Assessing the Accuracy and Precision of Inorganic Geochemical Data Produced through Flux Fusion and Acid Digestions: Multiple (60+) Comprehensive Analyses of BHVO-2 and the Development of Improved “Accepted” Values

Abstract:

The use of geological standard reference materials (SRMs) to assess both the accuracy and the reproducibility of geochemical data is a vital consideration in determining the major and trace element abundances of geologic, oceanographic, and environmental samples. Calibration curves commonly are generated that are predicated on accurate analyses of these SRMs. As a means to verify the robustness of these calibration curves, a SRM can also be run as an unknown item (i.e., not included as a data point in the calibration). The experimentally derived composition of the SRM can thus be compared to the certified (or otherwise accepted) value. This comparison gives a direct measure of the accuracy of the method used. Similarly, if the same SRM is analyzed as an unknown over multiple analytical sessions, the external reproducibility of the method can be evaluated.

Two common bulk digestion methods used in geochemical analysis are flux fusion and acid digestion. The flux fusion technique is excellent at ensuring complete digestion of a variety of sample types, is quick, and does not involve much use of hazardous acids. However, this technique is hampered by a high amount of total dissolved solids and may be accompanied by an increased analytical blank for certain trace elements. On the other hand, acid digestion (using a cocktail of concentrated nitric, hydrochloric and hydrofluoric acids) provides an exceptionally clean digestion with very low analytical blanks. However, this technique results in a loss of Si from the system and may compromise results for a few other elements (e.g., Ge). Our lab uses flux fusion for the determination of major elements and a few key trace elements by ICP-ES, while acid digestion is used for Ti and trace element analyses by ICP-MS.

Here we present major and trace element data for BHVO-2, a frequently used SRM derived from a Hawaiian basalt, gathered over a period of over two years (30+ analyses by each technique). We show that both digestion techniques are well suited to our applications and that it is possible to achieve a high degree of accuracy and reproducibility using a combination of these methods. For elements analyzed by both digestions and instruments, agreement is strong. Lastly, we recommend new and improved elemental concentrations for BHVO-2 based on our analyses and literature/database values.