B. G. Brunetti

The application of in situ mid-FTIR fibre-optic reflectance spectroscopy and GC―MS analysis to monitor and evaluate painting cleaning

The development of non-invasive methodologies and portable instrumentation for in situ studies has been subject to great research and development in recent years in the field of conservation science. Despite such interest, very few reported studies employ these versatile techniques in the monitoring of cleaning treatments. This paper describes the application of mid-FTIR fibre-optic reflectance spectroscopy to monitor and evaluate the cleaning treatment of an oil painting using the chelating agent, triammonium citrate, a task undertaken in close collaboration with the painting conservator. Results obtained on site verify the removal of calcium oxalate and an organic component from the surface of the painting, later identified as a terpenic varnish. The subsequent, in laboratory FTIR and GC-MS analysis of the cotton swabs employed during the cleaning treatment acts as an additional non-invasive manner to support the results obtained in situ by mid-FTIR spectroscopy and to better understand the mechanism of the chosen cleaning agent.

Identification of animal glue and hen-egg yolk in paintings by use of enzyme-linked immunosorbent assay (ELISA)

AbstractWe report the development of an indirect ELISA procedure for specific identification of chicken-egg yolk and animal glues in painting micro-samples. The results presented integrate previously published work on ELISA recognition of bovine β-casein and chicken ovalbumin in painting materials. The integrated final ELISA procedure—optimised for protein extraction, immuno-reagent concentrations, blocking solution, incubation time, and temperature—enables multiplex identification, in single samples, of proteinaceous materials, i.e. chicken-egg yolk and albumen, animal glues, and bovine milk and/or casein, mainly used by painters in the past. The procedure has been systematically tested on laboratory models of mural and easel paintings, both naturally and artificially aged, to assess possible inhibitory effects on the immuno-reaction caused by inorganic painting materials (pigments and substrates) and by protein degradation resulting from aging processes. Real samples from case studies, which had previously been investigated and characterised by spectroscopy and chromatography, were successfully studied by use of the developed ELISA procedure. The commercial availability of all the immuno-reagents used, the affordable analytical equipment, and the specificity, sensitivity, and rapidity of ELISA make this method very attractive to diagnostic laboratories in the field of cultural heritage science. Possible further developments to the analytical potential of this technique include improvement of antibody performance and inclusion of other classes of bio-molecules as analytical targets. FigureAn ELISA indirect procedure is reported for the specific identification of chicken egg-yolk and animal glues in micro-samples from historical paintings; the method was experimented on laboratory models of mural and easel paintings, both naturally and artificially aged

A vibrational spectroscopic and principal component analysis of triarylmethane dyes by comparative laboratory and portable instrumentation.

This contribution examines the utility of vibrational spectroscopy by bench and portable Raman/surface enhanced Raman and infrared methods for the investigation of ten early triarlymethane dye powder references and dye solutions applied on paper. The complementary information afforded by the techniques is shown to play a key role in the identification of specific spectral marker ranges to distiguish early synthetic dyes of art-historical interest through the elaboration of an in-house database of modern organic dyes. Chemometric analysis has permitted a separation of data by the discrimination of di-phenyl-naphthalenes and triphenylmethanes (di-amino and tri-amino derivatives). This work serves as a prelude to the validation of a non-invasive working method for in situ characterization of these synthetic dyes through a careful comparison of respective strengths and limitations of each portable technique.

Scientific Investigation of an Important Corpus of Picasso Paintings in Antibes: New Insights into Technique, Condition, and Chronological Sequence

Abstract The Musée Picasso in Antibes (France) houses a unique collection of 23 paintings and 44 works on paper by Pablo Picasso, completed during the fall of 1946 by the artist, working on the same premises occupied today by the Museum. Picasso painted with readily available materials including oleoresinous enamel paints, fibrocement, wood panels, paper sheets, and re-used canvases. In this paper the results of an extensive campaign of scientific analysis of 17 of these works with both non-invasive and micro-invasive techniques are described. The project elucidated the full palette of the paintings, dispelling myths about their execution solely with the renowned brand of enamel paint Ripolin. The effective combination of elemental and spectroscopic methods of analysis enabled fine discriminations among various types of white enamel paint used by Picasso in Antibes. Because the artist appeared to have used such paints in chronological sequence, the precise identification of the type of white paint present on each of the works allowed the assignment of revised dates to some of the undated paintings. Important new information on surface coatings of wax and modern polymeric varnishes, as well as the widespread presence of metal soaps including zinc oxalates, was also uncovered.

Chromatographic and spectroscopic identification and recognition of ammoniacal cochineal dyes and pigments

In this work a combined chromatographic and spectroscopic approach is used to provide a diagnostic assessment of semi-synthetic ammoniacal cochineal through the syntheses of its dyes and lakes according to art historical recipes. Commercially introduced in the late XIX century as a dye and pigment, it was used to obtain a brilliant purplish/violet nuance which provided a more stable option over carminic acid although its evidenced use in manufacts and artworks of heritage importance have been scarcely documented. Through HPLC-DAD, it has been possible to identify 4-aminocarminic acid as the main component of ammoniacal cochineal highlighting a chemical formula analogous to acid stable carmine, a recent patented food dye. FTIR clearly distinguishes the amine group in the ammoniacal cochineal dye preparation and TLC-SERS allows for an adequate separation and spectral differentiation in its main components to be evidenced. Colloidal SERS has permitted spectral markers useful in discerning ammoniacal cochineal over carminic acid to be highlighted and discussed. Finally, the methods experimented in this study for the identification of ammoniacal cochineal have been validated on analyzing a sample of dyed wool.

A non-invasive NMR relaxometric characterization of the cyclododecane-solvent system inside porous substrates.

With the aim of deepening the knowledge on the behavior of cyclododecane (CDD) as a temporary consolidant agent for weathered stones, NMR longitudinal and transverse relaxation decays have been exploited to follow the distribution of cyclododecane solutions into porous matrices. By measuring as function of time the relaxation decay constants of CDD solutions dropped onto porous supports, it has been possible to differentiate the step encompassing the solvent evaporation, which determines the consolidant migration within the matrix, from that governing the consolidant sublimation, which is related to the consolidation effectiveness over time. Copyright