Eloisa Manzano

Simultaneous determination of aluminium and beryllium by first-derivative synchronous solid-phase spectrofluorimetry.

A method for the simultaneous determination of aluminium and beryllium in mixtures by first-deravative synchronous solid-phase spectrofluorimetry has been developed. Aluminium and beryllium reacted with morin to give fluorescent complexes, which were fixed on a dextran-type resin. The fluoresnce of the resin, packed in a 1-mm silica cell, was measured directly with a solid-surface attachment. The constant wavelength difference chosen to optimize the determination was Deltalambda = lambda(em) = 75 nm. Aluminium was measured at lambda(em)lambda = 445/520 nm and beryllium at lambda(em)lambda(em) = 430/505 nm. The range of application is between 0.5 and 5.0 ng/ml for both aluminium and beryllium. The accuracy and precision of the method are reported. The method has been successfully applied to the determination of aluminium and beryllium in synthetic mixtures and natural waters.

Determination of beryllium in water by ion-exchange spectrofluorimetry

A method for the determination of trace amounts of beryllium has been developed, based on ion-exchange spectrofluorimetry. Beryllium reacts with morin to give a highly fluorescent complex, which was fixed on a dextran-type anion-exchange resin. The fluorescence of the resin, packed in a 1-mm quartz cell, was measured directly using a solid-surface attachment. The concentration range of the method is 0.10–0.70 µg l–1, the relative standard deviation 1.4% and the detection limit 0.02 µg l–1. The method was applied to the determination of beryllium in natural waters. The aluminium and calcium levels can be determined first in order to reduce their interfering effect. The proposed method is more sensitive and selective than that using morin alone.

Preliminary study of UV ageing process of proteinaceous paint binder by FT-IR and principal component analysis

This work presents a preliminary study on the ageing process of proteinaceous binder materials used in painting under UV light. With this aim, two sets of model samples were prepared: samples prepared using a single protein material and complex samples prepared in a similar way to the sequence of layers in a real painting from lowest to highest complexity (protein, drying oils, pigment and varnish). The study focuses on acquiring information about the possible degradation process of proteinaceous binders due to ageing and how this process be affected by the presence of characteristic non-proteinaceous painting materials, such as lipids from linseed oil, terpenic compounds from varnish and inorganic pigments. Samples simulated the accelerated ageing process, as did the UV light exposition. The FT-IR spectra were recorded after 100, 500, 1000 and 1500 h of exposition. The study of the accelerated ageing process was performed by means of principal component analysis (PCA) using the FT-IR spectra obtained. Loadings from the significant principal components were analysed to find the FT-IR frequency (cm(-1)) involved in the degradation process. The study showed the lack of any relevant modification on the proteins in the single model samples. On the contrary, the complex model samples showed the ageing process. The accelerated ageing process can be explained by a principal component from PCA. The most affected IR region was 2900-3600 cm(-1), where the amide band was included.

Comparison between traditional strategies and classification technique (SIMCA) in the identification of old proteinaceous binders

In this paper, we performed a comparison between commonly used strategies amino acid ratios (Aa ratios), two-dimensional ratio plots (2D-Plot) and statistical correlation factor (SCF) and a classification technique, soft independent modelling of class analogy (SIMCA), to identify protein binders present in old artwork samples. To do this, we used a natural standard collection of proteinaceous binders prepared in our laboratory using old recipes and eleven samples coming from Cultural Heritage, such as mural and easel paintings, manuscripts and polychrome sculptures from the 15-18th centuries. Protein binder samples were hydrolyzed and their constitutive amino acids were determined as PITC-derivatives using HPLC-DAD. Amino acid profile data were used to perform the comparison between the four different strategies mentioned above. Traditional strategies can lead to ambiguous or non-conclusive results. With SIMCA, it is possible to provide a more robust and less subjective identification knowing the confidence level of identification. As a standard, we used proteinaceous albumin (whole egg, yolk and glair); casein (goat, cow and sheep) and collagen (mammalian and fish). The process results in a more robust understanding of proteinaceous binding media in old artworks that makes it possible to distinguish them according to their origin.

Study of the GC–MS determination of the palmitic–stearic acid ratio for the characterisation of drying oil in painting: La Encarnación by Alonso Cano as a case study

The correct identification of drying oils plays an essential role in providing an understanding of the conservation and deterioration of artistic materials in works of art. To this end, this work proposes the use of peak area ratios from fatty acids after ensuring that the linear responses of the detector are tested. A GC-MS method, previously reported in the literature, was revisited to its developed and validated in order to identify and quantify of eight fatty acids that are widely used as markers for drying oils in paintings, namely myristic acid (C(14:0)), palmitic acid (C(16:0)), stearic acid (C(18:0)), oleic acid (C(18:1)), linoleic acid (C(18:2)), suberic acid (2C(8)), azelaic acid, (2C(9)) and sebacic acid (2C(10)). The quaternary ammonium reagent m-(trifluoromethyl)phenyltrimethylammonium hydroxide (TMTFAH) was used for derivatization prior to GC-MS analysis of the oils. MS spectra were obtained for each methyl ester derivative of the fatty acids and the characteristic fragments were identified. The method was validated in terms of calibration functions, detection and quantification limits and reproducibility using the signal recorded in SIR mode, since two of the methyl derivatives were not totally separated in the chromatographic run. The proposed method was successfully applied to identify and characterise the most widely used drying oils (linseed oil, poppy seed oil and walnut oil) in the painting La Encarnación. This 17th century easel painting is located in the main chapel of the cathedral in Granada (Spain) and was painted by the well-known artist of the Spanish Golden Age, Alonso Cano (1601-1667).

Revisitation of the phenylisothiocyanate-derivatives procedure for amino acid determination by HPLC-UV.

A revisitation of the well known chromatographic procedure for the determination of amino acids as phenylthiocarbamyl derivatives (PTC) is performed. The method was developed for a microbore column that it is more appropriate to our later aims, the characterization of proteinaceous binders present in microsamples coming from the Cultural Heritage field. Several variables relating to chromatographic aspects were studied such as the pH and temperature of the mobile phase, buffer and modifier (triethylamine) concentrations in mobile phase and the stability of PTC-derivatives in solution. The calibration function was studied in depth. To prevent the heteroscedastic behaviour that it is observed, we used the weighed least squares fitting as the best strategy among other normalizing transformations, such as square root and logarithmic functions. Finally, the proposed method showed results similar to the traditional method in terms of efficiency, runtime, LODs and other characteristics, but with two additional advantages: a lower mobile phase consumption and the possibility of working with a lower sample volume. The usefulness of proposed method is checked against easel painting samples of Pictorial Heritage.

Mortars, pigments and binding media of wall paintings in the ‘Carrera del Darro’ in Granada, Spain

Abstract The Carrera del Darro is a street within the city of Granada, Spain, which is emblematic owing to the architectural value of its buildings, to its significance for the urban structure of the city and to the implications it has for the surroundings of the Alhambra. Our study concerns the chemical analysis of the mural paintings on four facades, corresponding to numbers 23, 25, 27 and 29 of the Carrera del Darro. From the analysis of the mortar, it may be concluded that the composition is very similar, though not identical, in the four paintings studied: a limestone mortar. Ochre, white, black and red were used for the decoration of the four facades; green pigment was also observed in the second decoration of no. 29. The results of the morphological examination and EDX microanalysis of the paint samples are shown. By means of the thermogravimetric analysis we established the existence of an organically derived compound. After the existence of an oleaginous binder had been discounted by gas chromatography/mass spectrometry (GC/MS) analysis, we continued with the extraction and determination of proteins by spectrophotometry analysis, detecting low levels of proteins in the paint on the four facades analysed. The study was completed by evaluating the influence on the deterioration of the paintings by the possible surface presence of salts (such as nitrates or chlorides) and organic compounds.

Study of modern artistic materials using combined spectroscopic and chromatographic techniques. Case study: painting with the signature “Picasso”

A painting bearing the signature “Picasso” was investigated and its components – pigments and binders – were characterised using micro-Raman spectroscopy (mRS) combined with other analytical techniques such as Scanning Electron Microscopy with Energy Dispersive X-ray analysis (SEM/EDX), Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Gas Chromatography-Mass Spectrometry (GC-MS). We identified the pigments in order to assess chronological inconsistency (anachronistic pigments) with the work of the Spanish artist Pablo Picasso (1881–1973) by means of in situ and cross-section analyses by mRS. Using mRS we identified the pigments ‘phthalocyanine blue’, ‘phthalocyanine green’, ‘pyrazolone orange’, ‘anatase’ and ‘rutile’ (titanium dioxide). These results were corroborated by SEM/EDX elemental analysis, which detected Ba, S and Zn among others, so prompting discussion about the use of ready-mixed house paints (Ripolin®). The ground layer was also investigated by mRS, which confirmed the use of rutile (titanium dioxide), calcite and phyllosilicates (Al, Fe). mRS on the white area identified the binding media as beeswax, the most important wax used in art. ATR-FTIR and GC-MS analysis support the presence of a wax and an oil–resin mixture as the binder, described in previous research as being used by Picasso. All the artist materials identified were widely used in art at the beginning of the twentieth century according to the available bibliography and are therefore consistent with the Picasso era. To the best of our knowledge this is the first attempt to investigate a painting related to Picasso using the combination of analytical techniques proposed here.

Determination of boron with chromotropic acid by first-derivative synchronous spectrofluorimetry

SummaryA method for the determination of traces of boron by first-derivative synchronous spectrofluorimetry is proposed. It is based on the formation of a fluorescent complex with chromotropic acid at pH 6.7. The constant wavelength difference chosen to optimize the determination is Δλ=λem−λex=24 nm. The range of application is between 2.0 and 20.0 μ/l of boron, the detection limit 0.4 μg/l and the relative standard deviation 3.2%. A study was made of the influence of several ions as potential interferents. The method has been satisfactorily applied to the determination of boron in plants, fertilizers and natural waters.

Spectrofluorimetric determination of traces of bromide

A Spectrofluorimetric method for the determination of traces of bromide has been developed. The method is based on the bromination of fluorescein after bromide and hypochlorite form bromine, giving the less fluorescent eosin. The fluorescence decrease is used as the analytical signal. The calibration graph is linear over the range 10 to 80 μg/1. The detection limit is 3 μg/1 and the relative standard deviation 1.0%. The method has been satisfactorily applied to the determination of bromide in natural waters.