Abstract Germanium (Ge) is commonly an unreported trace element in environmental samples due to the lack of reliable analytical methods. Besides atomic mass spectrometric methods (ICP-MS) and atomic emission spectroscopy (OES), graphite furnace atomic absorption spectrometry (GFAAS) offers the sensitivity that is needed in biological and environmental analysis. However, until recently AAS-techniques for the quantification of Ge were solely described for liquid samples and require time consuming sample preparation steps involving total dissolution of the sample matrix. In the present study we modified an existing method for the determination of Ge in liquid samples by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR CS GFAAS) towards its applicability to solid samples. Similar to liquid HR CS AAS, the addition of Pd/Mg(NO3)2 as modifier was necessary to avoid analyte losses. To achieve a homogeneous wetting of the solid sample Triton X-100, a non-ionic surfactant, was added together with the modifier. A biomass weight of 0.1–0.2 mg was appropriate for the solid sampling set-up, to which 20 μL of modifier, including 0.1% surfactant, was added. The furnace temperatures were adjusted to 90–140 °C for the drying process, to 1500 °C for pyrolysis and to 2550 °C for the atomisation step. Various calibration options were also considered realising routine analysis. Considering Ge concentrations in various environmental samples we observed no significant differences between results obtained from HR CS AAS and ICP-MS, respectively. The analytical technique demonstrated a detection limit for Ge down to 500 μg kg−1 Ge by a characteristic mass of 50 pg for selected biomass samples. The novel method can be applied in geochemical laboratories equipped with HR CS GFAAS devices to determine Ge in range of 0.7–360 mg kg−1 Ge in solid environmental samples without any sample preparation steps except of grinding.

中文翻译：

---

使用高分辨率连续源石墨炉原子吸收光谱法 (HR CS AAS) 和固体取样测定植物和土壤样品中的锗

摘要 由于缺乏可靠的分析方法，锗（Ge）通常是环境样品中一种未报告的微量元素。除了原子质谱法 (ICP-MS) 和原子发射光谱法 (OES)，石墨炉原子吸收光谱法 (GFAAS) 还提供生物和环境分析所需的灵敏度。然而，直到最近，用于 Ge 定量的 AAS 技术仅适用于液体样品，并且需要耗时的样品制备步骤，包括样品基质的完全溶解。在本研究中，我们修改了现有的通过高分辨率连续源石墨炉原子吸收光谱法 (HR CS GFAAS) 测定液体样品中 Ge 的方法，使其适用于固体样品。类似于液体 HR CS AAS，添加 Pd/Mg(NO3)2 作为改性剂是必要的，以避免分析物损失。为了实现固体样品的均匀润湿，将非离子表面活性剂 Triton X-100 与改性剂一起加入。0.1–0.2 mg 的生物量重量适合固体采样装置，其中添加了 20 μL 改性剂，包括 0.1% 表面活性剂。干燥过程的炉温调整到 90-140°C，热解调整到 1500°C，雾化步骤调整到 2550°C。还考虑了各种校准选项以实现常规分析。考虑到各种环境样品中的 Ge 浓度，我们观察到分别从 HR CS AAS 和 ICP-MS 获得的结果之间没有显着差异。分析技术表明，所选生物质样品的特征质量为 50 pg，Ge 的检测限低至 500 μg kg-1 Ge。该新方法可应用于配备 HR CS GFAAS 设备的地球化学实验室，以测定固体环境样品中 0.7-360 mg kg-1 Ge 范围内的 Ge，除研磨外无需任何样品制备步骤。