Geochemical sampling problems in the analytical laboratory

There have been very few attempts to isolate the various factors that contribute to the overall imprecision of geochemical analytical procedures, due in part to the difficulty of distinguishing between them. The technique of spark source mass spectrography permits a ready distinction between the contributions to overall precision from sampling error and instrumental and other errors. With conventional methods of sample preparation for this technique sampling difficulties are responsible for 80-90 per cent of the overall imprecision. Examination of the probable location of the major difficulties in sample preparation indicates that the preliminary stage of grinding, mixing and extraction of a first aliquot (about 1/100 of the original sample) is generally perfectly adequate. The difficulty lies in the subsequent stages of sample preparation. Dry mixing techniques are unlikely to give good precision if the sub-samples actually examined by the analytical technique are less than 10 mg in amount. Solution techniques are less prone to sampling difficulty. Fusion techniques, unless conducted with great care, can produce more difficulty than dry mixing. Sample preparation is critical to the success of many analytical procedures. Selection of appropriate sample preparation techniques requires just as much care as the selection of techniques for the actual analysis.