X-ray fluorescence analysis with micro glass beads using milligram-scale siliceous samples for archeology and geochemistry

• X-ray fluorescence determination of major oxides was performed using 1.1 mg of sample.
• Preparation and measurement techniques of the XRF micro glass bead specimen were optimized.
• Calibration curves using synthetic standards showed good accuracy and precision.
• Our method presented applicability to various types of siliceous samples.
• Our method might be useful for analyses of precious/limited samples in many fields.

A micro glass bead technique was developed to assay precious siliceous samples for geochemical and archeological analyses. The micro-sized (approximately 3.5 mm in diameter and 0.8 mm in height) glass beads were prepared by mixing and fusing 1.1 mg of the powdered sample and 11.0 mg of the alkali lithium tetraborate flux for wavelength-dispersive X-ray fluorescence determination of major oxides (Na2O, MgO, Al2O3, SiO2, P2O5, K2O, CaO, TiO2, MnO, and total Fe2O3). The preparation parameters, including temperature and agitation during the fusing process, were optimized for the use of a commercial platinum crucible rather than a custom-made crucible. The procedure allows preparation of minute sample amounts of siliceous samples using conventional fusing equipment. Synthetic calibration standards were prepared by compounding chemical reagents such as oxides, carbonates, and diphosphates. Calibration curves showed good linearity with r values > 0.997, and the lower limits of detection were in the 10s to 100s of μg g− 1 range (e.g., 140 μg g− 1 for Na2O, 31 μg g− 1 for Al2O3, and 8.9 μg g− 1 for MnO). Using the present method, we determined ten major oxides in igneous rocks, stream sediments, ancient potteries, and obsidian. This was applicable to siliceous samples with various compositions, because of the excellent agreement between the analytical and recommended values of six geochemical references. This minimal-scale analysis may be available for precious and limited siliceous samples (e.g., rock, sand, soil, sediment, clay, and archeological ceramics) in many fields such as archeology and geochemistry.