Multi-analytical Study Research Articles

A multi-analytical study of Bronze Age pottery from the UNESCO site of Al-Khutm (Bat, Oman)

The extensive investigation carried out in recent years at the UNESCO site of Al-Khutm (Ibri, Oman) has allowed to uncover the monumental remains of a tower dated back to the third millennium BC and to collect an abundant ceramic assemblage from the associated soil deposits. Eighteen selected pottery samples have been investigated using a multi-analytical approach including microfocus X-ray computed tomography, X-ray diffraction, optical microscopy and prompt gamma activation analysis to analyse the vessel-forming technique and to characterise their micro-structure, mineralogical and chemical composition to recognise possible local vs. non-local raw materials. The results provided new insights on ancient manufacturing processes and revealed that most of the vessels were locally produced exploiting raw materials from the surroundings of the site with the exception of a fragment of a black slipped jar. The chemical results suggest that the latter was imported from the Indus area in nowadays Pakistan. This evidence integrates our knowledge about the presence of this type of vessels in Oman and confirms the involvement of inland centres like Bat and Al-Khutm into a large-scale exchange system.

A Preliminary Spectroscopic Approach to Evaluate the Effectiveness of Water- and Silicone-Based Cleaning Methods on Historical Varnished Brass

Soiling deposition and wrong conservation practices are among the causes of the decay process that can affect the morphological, mechanical, and compositional features of the varnish, the most exposed layer of an artefact. In this perspective, the identification of the best cleaning practices is a priority. During the 18th century, scientific instruments of the highest quality were built, and peculiar varnishes were produced to confer protection and elegance to their metal elements. For this study, based on a historical recipe, we have reproduced a peculiar spirit varnish, enriched with natural resins and colorants, and we have applied on it a synthetic soiling mixture to simulate the aging conditions. We have then performed a non-invasive multi-analytical study to monitor the effectiveness of two water-based and a silicone-based, cleaning methods, namely, water in agarose, Tween 20 (3%) in agarose, and Velvesil™ Plus. The study includes colorimetry, Fourier transform infrared (FTIR) spectroscopy and X-ray fluorescence (XRF) mapping, coupled with chemometrics. Principal component analysis applied to FTIR spectral data has been demonstrated to be a powerful tool to enhance weak variations in the IR spectra, empowering the interpretation of cleaning effect versus the application time of each cleaning test.

Short-term effects of dietary bovine milk on fatty acid composition of human milk: A preliminary multi-analytical study

The fatty acid (FA) composition of human milk (HM) from N = 9 Italian healthy donors following a free diet exhibited FA-dependent ranges of variability, as assessed by GC-FID. The possible short-term changes in the FA profile were monitored in the milk of lactating mothers (three) collected at five time points over a 6 h period, following an oral load (200 mL) of bovine milk. An array of techniques was exploited, including UHPLC-ESI-MS/MS of intact lipids and MALDI-TOF MS before and after chemical hydrogenation or bromination, in addition to MALDI-TOF MS analysis of FA after saponification, to monitor short-chain and odd-chain FA in HM as markers of bovine milk fat.A single administration of bovine milk did not appreciably modify the lipid pattern, suggesting that the maternal diet could induce not detectable short-term changes on the lipid composition of HM. Diet-induced increase of butyric acid was also excluded by 13C NMR.The functions that HM FA exert in infant physiology appear finely regulated through maternal metabolism.

Planetary Terrestrial Analogues Library project: 1. characterization of samples by near-infrared point spectrometer

The PTAL project aims at building and exploiting a database involving several analytical techniques, the Planetary Terrestrial Analogues Library, to help characterizing the mineralogical evolution of terrestrial bodies, starting with Mars. A total of 94 natural Earth rocks have been collected from selected locations around the world to get a selection of analogues for Martian geology. The PTAL library gathers a variety of igneous rocks from different plutonic and volcanic origins and compositions, associated to different environments and levels of aqueous alteration. Samples of impact craters and sedimentary units are also present.The full set of samples will be characterized with optical thin section analysis and XRD (Oslo University, Norway), NIR spectroscopy (Paris-Saclay University, France), Raman spectroscopy (Valladolid University, Spain) and LIBS (Paul Sabatier University, France). The multianalytical study used within the PTAL project provides an unique opportunity to coordinate minerals/elements detection by different techniques that are similar to the instruments onboard current and forthcoming Martian missions. Such combined analysis should give the opportunity to prepare and improve ExoMars/ESA-Roscosmos and Mars2020/NASA observations. This paper focuses only on the NIR measurements and interpretations.The diversity of the PTAL samples is well revealed by the diversity of spectra from the NIR observations. The detected minerals are representative of various formation, alteration and geochemical environments. The major diagnostic features observed are those of primary Fe2+ bearing silicates like olivine or pyroxene with low and/or high calcium content; altered silicates detected with vibrational features associated to OH and/or H2O and/or metal-OH features; oxides; zeolites; and carbonates.This collection brings together a set of rocks and minerals that have been reported elsewhere in the Solar System and particularly on Mars.

An integrated approach to the recovery of travertine biodegradation by combining phyto-cleaning with genomic characterization

Travertine is a sedimentary carbonate rock widely used in Roman arts and frequently subjected to biodeterioration. In this preliminary multi-analytical study, three essential oils (EOs) from T. vulgaris, O. vulgare, C. nepeta and their respective phenolic major components (thymol, carvacrol, pulegone) were selected to evaluate their biocidal potential against a multi-species biofilm grown on a travertine test wall located inside Sapienza University Campus in Rome. A preliminary characterization of the biofilm occurred through the employment of genomic methodologies. It has been confirmed the presence of microorganisms belonging to fungi, plant and bacteria kingdoms amplifying the rDNA in the characteristic regions (ITS, 18S, 16S) by performing PCR amplification with specific primers. For this purpose, two different biofilm sampling procedures, one completely non-invasive (swab in physiologic saline solution) and one micro-invasive (adhesive tape) have been employed: the adhesive tape performed better than swab in relation to DNA purity and quantity. After the biofilm characterization, the application of the phytochemicals occurred. For the realization of formulations, the EOs and their major components have been incorporated inside an innovative hydrogel matrix conceived for the cleaning of cultural heritage. The biocidal and cleaning action was evaluated with colorimetric measurements before and after the application of the products and, in the case of the surfaces treated with the essential oils, these measurements have been repeated 6 weeks after the end of the treatment. It emerged that the formulations containing the active phenolic compounds have, in most cases, a better efficacy against the multispecies biofilm. Anyway, it was verified that the biocidal action of the essential oils lasts in time, since colour variation towards the original colour of the surface have been determined 6 weeks after the end of the procedure.

The Tomb of the Diver and the frescoed tombs in Paestum (southern Italy): New insights from a comparative archaeometric study.

The Tomb of the Diver has been subject for many decades of fierce debate among archaeologists and classicists. Since its discovery in 1968, some scholars have considered it a unique example of the lost tradition of Greek painting, others have emphasized Etruscan or Italic parallels. More recently, a possible local production has been suggested. With the aim of trying to solve the archaeological question, an archaeometric comparison among this well-known artwork and several frescoed tombs coming from Hellenistic and Lucan necropolis was carried out. The multi-analytical study was focused on the identification of peculiar features of executive techniques and raw materials since the first period of the archaeological site. The analytical investigation has been preliminary based on a non-destructive approach, performed in-situ by portable equipment including imaging diagnostics and compositional spectroscopic techniques for identifying pigments and the conservation state of original painted surface; subsequently, a further deepening by using destructive techniques was performed in-lab for the mortar-based supports characterization. Archaeometric study suggested that technological choices slightly changed in a time span of about two centuries, highlighting important markers that allow clustering the contemporary artistic productions. Moreover, a comparison with mortars from temples decorations was provided to better understand the whole artistic context. The archaeometric data showed that the Tomb of the Diver could be traced back to a local artisanal tradition and therefore is neither Etruscan nor Greek, but the first and foremost an expression of the local elite culture of Paestum.

Geochemical and petrographic identification of stone quarries used for the construction of the Anahita Temple of Kangavar (West Iran)

The archaeological site of the Anahita Temple in Kangavar is one of the best-known stone monuments in western Iran and dates back to the Persian Empire period of Iranian history (about 550 BC to 650 AD). The Temple was constructed on a semi-artificial hill out of large stone blocks, many of which are cubic in shape, and short thick columns. In the Kangavar area (basin) there are various sites in which there is evidence of stone extraction. The aim of this paper is to characterize the stones used in the Anahita Temple of Kangavar and their correlations with the quarrying activities observed in the Kangavar regions. In fact, we tried to find out which of these quarries may have been the source of the stone blocks used in the construction of the Anahita Temple. To this end the stones used in the Temple have been characterized by conducting a multi-analytical study involving chemical, mineralogical and textural analyses including XRF, XRD and thin section petrography. The results show that although all the quarries could have provided the stone used in the construction of the Temple, the largest, most probable source was the Chel Maran quarry. It is due to the more similarity of stones used in the Anahita Temple and the samples from this quarry from geochemical point of view as well as the archaeological evidences present in this quarry. The results are also useful for conservators to select appropriate materials for reconstruction of the decayed parts of the Anahita Temple.

A multi-analytical study of a wall painting in the Satyr domus in Córdoba, Spain.

In this work, we conducted a careful study of the mortar and paint in the Roman wall painting housed by the triclinium of the so-called Domus in the Road Safety Education Park of Córdoba, Spain. A combination of X-ray diffraction, Raman and X-ray fluorescence spectroscopies allowed the different substances used to obtain the pigments present in the painting to be identified. The painting was found to contain five different colours (red, yellow, blue, green and white) in various hues. The red pigment was obtained from hematite and the yellow pigment from goethite. The blue pigment, which was the least abundant, was prepared from Egyptian blue, and the green pigment from green earths. Finally, the white pigment came from lime. The binders used were identified by infrared spectroscopy and gas chromatography with mass spectrometry detection. The painting fragments studied contained vestiges of bee wax or its decomposition products, which suggests that the paint was applied encaustically.

Multi-technical approach for the characterization of polychrome decorative surfaces at Spanish Mission Churches in Nueva Vizcaya (Chihuahua, Mexico)

ABSTRACT An interdisciplinary and multi-institutional group of science and art conservation specialists has provided new insight into the painting materials used in the polychrome walls and wooden ceilings in four seventeenth century Spanish colonial churches of Nueva Vizcaya (Chihuahua, Mexico). A multi-analytical study of the decorative surfaces was performed in situ using spectroscopic approaches (XRF, FORS), False Colour Infrared Reflectography – IRFC, as well as micro sampling for ATR-FTIR, LM and GC/MS laboratory analyses. A survey of natural resources were also studied by ATR-FTIR and LM to elucidate the natural occurrence of a select number of materials found in the surrounding areas of the churches. The present paper presents a multi-analytical study and characterization of green, red-orange and black colour pigments and binders selected from the decorative surfaces. The aim of this study is to highlight relationships between local materials and those from the original polychrome ceilings, in order to understand the material and technological influences that converged in the Spanish colonial architecture of northern Mexico.

A multi-analytical characterization of artists’ carbon-based black pigments

The most common synthetic carbon-based black pigments can be divided into three main groups on the basis of the material used for their production: bone blacks, vine blacks and lampblacks. This work reports on the physicochemical characterization of the three commercial pigments purchased from Kremer Pigmente (Germany) and Zecchi (Italy) by means of a multi-analytical approach, which included thermoanalytical (thermogravimetry, thermogravimetry coupled with FTIR and differential scanning calorimetry) and spectroscopic techniques (laser-induced breakdown spectroscopy, Fourier-transform infrared spectroscopy, Raman spectroscopy and X-ray powder diffraction). Combining the results obtained from this multi-analytical approach, qualitative and quantitative conclusions are drawn for the first time. Lampblacks are mainly composed of amorphous carbon. In vine black (Kremer), amorphous carbon and cellulose pyrolysis by-products are the main constituents. In bone blacks and vine black (Zecchi), carbonaceous materials are minor components. Hydroxyapatite and calcium carbonate are the main constituents of bone blacks, and iron and magnesium oxides are the main constituents of vine black (Zecchi). Results from this multi-analytical study on the composition of such widespread pigments can provide valuable information in the decision-making process for restorers and conservators.

Multi-analytical study of 14th to 19th century illuminated Moroccan manuscripts

Moroccan manuscripts heritage preserves valuable information regarding different fields of Arabian history and culture. Despite this fact, analytical studies carried out in Moroccan manuscripts are scarce. In this work, we made use of a multi-analytical methodology to study, for the first time, four illuminated manuscripts from the Royal library of Rabat covering the span 14th to 19th centuries. The chemical structure of inks and paper support was identified. Elemental distribution obtained by micro-energy dispersive X-ray fluorescence (μ-EDXRF) showed the use of iron, copper and vermillion in black, blue and red inks, respectively. Arsenic and lead were identified as orange inks in the 17th and 19th century manuscripts, respectively. Quantitative characterization of the paper supports obtained by triaxial geometry EDXRF spectrometry showed high levels of sulphur, chlorine and potassium. Regarding the study of the manuscripts support, cellulose $I_{\beta}$ was determined by X-ray diffraction (XRD) in all the analyzed samples. Cellulose fibers observations by scanning electron microscopy showed that the manuscripts are in general, in a good condition. Calcite is the main filler determined by XRD.

Multianalytical Study for Establishing the Historical Contexts of the Church of the Holy Archangels from Cicau, Alba County, Romania, for its Promotion as a World Heritage Good I. Assessing the preservation-restoration works from the 18th century

The present paper is the first instalment of a series focused on establishing some archaeometric characteristics of the modern finishings (mortars, fresco and layers of whitewash) of the Church of the Holy Archangels from Cic�u, Alba County, Romania, in order to assess the shape, with the structural-functional integrity and architectural and artistic aspect of the monument for the last historical context, between 1710 and 1790. This period is the most extensive and less known of the church�s stages of transformation: 11th�12th century (unknown), 15th century (known) and 18th century (partially known), which was very tumultuous from the socio-economic and political point of view. Thus, in the following pages we present the resulting archaeometric characteristics of optical microscopy (OM), scanning electron microscopes in combination with energy-dispersive X-Ray spectrometry (SEM-EDX) and thermal derivatography (TG/DTA/DTG) analyses of two pigments from the exonarthex fresco (made in 1781) and the later eight layers of whitewash applied over it, which allowed assessing the periods with marked changes in the architecture and polychrome finishings.

Multi-Analytical Study of Copper-Based Historic Pigments and their Alteration Products

Copper-containing materials such as verdigris are commonly found in historic and artistic works of art, often at advanced states of decay. Applied on paper as inks and watercolors, many of which needed a binder such as gum arabic, the intrinsic instability of this pigment was known since the medieval period. The decay of verdigris (a mixture of copper acetates) as a pigment, as watercolor, and as a dye, was studied using a combination of vibrational (Fourier transform infrared) and X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) instrumental techniques. Changes in the copper oxidative states and the formation of copper oxide were monitored during accelerated degradation as powdered solids and applied on mockup samples (with and without binder). Accelerated aging of both commercially available and synthesized verdigris pigments showed the presence of an intermediate species, Cu(CH3COO)2•3Cu(OH)2•2H2O, which points to the beginning of the decay processes, that culminates in the formation of Cu(II) oxide. However, the presence of gum arabic seems to delay deterioration, by temporarily reducing Cu(II) to Cu(I), even when the final product includes Cu(II). This novel application of XPS and supporting techniques has significant implications in art conservation, as the identified behavior helps explain the better preservation state of some works of art.

Minero-Petrographic Characterization of Chianocco Marble Employed for Palazzo Madama Façade in Turin (Northwest Italy)

The study of ancient marble plays an important role in the interpretation of historical and archaeological sites and gives interesting information about building materials used in ancient times and their trade routes. The present work focuses on Chianocco marble that represents one of the most important ancient white marbles for cultural heritage exploited in the Piedmont region (Northwest Italy) and employed for the Palazzo Madama façade. A multi-analytical study based on petrographic (optical and scanning electron microscopy), electron microprobe, cathodoluminescence and stable isotope analyses was carried out on these marbles in order to perform an archaeometric study. Chianocco marble was used in Turin during the baroque era by the Savoy architect Filippo Juvarra (1678–1736) in historical buildings, such as the façade of the Palazzo Madama, the plinth of the façade of the town Cathedral and the columns (now plastered) of the portico of Piazza San Carlo. This stone is a dolomitic rock belonging to the Mesozoic cover of the Dora Maira Massif (Pennidic Unit). It shows a vuggy fabric characterized by a vacuolar texture due to tectonic brecciation and subsequent selective dissolution during subaerial exposure. This kind of research is useful to highlight the importance of the use of local stones as building materials and to investigate stone materials for the restoration and maintenance of historical buildings.

Planetary Terrestrial Analogues Library (PTAL) project: Raman data overview

AbstractThe multianalytical study of terrestrial analogues is a useful strategy to deepen the knowledge about the geological and environmental evolution of Mars and other extraterrestrial bodies. In spite of the increasing importance that laser‐induced breakdown spectroscopy (LIBS), near‐infrared spectroscopy (NIR), and Raman techniques are acquiring in the field of space exploration, there is a lack Web‐based platform providing free access to a wide multispectral database of terrestrial analogue materials. The Planetary Terrestrial Analogues Library (PTAL) project aims at responding to this critical need by developing and providing free Web accessibility to LIBS, NIR, and Raman data from more than 94 terrestrial analogues selected according to their congruence with Martian geological contexts. In this framework, the present manuscript provides the scientific community with a complete overview of the over 4,500 Raman spectra collected to feed the PTAL database. Raman data, obtained through the complementary use of laboratory and spacecraft‐simulator systems, confirmed the effectiveness of this spectroscopic technique for the detection of major and minor mineralogical phases of the samples, the latter being of critical importance for the recognition of geological processes that could have occurred on Mars and other planets. In light of the forthcoming missions to Mars, the results obtained through the Raman Laser Spectrometer (RLS) ExoMars Simulator offer a valuable insight on the scientific outcome that could derive from the RLS spectrometer that will soon land on Mars as part of the ExoMars rover payload.

Multi-Analytical Study of Degradation Processes in Perovskite Films for Optoelectronic Applications

Multi-Analytical Study of Degradation Processes in Perovskite Films for Optoelectronic Applications

Marble Pieces in the Romanesque Portal of Glory of the Santiago de Compostela Cathedral. New Data through a Multi-Analytical Approach

ABSTRACT Probably the most important Romanesque artwork in Spain, the Portal of Glory of Santiago de Compostela is essentially made in granite, the most abundant stone in the NW of Iberia, with the only exception of five marble pieces. Different hypothesis on the origin of these marbles have previously been proposed based on visual assessment or by directly assuming a local source. To shed light on their quarry provenance, a multi-analytical study was performed combining polarized-light optical microscopy, cathodoluminescence microscopy, XRPD, SEM-EDS and stable C and O isotopes. The comparison of the results with the available databases reveals the use of marbles from the Estremoz Anticline (Portugal) in the three exquisitely carved columns strategically placed in the central arcade, whereas the other two pieces are local marbles, illustrating a more complex consumption of this noble material than that initially expected.

Crystal structure model development for soil clay minerals – I. Hydroxy-interlayered smectite (HIS) synthesized from bentonite. A multi-analytical study

During the acidic weathering of soils, aluminum (Al) is dissolved from primary silicates such as feldspars or chlorites and intercalated in layer silicates. Part of this Al polymerizes in the interlayer of former smectites or vermiculites and the resulting phases are called hydroxy-interlayered minerals. These phases are known for a long time but are still insufficiently understood in terms of chemical composition and crystallographical structure. In the present study a sample set consisting of a continuous series of hydroxy-interlayered smectite samples with different degrees of hydroxy-interlayering ranging from 0 to 96% mol/mol smectite/HIS was prepared from a bentonite sample by adding different amounts of a 0.1 mol/L AlCl3 solution and different reaction times. The products were investigated by a multi-analytical approach using X-ray diffraction, Infrared spectroscopy, X-ray Fluorescence spectrometry, Fe2+:Fetotal determination, Nuclear Magnetic Resonance spectroscopy, Simultaneous Thermal Analysis coupled with mass spectrometry and Cation Exchange Capacity to provide an in-depth characterization. X-ray diffraction indicated that the turbostratic disorder typical for smectite did not change during hydroxy-interlayering. Nuclear Magnetic Resonance spectroscopy proved the exclusive six-fold coordination of interlayer Al and based on chemical calculations the average size and charge of the interlayer structures were characterized. Hydroxy-interlayers evolved in-situ in the smectite interlayers by polymerization. These interlayer “polymers” were small oligomers, the average size of which increased from monomers to pentamers with increasing degree of hydroxy-interlayering while the average net charge of each oligomer decreased. An average structural formula of each interstratified smectite-hydroxy-interlayered smectite was calculated from X-ray Fluorescence data including Fe2+:Fetotal ratios. If all exchangeable cations are attributed to smectite layers and all hydroxy-interlayers are attributed to hydroxy-interlayered smectite layers, the degree of hydroxy-interlayering ranged from 0 to 96% mol/mol smectite/HIS. The analysis provides an improved structural model of hydroxy-interlayered smectite suitable for Rietveld refinement which can be used to quantify the amounts of hydroxy-interlayered smectite in natural samples.

The role of the polymeric network in the water sensitivity of modern oil paints

Spectroscopic and mass spectrometric analytical techniques were used to characterise two naturally aged Winsor & Newton (W&N) Winsor Green (phthalocyanine green, PG7) artists’ oil colour paint swatches dating to 1993 and 2003. Infrared and Energy Dispersive X-ray (EDX) analysis indicated that the swatches were of closely similar composition, yet the swatch from 2003 was water-sensitive whilst the swatch from 1993 was not. Water-sensitivity is a conservation challenge associated with significant numbers of modern oil paintings and this study aimed to further develop our understanding of the molecular causes of water sensitivity. SEM elemental mapping of samples taken from both swatches provided no indication for the formation of epsomite – a known cause of water sensitivity in some modern oil paintings. Liquid chromatography coupled with mass spectrometry (HPLC-MS) and gas chromatography coupled with mass spectrometry (GC-MS) also revealed very similar qualitative-quantitative composition in terms of unbound and esterified medium fractions. The polymeric network was investigated using analytical pyrolysis. A combination of flash pyrolysis coupled with gas chromatography mass spectrometry (Py-GC-MS) together with evolved gas analysis mass spectrometry (EGA-MS) revealed that the polymeric material was relatively more abundant in the non-water-sensitive paint. This is the first multi-analytical study that has demonstrated a correlation between water-sensitivity and the degree of polymerisation of the oil medium; independent of other known causes of water-sensitivity.

The bricks of Hagia Sophia (Istanbul, Turkey): a new hypothesis to explain their compositional difference

Abstract The work shows the results of a multi-analytical study performed on twenty-nine brick samples taken from Hagia Sophia in Istanbul (Turkey). Hagia Sophia, one of the most important historical buildings in the world, has a very complex construction history. This complexity is also reflected in the materials that were used for its construction. The main purpose of this work is to verify whether there are any compositional differences in the bricks used in different historical periods, but also to understand the reasons for any compositional differences between one period and another. The samples were studied by optical microscopy (OM), X-ray fluorescence (XRF), X-ray powder diffraction (XRPD) and thermogravimetric analysis (TGA), coupled with a new approach, based on the micro-chemical EDS analysis used to obtain information on the clay fraction of the matrix. The study showed that, most probably, the differences between the bricks belonging to the different construction phases are due to the composition of the clays used for their preparation.