Laying hens develop a type of osteoporosis that arises from a loss of structural bone, resulting in high incidence of fractures. In this study, a comparison of bone material properties was made for lines of hens created by divergent selection to have high and low bone strength and housed in either individual cages, with restricted mobility, or in an aviary system, with opportunity for increased mobility. Improvement of bone biomechanics in the high line hens and in aviary housing was mainly due to increased bone mass, thicker cortical bone and more medullary bone. However, bone material properties such as cortical and medullary bone mineral composition and crystallinity as well as collagen maturity did not differ between lines. However, bone material properties of birds from the different type of housing were markedly different. The cortical bone in aviary birds had a lower degree of mineralization and bone mineral was less mature and less organized than in caged birds. These differences can be explained by increased bone turnover rates due to the higher physical activity of aviary birds that stimulates bone formation and bone remodeling. Multivariate statistical analyses shows that both cortical and medullary bone contribute to breaking strengthThe cortical thickness was the single most important contributor while its degree of mineralization and porosity had a smaller contribution. Bone properties had poorer correlations with mechanical properties in cage birds than in aviary birds presumably due to the greater number of structural defects of cortical bone in cage birds.

This work explores the application of principal component analysis (PCA) on first-derivative Raman spectra to investigate historical tempera paint model samples. Various paint model samples were prepared containing pure blue pigments (azurite, lapis lazuli and smalt), pure red pigments (cinnabar, minium and raw Sienna), pure white pigments (lead white, chalk and gypsum), pure egg yolk as binder and tempera model samples obtained by mixing each of the pigments with the binder, and further characterized by Raman spectroscopy. The corresponding Raman spectra were used to apply PCA in order to test whether spectral differences allowed discrimination of samples based on their composition. Multivariate analyses were performed separately on three data matrices, one for each color, namely, white, blue and red, corresponding to the model samples, and all containing the spectral data of the binder model sample. Different pretreatments, that is log and derivative spectra, were performed on the spectra since no pattern distributions were obtained when the original Raman spectra were analyzed. Nevertheless, the multivariate analysis of the original Raman spectra was able to track alterations of sensitive pigments due to laser interaction. Results showed the excellent ability of PCA, when applied to the derived Raman spectra, to discriminate model samples according to their differing compositions in the three groups of model samples tested. This is the first attempt to use this approach in the field of cultural heritage and demonstrates the potential benefits for identifying historical pigments and binders for purposes of conservation and restoration.

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This work seeks to identify the slight changes in the characteristic C-H stretching region (3100-2800 cm −1 ) of a protein-based binder and fatty acid esters from egg yolk, which may occur in complex paint samples due to the presence of particular pigments. To date, this protein region -where historic pigments do not show characteristic Raman bands -has not been used to identify possible interactions between painting materials, in spite of its potential due to the mentioned feature. This study is based on the investigation of pure egg yolk model samples and tempera model samples prepared by mixing this binder with some historic pigments (cinnabar, raw Sienna, lead white, gypsum, calcite, azurite, lapis lazuli and smalt) as binary samples. All samples were analyzed in this region by Raman microscopy (RM) coupled with principal component analysis (PCA) for three color groups (red, white and blue) separately. The results show relevant spectral changes in the C-H stretching region of amino acids and polyunsaturated fatty acids esters of the egg yolk binder, particularly in the azurite, lead white and gypsum-based tempera samples. Lesser interactions were discerned in the tempera samples made with smalt, as well as shift in the region of polyunsaturated fatty acid esters of the egg yolk binder in the cinnabar and rawSienna-based tempera paintings. No interactions were recognized between the egg yolk and the pigments calcite and lapis lazuli. The effectiveness of applying RM combined with PCA for identifying interaction processes between binders and pigments is demonstrated.

This study focuses on acquiring information on the degradation process of proteinaceous binders due to ultra violet (UV) radiation and possible interactions owing to the presence of historical mineral pigments. With this aim, three different paint model samples were prepared according to medieval recipes, using rabbit glue as proteinaceus binders. One of these model samples contained only the binder, and the other two were prepared by mixing each of the pigments (cinnabar or azurite) with the binder (glue tempera model samples). The model samples were studied by applying Principal Component Analysis (PCA) to their mass spectra obtained with Matrix-Assisted Laser Desorption/Ionization-Time of Flight Mass Spectrometry (MALDI-TOF-MS). The complementary use of Fourier Transform Infrared Spectroscopy to study conformational changes of secondary structure of the proteinaceous binder is also proposed. Ageing effects on the model samples after up to 3000 h of UV irradiation were periodically analyzed by the proposed approach. PCA on MS data proved capable of identifying significant changes in the model samples, and the results suggested different aging behavior based on the pigment present. This research represents the first attempt to use this approach (PCA on MALDI-TOF-MS data) in the field of Cultural Heritage and demonstrates the potential benefits in the study of proteinaceous artistic materials for purposes of conservation and restoration.

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Excavations at the 14th century Moorish rampart (Granada, Spain) unearthed a brick oven alongside black ash and bone stratigraphic layers. In situ evidence suggests the oven served to fabricate a wall coating including powdered burnt bones. Original ad hoc analyses improved on conventional methods were used to confirm this hypothesis. These methods enable (i) nondestructive micro-X-ray diffraction (mu-XRD) for fast mineralogical data acquisition (approximately 10 s) and moderately high spatial (approximately 500 microm) resolution and (ii) identification and imaging of crystalline components in sample cross-sections via mineral maps, yielding outstanding visualization of grain distribution and morphology in composite samples based on scanning electron microscopy-energy dispersion X-ray spectrometry (SEM-EDX) elemental maps. Benefits are shown for applying diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) vs transmittance-FT-IR (T-FT-IR) to analyze organic and inorganic components in single samples. Complementary techniques to fully characterize artifacts were gas chromatography/mass spectroscopy (GC/MS), optical microscopy (OM), conventional powder XRD, and (14)C dating. Bone-hydroxyapatite was detected in the coating. Mineralogical transformations in the bricks indicate oven temperatures well above 1000 degrees C, supporting the hypothesis.

We studied ancient enamels on gilded copper from a collection of archeological horse harness pendants of the Museo Instituto Valencia de Don Juan (Madrid, Spain) to test the benefits of a new, nondestructive analytical methodology based on chemometric analysis (i.e., Principal Component Analysis, PCA) on micro‐ATR‐FTIR spectral data and chemical quantification using SEM‐EDS. The novelty of this approach was threefold: (i) PCA allowed the discrimination of the different harness pendants of known origin and attributed to the 14th and 15th centuries according to the chemical complex composition, nanostructure, glass weathering, and/or coloring mechanisms of each colored enamel, separately (i.e., red, purple, blue, and white), (ii) it is a cheap, easily available and nondestructive methodology that enables us to (iii) draw archeological conclusions about the quality of the manufacturing process, reassess the chronology of these objects and attempt to attribute them to different workshops according to the different traditional recipes identified. In particular, the enamels were made of alkali and/or alkaline earth lead‐glass with a wide range of chemical compounds in the form of pigments or opacifiers. Two types of coloring mechanisms were identified, colloidal particles such as copper‐ruby for red enamels, and ionic mechanisms such as Fe(II) and Co(II) to achieve a blue pigments; Mn(III) in the purple pigment; and two kind of white enamels were identified, i.e., tin oxide as an opacifier and uranium oxide. In addition, we established the reason for the poor state of conservation of some of the enamels by means of the identification of depolymerization and ion exchanges, well‐known harmful effects of glass weathering, and finally a chronology was assigned for some of these pieces according to the enamel composition.