Physical mechanical consolidation and protection of Miocenic limestone used on Mediterranean historical monuments: the case study of Pietra Cantone (southern Sardinia, Italy)

The present work aims to study the consolidating and protective chemical treatments of the Pietra Cantone, a Miocenic (lower Tortonian) limestone widely used in important monuments and historical buildings of Cagliari (southern Sardinia, Italy). Similar limestones of the same geological period have also been used in several important monuments of Mediterranean area, i.e., Malta and Gozo Islands, Matera (central Basilicata, Italy), Lecce (southern Puglia, Italy) and Balearic Islands (Spain). The Pietra Cantone limestone shows problems of chemical–physical decay, due to their petrophysical and compositional char- acteristics: high porosity (on average 28–36 vol%), low cemented muddy-carbonate matrix, presence of phyllosil- icates and sindepositional sea salts (\3%). So, after placed in the monument, this stone is easily alterable by weath- ering chemical processes (e.g., carbonate dissolution and sulfation) and also by cyclic mechanisms of crystalliza- tion/solubilization of salts and hydration/dehydration of hygroscopic phases of the clay component. To define the mineralogical-petrographic features (composition, texture) of limestone, the clay and salt crystalline phases, the optical microscope in polarized light and diffraction anal- ysis were used. To define the petrophysical characteristics (i.e., shape and size distribution of porosity, surface area(SBET), matrix microstructures, rock composition) and interactions of chemical treatments with rock, SEM–EDS analysis and N2 porosimetry with BET and BJH methods were used. To evaluate the efficacy of Na/K-silicates, ethyl silicate consolidants and protective nano-molecular silane monomer water repellent, the mechanical strengths (uni- axial compressive strength, point load and flexural resis- tance), water/helium open porosity, water absorption and vapour permeability data determined before and after the chemical treatments of the Pietra Cantone samples from monument were compared

Romanesque and territory. The construction materials of Sardinian medieval churches: new approaches to the valorization, conservation and restoration

This paper is intended to illustrate a multidisciplinary research project devoted to the study of the constructive materials of the Romanesque churches in Sardinia during the “Giudicati” period (11th -13th centuries). The project focuses on the relationship between a selection of monuments and their territory, both from a historical-architectural perspective and from a more modern perspective addressing future restoration works. The methodologies of the traditional art-historical research (study of bibliographic, epigraphic and archival sources, formal reading of artifacts) are flanked by new technologies: digital surveys executed with a 3D laser-scanner, analyses of the materials (stones, mortars, bricks) with different instrumental methods: X-ray fluorescence (XRF) and inductively coupled mass spectrometry (ICP-MS) for chemical composition, X-ray diffractometer (XRD) to determine the alteration phases (e.g., soluble salts), optical microscopy and electronic (SEM) to study textures, mineral assemblages and microstructures, termogravimetric/differential scanning, calorimetric analysis (TG/DTA) for the composition of the binder mortars. This multidisciplinary approach allows the achieving of important results in an archaeometric context: 1) from a historical point of view, with the possible identification of ancient traffics, trade routes, sources of raw materials, construction phases, wall textures; 2) from a conservative point of view, by studying chemical and physical weathering processes of stone materials compatible for replacement in case of future restoration works. Sardinian Romanesque architectural heritage is particularly remarkable: about 200 churches of different types and sizes, with the almost exclusive use of cut stones. Bi- or poly-chromy, deriving from the use of different building materials, characterizes many of these monuments, becoming also a vehicle for political and cultural meanings. The paper will present some case studies aimed to illustrate the progress of the project and the results achieved

How does informational heterogeneity affect the quality of forecasts?

We investigate a toy model of inductive interacting agents aiming to forecast a continuous, exogenous random variable E. Private information on E is spread heterogeneously across agents. Herding turns out to be the preferred forecasting mechanism when heterogeneity is maximal. However in such conditions aggregating information efficiently is hard even in the presence of learning, as the herding ratio rises significantly above the efficient-market expectation of 1 and remarkably close to the empirically observed values. We also study how different parameters (interaction range, learning rate, cost of information and score memory) may affect this scenario and improve efficiency in the hard phase.Comment: 11 pages, 5 figures, updated version (to appear in Physica A

Pyroclastic Stones as Building Materials in Medieval Romanesque Architecture of Sardinia (Italy): Chemical-Physical Features of Rocks and Associated Alterations

The paper discusses the chemical-physical-petrographic features and decay processes of San Nicola Church (11th−14th century) building materials, one of the most representative Medieval Churches in Sardinia, stylistically attributable to the Romanesque architecture. The monument was built up into two stages and shows a characteristic size uniformity of the ashlars. The masonry is mainly made up of rhyodacitic pyroclastites belonging to the Sardinian Eocene-Miocene magmatic phase (38–15 My). These volcanic rocks were widely used in Medieval architecture for the excellent workability, but its minero-petrographic features greatly favor the decay, due to the action of chemical-physical alteration processes. Although the alteration degree and macroscopic forms of decay vary from zone to zone in the monument, according to the different compositional features of the volcanic stones, weathering and exposure condition, the pyroclastic rocks are generally affected by greater alteration than other igneous lithotypes, due to their petrographic-volcanological characteristics (e.g., low-medium welding grade, medium-high porosity). The results concerning mineralogical and petrographic features, respectively, carried out by the application of X-Ray Powder Diffraction (XRPD), Optical Microscope (OM), and Scanning Electron Microscope (SEM) techniques, both on fresh building rocks and associated alterations, are here presented and discussed. Furthermore, the relationships between fresh pyroclastites and alteration processes affecting these rocks will be discussed

Multi-Analytical Techniques to Define the Mineralogical and Petrophysical Characteristics and Provenance of Siliceous Lithic Findings: The Case Study of La Calvera Rock Shelter (Cantabria, Spain)

This archaeometric study aims at characterizing the archaeological finds belonging to the lithic industry from La Calvera rock shelter (Camaleño, Cantabria) and at hypothesizing the possible provenance of each material. The site, located in the mountainous area of Picos de Europa National Park (more than 1000 m a.s.l.) close to the megalithic complex of Peña Oviedo, is characterized by the presence of hearths and charcoal remains, ancient pottery, and a rich lithic assemblage composed of siliceous rocks dating back to >8000 BP and linked to the first Holocene occupations of the Cantabrian Mountains. For the study of the rock shelter’s lithic assemblage, a multi-analytical approach was used: SEM-EDS and XRD analyses were performed to define the microtextural characteristics of samples and to identify the amorphous/crystalline phases; physical and mechanical tests were conducted to define the petrophysical properties (density, porosity, imbibition and saturation indexes, mechanical strength) of the samples. Preliminary data of chemical compositions, obtained by portable XRF, are also presented. The results show that the different siliceous materials (quartzite, cherts, hyaline quartz) can be distinguished through the basic analytical techniques used here. In addition, most of the archaeological samples have mineralogical and petrographic features similar to the natural samples coming from nearby outcrops, corroborating the hypothesis of a local material supply. The presence of local sources of useful raw materials could have favoured the site’s occupation. Finally, the diverse compositional and textural feature of the analysed materials result in different mechanical properties (porosity, density, hardness, workability), so they likely had different uses and technical functions

Archaeometric approach for studying architectural earthenwares from the archaeological site of s. Omobono (Rome-Italy)

This paper reports the findings of an archaeometric study performed on 14 architectural earthenwares from the archaeological site of S. Omobono, located in the historic center of Rome (Italy). The archaeological site, accidentally discovered in 1937, includes the remains of a sacred area previously occupied by two temples, one of which was converted into the church of S. Omobono, in 1575. The samples, dated between the 7th and the 6th century BC, belong to different sectors of the site. Their petrographic, mineralogical and geochemical characterization was performed by optical microscopy (OM), X-ray powder diffraction (XRPD), X-ray fluorescence (XRF), electron probe micro-analysis (EPMA), and Raman spectroscopy (RS). The compositional data obtained were also subjected to the principal component analysis (PCA) in order to highlight similarities and differences among the samples. By combining geochemical and petrographic data, we were able to identify several different fabrics. Furthermore, the study provided valuable information on the firing temperatures of some samples and the provenance of the raw materials, by analyzing the chemical composition of clinopyroxenes present as non-plastic inclusions. View Full-Tex

A petro-chemical study of ancient mortars from the archaeological site of Kyme (Turkey)

Fourteen samples of ancient mortars (joint mortars and plasters) from the archaeological site of Kyme (Turkey) were studied by optical microscopy (OM), X-ray fluorescence (XRF), X-ray powder diffraction (XRPD), scanning electron microscopy (SEM-EDS) and micro- Raman spectroscopy to obtain information about their composition.The study allowed us to identify a new type of plaster inside the archaeological site of Kyme, not detected by previous studies of this site, in which vegetable fibers were intentionally added to the mixture. The combination of a petrographic analysis on thin sections by polarized light microscopy with a chemical analysis, has allowed us to highlight similarities and differences between the mortars and to get information about the evolution of constructive techniques in the archaeological area

Detecting the impacts of harbour construction on a seagrass habitat and its subsequent recovery

Managing coastal development requires a set of tools to adequately detect ecosystem and water column degradation, but it also demands tools to detect any post-disturbance improvement. Structural seagrass indicators (such as shoot density or cover) are often used to detect or assess disturbances, but while they may be very sensitive to the impact itself, it is unclear if those indicators on their own can effectively reflect recovery at time scales relevant to managers. We used the construction of a harbour affecting a nearby Posidonia oceanica seagrass community to test the ability of a set of indicators (structural and others) to detect alterations and to evaluate their sensitivity to recovery of environmental quality after harbour construction was complete and the disturbance ceased. We used a Beyond Before After Control Impact (BBACI) design to evaluate effects on one impacted and three control meadows where we used structural, morphological, community and physiological indicators (26 in total) to asses disturbance impacts. Additionally, we measured some of the potential environmental factors that could be altered during and after the construction of the harbour and are critical to the survival of the seagrass meadow (light, sediment organic matter, sediment accrual). Harbour construction caused a clear increase in sediment organic matter and in sediment deposition rates, especially fine sand. Light availability was also reduced due to suspended sediments. Sediment and light conditions returned to normal levels 5 and 15 months after the construction began. As expected, seagrass structural indicators responded unequivocally to these environmental changes, with clear reductions in shoot density. Additionally, reduced light conditions quickly resulted in a decline in carbohydrate content in affected meadows. Unexpectedly, we also recorded a significant increase in metal content in plant tissues. No response was detected in the physiological indicators related to eutrophication (e.g. N and P content in tissues) and in morphological (shoot biomass) and community (epiphyte biomass) indicators. More than three years after the completion of the harbour, structural indicators did not show any sign of recovery. In contrast, physiological indicators, mainly heavy metal and carbohydrates content, were much better in detecting the improvement of the environmental conditions over the fairly short period of this study. These results indicate that while structural indicators are critical to evaluate the immediate effect of disturbances and the recovery on impacted systems, specific physiological indicators may be much better suited to determining the timing of environmental quality recovery. The design of impact and monitoring protocols in the wake of coastal developmental projects need to consider the differential effectiveness and time-response of measured indicators carefully

Morpho-Mineralogical and Bio-Geochemical Description of Cave Manganese Stromatolite-Like Patinas (Grotta del Cervo, Central Italy) and Hints on Their Paleohydrological-Driven Genesis

Caves are dark subsurface environments with relatively constant temperatures that allow studying bio-mineralization processes and paleoenvironmental or climate changes in optimal conditions. In the extreme and oligotrophic cave environment, manganese patinas having stromatolite-like features are uncommon. Here we provide the first detailed mineralogical, geochemical, and microbiological investigation of fine-grained and poorly crystalline MnFe stromatolite-like wall patinas formed in a deep-cave environment in Italy. These mineralizations, about 3 mm thick, consist of an alternation of Mn-layers and Fe-lenses. We show that the microbial communities' composition is dominated by Mn-oxidizing bacteria, such as Bacillus, Flavobacterium, and Pseudomonas. Our multidisciplinary investigation, integrating data from different analytical techniques (i.e., optical microscopy, SEM-EDS, μXRF, XRPD, FT-IR, Raman spectroscopy, and DNA sequencing), revealed peculiar chemical, mineralogical, and biological features: 1) A cyclical oscillation of Mn and Fe along the growth of the patinas. We propose that this oscillation represents the shift between oxic and suboxic conditions related to different phases occurring during paleo-flood events; 2) A typical spatial distribution of mineralogy and oxidation state of Mn, bacterial imprints, detrital content, and stromatolite-like morphologies along the Mn-layers. We propose that this distribution is controlled by the local hydraulic regime of the paleo-floods, which, in turn, is directly related to the morphology of the wall surface. Under less turbulent conditions, the combination of clay mineral catalysis and biological oxidation produced vernadite, a poor-crystalline phyllomanganate with a low average oxidation state of Mn, and branched columnar stromatolite-like morphologies. On the other hand, under more turbulent conditions, the sedimentation of clay minerals and microbial communities' development are both inhibited. In this local environment, a lower oxidation rate of Mn2+ favored the formation of todorokite and/or ranciéite, two compounds with a high average oxidation state of Mn, and flat-laminated or columnar stromatolite-like morphologies