As a strategic critical metal, beryllium (Be) requires accurate quantification in complex geological matrices and characterization of its occurrence states, which are essential for elucidating metallogenic mechanisms and supporting mineral resource assessments. The quantitative analysis of beryllium has long been challenging due to its low atomic number, the high thermodynamic stability of beryllium-bearing minerals (especially silicate minerals), and severe matrix interference. This review summarizes recent advances in sample pretreatment methods for beryllium-bearing samples, bulk beryllium content analysis, and micro-scale in situ analytical techniques for the determination of beryllium in geological samples. The complete decomposition of beryllium-bearing minerals, particularly refractory silicate minerals such as beryl and phenakite, is a critical factor affecting the accuracy of analytical results. Targeted sample preparation methods are therefore required for different mineral types. Graphite furnace atomic absorption spectrometry (GFAAS), inductively coupled plasma-optical emission spectrometry/mass spectrometry (ICP-OES/MS) are the main analytical techniques for beryllium determination, enabling accurate measurement of beryllium concentrations ranging from 0.018 to 100000 μg/g in samples. Among these techniques, GFAAS exhibits high sensitivity but is limited to single-element determination and requires the selection of appropriate matrix modifiers to eliminate interferences. ICP-OES enables simultaneous multi-element determination but generally has higher detection limits and is susceptible to spectral interferences. ICP-MS provides low detection limits and allows simultaneous determination of multiple elements, but suffers from mass spectral interferences. Laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) enables the determination of beryllium concentrations as low as 0.200 μg/g using a 13 μm laser spot size. Combined with electron probe microanalysis (EPMA) and laser-induced breakdown spectroscopy (LIBS), it allows the simultaneous characterization of beryllium occurrence and spatial distributions. Currently, beryllium analytical techniques have developed into a complementary system integrating bulk concentration analysis and micro-scale in situ analysis. For single-element analysis, conventional chemical analysis methods are suitable for samples with high beryllium concentrations, whereas GFAAS is preferred for low-concentration samples. Multi-element simultaneous analysis mainly relies on ICP-OES and ICP-MS. For micro-scale in situ analysis, EPMA is applicable for the quantitative determination of beryllium in minerals with medium to high concentrations, LA-ICP-MS is suitable for highly sensitive determination of low-level beryllium, and LIBS is applicable for rapid on-site semi-quantitative screening. Different analytical methods exhibit strong complementarity in terms of detection range, multi-element determination capability, spatial resolution, and analytical scale, enabling their application to regional geochemical surveys, mineral resource assessments, and micro-scale characterization of minerals.
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