Non-Destructive Multi-Analytical Approach to Study the Pigments of Wall Painting Fragments Reused in Mortars from the Archaeological Site of Pompeii (Italy)

During the excavations carried out in Via di Mercurio (Regio VI, 9, 3) in Pompeii, in 2015, some red, green, black, and brown wall painting fragments were found in the preparatory layer of an ancient pavement which was probably built after the 62 AD earthquake. These fragments, derived from the rubble, were used as coarse aggregate to prepare the mortar for building the pavement. The wall painting fragments are exceptionally well preserved, which is an uncommon occurrence in the city of Pompeii. However, as they were enclosed in the mortar, the wall painting fragments were protected from the high temperatures (probably ranging between 180 ◦C and 380 ◦C) produced by the eruption in 79 AD. The pigmented outer surface of each sample was analyzed using a non-destructive multi-analytical approach, by combining spectrophotometric colorimetry and portable X-ray fluorescence with micro-Raman spectroscopy. The compositional characterization of the samples revealed the presence of cuprorivaite, goethite, and celadonite in the green pigments; hematite in the red pigments; goethite in the brown pigment; and charcoal in the black pigment. These data probably provide us with the most "faithful picture" of the various red, green, black, and brown pigments used in Pompeii prior to the 79 AD eruptio

In situ non-invasive multianalytical methodology to characterize mosaic tesserae from the House of Gilded Cupids, Pompeii

Mosaics, one of the most important decorative artworks in the Roman culture, were usually elaborated with a set of tesserae joined with lime or others binders to form geometric or figurative decorations. The identification of both substrate and colored compounds of the tesserae is a challenge for chemists and archaeologists. In this work, two mosaics present in the House of Gilded Cupids from the Archaeological Park of Pompeii were analyzed in situ by non destructive techniques. Raman and Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectroscopies were used for the molecular and mineralogical characterization, and hand-held energy dispersive X-ray fluorescence (HH-EDXRF) spectrometry and Laser Induced Breakdown Spectroscopy (LIBS) for the elemental analysis. LIBS in-depth analysis was performed to obtain insights about the thickness of the pictorial layer determining that the thickness of red and orange pictorial layers was higher than 140 μm. The results showed that white tesserae were mainly composed by calcite, while local black colored volcanic rocks were used to manufacture black tesserae. Red and orange tesserae were composed by a calcite-based matrix with a hematite pictorial layer applied over it. Orange color was obtained by diluting hematite in the calcite matrix. Principal component analysis (PCA) of the XRF data was performed to observe differences and/or similarities between the analyzed mosaics; the samples projection of the PCA showed clear groupings.Iker Marcaida is grateful to the Basque Government who funded his predoctoral fellowship. This work has been supported by the project MADyLIN (BIA2017‑87063‑P) funded by the Spanish Agency for Research AEI (MINEICO‑FEDER/ UE)

When Red Turns Black: Influence of the 79 AD Volcanic Eruption and Burial Environment on the Blackening/Darkening of Pompeian Cinnabar

It is widely known that the vivid hue of red cinnabar can darken or turn black. Many authors have studied this transformation, but only a few in the context of the archeological site of Pompeii. In this work, the co-occurrence of different degradation patterns associated with Pompeian cinnabar-containing fresco paintings (alone or in combination with red/yellow ocher pigments) exposed to different types of environments (pre- and post-79 AD atmosphere) is reported. Results obtained from the in situ and laboratory multianalytical methodology revealed the existence of diverse transformation products in the Pompeian cinnabar, consistent with the impact of the environment. The effect of hydrogen sulfide and sulfur dioxide emitted during the 79 AD eruption on the cinnabar transformation was also evaluated by comparing the experimental evidence found on paintings exposed and not exposed to the post-79 AD atmosphere. Our results highlight that not all the darkened areas on the Pompeian cinnabar paintings are related to the transformation of the pigment itself, as clear evidence of darkening associated with the presence of manganese and iron oxide formation (rock varnish) on fragments buried before the 79 AD eruption has also been found.The research leading to these results has received funding from “la Caixa” Foundation (Silvia Pérez-Diez, ID 100010434, Fellowship code LCF/BQ/ES18/11670017). A.P.M. is a Serra Húnter fellow. A.P.M’s research was supported by a Beatriu de Pinós postdoctoral grant (2017 BP-A 00046) of the Government of Catalonia’s Secretariat for Universities & Research of the Ministry of Economy and Knowledge. This work has been supported by the project MADyLIN (BIA2017-87063-P) funded by the Spanish Agency for Research AEI (MINECO-FEDER/UE). The authors thank for the funding provided by University of the Basque Country through the Institutionally Sponsored Open Access

Elucidation of the chemical role of the pyroclastic materials on the state of conservation of mural paintings from Pompeii

Pyroclastic strata have always been thought to protect the archaeological remains of the Vesuvian area (Italy), hence allowing their conservation throughout the centuries. In this work, we demonstrate that they constitute a potential threat for the conservation state of the mural paintings of Pompeii. The ions that could be leached from them and the ion‐rich groundwater coming from the volcanic soil/rocks may contribute to salt crystallisation. Thermodynamic modelling not only allowed to predict which salts can precipitate from such leaching events but also assisted the identification of additional sources of sulfates and alkali metals to explain the formation of the sulfates identified in efflorescences from the mural paintings of Pompeii. For the future, fluorine, mainly related to a volcanic origin, can be proposed as a marker to monitor the extent of the impact in the mural paintings of Pompeii in situ

Elucidation of the Chemical Role of the Pyroclastic Materials on the State of Conservation of Mural Paintings from Pompeii

Pyroclastic strata have always been thought to protect the archaeological remains of the Vesuvian area (Italy), hence allowing their conservation throughout the centuries. In this work, we demonstrate that they constitute a potential threat for the conservation state of the mural paintings of Pompeii. The ions that could be leached from them and the ion‐rich groundwater coming from the volcanic soil/rocks, may contribute to salt crystallisation. Thermodynamic modelling not only allowed to predict which salts can precipitate from such leaching events, but also assisted the identification of additional sources of sulfates and alkali metals, to explain the formation of the sulfates identified in efflorescences from the mural paintings of Pompeii. For the future, fluorine, mainly related to a volcanic origin, can be proposed as a marker to monitor in situ the extent of the impact in the mural paintings of Pompeii.The research leading to these results has received funding from “la Caixa” Foundation (Silvia Pérez-Diez, ID 100010434, Fellowship code LCF/BQ/ES18/11670017). This work has been supported by the projects MADyLIN (Ministry of Economy, Industry and Competitiveness from Spain, Grant No. BIA2017‐87063‐P) funded by the Spanish Agency for Research AEI (MINECO-FEDER/UE) and MINECO-17-CTQ2016-77887-C2-1-R

Chemometrics and elemental mapping by portable LIBS to identify the impact of volcanogenic and non-volcanogenic degradation sources on the mural paintings of Pompeii

Crystallization of soluble salts is a common degradation phenomenon that threatens the mural paintings of Pompeii. There are many elements that contribute to the crystallization of salts on the walls of this archaeological site. Notably, the leachates of the pyroclastic materials ejected in 79 AD by Mount Vesuvius and local groundwater, rich in ions from the erosion of volcanic rocks. Both sources could contribute to increase the concentration of halides (fluorides and chlorides) and other salts in these walls. The distribution of volcanogenic salts and their impact on the conservation of Pompeian mural paintings have however not yet been fully disclosed. In this work, an analytical methodology useful to determine the impact of the main sources of degradation affecting the mural paintings of Pompeii is presented. This methodology combines the creation of qualitative distribution maps of the halogens (CaF and CaCl) and related alkali metals (Na and K) by portable Laser Induced Breakdown Spectroscopy (LIBS) and a subsequent Principal Component Analysis of these data. Such maps, together with the in-situ identification of sulfate salts by portable Raman spectroscopy, provided information about the migration and distribution of volcanogenic halides and the influence of ions coming from additional sources (marine aerosol and modern consolidation mortars). Additionally, the thermodynamic modeling developed using the experimentally determined ionic content of Pompeian rain- and groundwater allowed to determine their specific role in the formation of soluble salts in the mural paintings of Pompeii.The research leading to these results has received funding from “la Caixa” Foundation (Silvia P erez-Diez, ID 100010434, Fellowship code LCF/BQ/ES18/11670017). This work has been supported by the Spanish Agency for Research AEI (MINECO- FEDER /UE) through the projects MADyLIN (BIA2017-87063-P) and MINECO-17-CTQ2016-77887-C2-1-R, and the Government of the Principality of Asturias (GRUPIN IDI/2018/000186). The authors thank for technical and human support provided by the laboratory Raman-LASPEA of SGIker (UPV/EHU/ ERDF, EU)

Non-Destructive Multi-Analytical Approach to Study the Pigments of Wall Painting Fragments Reused in Mortars from the Archaeological Site of Pompeii (Italy)

During the excavations carried out in Via di Mercurio (Regio VI, 9, 3) in Pompeii, in 2015, some red, green, black, and brown wall painting fragments were found in the preparatory layer of an ancient pavement which was probably built after the 62 AD earthquake. These fragments, derived from the rubble, were used as coarse aggregate to prepare the mortar for building the pavement. The wall painting fragments are exceptionally well preserved, which is an uncommon occurrence in the city of Pompeii. However, as they were enclosed in the mortar, the wall painting fragments were protected from the high temperatures (probably ranging between 180 °C and 380 °C) produced by the eruption in 79 AD. The pigmented outer surface of each sample was analyzed using a non-destructive multi-analytical approach, by combining spectrophotometric colorimetry and portable X-ray fluorescence with micro-Raman spectroscopy. The compositional characterization of the samples revealed the presence of cuprorivaite, goethite, and celadonite in the green pigments; hematite in the red pigments; goethite in the brown pigment; and charcoal in the black pigment. These data probably provide us with the most “faithful picture” of the various red, green, black, and brown pigments used in Pompeii prior to the 79 AD eruption

In-situ multi-analytical characterization of original and decay materials from unique wall mirrors in the House of Gilded Cupids, Pompeii

Abstract The House of Gilded Cupids (Regio VI, Insula 16, 7, 38) was unquestionably one of the most important residences of Ancient Pompeii, where important archaeological artefacts such as mural paintings, mosaics, sculptures and lalariums were rediscovered. This work characterizes two wall mirrors that, together with those recovered from the House of Efebo and the Domus of Euplia, represent the only ones found in the archaeological site of Pompeii. The 2015 and 2016 expeditions of the Analytica Pompeiana Universitatis Vasconicae project performed an in situ multi-analytical study, using only portable non-destructive analytical techniques. Molecular data provided by Raman spectroscopy suggested obsidian was the reflective matrix for both mirrors. Elemental data provided by energy dispersive X-ray fluorescence and laser induced breakdown spectroscopy (LIBS) systems were concordant with Raman spectroscopic results, enabling the detection of Ca, K, Al and Na as the main elements included in the Si matrix characteristic of obsidian igneous rocks. The LIBS data confirmed the presence of obsidian hydration layers. All techniques were used to investigate the degraded white and yellow crusts of the mirrors. Gypsum (CaSO4·2H2O) and nitrocalcite (Ca(NO3)2·4H2O) were identified in the white areas and gypsum and goethite (α-FeOOH) in the yellow crusts. LIBS depth profiling on the white crusts found a layer of nitrocalcite on top of the gypsum layer. Gypsum and goethite were proposed to form after partial dissolution of the mortars patches (with high iron contents) used in modern restorations around the mirrors, followed by a reprecipitation on the surface of the mirrors. Nitrocalcite was proposed to form after the attack of atmospheric NOx on gypsum crusts. These results represent the first analytical work focused on the study of these unique mirrors and provide the knowledge needed for defining more adequate conservation treatments

Testing the volcanic material burying Pompeii as pozzolanic component for compatible conservation mortars

The aim of this work is to evaluate the potential use of ashes and lapilli that buried Pompeii as pozzolanic material for the formulation of conservation mortars. XRD analyses proved that the mineralogical composition of these volcanic products is consistent with the original pozzolanic mortars preserved at the archaeological site. A first set of pozzolanic mortars were prepared by using silica sand as aggregate. After curing the lapilli-based mortars, the measured compressive and flexural strengths proved to be higher than those of the control samples made of commercial pozzolan. A second set of samples, prepared by replacing silica sand with similar size coarse ash and lapilli, proved that volcanic aggregates further enhanced the mechanical properties by the formation of interfacial transition zones. The result of this research demonstrates that the volcanic material burying the archaeological site of Pompeii could be used as raw material in the formulation of compatible conservation mortars. As volcanic pozzolan is increasingly investigated as potential Supplementary Cementitious Material (SCM) for the production of sustainable concretes, preliminary considerations about the impact of the present work to this field of research are also provided