Graphical Discrimination of New Zealand Honey from International Honey Using Elemental Analysis.

This study investigated the potential of utilising the elemental fingerprinting of honey to differentiate New Zealand (NZ) honey from that of international origin. Twenty elements were analysed by ICP-MS in 352 honeys from 34 various countries. Of these, 323 honeys (245 New Zealand honeys, 78 international) and two subsets of data (NZ and European origin, n = 306, and, NZ and Denmark/Germany, n = 280) were visualised using principal component analysis (PCA). For the NZ/Europe subset, 42.2% of data was explained in the first two principal components. Statistical classification rules were also derived using linear discriminant analysis (LDA) and decision tree analysis. Various combinations of elements were explored for classification, considering the effect of soil-derived elements and those from anthropogenic sources. A high degree of accuracy (at least 90%) for the characterisation of New Zealand honey was observed for all statistical models, showing the robustness of these analyses. When using decision tree analysis to distinguish New Zealand samples from international samples, a tree with five terminal nodes (using Cs, Ba and Rb) was created with 92.4% accuracy. This work has demonstrated that elemental fingerprints of honey are a promising tool for categorising New Zealand honey from other geographical locations.

Investigation of inorganic elemental content of honey from regions of North Island, New Zealand.

Determination of geographical origin of honey is important to consumers to confirm authenticity. This study investigated the elemental fingerprint of 181 honey samples collected from apiary sites in six regions of North Island, New Zealand to determine if differences were observed due to region of collection or land use surrounding the hive (e.g. agricultural, rural, urban). Using principal component analysis, soil related elements (Ca, K, Mg, Mn, Na) provided 75.2% discrimination of samples in the first two principal components. Overall, low concentrations of heavy metals were observed; lead was present in close proximity to highly trafficked roads (28.1% of samples; 9.50-76.5 µg kg-1) and cadmium was primarily present in honey collected from agricultural land in the Waikato (<51.6 µg kg-1). The use of an elemental fingerprint of New Zealand honey may be advantageous to determine the geographical origin compared to honey produced from other countries.

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-1 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.