José Vicente Gimeno-Adelantado

Comparative assessment of solid-phase extraction clean-up procedures, GC columns and perfluoroacylation reagents for determination of type B trichothecenes in wheat by GC-ECD.

Various solid-phase extraction (SPE) procedures for clean-up, two perfluoroacylation reagents (pentafluoropropionic anhydride (PFPA) and heptafluorobutyric anhydride (HFBA)) and two chromatographic columns (HP-1701 and HP-5) have been assessed comparatively to achieve the determination of type B trichothecenes (deoxynivalenol (DON), nivalenol (NIV), 3- and 15-acetyldeoxynivalenol (3- and 15-ADON)) in wheat grain by gas chromatography (GC)-electron-capture detection (ECD). Spiked wheat samples were extracted with acetonitrile-water (84:16, v/v). Tested SPE procedures were MycoSep 225 column, Florisil and different cartridges prepared in the laboratory with mixtures of various sorbents like alumina, Celite 545, C18, silica and charcoal. We propose MycoSep 225 column, and cartridges made with alumina-charcoal-silica and alumina-charcoal-C18 silica mixtures as clean-up procedures on the basis of recovery values (89.6, 87.3 and 86.1% for deoxynivalenol, respectively, at 1.0mg/kg spiking level). The two last procedures are less expensive. Pentafluoropropionic anhydride was more stable against moisture and less expensive, while recoveries were similar to those obtained with heptafluorobutyric anhydride. HP-1701 column can separate 3- and 15-acetyldeoxynivalenol derivatives while HP-5 cannot, although this last column provided lower bleed and better sensitivity.

Changes in ochratoxin A and type B trichothecenes contained in wheat flour during dough fermentation and bread-baking.

Ochratoxin A (OTA) and type B trichothecenes are mycotoxins that occur frequently in cereals and thus can be found in cereal by-products such as bread. The aim of this work was to study the variation of the levels of OTA, deoxynivalenol (DON), 3-acetyldeoxynivalenol (3-ADON) and nivalenol (NIV) during the bread-making process. This was done by using wheat flour spiked with different levels of toxins. Mycotoxin levels were controlled after fermentation of the dough with yeasts (Saccharomyces cerevisiae) and after further baking at different temperature–time combinations. Analysis of variance (ANOVA) of the results showed a significant reduction in OTA level (p < 0.05) during fermentation of the dough. The reduction ranged between 29.8% and 33.5%, depending on the initial concentration of toxin in the flour. During this period, the level of the other mycotoxins studied was not modified. By contrast, in the baking phase there were significant changes in the levels of the four mycotoxins, although the reduction was similar under all the baking conditions. Considering all the temperature–time conditions tested, it can be concluded that during the baking period the average reduction of OTA, NIV, 3-ADON, and DON was 32.9%, 76.9%, 65.6%, and 47.9%, respectively.

Analytical study of proteinaceous binding media in works of art by gas chromatography using alkyl chloroformates as derivatising agents

In this work, we present the results obtained in an analytical study of the different types of proteinaceous binding media most commonly used in paintings, using GC-FID as the technique of analysis and GC-MS as a confirmatory technique. The application of this methodology requires prior hydrolysis of the proteins in the binding media to obtain free amino acids and then volatile derivatives, in this case by reaction with chloroformates due to advantages of speed, safety and the aqueous medium in which the reaction occurs. The method proposed for the proteinaceous binding media study is to calculate the proportions of the different amino acids with respect to alanine. This method provided good characterisation of different binding media, such as pork gelatine, beef gelatine, albumin, egg white and casein. The proposed method is used for the identification of binding media (including mixtures of binders) present in real samples from paintings in the city of Valencia, Spain.

Identification of Synthetic Resins Used in Works of Art by Fourier Transform Infrared Spectroscopy

Differentiation between the synthetic polymers used in former restorations of works of art and the original materials used by the artist is of great interest; such differentiation is needed to establish an adequate process of restoration for the work of art. A specific method of sample preparation based on a filtration and deposition-evaporation sequence is proposed, which permits the separation and preconcentration of the synthetic polymer that is being analyzed and avoids problems arising from the simultaneous interpretation of IR spectra obtained from complex mixtures of organic and inorganic compounds present in small artistic samples. In addition to the identification of characteristic IR absorption bands, quantitative diagnostic criteria based on two-dimensional diagrams of relative intensity of selected peaks have been developed. Standards of acrylic, alkyd, cellulose nitrate, epoxy, ketone, poly(vinyl acetate), polyurethane, silicone synthetic polymers and semi-synthetic wax used as binding media, adhesives, and coatings have been prepared by this proposed experimental procedure, and IR spectra have been obtained. Finally, several samples from paintings and artistic objects dating from the 16th to the 20th century have been analyzed, and synthetic and semi-synthetic organic materials have been successfully identified by comparison with the standards using the proposed method of analysis.

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 characterising the different species.

Electrochemical Determination of the Fe(III)/Fe(II) Ratio in Archaeological Ceramic Materials Using Carbon Paste and Composite Electrodes

A method for determining the iron(III)/iron(II) ratio in ceramic materials based on microsample attachment to graphite/polyester composite electrodes is presented. This quotient is of considerable interest for determining the nature and firing conditions of the original materials in archaeological ceramics. The electrochemistry of iron in ceramic materials in acetic/acetate and Na2EDTA aqueous solutions is described in terms of reductive dissolution processes of iron(III) materials and oxidative dissolution processes of iron(II) ones. The iron(III)/iron(II) ratio is determined from peak area measurements in linear scan voltammograms performed in 0.10 M acetic/acetate buffer (pH 4.70) and 0.10 M Na2EDTA solutions. A second semiempirical method based on peak current measurements in repetitive cyclic voltammetry is also described. Both procedures were satisfactorily tested using a set of certified clays and applied to the study of a series of ceramic samples from Manises (Spain), dated on XVth and XVIIth–XVIIIth centuries. Results in agreement with SEM and XRD data are obtained.

Electrochemistry of iron oxide pigments (earths) from pictorial microsamples attached to graphite–polyester composite electrodes

The electrochemical response of different iron pigments attached to graphite–polyester composite electrodes is described. Characteristic differential pulse voltammetric profiles were obtained for green earth, iron oxide red, Mars black, ochre yellow, Sienna raw, umber raw and Van Dyke brown. Proton-assisted reductive dissolution processes occur at the three-phase boundary of the substrate electrode–attached solid–electrolyte solution system. Microsamples extracted from polychromed sculptures, canvas paintings, wall paintings, altarpieces and panel paintings from Spain, Ethiopia and Italy from the 12th to the 20th centuries were electrochemically identified in agreement with polarized light microscopy, SEM/EDX, XRD and FT-IR data.

Determination of type A and type B trichothecenes in paprika and chili pepper using LC-triple quadrupole-MS and GC-ECD.

There is a need to develop sensitive and accurate analytical methods for determining deoxynivalenol (DON), HT-2 toxin and T-2 toxin in paprika to properly assess the relevant risk of human exposure. An optimized analytical method for determination of HT-2 toxin and T-2 toxin using capillary gas chromatography with electron capture detection and another method for determination of DON by liquid chromatography-mass spectrometry in paprika was developed. The method for determination of HT-2 toxin and T-2 toxin that gave the best recoveries involved extraction of the sample with acetonitrile-water (84:16, v/v), clean-up by solid-phase extraction on a cartridge made of different sorbent materials followed by a further clean-up in immunoaffinity column that was specific for the two toxins. The solvent was changed and the eluate was derivatized with pentafluoropropionic anhydride and injected into the GC system. The limits of detection (LOD) for T-2 and HT-2 toxins were 7 and 3 μg/kg, respectively, and the recovery rates for paprika spiked with 1000 μg toxin/kg were 71.1% and 80.1% for HT-2 and T-2 toxins, respectively. For DON determination, the optimized method consisted of extraction with acetonitrile-water (84:16, v/v) solution followed by a solid-phase extraction clean-up process in a cartridge made of different sorbent compounds. After solvent evaporation in N(2) stream, the residue was dissolved and DON was separated and determined by LC-MS/MS. The LOD for this method was 14 μg DON/kg paprika sample and the DON recovery rate was 86.8%.

Study of behaviour on simulated daylight ageing of artists’ acrylic and poly(vinyl acetate) paint films

AbstractThis work proposes a multi-method approach that combines advanced microscopy (SEM/EDX, AFM) and spectroscopy (UV-vis and FTIR) techniques. This approach not only characterises the behaviour of the additives of two commercial poly(vinyl acetate) (PVAc) and acrylic emulsion paints but also simultaneously characterises the changes in chemical composition and morphology observed in the paint films as a result of ageing due to the paints being exposed to an intense source of simulated daylight. In parallel, a series of mechanical tests were performed that correlate the chemical changes in composition and the changes observed in the films’ mechanical properties. This work was a comparative study between both types of acrylic and PVAc paints. The results obtained are of great interest for the modern paint conservation field as they provide valuable information on the mid- and long-term behaviours of these synthetic paints. FigureTensile test of phthalocianyne blue Liquitex® paint film

Voltammetric Identification of Lead(II) and (IV) in Mediaeval Glazes in Abrasion‐Modified Carbon Paste and Polymer Film Electrodes. Application to the Study of Alterations in Archaeological Ceramic

Direct identification of lead(II) and (IV) in glazed ceramics by cyclic voltammetry and differential pulse voltammetry is described. Characteristic cathodic and anodic profiles are obtained for microsample coatings in Paraloid B72-film electrodes immersed in NaCl and HAc/NaAc media. The electrochemical response of PbO, PbO2 and Pb3O4, and a series of test specimens of glaze is compared with that of microsamples extracted from the glaze of blue and white decorated ceramic produced in Manises (Spain) in the 15th century which have been buried in a damp place. Under abrasive conditions, striping peaks at –0.12 and –0.25 V (vs. SCE) appear for Pb(IV) centers and, at –0.55 and –0.75 V, for Pb(II) centers. The weathering process is accompanied by a significant decrease of the total lead content and an enhancement of the Pb(IV)/Pb(II) ratio suggesting that a significant fraction of Pb(II) ions is released. Electrochemical data are compared with those obtained from SEM/EDX.