Review of U and Th analysis—standards and methods

Introduction Zircon is a natural occurring mineral and may exhibit natural low level radioactivity. It contains trace levels (90 to120 pCi/g and 110 to 115 pCi/g respectively or 3.3 to 4.4Bq/g and 4.1 to 4.3 Bq/g) of naturally occurring radioactive uranium and thorium. This mineral is often found in a suiteof minerals (rutile, ilmenite and monazite) Due to the overlap in physical properties of monazite (containing 4–7% thorium) with some of the zircon (slight magnetic susceptibility) it often contaminates the zircon, adding to the levels of thorium in the product. Hazards associated with the products from zircon and its processing is inhalation of respirable dust (generated by milling) containing radioactive uranium and thorium which may cause cancer of the lungs. Legislature regulates the transport, use, workplace environment exposure and storage of radioactive material. In America the general regulation for the unlicensed use of low levels of radioactive materials limits the concentration to 500 ppm (U plus Th). Europe (IAEA) specifies a limit of10 Bg/g (Bequerels per gram) on the parents for transport only which is a higher level of U+Th. Companies selling into these markets need to comply with these regulations and certification is therefore required, not only of the major constituents determining the price, but of the U and Th levels as well. Exceeding the limits for U and Th may result in material being returned to the country of origin. However, for the analyst the requirement is to analyse for these elements throughout the production process as well as the analysis of the ‘tails’ that is returned to the mine area. This requires a wide range of concentration to be analysed. Methods of analysis A wide variety of methods exist for the analysis of U and Th in a range of matrices. (Table I) All these methods have been used with varying degrees of success in terms of accuracy. Overall precision for the different techniques varies from 5 to 25% relative. Time to produce results from these methods vary from a few minutes to several days. The Production Chemist is expected to produce between5 and 10 analyses per hour for process control purposes. A suitable technique that fits this requirement is X-Ray Fluorescence. Both Wavelength Dispersive (WDXRF) and Energy Dispersive X-Ray (EDX) instruments are suitable. X-Ray analysis in general has a few major advantages over competitive techniques. •It is fairly simple to set up and interferences are known and easy to correct •It has multi-element analysis capabilities •Clean spectral lines for U and Th (in zircon specifically) •Uncomplicated and easy to measure background •Low detection limits (3 to 5 ppm) •A very high degree of precision •Sample preparation is uncomplicated and fast (pressed powders and fused beads). In Zircon (ZrSiO4) processed sands the matrix is constant(>99% ZrSiO4) and the background is thus essentially constant. A typical set up for the analysis of U and Th by WDXRFis given below: X-Ray Tube Tungsten (W) Target, 2.5 to 3kW operated at 50mA/50kV Crystal LiF200 (or LIF220 for higher resolution) Analytical Lines (2?)U La1,226.14Th La1,227.47 Detector Scintillation Counter Analysis time, depending on the concentration can vary from as little as 20 seconds up to 5 minutes. Standards As with any other comparative technique XRF analysis relies heavily on the quality of the standards used. Assuming proper set-up and operation of the instrumentation as well as consistent sample preparation, accuracy is determined by the quality of the initial calibration standards. A search for the available zircon certified reference materials (CRMs) shows that there are only a few CRMs