For centuries, natural stone has adorned facades, evolving from thick construction elements to thin cladding applications due to advanced cutting technologies. However, durability issues, especially in thin marble cladding, have surfaced after approximately 50 years of installation, as seen in iconic structures like the Amoco Building and Finlandia Hall. This study focuses on characterizing Carrara and Ruivina marbles, Pedra de Ana and Estremadura limestones, worldwide used in cladding. Through a comprehensive analysis of physical, mechanical, and aging properties, including bending strength, thermal shock, and freeze-thaw tests, the research aims to understand potential mechanical decay over time. Results reveal a connection between temperature variations, moisture, and the decay of marbles and limestones. This study provides a crucial contribution to the understanding of structural degradation in facades, essential for sustainable and enduring architectural solutions.

Biodeterioration of construction materials is still a major challenge that conservator-restorers face, especially in historic monuments with high cultural value. Natural stone is highly susceptible to deterioration through physical, chemical, and biological ways, whereas biological proliferation may potentiate both chemical and physical deterioration. The composition of the colonizers and their proliferation are highly dependent on climatic parameters like temperature and humidity, which are distinct from place to place. The present work proposes the execution of an innovative methodology that enables the determination of the susceptibility of natural stone to biocolonization, a parameter denominated as biosusceptibility. The study aims to contribute to the creation of models by predicting their deterioration even before the objects’ manufacture, promoting the sustainability of one of the most valuable natural resources. The methodology proposed here was performed on limestones, marbles and slates—exploited in the Portuguese territory—by using colonizing strains typically found on stones exposed to the Mediterranean climate. The results have demonstrated that the stones with higher porosity are less susceptible to epilithic colonization and, consequently, with a moderate alteration of their aesthetic appearance. However, the metabolic activity determined in these stones is higher, which indicates that biocolonization will cause more severe damage to their structure in the future. The first significant changes on the stones’ matrix were assessed one year after the inoculation, using cutting-edge technology of 3D surface micro-reconstruction. Due to its relevance in natural stone deterioration processes, the inclusion of the biosusceptibility information in technical brochures is strongly encouraged.

Coastal systems are especially vulnerable to human activities resulting from a range of direct physical modifications of the ecosystems to the biological, chemical, and physical impacts of pollutants. For the most recent decades, these modifications can be accurately tracked by industrial development indicators, providing an exceptional record of historical changes. In return, when such changes are identified in the sedimentological record, they can serve as precise chronological markers. Here, we examined the potential of petcoke particles, a by-product of crude oil refining, as an emergent sediment dating tool. To this end, giant (63-similar to 200 mu m) black spheroidal petcoke particles - present in cores retrieved in the salt marshes of the Sado estuary (SW Portugal) were used. These anthropogenic particles were counted and identified according to their morphology, structure, and chemical composition, using complementary micro-beam techniques: Scanning Electron Microscope and Energy Dispersive Spectroscopy, and Micro X-Ray Diffraction. The analyses revealed shot-type green petcoke particles containing a set of elements, which are well-known metallic/non-metallic impurities in petcoke. Based on the available historical data on petcoke imports in the port of Setubal (Sado estuary) and Portugal, their first appearance in sediments can be dated to 1996 +/- 2, with maxima in 2006 +/- 4. Both the presence and the historical evolution of the use of petcoke in the region were recorded in all sediment cores, with higher particle density in locations aligned with the prevailing winds. The combination of petcoke and Cs-137 data provided accretion rates for the 1963-2006 period ranging from 0.1 to 0.3 cm yr(-1) (average: 0.2 cm yr(-1)), while these rates significantly increased from 2006 onwards (avg. rate: 1.1 cm yr(-1); range: 0.6-2.1 cm yr(-1)). The widespread handling of petcoke worldwide leads us to suggest petcoke particles as a reliable chronological marker at local and regional scales, to be used in combination with other dating methods to build more exact sediment chronologies.

This study focuses on the analysis of Islamic ceramics from the Alcaçova of Santarém, Portugal. To establish the ceramic raw material provenance and ceramic technology, a set of raw materials was sampled and compared with the archaeological ceramics. Raw materials were dry sieved to increase the clay content, to reconstruct the ceramist homogenization process, and to evaluate chemical and mineralogical variation. Results showed that two raw materials were selected for local ceramic production, whereas some artefacts were imported.

The InCarbon project based on the principles of CO2 capture and storage technologies, aims to study the potential of in situ mineral carbonation in mafic rocks in Alentejo. The gabbro of Sines massif was selected for the first laboratory test of mineral carbonation due to its geochemical, mineralogical and textural characteristics and proximity to the main focus of CO2 emissions in the region. Gabbro specimens were submerged in natural brine and supercritical CO2 for periods of 1, 4, 16 and 64 days, under 80 bar and 40 oC. The specimens were characterized before and after the experiments by means of XRD, OM, VP-SEM-EDS and ATR-FTIR, and the brine composition was analysed. Results show dissolution of silicates and textural roughness increasing with the number of days of immersion into brine. The behaviour of cations in solution after several days of testing is irregular and carbonate precipitation was not detected.

This study characterises and compares tin-opacified underglaze-decorated tiles from Valencian and Sevillian provenances. This technique, where the cobalt and manganese pigments are applied below an opaque white glaze, was used in the Iberian Peninsula between the 14th and early 16th centuries. The chemical and morphological characterisation of the glazes was performed by Optical Microscopy (OM), Scanning Electron Microscopy with Energy-Dispersive X-Ray Spectroscopy (SEM-EDS), mu-Raman Spectroscopy, and mu-Particle-Induced X-Ray Emission (mu-PIXE). Both the morphology of the glazes and their chemical composition allowed for the distinction between the two production centres. Sevillian glazes exhibit a thicker pigment layer, as well as higher SnO2 and lower K2O contents than the Valencian ones. Furthermore, the SEM analysis of cobalt pigment particles identified an interior nucleus rich in Co, Fe and Ni, and an exterior layer rich in Si, Ca, Mg and Na, suggesting that the pigment was used mixed with clay or sand.

This study aimed at evaluating the influence of ageing on the bioreceptivity and biodeterioration of glazed tiles by fungi. These microorganisms have been identified in historical tile colonizing microbial communities. A 12-month laboratory colonization experiment was conducted using pristine and artificially aged tile models inoculated with Devriesia imbrexigena. Fungal growth was evaluated by digital image analysis after incubation. Scanning electron microscopy and micro-Raman spectroscopy were performed to assess tile biodeterioration, revealing that organic acids exuded by D. imbrexigena induced the precipitation of calcium oxalate on the glazed surfaces. Results also showed that the ageing degree was not related to bioreceptivity.

Four distinct Palaeozoic episodes of marine carbonate sedimentation are reported in the Ossa-Morena Zone (SW Iberian Variscides). Among them, the Cambrian and the Devonian episodes are those that are well represented in the Portuguese domains of the Ossa-Morena zone. In this zone, the strong Variscan deformation and metamorphic recrystallization obliterate the biostratigraphic contents of some carbonate local successions and their ages have been based on lithostratigraphic correlations. The 87 Sr/ 86 Sr values for the Ossa-Morena zone carbonate rocks allow to make an isotopic–lithostratigraphic correlation, based on the comparison between strontium ratios of marine carbonate rocks without chronological data and carbonate rocks with a good age control. Moreover, the established 87 Sr/ 86 Sr fingerprints of the marine carbonate episodes from Ossa-Morena zone should be simultaneously correlated with the worldwide seawater 87 Sr/ 86 Sr curve. Despite the interaction of the marine carbonate sedimentation with late secondary dolomitization processes or with high-temperature metamorphic/metasomatic fluids, which increases the primary 87 Sr/ 86 Sr ratios, this methodology allows to define two main distinct clusters of 87 Sr/ 86 Sr for the Ossa-Morena zone marine carbonates: a Devonian cluster with strontium ratios lower than 0,708000; and a Cambrian cluster ranging from 0.708777 to 0.708299 (0.708575 ± 0,000161), that can reach 0.709227–0.708866 (0.709087 ± 0,000118) if incipient late secondary dolomitization or high-temperature metamorphism/metasomatism operated. The obtained 87 Sr/ 86 Sr isotopic ratios corroborate the lithostratigraphic correlations between the carbonate rocks of Abrantes, Assumar, Estremoz, Viana-Alvito, Ficalho and Escoural successions with the Ovetian–Marianian limestones of Alter-do-Chão–Elvas Succession. Moreover, this methodology allows to establish the isotopic discrimination between the Upper Silurian–Devonian limestones of Ferrarias, Barrancos and Bencatel successions and the marbles of Estremoz Succession.

The analytical characterization of mortar samples from the roman archaeological site of Pisoes, located in Southern Portugal, were carried out by means of X-ray diffractometry (XRD), thermogravimetry (TGA-DTA), optical and electron scanning microscopy (SEM-EDS), potentiometry and combustion analysis. The Pisoes archaeological complex includes a villa rustica, characterized by well-preserved mosaics and thermal baths, as well as a mill and a mausoleum. Countryside villae epitomized the Romanization of the Iberian Peninsula for over six centuries (2nd century BCE-4th century CE). Nevertheless, most of the Roman villae identified in Portugal have not yet been systematically explored and studied. This study provides valuable data on the construction materials and techniques used in Roman times in the Iberian Peninsula. The careful selection of raw materials and the use of natural and artificial pozzolanic materials can explain the favourable state of conservation, mechanical strength and long-term durability of these mortars. (C) 2019 Elsevier Ltd. All rights reserved.

Tin (Sn) or a Sn-rich solder applied to copper-based artefacts has been frequently used at least, since the Ancient Greece, although scarce studies have been published concerning the technology of this metallurgical joining technique. Several filler remnants were reported to be found in a Roman collection of handle attachments of situlae or cauldrons (2nd century BCE-5th century CE) from the archaeological site of Conimbriga, a Roman city from the Lusitania Province (Portugal). All these artefacts were cast in high leaded coppers and bronzes. The present study aims to contribute to the knowledge of Sn-rich soldering, an ancient metallurgical joining technique, by the characterisation of the fusible metallic alloy present in 10 Roman artefacts by means of micro-energy dispersive X-ray fluorescence spectrometry (micro-EDXRF), scanning electron microscopy with energy dispersive X-ray (SEM-EDS) microanalysis and optical microscope (OM) observations. Results of studied solders show the presence of Cu-Sn alloys, with Sn contents ranging from 8 toll phase composition (30-60 wt% Sn). As the attachments were made in leaded copper alloys, it was also observed, in some cases, the melting of the interdendritic Pb-rich chains with long-range diffusion of the solder alloy into the substrate. The fillers compositions suggest that the handle attachments have been joined to a situla body by the soldering metallurgical process with Sn or a Sn-rich alloy. The studied leaded Cu-Sn attachments, probably formulated by local craftsman, were joined into the body of a situla or cauldron with a soft solder (soldering), a common metallurgical joint from Antiquity, although no relation was found between composition or typology and the Sn or Sn-rich solder. (C) 2018 Elsevier B.V. All rights reserved.

In the present study a set of common, painted and glazed ceramic were analysed using a pXRF spectrometer. Ceramic paste characteristics were utilised to identify possible trade between the cities of Evora and Mertola during the Muslim domination. Ceramic paste analysis revealed that unpainted and painted ceramic were enriched in Fe while glazed ceramics were enriched in Ca. Moreover, comparative analysis of the whole assemblage suggests that ceramics from Evora and Mertola have different Ti/Fe ratio indicating different origins and consequently different productive centres. For what concerns the decorative layers, results showed that white and red painted decorations were obtained using Ca and Fe oxides respectively. Glaze decorations were obtained with a silicon lead mixture. Oxide of tin was utilised as opacify agent. Green, light blue, black and yellow glazes were obtained using Cu, Mn+Fe and Fe oxides respectively.

Convent of Christ (UNESCO'sWorld Heritage Monument, Tomar-Portugal) is one of the most expressive testimonies of Portuguese architecture, whose huge structure include seven cloisters, different monastic constructions and the emblematic Chapter Window (or Manueline Window). Unfortunately, over the years the stone materials have been subjected to several damages, which have modified the appearance of the surfaces and their integrity. Attending to the negative effects of the microbial population on the rock surfaces, our research is actively pursuing the microorganisms responsible for biodeterioration/biodegradation and attempting signalise the biodeteriogenic agents. Furthermore, the development of mitigation strategies based on alternative green solutions, have been successfully tested in simulation assays, for promoting the safeguard of these stone materials. Natural biocompounds produced in our laboratory (Bevotech) reveal effective inhibition capacity (in vitro and in situ assays) and do not induce alterations on the rock materials. These compounds seem to be a green/ecofriendly solution for Cultural Heritage safeguard plan.

The ruins and artifacts of Domus dei Dolia testify to its tragic end and the hasty scape of its wealthy owners in the 1st century BC. The excavating campaigns that started at 2009 have revealed several materials of personal and constructive use that allow an integrated archaeometric study on the way of life of Etruscan owners and excellence of construction. This work intends to contribute to the characterization of mortars and construction materials within a broader multidisciplinary study. The data obtained in renders show a careful selection of materials and applied techniques whereas the provenance of the raw materials is in agreement with a distance until 8 km.

Aiming to develop a straightforward magnetic-based sample preparation methodology for the selective extraction of dimethoate from olive oil, the synthesis of dimethoate-imprinted polymer on the surface of modified magnetic nanoparticles has been attempted. Molecular recognition assays have proven their suitability for the selective pre-concentration of dimethoate. Mechanistic basis for template selective recognition has been explored using a quantum chemical approach, providing new insights about the mechanisms underlying template recognition. Thus, a magnetic molecularly imprinted solid-phase extraction method was developed allowing the extraction of dimethoate from spiked olive oil samples, at levels similar to the maximum residue limits imposed by legislation, followed by the quantification of their levels by high-performance liquid chromatography with diode-array detection. Recoveries of 94.55% were obtained, with relative standard deviations lower than 0.53% (n = 3). The developed sample preparation technique enables a selective pre-concentration/enrichment of dimethoate from olive oil matrix with minimum handling and less solvent consumption.

For the first time, Hispano‐Moresque glazed tiles from Portuguese and Spanish collections were studied together and compared. This work is included in a wider study tackling the technology of Hispano‐Moresque tile production from several collections in the Iberian Peninsula. While showing many similarities, differences were identified between collections, regarding both chemical and morphological characteristics. The collection from the Mosteiro de Santa Clara‐a‐Velha (Coimbra) stands out from the other collections, with higher SnO 2 content (up to 14 wt%), the highest Fe 2 O 3 contents in amber glazes and a Ca‐rich interface layer (mostly comprised of wollastonite, CaSiO 3 ). Samples from Palácio Nacional de Sintra (near Lisbon) and Seville‐attributed samples (from the Instituto Valencia de Don Juan) are chemically similar, except that most Sintra's samples display a K‐rich glaze/ceramic interface, whereas the ones from Seville exhibit both K‐rich and Ca‐rich inclusions. The samples attributed to Toledo show glazes with many inclusions, contrasting with the homogeneous glazes in most Hispano‐Moresque tiles. From these results, we identify differences that can be used as markers in future studies on Hispano‐Moresque tiles .

Uranyl phosphate minerals play an important role in the uranium immobilization within weathering and supergene enrichment profiles. This work consists on the morphological, structural and chemical characterization of natural and synthetic minerals of Cu and Ba – metatorbernite and metauranocircite, respectively. SEM imaging has revealed an extended range of morphologies, from tabular to rosette-like crystals, with the presence of epitaxial growths. These studies have also revealed natural heterogeneities affected by cationic substitution along preferred crystallographic directions. The experimental results suggest that the precipitation of metatorbernite is easier than metauranocircite. Simulations of the chemical system show that precipitation depends on supersaturation evolution, which in turn in a function of aqueous complex formation between phosphate and free uranyl ions. An electron probe microanalysis suggests that the failure to precipitate metauranocircite may be due to later ionic depletion of the solution media (phosphate and uranyl), because of the early metatorbernite precipitation.

The glaze and in-glaze pigments of the historical nineteenth-century glazed tiles from the Pena National Palace (Sintra, Portugal) were characterized using a multi-analytical approach. Chemical composition and microstructural characterization were ascertained by µ-PIXE, µ-Raman, optical microscopy and VP-SEM–EDS. The manufacturing technique and colour palette in these tiles were found to be close to the ceramic pigments used in traditional majolica. The blue and purple colours derive from cobalt oxide and manganese oxide, respectively. A mixture of Pb–Sn–Sb yellow with cobalt oxide and iron oxide was used for green and dark yellow, respectively, while grey tonalities consist of a complex mixture of cobalt oxide, manganese oxide and Pb–Sn–Sb yellow in different proportions. Results obtained allowed the determination of the oxides and elements used in pigments as well as production techniques, resorting to traditional majolica manufacture, although the tiles were produced by the end of the nineteenth century.

A laboratory-based methodology was designed to assess the bioreceptivity of glazed tiles. The experimental set-up consisted of multiple steps: manufacturing of pristine and artificially aged glazed tiles, enrichment of phototrophic microorganisms, inoculation of phototrophs on glazed tiles, incubation under optimal conditions and quantification of biomass. In addition, tile intrinsic properties were assessed to determine which material properties contributed to tile bioreceptivity. Biofilm growth and biomass were appraised by digital image analysis, colorimetry and chlorophyll a analysis. SEM, micro-Raman and micro-particle induced X-ray emission analyses were carried out to investigate the biodeteriorating potential of phototrophic microorganisms on the glazed tiles. This practical and multidisciplinary approach showed that the accelerated colonization conditions allowed different types of tile bioreceptivity to be distinguished and to be related to precise characteristics of the material. Aged tiles showed higher bioreceptivity than pristine tiles due to their higher capillarity and permeability. Moreover, biophysical deterioration caused by chasmoendolithic growth was observed on colonized tile surfaces.