Kinetics of accelerated degradation of historic iron gall ink-containing paper

Although degradation of iron gall ink containing paper has been scientifically studied for almost 250 years, we still do not have a good understanding of the kinetics of the process. While many studies focussed on model samples to avoid the inhomogeneity of real historic samples or the need for sampling, this research was conducted on a selection of real documents. Accelerated degradation experiments were performed at six combinations of temperature and relative humidity (RH) in the intervals 50–80 °C/20–80% RH. The analytical methods were optimised such that sample consumption was minimised and errors and uncertainties were evaluated. The results show that the rate of degradation, measured as change in the degree of polymerisation of cellulose in paper beneath ink, can be described in Arrhenius terms, and that the apparent activation energy for the process depends on the moisture content in the material. The variation is consistent with the process of hydrolysis becoming less prominent at lower moisture content values, although the results indicate that hydrolytic degradation predominates during natural ink-induced degradation. In the context of the historic samples used in the study, the presence of ink accelerated the degradation of paper by a constant factor of 1.59 in comparison to paper without ink, across the range of experimental T and RH. This indicates that a dose-response function could be developed for ink-induced degradation of paper

Damage function for poly(vinyl chloride) in heritage collections

Yellowing of plastic objects as a consequence of chemical degradation is a common heritage conservation challenge. In the case of poly(vinyl chloride) elimination of hydrogen chloride leads to the formation of polyene sequences that act as chromophores. The objective of this work was to quantitatively evaluate the rate of degradation observed as yellowing, as relevant to room conditions during long-term storage of heritage collections. Degradation was quantified as increase in the b* colour coordinate during accelerated degradation at 50 and 70 °C as a function of temperature, relative humidity, plasticizer content, and polymer molecular weight. The significance of each variable was investigated with multiple linear regression. Lower temperature, lower relative humidity, higher polymer molecular weight and higher plasticizer content were associated with lower degradation rates. The activation energy of 86 kJ/mol was calculated. The concept of ‘1- °C-equivalent’ is introduced to enable variable prioritisation from a heritage management aspect. The resulting model can be used to shape environmental management guidelines and identify the most vulnerable objects in heritage collections

Machine learning-assisted non-destructive plasticizer identification and quantification in historical PVC objects based on IR spectroscopy

Non-destructive spectroscopic analysis combined with machine learning rapidly provides information on the identity and content of plasticizers in PVC objects of heritage value. For the first time, a large and diverse collection of more than 100 PVC objects in different degradation stages and of diverse chemical compositions was analysed by chromatographic and spectroscopic techniques to create a dataset used to construct classification and regression models. Accounting for this variety makes the model more robust and reliable for the analysis of objects in museum collections. Six different machine learning classification algorithms were compared to determine the algorithm with the highest classification accuracy of the most common plasticizers, based solely on the spectroscopic data. A classification model capable of the identification of di(2-ethylhexyl) phthalate, di(2-ethylhexyl) terephthalate, diisononyl phthalate, diisodecyl phthalate, a mixture of diisononyl phthalate and diisodecyl phthalate, and unplasticized PVC was constructed. Additionally, regression models for quantification of di(2-ethylhexyl) phthalate and di(2-ethylhexyl) terephthalate in PVC were built. This study of real-life objects demonstrates that classification and quantification of plasticizers in a general collection of degraded PVC objects is possible, providing valuable data to collection managers

Volatile aldehydes in libraries and archives

Volatile aldehydes are produced during degradation of paper-based materials. This may result in their accumulation in archival and library repositories. However, no systematic study has been performed so far. In the frame of this study, passive sampling was carried out at ten locations in four libraries and archives. Despite the very variable sampling locations, no major differences were found, although air-filtered repositories were found to have lower concentrations while a non-ventilated newspaper repository exhibited the highest concentrations of volatile aldehydes (formaldehyde, acetaldehyde, furfural and hexanal). Five employees in one institution were also provided with personal passive samplers to investigate employees’ exposure to volatile aldehydes. All values were lower than the presently valid exposure limits. The concentration of volatile aldehydes, acetic acid, and volatile organic compounds (VOCs) in general was also compared with that of outdoor-generated pollutants. It was evident that inside the repository and particularly inside archival boxes, the concentration of VOCs and acetic acid was much higher than the concentration of outdoor-generated pollutants, which are otherwise more routinely studied in connection with heritage materials. This indicates that further work on the pro-degradative effect of VOCs on heritage materials is necessary and that monitoring of VOCs in heritage institutions should become more widespread

Development and mining of a database of historic European paper properties

A database of historic paper properties was developed using 729 samples of European origin (1350–1990), analysed for acidity, degree or polymerisation (DP), molecular weight of cellulose, grammage, tensile strength, as well as contents of ash, aluminium, carbonyl groups, rosin, protein, lignin and fibre furnish. Using Spearman’s rank correlation coefficient and principal component analysis, the data were examined with respect to methods of manufacture, as well as chemical stability of paper. Novel patterns emerged related to loss of DP and accumulation of carbonyl groups and acidity with time and the role of lignin and rosin, as well as rate of degradation (k = 10−5 year−1) at room conditions. In-depth understanding of long-term degradation of lignin and rosin is needed to better understand the relationships between composition and degradation of historic paper. This study highlights the importance of mining significant volumes of analytical data, and its variability, obtained from real historic objects

On the Age and Content of Jar-35—A Sealed and Intact Storage Jar Found on the Southern Plateau of Qumran

An intact and sealed storage jar known as Jar-35 was found in 2004, south of the Qumran settlement. A previous study identified tartrate in the deposit of the jar, indicating the possible past presence of wine. However, we cannot confirm this finding. Using liquid and gas chromatography with mass spectrometric detection, no trace of tartaric acid or salts thereof could be detected in our samples. We show that the major component of the deposit is gypsum. No other organic compounds were identified with the methods that we have applied. Both radiocarbon dating of charcoal in the deposit and thermoluminescence dating of the ceramic jar show that it dates to the main period of habitation at Qumran (c. 100 BC to AD 70).