Periodic Reporting for period 1 - RED-OPEN (Unravelling Discoloration Mechanisms of Red Organic Pigments in Historical Art Works.)
Período documentado: 2021-09-01 hasta 2023-08-31
An important issue encountered in the historical artworks is the fading of the original colors because of their strong light sensitivity, infamously leading to the discoloration of masterworks even within an artist's lifetime. This phenomenon is clearly evidenced in many paintings of 19th century European impressionist artists, such as van Gogh, in particular when Organic Red Pigments (ORP) have been used. The identification of these ORP in historical paintings remains a main challenge because of (1) the generally low concentration of the original pigment remaining after an aging period of ca. 100 years, (2) the scarcity of the paint micro samples available for analysis and the difficulty of obtaining additional ones and (3) the complexity of degradation behavior in the presence of oxygen, inorganic semiconductor pigments, binding media or varnish.
This project will expand the currently limited understanding of the main causes of discoloration and how this knowledge can be transferred to cultural institutions in order to propose mitigation strategies to slow down the degradation of unstable organic red pigments in works of art. The successful completion of RED-OPEN will have a major impact in the understanding of the original artwork's appearance and will provide comprehensive and detailed knowledge of the progressive changes throughout the painting's history. RED-OPEN will generate knowledge that will help conservators and conservation scientists to understand the causes of discoloration and formulate mitigating actions, preserving invaluable art for future generations and further proposing a digital reconstruction of its originally intended appearance.
The objective of the RED-OPEN project is to develop a multi-analytical approach based on mass spectrometry and spectroscopic techniques (A) to understand their discoloration mechanism and (B) to identify their breakdown products, even if the original molecules are no longer present in the artworks.
The unwanted fading of ORP poses two main research questions: (1) what are the causes that drive their discoloration? and (2) which molecular changes are associated to the color change observed in paintings?
To answer the research questions of RED-OPEN, the following research objectives (RO) will be accomplished:
RO1- Evaluate the influence of external factors in the discoloration of ORP: (RO1.1) oxygen, and (RO1.2) 19th century inorganic pigments with semiconductor properties.
RO2- Evaluate molecular changes during ORP discoloration: (RO2.1) identification of fragmentation products and elucidation of discoloration pathways, (RO2.2) study the distribution of fragments/markers within the paint layers and (RO2.3) elucidate the structural conformation of ORP and its changes during the discoloration process.
The outcome of each objective will also generate stand-alone advancements beyond the current state of the art:
Added value RO1- museums can adapt or implement a conservation strategy to prevent (further) fading.
Added value RO2- the identification of molecular markers will provide information about the original ORP used by the artist, even if the original molecules are no longer present in the painting.
This project will expand the currently limited understanding of the main causes of discoloration and how this knowledge can be transferred to cultural institutions in order to propose mitigation strategies to slow down the degradation of unstable organic red pigments in works of art. The successful completion of RED-OPEN will have a major impact in the understanding of the original artwork's appearance and will provide comprehensive and detailed knowledge of the progressive changes throughout the painting's history. RED-OPEN will generate knowledge that will help conservators and conservation scientists to understand the causes of discoloration and formulate mitigating actions, preserving invaluable art for future generations and further proposing a digital reconstruction of its originally intended appearance.
The objective of the RED-OPEN project is to develop a multi-analytical approach based on mass spectrometry and spectroscopic techniques (A) to understand their discoloration mechanism and (B) to identify their breakdown products, even if the original molecules are no longer present in the artworks.
The unwanted fading of ORP poses two main research questions: (1) what are the causes that drive their discoloration? and (2) which molecular changes are associated to the color change observed in paintings?
To answer the research questions of RED-OPEN, the following research objectives (RO) will be accomplished:
RO1- Evaluate the influence of external factors in the discoloration of ORP: (RO1.1) oxygen, and (RO1.2) 19th century inorganic pigments with semiconductor properties.
RO2- Evaluate molecular changes during ORP discoloration: (RO2.1) identification of fragmentation products and elucidation of discoloration pathways, (RO2.2) study the distribution of fragments/markers within the paint layers and (RO2.3) elucidate the structural conformation of ORP and its changes during the discoloration process.
The outcome of each objective will also generate stand-alone advancements beyond the current state of the art:
Added value RO1- museums can adapt or implement a conservation strategy to prevent (further) fading.
Added value RO2- the identification of molecular markers will provide information about the original ORP used by the artist, even if the original molecules are no longer present in the painting.
To achieve the goals of RED-OPEN, the project is organized into 5 work packages (WPs):
WP 1: Synthesis and analytical characterization of historical red lakes (dye-metal complex)
WP 2: Study of the influence of oxygen and semiconductor pigments during the photodegradation of ORP
WP 3: High Resolution Mass spectrometry approach (HRMS)
WP 4: A first approach on modelling color change of red lakes in oil paint
WP 5: Includes dissemination and awareness building
WP 1: Synthesis and analytical characterization of historical red lakes (dye-metal complex)
WP 2: Study of the influence of oxygen and semiconductor pigments during the photodegradation of ORP
WP 3: High Resolution Mass spectrometry approach (HRMS)
WP 4: A first approach on modelling color change of red lakes in oil paint
WP 5: Includes dissemination and awareness building
Since museum conservation labs lack chemical expertise and have limited resources and funding, the understanding of the fading of organic pigments remains a challenge for conservation scientists. Traditional spectroscopic techniques, such as Raman and FTIR have already been used for identification of organic substances. However, these techniques measure the bulk sum of all species, which can result in overlapping signals from different components. The identification of organic pigments by traditional separation techniques (e.g. TLC, HPLC-DAD and Py-GC-MS) involves time consuming preparation steps and long analysis times with poor sensitivity owing to the sample’s size. Moreover, traditional extraction methods may cause chemical modification through hydrolysis, esterification or breaking of the original conformation of the pigment. This project overcomes these limitations by monitoring the molecular changes of organic red pigments (ORP) during the discoloration process by using soft extraction protocols (avoiding HF and DMSO, traditionally used for the extraction of organic pigments) preceded by HRMS and MS imaging techniques.
The main achievement of the project has been the integration of Matrix-Assisted Laser Desorption Ionization – Mass Spectrometry Imaging (MALDI-MSI) to visualize the spatial distribution of organic pigments without extraction, purification and separation of the sample. This new collaborative initiative between the Antwerp X-ray Imaging and Spectroscopy laboratory and the Centre for Proteomics will open new opportunities for future analysis not only focused on the analysis of organic pigments but also of other organic artistic materials such as oils, varnishes or waxes.
The data generated in this study will help to us answer the following research questions: (a) Is the lateral distribution of the degradation products of eosin the same as that of the parent molecule or do these distributions show evidence of significant migration of the secondary products throughout the paint after their formation? (b) Is the pattern of secondary products everywhere the same vs. depth below the surface or is it significantly different at the light-exposed paint surface than in the bulk?
The main achievement of the project has been the integration of Matrix-Assisted Laser Desorption Ionization – Mass Spectrometry Imaging (MALDI-MSI) to visualize the spatial distribution of organic pigments without extraction, purification and separation of the sample. This new collaborative initiative between the Antwerp X-ray Imaging and Spectroscopy laboratory and the Centre for Proteomics will open new opportunities for future analysis not only focused on the analysis of organic pigments but also of other organic artistic materials such as oils, varnishes or waxes.
The data generated in this study will help to us answer the following research questions: (a) Is the lateral distribution of the degradation products of eosin the same as that of the parent molecule or do these distributions show evidence of significant migration of the secondary products throughout the paint after their formation? (b) Is the pattern of secondary products everywhere the same vs. depth below the surface or is it significantly different at the light-exposed paint surface than in the bulk?