Carolina Cardell

Black soiling of an architectural limestone during two-year term exposure to urban air in the city of Granada (S Spain).

A two-year term aging test was carried out on a building limestone under different urban conditions in the city of Granada (Southern Spain) to assess its Cultural Heritage sustainability. For this purpose stone tablets were placed vertically at four sites with contrasting local pollution micro-environments and exposure conditions (rain-sheltered and unsheltered). The back (rain-sheltered) and the front (rain-unsheltered) faces of the stone tablets were studied for each site. The soiling process (surface blackening) was monitored through lightness (ΔL*) and chroma changes (ΔC*). Additionally atmospheric particles deposited on the stone surfaces and on PM10 filters during the exposure time were studied through a multianalytical approach including scanning electron microscopy (SEM-EDX), transmission electron microscopy (TEM) and micro-Raman spectroscopy. The identified atmospheric particles (responsible for stone soiling) were mainly soot and soil dust particles; also fly ash and aged salt particles were found. The soiling process was related to surface texture, exposure conditions and proximity to dense traffic streets. On the front faces of all stones, black soiling and surface roughness promoted by differential erosion between micritic and sparitic calcite were noticed. Moreover, it was found that surface roughness enhanced a feedback process that triggers further black soiling. The calculated effective area coverage (EAC) by light absorbing dust ranged from 10.2 to 20.4%, exceeding by far the established value of 2% EAC (limit perceptible to the human eye). Soiling coefficients (SC) were estimated based on square-root and bounded exponential fittings. Estimated black carbon (BC) concentration resulted in relatively similar SC for all studied sites and thus predicts the soiling process better than using particulate matter (PM10) concentration.

Innovative Analytical Methodology Combining Micro-X-Ray Diffraction, Scanning Electron Microscopy-Based Mineral Maps, and Diffuse Reflectance Infrared Fourier Transform Spectroscopy to Characterize Archeological Artifacts

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.

Collagen-based proteinaceous binder-pigment interaction study under UV ageing conditions by MALDI-TOF-MS and principal component analysis

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.

Compositional and quantitative microtextural characterization of historic paintings by micro-X-ray diffraction and Raman microscopy.

This work shows the benefits of characterizing historic paintings via compositional and microtextural data from micro-X-ray diffraction (μ-XRD) combined with molecular information acquired with Raman microscopy (RM) along depth profiles in paint stratigraphies. The novel approach was applied to identify inorganic and organic components from paintings placed at the 14th century Islamic University-Madrasah Yusufiyya-in Granada (Spain), the only Islamic University still standing from the time of Al-Andalus (Islamic Spain). The use of μ-XRD to obtain quantitative microtextural information of crystalline phases provided by two-dimensional diffraction patterns to recognize pigments nature and manufacture, and decay processes in complex paint cross sections, has not been reported yet. A simple Nasrid (14th century) palette made of gypsum, vermilion, and azurite mixed with glue was identified in polychromed stuccos. Here also a Christian intervention was found via the use of smalt, barite, hematite, Brunswick green and gold; oil was the binding media employed. On mural paintings and wood ceilings, more complex palettes dated to the 19th century were found, made of gypsum, anhydrite, barite, dolomite, calcite, lead white, hematite, minium, synthetic ultramarine blue, and black carbon. The identified binders were glue, egg yolk, and oil.

Potential thermal expansion of calcitic and dolomitic marbles from Andalusia (Spain)

Marble has historically been used as an ornamental stone because of its aesthetic appeal, ease of polishing and ex;cellent physical properties. One of the main factors affecting the durability of marbles is their thermal behaviour. Although marble is used extensively in Spain as a building and decorative material, little research has been done into its thermal behaviour. In this work, the textural and microstructural properties of seven calcitic and dolomitic marbles from Andalusia (southern Spain) were characterized to assess how these properties affect their thermal response. Rock fabric properties (grain morphology, boundaries and micro-crack populations) were studied by polarized microscopy and lattice preferred orientation using X-ray texture goniometry. Elastic properties were measured by ultrasound, thermal properties were determined by a six-rod dilatometer (thermal expansion) and the opening of micro-cracks was observed using environmental scanning electron microscopy. For each marble, thermal coefficients of calcite and dolomite crystals were calculated using thermo-X-ray diffraction, a novel application to characterize historic marbles. The results show that marble thermal expansion coefficients are related to preferred crystallographic orientation, which can help to identify the directions along which decay occurs. The results also show for the first time that the thermal expansion coefficient of the main components of marble, i.e. calcite and dolomite, is specific to each marble, and plays a key role in their different thermal behaviours. Thermal properties also depend on mineral composition, the existence of micro-cracks and hydric properties.

SEM-EDX at the Service of Archaeology to Unravel Historical Technology

It is well known that there is a profitable cooperation between archaeology and the scientific disciplines of chemistry, geology, biology, and physics with the aim of producing better interpretations of archaeological materials. This field of science is known as archaeometry. Two main goals of archaeometry are to analyze and characterize historic objects to preserve them and to investigate the knowledge and skills required to fabricate them. This latter information is essential in the evaluation of cultural and technological aspects of past societies and to further understand the transference of technological knowledge through time periods and geographical contexts.