Analytical pyrolysis evidences the presence of granaticins in the violet stains of a Roman tomb

Diaz-Herraiz, Marta; Láiz, Leonila; Jurado, Valme; Miller, Ana Z.; González‐Pérez, José Antonío; Santos, Juan Luís; Alonso, Esteban; Sáiz‐Jiménez, Cesáreo

doi:10.1016/j.jaap.2015.10.018

Cited by 9 publications

(10 citation statements)

References 14 publications

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“…The microbiology of subterranean environments has received increasing attention due to the biodeterioration processes affecting the integrity of rock art and mural paintings 1 , 2 . Bacteria have colonised the rock art paintings in Altamira Cave, Spain 3 , and the mural paintings in Etruscan 4 , 5 and Roman tombs 6 , 7 . Fungi have originated several outbreaks in Lascaux Cave, France 8 , 9 , and colonised Japanese tombs 10 .…”

Section: Introductionmentioning

confidence: 99%

“…lascauxensis was pyrolysed in order to provide insight into the precursors. Analytical pyrolysis has become an important tool for the characterization of complex carbonaceous matrices because most of the pyrolysis products have a well-known origin, thus they yield valuable fingerprint information on the molecular structure of macromolecular substances 6 .…”

Section: Introductionmentioning

confidence: 99%

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Structure of melanins from the fungi Ochroconis lascauxensis and Ochroconis anomala contaminating rock art in the Lascaux Cave

Rosa

Martin‐Sanchez

Sánchez-Cortés

et al. 2017

Sci Rep

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Two novel species of the fungal genus Ochroconis, O. lascauxensis and O. anomala have been isolated from the walls of the Lascaux Cave, France. The interest in these fungi and their melanins lies in the formation of black stains on the walls and rock art which threatens the integrity of the paintings. Here we report solid-state cross polarization magic-angle spinning 13C and 15N nuclear magnetic resonance (NMR) spectroscopy and surface-enhanced Raman spectroscopy (SERS) of the melanins extracted from the mycelia of O. lascauxensis and O. anomala in order to known their chemical structure. The melanins from these two species were compared with those from other fungi. The melanins from the Ochroconis species have similar SERS and 13C and 15N NMR spectra. Their chemical structures as suggested by the data are not related to 3,4-dihydroxyphenylalanine, 5,6-dihydroxyindole or 1,8-dihydroxynaphthalene precursors and likely the building blocks from the melanins have to be based on other phenols that react with the N-terminal amino acid of proteins. The analytical pyrolysis of the acid hydrolysed melanin from O. lascauxensis supports this assumption.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Structure of melanins from the fungi Ochroconis lascauxensis and Ochroconis anomala contaminating rock art in the Lascaux Cave

Rosa

Martin‐Sanchez

Sánchez-Cortés

et al. 2017

Sci Rep

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“…One of the major violet pigments, granaticin A, was detected in the tomb walls by using analytical pyrolysis (Diaz-Herraiz et al, 2016). Granaticin A is soluble in alkaline water but the solubility of the pigment decreased with pH value.…”

Section: Discussionmentioning

confidence: 99%

Nature and origin of the violet stains on the walls of a Roman tomb

Domínguez-Moñino

Diaz-Herraiz

Jurado

et al. 2017

Science of The Total Environment

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The Circular Mausoleum tomb (Roman Necropolis of Carmona, Spain) dates back from the first century AD and is characterized by a dense microbial (phototrophic) colonization on the walls and ceiling. However, some walls exhibited an important number of violet stains of unknown origin. The microbial communities of these violet stains are mainly composed of cyanobacteria, streptomycetes and fungi. A strain of Streptomyces parvus, isolated from the walls, produces a violet pigment in culture media. High performance liquid chromatography-mass spectrometry of the culture extracts obtained from this Streptomyces revealed the presence of a few granaticins, pigments with a benzoisochromanequinone structure. When metabolically active in the tomb, S. parvus synthesizes the pigments that diffuse into the mortar. During rain and/or wetting periods, the pigments are solubilized by alkaline waters and elute from the starting position to the surrounding mortar, enlarging the pigmented area and thus contributing to this exceptional biodeterioration phenomenon.

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“…When desiccation occurs, for example by intense direct sunlight or dryness periods, the mats turn dark to black and its association with saline efflorescence or other surface deposits is common. • Colonizations by non-phototrophic microorganisms produce stains more restricted than the green mats; an example is the violet stains that appear inside the Circular Mausoleum which are caused by the excretion of pigments by Streptomyces [5,6,8]. In addition, a number of bacteria have been described in the tombs, including some novel species [4,20,21].…”

Section: Biological Colonizationsmentioning

confidence: 99%

“…The seepage of rain water and/or irrigation favour the existence of damp vertical surfaces in the tombs, which are readily colonized by bacteria, cyanobacteria, algae, fungi, and in the extreme cases by bryophytes, ferns and a small number of vascular plants. A few reports on the biological deterioration of some tombs have been published [1][2][3][4][5][6] and comparatively less data are available on the mineralogy and weathering of the calcarenite rock [7,8].…”

Section: Introductionmentioning

confidence: 99%

A study on the state of conservation of the Roman Necropolis of Carmona (Sevilla, Spain)

Sánchez‐Moral

Cañaveras

Benavente

et al. 2018

Journal of Cultural Heritage

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The Roman Necropolis of Carmona (Sevilla, Spain) has experienced a severe deterioration since the accidental discovery in 1868, subsequent archaeological excavations starting in 1882 and adaptations of the whole archaeological area for visits. To this deterioration contributed the location in a soft calcarenite rock quarry, the adverse environmental conditions and the numerous and extensive wrong archaeological and managing interventions along more than a century. The cultural, artistic and religious importance of this Necropolis converts the protection and conservation of this archaeological site in a major issue. This work present the data obtained in a multidisciplinary research in which geology, geomorphology, micro-environmental and climatic monitoring, description of weathering forms and biological colonization were considered in order to propose corrective measures to minimize further deterioration.

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Analytical pyrolysis evidences the presence of granaticins in the violet stains of a Roman tomb

Cited by 9 publications

References 14 publications

Structure of melanins from the fungi Ochroconis lascauxensis and Ochroconis anomala contaminating rock art in the Lascaux Cave

Structure of melanins from the fungi Ochroconis lascauxensis and Ochroconis anomala contaminating rock art in the Lascaux Cave

Nature and origin of the violet stains on the walls of a Roman tomb

A study on the state of conservation of the Roman Necropolis of Carmona (Sevilla, Spain)

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