Special Issue of "Material Analysis in Cultural Heritage".

The objects of cultural heritage represent memories of human activities from the past [...].

Characterization of fresh PM deposits on calcareous stone surfaces: Seasonality, source apportionment and soiling potential.

Particulate matter (PM) pollution is one of the major threats to cultural heritage outdoors. It has been recently implied that organic aerosols will prevail over inorganic carbon particulates in the future, changing the main mechanisms of damage caused by poor air quality to calcareous heritage in particular. We studied fresh particulate deposits on marble and limestone surfaces exposed to urban air in sheltered and unsheltered configurations. Due to different air pollution sources in different seasons, the amount and composition of surface deposits varied throughout the year. The main and most constant contributor to PM2.5 (particles smaller than 2.5 µm) were primary traffic emissions (30 %), followed by secondary formation of acidic inorganic aerosols, such as sulphate in summer and nitrate in winter (33 % altogether), and seasonal biomass-burning emissions (14 %). Although biomass burning is the major source of primary organic aerosols including the light-absorbing fraction that prevailed over black carbon (BC) in colder months (up to 60 % carbonaceous aerosol mass), we show that surface darkening causing the soiling effect is still governed by the minor BC fraction of atmospheric aerosols, which remained below 20 % of the carbonaceous aerosol mass throughout the year. This, however, can change in remote environments affected by biomass-burning emissions, such as winter resorts, or by rigorous BC mitigation measures in the future. In the short run, sheltered positions were less affected by different removal processes, but we show that surface deposits are not simply additive when considering longer periods of time. This must be taken into account when extrapolating surface accumulation to longer time scales.

Impact of air pollution on outdoor cultural heritage objects and decoding the role of particulate matter: a critical review.

Atmospheric gases and particulate matter (PM) in contact with the material's surface lead to chemical and physical changes, which in most cases cause degradation of the cultural heritage material. Atmospheric damage and soiling are recognized as two pivotal forms of deterioration of cultural heritage materials caused by air pollution. However, the atmospheric damage effect of PM is rather complicated; its variable composition accelerates the deterioration process. Considering this, one of the important contributions of this work is to review the existing knowledge on PM influence on atmospheric damage, further recognize, and critically evaluate the main gaps in current understanding. The second phenomenon related to cultural heritage material and PM pollution is soiling. Even if soiling was recognized long ago, its definition and knowledge have not changed much for several decades. In the past, it was believed that black carbon (BC) was the primary soiling agent and that the change of the lightness could effectively measure the soiling. With the change of pollution situation, the lightness measurements do not represent the degree of soiling correctly. The additional contribution of this work is thus, the critical evaluation of soiling measurements, and accordingly, due to the change of pollution situation, redefinition of soiling is proposed. Even though numerous studies have treated soiling and atmospheric damage separately, there is an overlap between these two processes. No systematic studies exist on the synergy between soiling and atmospheric damage caused by atmospheric PM.

Emerging nuclear methods for historical painting authentication: AMS-14C dating, MeV-SIMS and O-PTIR imaging, global IBA, differential-PIXE and full-field PIXE mapping.

There is a considerable interest in developing new analytical tools to fight the illicit trafficking of heritage goods and particularly of easel paintings, whose high market values attract an ever-increasing volume of criminal activities. The objective is to combat the illicit traffic of smuggled or forged paintworks and to prevent the acquisition of fakes or looted artefacts in public collections. Authentication can be addressed using various investigation techniques, such as absolute dating, materials characterization, alteration phenomena, etc.; for paintings this remains a challenging task due to the complexity of the materials (paint layers, ground, varnish, canvas, etc.) and preferable use of non-destructive methods. This paper outlines results from concerted action on detecting forged works of art within the framework of a Coordinated Research Project of the International Atomic Energy Agency (IAEA) called Enhancing Nuclear Analytical Techniques to Meet the Needs of Forensic Sciences1. One of the main objectives is to foster the use of emerging Nuclear Analytical Techniques (NAT) using particle accelerators for authentication of paintings, with potential application to other forensics domains, by highlighting their ability to determine painting authenticity and to track restorations or anachronistic clues. The various materials comprising a test painting were investigated using an array of NAT. Binder, canvas and support were directly dated by 14C using Accelerator Mass Spectrometry (14C-AMS); binder and pigments' molecular composition was determined using Secondary Ion Mass Spectrometry with MeV ions (MeV-SIMS); paint layer composition and stratigraphy were accurately determined using Ion Beam Analysis (IBA) and differential Particle-Induced X-ray Emission (PIXE); and pigment spatial distributions were mapped using full-field PIXE. High resolution Optical Photothermal Infrared Spectroscopy (O-PTIR) molecular imaging was also exploited. Obtained results are presented and discussed. It is shown that the combination of the above-mentioned techniques allowed reconstructing the history of the test painting.

Sodium-Polyacrylate-Based Electrochemical Sensors for Highly Sensitive Detection of Gaseous Phenol at Room Temperature.

The detection of volatile organic compounds with electrochemical gas sensors is still very challenging regarding their sensitivity, selectivity, and operation at room temperature. There is a need for robust, sensitive, inexpensive, and yet easy-to-operate sensors for phenol and other phenolic compounds that function reliably under ambient conditions. Herein, we present a phenol gas sensor based on a combination of a semisolid, alkaline sodium polyacrylate, and commercial screen-printed electrodes. Sodium polyacrylate was employed as a multifunctional sensing material serving as a (i) gel-like electrolyte, (ii) accumulation milieu, and (iii) derivatization medium. Under ambient conditions, the sensor showed excellent sensitivity in the low ppbv (µg m-3) range, a good linear operation in the examined concentration range of 0.1-1.0 ppmv for up to 105 min accumulation, and low sensitivity toward examined interferences. The sensor also indicated a possibility to differentiate between several phenolic compounds based on their oxidation potential. Given its favorable electroanalytical performance, a strong application potential is envisioned in topical fields such as environmental monitoring, cultural heritage preservation, and occupational health and safety.

Non-destructive characterisation of iron gall ink drawings: not such a galling problem.

Iron gall inks are of extraordinary historical significance considering their widespread use for over a millennium. Due to their corrosiveness, which is a consequence of their acidity and content of transition metals, iron gall inks accelerate the degradation of the writing or drawing support, which in this study is rag paper. Characterisation of acidity (pH) and degree of polymerisation (DP) of cellulose in paper is thus of high interest as it enables the estimation of material stability and assessment of risks associated with its handling. Based on a well-characterised set of samples with iron gall ink from the 18th and 19th centuries, we developed a near infrared spectroscopic method with partial least squares calibration for non-destructive determination of pH and DP of both inked areas and paper. Using this method, 27 18th and 19th century iron gall ink drawings from the British Museum collection were analysed and in all cases, inked areas turned out to be more acidic and degraded than the surrounding paper. Based on the obtained DP data, we were able to estimate the time needed for the inked areas to degrade to the point when they become at risk of damage due to handling. Using the average uncertainty of the calculated lifetime, we propose a quantitative stability classification method which could contribute to the curatorial and conservation decision-making process.