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Correctly describing the deterioration patterns is of great importance for the conservation of built cultural heritage. Also, their rapid in situ quantification is an essential requisite when studying exposed stone objects, to define satisfactory restoration actions and to avoid greater damage due to the application of incorrect treatments. The research described in this paper targets developing a methodology to compute the extent of different deterioration patterns on a granitic cultural heritage object using as a case study an overpass bridge called Puente Nuevo in Ourense (NW Spain). The applied methodology consisted of the combination of the geometric and radiometric information collected from a non-invasive and in situ mobile LiDAR system (MLS) and micro destructive analytical techniques. Laser scanning points were used as a base to create orthophotos, being their intensity values the input for an unsupervised classification method to determine the areas occupied for those different deterioration patterns. In parallel, as part of this multi-analytical approach different conventional analytical techniques (X ray diffraction, Fourier transform infrared spectroscopy and optical microscopy) were applied to chemically and mineralogically characterize those deterioration patterns, namely, gypsum black crust, calcite encrustations and biological colonization (mosses). LiDAR technology allowed to determine three different clusters considering the reflectance of those surfaces: uncoated granite, calcite encrustations and black crusts and biological colonization patinas in a combined cluster due to their close reflectance spectra. The computed extent and the location of those deterioration patterns will allow to identify the most suitable cleaning treatment saving money and time.

Findings of Iron Age metallurgical activities related to tin metal and mining are very rare. In the present work, we present a detailed study of the Outeiro de Baltar hillfort, dated to the Late Iron Age/Early Roman period, located in a place where 20th century tin mining work took place. Elemental and microstructural analysis by portable, micro and wavelength dispersive X-ray fluorescence spectrometry (pXRF, micro-XRF and WDXRF) and scanning electron microscopy with energy dispersion spectrometer (SEM-EDS) showed that metallurgical debris found at the archaeological site is related to tin smelting and binary and ternary bronze productions. Analysis of the artefacts of diverse typologies found at the site showed that a variety of metals and alloys were in circulation and use. Samples of tin ores (cassiterite) from the region were analyzed for comparison with an archaeological tin slag from the site. The analytical results point to the production of tin metal using local cassiterite and the production of bronze by directly adding cassiterite into a smelting process. Furthermore, data of remote sensing (airborne Light Detection and Ranging (LiDAR) and historical aerial imagery) and Geographical Information System (GIS) mapping were combined with archival mining documentation and maps to retrieve a landscape context for the site. The study showed that the place of the Outeiro de Baltar hillfort (NW Iberia) was mined periodically over time. publishersversion published

The on-board identification of ore minerals during a cruise is often postponed until long after the cruise is over. During the M127 cruise, 21 cores with deep-seafloor sediments were recovered in the Trans-Atlantic Geotraverse (TAG) field along the Mid Atlantic Ridge (MAR). Sediments were analyzed on-board for physicochemical properties such as lightness (L*), pH and Eh. Selected samples were studied for mineral composition by X-ray powder diffraction (XRD). Based on XRD data, sediment samples were separated into high-, low- and non-carbonated. Removal of carbonates is a common technique in mineralogical studies in which HCl is used as the extraction agent. In the present study, sequential extraction was performed with sodium acetate buffer (pH 5.0) to remove carbonates. The ratio between the highest calcite XRD reflection in the original samples (Iorig) vs its XRD-reflection in samples after their treatment with the buffer (Itreat) was used as a quantitative parameter of calcite removal, as well as to identify minor minerals in carbonated samples (when Iorig/Itreat &gt, 24). It was found that the lightness parameter (L*) showed a positive correlation with calcite XRD reflection in selected TAG samples, and this could be applied to the preliminary on-board determination of extraction steps with acetate buffer (pH 5.0) in carbonated sediment samples. The most abundant minerals detected in carbonated samples were quartz and Al- and Fe-rich clays. Other silicates were also detected (e.g., calcic plagioclase, montmorillonite, nontronite). In non-carbonated samples, Fe oxides and hydroxides (goethite and hematite, respectively) were detected. Pyrite was the dominant hydrothermal mineral and Cu sulfides (chalcopyrite, covellite) and hydrothermal Mn oxides (birnessite and todorokite) were mineral phases identified in few samples, whereas paratacamite was detected in the top 20 cm of the core. The present study demonstrates that portable XRD analysis makes it possible to characterize mineralogy at cored sites, in particular in both low- and high-carbonated samples, before the end of most cruises, thus enabling the quick modification of exploration strategies in light of new information as it becomes available in near-real time.

The archaeological site of Almaraz is located in the old part of the city of Almada, in the south shore of Tagus River, region of Lisbon. The excavated findings and the radiocarbon dating of the contexts where these were found show an occupation that can in fact be dated from the 8th to the 7th c. BCE period, thus a very early stage of the Phoenician occupation in the Iberian Peninsula. Numerous amphorae sherds were found at Almaraz. A spectroscopic characterization of those ceramics was made and is presented here, to help us understand if they were produced locally, in Lisbon workshops, or imported. Sixteen sherds representative of the thousands found at Almaraz were studied with the use of non-invasive spectroscopies, namely by crossing information from micro-Raman and X-ray fluorescence emission data. X-ray diffraction experiments were also performed. In spite of the fact that no ceramic kilns were found at Almaraz until now, the results point to two major groups of amphorae of local origin: one which used clays of Miocene origin, found on the southern shores of the Tagus River, very close to the Almaraz site, at Palenca (with quartz, anorthite, diopside and hematite). Another group, remarkably different, made use of clays of Pliocene origin also from the Tagus Estuary, the Fontainhas clay source (where quartz, anorthite, muscovite and hematite were found).

22 páginas.-- 6 figuras.-- 115 referencias.-- Additional Supporting Information may be found in the online version of this article: http://dx.doi.org/10.1111/sed.12431, Subsurface granitic environments are scarce and poorly investigated. A multi‐disciplinary approach was used to characterize the abundant moonmilk deposits and associated microbial communities coating the granite walls of the 16th Century Paranhos spring water tunnel in Porto city (north‐west Portugal). It is possible that this study is the first record of moonmilk in an urban subsurface granitic environment. The morphology and texture, mineralogical composition, stable isotope composition and microbial diversity of moonmilk deposits have been studied to infer the processes of moonmilk formation. These whitish secondary mineral deposits are composed of very fine needle‐fibre calcite crystals with different morphologies and density. Calcified filaments of fungal hyphae or bacteria were distinguished by field emission scanning electron microscopy. Stable isotope analysis revealed a meteoric origin of the needle‐fibre calcite, with an important contribution of atmospheric CO2, soil respiration and urn:x-wiley:00370746:media:sed12431:sed12431-math-0001 from weathering of Ca‐bearing minerals. The DNA‐based analyses revealed the presence of micro‐organisms related to urban contamination, including Actinobacteria, mainly represented by Pseudonocardia hispaniensis, Thaumarchaeota and Ascomycota, dominated by Cladosporium. This microbial composition is consistent with groundwater pollution and contamination sources of the overlying urban area, including garages, petrol stations and wastewater pipeline leakage, showing that the Paranhos tunnel is greatly perturbed by anthropogenic activities. Whether the identified micro‐organisms are involved in the formation of the needle‐fibre calcite or not is difficult to demonstrate, but this study evidenced both abiotic and biogenic genesis for the calcite moonmilk in this subsurface granitic environment., The authors acknowledge the Spanish Ministry of Economy, Industry and Competitiveness (MINEICO, project CGL2011-2569) and the Portuguese Foundation for Science and Technology, FCT (UID/GEO/04035/2013, UID/ECI/04028/2013, PEst-OE/CTE/UI0098/2011) and the LABCARGA| ISEP re-equipment program (IPP-ISEP|PAD’2007/ 08) for financial support. AZM thanks MINEICO for the ‘Juan de la Cierva – Incorporación’ postdoctoral contract (IJCI-2014-20443). PMMS thanks the Spanish Ministry of Science and Innovation for his contract associated with the ‘Research Programme in Technologies for the Assessment and Conservation of Cultural Heritage’ (TCP CSD2007-0005

Black crusts on different substrates (carbonate and silicate stones, cement-based mortar and carbonate detrital deposits) in urban environments were characterized microscopically by analysing their morphologies and compositions. The objective of this article is to study the interaction between the substrate and the crust and the influence of the environmental conditions on the crust development. On the one hand, the internal structure and morphology of each sample were evaluated with stereo and scanning electron microscopies. On the other hand, the black crust composition was accessed by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy in backscattered electron mode combined with energy dispersive x-ray spectroscopy. The results of these analytical techniques provided interesting information about the composition and the mineralogical phases present in the collected black crusts. In most of the cases, gypsum was detected as the main component exhibiting different habits. Calcite was also detected in all the evaluated gypsum black crusts; its presence was attributed to different origins. The substrate-crust interaction was also evaluated, contributing to distinguish different crust development processes in relation to the substrate. In carbonate substrates (limestones, mortar and carbonate detrital deposits), it was detected a continuous diffuse boundary related to the replacement of Ca-carbonate by Ca-sulphate, while this boundary was significantly more defined for the granitic stone. This study shows that the substrate, the presence of different construction materials, (e.g. mortars), the motor exhaust particulate substances and the concentrations of atmospheric pollutants, the marine influence as well as biological or other anthropogenic compounds are decisive factors in the development of the black crust. Some ideas about the establishment of conservation strategies are also shown.

Calcification, or mineralisation, can occur as part of a natural process, or by pathological processes. The purpose of this work is to examine an unidentified semi-spherical and perforate hollow mass, found near the pelvis of an adult female, dated 12th–13th century AD, exhumed of the Church of Santo Domingo de Silos (Pradena del Ricon, Madrid, Spain). The mass was examined by SEM and Energy Dispersive X-Ray Spectroscopy. These procedures revealed a heterogeneous inner surface with both smooth and irregular areas. A larger spherical and several smaller crescent-shaped perforations were noticed. X-ray microanalysis revealed the presence of the elements C, K, P, Ca, Al, Si, Fe, and Mg. The co-localisation of Ca and P suggests that they may be combined in a mineral matrix, likely formed in vivo. Other minerals probably came from the soil, although Fe could be related to the presence of blood. The macroscopic and microscopic appearances, chemical composition, and location of the calcified mass point to a possible hydatid cyst from Echinococcus granulosus, common in agricultural populations. This study used a suite of analytical techniques that are useful in the diagnosis of unknown calcified masses and can, therefore, be recommended for use in future analytical work.

Stone coatings, biological colonization, efflorescence and detachments are frequent on granitic surfaces of our cultural heritage infrastructure. In order to find the different origins for each deterioration form, this paper studies and compares several coatings, efflorescence and flakes found on granitic surfaces of bridges from different ages built in the same area (Ourense in NW Iberian Peninsula at 90 km from the sea) under the same environmental and traffic conditions. The most recent bridge was the New Bridge built in the beginning of 20th century and the oldest one was the Roman Bridge with the 1st century AD foundations but its current structure was built in 17th century. The New Bridge has exhibited a greater variety of deterioration forms such as black crusts, carbonate crusts, efflorescence and biological colonization. On the Roman Bridge, black crusts, efflorescence to a greater extent, and flakes associated with salt crystallization processes have been identified. Scanning electron microscopy with energy dispersive X-ray spectroscopy, X-ray diffraction and Fourier transform infrared (FTIR) spectroscopy studies were carried out in order to establish their composition, and optical and electronic microscopies and X-ray microtomography were used to study their morphologies. As a result, anthropogenic factors (industrial activities, traffic pollution and fertilizers) are considered to be the main contributors to crusts, efflorescence and flake formation on both studied substrates (granite ashlars and mortars). To a lesser extent, natural factors (marine influence and bird droppings) should be taken into account.

A detailed archaeometric study of pottery was made of a fifteenth-to-sixteenth-century kiln located inside the walls of the Castle of Alenquer. The locally collected sherds are lead glazed, and mostly exhibit a green or dark yellow decoration. Only in one case, a fragment of a bowl, tin oxide was detected in the white glaze. Pastes from the ceramics of the Alenquer kiln were spectroscopically characterized in terms of their mineralogical and elemental composition. This pottery was fired twice, the first time at high temperatures to produce the biscotto, and the second time at lower temperatures to glaze the ceramics. Although only one type of raw material collected locally was used, two types of ceramic pastes were detected and organized into two groups: one produced at about 850 °C and another at about 950 °C. Pastes from Group 1 were converted into Group 2 pastes whenever the temperature of the kiln was raised from 850 to 950 °C, as confirmed by firing Group 1 pastes in an oven. These results were compared with those obtained for coeval ceramics, namely at Santo Antonio da Charneca and Mata da Machada. Both kilns were located on the south shore of the river Tagus (Lisbon), as previously reported. The first archaeometric study of ceramics produced in the kiln of Alenquer, (Portugal, fifteenth to sixteenth centuries) is reported, with the use of surface spectroscopies techniques, namely micro-Raman. Significant differences were found from two coeval kilns also located at the Tagus basin, Santo Antonio da Charneca and Mata da Machada.

An excavation in a 14th c. church at Torres Novas, named Santa Maria do Castelo, provided some green glazed ceramic sherds, archaeologically dated from 14th c. to the 16th c. The town of Torres Novas is located at the center of Portugal, about 100 km north of Lisbon. The obtained results evidence three types of pastes of the pottery: type 1 with Quartz, Illite, Muscovite and Microcline as the main constituents, type 2 with Quartz, Calcite and Gehlenite; and finally type 3 with Quartz, Calcite and Diopside being the major components. Type 1 pastes are related to clay sources of Pliocene origin, and all this pottery was most probably made in Portuguese kilns. However, types 2 and 3 spectroscopic trends are remarkably different, indicating that those ceramics were produced in Seville. All the studied ceramics are lead glazed, and green glazed. In one of the samples from the Seville kiln, Cerusite was the main pigment used to obtain the greenish colouration. In what regards the origin of all samples produced with Pliocene clays, the 16th c. ones were most likely produced in the Santo Antonio da Charneca or Mata da Machada kilns, both located in the south shore of the Tagus river, region of Lisbon. In what regards the green glazed jug rim (14th c.) and the jug spout (15th c.) they could also have been produced in the two mentioned kilns south of Lisbon city, but another interesting hypothesis - due to richness of the decoration - is the production in Lisbon workshops, with the use of Pliocene clays imported by Lisbon potters, now documented both in Lisbon archaeological findings and also in documental sources.

2 páginas.-- 2 figuras, Coralloid-type speleothems were found in Ana Heva lava tube from Easter Island (Chile). The ceiling of the lava tube presents light to dark brown speleothems with globular coral-like shape. To appraise their internal structure and composition, optical microscopy (OM) of cross-sections, field emission scanning electron microscopy with energy dispersive X-ray spectroscopy (FESEM-EDS) and X-Ray micro-computed tomography ( CT) were performed. The latter is a non-destructive method (NDM), performed to assess physical and compositional heterogeneities of the coralloids. The internal structure of these speleothems comprises a succession of thin layers, ranging from white to brown, with vitreous to resinous luster (Fig. 1A). According to their color and texture, four major layers are easily distinguishable, from the surface to their inner part: a superficial dark brown to black coating, with approximately 0.1 mm thick (L1); a 0.1-1 mm thick semi-transparent grayish layer (L2); a 0.1-1 mm thick white layer (L3), and a heterogeneous honey brown layer, with 1-5 mm thick and shades ranging from yellowish to honey brown (L4). FESEM-EDS microanalyses performed on the internal layers of longitudinally cut coralloid samples (Fig. 1B) showed systematic differences in chemical composition of the different color inner layers. In general, they contain variable proportions of Si, Mg and Ca (Fig. 1C-G). According to a previous study [1], the thin dark brown to black coating of the coralloid surfaces is probably derived from the weathering of the overlying volcanic rock and microbial activity [1]. The semi-transparent grayish layer (L2) is composed of low crystalline silica (opal-A), whereas the whitish layers (L3) are calcium carbonate (calcite). In contrast, the honey-brown layers (L4) present an unusual composition characterized by high levels of Mg, corresponding to an amorphous Mg hydrate silicate. Significant content of organic carbon was also found in these layers [1]. The CT study allowed us to confirm the existence of internal zoning in the studied coralloids (Fig. 2), and between them and the basaltic substrate. The brighter domains in the reconstructed images (Fig. 2D,E) correspond to the vacuolar basaltic. The other opaque domains, comprising thin spheroidal precipitates or dispersed spots within the coralloids (Fig. 2F-I), are calcium rich phases. According to mineralogical data and FESEM-EDS analysis, the inner/older spots correspond to apatite and the outer/more recent spots correspond to calcite. In contrast, the Si, Mg and C enriched domains are more transparent to X-ray radiation, combining at least two main phases (siliceous and magnesium silicate compounds). The proposed methodology was considered adequate for studying coralloid samples, by combining a NDM (μCT) with other microanalytical techniques. Investigations of speleothems using the potentialities of μCT provide general morphological and compositional information, suggesting the best approach for selecting and sectioning the samples. The FESEM-EDS provides characteristic information on the morphological, mineral and chemical composition., The authors acknowledge FCT for PEst-OE/CTE/UI0098/2011, AZM (SFRH/BPD/63836/2009) grant, and Spanish Ministry of Science and Innovation (Project CGL2011-2569) and CSIC 210230E125.

11 páginas.-- 8 figuras.-- 1 tabla.-- 33 referencias, Coralloid-type speleothems were recorded on the ceiling of the Ana Heva lava tube in Easter Island (Chile). These speleothems were morphologically, geochemically and mineralogically characterized using a wide variety of microscopy and analytical techniques. They consist dominantly of amorphous Mg silicate and opal-A. Field emission scanning electron microscopy revealed a variety of filamentous and bacillary bacteria on the surface of the Ana Heva coralloid speleothems, including silicified filamentous microorganisms. Among them, intriguing reticulated filaments resemble those filaments documented earlier in limestone caves and lava tubes. The identification of silicified microorganisms on the coralloid speleothems from the Ana Heva lava tube suggests a possible role of these microorganisms in silica deposition. © 2014 Copyright Taylor and Francis Group, LLC., This research was partially financed by Portuguese Funds through FCT- Fundaçao para a Ciencia e a Tecnologia (PEst-OE/CTE/UI0098/2011) and also by the Spanish Ministry of Science and Innovation (Project CGL2011–2569). This work was supported by FCT grant to AZM (SFRH/BPD/63836/2009).

The aim of this study is to apply X-ray microfocus computed microtomography (μ-XCT), a promising non-destructive 3D microscopy imaging technique, based on measurements of X-ray linear path attenuation coefficient, in order to study a Portuguese travertine, a random heterogeneous geomaterial used in urban heritage constructions. This study evaluates the impact of soluble sulphate salt–induced decay phenomena on texture characteristics at a micrometric scale. This is done to better describing, imaging, measuring and understanding the impact of an artificially induced sulphate-decay process on petrographic/petrophysical properties. A Portuguese travertine was chosen as the object of our study. Its laboratory-induced changes were systematically monitored, using non-destructive techniques, to determine voids (pores + fractures)/matrix fractions and size spectrum evolution based on 3-D images. This investigation demonstrates that the μ-XCT potential constitutes a valid complementary tool when analysing decay processes of complex natural materials in different environmental conditions. It clearly provides suggestive and important qualitative and/or quantitative estimates, at different spatial scales, of environmentally induced stone voids/matrix network spatial structure-texture evolution correlations. Further qualitative/quantitative parameterization assessment and statistical validation will be the next step to be taken on this study., Fundação para a Ciência e a Tecnologia (FCT) através do projeto POCTI\CTA\44940\2002_PORENET e os projetos estratégicos PEstOE/CTE/UI0697/2011 and PEst-OE/CTE/UI0098/2011 (fundos nacionais e europeus - FEDER)