Cultural heritage-materials, techniques and knowledge perspectives on a common identity

Resume : The project "Castulo: archaeometric research and social transfer" proposes an archaeometric research carried out jointly by the Universities of Jaén (Spain) and Ghent (Belgium), within the framework of the general plan of intervention in the Iberian-Roman Archaeological Area of Cástulo (6th ct. BC-5th ct. AD). The objective of this plan is to generate a first level tourist resource that contributes to the social and economic recovery of the city of Linares (Spain) after the crisis generated by the disappearance in the region of mining and industrial activity. The analyses are being applied to a group of new materials (Iberian and Roman chronology) that come from the last excavation campaigns implemented between 2010 and 2016. These are: a) mineralogical and elemental analysis by non-destructive physical-chemical techniques (MRS, EDXRF) in ceramics, pavements, mosaics and stuccos; b) analysis of contents (lipids, waxes, sulphur, wine, etc) in ceramic vessels by chromatographic techniques (GC-MS and HPLC-MS); c) paleoenvironmental analysis on charcoal and seeds (anthracological and carpological analysis). The data obtained allow us to provide key information for the design of the best strategies for conservation and restoration and to establish an updated transfer of information to visitors of Cástulo, namely: Symbolic and social meanings, work processes and technology, sources or supply areas, exploitation of environment, types of crops, landscape reconstruction.

Resume : affect cultural heritage sites. Sea Level Rise and increased storm events can damage structures that were not designed to withstand prolonged structural pressure, erosion, and immersion. Risks affecting coastal cultural heritage may stem from exposure to one or more hazards and it is important to facilitate a holistic understanding of factors driving them. This demands that the relation of cultural heritage’s physical vulnerability resulting from social, economic and “development” processes, is understood. Risk is defined as “the probability of harmful consequences, resulting from the interaction between vulnerability and exposure”. However, vulnerability is not only a “product” but a “process” as well governed by various factors, which eventually drive its change over time. Therefore, an assessment of vulnerability variation in time is needed. A comprehensive understanding of risks will build a basis for taking proactive rather than reactive measures to control vulnerability processes and reduce the anticipated risks in the future, in an innovative paradigm for conservation. In this study an initial risk assessment analysis related to increasing sea level and storm frequency for the Venetian Coastal fortress of Heraklion is presented. Towards this aim the use of laser diagnostic tools for the in-situ analysis and monitoring of deterioration products is of high importance.

Resume : Cultural Heritage (CH) assets are endangered by climate change (CC) and natural hazards. In Europe, their huge number and diversity, together with the different climatic sub-regions generate a complex scenario. Experts from many domains need to cooperate towards their conservation goals. Same scientific and technological terms with clear relationships among them, have to be used. To this aim, ontologies can provide a semantically unified domain representation, with superior capabilities in querying and information retrieval. No attempts were undertaken so far to model the risks and effects of CC on CH assets, on the caused damage and on materials for conservation. Until now, ontologies proposed only cover relevant concepts subsets. This paper proposes a more "all-around" lightweight ontology for CH materials in relation to CC, which greatly facilitates decision support and merges several pertinent aspects: CH Assets, Stakeholders and Roles, Climate Effects, Risk Management, conservation actions, materials, models, sensors and observations. The ontology could constitute the decision support systems backbone for the field. In general, the ontology can be used as a basis for new research projects, which need to tackle the problems of CC effects and involve a set of heterogeneous sensors and processing algorithms. HERACLES project is funded from the EU Horizon 2020 research and innovation programme under grant agreement No 700395.

Resume : The work presents a multidisciplinary approach for assessing the combined effects of environmental actions, related to climate change, and natural events, such as earthquakes, on cultural heritage buildings. This approach includes (i) architectural, damage and material degradation survey, (ii) in situ ambient vibration testing, (iii) in situ environmental monitoring, (iv) structural modeling through the Finite Element Method, (v) thermo dynamic simulations and (vi) structural health monitoring. As illustrative case study, the iconic Italian monumental building called "Palazzo dei Consoli", located in Gubbio, Italy, is considered. Built between 1332 and 1349, the Palace has a regular rectangular shape in plan with 20x40m dimensions and a total height of about 60m. Apart from some internal walls and vaults on the top part of the building that are made of brickwork masonry, the building is mainly constituted by calcareous rock. After presenting survey operations of both material and structural degradation, the current building state is discussed and different pathologies are classified. An integrated numerical simulation is then presented considering both structural and thermo-dynamical aspects. Results of such a numerical simulations have allowed to perform consistent interpretations of the observed damage state, as well as to emphasize the most critical regions where structural damage and climate-induced degradation may negatively interact in the future.

Resume : Mineral gypsum (selenite) has been used extensively for building and ornamental purposes in the Minoan Palace of Knossos. The mineral gypsum building and ornamental elements catalogue of the palatial complex of Knossos consists of 2.185 entries. One of the problematic issues of the Knossian mineral gypsum is its rather high water solubility and its softness. Hence, exposed gypsum to environmental stresses leads to solubility-driven degradation, and loss of cohesion of the crystal aggregates, with resulting aesthetic degradation. Among the plethora of organic and inorganic chemical consolidants for gypsum that have been tested in our laboratory, many of them possess chemical moieties that are capable of interacting with surface calcium ions. Anionic groups, such as carboxylate and phosphonate stand out. The layered structure of gypsum possesses calcium ions that are “exposed” to the inter-layer space. Furthermore, each calcium ion is coordinated to two water molecules. In this presentation, we will interpret and discuss the efficiency of a number of anionic consolidants by using “tools” provided by surface coordination chemistry. Consolidation efficiency (i.e. the ability of a chemical compound to provide cohesion to the stone of the different mineral gypsum varieties) is based on the utilization of a drilling resistance measuring system (DRMS). Acknowledgment. We thank the European Union's Framework Programme for Research and Innovation HORIZON 2020 for funding the project HERACLES under grant agreement No 700395.

Resume : Gypsum-based stucco is made by dehydrating gypsum (CaSO4-2H2O) at 100-200°C to form highly reactive Bassanite (CaSO4-0.5H2O), that dissolves in water to precipitate new gypsum crystals. This common material has gathered much academic attention, but previous cultural heritage research has focused on composition (secondary phases, additives, impurities...). We will show here how the observation of the microstructures gives us access to previously untapped information regarding the thermal process applied to the material, the morphology of the reactive plaster powder and the water-to-plaster ratio of the slurry. Synchrotron microtomography was used to image samples (around 1mm3) taken from 15th century Florentine reliefs (including works by Donatello, A. Rossellino and Desiderio da Settignano). We measured the porosity "ghost" imprints left by the dissolved grains of the reactive powder, from which conclusions were drawn on the crystal habitus of the raw material and the manufacturing process. Likewise, we showed that under- and overcooked materials - identical in composition to the bulk of the samples - can be identified from their microstructures. Finally, by measuring the total porosity, we were able to estimate the water-to-plaster ratio on a much smaller sample than with conventional methods. This innovative method is expected to unravel the materials and workshop practices of past stucco-makers and help define criteria of authentication for ancient works of art.

Resume : The wall-painting Annunciazione by Beato Angelico in the Museum of San Marco in Florence, one of the masterpiece fresco paintings around the world, was studied by non-invasive electromagnetic waves from microwave to X-ray. For the visible region, an extremely high-resolution image (1000 pixels per inch) was obtained by using an automatic divisional photography and post processing system developed by Hitachi Ltd. The image allowed us to improve the readability of the artwork and specifically to recognise details of brush strokes and the presence of colours particles left in small cracks. The diagnostic imaging techniques, below or above visible region, provided information on the compositional scheme of the work and its partial stratigraphy. Specifically, the Infrared Reflectography acquired over the entire work made it possible to reveal the presence of preparatory drawings. Ultraviolet fluorescence revealed the presence of specific pictorial material. On a few selected areas of the painting, the THz imaging technique was applied to obtain information on the stratigraphic sequence. The GPR data acquired from the back of the wall on which the ?Annunciazione? was painted made it possible to investigate the wall structure supporting the fresco. XRF, FORS and TR-FT-IR measurements were used to characterise the materials making up the pictorial film on selected spots of the painting. This wide-band electromagnetic examination gives the role of each frequency band in heritage science.

Resume : Minoan palatial architecture makes impressive use of mineral gypsum (selenite) for building and ornamental purposes. Despite its susceptibility to weathering, Minoans used it extensively most likely due to its unique aesthetic values. Interestingly, the mineral gypsum building and ornamental elements catalogue of the palatial complex of Knossos consists of 2.185 entries [1]. One of the main issues concerning the state of preservation of the Knossian mineral gypsum (selenite) is its solubility, given that gypsum is a rather soft and water-soluble mineral, with a Ksp of ~ 3.14×10-5mol2L-2. The dissolution of gypsum, leads to loss of cohesion of the crystal aggregates and eventually to degradation and loss of original material. Several organic and inorganic chemical consolidants (TESPSA, APTES, TEOS) have been tested taking into account the macroscopic properties of the different gypsum varieties. In all cases the main parameter was the compatibility of the consolidating material with the sulfate substrate in terms of surface coordination chemistry. This work focuses on the evaluation of consolidation efficiency (i.e. the ability of a chemical compound to provide cohesion to the stone of the different mineral gypsum varieties) based on the utilization of a drilling resistance measuring system (DRMS). It is demonstrated how this test can provide information on the penetration depth of the consolidant as well as the penetration resistance variations [2, 3]. Concurrently, DRMS is used as a high precision sampling tool, because the drilling residue (dust) can be collected from specific interval depths and then analyzed with several other analytical techniques (eg. powder X-ray diffraction, SEM, etc.). Hence, useful information regarding both the state of preservation of the successive strata of the examined rock as well as the performance of the consolidants can be extracted. Acknowledgment. We thank the European Union's Framework Programme for Research and Innovation HORIZON 2020 for funding the project HERACLES under grant agreement No 700395. [1] Hood S.; Smyth D. Archaeological Survey of the Knossos Area, 2nd edition; London: Thames and Hudson, 1981. [2] J. Delgado Rodrigues, A. Grossi, Journal of Cultural Heritage, 8 (2007), 32-43. [3] H.R. Sasse, Engineering Aspects of Monument Preservation, Restoration of Buildings and 542 Monuments, 2001, pp. 197.

Resume : Preservation of cultural heritage artefacts increasingly involves laser techniques [1,2]. The cleaning of painted, fibrous, or polymeric substrates has been studied systematically [2-5]. The treatment of organic materials is characterized by the limitation of photochemical and photothermal destruction. This can be minimized by the choice of visible wavelengths [2,3]. Particle removal investigations based on laser pulse interactions and atomic force measurements led to thermomechanical models [6,7]. Stratigraphy is an essential technique in preservation procedures. A novel depth profiling down to single µm range was developed based on laser-induced breakdown spectroscopy [8,9]. [1] Handbook on the Use of Lasers in Conservation and Conservation Science, COST Office, Brussels, 2008. http://www.science4heritage.org/COSTG7/booklet/. [2] W. Kautek, Springer Series in Materials Science 130 (2010) 313. [3] W. Kautek, in [2]. [4] J. Colson, J. Nimmrichter, W. Kautek, Appl. Surf. Sci. 302 (2014) 314-317. [5] S. Arif, W. Kautek, Studies in Conservation 60 (2015) S97-S105. [6] S. Arif, O. Armbruster, W. Kautek, Appl. Phys. A 111 (2013) 309-317. [7] S. Arif, O. Armbruster, W. Kautek, Appl. Phys. A 111 (2013) 539-548. [8] T. Nagy, U. Pacher, H. Pöhl, W. Kautek, Appl. Surf. Sci. 302 (2914) 189-193. [9] U. Pacher, M. Dinu, T.O. Nagy, R. Radvan, W. Kautek, Spectrochimica Acta (2018), in press.

Resume : Stone monuments, are continuously threatened by climatic change, extreme meteorological phenomena, human and natural hazards. Towards their safeguarding research within HERACLES project (“HEritage Resilience Against CLimate Events on Site”, GA 700395) is dedicated to the design, testing and promotion of responsive systems, methodologies and techniques with the aim to mitigate the impact of climate changes and natural hazards. In this respect the characterization and monitoring of deterioration products on stone monuments and their correlation with environmental changes and climatic data is of high priority. This study aims at presenting the research performed on two of the HERACLES test beds as regards the in-situ analysis of weathering features and their monitoring along the year and the variable weather conditions. Specifically a number of insoluble crusts and accumulations (i.e. efflorescence salts) found on the surface of the Palace of Knossos and the Venetian fortress of Koules, both located in the city of Heraklion, Crete, Greece, are investigated in-situ using advanced, non-contact laser-based technologies. Both monuments of different historical eras and construction materials are subject to variable climatic conditions and their study is expected to enlighten the influence of climatic change to the safeguarding of CH assets. The chemical composition of these decay products in relation to the substrate material, the various conservation and restoration historic phases is discussed along with their spatial distribution on the monument’s surfaces and also in correlation with environmental and climatic data. This information will intent to elucidate their nature, the conditions that trigger their presence and moreover the factors responsible for their expansion, especially the ones related to the climate change. Data obtained through sampling has been incorporated to a data –base which in combination with regular measurements recorded from portable instruments (Multispectral Imaging, portable Raman and Laser Induced Breakdown spectroscopy) is investigated and cross-correlated to produce maps that will indicate expansion trends and risks.

Resume : Salt weathering is a major cause of the deterioration of porous artworks such as Frescos, scultptures and historical monuments and there is compelling evidence that its influence will increase due to the global climate change. We present data on the kinetics of wetting/drying and humidity cycling on the precipitation and distribution of salt crystals within the pore space of sandstone. Advanced techniques such as 4D laboratory X-ray computed tomography and Scanning Electron Microscopy are used to study the dynamics of salt crystallization in the porous network. Our results show that when the same amount of water is used to dissolve the salt present in a stone, depending on whether this is done by a rapid saturation with liquid water or by a slow saturation using water vapor, different evaporation kinetics and re-crystallization pattern are observed. X-ray µCT datasets reveal the direct coupling between the transport and crystallization dynamics through quantitative image analysis of the simultaneous visualization of both processes in 4D. Efflorescence (crystallization at the surface) is often an aesthetic problem on buildings or wall paintings. Our results suggest that in any case for NaCl this problem becomes worse if one tries to wash the salt off with liquid water but could be avoided by humidity cycling. However, the humidity cycling causes the migration of the salt in the subsurface with the formation of larger and larger crystals at high supersaturations. Since the crystallization pressure is directly given by the supersaturation, this may lead to severe damage of sodium chloride contaminated sandstone. The experimental data were complemented with numerical simulations to describe the transport and crystallization dynamics. Our results provide explanation on why a givent salt can cause damage in some conditions and not others.

Resume : The Effect of the Tanghe Bolaghi Dam on the Antiquities of the Pasargad Region The ancient Pasargadae area, located in the Murghab plain of Fars province, was registered in 2004 on the Global List of World heritage; it has a unique civilization from the Neolithic to the advent of the great Achaemenid Empire and subsequent civilizations. The formation of this rare human civilization more than anything, is thanks to the river SIVAND (Polvar), which originated from the high mountains of the White Mountains in Guk and Tange gurk and after a distance of about 30 km, enter in the Strait called Tang Bollagi. In the strait; that is linked to the Pasargad Plain from the southwest, there are also sites and settlements dating from prehistoric times to the Sassanid era. In 1988, the construction of the Sivand Dam was began in the Strait and with the construction of this dam (the dam of Sivand), were exposed of danger, not only the Antiquities of the Tange Bollagi area (The only healthy part of the kingdom road, the ancient villages, Dariush Achaemenid Palace, metal smelter and beverage manufacturing workshops, Ashkani cemetery and places that have not been explored yet), but because of loose and alluvial soils in the area after the rise of groundwater due to dam drainage, will be exposed to destruction Achaemenid unique monuments in the Pasargad plain (including general visiting palace, Gate palace, private palace, Cambozia tomb, Tele Takht, especially the tomb of Cyrus that the is closest building to the dam). Since Pasargad antiquity are of limestone type and moisture absorbent it seems that after damping the dam, because of climate change and rising humidity in the area, gradually, the eroded stone buildings of Pasargadae, and will be destroyed in particular the Tomb of Cyrus. In this research, we try to answer some questions about the effect of increasing the humidity on the destruction of the artifacts, as well as the effects of rising water in the subsurface on the buried ancient art. For this purpose, while measuring the amount of environmental changes and determining the degree of growth of destructive environmental factors in the architecture of Pasargad plain, also will be provided the impact of the destruction of the dam on relics recorded in the global list of measures and ways to protect them. Key words: Pasargad, Sivand River, Tange Bollagi Dam, Protection of Achaemenid Relics

Resume : Islamic Revolution of Iran and its impact on the protection of cultural heritage Abstract: Iran is one of the oldest centers for the formation of human civilization, which history of settlement in its central plateau back to the Neolithic period. The extent of cultural relics in this country so that it knows as archaeologists paradise. For this reason, so far, 32,000 cultural relics have been registered in the national list of works and 21 relics in the world record list. Since the archeological activities before the Islamic Revolution of Iran (1960-1979) generally, focused on introduction the greatness of the country in the era of rule of the Achaemenid and Sasanian kings, Protection of ancient monuments could have been meant to be protection of symbol of royal. Considering that the Islamic Revolution of Iran was meaningful, the revolution of the oppressed against the mercenaries, this sort of impression could have led to destruction or neglect of the country's ancient monuments. The question of how much of Iran's historical monuments has been damaged by this typ and the efforts of the Government of the Islamic Republic for the protection of antiquities has been, to what extente of thinking after the Islamic Revolution, caused to authors of the present text do research on this issue. In other words, the present paper attempts to bring the results of field studies of writers on the impact of the Islamic Revolution on the protection of the country's ancient artifacts. Keywords: Islamic Revolution of Iran, to protect ancient monuments, national heritage list.

Resume : Changes in humidity can affect the conservation of wall paintings, wooden altarpieces and other elements of the cultural heritage in churches or chapels of Mondoñedo-Ferrol Diocese. Isolated or networked wireless sensor systems have been used in many contexts: structural control, medicine, heritage conservation, etc. There are commercial monitoring systems with wireless sensors that perform these functions, but at a relatively high cost. Nowadays, the continuous development of miniaturized sensors in addition with the use of free software means that custom systems can be developed with adequate precision for many applications at a lower cost. In this work a customized, low cost, wireless registration system is presented for the monitoring of different environmental parameters as humidity or temperature inside churches in Diocese of Mondoñedo-Ferrol (Galicia, Spain). The objective is to show the capacity of the system, which requires a quite simple installation, to capture and record data which will be available through a web server for the users to view, analyze and even accomplish automatically control of different devices. This will allow which can be used to make decisions about specific maintenance or repair actions to preserve the Cultural Heritage.

Resume : Since the beginning of the GIPRI´s research, towards the 70s of the XX century, the main concern has been the exhaustive documentation of each of the elements that constitute the rock stations. In addition to the different symbolic motifs of the panels, it is essential to study different relevant aspects that account for the rock art and its environment. The recording of the Serrania de La Lindosa, has had the collaboration of an interdisciplinary group to cover all these relevant aspects. One dedicated to the documentation of the conservation state of the sites and the biological environment of the area, another to photographic register of the rock paintings murals, another to the geological and archaeological analysis of the pigments and finally a team has been responsible to make an audiovisual of the aforementioned recesses. The results and implications of this documentation will be the central theme of this paper, placing special emphasis on rock paintings panels, which due to their size have involved the preparation of adjustments in new documentation formats. This project has been financed by the National Archaeological Research Foundation of Colombia.

Resume : An important set of historical samples from three classified national monuments, were characterized using XRD, µ-PIXE, µ-Raman, µ-XRF, OM and VP-SEM [1,2]. The samples are glazes from the National Palace of Sintra, lustres from the Fronteira Palace in Lisbon, and porcelains belonging to the Santa Clara Monastery in Coimbra. The glazes display different silicate glass compositions with low melting point metals and chromophores based on Co and Cu for the blue and green colouring and Sb for yellow. In lustres the colourless glaze has a lead-alkali silicate composition and a copper-rich lustre overlay. From Coimbra the blue and white porcelains have Co as the colouring agent in the blue inlays and Cu in the green enamel. Synchrotron radiation at the ESRF was used to try to achieve a comparison between manufacturing techniques, pigments used, conservation status and origin of the pieces through elemental speciation using XANES. XAS techniques can provide information on the structural behaviour of these transition metals in the vitreous matrix and increase the knowledge on these materials. [1] M.L. Coutinho et al, Characterization of the glaze and in-glaze pigments of the 19th century relief tiles from the Pena National Palace, Sintra, Portugal. Applied Physics A 122 (7) 1-10 (2016). [2] M.L. Coutinho et al, Non-destructive characterization of oriental porcelain glazes and blue underglaze pigments using µ-EDXRF, µ-Raman and VP-SEM. Applied Physics A, 114, 695-703 (2014).

Resume : Good conservation and restoration practices of CH assets rely on original materials knowledge to allow the best compatibility with new ones for restoration/conservation actions to face ageing and degradation due to natural hazards, climatic changes and anthropic pressure. In the frame of the HERACLES project [1], a set of heritage sites are currently under study to improve their resilience against climate events. Among these is the medieval Gubbio Town Wall in Italy. The present work focuses on mortars and binders of this monument and collected samples relate to different parts of the Wall, corresponding to different historical periods and interventions. They were characterized to determine minerochemical compositions along with their thermal behaviour and morphology. For that purpose, ex-situ laboratory techniques such as X-ray diffraction (XRD), X-ray fluorescence (XRF), optical microscopy (OM), polarised light microscopy (PLM), Scanning. Electron Microscopy (SEM) and simultaneous differential thermal analysis and thermogravimetry (TG-DTA) were used to discern trends in different sampling areas due to construction/reconstruction periods, trying to relate them to used building techniques. [1] HERACLES – HEritage Resilience Against CLimate Events on Site. The HERACLES project has received funding from the European Union Framework Programme for Research and Innovation HORIZON 2020 under Grant Agreement nº700395.

Resume : Lichen growing on granites used in Cultural Heritage cause damage due to physical and chemical processes (Silva et al., 1999), being in consequence a deteriorating agent that must be controlled. Also, being ubiquitous organisms, the problems derived from their growth in the heritage affect a great variety of situations and circumstances. The usual direct intervention to control the deterioration caused by lichens is cleaning. The conventional methods are mechanical (scalpels) or chemical (application of biocides) but the application of abrasives of different nature are also indicated; laser cleaning has also shown a great progress in recent years (Pozo-Antonio et al. 2016). Despite the wide possibilities for cleaning, most of these methods are not capable, by themselves, of completely extracting lichens, especially inside fissures, so the combination of methods could be considered as an alternative to improvement. However, there are no enough scientific works focusing on the evaluation of the effectiveness of combined cleaning methods, especially in granites, rocks poorly studied from this point of view in spite of being as bioreceptive as the sedimentary rocks. This work provides the first data on the effectiveness of the combination of several cleaning methods (chemical, mechanical, laser) to extract a crustose lichen (Disploschistes scruposus) from an ornamental granite used in cultural heritage on NW Iberian Peninsula; scalpel, patented abrasive methods (Hydrogommage, dry-ice cleaning and IBIX), biocide cleaning (Biotin T) and laser (a nanosecond Nd:YVO4 at 355 nm) were applied individually and combined. Effectiveness and damage on granite were evaluated by optical microscopy, SEM-EDS, FTIR and color spectrophotometry. The combination of cleaning procedures resulted to be useful to achieve a higher lichen extraction and also diminished the damage caused by the overcleaning that can be induced by the application of each cleaning procedure by itself. ACKNOWLEDGEMENTS This work was supported by BIA2014-54186-R Project; (Spanish Government, Ministry of Economy and Competitiveness). J.S. Pozo-Antonio was supported by a postdoctoral contract with the University of Vigo within the framework of the 2011–2015 Galician Plan for Research, Innovation and Growth (Plan I2C) for 2014. REFERENCES: Silva B., Rivas T., Prieto B. 1999. Effects of lichens on the geochemical weathering of granitic rocks, Chemosphere 39(2) (1999) 379-388. doi.org/10.1016/S0045-6535(99)00116-2 J.S. Pozo-Antonio, T. Rivas,¸A.J. López, M.P. Fiorucci, A. Ramil. Effectiveness of granite cleaning procedures in cultural heritage: A review. Science of the Total Environment Volume 571, 15 November 2016, Pages 1017-1028.

Resume : In the framework of a study devoted to ancient architectural fragments belonging to a collection of Archaeological Museum ‘B. Brea’ in Lipari (Aeolian Islands) we analysed, by means of the X-Ray Fluorescence (XRF) method, some findings dating VI cent. BC. The aim was that to identify the origin of the raw materials used for the realization of the ceramic artefacts by local artisans. The results of our quantitative analyses suggest that the construction material used has local origin, given the presence of kaolinite quarries in the north of the island of Lipari (Italy).

Resume : Nowadays, there is minimal information on the characterization of cuticles of plants. We present preliminary data of cuticles of nopal cladodes (Opuntia ficus indica var. Atlixco), with respect to water permeation and surface expansion-contraction dependent on water content. The stomatal density (16 / mm2External_face, 28 / mm2Internal_face), pore zise (30-35 ?External_face, 5-3.5 ?Internal_face) and type of stomata (parasitic) it was determined by SEM, thickness 0.07-0.14 mm and density 5.7-6.8 mg / cm2 were employed. The experiment for the measurement of water permeability consists of placing a water column (diameter 1 cm and fixed volume), on the external or internal base of a cuticle´s piece, demonstrating wide asymmetry of both faces. For the tests for the contraction of the dry cuticle (25 ºC and 50 % RH), regarding its state (in situ), they showed a dramatic decrease of 14.68 % surface area (cm2) for the corresponding environmental conditions (25 ºC and 50% RH). Additionally, the cuticle was examined for resistance to dry heat (90 ºC for 4 h) and wet (121ºC, 15 min and 15 lb of presure), no abrupt changes were observed as indicated by its color characteristic CIELAB scale (Internal face: L*=90.45, a*=-835, b*=10.073; External face: L*=90.763, a*=-0.81, b*=9.37). According with the results presented in this work, the nopal cuticles offer an excellent option with promising applications in the industry of filters, bio-packages, etc. They operate in humid or dry environments with a wide range of temperatures.

Resume : In the present work, the natural biofilm of agave leaf (Agave salmiana) called "cuticle" were studied. The stomatal density (60 / mm2External_face , 64 / mm2Internal face), type of stoma (parasitic) and pore length (56 ? External face, 38 ? Internal face ) it was determined by SEM (for thickness cuticle 0.14-0.07 mm and density 6.4mg/ cm2). We examined the evaluation of the surface shrinkage capacity dependent on the water content of dry cuticle (25 oC and 50% RH), with respect to its fresh condition in the plant, the results show a dramatic decrease of 11.91% surface area for the corresponding environmental conditions (25 oC and 50% RH). Additionally, the cuticle (dry) was characterized in color by the CIELB scale (internal face: L * = 87.75, a * = - 2.45, b * = 25.7 and external face: L * = 88.63, a * = - 2.35, b * = 25.76). On the other hand, preliminary experiments were carried out to identify the major chemical components of cutine (fatty acids) of the cuticle, extraction with soxhlet apparatus (for 8 h) using solvents: a) hexane and b) petroleum ether, showed two fractions with characteristic melting point: a) 69.3-71.8 oC, 0.4107% extraction, and b) 58.4-61.2 oC, 1.1303% extraction); presumptively waxes of long chain fatty acids (C14, C16, C18), all saturated.

Resume : During the 18th to the early 20th century, many artistic workshops that dealt with ecclesiastical iconography were operating in Northern and Central Greece. Each of these guilds is characterized by distinct elements e.g. technique, iconographic styles, themes, inscriptions etc. The wall paintings of three churches are studied: 1. The catholicon of Saint George’s Monastery of Myrofyllo, Thessaly, attributed to two painters from Samarina (1869). 2. Saint Demetrius of Dion. Its iconographic program was completed in the early 18th century, with overpaintings attributed to the guild of Samarina (1904). 3. The monastery of the Dormition of the Virgin Mary and the Ascension, Mount Olympus. Its catholicon’s iconographic program was completed in the mid-17th century, but the murals of one of its chapels are believed to be posterior. The purpose of this study is to identify the manufacturing techniques of the wall paintings of the above mentioned monuments in an attempt to document the late post-Byzantine artistic workshops of Central and Northern Greece. Samples containing plaster and painting layers were collected from the wall paintings of the above mentioned churches before the works of restoration. Their microstratigraphic, elemental and the complementary chemical bond/molecular analyses were performed by means of SEM-EDS and μ-FTIR, respectively. The combined analysis showed results regarding the applied painting techniques of the aforementioned monuments.

Resume : Constructed in the early 4th century AC, as a part of the Galerian Palace Complex in Thessaloniki, Rotunda is a monumental circular domed structure decorated with marvelous mosaics. The monument withstood several earthquakes due to its robust structure. However, after its conversion into a church and the addition of a sanctuary, its static equilibrium changed causing the collision of the eastern part of the dome. The wall-painting under study was created in the late 19th century by an Italian artist, named S. Rossi, as an overpainting on the inpaintings filling the lost mosaics of the eastern part of the dome. The applied painting techniques, the previous pictorial phases, the existence of overpaintings and the restoration problems of the Rossi wall painting are matters which have concerned conservators, archaeologists and scholars. Samples collected from the lower area of the Rossi wall painting were examined by means of optical microscopy, FTIR/μ-FTIR spectroscopy, SEM-EDS electron microscopy and XRD analysis. The applied pigments and materials, the microstratigraphy of the samples and the different pictorial phases and their techniques were identified. Additionally, the inability of the painting to be cleaned was explained; the dark color of the wall painting was originally used for aesthetical reasons and was not caused by varnish darkening, accumulated dirt or soot.

Resume : With the aim of finding an interpretation for the isomerization reaction of decapentaene by quantum methods, we have studied a series of three molecules giving the following results:  The studied segments (C10H12, C10H6Br6,C10H6I6) are very stable. This stability is justified by the HOMO-LUMO found energy gap. However, examination of the stability of several conformations shows that the trans conformer is more stable than the cis conformer in the general assembly.  According to the study of different reaction profiles, we noticed that the size and nature of the dopant plays a very important role on the evolution of the activation energy.  From the obtained values of the activation energy, we find that the speed constants of the isomerization reaction are in the order: kC10H12 >>kC10H6Br6>> kC10H6I6  The search for intermediate products during the transition Cis-Trans shows that the geometric parameters (angles and dihedral angles) are the most varied settings, this remark has been observed in the case of substituted and non-substituted PA.  The methods of calculations performed in this work are the Ab-initio and DFT methods, with the bases (6-31G, 3-21G **). All these calculations are performed with the Hyperchem software, where parameters obtained are in a closer order to those obtained with the Gaussian 03W software  Examination of different molecules obtained during the Cis-Trans isomerization reaction shows that the total energy of the resulting intermediate product is of the order of -10487.05 eV, corresponding to a 0.87 eV activation energy (23.67 kcal / mol).  With the same HF method (6-31G and 3-21 G**), a close geometry was obtained for the intermediate product in the isomerization reaction with a total energy of 0.93 eV (25.30 kcal/mole), which shows that the different values of the activation energy obtained by the HF and DFT methods at the 6-31G level can be compared to those obtained by Ito, Montaner and Bernier. Keywords: Ab-initio; DFT; kinetics; isomerisation; substituted decapentaene

Resume : In this work, four nanocomposites have been studied as potential biocide over limestone matrices. These biocidal treatments are based on silver and silver/titanium dioxide nanoparticles synthesized by a bottom-up method with sodium borohydride as reduction agent. The physicochemical characterization of nanocomposites has been realized using UV-Visible (UV-Vis) spectrophotometry, Dynamic Light Scattering (DLS), Raman spectroscopy and Electron Microscopy. These treatments have been tested on limestones coming from the four quarries used during the building of the Town hall of Seville (Spain). These quarries are sited in Utrera (Seville), El Puerto de Santa María and Jerez de la Frontera (Cádiz) and Novelda (Alicante). The effective protection against bacteria development of these nanomaterials is well known, and has been corroborated in this study. However, their effectiveness over stone depends on the in-depth penetration of the nanocomposites. The location of the deposited nanocomposites in the stone matrix has been carried out by LIBS depth-profiling, obtaining successful results and placing this technique as the main option for this kind of studies. The aesthetical compatibility has been measured by colorimetric techniques. The results of these studies demonstrate the biocidal activity of all nanocomposites and their applicability on historical building and archaeological site depends on the intrinsic characteristics of the original material. In this sense, in porous stones is easier to achieve a higher penetration of the treatment, decreasing the colour change of the limestone surface. Only in microporous limestones, the most unstable nanocomposites obstructed the porous system and generated a higher colour changes. Furthermore, it has been demonstrated the capability of LIBS technique for the detection and generation of depth profiles by the analysis of the nanoparticles diffusion in the stone matrix after treatments employed in historical buildings.

Resume : Nowadays, the application of consolidation treatments based on nanolime (CaOH2 nanoparticles) is one of the most common practices during the restoration of historical buildings. However, recent studies have showed that their effectiveness on stone materials is lower than expected. It is due to the accumulation of the nanolimes near the surface, decreasing their depth into stone matrix and, consequently, resulting in a low effectiveness. This research is focused on studying the affinity between nanolimes and the solvent used in the application, in order to improve the penetration of the treatment in stones. For that reason, we have decorated CaOH2 nanoparticles with fluorescent quantum dots in order to show the real penetration of the nanomaterial, and not the solvent. Different mixtures of solvents have been probed, using thin layer chromatography to evaluate their capacity to transport the nanolimes. Moreover, the evaluation of the depth has been carried out on El Puerto de Santa María limestones, high porous stones widely used in historical buildings in the southwest of Spain. The selection of an optimal mixture of solvents improves significantly the depth penetration of the treatment, decreasing the chromatic change on the surface of stones. The fluorescence of the Quantum Dots when are lighted by UV radiation, allows to evaluate easily the depth of the treatment.

Resume : The subject of the present work is the thorough study of different archaeological ceramic artifacts with the use of various physical chemical techniques, in order to derive information about their main components and manufacturing conditions (firing temperature and atmosphere). Ceramics usually consist of a large number of minerals, including mixtures of different clay minerals as well as clastic grains, and several other accessory minerals. They undergo physical and chemical alterations during firing, which depend on their original composition, but also on the highest temperature, the duration and the conditions of firing. For this reason, the use of just one analytical technique is not sufficient for their study. In this work, the supplementary techniques of Optical Microscopy, Scanning Electron Microscopy – Energy Dispersive Spectroscopy (SEM-EDS), X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Thermogravimetric Analysis (TGA) are used complementary for the examination of four ceramic objects that belong to the Museum of Byzantine Culture in Thessaloniki. Two of them, a fragment of a vessel that looks like a handle and an oil lamp, date back to the 6th century A.C., while the other two, an ottoman and a western type tobacco pipes, belong to the 17th century A.D. As it was revealed by their study, they are utilitarian objects that exhibit differences in the composition of the raw materials, as well as the firing process applied for their fabrication.

Resume : A large number of buildings with artistic components inside (stucco decorations, frames, pilasters, statues, arches, bosses), need works of conservation and restoration for maintenance of the building. Significant deterioration of some buildings are produced when they come in direct contact with light, moisture or freeze, biological attack or even human attacks. Despite the increase of research being developed concerning cultural heritage, most of the restoration works were not entirely successful. In this paper, the materials of three architectural buildings, will be evaluated as follows: Nanu Maniu Building, as a neo-romantic style house with Art Nouveau influences, that contains facades of colossal pilasters of gypsum, facade decorations with laurel leaves and garlands, or symbolic objects: violin, bow with arrows; Fantaneanu House, building with "art nouveaux" elements, as bosses and windows frames, floral elements, columns of the groove and Cioflea House, an unique architectural house from the south part of Romania region with florish wood decorations. Specific techniques as microscopy, EDXRF and ICP-AES, FTIR and Raman spectroscopy methods, gas-chromatography, CIELAB color parameters, consolidation with nanomaterials, have been tested and discussed in this paper. Acknowlegements: This work was supported by a grant of the Romanian Ministry of Research and Innovation CCCDI-UEFISCDI, project number PN-III-P1-1.2-PCCDI-2017-0476 within PNCDI III.

Resume : Unbaked earth has been used as building material since ancient times, especially in hot climate regions. The good thermal and acoustic properties, eco-friendliness, availability and low cost are spreading its use also in industrialized countries. Among the variety of techniques and local traditions, the adobe technique is one of the most common worldwide. Earth and water are mixed to a liquid state, often stabilized with organic fibres and lime, shaped as bricks and sun-dried. Such materials are particularly susceptible to wind and water erosion and have low mechanical properties, so their conservation is challenging. Consolidation is to apply a chemical that penetrates and restores the substrate cohesion: in order to overcome the shortcomings of the commonly used products, we experimented the formulation of a compatible and long-lasting treatment where nanosilica, nanolime and a cellulose derivative are combined, reflecting the adobe recipe. We obtained a stable hydro-alcoholic dispersion with suitable components proportions and minimum water content, still necessary for consolidation reactions. Turbidimetry indicated that the formulation is stable over days; FT-IR and XRD showed evidence of the possible formation of calcium silicate hydrate, the main binding phase of cements; SEM showed the formation of a homogeneous and compact matrix. Promising results are emerging from preliminary application tests on adobe samples from Mexico.

Resume : Ground Penetrating Radar (GPR) is a flexible diagnostic technology suitable to perform non-invasive and cost effective surveys aimed at inferring constructive modalities, anomalies or damages characterizing manmade structures, among which cultural heritage (CH) assets [1]. However, the issues related to the result interpretation deserve huge attention towards development and validation of application oriented data processing capable of providing reliable and high resolution images of the investigated scenario. Accordingly, this communication provides a proof of the usefulness of GPR surveys, enhanced by the use of a Microwave Tomographic data processing approach [2], as a methodology for diagnosis and monitoring of CH exposed to climate events and natural hazards. In detail, we present the results of a GPR measurement campaign carried out at the Consoli Palace of Gubbio (Italy), one of most representative and spectacular building of the monumental town. The Consoli Palace was built between 1332 and 1349 on the slope of the mountain mainly by using limestone, travertine, sandstones, plasters, blinders and mortars and its foundations are placed at two different levels with a difference in height of about 10 meters. Such a difference, together with environmental actions and other natural hazards (e.g., earthquakes) could be the reasons of differential displacements, whose effects are visible in some parts of the Palace. As a consequence, Microwave Tomography enhanced GPR surveys were performed in order to characterize the constructive modalities and the deterioration phenomena related to material aging and natural or anthropic issues. In detail, data were acquired by using the IDS manufactured RIS K2_FW GPR system [3]. This system was equipped with a 2 GHz single fold shielded antenna to survey vertical structures and with a dual frequency single fold shielded antenna, whose nominal central frequencies are 200 MHz and 600 MHz, to perform foundation investigations. The data were processed by means of widespread used filtering procedures, which were chosen by taking into account the peculiarities of the investigated scenario, i.e. the kind of targets that are expected to be reconstructed. Moreover, a microwave tomographic approach, which is based on a linear model of the scattering phenomenon underling the GPR survey, was taken into account to improve the results accuracy. These obtained results allowed us to improve knowledge about the architecture of the surveyed zones and their structural hazards. Acknowledgments: This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 700395. References [1] D. J. Daniels, Ground Penetrating Radar, in IEE Radar, Sonar and Navigation Series 15, London, U.K.: IEE, 2004. [2] I Catapano, L Crocco, R Di Napoli, F Soldovieri, A Brancaccio, F Pesando, Microwave tomography enhanced GPR surveys in Centaur’s Domus, Regio VI of Pompeii, Italy,Journal of Geophysics and Engineering, 2012, Volume 9, Issue 4, pp. S92-S99 [3] https://idsgeoradar.com/products.

Resume : Nonlinear optical microscopy (NLOM) is being investigated for non-invasive 3D imaging with micrometric superficial and in-depth resolution of multilayer, multicomponent samples of interest in various domains from biomedicine to cultural heritage (i.e. Phys. Chem. Chem. Phys., 2017, 19, 22836). NLOM relies on near-IR, femtosecond laser excitation of transparent substrates to exploit nonlinear optical effects, including multiphoton excitation fluorescence (MPEF) and second and third harmonic generation (SHG, THG). MPEF provides information related to the chemical composition, SHG identifies the presence of non‐centrosymmetric structures and THG allows imaging interfaces between optically dissimilar materials. Here we present the application of NLOM in MPEF mode to study layered painting substrates (tempera and acrylics). Measurements were carried out with a custom-made laser scanning microscope based on a Ti:Sapphire laser oscillator (800 nm, 80 MHz, 70 fs). MPEF measurements were supported by morphological and chemical assessment of samples using, among other techniques, linear laser-induced fluorescence and micro-Raman spectroscopies. The results obtained provide guidelines on how the MPEF modality of NLOM serves for the non-destructive analysis of multicomponent, layered painting substrates. This work is funded by projects IPERION-CH (H2020-INFRAIA-2014-2015, nº 654028), GEOMATERIALES 2-CM (S2013/MIT-2914, Autonomous Community of Madrid) and CTQ2016-75880-P (MINECO, Spain).

Resume : The study of anoxic corrosion process of ferrous metals is a matter of concern for industrial sector but also for cultural heritage objects conservation. The determination of the iron sulfides nature, their distribution in the corrosion product layer and their origin (possible action of Sulfate-Reducing Bacteria) is a crucial issue to address in order to determine the corrosion mechanism and anticipate the degradation of ferrous objects during extraction, storage or conservation operations. In the present work, an analytical strategy combining characterization techniques (FE-SEM imaging coupled with EDS, µ-Raman and nano-Auger spectroscopies, nano-SIMS) bringing an overall physico-chemical insight from micrometric to nanometric scale has been developed and employed to the study of archeological ferrous samples, representative of long term corrosion systems. Mix of phases of greigite (Fe3S4) and mackinawite (FeS) in a corrosion layer mainly constituted of iron carbonates were observed at a sub-micrometric scale, in consistency with the literature [1], showing the precipitation of greigite, mackinawite and/or pyrite (FeS2) in the presence of bacteria or in sulfur environment. Finally, the spatial distribution of the different phases at the nanometer scale was succeeded thanks to Scanning Auger Microscopy and could be compared with nano-SIMS experiments informing about the sulfur isotopic composition variations and the bio-origin of the sulfur phases. [1] S. Grousset et al., Corrosion Science 112 (2016) 264–275.

Resume : Historic paintings made with green copper-based organometallic pigments (verdigris and copper resinate) in an oil matrix are often susceptible to degradation, occurring as a browning of the green layers during ageing. This is especially true for easel paintings from the 15th to 17th centuries containing these pigments, used for their advantageous optical properties. Understanding the alteration mechanism of this phenomenon is crucial for painting conservation issues. The pigment-binder system is complex: degradation may concern both the copper cluster [1] and the organic matrix surrounding the complex. To study the effect of darkening on the latter, different analyses have been performed on both model samples prepared in laboratory (mixtures of verdigris/resinate and linseed oil, some of them subjected to artificial ageing) and multi-layered “real” samples, taken from historical masterpiece paintings. Mappings of altered and non-altered areas have been done by FTIR spectroscopy and photoluminescence. The luminescence intensity increases with alteration. FTIR and Raman spectroscopies have been used to compare degraded zones with green ones. No new species are formed, but changes are detected within the molecular structure of the pigment-binder system during the darkening. [1] C. Santoro, K. Zarkout, A.-S. Le Hô, F. Mirambet, D. Gourier, L. Binet, S. Pagès-Camagna, S. Reguer, S. Mirabaud, Y. Le Du, P. Griesmar, N. Lubin-Germain, M. Menu, Applied Physics A. (114), 2014, 637-645

Resume : Egyptian Yellow Coffins from the 21st Dynasty are a very specific production found in the Theban area. The main goal of the study is to identify materials used in order to determine the manufacturing process, and try to isolate specific workshops. For this purpose, a methodology for analysis has been developed at the C2RMF. A dozen funerary sets from the Egyptian Antiquity Department of the Louvre Museum are under study. This preliminary work highlights the complexity in identifying precisely the chemical nature of organometallic green pigments. For all cases studied, the detection by SEM-EDS of tin or lead traces proves that the copper used in the fabrication of synthetic green pigments comes from bronze scraps. It also allows the identification of two possible types of initial pigments. One, with silica amorphous phases made by a heat treatment, and the other one without; possibly copper acetate. The SEM-FEG imaging provides new information concerning texture layer or grain morphology and suggests a pigment largely altered. Copper greens are quite unstable, and especially in environments conducive to their alteration. This hypothesis has been confirmed by the identification (µFTIR) of copper chlorides neoformed, and copper oxalates; possible products of copper-protein complex degradation. The identification of alteration mechanisms will enable us to know the precise nature of initial pigments and maybe even the fabrication recipes.