Figure 4 - uploaded by Stefano Ridolfi
Content may be subject to copyright.
Source publication
An important part of the world's cultural heritage is represented by stone monuments. A very dangerous weathering process that deteriorates stone monuments and is caused by human activity is air pollution. One of the worst pollutants for stone monuments is associated with sulfur compounds, especially with gypsum. Gypsum is a rather soluble compound...
Context in source publication
Similar publications
Marine aerosols have extensively been monitored in the framework of a research project to investigate the inorganic and organic nutrient fluxes of the atmospheric nitrogen input into the North Sea. As a part of this project bulk analysis was also performed by energy dispersive X-ray fluorescence (EDXRF) on a total of 366 samples in order to provide...
The research has been focusing on some connection between the chemical composition of the papers obtained by Fourier transform infrared (FTIR) spectroscopy and the nature of the fillers, determined by energy dispersion X-ray fluorescence (EDXRF) spectroscopy. The present paper corroborates the FTIR and EDXRF results obtained for some historical pap...
The scientific interest in air pollution comes from its influence on human health, the condition of cultural heritage and climate. The PM2.5 fraction (particles of a diameter of 2.5 mm or below), indirectly, has a significant impact on health which is associated with respiratory tract and blood vessel related diseases. However, not only the size, b...
W artykule omówiono wyniki badań archeometalurgicznych przeprowadzonych na tzw. siekierze miedzianej z Antonin, pow. chodzieski. W pobliżu miejsca odkrycia zabytku ujawniono pozostałości intensywnej aktywności osadniczej ludności kultury pucharów lejkowatych. Ocena typologiczna tzw. siekiery z Antonin wskazuje, że zabytek ten jest fragmentem siekie...
Citations
... The SO 3 molecule abstracts a hydroxyl group from the surface to generate an HSO 4 − anion, a transformation that parallels the hydration of SO 3 to generate sulfuric acid in the formation of acid rain. The adverse effects observed here support previously reported results that sulfur compounds are a concern within cultural heritage, as they can promote degradation pathways and cause the deterioration of pigments (Coccato et al., 2017), stone monuments and buildings (Diana et al., 2007;Belfiore et al., 2013), and paper (Williams and Grosjean, 1992). Interestingly, hydrogen sulfidewhich also has a central sulfur atom, but with a negative oxidation state only weakly interacts with the surface via hydrogen bonding. ...
The physio-chemical properties of the clay mineral kaolinite – the main component of porcelain – play a vital role in understanding how a porcelain object interacts with its environment. Understanding these interactions is imperative for the development of non-destructive yet effective conservation methods to preserve, treat, and restore porcelain objects of cultural heritage importance. To gain insight into the surface properties and behavior of kaolinite across a wide range of environments, we use density functional theory (DFT) to probe how a representative set of small molecules and atmospheric pollutants interact with a native kaolinite (001) surface, both in vacuum and with explicit hydration. By investigating selected atmospheric pollutants, acids, and sodium salts under different conditions, we identify the scenarios that are most disruptive to the native kaolinite surface. Specifically, we demonstrate that protic acids and sodium salts generally interact with the surface more strongly than common small molecule pollutants. Our results also indicate that adsorbates containing a central sulfur atom with a positive oxidation state are particularly deleterious to the kaolinite surface. Furthermore, to explore the interactions between a fired or partially fired porcelain object and relevant chemicals, we also model a partially dehydrated kaolinite surface and probe its interactions with three selected adsorbates. The trends elucidated throughout this study allow us to suggest a series of guidelines for the care of porcelain objects.
... Chemical, physical and biological damages come from the water as such or as vehicle of salts (Kloppmann et al. 2014) and from air pollutants (Prieto-Taboada et al. 2013;Nuno et al. 2015). Sulphate must be considered the most dangerous salt (Tropea et al. 2010) due to its capacity to crystallise in different forms that can include until ten water molecules in their crystalline structure; its presence must be mainly attributed to the attack of sulphuric acid, formed by the reaction amongst SO x combustion gases and calcareous stones being the precursor of the black crusts (Diana et al. 2007;Prieto-Taboada et al. 2013). In turn, dangerousness of soluble salts depends from the thermo-hygrometric conditions, especially from the frequency of their variation due to the cycles of solubilisationcristallisation of soluble salts (Germinario et al. 2015;Visco et al. 2012a, b, submitted). ...
Due to the bad state of conservation, “Palazzo Governi”, a seventeenth-century building located in the old town district of “Stampace” in Cagliari (Sardinia, Italy), was subjected to restoration. Thus, according to the Italian Law n. 1089, the main façade colour must be reproduced, and therefore, its identification was required. The available samples looked fairly degraded, in particular as an easy plaster to crumble; so, some other analyses able to identify the degradation cause were performed. Two different approaches were adopted to attain the first goal, the visual colour assessment by a sensory panel (subjective) and the instrumental measurement by colorimetry (objective). Ion chromatography and inductively coupled plasma–optical emission spectroscopy analyses, as well as conductivity and pH measurements, were performed to evaluate the presence of water-soluble salts inside the plaster, as possible cause of degradation; the binder/aggregate ratio was also evaluated. A full mineralogical and petrographic characterisation of the materials constituting the samples, as well as the identification of their stratigraphy and some other morphologic and structural features suitable to highlight eventual forms of degradation, were performed by optical microscopy. Scanning electron microscopy coupled to X-ray microanalysis was been also used in order to confirm and/or to integrate data obtained by optical microscopy. The samples have been compared with two samples coming from two other buildings, also located in Sardinia, that looked in good conservation state. The results evidenced that the causes of degradation come from a high salt (especially sulphate) content and a scarce presence of binder in the plaster that can be imputed to a wrong initial composition and/ or to a leaching by acidic rain.
... In the presence of lead it is very hard to meaningfully determine the presence of low quantities of sulfur. As a manner of fact, the M line of lead (2.35 keV) and the K alfa line of sulfur (2.30 keV) fall within the energy resolution of most of portable EDXRF systems [16]. This means that the calcium can derive from the gypsum or calcite. ...
... An portable EDXRF system was assembled using an air-cooled X-ray tube with an active spot of 1.5 mm, working with 38 kV high voltage and 0.2 mA current together with a Peltier cooled SDD (Silicon Drift Detector) detector with an energy resolution of 150 eV at 5.9 keV. A photo of the system at work on the monument is shown in Fig. 2 [10]. The EDXRF investigations were carried out in two different ways: ...
It has become a common practice to include diagnostics and archaeometric studies during a masterpiece restoration. The advantages and limits of this approach are now topic of discussion in the community of researchers that is growing up quickly. The bronze burial monument of Pope Sixtus IV (1471–84) by Antonio del Pollaiolo, now in the Treasure Museum in the Vatican was intended to be located at the center of a chapel, this explains its apparent asymmetry: lack of height and large base. The restoration of the burial monument started in May 2007, it was carried out by first fulfilling a series of non-invasive analyses using a transportable EDXRF to map the composition of the alloy and evaluate the diagnostic capabilities for deterioration processes of the bronze surface. As a consequence of the first non-invasive diagnostic campaign, a second campaign of micro invasive tests was planned and carried out. The samples were analysed with SEM-EDS and XRF techniques. In this article some of the results of the EDXRF tests will be shown together with the procedures set up to maximize the diagnostic information obtained and minimize the need of microsampling from the artefact. The results and the statistical analysis of data show that a straightforward planning of the measurements can give several, sometimes unexpected, results in the definition of the state of conservation of the monument and also from an archaeometric point of view. With a high amount of data, the use of statistical analysis is necessary, for example in our case, the analysis of the variance confirmed the hypothesis of the use of different alloys for the elements of the panels.
... In the last two decades the use of mobile or Field Portable (FP) spectrometers, mostly for Energy Dispersive X-Ray Fluorescence (EDXRF), in the archaeometric study of ancient artifacts has become a very common practice as testified by the very large number of papers that appeared in the scientific literature and in the presentations of the main archaoemetric conferences ( [1], [2], [3], [4], [5]). The use of a EDXRF mobile system for the characterization of an ancient artifacts is commonly judged as a precious tool in order to formulate initial hypotheses, to be verified through other kinds of analysis, often destructive. ...
Field Portable Energy Dispersive X Ray Fluorescence (FP-EDXRF) is
particularly useful to analyze works of art, mainly because of his
noninvasive and multielemental capability. In many situations FP-EDXRF
is the only non invasive technique that can be realistically used to
gain some information about the chemical composition of precious and
unique objects. Many kind of works, such as paintings, bronzes, precious
metals alloys, inks, stones, stamps and more can be studied using a
field portable EDXRF system. This manuscript highlights some drawbacks
that have to be kept in mind to fulfill a valid measurement such as the
need for other backup methods to support portable XRF results or the
problem of the non-homogeneity of the sample. This manuscript will also
present three examples to demonstrate the usefulness of FP-EDXRF with
paintings on canvas, ancient bronzes and sulfur surface analyses.
... Total sulfur concentration of minerals, rocks and glasses using X-ray fluorescence X-ray fluorescence (XRF) is a widely used method for analysis of rocks, owing to its ability to simultaneously analyze a wide range of elements in different matrices with a modest level of sample preparation. Newer machines will in fact take unprocessed samples such as archeological artifacts (e.g., Diana et al. 2007) and it is straightforward to do direct analyses of metals if a flat surface can be machined and polished. ...
... Total sulfur concentration of minerals, rocks and glasses using X-ray fluorescence X-ray fluorescence (XRF) is a widely used method for analysis of rocks, owing to its ability to simultaneously analyze a wide range of elements in different matrices with a modest level of sample preparation. Newer machines will in fact take unprocessed samples such as archeological artifacts (e.g., Diana et al. 2007) and it is straightforward to do direct analyses of metals if a flat surface can be machined and polished. ...
The analytical methods described above are all in use for the detection of sulfur concentration in a range of materials (Table 4). Choice of the most appropriate method is a function of the type of material to be analyzed, sample availability, and to some extent the (Figure presented) expected sulfur concentration. A review of the literature shows that the method of choice for bulk sulfur analyses of rocks (including ores) involves an elemental analyzer coupled with an infrared detection cell (e.g., LECO, ELTRA systems). The "Kiba" method of sulfur extraction followed by gravimetric analysis allows the detection of sulfur in the range of 50-100 ppm, but care must be exercised in the collection of produced sulfide and final weighing. The method is particularly suitable for the collection of finely disseminated sulfides in rocks for isotopic analysis. For routine determination of sulfur in minerals and glasses the electron microprobe remains the most utilized technique, unless sulfur is present at concentrations less than 50 to 100 ppm. For the detection of low-levels of sulfur in minerals and glasses Secondary Ion Mass Spectrometry may become the norm. Only a few labs in the world at present are capable of exploring sulfur determination by SIMS; the future for routine sulfur analysis may be a function (Table presented) of instrument availability. Nuclear methods of sulfur analyses offer the potential for low-level sulfur determination, but standards and samples with known isotopic compositions must be run together to reduce large variations in accuracy. Laboratory availability will limit the routine use of nuclear methods of analyses for most geologic materials. Sulfur analyses using LA-ICP-MS technology is in its infancy, but the potential to determine low-levels of sulfur concurrently with other trace-elements ensures that research will continue to be directed at making sulfur analyses via LA-ICP-MS routine. Analyses of sulfur in fluid inclusions via LA-ICP-MS will advance research on ore genesis and volatile interaction with rocks. Microanalytical tools involving the ion probe and LA-ICP-MS offer an additional benefit of potential determination of sulfur isotope ratios (see the contributions in this volume by Marini et al. 2011 and Simon and Ripley 2011). Samples analyzed via mass spectrometry following high-temperature combustion offer a similar benefit, but the extraction of sulfur species dissolved in glass by this method has proven difficult with most EA systems.
... About the EDXRF system we worked with an X Ray tube tension of 35 kV and a tube current of 0.2 mA; the detector is a SDD (Silicon Drift Detector) with a resolution of 150 eV at 6.4 keV. The analysed areas on the surfaces have a diameter of 2 mm [3]. ...
It is of paramount importance, for preservation and conservation means, to understand the need of periodic checks to avoid the definitive decay of works of art. And nevertheless it is not to be ignored the economical cost of the diagnostic analysis that together with a structural lack of funds that are at disposal of the preservation of works of art make the planning of periodic checks very difficult or limited only to the more important masterpieces leaving out the majority of art works.
Energy‐dispersive X‐ray fluorescence (EDXRF) is a physical rapid detection method to analyze the types of elements through the energy characteristics of fluorescent X‐ray particles. When applied to the detection of food element content, it not only needs simple sample pretreatment but also the element measurement time generally does not exceed 10 min to have the accuracy of μg/g, which can greatly reduce the time and cost of detection. Due to the limitations of the EDXRF instrument and measurement mechanism, it has low sensitivity to light elements in food, and the detection sensitivity varies with elements in food element analysis. For example, the detection sensitivity of Ca, Mg, Fe, Zn, Cu and other elements concerned by people is not high when the content is low, and the measurement accuracy is extremely dependent on the detector resolution. However, with the improvement of detector performance and algorithm optimization of EDXRF, the detection limit of this technology can reach 0.1 μg/g, the detection of trace elements has also been improved, which has made a new breakthrough in the field of food element detection. Therefore, this paper reviews that in recent 20 years, in order to overcome the various difficulties of EDXRF in food detection, the hardware optimization of EDXRF (For example, the development of an analyzer without sample preparation can greatly reduce the time required for the detection of food elements, and a series of instruments combined with EDXRF and cluster capillary technology can greatly improve the excitation efficiency of lighter elements in food. The spectrometer with a high‐resolution detector can improve the detection accuracy of target elements with low content in food) and in order to solve the problem of spectrum resolution in food detection, (For example, the wavelet transform method which has good performance in spectrum smoothing, identifying weak peaks and maintaining peak shape is applied to EDXRF spectrum resolution, which can better solve the problem that the X‐ray characteristic peaks of elements with a low atomic number in food are submerged) the reform and innovation of spectrum resolution methods are introduced. This paper summarizes and analyzes the representative application examples of EDXRF in food safety detection, discusses the advantages and disadvantages of EDXRF compared with other rapid detection or food detection methods in different situations, concludes its application conditions, and discusses the application prospect of EDXRF technology in the field of food detection.
In this chapter an overview of the main invasive/non-invasive techniques used in situ for the evaluation of conservation treatments is provided. The conservation treatments considered are cleaning, consolidation, and protection of stone, mainly for architectural heritage. After a brief introduction, a paragraph is dedicated to the current process of drafting the standards, starting from previous experiences. In each paragraph dealing with conservation treatments, a reminder of commonly used laboratory tests carried out on stone samples, following either standardized protocols or not, are briefly reported. Details about testing protocols and threshold values for the selection of the best conservation treatment and for the monitoring will be described.
