a b s t r a c tPulsed laser induced breakdown spectroscopy (LIBS) and Raman spectroscopy were performed using a novel laboratory setup employing the same Nd:YAG laser emission at 532 nm for the analysis of five commercially available pigments collectively known as "ultramarine blue", a sodium silicate material of either mineral origin or an artificially produced glass. LIBS and Raman spectroscopy have provided information regarding the elemental and molecular composition of the samples; additionally, an analytical protocol for the differentiation between natural (lapis lazuli) and artificial ultramarine blue pigments is proposed. In particular LIBS analysis has allowed the discrimination between pigments on the basis of peaks ascribed to calcium. The presence of calcite in the natural blue pigments has been confirmed following Raman spectroscopy in specific areas of the samples, and micro-Raman and optical microscopy have further corroborated the presence of calcite inclusions in the samples of natural origin. Finally multivariate analysis of Laser induced breakdown spectra using principal component analysis (PCA) further enhanced the differentiation between natural and artificial ultramarine blue pigments.

One degradation phenomenon that occurs in artworks is the formation of metal oxalates on their surfaces. In order to gain insight into the inclination of pigments to produce oxalates, nine pigments including Na, Ca, Fe, Pb and Cu cations were selected to react with oxalic acid solutions at different concentrations (1 M, 0.1 M, 0.01 M and 0.005 M). Micro-Raman spectroscopy was used to detect the different reaction products. Pigments containing calcium (calcite, gypsum and Volterra gypsum) showed a high tendency to form weddellite as well as whewellite, especially at high acidic concentrations; among copper-based pigments (malachite, azurite, verdigris), the formation of moolooite was observed for high concentrations of acid and down to the lowest concentration (0.005 M) in the case of verdigris. Lead oxalate was detected on lead white. No iron oxalates were observed for hematite; the formation of calcium oxalate crystals was observed instead. Ultramarine blue reacted to produce elemental sulfur. According to the results obtained, calcite and verdigris showed the highest reactivity in oxalic acid environments, resulting in a high tendency to form calcium and copper oxalates, even at very low acidic concentrations; this behavior seems to arise from the high solubilities of these pigments in acidic environments.

A nanosecond pulsed laser setup has been optimized to perform laser-induced breakdown spectroscopy (LIBS) and pulsed Raman spectroscopy measurements in the field of cultural heritage. Three different samples of artistic/architectural interest with different typologies have been analyzed. The results from the two techniques allowed the identification of the materials used in their manufacture or contaminating them, probably coming from atmospheric pollution and biological activity. No sampling and sample preparation was required before the measurements, and no visual or structural damage was observed. Depth profiling using LIBS was performed in one of the samples, providing elemental information along the different layers composing the object and covering its surface. The quality of the results and the rather short time needed for the measurements and for switching between techniques confirmed the instrument's capabilities and specificity for dealing with objects of artistic or historical interest.

A small, potentially transportable prototype instrument capable of carrying out Raman, laser-induced breakdown (LIB), and laser-induced fluorescence (LIF) spectroscopy using a single pulsed laser source was developed for the analysis of cultural heritage objects. The purpose of this instrumentation is to perform fast and reliable analysis of surfaces with minimum damage to an object. For this purpose, a compact (51 x 203 x 76 mm) nanosecond Q-switched neodymium doped yttrium aluminum garnet laser (8 ns, 20 Hz, 0.01-115 mJ/pulse) was used as an irradiation source. The use of a nanosecond-gated detector sensitive between 180 and 900 nm allows the acquisition of elemental emissions in LIB spectroscopy and can also be employed for both LIF and time-resolved Raman spectroscopy. In this work, attention is focused on the description of the instrument and its optical components, and two examples of applications for the analysis of pigments and binding media used in works of art are presented.

Knowledge and control of the solid forms of active pharmaceutical ingredients are important aspects of drug development in the pharmaceutical industry. In this paper, the process of the molecular selfassembly of saccharin cocrystals and the 2-amino-5-methylpyridine salt of indomethacin, in terms of the hydrogen bonding patterns, has been studied in the solid-state using vibrational spectroscopy (Raman and infrared). Interaction patterns in the respective crystalline states were obtained from the single crystal data. The effects of cocrystal and salt formation on the frequencies of the vibrational modes of motion were explained by vibrational spectroscopy and supported by quantum chemical calculations at the density functional theory level, leading to unambiguous assignment of the vibrational spectra of the starting materials and their respective products. Both Raman and infrared spectroscopies were useful, reliable tools for characterizing and distinguishing the indomethacin cocrystals and salt.