A metallurgical assay is a compositional analysis of an ore, metal, or alloy, usually performed in order to test for purity or quality. Some assay methods are suitable for raw materials; others are more appropriate for finished goods. Raw precious metals (bullion) are assayed by an assay office. Silver is assayed by titration, gold by cupellation and platinum by inductively coupled plasma optical emission spectrometry (ICP OES). Precious metal items of art or jewelry are frequently hallmarked (depending upon the requirements of the laws of either the place of manufacture or the place of import). Where required to be hallmarked, semi-finished precious metal items of art or jewelry pass through the official testing channels where they are analyzed or assayed for precious metal content. While different nations permit a variety of legally acceptable finenesses, the assayer is actually testing to determine that the fineness of the product conforms with the statement or claim of fineness that the maker has claimed (usually by stamping a number such as 750 for 18k gold) on the item. In the past the assay was conducted by using the touchstone method but currently (most often) it is done using X-ray fluorescence (XRF). XRF is used because this method is more exacting than that of a touchstone test. The most exact method of assay is known as fire assay or cupellation. This method is better suited for the assay of bullion and gold stocks rather than works of art or jewelry because it is a completely destructive method.
Touchstone The touchstone method is most common by far and does not damage the item in question. A rubbing of the item is made on a special stone, treated with acids and the result is compared to the result of the same process done on a sample of gold with a known purity. Red radiolarian chert or black siliceous slate were used for this. Differences in precious metal content as small as 10 to 20 parts per thousand can often be established with confidence by the test, using acids and gold samples both of a specific, known concentration.
X-ray fluorescence
The modern X-ray fluorescence (XRF) is also a non-destructive technique that is suitable for normal assaying requirements. It typically has an accuracy of 2 to 5 parts per thousand and is well-suited to relatively flat and large surfaces. It is a quick technique taking about three minutes, and the results can be automatically printed out by computer. One process for X-ray fluorescence assay involves melting the material in a furnace and stirring to make a homogeneous mix. Following this, a sample is taken from the centre of the molten sample. Samples are typically taken using a vacuum pin tube. The sample is then tested by X-ray fluorescence spectroscopy. For quantitative XRF assays, calibration and control of sample geometry and matrix effects are important for reliable results.
Fire assay/cupellation
The most elaborately accurate, but totally destructive, precious metal assay is fire assay. (It may also be called by the critical cupellation step that separates precious metal from lead.) If performed on bullion to international standards, the method can be accurate on gold metal to 1 part in 10,000. If performed on ore materials using fusion followed by cupellation separation, detection may be in parts per billion. However, accuracy on ore material is typically limited to 3 to 5% of reported value. Although time-consuming, the method is the accepted standard applied for valuing gold ore as well as gold and silver bullion at major refineries and gold mining companies. In the case of fire assaying of gold and platinum ores, the lengthy time required to carry out an assay is generally offset by carrying out large numbers of assays simultaneously, and a typical laboratory will be equipped with several fusion and cupellation furnaces, each capable of taking multiple samples, so that several hundred analyses per day can be carried out. The principal advantage of fire assay is that large samples can be used, and these increase the accuracy in analyzing low-yield ores in the <1g/T range of concentration.
Fusion: the process requires a self-generating reducing atmosphere, and so the crushed ore sample is mixed with fluxes and a carbon source (e.g. coal dust, ground charcoal, flour, etc.) mixed with powdered lead oxide (litharge) in a refractory crucible. In general, multiple crucibles will be placed inside an electric furnace fitted with silicon carbide heating elements, and heated to between 1,000 and 1,200 °C. The temperature required, and the type of flux used, are dependent on the composition of the rock in which the precious metals are concentrated, and in many laboratories an empirical approach based on long experience is used. A complex reaction takes place, whereby the carbon source reduces the lead oxide to lead, which alloys with the precious metals: at the same time, the fluxes combine with the crushed rock, reducing its melting point and forming a glassy slag. When fusion is complete, the sample is tipped into a mold (usually iron) where the slag floats to the top, and the lead, now alloyed with the precious metals, sinks to the bottom, forming a 'button'. After solidification, the samples are knocked out, and the lead bullets recovered for cupellation, or for analysis by other means. Method details for various fire assay procedures vary, but concentration and separation chemistry typically comply with traditions set by Bugby or Shepard & Dietrich in the early 20th century. Method advancements since that time primarily automate material handling and final finish measurements (i.e., instrument finish rather than physical gold product weighing). Arguably, even these texts are largely an extension of traditions that were detailed in De re metallica by Agricola in 1556. Variation from skills taught in modern standard adaptations of fire assay methodology should be viewed with caution. The standard traditions have a long history of reliability; "special" new methods frequently associate with reduced assay accuracy and fraud.
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