Abstract In the recent years, an increasing interest has been devoted to the development of compact macro X-ray fluorescence (MA-XRF) systems, establishing the technique as one of the most powerful non-invasive method for the characterization of artworks. Nevertheless, important information may be lost due to the poor signal-to-noise ratio, which characterises spectra collected with a limited acquisition time. Moreover, well-known drawbacks of the XRF analysis, such as the matrix effect and the penetration depth of X-rays, have to be also considered. In the attempt to overcome such limitations, without compromising the potentialities of a MA-XRF imaging analysis in terms of dimension of investigated surface and time of analysis, a specific methodological strategy is proposed. In particular, high signal-to-noise ratio maps were acquired on regions of interest selected after preliminary fast scans on the entire painting. Subsequently, the elaboration of the dataset was supported by the use of ad hoc analytical tools, such as correlation diagrams, averaged extracted spectra and line emission maps for each element. The correct interpretation of the non-invasive results allowed to define a proper sampling strategy. The proposed experimental workflow has been applied to a masterpiece panel painting by Cimabue (1240–1302) depicting “Madonna Enthroned with the Child and Two Angels”, disclosing new knowledge on the adopted execution technique, about which little is known. Thus, for the first time a painting created by Cimabue was investigated under a material and technical point of view. Due to the relevance of the information obtained by MA-XRF analyses, micro-destructive investigations were carried out. Thus, the joint evaluation of elemental distribution and the stratigraphic composition of the selected samples allowed to obtain information about Cimabue painting technique. Particular attention was devoted to the characterization of the throne decorations, pointing out new questions on a non-conventional middle-age gilding technique that need still to be investigated.

中文翻译：

---

从宏观到微观：用于研究涂漆表面的先进宏观 X 射线荧光 (MA-XRF) 成像方法

摘要 近年来，人们对紧凑型宏观 X 射线荧光 (MA-XRF) 系统的开发越来越感兴趣，将该技术确立为最强大的非侵入性艺术品表征方法之一。然而，由于信噪比较差，重要信息可能会丢失，这表征了在有限的采集时间内收集的光谱。此外，还必须考虑 XRF 分析众所周知的缺点，例如基质效应和 X 射线的穿透深度。为了克服这些限制，同时不影响 MA-XRF 成像分析在被调查表面的尺寸和分析时间方面的潜力，提出了一种特定的方法策略。特别是，在对整个绘画进行初步快速扫描后，在选定的感兴趣区域上获得了高信噪比图。随后，数据集的细化得到了使用特殊分析工具的支持，例如相关图、平均提取光谱和每个元素的线发射图。对非侵入性结果的正确解释允许定义适当的采样策略。提议的实验工作流程已应用于 Cimabue（1240-1302）的杰作面板绘画，描绘了“麦当娜与孩子和两个天使登基”，揭示了关于所采用的执行技术的新知识，对此知之甚少。因此，第一次从材料和技术的角度研究 Cimabue 创作的绘画。由于 MA-XRF 分析获得的信息的相关性，进行了微观破坏性调查。因此，元素分布和所选样品的地层组成的联合评估允许获得有关 Cimabue 绘画技术的信息。特别关注宝座装饰的特征，指出了仍需研究的非常规中年镀金技术的新问题。