showing 30 related works from this author
Electrochemical Characterization of Egyptian Blue Pigment in Wall Paintings Using the Voltammetry of Microparticles Methodology
2013
The solid state voltammetric response of Egypt blue, Han blue and ploss blue pigments upon attachment to graphite electrodes in contact with aqueous phosphate buffer at pH 7.0 is studied by voltammetry of microparticles and scanning electrochemical microscopy. Such voltammetric responses, combined with those for synthetic specimens consisting of binary mixtures of the pigment and SiO2 or CaCO3 as well as ternary ones of CaCO3 and SiO2 mixtures allow for the identification of the pigment and the support in samples from wall paintings using different electrochemical parameters, in particular upon performing the Tafel and modified Tafel analysis of voltammetric peaks. Identification of Egypt b…
Study on the effects of chemical cleaning on pinaceae resin-based varnishes from panel and canvas paintings using pyrolysis-gas chromatography/mass s…
2006
Abstract Cleaning of varnish coatings is one of the most critical steps in the restoration treatment of paintings and characterization of physical and chemical processes involved in this practical procedure has attracted interest of scientists in the field of conservation. Evaluation of chemical cleaning methods based on the application of organic solvents and detergents on Pinaceae resin-based varnishes from panel and canvas paintings has been successfully carried out using pyrolysis-gas chromatograpy/mass spectrometry (Py-GC/MS). The proposed method includes the on-line derivatization of the diterpenoid resin using hexamethyldisilazane (HMDS). Analyses performed on a series of model varni…
Identification of lipid binders in paintings by gas chromatography
2001
Abstract The influence of the presence and the type of pigments in the lipid binding media of paintings were studied by gas chromatography with flame ionization detector. The drying oils were linseed stand oil, poppy oil and sunflower oil, and the pigments studied were cadmium red, cobalt blue, tin white, lead white, chalk and plaster of Paris, commonly used in paintings. The results indicate that the stearic/palmitic ratio and the presence of pigments are quite stable during ageing. However, some differences in the oleic acid/palmitic acid ratio were found, depending on the type of pigment present in the lipid binding media. These variations are related to the drying effect of the pigments…
Characterization of prehispanic cosmetics found in a burial of the ancient city of Teotihuacan (Mexico)
2012
The present paper reports the chemical data obtained on samples of pigmenting materials contained in 31 miniature vessels found in a burial found in Teopancazco, a multiethnic neighborhood center located in the southeastern sector of the archaeological site of Teotihuacan (Central Mexico) and the analytical protocol established for the complete characterization of these archaeological materials. For this purpose a multi-technique approach based on the combination of several non destructive and micro-destructive instrumental techniques, namely, light microscopy (LM), scanning electron microscopy-X-ray micro-analysis (SEMe EDX), transmission electron microscopy (TEM), voltammetry of micropart…
Potential Application of Voltammetry of Microparticles for Dating Porcine Blood-based Binding Media used in Taiwanese Architectural Polychromies
2012
A method for dating Hemoglobine-containing archaeological samples using the voltammetry of microparticles is described. This is based on the record of the voltammetric response of such materials attached to paraffin-impregnated graphite electrodes in contact with aqueous acetate buffer. Signals attributable to the Fe(III)/Fe(II) iron couple and their catalytic enhancement in the presence of H(2)O(2) can be correlated, via first-order reaction kinetics, with the time of aging of the samples. The method has been applied to the study and dating of the polychromed architectural decoration of different parts of the architectural complex of the Longshan Temple in Lukang (18(th) century, Taiwan).
Polysaccharide remains in Maya mural paintings: is it an evidence of the use of plant gums as binding medium of pigments and additive in the mortar?
2020
A number of monosaccharides characteristic of plant gums were found in paint layers and preparation layers of samples of Maya mural paintings of 10 archaeological sites located in Campeche and Yucatan regions. This finding opens the question about the deliberate use of these organic polymers as additives for improving workability and mechanical properties in the preparation layer mortar and conferring cohesion to the pigments in the paint layer. The study performed by GC-MS has confirmed the presence, in significant amounts, of a series of monosaccharides, being glucose and mannose between the most abundantly found. Nevertheless, the low amount present in most of the samples hindered the qu…
Electrochemical Characterization and Dating of Archaeological Leaded Bronze Objects Using the Voltammetry of Immobilized Particles
2017
Financial support from the MINECO Projects CTQ2014-53736-C3-1-P and CTQ2014-53736-C3-2-P, which are supported by ERDF funds, is gratefully acknowledged. We wish to thank the Fondo de Arte y Patrimonio of the Universitat Politecnica de Valencia; the Museu de Prehistoria of Valencia, and its director Helena Bonet and curator Jaime Vives-Ferrandiz; and the Museu Municipal of Xativa and its director Angel Velasco. We also wish to thank Dr Jose Luis Moya Lopez and Mr Manuel Planes Insausti (Microscopy Service of the Universitat Politecnica de Valencia) for technical support.
Electrochemical Characterization of Corrosion Products in Leaded Bronze Sculptures Considering Ohmic Drop Effects on Tafel Analysis
2015
[EN] The characterization of corrosion products in leaded bronze based on the voltammetry of immobilized particles methodology is described. Voltammetric data, supported by Fourier transform infra-red spectroscopy, field emission scanning electron microscopy-energy dispersive X-ray microanalysis (FESEM-EDX) and scanning electrochemical microscopy (SECM) allow the identification of copper and lead corrosion materials. The mutual influence of such products is modeled upon considering uncompensated ohmic drops in the Tafel analysis of the rising portion of the respective voltammetric signals for their electrochemical reduction.
Application of solid-state electrochemistry techniques to polyfunctional organic–inorganic hybrid materials: The Maya Blue problem
2013
Abstract The time evolution of indigo plus palygorskite powdered mixtures during isothermal heating at different temperatures between 120 and 180 °C to form Maya Blue-type materials has been monitored by means of infrared spectrometry, diffuse reflectance spectrometry in the visible region and solid state electrochemical techniques. The kinetics of the formation process of such materials can be described in terms of two consecutive reactions, the first one consisting of the loss of zeolitic water of the palygorskite coupled with clay-indigo attachment and partial indigo to denydroindigo oxidation. The palygorskite dehydration acts as a rate-determining step fitting to a 3D Avrami-Erofe’ev k…
Isomerization and redox tuning in ‘Maya yellow’ hybrids from flavonoid dyes plus palygorskite and kaolinite clays
2014
Abstract The composition of the organic fraction of organic–inorganic hybrid materials prepared upon attachment of different natural, ‘historical’ flavonoid yellow dyes (zacatlaxcalli, fustic, marigold and cosmos) to palygorskite and kaolinite clays is described. Upon thermal treatment between 100 and 180 °C, significant isomerization and oxidation reactions occur thus resulting in the formation of polyfunctional materials potentially usable for therapeutic, catalytic and art purposes. The dye attachment to the clays would define a ‘Maya chemistry’ whose complexity could explain the versatile use of such materials in the pre-Columbian cultures.
Characterization of acrylic resins used for restoration of artworks by pyrolysis-silylation-gas chromatography/mass spectrometry with hexamethyldisil…
2006
A procedure based on the technique of the pyrolysis-GC/MS has been applied, in this work, in order to determine the composition of synthetic acrylic resins employed in artworks. The method is based on the on line derivatization of these resins using hexamethyldisilazane (HMDS). Results obtained have been compared with those others from direct pyrolysis and in situ thermally assisted hydrolysis and methylation with tetramethylammonium hydroxide (TMAH). Sensitivity using HMDS as derivatising reagent is found similar to that from direct pyrolysis and methylation with TMAH. Better resolution of the most representative peaks has been also obtained. Additionally, this method reduces the formation…
Study of the influencing effect of pigments on the photoageing of terpenoid resins used as pictorial media
2006
Abstract Terpenoid resins have been mainly used as components of pictorial varnishes and binding media from ancient times. In such latest instances, the resin is mixed with pigments affecting its physical and chemical properties. A new procedure based on gas chromatography–mass spectrometry (GC/MS) has been applied, in this work, in combination with Fourier transform infrared spectroscopy (FTIR), with the aim of determining the changes undergone by di- and triterpenoid resins employed as components of binding media. The GC/MS method is based on the derivatisation of these resins using trimethylsilylimidazol. Characterization of the main components of the di- and triterpenoid fractions and t…
ELECTROCHEMISTRY AND AUTHENTICATION OF ARCHAEOLOGICAL LEAD USING VOLTAMMETRY OF MICROPARTICLES: APPLICATION TO THE TOSSAL DE SANT MIQUEL IBERIAN PLATE
2011
The authors wish to thank the Museu de Prehistoria de Valencia, Museu Arqueologic de Borriana and Museu Municipal de Montcada for the access to their archives and funds. Financial support is gratefully acknowledged from the Spanish 'I+D+I MICINN' project CTQ2008-06727-C03-01 and 02/BQU, supported by ERDEF funds. The authors wish to thank Mr Manuel Planes i Insausti and Dr Jose Luis Moya Lopez, the technical supervisors responsible for the UPV Electron Microscopy Service.
Identification of Manganese(IV) Centers in Archaeological Glass Using Microsample Coatings Attached to PolymerFilm Electrodes
2001
Identification of MnO2 nodulae in archaeological glass by linear scan and differential pulse voltammetry using abrasive-conditioned microsamples attached to polymer film (Elvacite 2044) electrodes is described. Voltammetric responses for manganese-containing samples parallels to those obtained for β- and γ-MnO2 upon immersion of modified electrodes into NaCl, KCl and acetic/acetate aqueous media. The observed electrochemical response provides information on the open microporous structure of the MnO2 forms and the conditions of their formation during the weathering process of buried glass.
Analytical characterisation of the biodeterioration of diterpenoid labdanic varnishes used in pictorial techniques: Sandarac and Manila copal
2014
Abstract The deterioration produced by fungal and bacterial growth on the sandarac and Manila copal, diterpenoid varnishes traditionally used as art materials, was evaluated by gas chromatography–mass spectrometry (GC–MS), and pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS). Test specimens, coated with a solidified thin layer of the studied varnishes, were inoculated and incubated with selected fungi and bacteria obtained from collections and oil paintings affected by biodeterioration, and analysed by the above mentioned techniques. Significant changes were detected, showing evidence of deterioration processes caused or favoured by some of the studied microorganisms.
Analyzing chemical changes in verdigris pictorial specimens upon bacteria and fungi biodeterioration using voltammetry of microparticles
2017
[EN] It is reported the application of the voltammetry of microparticles (VMP), complemented with attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and field emission scanning electron microscopy (FESEM) techniques, to monitor the deterioration of verdigris pictorial specimens under the action of different biological agents. This methodology would be of application for identifying the type of biological agent causing deterioration of paintings, which is an important problem affecting cultural heritage. The analysis of biodeterioration processes is complicated by the fact that the action of microorganisms can affect both pigment and binding media. The deteriorat…
Response to “C. Tsiantos, M. Tsampodimou, G.H. Kacandes, M. Sánchez del Río, V. Gionis, G.D. Chryssikos. Comment to the paper: Identification of indi…
2014
Quantitation of Metal Ions in Archaeological Glass by Abrasive Stripping Square-Wave Voltammetry Using Graphite/Polyester Composite Electrodes
2003
A method for identifying Co, Cu, Sb, Sn, Fe, Zn, and Zr pigments in glasses using square-wave voltammetry as the detection mode is described. It is based on the abrasive attachment of glass microsamples to graphite/polyester composite electrodes. Sample amounts less than 1 μg are used allowing for the study of archaeological samples. In all cases well-defined anodic stripping peaks corresponding to the oxidation of metal deposits generated at potentials ranging from −0.6 to −1.6 V (vs. SCE) are obtained. This response is in agreement with that displayed by the corresponding metal oxides. Quantitative estimates of the relative population of metal ions in glasses are obtained from peak area m…
Identification of indigoid compounds present in archaeological Maya blue by pyrolysis-silylation-gas chromatography–mass spectrometry
2014
Abstract A study based on the use of pyrolysis-silylation-gas chromatograpy–mass spectrometry (Py-GC–MS), which aimed to identify indigoid compounds and to clarify the multicomponent composition of Maya blue (MB) pigment, has been carried out. A series of reference compounds and synthetic MB specimens prepared in the laboratory have been analysed by this technique. An analysis of archaeological MB samples from 14 Maya archaeological sites from Mexico and Guatemala has also been performed. The obtained results demonstrate that, in addition to indigo, oxidised species such as dehydroindigo, which is formed as a result of redox processes taking place while preparing the pigment, are present in…
Discovery of indigoid-containing clay pellets from La Blanca: significance with regard to the preparation and use of Maya Blue
2014
Analytical studies using extraction/liquid chromatography, pyrolysis–silylation gas chromatography–mass spectrometry, visible and infrared spectroscopies, solid state voltammetry and electron microscopy on a set of spherical greenish pellets discovered in the Structure 4H1 of the ancient Maya site of La Blanca (Peten Department, Guatemala), dated in the Terminal Classic period, confirm the presence of indigoids (dehydroindigo, indigo) associated to palygorskite. The appearance of such pieces, whose origin and function is uncertain, but most likely correspond to residuals of a decorative plaster, can be considered as indicative of the use of Maya Blue in a quotidian context, thus suggesting …
Ageing behaviour and analytical characterization of the Jatobá resin collected from Hymenaea stigonocarpa Mart.
2009
Abstract This paper reports the results of an analytical study to characterize the trunk resin collected from the Hymenaea stigonocarpa Mart. species from the region of Minas Gerais (Brazil), popularly known as Jatoba resin. Hymenaea resins are reported to have been used in artistic applications such as protective varnishes in polychromed sculptures and paintings. Therefore, the identification of the main chemical changes that take place in the resin when it is prepared as a thin film exposed to atmospheric effects have been considered herein. Changes due to the degradation effect of light have been studied on a series of specimens prepared as a thin films and subjected to accelerated UV li…
‘Maya chemistry’ of organic–inorganic hybrid materials: isomerization, cyclicization and redox tuning of organic dyes attached to porous silicates
2013
[EN] Association of indigo and lapachol dyes to aluminosilicate clays yields polyfunctional organic – inorganic hybrid materials forming Maya Blue-like systems. Upon partial removing of clay's zeolitic water by moderate thermal treatment, abundant isomerization, cyclicization and oxidation reactions occur defining a‘ Maya chemistry whose complexity could explain the versatile use of such materials in the pre-Columbian cultures and permits the preparation of polyfunctional materials potentially usable for therapeutic and catalytic purposes.
Identification by GC-FID and GC-MS of amino acids, fatty and bile acids in binding media used in works of art.
2001
GC-FID was used as single methodology for the identification and differentiation of proteins, lipids and ox bile from binders used in artistic paintings. The samples were hydrolyzed by HCl. Subsequently, the simultaneous formation of volatile derivatives of the amino, fatty and bile acids with ethyl chloroformate was performed quickly and safely in an aqueous medium. The derivatives were separated by capillary GC and characterized by GC-MS. The ageing of drying oils was studied, identifying pelargonic acid among other degradation products. Proteinaceous and lipoid binding media were characterized by means of the quotients between the areas of the peaks for each amino or fatty acid with resp…
Analytical characterization of diterpenoid resins present in pictorial varnishes using pyrolysis–gas chromatography–mass spectrometry with on line tr…
2005
Abstract A procedure based on the technique of the pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS) has been applied, in this work, in order to determine the composition of diterpenoid resin employed in art works. The method is based on the on line derivatization of these resins using hexamethyldisilazane (HMDS). Results obtained were compared with those previously reported in literature from Venice turpentine, Strasbourg turpentine, colophony, sandarac and Manila copal using this same method and with those others from in situ thermally assisted hydrolysis and methylation with tetramethylammonium hydroxide (TMAH). Canada balsam, copper resinate and Copaiba balsam have been also ana…
On-line database of voltammetric data of immobilized particles for identifying pigments and minerals in archaeometry, conservation and restoration (E…
2016
[EN] A web-based database of voltammograms is presented for characterizing artists' pigments and corrosion products of ceramic, stone and metal objects by means of the voltammetry of immobilized particles methodology. Description of the website and the database is provided. Voltammograms are, in most cases, accompanied by scanning electron microphotographs, X-ray spectra, infrared spectra acquired in attenuated total reflectance Fourier transform infrared spectroscopy mode (ATR-FTIR) and diffuse reflectance spectra in the UV-Vis-region. For illustrating the usefulness of the database two case studies involving identification of pigments and a case study describing deterioration of an archae…
Electrochemical identification of metal ions in archaeological ceramic glazes by stripping voltammetry at graphite/polyester composite electrodes
2002
The electrochemical response of metal ions in different samples of coloured ceramic tin-lead glazes attached to graphite/polyester composite electrodes is described. In addition to the ubiquous signals for lead, reductive dissolution processes are followed by anodic stripping peaks for Co, Cu, Sb, Mn, Sn and Fe, enabling the direct identification of such elements in microsamples proceeding from archaeological glazed tiles from Valencia (Spain) workshops (16th-18th century). Additional anodic and cathodic peaks corresponding to redox processes involving metal species in solution generated during stripping processes are also used. Peak potentials, Tafel plots and shape parameters are used for…
Redox tuning and species distribution in Maya Blue-type materials: a reassessment.
2013
Maya Blue-type specimens prepared from indigo (1 wt %) plus kaolinite, montmorillonite, palygorskite, sepiolite, and silicalite are studied. Liquid chromatography with diode array detection, ultra-performance liquid chromatography coupled with mass spectrometry, and pyrolysis-silylation gas chromatography-mass spectrometry analyses of the extracts from these specimens combined with spectral and solid-state voltammetry, electrochemical impedance spectroscopy, and scanning electrochemical microscopy techniques provide evidence for the presence of a significant amount of dehydroindigo and isatin accompanying indigo and other minority organic compounds in all samples. Solid-state electrochemist…
Analytical Study of a Resinous Material Used as Sealing in Ancient Pottery Found in an Archaeological Site by Thermally Assisted Hydrolysis Methylati…
2009
Abstract A resin sample was found in the archaeological site of Lixus (Morocco), belonging to the second century BC. The resinous material was found inside an amphora containing iron remains used in the plug as sealing material to hermetically close the pottery. The resinous sample was studied by several analytical techniques, as thermally assisted hydrolysis and methylation–gas chromatography–mass spectrometry (THM–GC–MS), Fourier transformed infrared spectroscopy (FTIR), and light microscopy. The material was identified as a Pinaceae resin. Therefore, a modern pine resin was also analyzed to consider the influence of aging in the archaeological sample. The ancient material was found not t…
Microchemical surface analysis of historic copper-based coins by the combined use of FIB-FESEM-EDX, OM, FTIR spectroscopy and solid-state electrochem…
2019
[EN] A multi-technique strategy, including microscopy, spectroscopic and electrochemical techniques, is proposed to study thin corrosion layers that form on the surface of historic copper-based coins. An accurate characterisation of this external corrosion layer is important for selecting a suitable conservation and/or restoration treatment. For this purpose, a series of copper-based coins from different historical periods and provenances, which mainly exhibited atmospheric corrosion, was analysed. The morphology of the corrosion layer and the upper core of coins was studied in trenches done on coin surfaces with a focused ion beam gun, coupled to a field emission scanning electron microsco…
Identification of diterpenes in canvas painting varnishes by gas chromatography-mass spectrometry with combined derivatisation.
2004
A derivatisation method that combines the formation of ethyl esters from the carboxylic groups and trimethylsilyl ethers from hydroxyl groups of the components of diterpenic resins is presented in this paper. This methodology involves two experimental steps: (1) formation of ethyl esters using ethyl chloroformate; and (2) the esterified compounds are lead to react with trimethylsilylimidazole to form the corresponding trimethylsilyl ethers. The main advantage of the proposed method is the possibility of performing simultaneously the analysis of amino acids from proteins, fatty acids from drying oils, and diterpenic compounds from natural resins usually found in works of art. This methodolog…