Red stains on heritage marbles: application of micro-scale analyses to assess the presence and distribution of lead compounds.

Stone cultural heritage buildings are frequently affected by different alteration phenomena and in particular, on heritage marbles the presence of chromatic discolouration, as the red stains, is one of the most widespread. In this paper, small fragments of red stains originated on marble exposed to different environmental contexts were analysed to reveal the presence and distribution of lead compounds at the micro-scale level. The samples come from slabs of historical religious buildings in Florence (Santa Maria del Fiore Cathedral and the San Giovanni Baptistery) and from the monumental fountains conserved in the Medicean Villa La Petraia (Florence). The presence and distribution of lead compounds: minium (Pb3O4), carbonates such as cerussite (PbCO3) and hydrocerussite (Pb3(CO3)2(OH)2) and plattnerite (PbO2), was revealed using 2D high lateral resolution micro-X-Ray Powder Diffraction (µ-XRPD) and µ-Raman spectroscopy. Additional information were provided by Scanning Electron Microscopy, the elemental distribution performed with micro-X-Ray Fluorescence mapping enable to verify the possible presence of light elements and the use of FTIR chemical imaging confirmed the absence of organic compounds.

Non-destructive distinction between geogenic and anthropogenic calcite by Raman spectroscopy combined with machine learning workflow.

Here, we demonstrate, for the first time, the possibility of distinguishing between geogenic and anthropogenic calcite in a non-destructive and effective way. Geogenic calcite derives from natural sedimentary and metamorphic rocks whereas anthropogenic calcite is formed artificially due to the carbonation process in mortars and plaster lime binders. Currently, their distinction is a major unaddressed issue although it is crucial across several fields such as 14C dating of historical mortars to avoid contamination with carbonate aggregates, investigating the origins of pigments, and studying the origins of sediments, to name a few. In this paper, we address this unmet need combining high-resolution micro-Raman spectroscopy with data mining and machine learning methods. This approach provides an effective means of obtaining robust and representative Raman datasets from which samples' origins can be effectively deduced; moreover, a distinction between sedimentary and metamorphic calcite has been also highlighted. The samples, chemically identical, exhibit systematic and reliable differences in Raman band positions, band shape and intensity, which are likely related to the degree of structural order and polarization effects.

Gold Mine Wooden Artefacts: Multianalytical Investigations for the Selection of Appropriate Consolidation Treatments.

Environmental conditions present in mines generally are very favourable to decay; high temperature, high humidity, variable oxygen content, numerous metal-wood connections and the presence of a high content of inorganic compounds typical of mines have a significant impact on the biotic and abiotic degradation factors. The state of conservation of wooden artefacts from the Zloty Stok (Poland) gold mine was investigated using a multi-analytical approach. The aim was to select the conservation treatments that would stop decay and improve the conditions and dimensional stability of the wood. FT-IR and Py-GC/MS were used to assess the state of preservation of lignocellulosic material. ED-XRF and SEM-EDS were used to determine-and XRD to identify crystalline phases-salts and minerals in the wood structure or efflorescence on the surface. Highly degraded lignocellulosic material that had undergone depolymerisation and oxidation was found to be severely contaminated by iron-based mineral substances, mainly pyrite, and in some cases greigite and magnetite. The presence of inorganic salts made it difficult to choose the best consolidating material to reduce the level of decay and improve the dimensional stability of the wood.

A multi-analytical approach for the study of red stains on heritage marble.

Red stains are a common discolouration on stone cultural heritage all over the world. These are very difficult to remove and little is known about the reddish pigmentation. Numerous red stains were mapped on the Baptistery of San Giovanni in Florence, one of the most important monuments in Italy. This paper is focused on red stains on marble stone and the results of a detailed multidisciplinary approach are presented. Several analytical and investigation techniques (such as optical microscopy, X-ray fluorescence mapping, X-ray micro-tomography, micro-Raman spectroscopy, scanning electron microscopy with energy dispersive spectroscopy, microbial isolation, colorimetric measurements and isotopic analyses) were used to better understand the origin and processes involved in this kind of alteration. Analyses of the red stains led us to believe the presence of minium (lead tetroxide) and Pb are usually concentrated in the spaces between calcite grains. Red stains of Pb isotopic composition also overlap with data from Sardinian mines. These preliminary data seem to reinforce the suggestion of a source of lead from some metallic items (during restoration campaigns between 1938 and 1944, damaged parts were removed and replaced, and the new marble cladding was fixed with iron brackets treated with minium).

A new multi-analytical procedure for radiocarbon dating of historical mortars.

The overarching challenge of this research is setting up a procedure to select the most appropriate fraction from complex, heterogeneous materials such as historic mortars in case of radiocarbon dating. At present, in the international community, there is not a unique and fully accepted way of mortar sample preparation to systematically obtain accurate results. With this contribution, we propose a strategy for selecting suitable mortar samples for radiocarbon dating of anthropogenic calcite in binder or lump. A four-step procedure is proposed: (I) good sampling strategies along with architectural and historical surveys; (II) mineralogical, petrographic, and chemical characterization of mortars to evaluate the feasibility of sample dating; (III) a non-destructive multi-analytical characterization of binder-rich portions to avoid geogenic calcite contamination; (IV) carbonate micro-sample preparation and accelerator mass spectrometer (AMS) measurements. The most innovative feature of the overall procedure relies on the fact that, in case of positive validation in step III, exactly the same material is treated and measured in step IV. The paper aims to apply this procedure to the ancient mortar of the Florentine historical building (Trebbio Castle), selecting micro-samples suitable for dating in natural hydraulic mortars. The discussion of the mortar dating results with the historical-archaeological hypotheses provided significant insights into the construction history of the building.

Development of a Quartz-Based Photo-Mobile Polymer Film for Controlled Motion Triggered by Light or Heat.

We have developed a photo-mobile polymer film, that combines organic and inorganic materials, to allow for controlled motion that can be triggered by light or heat. Our film is made using recycled quartz and consists of two layers: a multi-acrylate polymer layer and a layer containing oxidized 4-amino-phenol and N-Vinyl-1-Pyrrolidinone. The use of quartz in our film also gives it a high temperature resistance of at least 350 °C. When exposed to heat, the film moves in a direction that is independent of the heat source, due to its asymmetrical design. Once the heat source is removed, the film returns to its original position. ATR-FTIR measurements confirm this asymmetrical configuration. This technology may have potential applications in energy harvesting, due to the piezoelectric properties of quartz.

Enriching the knowledge of Ostia Antica painted fragments: a multi-methodological approach.

This paper presents the study of selected painted fragments from different contexts of Ostia Antica city, dating between 2nd century BCE and the end of the 1st century CE. The aim is to identify the raw materials used and to understand the execution techniques through a non-invasive protocol including techniques based either on multiband imaging (Visible-VIS, Ultraviolet induced Luminescence - UVL and Visible Induced Luminescence - VIL) and single spot analyses (Fiber Optic Reflectance Spectroscopy- FORS and portable X-Ray Fluorescence spectrometry - XRF). The most representative and interesting fragments were sampled for further studies with laboratory techniques such as optical microscopy (OM) and electron microscopy (SEM), Fourier Transform Infrared and micro-Raman Spectroscopies (FT-IR and µRaman). The extensive use of non-invasive techniques, even working on fragments, is proved to be the most robust and effective approach enabling the analysis of a high number of areas, dramatically increasing the statistical meaning of the collected data. The elaboration of such a huge number of data allows highlighting differences and similarities, thus achieving a more realistic overview of the materials composition and addressing the sampling to the more significant and complex areas.

Non-invasive techniques applied to the alchemical codex of the State Archive of Florence.

This paper focuses on the application of non-invasive techniques to study a peculiar object, an alchemical codex completely made of lead stored at the State Archive of Florence.1 The sheets of the codex appeared entirely covered by thick and heterogeneous corrosion patinas for which a restoration was planned for their removal. This activity was supported by analytical investigations to characterise the materials that made up the patinas using non-invasive techniques. The codex pages were initially documented with imaging techniques. Subsequently, spectroscopic data were acquired on each sheet using spot analytical techniques: Total Reflectance Fourier Transform Infrared Spectroscopy (TR FT-IR), Fibre Optics Reflectance Spectroscopy (FORS), X-Ray Fluorescence (XRF), Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD). The identification of deterioration compounds has been extremely useful for the conservator to deal with the removal of dangerous and disfiguring patinas.

Environmental impact assessment on the stone decay in the archaeological site of Hierapolis (Denizli, Turkey).

The archaeological site of Hierapolis (Denizli province, Turkey) is unique in terms of the conservation of marbles and travertines. Environmental factors (i.e. interaction with thermal waters, high thermal stress, CO2 degassing) and geological aspects (presence of seismic faults, frequent earthquakes, formation of travertine) play a fundamental role in the durability and conservation state of the stone materials. This paper presents a multi-analytical approach aimed to identify the phenomena and causes of stone decay related to environmental conditions. The analyses of alteration and decay phenomena are discussed together with the monitoring of the main environmental parameters and with analyses of waters and gases present in the archaeological site. Finally, the need of a continuous monitoring of the environmental parameters affecting the archaeological site is stressed.

Contemporary artists' spinel pigments: Non-invasive characterization by means of electronic spectroscopy.

The identification of artistic materials represents a fundamental step in supporting the conservation of cultural heritage objects. The importance of their appropriate characterization is particularly relevant in modern-contemporary art, since they could be affected by the occurrence of rapid changes in chemical formulation over time. This paper focuses on an investigation of a series of contemporary blue-green commercial acrylic paints constituted of spinel pigments, using non-invasive spectroscopic techniques. The spectroscopic and color measurements obtained make it possible to characterize the acrylic paints under investigation and to compare the results obtained with those reported in the literature and in spectral databases. To be more precise, the proposed UV-vis-NIR reflectance spectroscopic technique was sensitive enough to characterize the acrylic paints according to their d-d ligand field and the charge transfer (CT) electronic transitions involved in the spinel structures. In addition, an overview of this class of inorganic pigments is also given.

A follow-up on the analytical study of discolouration of the marble statues of Orsanmichele in Florence.

The research complements the complex study carried out to understand the source of brown discolourations of ten marble statues in the Church of Orsanmichele in Florence, Italy. Originally located in exterior niches, the statues were restored to reverse the extensive alterations they had undergone throughout the centuries. One of the major alterations was the application of a dark brown patina that dated just after 1789. After the statues were placed indoors, brownish discolourations started to appear on their surfaces. Cross sections were examined using FTIR mapping and immunological methods. In parallel, the pyrolysis-gas chromatography/mass spectrometry (py-GC/MS) data already obtained from the statues' scrapings were compared with data from aged casein films applied to microscope glass slides and aged milk-treated marble. All the statues had been treated with milk-based substances before the time the bronze patina was applied. The values of temperature and illumination of the room were important factors in the ageing of organic substances and in the formation of calcium oxalates. It is likely that products of thermo-oxidation and photo-oxidation of the oils together with the oxalates caused the darkening. The marble samples corresponded to a Lunense provenance.

A multi-analytical approach for the characterization of wall painting materials on contemporary buildings.

Samples from Keith Haring's wall painting of the Necker Children Hospital in Paris were studied by a multi-analytical protocol. X-ray fluorescence (XRF), powder X-ray diffraction (XRDP), Electron microscope (SEM-EDS), Infrared and Raman spectroscopy (µ-FT-IR and µ-Raman) measurements were performed in order to characterize the materials and to identify the art technique used to produce this contemporary work. Materials from the mural suffered from severe detachments of materials and several fragments were found on the ground beneath. Some of these fragments, which were representative of the whole palette and stratigraphic sequence, were collected and studied. The fragments were sufficiently large to enable non-invasive measurements to be performed in order to characterize the materials. A comparison of the data of the techniques applied revealed that Haring's palette was composed of organic pigments such as Naphtol red, phthalocyanine blue and green and Hansa yellow, in accordance with those used previously by the artist in other painted murals.

Painted Fiberglass-Reinforced Contemporary Sculpture: Investigating Composite Materials, Techniques and Conservation Using a Multi-Analytical Approach.

A multi-analytical approach was used to study the constituent materials, manufacturing technique, and state of conservation of a contemporary sculpture. This sculpture, entitled Nuredduna, was created by Aligi Sassu in 1995 and is located in the "Bellariva garden" in Florence (Italy). Fourier transform infrared spectroscopy (FT-IR), optical and electronic microscopy (OM and SEM-EDS), X-ray diffraction (XRD), and portable X-ray fluorescence (XRF) highlighted the multi-layered structure of the statue: fiberglass and an overlay of different layers (gel coat) applied with an unsaturated polyester resin added with aggregate materials and bromine compounds. A top-coat in acrylic black varnish, used as a finish, was also found. The combination of these materials with their different compositions, environmental impact, and even vandalism have negatively affected the state of conservation of Nuredduna, causing the loss of strata in its lower parts (legs and feet).