The early modern period is mainly characterised by High Lime-Low Alkali (HLLA) glass, a lime-rich glass made from plant or tree ashes, originating from 14th-century Germany and later used all over Europe. Attempts to link HLLA chemical subgroups to a particular point in time have failed so far. Driven by a request from the archaeological community, our research group has been exploring the feasibility of UV–Vis-NIR absorption spectroscopy as a non-destructive and in-situ applicable analysis technique for more than a decade. The main goal of this research is to provide a better understanding of the subgroups of HLLA glass and their respective dating via non-destructive means. A second topic relates to the role of cobalt as a potential indicator for either the type of applied ashes or for glass recycling.

In this paper, we present the UV–Vis-NIR and LA-ICP-MS results of a total of 45 HLLA colourless glass objects or fragments, supplemented with three blue glasses from the 15th to the 17th centuries. First, we observed a correlation between iron and cobalt contents and that these two elements show more elevated concentrations starting from the middle of the 16th century. Different types of sources can be responsible, such as the type of raw materials, the tools employed, and recycling. We hypothesised that both elements were introduced through the wood or plant ashes used as fluxing agent. Then, we noted that the presence of low amounts of cobalt in colourless glass, can be observed through the analysis of the Co²⁺ absorption bands in the optical spectra down to 18 ppm. Next, we describe an approach to quantify iron and cobalt from the optical spectra and to date HLLA material by means of absorption spectroscopy, a valid, rapid, and non-destructive alternative for laboratory measurements. Finally, we show that the optical parameters (the Ultra-violet Absorption Edge (UVAE), the calculated Fe²⁺ and total iron contents, and the Co²⁺ absorption bands characteristics) allow discerning two glass groups: one dating to the end of the 15th-middle of the 16th centuries, and the other to the second half 16th-17th centuries. These results gain valuable information to further resolve the study on recycling, on the influence of the glassmaking tool on the glass batch composition and/or on the selection or treatment of the raw materials in HLLA glass.

现代早期的主要特点是高石灰-低碱（HLLA）玻璃，一种由植物或树灰制成的富含石灰的玻璃，起源于 14 世纪的德国，后来遍及欧洲。迄今为止，将 HLLA 化学亚组与特定时间点联系起来的尝试都失败了。应考古界的要求，我们的研究小组十多年来一直在探索紫外-可见-近红外吸收光谱作为一种无损和原位适用的分析技术的可行性。这项研究的主要目标是通过非破坏性方法更好地了解 HLLA 玻璃的亚群及其各自的年代学。第二个主题涉及钴作为应用骨灰类型或玻璃回收的潜在指标的作用。

在本文中，我们展示了 45 个 HLLA 无色玻璃物体或碎片的 UV-Vis-NIR 和 LA-ICP-MS 结果，并辅以 15 至 17 世纪的三个蓝色玻璃。首先，我们观察到铁和钴含量之间的相关性，并且这两种元素从 16 世纪中叶开始显示出更高的浓度。可以对不同类型的来源负责，例如原材料的类型、使用的工具和回收利用。我们假设这两种元素都是通过用作助熔剂的木材或植物灰烬引入的。然后，我们注意到在无色玻璃中存在少量钴，可以通过对 Co ^{2+的分析观察到}光谱中的吸收带低至 18 ppm。接下来，我们描述了一种从光谱中量化铁和钴的方法，以及迄今为止通过吸收光谱法对 HLLA 材料进行量化的方法，这是一种有效、快速和非破坏性的实验室测量替代方案。最后，我们展示了光学参数（紫外吸收边缘 (UVAE)、计算的 Fe ²⁺和总铁含量，以及 Co ²⁺吸收带特征）允许辨别两个玻璃组：一个可追溯到 16 世纪 15 世纪中叶末，另一个可追溯到 16-17 世纪下半叶。这些结果为进一步解决回收研究、玻璃制造工具对玻璃配合料成分的影响和/或对 HLLA 玻璃中原材料的选择或处理的影响提供了有价值的信息。