Irena Kralj Cigić

Non-Destructive Evaluation of Historical Paper Based on pH Estimation from VOC Emissions

Volatile organic compounds (VOCs) emitted from materials during degradation can be a valuable source of information. In this work, the emissions of furfural and acetic acid from cellulose were studied using solid-phase micro-extraction (SPME) in combination with gas chromatography-mass spectrometry. Two sampling techniques were employed: static headspace sampling using SPME for 1 h at 40 °C after 18-h sample preparation at 80 °C in a closed glass vial, and contact SPME in a stack of paper (or a book). While a number of VOCs are emitted from paper under conditions of natural or accelerated degradation, two compounds were confirmed to be of particular diagnostic value: acetic acid and furfural. The emissions of furfural are shown to correlate with pH of the cellulosic environment. Since pH is one of the most important parameters regarding durability of this material, the developed method could be used for non-destructive evaluation of historical paper.

A study of degradation of historic parchment using small-angle X-ray scattering, synchrotron-IR and multivariate data analysis

Parchment has been in use for thousands of years and has been used as the writing or drawing support for many important historic works. A variety of analytical techniques is currently used for routine assessment of the degree of denaturation of historic parchment; however, because parchment has a heterogeneous nature, analytical methods with high spatial resolution are desirable. In this work, the use of small-angle X-ray scattering (SAXS) and synchrotron-IR (SR-IR) was examined in conjunction with multivariate data analysis to study degradation of an extended set of historic parchment samples, and particularly to investigate the effect of lipids and the presence of iron gall ink on the degradation processes. In the data analysis, shrinkage temperature, lipid content, sample age, presence of ink and accelerated degradation were included. The analysis of loading factors in partial least-squares regression and principal component analyses based on SAXS, SR-IR and other analytical and descriptive data reveals the effect of lipid removal on diffraction patterns, and lipids are found to cause the degradation process in parchment to accelerate. The effect of iron gall ink is also evident, although the mechanism of ageing is different to that of natural ageing in the absence of ink. In addition, a historic parchment score from ca. 1750 is examined, demonstrating the significant effect of iron gall ink, and lipids and inorganic soiling on its increased degradation.

Ochratoxin A in Wine: Its Determination and Photostability

Abstract Due to the growing public concern regarding food safety, reliable, nondemanding and robust analytical methods are needed for quantitative determination of toxic compounds in complex matrices. Sample preparation is frequently a crucial step in determination of ochratoxin A (OTA) in wine, and a simplified and automated procedure is described, using solid‐phase extraction coupled on‐line to high pressure liquid chromatography (HPLC) with fluorimetric detection (λex=333 nm, λem=460 nm). While the limit of quantitation is frequently better compared to off‐line procedures (30 ng/L), the decisive advantages of the new procedure are the absence of all sample manipulation during preconcentration and subsequent analysis, and consequentially no risk of analyte loss or sample contamination. Furthermore, using the standard addition method, matrix interferences can be avoided and the determination of extraction efficiency is unnecessary. These improvements have important consequences for the overall uncertainty of the analytical procedure. The developed method was applied for determination of OTA in 12 selected Slovenian wines. The typical relative standard deviation (RSD) was 10%. In none of the samples, did the OTA amount exceeded 2 µg/kg, the limit regulated by the EC. The photo‐stability of the mycotoxin in solutions was examined. During irradiation of OTA solutions, its content was quickly reduced, while three fluorescent degradation products were detected. The degradation proceeds faster in water and 12% ethanolic solutions than in organic solvents or wine. Identification of the fluorescent degradation products was attempted using LC‐MS/MS with electrospray ionization.

Material properties of historic parchment: A reference collection survey

Abstract Historic parchment is a complex biological material, and due to various methods of production or inks used, unknown environmental histories of objects and heterogeneous nature of animal skin, it represents a particular analytical challenge. Due to the number of variables it is likely that patterns in degradation of these historic objects can only be revealed by surveying the material properties of a significant number of real objects. In this work, a sacrificial collection of ca. 100 historic parchments (fifteenth to twentieth century) was characterized using a range of techniques available to conservation practitioners that can usefully be used to reliably and rapidly characterize parchment. We focused on micro-destructive methods, such as shrinkage temperature (Ts), as the most widely used indicator of parchment degradation. Lipid content, roughness, and ink pH were additionally measured, while a limited number of samples containing iron gall ink were also examined using scanning electron microscopy (SEM) and SEM-EDX, to explore the distribution of ink components. Even in the absence of detailed environmental histories, it is possible to acknowledge the significance of the effect of iron gall ink and its acidity, and of lipids on parchment degradation, as measured using Ts. This research reports valuable reference data, while the collection remains accessible for further research.

Rapid Estimation of Tocopherol Content in Linseed and Sunflower Oils-Reactivity and Assay.

The reactivity of tocopherols with 2,2-diphenyl-1-picrylhydrazyl (DPPH) was studied in model systems in order to establish a method for quantifying vitamin E in plant oils. The method was optimized with respect to solvent composition of the assay medium, which has a large influence on the course of reaction of tocopherols with DPPH. The rate of reaction of α-tocopherol with DPPH is higher than that of γ-tocopherol in both protic and aprotic solvents. In ethyl acetate, routinely applied for the analysis of antioxidant potential (AOP) of plant oils, reactions of tocopherols with DPPH are slower and concentration of tocopherols in the assay has a large influence on their molar reactivity. In 2-propanol, however, two electrons are exchanged for both α- and γ-tocopherols, independent of their concentration. 2-propanol is not toxic and is fully compatible with polypropylene labware. The chromatographically determined content of tocopherols and their molar reactivity in the DPPH assay reveal that only tocopherols contribute to the AOP of sunflower oil, whereas the contribution of tocopherols to the AOP of linseed oil is 75%. The DPPH assay in 2-propanol can be applied for rapid and cheap estimation of vitamin E content in plant oils where tocopherols are major antioxidants.