Application of FTIR microscopy to cultural heritage materials

Research in art conservation has been developed from the early 1950s, giving a significant contribution to the conservation-restoration of cultural heritage artefacts. In fact, only through a profound knowledge about the nature and conditions of constituent materials, suitable decisions on the conservation and restoration measures can thus be adopted and preservation practices enhanced. The study of ancient artworks is particularly challenging as they can be considered as heterogeneous and multilayered systems where numerous interactions between the different components as well as degradation and ageing phenomena take place. However, difficulties to physically separate the different layers due to their thickness (1-200 µm) can result in the inaccurate attribution of the identified compounds to a specific layer. Therefore, details can only be analysed when the sample preparation method leaves the layer structure intact, as for example the preparation of embedding cross sections in synthetic resins. Hence, spatially resolved analytical techniques are required not only to exactly characterize the nature of the compounds but also to obtain precise chemical and physical information about ongoing changes. This thesis focuses on the application of FTIR microspectroscopic techniques for cultural heritage materials. The first section is aimed at introducing the use of FTIR microscopy in conservation science with a particular attention to the sampling criteria and sample preparation methods. The second section is aimed at evaluating and validating the use of different FTIR microscopic analytical methods applied to the study of different art conservation issues which may be encountered dealing with cultural heritage artefacts: the characterisation of the artistic execution technique (chapter II-1), the studies on degradation phenomena (chapter II-2) and finally the evaluation of protective treatments (chapter II-3). The third and last section is divided into three chapters which underline recent developments in FTIR spectroscopy for the characterisation of paint cross sections and in particular thin organic layers: a newly developed preparation method with embedding systems in infrared transparent salts (chapter III-1), the new opportunities offered by macro-ATR imaging spectroscopy (chapter III-2) and the possibilities achieved with the different FTIR microspectroscopic techniques nowadays available (chapter III-3). In chapter II-1, FTIR microspectroscopy as molecular analysis, is presented in an integrated approach with other analytical techniques. The proposed sequence is optimized in function of the limited quantity of sample available and this methodology permits to identify the painting materials and characterise the adopted execution technique and state of conservation. Chapter II-2 describes the characterisation of the degradation products with FTIR microscopy since the investigation on the ageing processes encountered in old artefacts represents one of the most important issues in conservation research. Metal carboxylates resulting from the interaction between pigments and binding media are characterized using synthesised metal palmitates and their production is detected on copper-, zinc-, manganese- and lead- (associated with lead carbonate) based pigments dispersed either in oil or egg tempera. Moreover, significant effects seem to be obtained with iron and cobalt (acceleration of the triglycerides hydrolysis). For the first time on sienna and umber paints, manganese carboxylates are also observed. Finally in chapter II-3, FTIR microscopy is combined with further elemental analyses to characterise and estimate the performances and stability of newly developed treatments, which should better fit conservation-restoration problems. In the second part, in chapter III-1, an innovative embedding system in potassium bromide is reported focusing on the characterisation and localisation of organic substances in cross sections. Not only the identification but also the distribution of proteinaceous, lipidic or resinaceous materials, are evidenced directly on different paint cross sections, especially in thin layers of the order of 10 µm. Chapter III-2 describes the use of a conventional diamond ATR accessory coupled with a focal plane array to obtain chemical images of multi-layered paint cross sections. A rapid and simple identification of the different compounds is achieved without the use of any infrared microscope objectives. Finally, the latest FTIR techniques available are highlighted in chapter III-3 in a comparative study for the characterisation of paint cross sections. Results in terms of spatial resolution, data quality and chemical information obtained are presented and in particular, a new FTIR microscope equipped with a linear array detector, which permits reducing the spatial resolution limit to approximately 5 µm, provides very promising results and may represent a good alternative to either mapping or imaging systems.

Eco-Management and Audit Scheme (EMAS): An evaluation of success factors in the agricultural sector. The case of Italy's Emilia Romagna region.

Different tools have been used to set up and adopt the model for the fulfillment of the objective of this research. 1. The Model The base model that has been used is the Analytical Hierarchy Process (AHP) adapted with the aim to perform a Benefit Cost Analysis. The AHP developed by Thomas Saaty is a multicriteria decision - making technique which decomposes a complex problem into a hierarchy. It is used to derive ratio scales from both discreet and continuous paired comparisons in multilevel hierarchic structures. These comparisons may be taken from actual measurements or from a fundamental scale that reflects the relative strength of preferences and feelings. 2. Tools and methods 2.1. The Expert Choice Software The software Expert Choice is a tool that allows each operator to easily implement the AHP model in every stage of the problem. 2.2. Personal Interviews to the farms For this research, the farms of the region Emilia Romagna certified EMAS have been detected. Information has been given by EMAS center in Wien. Personal interviews have been carried out to each farm in order to have a complete and realistic judgment of each criteria of the hierarchy. 2.3. Questionnaire A supporting questionnaire has also been delivered and used for the interviews . 3. Elaboration of the data After data collection, the data elaboration has taken place. The software support Expert Choice has been used . 4. Results of the Analysis The result of the figures above (vedere altro documento) gives a series of numbers which are fractions of the unit. This has to be interpreted as the relative contribution of each element to the fulfillment of the relative objective. So calculating the Benefits/costs ratio for each alternative the following will be obtained: Alternative One: Implement EMAS Benefits ratio: 0, 877 Costs ratio: 0, 815 Benfit/Cost ratio: 0,877/0,815=1,08 Alternative Two: Not Implement EMAS Benefits ratio: 0,123 Costs ration: 0,185 Benefit/Cost ratio: 0,123/0,185=0,66 As stated above, the alternative with the highest ratio will be the best solution for the organization. This means that the research carried out and the model implemented suggests that EMAS adoption in the agricultural sector is the best alternative. It has to be noted that the ratio is 1,08 which is a relatively low positive value. This shows the fragility of this conclusion and suggests a careful exam of the benefits and costs for each farm before adopting the scheme. On the other part, the result needs to be taken in consideration by the policy makers in order to enhance their intervention regarding the scheme adoption on the agricultural sector. According to the AHP elaboration of judgments we have the following main considerations on Benefits: - Legal compliance seems to be the most important benefit for the agricultural sector since its rank is 0,471 - The next two most important benefits are Improved internal organization (ranking 0,230) followed by Competitive advantage (ranking 0, 221) mostly due to the sub-element Improved image (ranking 0,743) Finally, even though Incentives are not ranked among the most important elements, the financial ones seem to have been decisive on the decision making process. According to the AHP elaboration of judgments we have the following main considerations on Costs: - External costs seem to be largely more important than the internal ones (ranking 0, 857 over 0,143) suggesting that Emas costs over consultancy and verification remain the biggest obstacle. - The implementation of the EMS is the most challenging element regarding the internal costs (ranking 0,750).

Entomological monitoring in the cultural heritage facilities as prerequisite for a successful IPM programme

The European Committee for Standardization is working on a standard for the application of IPM (Integrated Pest Management) in museums and cultural heritage facilities. Since one of the aims of this research was to verify the approach against pests adopted in Italian conservation facilities, a survey was conducted. The results show that for the Italian museums, archives, libraries and historical houses pests are a problem, but IPM is unknown and prevention programmes to avoid damages caused by them, are not applied. In the most of cases pests problems are solved only when the risk is high and damages are visible. Also entomological monitoring, which represents a crucial part of IPM and could be very useful, is not included among the ordinary prevention activities. In addition, at present, the scientific researches on entomological traps, whether light or pheromones, for “cultural heritage pests” is extremely poor and only recently the behaviour and/or the physiology of the insects “of museums” have been investigated. For these reasons, tests to increase the traps using are performed. In particular, S. paniceum behaviour towards different attraction systems was investigated and the results indicate that the light traps efficiency could be improved using specific wavelengths and light sources.

Influence of plant structure, cultural pratices and environmental conditions on the development of the bacterial canker of kiwifruits

Italy has a preeminent rank in kiwifruit industry, being the first exporter and the second largest producer after China. However, in the last years kiwifruit yields and the total cultivated area considerably decreased, due to the pandemic spread of the bacterial canker caused by Pseudomonas syringae pv. actinidiae (Psa). Several climatic conditions and cultural practices affect the development of the bacterial canker. This research work focused on the impact of agricultural practices and microclimate conditions on the incidence and epidemiology of Psa in the orchard. Therefore, the effect of fertilization, irrigation, use of bio-regulators, rootstock, training system and pruning were examined. The effect of different tunnel systems was analyzed as well, to study the plant-pathogen interaction. Considering the importance of insects as vectors in other pathosystems, the role of Metcalfa pruinosa in the spread of the bacterial canker was investigated in controlled conditions. In addition, quality and storage properties of fruits from infected plants were assessed. The study of all these aspects of the agronomic practices is useful to define a strategy to limit the bacterial diffusion in the orchard. Overall, excess nitrogen fertilization, water stress, stagnant water supplies, pruning before summer and the high number of Metcalfa pruinosa increased the Psa incidence. In contrast, tunnel covers may be useful for the control of the disease, with special attention to the kind of material.