ATR-FTIR and XRD quantification of solid mixtures using the asymptotic constant ratio (ACR) methods. Application to geological samples of sodium and potassium feldspars.

Two asymptotic constant ratio methods applied to the quantification of individual components of solid samples using attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray diffraction (XRD) are described. The methods involve the measurement of the peak current/peak areas of selected signals (diffraction peaks in XRD and absorption bands in ATR-FTIR) relative to the signal of standard added in constant proportion to the sample and the sample enriched with the analyte following the usual standard additions methodology. The proposed method compensates the absorption effects appearing in XRD and the presence of overlapping absorption bands of interferents by means of an asymptotic representation thus avoiding the need of the knowledge of the absorption parameters of the matrix and analytes. The method was tested for mixtures of different metal oxides and sodium and potassium feldspars with satisfactory results.

Hyperbolic subtraction method: Determination of the concentration of an analyte in the presence of an unknown interferent via spectral data.

A theoretical model to determine the concentration of an analyte in the presence of unknown interferents using spectral-type data is described. The method involves absorbance measurements at three wavelengths and the calculation of specific absorbances yielding a hyperbolic relationship between absorbance ratios and analyte concentrations. The concentration of the analyte of known spectrum can be determined in the presence of an interferent or mixture of interferents of unknown concentration(s) and spectra can be determined combining data for different sets of wavelengths. Application to indigo and isatin solutions in DMSO related to the so-called Maya blue problem is reported as an illustrative application example.

Quantification of minerals from ATR-FTIR spectra with spectral interferences using the MRC method.

A method for quantifying the individual components of mineral samples based on attenuated total reflectance - Fourier transform infrared spectroscopy (ATR-FTIR) is described, extending the constant ratio (CR) method to analytes absorbing in a common range of wavenumbers. Absorbance values in the spectral region where the analytes absorb relative to the absorbance of an internal standard absorbing at a wavenumber where the analytes do not absorb, permits the quantification of N analytes using measurements at N fixed wavenumbers. The method was tested for mixtures of albite, orthoclase, kaolin and quartz.

On-line database of voltammetric data of immobilized particles for identifying pigments and minerals in archaeometry, conservation and restoration (ELCHER database).

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 archaeological metallic object are presented.

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.

Study of Burseraceae resins used in binding media and varnishes from artworks by gas chromatography-mass spectrometry and pyrolysis-gas chromatography-mass spectrometry.

In the present work, a study attempting to characterize the Manila elemi and Mexican copal resins from the Burseraceae family, which are used as components of varnishes and binding media of artworks, has been carried out. A new GC-MS method involving the use of methyl chloroformate as derivatisation reagent has been proposed. A second method which uses pyrolysis-GC-MS and hexamethyldisilazane as derivatization reagent has also been applied. Characterization of the main components of the mono-, sesqui- and triterpenoid fractions occurring in the raw materials has been achieved. Both alpha- and beta-amyrin have been established as the major triterpenoid compounds occurring in these resins together with hop-22(29)-en-3beta-ol, found only in the Mexican copal. Artificially aged samples of Manila elemi and Mexican copal have also been analysed in order to study the stability of the triterpenoid components of the resins and their possible use as marker molecules. The results obtained indicate that these molecules, in particular, alpha- and beta-amyrin undergo oxidation processes during both artificial and natural ageing. Nevertheless, hop-22(29)-en-3beta-ol could be selected as marker compound for Mexican copal. The proposed methods of analysis have been applied to real paint samples extracted from paintings in which Mexican copal was present as the main component of an "oleoresin" binding medium to assess their ability for identifying this product when used in artworks. Satisfactory identification of this resin is obtained by means of GC-MS whereas Py-GC-MS provides, in general, weaker signals for the components of the resin. Additionally, the influence of the pigments present in real samples on the resin ageing process has been considered.