Trace and Minor Element Analysis of Azurite Blues in Fine Arts: Possibilities and Limitations in Provenance Studies.

IF 2.2 3区 化学 Q2 INSTRUMENTS & INSTRUMENTATION Applied Spectroscopy Pub Date : 2024-11-01 Epub Date: 2024-09-28 DOI:10.1177/00037028241280989
David Hradil, Zdeňka Čermáková, Janka Hradilová, Petr Bezdička, Jitka Míková
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Abstract

Azurite, a historical blue mineral pigment, has previously been described to contain certain elemental impurities. These may originate from host rocks, vein fillings, or the primary copper ore mineralization. In this study, azurites (and also green malachites) from three important Central European deposits with a potential of being exploited for pigment usage already in the Middle Ages have been studied, together with azurite from Chessy, France, with a different geological setting. Using electron probe microanalysis and, more importantly, laser ablation inductively coupled plasma mass spectroscopy for trace elemental analysis, several indicators were pinpointed as important for provenance: characteristic elemental fingerprint of the deposit, e.g., elevated lead (Pb) in combination with rare earth elements, may be combined with zinc (Zn)/arsenic (As) ratio (indicating sources of excess Zn in the primary deposit) and the overall amount of metal impurities (suggesting the source mineral of copper for azurite formation). In addition, malachites from the same deposits were found to preferentially incorporate primary ore metal elements as well as Cd, Mg, Mn, or U. Therefore, if azurite pigment contains an elevated amount of malachite as an impurity, it may significantly influence the overall elemental composition. The results obtained on geological samples were applied to two micro-samples of works of art containing azurite-rich layers originating from the 13th-14th and 16th centuries. It was shown that it is highly beneficial to focus on the overall trace elemental composition of the paint layer and not on the admixed mineral grains, as their presence, especially in minute micro-samples, is largely accidental and thus not representative. Although a higher number of samples need to be studied in the future, the newly described criteria made it possible to exclude some of the localities of the employed azurite pigment. This confirmed the key importance of trace elements analysis of mineral pigments for the provenance studies of fine arts.

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美术作品中天青石蓝的微量和次要元素分析:来源研究的可能性和局限性。
天青石是一种历史悠久的蓝色矿物颜料,以前曾被描述为含有某些元素杂质。这些杂质可能来自寄主岩、矿脉填充物或原生铜矿成矿过程。在这项研究中,我们对中欧三个重要矿床中的天青石(以及绿色孔雀石)进行了研究,这些矿床在中世纪就有可能被用作颜料,同时我们还研究了法国切斯西(Chessy)的天青石,该矿床的地质环境与天青石不同。利用电子探针显微分析法,更重要的是利用激光烧蚀电感耦合等离子体质谱法进行痕量元素分析,确定了几个对产地非常重要的指标:矿床的特征元素指纹,例如铅(Pb)与稀土元素的结合,可能与锌(Zn)/砷(As)比率(表明原生矿床中过量锌的来源)和金属杂质的总量(表明形成天青石的铜源矿物)相结合。因此,如果天青石颜料中含有较多的孔雀石杂质,则可能会对整体元素组成产生重大影响。在地质样本上获得的结果被应用于两件富含天青石层的艺术品微观样本,这两件艺术品分别源于 13-14 世纪和 16 世纪。结果表明,关注油漆层的整体微量元素组成而非混合矿物颗粒是非常有益的,因为它们的存在,尤其是在微小样本中的存在,在很大程度上是偶然的,因此不具有代表性。尽管今后需要研究更多的样本,但新的标准使得我们可以排除一些使用天青石颜料的地方。这证实了对矿物颜料进行微量元素分析对于美术作品来源研究的重要性。
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来源期刊
Applied Spectroscopy
Applied Spectroscopy 工程技术-光谱学
CiteScore
6.60
自引率
5.70%
发文量
139
审稿时长
3.5 months
期刊介绍: Applied Spectroscopy is one of the world''s leading spectroscopy journals, publishing high-quality peer-reviewed articles, both fundamental and applied, covering all aspects of spectroscopy. Established in 1951, the journal is owned by the Society for Applied Spectroscopy and is published monthly. The journal is dedicated to fulfilling the mission of the Society to “…advance and disseminate knowledge and information concerning the art and science of spectroscopy and other allied sciences.”
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