Archeologica di Pompei ci ha consentito di accedere ai reperti e di eseguire per la prima volta prelievi di campioni da sottoporre all’analisi.I campioni si presentavano più o meno scuri, ma non contenevano pigmenti neri, bianchi o di altro colore chiaramente osservabili. Alcuni presentano un odore caratteristico, simile a quello della colofonia. Per i campioni è stata seguita una doppia strada di indagine: la spettroscopia FT-IR e la gascromatografia GC-MS su estratti ottenuti con le metodiche internazionali. Le analisi in GC-MS hanno mostrato che gli estratti metanolici presentano una serie di componenti che vanno dal patchoulolo ad acidi grassi liberi, ad esteri, ad idrocarburi e a terpeni classici. L’esame degli spettri IR ha evidenziato la presenza di acidi grassi liberi ed esteri e tracce di cere.La presenza del patchoulolo risulta di particolare interesse in quanto si tratta di un componente presente nell’estratto del Pogostemon cablin, una pianta originaria dell’India e dell’estremo Oriente, utilizzata anche in epoca recente per la produzione di profumi. La sua provenienza dall’area indiana consente di ipotizzare l’elevato pregio del cosmetico, che ne consentiva l’utilizzo alle classi sociali elevate quali quelle del contesto di Oplontis.

2002 - Colori e piante tintorie [Articolo su rivista]
Baroni, Roberta; Sgarbi, Elisabetta; Baraldi, Pietro
abstract

Vengono riportate le descrizioni botaniche di alcune piante molto diffuse nella Pianura Padana, utilizzate in passato come piante tintorie. Sugli estratti, ottenuti dalle parti della pianta più ricche di principi coloranti, sono state eseguite analisi spettrofotometriche.

2002 - Density, refractive index, and related properties for 2-butanone plus n-hexane binary mixtures at various temperatures [Articolo su rivista]
Baraldi, Pietro; M. G., Giorgini; M., Manfredini; D., Manzini; Marchetti, Andrea; Tassi, Lorenzo
abstract

Density refractive index n and the related properties molar volume V and molar refraction R have been investigated for 2-butanone + n-hexane liquid binary mixtures over the entire composition range and a wide range of temperatures. Some well-known relationships have been applied to study the temperature and composition dependence of the measured and derived quantities. Furthermore, the deviations of the respective excess properties V-E, n(E), and R-E have been examined, with the aim of identifying particular intermolecular interaction patterns responsible for the macroscopic behavior of these binary mixtures. The results have been interpreted on the basis of structural and geometric effects between the components.

2002 - Le ceramiche grezze nel Modenese: Studi recenti e prospettive di Ricerca [Relazione in Atti di Convegno]
Baraldi, Pietro; Corti, C.; Giordani, N.; LOSCHI GHITTONI, A.; Moze, O.; Tinti, A.
abstract

dalla composizione al riconoscimento delle tecniche impiegate nella preparazione e decorazione delle ceramiche

2002 - Mappatura e indagine sui reperti cosmetici rinvenuti a Pompei [Abstract in Atti di Convegno]
Ferioli, Valeria; Baraldi, Pietro; C., Fagnano; Gamberini, Maria Cristina; Baraldi, Cecilia
abstract

La città di Pompei rappresenta un unicum per qualità e quantità di reperti archeologici anche di tipo cosmetico. Da un’indagine condotta in archivio in collaborazione con il Laboratorio della Soprintendenza Archeologica di Pompei è emersa la presenza di un numero elevato di unguentari, balsamari e alabastra. Purtroppo le pratiche di reperimento e conservazione dei tempi passati ha eliminato il contenuto di gran parte dei contenitori considerati. In poco più di un centinaio di essi rispetto ad un totale di oltre un migliaio sono state rinvenute quantità più o meno cospicue del contenuto. Di questi è stato considerato un gruppo che presentava materiale polverulento colorato. A differenza dei balsamari di Oplontis, quelli di Pompei sono apparsi tutti di natura molto differente. Un gran numero conteneva polvere di un colore o nero vellutato o bianco candido e solo in alcuni casi si è rilevato un colore differente. Per l’identificazione della natura dei cosmetici sono state impiegate la spettroscopia FT-IR associata alla microscopia Raman e la gascromatografia abbinata alla spettrometria di massa GC-MS. Gli spettri infrarossi e Raman hanno consentito di accertare che i prodotti neri sono costituiti da carbone di probabile origine vegetale, un tipo di kohl facilmente reperibile, quelli bianchi da gesso diidrato, talora mescolato con calcite, il giallo da goethite. Non sono mancate identificazioni insolite, come ad es. cerussite, aragonite, anglesite, sulla cui origine sono possibili varie ipotesi. L’analisi degli estratti metanolici mediante GC-MS in molti casi non ha mostrato la presenza di componenti organici. Questo può indicare che venivano impiegati prevalentemente prodotti inorganici, ma anche che nei balsamari i cosmetici erano conservati allo stato di polvere e che solo al momento dell’uso una piccola quantità veniva mescolata con un legante che ne consentisse l’applicazione. La natura del contenuto dei balsamari fa propendere per un campionario di prodotti ristretto e di tipo popolare, rispetto a quelli corrispondenti di Oplontis. L’analisi della distribuzione statistica dei balsamari, anche non aventi contenuto, è risultato di interesse in quanto può, in qualche rispetto, essere collegato all’evento finale della città nel 79 d.C. e al valore e al significato attribuito ai balsamari in epoca Romana. La ricerca è stata condotta sul finanziamento CNRC00BEAC_002 Si ringrazia la Soprintendenza Archeologica di Pompei per aver reso possibile la Ricerca.

2002 - Pigments from Bowls and Walls of Pompeii [Abstract in Atti di Convegno]
Baraldi, Pietro; Fagnano, C.; Scagliarini, D.; Tinti, A.; Taddei, P.; Zannini, Paolo
abstract

analyses of some bowls from Pompeii carried out by IR and Raman spectroscopy; the results were compared with those from the wall paintings

2002 - Vibrational Spectra of some Pigments from Pompei [Relazione in Atti di Convegno]
Baraldi, Pietro; Fagnano, C.; Ghittoni, A. L.; Tassi, Lorenzo; Zannini, P.
abstract

identification of mural paintings in ancient excavations by Raman spectroscopy

2001 - Misure archeometriche su ceramiche grezze romande di area padana [Relazione in Atti di Convegno]
Baraldi, Pietro; Fagnano, C.; Giordani, N.; LOSCHI GHITTONI, A.; Moze, O.; Tinti, A.; Zannini, P.
abstract

studio dei materiali per la preparazione di impasti ceramici antichi.

2001 - On the dissociation dynamics of the benzyl chloride radical anion. An ab initio dynamic reaction coordinate analysis study [Articolo su rivista]
Fontanesi, Claudio; Baraldi, Pietro; Marcaccio, M.
abstract

The dynamics of the dissociation of the benzyl chloride radical anion to a benzyl radical and chloride anion was studied theoretically. To this end two different conformations of benzyl chloride were examined: one featuring a 90 degrees angle between the Cl-C bond and the aromatic ring (conformation S), the other with the Cl-C bond and the aromatic moiety lying coplanar (conformation E). The potential-energy (PE) surface shows the existence of a conical intersection when studied as a function of the C-Cl bond length and of the rotation angle around the C(sp(2))-C(sp(3)) bond. Information on the dynamics of this process was obtained using the dynamic reaction coordinate (DRC) algorithm for tracing reaction paths. The DRC method shows a qualitative difference in the dissociation mechanism of the two conformers. The lifetime of conformation E depends on the amount of kinetic energy assigned to the internal rotational mode motion, whereas that of conformation S does not. (C) 2001 Elsevier Science B.V. All rights reserved.

2001 - On the kinetics of chromium electrodeposition on copper electrodes [Articolo su rivista]
Baraldi, Pietro; Soragni, Ercole; Fontanesi, Claudio; V., Ganzerli
abstract

In a previous work, we observed that, during cyclic potentiodynamic curves of cathodic polarisation (from 0.00 to - 1.25 V/SCE, 5 mV s(-1)) in chromic acid solution of industrial composition, ARMCO iron undergoes a pitting corrosion, while carbon steels undergo a selective ferritic corrosion. Blisters of pure iron were also observed on ARMCO iron electrodes surface. These occurrences suggest a direct participation of the metal substrate to the overall reaction of reduction of the chromic acid to chromium metal. Therefore, the chemical nature of the electrode metal has been changed, in order to pl avc that the chromium reduction goes on through an ECE mechanism involving a fast chemical reaction between unstable intermediate chromium reduction goes and the metal substrate. Cathodic potentiodynamic polarisation curves were performed on copper electrodes and the scans were stopped at four different potentials (-0.90, - 1.00, -1.10 and -1.25 V/SCE). The copper surface undergoes a severe corrosion in all the experimental conditions. The morphology of the attack depends on the polarisation potential and on the presence of additives in solution, like iron sulphate. (C) 2001 Elsevier Science B.V. All rights reserved.

2001 - Study of the vibrational spectrum of cuprorivaite [Articolo su rivista]
Baraldi, Pietro; Bondioli, Federica; C., Fagnano; Ferrari, Anna Maria; A., Tinti; M., Vinella
abstract

In this research, after tracing a history of the pigment, the preparation and analysis of samples of Egyptian blue have been reported. The main reactions taking place during its preparation are indicated. X-ray diffractions show that, starting from mixtures of precursors with stoichiometric composition, the product is practically only cuprorivaite. The kind of flux and cristallinity of silica does not seem determining factors for the pigment formation. Infrared and Raman spectra and an assignment of the bands are reported, Impurities ascertained are discussed on the basis on the data available.

2001 - Una testimonianza di blu egiziano nella Bologna del '500 [Relazione in Atti di Convegno]
Baraldi, Pietro; Fagnano, C; Giordani, N.; Roversi, P.; Zannini, P.
abstract

Sulle pareti i una villa in restauro sono state rinvenute tracce evidenti di colore azzurro identificate come blu egiziano. Si tratta di una persistenza dell'uso del pigmento

2000 - Density and volume properties of ethane-1,2-diol + 1,2-dimethoxyethane + water ternary mixtures from -10° to 80°c [Articolo su rivista]
Baraldi, Pietro; Franchini, Giancarlo; Marchetti, Andrea; G., Sanna; Tassi, Lorenzo; Ulrici, Alessandro; G., Vaccari
abstract

Thermodynamic interactions in the ethane-1,2-diol (1) + 1,2-dimethoxyethane (2) + water (3) ternary system have been investigated in terms of the excess molar volume, derived from density measurements at 19 different temperatures from -10 degrees to 80 degrees C. Fourteen three-component mixtures have been considered, covering the entire composition range. The excess molar volumes are discussed in terms of conformational changes induced in each component by the presence of another one. The results obtained support the hypothesis of the absence of any three-component complex adducts under all experimental conditions investigated.

2000 - Qual è lo spettro vibrazionale della cuprorivaite? [Relazione in Atti di Convegno]
Baraldi, Pietro; Bondioli, F.; Fagnano, C.; Ferrari, A. M.; Tinti, A; Vinella, M.
abstract

Viene esposta la ricerca sul Blu egiziano e il suo spettro vibrazionale

2000 - Study of the effect of intermediate reactive species, adsorbed at the metallic surface/aqueous solution interface, on the chromium electrodeposition dynamics [Articolo su rivista]
Baraldi, Pietro; G., Barani; Fontanesi, Claudio; Soragni, Ercole
abstract

The chemical and physical nature of the stages preceding the massive electrochemical reduction of chromium is studied combining electrochemical, scanning electron microscopy (SEM) and vibrational spectroscopy (IR) techniques. The collected evidence indicates that the formation of intermediate species occurs in the adsorbed phase. (C) 2000 Elsevier Science Ltd. All rights reserved.

1999 - Primi risultati sui rivestimenti nelle produzioni ceramiche di età altomedievale del territorio di Mutina [Capitolo/Saggio]
Baraldi, Pietro; N., Giordani; LOSCHI GHITTONI, A; Medici, A.
abstract

Vengono analizzate alcune caratteristiche chimico fisiche e mineralogiche di ceramiche grezze della zona modenese.

1998 - Measurements of combustion enthalpy of solids by DSC [Articolo su rivista]
Baraldi, Pietro; Beltrami, C; Cassai, C; Molinari, L; Zunarelli, R.
abstract

A method is developed for the measurement of combustion enthalpy by DSC in a stream of oxygen. The relationship between the enthalpy measured and the sample mass was investigated and quantitative results were obtained. The instrument has been carefully calibrated and an allowance made for the gaseous products eluted. The results show that the DSC method is less precise than the calorimetric bomb method, although the mean values obtained by the two methods are in good agreement. (C) 1998 Elsevier Science S.A. All rights reserved.

1990 - A THERMAL STUDY ON ISOMORPHOUS METAL FORMATES [Articolo su rivista]
Baraldi, Pietro; Manfredini, Tiziano
abstract

vengono esaminate le proprietà di stabilità termica di una serie di formiati isomorfi mediante la considerazione degli spettri registrati in funzione della temperatura

1990 - Infrared Emission Spectra: a tool in research and application [Articolo su rivista]
Baraldi, Pietro
abstract

review

1989 - A spectral and thermal study on nickel(II) hydroxides [Articolo su rivista]
Baraldi, Pietro; Davolio, Giovanni; Fabbri, Gianfranco; Manfredini, Tiziano
abstract

The paper reports significative results about the spectral and thermal properties of nickel(II) hydroxides

1988 - Calorimetric and structural investigation of monomeric and dimeric copper(II)-N-protecetd aminoacidates [Articolo su rivista]
Antolini, Luciano; Baraldi, Pietro; Marcotrigiano, Giuseppe Onofrio; Menabue, Ledi; P., Morini; Saladini, Monica
abstract

A calorimetric investigation of the dehydration of structurally-known binary copper(II)-N-protected aminoacidates is reported to compare their relative stability. In order to consider a series of strictly related compounds, the crystal and molecular structure of N-benzoyl-α-alaninate (bz-α-ala) complex is also determined. The compound crystallizes in the triclinic space group P1− with 1 formula unit in a cell of dimensions a = 9.425(3), b = 9.579(3), c = 12.644 Å, α = 74.10(2)°, β = 78.95(2)°, γ = 88.32(3)°. The structure was solved using the Patterson and Fourier methods and refined by least-squares calculations to a conventional R factor of 5.6% for 3134 counter data. It consists of centrosymmetric tetracarboxylato bridged binuclear molecules showing the copper(II) acetate structure.The calorimetric analysis shows higher dehydration Ea values for dimeric species with respect to blue ones which assign a peculiar stability to dimeric structures. The crystal size strongly influences kinetic parameters because the proportion between water molecules on the surface and in the bulk varies with the crystal dimensions.