Solid-state electrochemical characterization of emissions and authorities producing Roman brass coins

[EN] The voltammetry of immobilized particles (VIMP) is applied to describe the solid state electrochemistry of brass. This methodology, which involves sampling at the nanogram level, is applied to discriminate mints/authorities producing different Roman monetary emissions covering since the Republic (88 BCE) to Domitianus (55-96 CE) Upon attachment to graphite electrodes in contact with aqueous acetate buffer at pH 4.75, well defined voltarnmetric responses were obtained centered on Cu- and Zn-localized signals whose intensity can be correlated to EMP data, being sensitive to the contents of Zn (15-30 wt.%) and Sn (0.01-1.1 wt.%). Voltammetric data, combined with ATR-FTIR and FIB-PESEM/EDS…

Use of linear discriminant analysis applied to vibrational spectroscopy data to characterize commercial varnishes employed for art purposes.

An improvement of methodologies for characterising synthetic resins used in varnishes employed for art purposes has been suggested. Several kinds of standard of the most common polymeric resins (acrylic, vinyl, poly(vinyl alcohol), alkyd, cellulose nitrate, latex, polyester, polyurethane, epoxy, organosilicic, and ketonic) were analyzed by Fourier transform infrared (FTIR) spectroscopy. Synthetic resins characterization is based on the mathematical treatment of their whole spectrum, dividing it in 13 sections, avoiding the one-by-one interpretation of the absorption bands. The mathematical model takes as variables the maximal absorbance of each section, and each synthetic standard resin as …

Electrochemical Characterization of Egyptian Blue Pigment in Wall Paintings Using the Voltammetry of Microparticles Methodology

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 spectrometry

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…

Mo-W-containing tetragonal tungsten bronzes through isomorphic substitution of molybdenum by tungsten

Mixed metal oxides based in Mo(W)–Nb–V–Te with tetragonal tungsten bronze (TTB) structure have been synthesized by a hydrothermal method from aqueous solutions of the corresponding Keggin-type heteropolyacids and further heat-treatment in N2 at 700 ◦ C. The materials have been characterized by several physico-chemical techniques, i.e. XRD, Raman, FTIR, SEM-EDS, and TEM. This procedure allows controlling the chemical species to be distributed in the different interstices of the TTB skeleton, which is a key factor to regulate the catalytic properties of the final solid. In this sense, the isomorphic replacement of Mo by W results in lattice parameter and crystal morphology variation, although…

Application of Modified Tafel Analysis to the Identification of Corrosion Products on Archaeological Metals Using Voltammetry of Microparticles

Voltammetry of microparticles is applied to the identification of lead corrosion products by means of an essentially non-invasive 'one-touch' technique based on the use of graphite pencil. This methodology permits the mechanical attachment of few nanograms of sample from the surface of lead archaeological artefacts to a paraffin-impregnated graphite electrode, which, upon immersion in aqueous electrolytes, provides distinctive voltammetric responses for litharge and cotunnite- anglesite-, cerusite-based corrosion products. The reported method is applied to the identification of corrosion products in archaeological lead pieces from different Iberian sites in Valencia (Spain). © 2011 WILEY-VC…

Layer-by-layer identification of copper alteration products in metallic works of art using the voltammetry of microparticles.

An in situ technique for layer-by-layer electrochemical analysis of solid surfaces using the voltammetry of microparticles is presented. The method is based on the determination of several shape-dependent parameters for voltammetric curves recorded at a graphite pencil working electrode in contact with the sample, all immersed into aqueous electrolytes. Repetitive square wave voltammetry and sequential application of constant potential reductive steps and voltammetric scans yield discernible responses for the corrosion products distributed in stratified layers on metal-based surfaces. This methodology is applied to identify alteration products of copper and copper alloys distributed in diff…

An authentication case study: Antonio Palomino versus Vicente Guillo paintings in the vaulted ceiling of the Sant Joan del Mercat church (Valencia, Spain)

In 1695, the Valencian artist Vicente Guillo was engaged in painting the vault of the Sant Joan del Mercat church in Valencia, Spain. After preliminary work was carried out, his contract was cancelled. In 1697, Antonio Palomino, renowned for the publication of his technical treatise entitled El Museo Pictorio y Escala Optica, was finally selected as the painter in charge of decorating the vaulted ceiling of Sant Joan del Mercat. This paper reports an analytical study focused on the characterisation and discrimination of the palette and painting procedures used by Palomino and Guillo in the frescoes of Sant Joan del Mercat. For this purpose, Raman spectroscopy combined with light microscopy,…

Square wave voltammetric determination of the redox state of a reversibly oxidized/reduced depolarizer in solution and in solid state

Abstract Square wave voltammetric measurements allows for determining the composition of system containing a reversibly reducible/oxidable electroactive species in two oxidation states. The method is based on recording the ratio of reverse to forward peak currents. That ratio can be correlated with the molar fraction of the oxidized (or reduced) form of the depolarizer. The method was compared with cyclic voltammetric methods suggested in literature and it was tested using Fe ( CN ) 6 3 - / Fe ( CN ) 6 4 - in solution phase. Application to solid state systems is illustrated by the dehydroindigo/indigo couple in synthetic Maya Blue-type specimens prepared from indigo plus different clays whe…

Sequential identification of organic dyes using the voltammetry of microparticles approach

An electrochemical method for identifying indigoid, anthraquinonic, naphtoquinonic, flavonoid, pyrone, pyran, and other related dyes in microsamples from works of art is reported using the voltammetry of microparticles methodology. Products of solid state oxidation/reduction of dyes form a layer on the lateral faces of the dye crystals as suggested by ATR-FTIR and AFM data. This method is based on the sequential application of oxidative and reductive constant-potential polarization steps coupled with the record of square wave voltammograms to solid microsamples of dyes in contact with aqueous electrolytes.

Independent friction-restitution modeling of two-disk collisions

[EN] The oblique collisions between two axisymmetric disks moving on a flat horizontal surface are described in terms of impact modeling based on the assumption that normal and tangential restitution mechanisms operate independently of friction. Describing these mechanisms in terms of the usual Coulomb formulation, the model allows for an interpretation of some ¿anomalous¿ experimental data reported in the literature. These experimental data, corresponding to the variation of the coefficients of friction and tangential restitution with the impact angle, remained unexplained in classic formulations, are understood within the framework of the independent friction-restitution closure. Experime…

Characterization of Iranian Moarraque glazes by light microscopy, SEM-EDX and voltammetry of microparticles

Abstract Glazed ceramics have been traditionally used in Iran for decorating mosques and some civil historical buildings. In particular, Moarraque glazes have been extensively used in the indoor and outdoor decoration of mosques in Iran since the middle 14th century. The pieces have a complex elaboration based on a main glazed piece corresponding to the skeleton structure of the Shah Abbasi flower, which contains a number of holes, where are placed, mosaic-like, smaller glazed pieces forming a compact and single tile. The present work describes the analytical study performed on the glazes of several pieces of Moarraque tiles from the Ali Ebn Abi Taleb Mosque (Esfahan, Iran), which date back…

Characterization of prehispanic cosmetics found in a burial of the ancient city of Teotihuacan (Mexico)

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

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?

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 of Corrosion Products in Leaded Bronze Sculptures Considering Ohmic Drop Effects on Tafel Analysis

[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.

Cover Picture: Electrochemical Characterization of Coinage Techniques the 17th Century: The maravedís Case (Electroanalysis 9/2017)

Application of solid-state electrochemistry techniques to polyfunctional organic–inorganic hybrid materials: The Maya Blue problem

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…

Modeling Corrosion of Archaeological Silver-Copper Coins Using the Voltammetry of Immobilized Particles

Two complementary models to describe the long-term corrosion of silver-copper coins, based on potential rate laws for smooth corrosion and those combined with diffusive law, for gross corrosion, are proposed. Theoretical kinetics can be tested using signatures of copper and silver corrosion products using the voltammetry of immobilized particles technique. The method is applied to silver coins minted during the 13th–14th centuries from the Libertad street hoard in Valencia (Spain) using non-invasive one-touch graphite pencil sampling. Voltammetric features yield functional dependences in agreement with the proposed model potentially useful for distinguishing between different mints.

Screening and mapping of pigments in paintings using scanning electrochemical microscopy (SECM)

The use of the scanning electrochemical microscopy (SECM) technique for identifying and mapping of both organic and inorganic pigments in sub-microsamples from pictorial specimens is described. This methodology, inspired by the voltammetry of immobilized particles technique, permits the study of textural properties of paint layers and mapping the distribution of pigment grains upon application of different potentials to the substrate. A combination of the redox competition SECM strategy with voltammetry yields a local identification methodology for different organic and inorganic pigments in paint samples.

On the interpretation of the Raman spectra of Maya Blue: a review on the literature data

The Raman spectroscopy of Maya Blue (MB), a nanostructured organic–inorganic hybrid material, has received considerable attention. A re-evaluation of the Raman literature data for indigo dye, genuine MB samples and model specimens obtained by the binding of indigo to phyllosilicate clays, such as palygorskite and sepiolite, using chemometric analysis of normalised spectra is reported. Available data present features in support of the following ideas: (1) dehydroindigo accompanies indigo in MB; (2) different topological isomers, i.e. dye molecules attached to different coordinative sites of the palygorskite framework, are involved in MB; and (3) different procedures were probably used for pr…

"One-touch" voltammetry of microparticles for the identification of corrosion products in archaeological lead

Voltammetry of microparticles is applied to the identification of lead corrosion products by means of an essentially non-invasive 'one-touch' technique based on the use of graphite pencil. This methodology permits the mechanical attachment of few nanograms of sample from the surface of lead archaeological artefacts to a paraffin-impregnated graphite electrode, which, upon immersion in aqueous electrolytes, provides distinctive voltammetric responses for litharge and cotunnite- anglesite-, cerusite-based corrosion products. The reported method is applied to the identification of corrosion products in archaeological lead pieces from different Iberian sites in Valencia (Spain). © 2011 WILEY-VC…

Characterization of traditional artificial patinas on copper using the voltammetry of immobilized particles

[EN] The voltammetry of immobilized particles methodology (VIMP) is used to characterize the composition of artificial patinas on copper. The voltammetric response of carbonate-, nitrate-, chloride-, sulfate-, and sulfide-based patinas is described using sub-microsamples attached to graphite electrodes in contact with aqueous acetate buffer. Patina-characteristic voltammetric profiles are obtained for the different artificial patinas that can be recognized using the generalized Tafel analysis of the voltammetric curves. VIMP data could also provide layer-by-layer information about composition and compactness/crystallinity of the patinas for which a simplified theoretical modeling is present…

CO 2 Fixation and Activation by Cu II Complexes of 5,5″‐Terpyridinophane Macrocycles

An aza-terpyridinophane receptor containing the polyamine 4,7,10,13-tetraazahexadecane-1,16-diamine linked through methylene groups to the 5,5″ positions of a terpyridine unit has been prepared and characterized (L). The acid-base behaviour, CuII speciation and ability to form ternary complexes (CuII-L-carbonate) have been explored by potentiometric titrations in 0.15 M NaClO4 and by UV/Vis and paramagnetic NMR spectroscopy. Comparisons are made with a previously reported terpyridinophane containing the polyamine 4,7,10-triazatridecane-1,13-diamine (L1). For this latter receptor, reductive coupling between indigo and carbon dioxide at indigo-modified electrodes produces carboxylated derivat…

Dating archeological lead artifacts from measurement of the corrosion content using the voltammetry of microparticles.

A methodology for dating archeological lead artifacts based on the voltammetry of microparticles is described. This methodology is based on the comparison of the height of speci¿c voltammetric features from PbO2 and PbO corrosion products formed under long-term alteration conditions. Calibration of the method was performed with the help of a series of well-documented lead pieces from the funds of di¿erent museums of the Comunitat Valenciana (Spain) covering from the ¿fth century B.C. to present day. The variation of peak currents with the time of corrosion can be¿tted to the same potential rate law as that found by Reich (R = 0.070 ( 0.005), using measurements on the Meissner fraction in th…

Isomerization and redox tuning in ‘Maya yellow’ hybrids from flavonoid dyes plus palygorskite and kaolinite clays

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.

ChemInform Abstract: Maya Blue as a Nanostructured Polyfunctional Hybrid Organic-Inorganic Material: The Need to Change Paradigms.

Maya Blue, an ancient nanostructured organic–inorganic hybrid material resulting from the attachment of indigo, a natural dye, to a phyllosilicate clay, palygorskite, has received considerable attention of late. Despite intensive research, several aspects remain unsolved, in particular the nature of the indigo–palygorskite association. Recent results suggest that the Maya Blue pigment is a complex system in which different topological isomers of various indigoid molecules attached to the palygorskite matrix coexist.

Multiple-scan voltammetry and OCP: Archaeometric tools for dating archaeological bronzes

[EN] The application of a multiple-scan strategy to nanosamples taken from 18 cross-sections of Bronze Age arms and armour, as well as two Roman coins using two solid-state electrochemical techniques, the voltammetry of immobilized microparticles (VIMP) and open circuit potential measurements (OCP) is described. The voltammetric responses in contact with aqueous acetate buffer can be attributed to the reduction of cuprite with variable degree of compaction and crystallinity revealing significant differences in the gradient of such properties with depth. Such differences are also revealed by "dry" OCP measurements connecting points in the cross section near and separated from the corrosion l…

CORRELATION BETWEEN SPECTRAL, SEM/EDX AND ELECTROCHEMICAL PROPERTIES OF MAYA BLUE: A CHEMOMETRIC STUDY*

Visible spectra, composition from SEM/EDX and solid-state electrochemical data are correlated for a set of 12 Maya Blue samples from different archaeological sites of Campeche and Yucatan (Mexico). In addition to indigo and dehydroindigo, indirubin and other possibly indigo-type compounds can be detected in Maya Blue samples. Application of hierarchical cluster analysis techniques allows similarity relationships to be established between samples from different sites, confirming prior results which suggest that the preparation of Maya Blue pigment evolved with time during the Maya culture following a ramified scheme.

Characterization of acrylic resins used for restoration of artworks by pyrolysis-silylation-gas chromatography/mass spectrometry with hexamethyldisilazane.

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

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…

Analytical study of canvas painting collection from the Basilica de la Virgen de los Desamparados using SEM/EDX, FT-IR, GC and electrochemical techniques

A new method, based on the combined use of scanning electron microscopy-x-ray microanalysis, Fourier transform infrared spectroscopy, gas chromatography and differential pulse voltammetry, is proposed which permits a parallel investigation of organic and inorganic materials and the characterization of the artistic technique employed in canvas painting. The proposed method has led to analyze succesfully the canvas painting collection exhibited in the Basílica de la Virgen de los Desamparados (Valencia, Spain) which includes art works from 17th to 20th century.

Screening of Iberian Coinage in the 2(th)-1(th) BCE Period Using the Voltammetry of Immobilized Particles

[EN] The voltammetry of immobilized particles (VIMP) was applied for grouping a series of 86 Iberian coins nominally minted in the cities of Iltirta, Castulo and Obulco in the 2(th)-1(th) BCE period for which there are no chronological data. Using characteristic signatures for the reduction of cuprite, tenorite and lead corrosion products in the patina of the coins, voltammetric grouping of coins was proposed. Voltammetric data were found to be consistent with textural and compositional properties of the surface and subsurface of selected coins using FIB-FESEM-EDX. The obtained data confirmed a clear separation between the productions of Iltirta on one side, and those of Castulo and Obulco …

Discrimination and provenances of Phoenician red slip ware using both the solid state electrochemistry and petrographic analyses

[EN] Solid state electrochemistry based on the voltammetry of immobilized microparticles (VIMP) methodology is applied to a series of 80 Phoenician Red Slip samples from the archaeological sites of Motya (Sicily, Italy), Mogador (Morocco), Ramat-Rahel (Israel), Sulky (Sardinia, Italy), Tas Silg (Malta), Pantelleria (Italy), and Cadiz (Spain), dated from the 8(th) to the 6(th) century BC. Upon attachment of sub-microsamples to graphite electrodes in contact with aqueous H2SO4 electrolyte, voltammetric features due to the reduction of Fe(III) minerals and the oxidation of Fe(II) ones, complemented with electrocatalytic effects on oxygen reduction and oxygen evolution reactions, provide charac…

Identification of inorganic pigments from paintings and polychromed sculptures immobilized into polymer film electrodes by stripping differential pulse voltammetry

Abstract Inorganic pigments in paintings and polychromed sculptures are studied by cyclic voltammetry and differential pulse stripping voltammetry using micro-sample coatings in Paraloid B72-film modified electrodes. Characteristic cathodic and anodic differential pulse profiles were obtained in the +0.4 to −1.0 V vs. SCE potential range for different cadmium, copper, lead, mercury and zinc pigments used in traditional colour palettes. Under optimized conditions, excellent reproducibility was obtained. Microsamples extracted from polychromed sculptures, wall paintings, canvas paintings, panel paintings and altarpieces from Spain, Ethiopia and Italy from the 12th to the 20th centuries have b…

Hematite as an Electrocatalytic Marker for the Study of Archaeological Ceramic Clay bodies: A VIMP and SECM Study**

[EN] The electrocatalytic effect exerted by hematite, a ubiquitous component of clay bodies, on the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) can be used to acquire information on archaeological ceramics. The solid-state voltammetric response of different hematite and ochre specimens, accompanied by SECM analysis in contact with 0.10 M HCl aqueous solution, is described. In air-saturated solutions, catalytic effects on the ORR and OER are accompanied by Fe(III)/Fe(II) and Fe(IV)/Fe(III) redox reactions. Such processes are conditioned by a variety of factors, the hydroxylation degree of the mineral surfaces being particularly influential, and exhibit significant var…

Dating archaeological strata in the Magna Mater temple using solid-state voltammetric analysis of leaded bronze coins

[EN] The application of solid state electrochemistry techniques for dating archaeological strata using lead-containing bronze coins is described. The proposed methodology was applied to samples coming from the Roman archaeological site of Magna Mater Temple (Rome, Italy) occurring in different strata dating back between the second half and the end of the 4(th) century A.D. and the 20(th) century. The voltammetric signatures of copper and lead corrosion products in contact with aqueous acetate buffer, as well as the catalytic effects produced on the hydrogen evolution reaction, were used for establishing the age of different strata and dating coins belonging to unknown age. Voltammetric data…

Composition and Color of Maya Blue: Reexamination of Literature Data Based On the Dehydroindigo Model

[EN] An analysis of literature data studying the composition and color of Maya blue (MB) type materials prepared from indigo, dehydroindigo, and different aluminosilicates, accompanied by new spectral data, is presented. After thermal treatment at above 100 degrees C, indigo-based specimens displayed Raman and UV-vis spectroscopic features common to those of equivalent dehydroindigo-based replicants, thus supporting the socalled dehydroindigo model (J. Phys. Chem. B 2006, 110, 6027-6039) in which the dehydroindigo/indigo ratio, increasing with temperature, is crucial to determine the color of MB and its variability. The current analysis supports the view of MB as a polyfunctional hybrid mat…

Maya Blue as a nanostructured polyfunctional hybrid organic–inorganic material: the need to change paradigms

Maya Blue, an ancient nanostructured organic–inorganic hybrid material resulting from the attachment of indigo, a natural dye, to a phyllosilicate clay, palygorskite, has received considerable attention of late. Despite intensive research, several aspects remain unsolved, in particular the nature of the indigo–palygorskite association. Recent results suggest that the Maya Blue pigment is a complex system in which different topological isomers of various indigoid molecules attached to the palygorskite matrix coexist.

Solid-state electrochemistry of LDH-supported polyaniline hybrid inorganic–organic material

Abstract The solid-state electrochemistry of a Zn–Al layered double hydroxide-supported polyaniline material (LDH-PANI) in contact with aqueous electrolytes is described. Interconversion processes between different forms (emeraldine, protoemeraldine, leucoemeraldine, nigraniline and pernigraniline) of the LDH-supported polyaniline units are involved in redox processes. This material exhibits significant variations of impedance upon application of different conditioning potentials, acting as an electrochemical frequency filter. Using Fe (CN) 6 4 - as redox probe, LDH-PANI can be used as a chemical–electrochemical information processing system equivalent to different combinational logic circu…

Analytical characterisation of the biodeterioration of diterpenoid labdanic varnishes used in pictorial techniques: Sandarac and Manila copal

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.

Electrochemical identification of painters/workshops: The case of Valencian Renaissance-Baroque painters (ca. 1550- ca. 1670)

[EN] The voltammetry of immobilized particles (VIMP) methodology was applied to discriminate the oil painting production of a series of seven painters/workshops that worked in Valencia (Spain) between ca. 1530 and ca. 1650. When submicrosamples used for cross-section FESEM/EDX analysis were attached to graphite electrodes in contact with aqueous acetate buffer, well-defined responses were obtained. The reductive processes of lead pigments (lead white and lead-tin yellow) overlapped those associated to the lead soaps and other species resulting from the pigment-oil binder interaction in the sample. Such responses, which are theoretically modeled, were sensitive to changes in paint type and d…

From Maya Blue to “Maya Yellow”: A Connection between Ancient Nanostructured Materials from the Voltammetry of Microparticles

The yellow hue of a series of samples from wall paintings in several Mayan archaeological sites can be attributed to the presence of indigoid compounds, including isatin and dehydroindigo, attached to palygorskite, a local phyllosilicate clay. SEM/EDX, TEM, UV/Vis spectroscopy, and voltammetry of microparticles show that the ancient Mayas could prepare indigo, Maya Blue, and "Maya Yellow" during successive stages. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical dating of archaeological gold based on refined peak current determinations and Tafel analysis

Abstract This report proposes a refined method to date archaeological gold samples based on the Tafel analysis of the ascending part of voltammetric curves corresponding to the oxidation of surface flakes of gold in contact with hydrochloric acid aqueous electrolyte. This allows estimating the equilibrium potential of gold oxidation correcting for irreversibility effects. This equilibrium potential can be correlated with the coverage of adsorbed oxygen species and hence the estimated age of the gold samples. A satisfactory potential/time calibration graph was constructed from a set of archaeological samples including two sets of samples from the Mapungubwe Gold Collection, South Africa (120…

Analyzing chemical changes in verdigris pictorial specimens upon bacteria and fungi biodeterioration using voltammetry of microparticles

[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…

Access to Phylogeny from Voltammetric Fingerprints of Seeds: the Apsparagus Case

A methodology for characterizing vegetal taxonomic groups from the voltammetric fingerprints of polyphenolic components of seeds is described. It is based on recording the voltammetric response of microparticulate films deposited on glassy carbon electrodes from seed extracts using different organic solvents. The obtained responses in contact with aqueous electrolytes provided characteristic voltammetric profiles at the level of genera/subgenera and/or families using bivariant and multivariant chemometric methods. The voltammograms of 14 species from 5 different families provided family-characteristic patterns. Analysis of voltammetric responses for a set of 20 species of the Asparagus genu…

FIB-FESEM and EMPA results on Antoninianus silver coins for manufacturing and corrosion processes

[EN] A set of ancient Antoninianus silver coins, dating back between 249 and 274¿A.D. and minted in Rome, Galliae, Orient and Ticinum, have been characterized. We use, for the first time, a combination of nano-invasive (focused ion beam-field emission scanning electron microscopy-X-ray microanalysis (FIB-FESEM-EDX), voltammetry of microparticles (VIMP)) and destructive techniques (scanning electron microscopy (SEM-EDX) and electron microprobe analysis (EMPA)) along with non-invasive, i.e., micro-Raman spectroscopy. The results revealed that, contrary to the extended belief, a complex Ag-Cu-Pb-Sn alloy was used. The use of alloys was common in the flourishing years of the Roman Empire. In th…

Response to “C. Tsiantos, M. Tsampodimou, G.H. Kacandes, M. Sánchez del Río, V. Gionis, G.D. Chryssikos. Comment to the paper: Identification of indigoid compounds present in archaeological Maya blue by pyrolysis-silylation-gas chromatography–mass spectrometry (M.T. Doménech-Carbó, L. Osete-Cortina, A. Doménech-Carbó, M.L. Vázquez de Agredos-Pascual, C. Vidal-Lorenzo, J. Anal. Appl. Pyrol. 105 (2014) 355–362)”

Dating archaeological copper/bronze artifacts by using the voltammetry of microparticles.

A method for dating copper/bronze archaeological objects aged in atmospheric environments is proposed based on the specific signals for cuprite and tenorite corrosion products measured through the voltammtry of microparticles method. The tenorite/cuprite ratio increased with the corrosion time and fitted to a potential law that yielded a calibration curve usable for dating purposes.

Identification of vegetal species in wooden objects using in situ microextraction-assisted voltammetry of microparticles

[EN] A method for identifying vegetal species in wooden objects using microextraction-assisted voltammetry of microparticles is described. The proposed methodology, aimed at facilitating tasks of patrimony conservation, is based on the recording of the voltammetric response of microparticulate films of compounds resulting from microextraction with organic solvents (ethanol, acetone, and chloroform) of micro- or sub-microsamples of wood in contact with aqueous buffers. Upon application of bivariate and multivariate chemometric techniques, the obtained voltammetric responses led us to identify different taxonomic groups from the characteristic voltammetric profiles. Application to a series of…

Identification of indigoid compounds present in archaeological Maya blue by pyrolysis-silylation-gas chromatography–mass spectrometry

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…

Electrochemical Characterization of Coinage Techniques the 17(th) Century: The maravedis Case

[EN] The voltammetry of immobilized particles (VIMP) methodology was applied to the discrimination of Spanish maravedis produced in 10 different mints between 1661 and 1664 using characteristic signatures for the reduction of cuprite and tenorite in the patina of the coins and catalytic effects on the hydrogen evolution reaction (HER). The variation of the apparent tenorite/cuprite ratio with depth was fitted to potential laws differing from one mint to another for A Coruna, Burgos, Cordoba, Cuenca, Granada, Madrid, Trujillo, Segovia, Sevilla and Valladolid coins. Electrochemical data permitted to detect the changes in the composition (with lowering of the silver content) and manufacturing …

Dating of Archaeological Gold by Means of Solid State Electrochemistry

[EN] In archaeology and history of art, age determination is a fundamental analytical problem. While several techniques for age determination of various materials, like radiocarbon dating, are established, these methods cannot be applied for metals, for which new techniques have to be developed. For the first time a dating method for archaeological gold objects is described which is based on a corrosion clock and electrochemical measurements, using the voltammetry of immobilized particles. Samples are prepared by one touch' with a graphite pencil, only transferring a few nanograms of the archaeological gold. The method has been calibrated with the help of a series of well-documented gold sp…

Identification of lead pigments in nanosamples from ancient paintings and polychromed sculptures using voltammetry of nanoparticles/atomic force microscopy.

Voltammetry of nanoparticles coupled with atomic force microscopy was used to identify lead pigments in nanosamples proceeding from works of art. Upon mechanical attachment of few nanograms of sample to a graphite plate, well-defined voltammetric responses were obtained for lead orange, lead yellow, lead white, litharge, minium, Naples yellow, and tin-lead yellow, allowing for an unambiguous identification of such pigments. Atomic force images provide evidence for the occurrence of pigment-characteristic reduction processes accompanied by metal deposition on the graphite substrate. Electrochemical parameters are used for pigment identification. Application to the method for identifying lead…

Standard additions-dilution method for absolute quantification in voltammetry of microparticles. Application for determining psychoactive 1,4-benzodiazepine and antidepressants drugs as adulterants in phytotherapeutic formulations

A standard additions-dilution solid-state electrochemical method for the determination of psychoactive 1,4-benzodiazepine and antidepressants drugs used as adulterants in commercial slimming herbal formulations is described and compared with conventional standard addition method. The proposed method, based on the voltammetry of microparticles approach, permits quantify, via standard additions methodology, 1,4-benzodiazepine and antidepressants drugs in phytotherapeutic formulations with no need of sample dissolution using dilution with a reference electroactive compound. The method was used to measure 1,4-benzobenzodiazepines (clonazepam, flurazepam, alprazolam, midazolam, bromazepam, chlor…

Discovery of indigoid-containing clay pellets from La Blanca: significance with regard to the preparation and use of Maya Blue

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.

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…

Electroanalytical techniques in archaeological and art conservation

[EN] The application of electrochemical techniques for obtaining analytical information of interest in the fields of archaeometry, conservation and restoration of cultural heritage goods is reviewed. Focused on voltammetry of immobilised particles and electrochemical impedance spectroscopy techniques, electrochemical measurements offer valuable information for identifying and quantifying components, tracing provenances and manufacturing techniques and provide new tools for authentication and dating.

Detection of archaeological forgeries of Iberian lead plates using nanoelectrochemical techniques. The lot of fake plates from Bugarra (Spain)

Identification of forgeries is of considerable interest in studies of archaeological signariums and written Iberian artifacts, elements of capital importance for the knowledge of that culture, because there are many Iberian inscribed lead plate counterfeits circulating in the market and among many museum funds. A case study of identification of forgeries of archaeological lead using voltammetry of microparticles (VMP) and scanning electrochemical microscopy (SECM), aided by conventional optical microscopy and scanning electron microscopy (SEM/EDX) is described. The electrochemical methods are essentially non-invasive so can be applied to samples of nanoscopic size. Application to the authen…

Electrochemistry of Iron-Doped Zircon and Zirconia Materials and Electrocatalytic Effects on Nitrite Oxidation and Reduction

Electrochemical analysis of the first Polish coins using voltammetry of immobilized particles

[EN] A series of 20 denarii from Boleslaus the Brave (992-1025) and Mieszko II Lambert (1025-1034), corresponding to the beginning of the Polish state were studied using the voltammetry of immobilized particles (VIMP) methodology. VIMP experiments, applied to nanosamples of the corrosion layers of the coins in contact with aqueous acetate buffer, provided well-defined responses mainly corresponding to the corrosion products of copper and lead. Such voltammetric responses, combined with X-ray fluorescence (XRF) spectroscopy experiments performed on the same set of coins, and complemented by focusing ion beam-field emission scanning electron microscope (FIB-FESEM) on silver coins from the 19t…

Cation and anion electrochemically assisted solid-state transformations of malachite green

[EN] The possibility of the electrochemical promotion of different solid-to-solid transformations including the performance of successive cation and anion insertion processes has been tested using malachite green, a triphenylmethane dye, in contact with aqueous NaCl electrolyte. Electrochemical data using the voltammetry of microparticles methodology reveal significant differences with the solution phase electrochemistry of the dye. Voltammetric data, combined with atomic force microscopy, focusing ion beam-field emission scanning electron microscopy, and high-resolution field emission scanning electron microscopy permit characterization of the oxidative dissolution, oxidation with anion in…

‘Maya chemistry’ of organic–inorganic hybrid materials: isomerization, cyclicization and redox tuning of organic dyes attached to porous silicates

[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.

In situ AFM study of proton-assisted electrochemical oxidation/reduction of microparticles of organic dyes

In situ atomic force microscopy (AFM) images of crystals of organic dyes alizarin, indigo and morin have been monitored during the course of their solid-state electrochemical oxidation/reduction in contact with aqueous acetate buffer. Such images indicate that proton-assisted reduction and oxidation processes are localized in a shallow layer in the vicinity of the particle/electrolyte interface, in agreement with expectances from the Lovric and Scholz model with significantly restricted proton diffusion across the solids. Keywords: Voltammetry of nanoparticles, Atomic force microscopy, Organic dyes, Diffusion

Analytical characterization of diterpenoid resins present in pictorial varnishes using pyrolysis–gas chromatography–mass spectrometry with on line trimethylsilylation

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 (ELCHER database)

[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…

Insights into the Maya Blue technology: greenish pellets from the ancient city of La Blanca.

Financial support is gratefully acknowledged from the MEC Projects CTQ2011-28079-CO3-01 and 02 which are also supported with ERDF funds. Research was conducted within the "Grupo de anlisis cientifico de bienes culturales y patrimoniales y estudios de ciencia de la conservacion" Microcluster of the University of Valencia Excellence Campus. The authors would like to thank Dr. Isabel Solana (SCSIE, UV), Dr. Jose Luis Moya Lopez, and Manuel Planes Insausti (Microscopy Service UPV) for their technical support.

Electrochemical identification of metal ions in archaeological ceramic glazes by stripping voltammetry at graphite/polyester composite electrodes

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.

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…

Raman spectroscopy characterization of 10-cash productions from the late Chinese emperors to the Republic

[EN] The use of Raman spectroscopy for discriminating monetary emissions, a recurrent problem in much archaeological studies, is described. The method involves the record of Raman signatures of tenorite and crystalline and defective cuprite in the patina based on the idea that subtle, mint-characteristic variations in the composition and metallography of the base metal during the manufacturing process are reflected in the variation in depth of the composition and crystallinity of the corrosion patina. The technique was applied to a series of 10-cash copper coins produced around the transition between the Kuang Hsu and Hsuan Tung last Chinese emperors and the first Republic whose averaged co…

Identification of Earth Pigments by Applying Hierarchical Cluster Analysis to Solid State Voltammetry. Application to Severely Damaged Frescoes

Multivariate chemometric methods are applied for identifying earth pigments from square-wave voltammetric measurements performed at pigment-modified paraffin-impregnated graphite electrodes allowing for a separation between hematite-based earths, French ochres, Spanish ochres, siennas, umbers and green earths. This methodology is applied to the identification of the pigments in samples from the ceiling frescoes of Antonio Palomino (dated 1707) in the vaulted nave of the Sant Joan del Mercat church in Valencia (Spain). These frescoes suffered considerable damage by fire during the Spanish Civil War in 1936, resulting in severe chemical and chromatic alterations. Electrochemical data, support…

Cover Picture: Access to Phylogeny from Voltammetric Fingerprints of Seeds: the Asparagus Case (Electroanalysis 2/2017)

Microchemical surface analysis of historic copper-based coins by the combined use of FIB-FESEM-EDX, OM, FTIR spectroscopy and solid-state electrochemical techniques

[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…

Characterizing archaeological bronze corrosion products intersecting electrochemical impedance measurements with voltammetry of immobilized particles

Application of electrochemical impedance measurements to microparticulate deposits of copper corrosion products attached to graphite electrodes in contact with 0.10 M aqueous HClO4 electrolyte is described. The impedance measurements were sensitive to the applied potential and the amount of solid sample and were modeled taking into account the contribution of the uncovered base electrode. Several pairs of circuit elements provide monotonic variations which are able to characterize different corrosion compounds regardless the amount of microparticulate solid on the electrode. Application to a set of archaeological samples from the archaeological Roman site of Gadara (Jordan, 4th century AD) …

Screening of pharmacologic adulterant classes in herbal formulations using voltammetry of microparticles.

A solid state electrochemical method for screening different families of adulterant chemicals illegally added to commercial phytotherapuetic formulations is described. The proposed method, based on the voltammetry of microparticles approach, permits a fast and sensitive way to distinguish between anorexics (amfepramone, fenproporex, sibutramine), benzozodiazepinic anxiolytics (clonazepam, flurazepam, alprazolam, midazolam, medazepam, chlordiazepoxide, diazepam), antidepressants (bupropione, fluoxetine, sertraline, paroxetine), diuretics (hydrochlorothiazide, furosemide, chlortalidone, amiloride, spironolactone), and hypoglycemics (glimepiride, chlorpropamide, glibenclamide) based on charact…

Electrochemical discrimination of mints: The last Chinese emperors Kuang Hsü and Hsüan T'ung monetary unification.

[EN] An electrochemical methodology for discriminating monetary emissions, a recurrent problem in much archaeological studies, is introduced. The method is based on the record of voltammetric signatures of cuprite and tenorite corrosion products in the patina using a minimally invasive nanosampling following the voltammetry of immobilized particles methodology. A model for the depth variation of voltammetric electrochemical parameters characterizing the composition of the corrosion patinas is presented. This model permits to rationalize electrochemical data and discriminate different monetary emissions. The application of this technique, corroborated by electrochemical impedance spectroscop…