Evaluation of the analytical methods used to determine the elemental concentrations found in the stream geochemical dataset compiled for Alaska

A recent U.S. Geological Survey data compilation of stream-sediment geochemistry for Alaska contains decades of analyses collected under numerous Federal and State programs. The compiled data were determined by various analytical methods. Some samples were reanalyzed by a different analytical method than the original, resulting in some elements having concentrations reported by multiple analytical methods. Consideration of the analytical methods used to determine the elemental concentrations is an important step in a mineral prospectivity analysis. We used the compiled data to compare concentrations of barium (Ba), cobalt (Co), copper (Cu), chromium (Cr), nickel (Ni), lead (Pb), and zinc (Zn) determined by different analytical methods to show how simple data comparisons can identify bias and provide a general sense of the comparability of different analytical methods. The elements were selected because they have a range of geochemical properties that may affect the performance of different analytical procedures.

Generally, agreement between Ba, Co, Cu, Cr, Ni, Pb, and Zn concentrations is good for most quantitative methods that use a total decomposition of the sample. However, Cr concentrations typically were lower for methods using quantitative-instrumental analysis following a multi-acid dissolution technique that included hydrofluoric acid compared to those using sinter decomposition. Additionally, low- to middle-range concentrations for Co, Cr, Cu, Ni, Pb, and Zn by instrumental neutron activation (NA) and energy-dispersive x-ray spectroscopy (EDX) analyzed by the National Uranium Resource Evaluation (NURE) program have high uncertainty. Concentrations determined by methods that use partial decomposition of the sample generally correspond well to concentrations determined by methods that use a total decomposition technique, except for Ba and Cr. For Ba and Cr, partial decomposition techniques yield lower concentrations than those determined by methods that use a total decomposition technique. Comparison of Ba, Co, Cr, Cu, Ni, Pb, and Zn concentrations determined by semiquantitative visual six-step direct-current arc emission spectrography (ES_SQ) to those determined by quantitative methods using either a total or partial decomposition technique consistently show scatter that exceeds the values expected based on the range represented by the semiquantitative concentration.

The data compilation includes a best-value determination that was selected based on the analytical method from the all concentration data for that sample. Ba, Cr, Co, and Zn concentrations determined by NA usually are selected as the best-value determination. However, the NURE-NA method was designed for high throughput and the uncertainty associated with low- and mid-range concentrations is greater than that of the multi-acid method used to reanalyze many samples. Selection of the multi-acid method over the NURE-NA method for Ba, Co, and Zn could be warranted. Additionally, concentrations determined by ES_SQ usually are selected as the best-value determination over all methods that use a partial decomposition of the sample. Substitution of concentrations determined by methods that use a partial decomposition for those of ES_SQ may be warranted for Co, Cu, Ni, Pb, and Zn. Regardless of the selection of the best-value determination, the dataset remains a mixed method dataset and the uncertainty due to differences in analytical methodology must be considered when using the dataset.