Independent macroscopic chemical mappings of cultural heritage materials with reflectance imaging spectroscopy: case study of a 16 century Aztec manuscript.

Reflectance spectral imaging is a powerful tool for the non-invasive study of cultural heritage objects. Particular visible to short wave infrared (400-2500 nm) spectral features are linked to compositional information. Spectral images can hence be used to generate useful chemical maps.

Multi-scale characterization of lead-rich deposited particles originating from the fire of Notre-Dame de Paris.

Fire is a major hazard for built heritage. The fire at Notre-Dame on April 15, 2019 completely destroyed the woodframe and the lead roof (about 285 tons) almost entirely melted due to high temperatures. A part of the molten lead escaped into the atmosphere in the form of aerosols while the majority remains within cathedral enclosure in the form of deposits, metallic remains, spatters etc.

Identification and tentative removal of collagen glue in Palaeolithic worked bone objects: implications for ZooMS and radiocarbon dating.

Collagen glue has been used for nearly two centuries to consolidate bone material, although its prevalence in museum collections is only now becoming visible. Identifying and removing collagen glue is crucial before the execution of any geochemical or molecular analyses. Palaeolithic bone objects from old excavations intended for radiocarbon dating were first analysed using ZooMS (Zooarchaeology by Mass Spectrometry) to identify the animal species, however peaks characteristic of both cattle and whale were discovered.

A Versatile Shaping Method of Very-High Loading Porous Solids Paper Adsorbent Composites.

Owing to their high porosity and tunability, porous solids such as metal-organic frameworks (MOFs), zeolites, or activated carbons (ACs) are of great interest in the fields of air purification, gas separation, and catalysis, among others. Nonetheless, these materials are usually synthetized as powders and need to be shaped in a more practical way that does not modify their intrinsic property (i.e.

Decoupling hydrolysis and oxidation of cellulose in permanent paper aged under atmospheric conditions.

In order to investigate a synergetic role of water and oxygen in the degradation of permanent paper in archiving climate, accelerated ageing in three different conditions was conducted: humid air, humid nitrogen and dry air. This allowed to decouple acid-catalysed hydrolysis versus oxidation of cellulose. After ensuring the reliability of the ageing experiment, the degradation state of the paper was assessed.

In Operando Spectroscopic Ellipsometry Investigation of MOF Thin Films for the Selective Capture of Acetic Acid.

The emission of polar volatile organic compounds (VOCs) is a major worldwide concern of air quality and equally impacts the preservation of cultural heritage (CH). The challenge is to design highly efficient adsorbents able to selectively capture traces of VOCs such as acetic acid (AA) in the presence of relative humidity (RH) normally found at storage in museums (40-80%). Although the selective capture of VOCs over water is still challenging, metal-organic frameworks (MOFs) possess highly tunable features (Lewis, Bronsted, or redox metal sites, functional groups, hydrophobicity, etc.

Methodology for dyes purification by preparative bidimensional offline reversed-phase high-performance liquid chromatography separation based on mobile phase pH change: Case study of Justicia spicigera.

The extensive characterization of the natural dyes involves the purification of their colored compounds for their structural analysis and stability studies. As most natural compounds being ionizable, herein is presented the optimization of an easy and affordable preparative bidimensional offline reversed-phase high-performance liquid chromatography purification based on mobile phase pH change. At the analytical scale, several combinations of stationary phases and mobile phases at different pH values were investigated first.

Diversity of spp. strains isolated from the cultural heritage environment: Phylogenetic diversity, phenotypical diversity, and occurrence.

is a fungal species that frequently occurs in the cultural heritage environment. Although three subclades were initially described in the species, no study has sought to determine the occurrence of each subclade in the cultural heritage context. These subclades are easily distinguishable phylogenetically, but their morphological identification is more difficult.

Mimicry can drive convergence in structural and light transmission features of transparent wings in Lepidoptera.

Müllerian mimicry is a positive interspecific interaction, whereby co-occurring defended prey species share a common aposematic signal. In Lepidoptera, aposematic species typically harbour conspicuous opaque wing colour patterns with convergent optical properties among co-mimetic species. Surprisingly, some aposematic mimetic species have partially transparent wings, raising the questions of whether optical properties of transparent patches are also convergent, and of how transparency is achieved.

2D macro-XRF to reveal redacted sections of French queen Marie-Antoinette secret correspondence with Swedish count Axel von Fersen.

During the French Revolution, Marie-Antoinette, queen of France and wife of Louis XVI, maintained a highly secret correspondence with the Swedish count Axel von Fersen, her close friend and rumored lover. An unidentified censor later redacted certain sections of the exchanged letters. This presumably sensitive content has been puzzling historians for almost 150 years.

Noninvasive quantitative assessment of collagen degradation in parchments by polarization-resolved SHG microscopy.

Nondestructive and noninvasive investigation techniques are highly sought-after to establish the degradation state of historical parchments, which is up to now assessed by thermal techniques that are invasive and destructive. We show that advanced nonlinear optical (NLO) microscopy enables quantitative in situ mapping of parchment degradation at the micrometer scale. We introduce two parameters that are sensitive to different degradation stages: the ratio of two-photon excited fluorescence to second harmonic generation (SHG) signals probes severe degradation, while the anisotropy parameter extracted from polarization-resolved SHG measurements is sensitive to early degradation.

Spectral characterisation of a traditional Mesoamerican dye: relationship between identification on the 16 century manuscript and composition of plant extract.

Characterisation of vegetal colourants in manuscripts is still a challenging task. Their identification using non-invasive techniques - since sampling is rarely possible - is valid only if there is evidence that the recorded signals are generated by compounds specific to the plant species. Otherwise, more extensive chemical characterisations are required to relate the non-invasive technique signals to the chemical composition of the dye extract and thus avoid misidentification.

A Preliminary Study on the Differentiation of Linseed and Poppy Oil Using Principal Component Analysis Methods Applied to Fiber Optics Reflectance Spectroscopy and Diffuse Reflectance Imaging Spectroscopy.

This paper presents results from the examination of a set of experimental samples using fibre optic reflectance spectroscopy (FORS) and diffuse reflectance imaging spectroscopy in the short-wave infrared (SWIR) range, combined with statistical analysis of the data for the discrimination and mapping of poppy and linseed oil. The aim was to evaluate the efficacy of this non-invasive approach for the study of paint samples with a view to the application of the method for characterisation of the two drying oils in painted art. The approach allowed discrimination between the two drying oils based on FORS spectra and the hyperspectral cube, indicating the influence of the spectral region around 1700 nm on the statistical discrimination based on the anti-symmetric and symmetric first overtone stretching of methylenic CH groups.

Regio- and Stereo-Specific Chemical Depolymerization of High Molecular Weight Polybutadiene and Polyisoprene for Their Analysis by High-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry: Comparison with Pyrolysis-Comprehensive Two-Dimensional Gas Chromatography/Mass Spectrometry, Atmospheric Solid Analysis Probe, Direct Inlet Probe-Atmospheric Pressure Chemical Ionization Mass Spectrometry, and Ion Mobility Spectrometry-Mass Spectrometry.

Polybutadiene (PB) and polyisoprene (PI), the two most common polydienes (PD), are involved in a large number of materials and used in a wide variety of applications. The characterization of these polymers by mass spectrometry (MS) continues to be very challenging due to their high insolubility and the difficulty to ionize them. In this work, a cross-metathesis reaction was used to generate end-functionalized acetoxy ionizable oligomers for the structural deciphering of different commercial PB and PI samples.

Palaeoproteomics gives new insight into early southern African pastoralism.

The advent of domestication is a major step that transformed the subsistence strategies of past human societies. In Africa, domestic caprines (sheep and goat) were introduced in the north-eastern part of the continent from the Near East more than 9000 years ago. However, their diffusion southwards was slow.

Short- and Long-Term Effects of X-ray Synchrotron Radiation on Cotton Paper.

X-ray analytical techniques are increasingly being used to study manuscripts and works of art on paper, whether with laboratory equipment or synchrotron sources. However, it is difficult to anticipate the impact of X-ray photons on paper- and cellulose-based artifacts, particularly due to the large variety of their constituents and degradation levels, and the subsequent material multiscale heterogeneity. In this context, this work aims at developing an analytical approach to study the modifications in paper upon synchrotron radiation (SR) X-ray radiation using analytical techniques, which are fully complementary and highly sensitive, yet not frequently used together.

Tracking the Near Eastern origins and European dispersal of the western house mouse.

The house mouse (Mus musculus) represents the extreme of globalization of invasive mammals. However, the timing and basis of its origin and early phases of dispersal remain poorly documented. To track its synanthropisation and subsequent invasive spread during the develoment of complex human societies, we analyzed 829 Mus specimens from 43 archaeological contexts in Southwestern Asia and Southeastern Europe, between 40,000 and 3,000 cal.

Spectroscopies and Electron Microscopies Unravel the Origin of the First Colour Photographs.

The first colour photographs were created by a process introduced by Edmond Becquerel in 1848. The nature of these photochromatic images colours motivated a debate between scientists during the XIX century, which is still not settled. We present the results of chemical analysis (EDX, HAXPES and EXAFS) and morphology studies (SEM, STEM) aiming at explaining the optical properties of the photochromatic images (UV-visible spectroscopy and low loss EELS).

Ancient Greek text concealed on the back of unrolled papyrus revealed through shortwave-infrared hyperspectral imaging.

Only a few Herculaneum rolls exhibit writing on their reverse side. Since unrolled papyri are permanently glued to paperboard, so far, this fact was known to us only from 18th-century drawings. The application of shortwave-infrared (SWIR; 1000-2500 nm) hyperspectral imaging (HSI) to one of them ( 1691/1021) has revealed portions of Greek text hidden on the back more than 220 years after their first discovery, making it possible to recover this primary source for the ongoing new edition of this precious book.

Ion beam analysis of silver leaves in gilt leather wall coverings.

An analytical methodology involving Particle Induced X-ray Emission (PIXE) and Rutherford Backscattering Spectroscopy (RBS) was implemented to respectively characterize the composition and the thickness of silver leaves on gilt leather decors. These objects, ancestors of our wallpapers, are nowadays still difficult to date and their provenance is generally determined from stylistic studies. The initial aim of this study was to identify markers that could be correlated with the object provenance to help distinguishing the different gilt leathers workshops in Europe.

Enhancement of Ethane Selectivity in Ethane-Ethylene Mixtures by Perfluoro Groups in Zr-Based Metal-Organic Frameworks.

A series of zirconium dicarboxylate-based metal-organic frameworks (Zr MOFs) of the UiO-66 (tetrahedral and octahedral cages) or MIL-140 (triangular channels) structure type were investigated for the separation of ethane/ethylene mixtures. The adsorption, investigated both experimentally and computationally, revealed that the size and type of pores have a more pronounced effect on the selectivity than the aromaticity of the linker. The increase in pore size when changing from benzene to naphthalene (NDC) dicarboxylate ligand makes UiO-NDC less selective (1.

A Combined Non-Invasive Approach to the Study of A Mosaic Model: First Laboratory Experimental Results.

This paper presents first laboratory results of a combined approach carried out by the use of three different portable non-invasive electromagnetic methods: Digital holographic speckle pattern interferometry (DHSPI), stimulated infrared thermography (SIRT) and holographic subsurface radar (HSR), proposed for the analysis of a custom-built wall mosaic model. The model reproduces a series of defects (e.g.

Identification of traditional East Asian handmade papers through the multivariate data analysis of pyrolysis-GC/MS data.

An analytical approach based on the multivariate analysis of on-line pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) data is proposed for the identification of traditional East Asian handmade papers from different fiber material origins. This approach utilized several biomarkers detected during the Py-GC/MS analysis of paper samples. At first, the total ion chromatogram (TIC) was taken as the response and then the extracted ion chromatograms (EICs) were considered to improve the discrimination of papers.

Pyrolysis comprehensive gas chromatography and mass spectrometry: A new tool to assess the purity of ancient collagen prior to radiocarbon dating.

Exogenous carbonaceous contaminants coming from sediments significantly bias the radiocarbon date of collagen samples extracted from archaeological bone and teeth. In this study, a new approach combining pyrolysis, comprehensive gas chromatography and mass spectrometry (Py-GC × GC/MS) was proposed to ensure their removal during the demineralization and bone collagen extraction. This approach permitted to identify hydrocarbon contaminants for archaeological samples from the Neolithic period, in 30-40 μg of collagen.