Optimised approach for small mass sample preparation and elemental analysis of bees and bee products by inductively coupled plasma mass spectrometry.

The elemental fingerprint of honey, pollen and bees are useful biomonitors of anthropogenic activities across the world. Elements in honey and pollen may also be analysed for their nutritional value and potential toxicity. There are currently limited studies that address the use of small sample masses while retaining good reproducibility and detection limits during elemental analysis. The aim of this study was to develop a simple analytical method to quantify 39 major, minor, trace and rare earth elements in small mass samples of bees, honey and pollen by inductively coupled plasma mass spectrometry. The final method was validated for 20-200 mg bee, 20-100 mg pollen or 50-200 mg of honey with 0.2 mL nitric acid followed by 0.1 mL hydrogen peroxide in a digestion block (80 °C, 2 h total); samples were made up to a final volume of approximately 6 mL. The method reduces the volume of chemicals used, limits sample manipulation and improves detection limits over traditional digestion methods. The sample preparation and analysis method were deemed to be satisfactory for the three matrices examined, with spike recoveries ranging from 96 (B) to 129% (As) for trace elements and 91 (Pr) to 112% (La) for rare earth elements, and acceptable detection limits (down to 5.07 μg kg for Co using 30 mg sample mass, pollen). Precision was acceptable with the relative percent standard deviation of fully homogenised samples ranging from 0.53 (K, bee, 20 mg) to 24% (As, 30 mg, bee) across the three matrices and all masses analysed. This small mass digestion method enables the analysis of a single bee allowing a more distinctive elemental signature to be determined. Similarly, pollen from fewer flowers of the same species can be pooled together which is advantageous for analysis of flowers that produce little pollen.