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In this study, we present the first characterisation of the polyvinyl acetate (PVAc) paints of commercial Spanish brand La Pajarita preserved in the studios of Joan Miró (1893-1983) in Mallorca, Spain. Investigation of several black and white paint samples using complementary analytical techniques (XRD, SEM-EDX, FTIR, and Py-GC-MS) allowed for the identification of pigments and binding media in studio materials, as well as in three artworks dating from the 1970s. Through comparative analysis, it was possible to find significant similarities between the composition of La Pajarita paints conserved in cans in the artist's studio with black and white painted layers from three artworks by Miró. Miró's use of La Pajarita paints is extensively documented in studio notes, photographs, and videos, and these paints are known to have been used by other significant Spanish artists. However, their composition has remained largely undiscovered until now. This research contributes to the knowledge of PVAc paints, providing evidence of their use by Joan Miró. The analytical results serve as a valuable reference for comparing and identifying these synthetic paints in other artworks, as well as aiding in attribution or dating studies. Furthermore, the study demonstrates the significance of materials found in artists' studios as a fundamental resource for identifying the materials present in artworks.

The main conservation problem of p-PVC artworks is phthalate-based plasticizer migration. Phthalate migration from the bulk to the surface of the materials leads to the formation of a glossy and oily film on the outer layers, ultimately reducing the flexibility of the material. This study aimed to develop a removable coating for the preservation of contemporary artworks and design objects made of plasticized polyvinyl chloride (p-PVC). Several coatings incorporating chitosan, collagen, and cellulose ethers were assessed as potential barriers to inhibiting plasticizer migration. Analytical techniques including optical microscopy (OM), ultraviolet/visible/near-infrared spectroscopy (UV/Vis/NIR), Fourier transform infrared spectroscopy with attenuated total reflection (FTIR-ATR), and scanning electron microscopy (SEM) were utilized to evaluate the optical and chemical stability of selected coating formulations applied to laboratory p-PVC sheet specimens. Subsequently, formulations were tested on a real tangible example of a design object, ©Barbie doll, characterized by the prevalent issue of plasticizer migration. Furthermore, the results obtained with the tested formulations were evaluated by a group of conservators using a tailored survey. Finally, a suitable coating formulation capable of safeguarding plastic substrates was suggested.

Wine production represents one of the most important agro-industrial sectors in Italy. Wine lees are the most significant waste in the winery industry and have high disposal and storage costs and few applications within the circular economy. In this study, anaerobic digestion and a microalgae coupled process was studied in order to treat wine lees and waste activated sludge produced within the same facility, with the aim of producing energy and valuable microalgae biomass that could be processed to recover biofuel or biostimulant. Chlorella vulgaris was cultivated on liquid digestate in a semi-continuous system without biomass recirculation. The best growth and phytoremediation performance were achieved applying a hydraulic retention time (HRT) of 20 days with a stable dry weight, lipid and protein storage of 1.85 ± 0.02 g l -1 , 33.48 ± 7.54 % and 57.85 ± 10.14 % respectively. Lipid characterization highlighted the potential use in high quality biodiesel production, according to EN14214 (<12 % v/v linolenic acid). The microalgae reactor's liquid output showed high removal of ammonia (95.72 ± 2.10 %), but low organic soluble matter reduction. Further semi-continuous process optimization was carried out by increasing the time between digestate feeding and biomass recovery at HRT 10. These operative changes avoided biomass wash-out and provided a stable phytoremediation of the digestate with 84.58 ± 4.02 % ammonia removal, 33.01 ± 1.44 % sCOD removal, 38.06 ± 2.65 % of polyphenols removal., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: [Paolina Scarponi has patent #102022000011675 licensed to Licensee.]., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Mattel's Barbie dolls are the most famous and iconic dolls since 1959. Today, they are being collected by individuals and often conserved in museum environments due to their cultural and historical significance reflecting everyday life and historical events. However, just like most museum objects made of plastics, both historical and more recent Barbies show evident degradation phenomena. Firstly, Barbies were made of plasticized polyvinyl chloride (PVC), affected by the migration of additives-mostly the plasticizers-from the bulk phase to the outermost layer, appearing as a tacky and glossy exudate. Over the years, Barbies' polymeric constituents were replaced with more stable ones, whose additives migration is limited compared to PVC, even though still occurring. Multispectral photography in visible (VIS) and ultraviolet (UV) light, microscopical observations in VIS and UV light, and Fourier Transform Infrared spectroscopy in the Attenuated Total Reflectance mode (FT-IR ATR) were performed to characterize the constituent materials of 15 Barbies produced between 1959 and 1976, bridging the information gap on their processing over the years. The micro-invasive multi-analytical approach also allowed for the characterization of the degradation products, permitting the reference of the exudated compound to the specific bulk polymer.

The potential toxicity deriving from the interaction between chemicals and manufactured nanoparticles (NPs) represents an emerging threat to the environment and human health. Several studies have focused on the risks and (eco)toxicity of manufactured NPs as a consequence of their extensive use in recent years, however, there is still a limited understanding of the combined effects caused by manufactured NPs in the presence of other environmental contaminants. This is particularly relevant to aquatic environments, where many types of pollutants are inevitably released and can be involved in many kinds of reactions. In this context, the interaction between catecholate type ligands and two different nanomaterials, namely TiO 2 and Fe 2 O 3 NPs, was investigated by performing cytotoxicity assays with the topminnow fish hepatoma cell line (PLHC-1) using: i) the original organic molecules, ii) pristine NPs alone, and iii) modified NPs obtained by grafting the ligands on the NPs surface. Cytotoxic effects were explored at three different levels, specifically on cellular metabolism, membrane integrity and lysosomal activity. The outcomes from these assays showed cytotoxicity only for the free catechol type ligands, while in general no significant decrease in cell viability was observed for pristine NPs, as well as for the modified NPs, regardless the initial cytotoxicity level of the organic ligands These results suggest that the binding of catechols on the NPs' surface inhibited their cytotoxicity, indicating that TiO 2 and Fe 2 O 3 NPs may act as sorbents of these contaminants, thus reducing their possible detrimental effects., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper, (Copyright © 2022. Published by Elsevier B.V.)

Knowledge of the chemical-physical reactions that determine the main degradation behaviour of artists' alkyd paints represents one of the main problems within the museum exhibitions. The collection and interpretation of these data on degradation phenomena, especially after ozone exposure at different relative humidity values, can be useful for their conservation needs. Therefore, a systematic investigation of these materials may help achieve this goal. Firstly, surface-level identification of the main functional groups of ad hoc created and aged alkyd paints was performed using attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR). Subsequently, these paints were investigated by pyrolysis-gas chromatography and mass spectrometry (Py-GC/MS), allowing for precise bulk identification of the organic compounds before and after accelerated ageing. A first successful attempt to provide quantitative Py-GC/MS data on alkyd-based paints is here presented and discussed. Comparing the results, it was possible to obtain new insights into the degradation behaviour of alkyd paints when exposed to ozone, allowing us to devise specific preventive and conservation strategies for these artistic materials.

The knowledge of the atmospheric degradation reactions affecting the stability of modern materials is still of current interest. In fact, environmental parameters, such as relative humidity (RH), temperature, and pollutant agents, often fluctuate due to natural or anthropogenic climatic changes. This study focuses on evaluating analytical and statistical strategies to investigate the degradation processes of acrylic and styrene-acrylic paints after exposure to ozone (O 3 ) and RH. A first comparison of FTIR and Py-GC/MS results allowed to obtain qualitative information on the degradation products and the influence of the pigments on the paints' stability. The combination of these results represents a significant potential for the use of data fusion methods. Specifically, the datasets obtained by FTIR and Py-GC/MS were combined using a low-level data fusion approach and subsequently processed by principal component analysis (PCA). It allowed to evaluate the different chemical impact of the variables for the characterization of unaged and aged samples, understanding which paint is more prone to ozone degradation, and which aging variables most compromise their stability. The advantage of this method consists in simultaneously evaluating all the FTIR and Py-GC/MS variables and describing common degradation patterns. From these combined results, specific information was obtained for further suitable conservation practices for modern and contemporary painted films.

Indoor air quality in buildings is strongly affected by chemical, physical, and biological agents. Long exposure to inadequate indoor air quality can be very dangerous for the building occupants and can lead to chronic diseases associated with the sick building syndrome (SBS). In this paper, the large presence of biological pollutants in the indoor rooms of an old building and its strict relationship with the outdoor/indoor air conditions were investigated studying Coronini Cronberg Palace Foundation, a historic house museum of the sixteenth century in Gorizia (Italy), where biological contamination affecting the artworks can soon become potentially harmful also for operators and visitors. Detailed aerobiological and microbiological analyses on organic natural materials, combined with a microclimate monitoring, were conducted to evaluate the influence of temperature and relative humidity levels within the Palace in the conspicuous growth and diffusion of microorganisms. Fungal and bacterial colonies damaging materials, mainly affected by the sudden fluctuations of hygrothermal values, were found to widely exceed Italian and international recommended levels for good air quality for both artworks and human beings. Understand their impact on human health would be strictly necessary to reduce biological risks for museum staff and cultural heritage users, but consequently to improve indoor air quality., (© 2021. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Up to 70 % of the oil paintings conserved in collections present metal soaps, which result from the chemical reaction between metal ions present in the painted layers and free fatty acids from the lipidic binders. In recent decades, conservators and conservation scientists have been systematically identifying various and frequent conservation problems that can be linked to the formation of metal soaps. It is also increasingly recognized that metal soap formation may not compromise the integrity of paint so there is a need for careful assessment of the implications of metal soaps for conservation. This review aims to critically assess scientific literature related to commonly adopted analytical techniques for the analysis of metal soaps in oil paintings. A comparison of different analytical methods is provided, highlighting advantages associated with each, as well as limitations identified through the analysis of reference materials and applications to the analysis of samples from historical paintings., (© 2021 The Authors. Published by Wiley-VCH GmbH.)

This paper reports a pioneering study of an unknown historical drug formulation preserved in the Spezieria of Santa Maria della Scala in Rome, founded at the end of the seventeenth century by the Discalced Carmelites. Due to limited literature related to pharmaceutical remedies and drugs of the Early Modern Era (between the XV and XVIII centuries) and the complexity in their formulations, the study of these drugs represents a great challenge. The untargeted nature of the selected drug required a multi-analytical approach with complementary techniques to formulate a compositional hypothesis: FT-IR spectroscopy, gas chromatography-associated/mass spectrometry (GC-MS) and nuclear magnetic resonance (NMR) were successfully employed to identify different organic compounds. Systematic archaeobotanical research was performed as well, allowing us to acquire data related to the possible genus of plants from which these natural compounds derive and their geographical origin. The unknown drug formulation turned out to be a complex mixture used as an ointment with an anti-inflammatory purpose. It mainly contains a mixture of Venetian turpentine; a Pine resin (colophony) from the Pinaceae family; an exudate of a plant from South America, whose identified components are triterpenic compounds such as alpha- and beta-amyrins, betulin and lupeol; and saturated fatty acids which act as carriers and/or to reduce the viscosity of abovementioned exudates and resins. The study of historical drugs is important not only in order to know the practices handed down by the speziali in the past but also to reconstruct historical recipes, which can inspire new dermatological, cosmetic, hygienic and current healing products.Graphical abstract.

The study and the characterisation of modern and contemporary oil paintings is still a challenging issue, in particular considering the significant changes in paint production across the 19th and 20th centuries. This paper presents the results of the first physico-chemical integrated study of the artistic materials used in six paintings from the School of Art and Higher Design of Valencia (Escola d'Art i Superior de Disseny, EASD-Valencia), artworks created between 1871 and 1943 by four famous Valencian artists: Salustiano Asenso Arozarena, Salvador Abril I Blasco, Enrique Navas Escuriet and José Bellver Delmás. A wide range of inorganic and organic compounds was identified through a multi-analytical approach by means of visible reflectance spectroscopy, XRF, μ-Raman, FTIR and GC-MS. The investigation on the binding media suggests the use of commercial paint formulations including mixtures of drying, slow- and non-drying oils and the presence of Gum Arabic as well. Traditional pigments (such as vermillion, earth pigments, lead white) and modern pigments (such as zinc white, cobalt and chromium-based pigments) were identified together with fillers and extenders. Degradation products, in particular zinc and lead soaps having strong conservation implications, were also detected. This work, focusing on the identification of the palettes and the binding media used by the selected artists, aims at providing meaningful data and interesting case studies that are useful beyond the Valencian painters solely. This study provides new insight into the use of 19th-20th century commercial oil paints and the selection of painters' palette and their artistic production techniques. Besides, this work highlights the necessity of a multi-analytical approach to obtain valuable information for documentation and preventive conservation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

This research evaluates the stability of an aqueous emulsion of acrylic copolymers and waxes. Edelwachs, generally applied on wood, has been recently used as an unconventional medium in contemporary painting. Through Pyrolysis-Gas Chromatography-Mass Spectrometry (Py-GC-MS) and Fourier Transformed Infrared Attenuated Total Reflectance (FT-IR-ATR) analyses, the composition of Edelwachs was defined as a mixture of acrylic polymers (MA, MMA, nBA, nBMA), Carnauba and microcrystalline waxes and additives. Mock-ups-obtained mixing Edelwachs with titanium white, zinc white and ultramarine blue were subjected to UV, high temperatures, and high relative humidity accelerated ageing. The effect of the ageing procedures was evaluated through optical microscopy, colourimetric measurements, FT-IR-ATR, Thermogravimetry and Differential Scanning Calorimetry (TG-DSC) and wettability measures. FT-IR-ATR spectra do not show significant variations in terms of chemical stability, indicating a fair stability of Edelwachs as a painting binder. UV and high temperature treatments show the most relevant effects in terms of colorimetric changes (increasing of b*) and thermal stability. The TG-DSC highlights the influence of the pigments (specifically zinc white) mainly on the thermal behaviour of the acrylates. The unexpected decrease of wettability of the paint films, registered after ageing, may indicate a possible phase separation among acrylates and waxes.

A complementary multi-analytical in-situ approach has been adopted for the investigation of a corpus of ten paintings dating from 1889 and 1940 by the Venetian painter Alessandro Milesi (1856-1945), from the collection of the International Gallery of Modern Art Ca' Pesaro in Venice. Analyses were performed in situ with digital imaging, elemental and spectroscopic analysis. The analysis of pigments and binding media and their possible deterioration patterns were studied with a combination of X-Ray Fluorescence (XRF) Spectroscopy, External Reflection- Fourier Transform Infrared Spectroscopy (ER-FTIR) and Raman Spectroscopy. These analytical methods provide information regarding the evolution of the artist's palette and the painting techniques adopted in painting. Data suggest the widespread detection of zinc carboxylates, with implications for conservation and display., (Copyright © 2019 Elsevier B.V. All rights reserved.)

We present a multi-analytical in situ non-invasive study of a series of emblematic paintings by Alessandro Milesi (1856-1945) from the collection of the International Gallery of Modern Art Ca' Pesaro in Venice. Eight paintings dated from 1897 to 1910 were studied with imaging and spectroscopic techniques. White pigments were characterized by a combination of X-ray fluorescence spectroscopy which traced the presence of zinc-based pigments in Milesi's paintings, Raman Spectroscopy, Laser Induced Fluorescence (LIF) Spectroscopy and Time-resolved Luminescence Imaging. Time-resolved analysis of luminescence emissions revealed the nanosecond emission from organic compounds and the slower emission from the luminescent inorganic pigment Zinc Oxide that varied between 1.1 and 1.6 microseconds. In this work, data regarding the distribution of luminescent pigments was acquired with a time-gated imaging detector. Furthermore, differences in emission decay kinetics recorded from different paintings can be ascribed to different paint formulations or origins of the Zinc white in paint., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The tempera painting technique is one of the most common methods used throughout art history. Tempera is defined by the type of binders used and in this work we study protein-based temperas. Proteinaceous binders can be characterized by the chromatographic determination of the amino acids present where techniques are either based on gas chromatography or high-performance liquid chromatography (HPLC) coupled to mass spectrometry. The objective of this work was to develop a derivatisation-free HPLC method with triple quadrupole tandem mass spectrometric detection (HPLC/ESI-MS/MS) of 21 amino acids contained in the protein-based binders of tempera paints. The analytical method identifies the painting techniques of two contemporary artists: Sironi and DeLuigi. The sample data are compared to painting material standards. The results show that the samples from works by DeLuigi contain mainly animal glue binders, while the samples from Sironi paintings contain binders that are an amino acid mixture with an overall composition between that of eggs and casein., (Copyright 2010 Elsevier B.V. All rights reserved.)