Total lead (Pb) concentration in oil shale ash samples based on correlation to isotope Pb-210 gamma-spectrometric measurements

Estonian oil shale consists of organic matter and mineral material and contains various amounts of heavy metals as well as natural radionuclides (from the U-238 and Th-232 series and K-40). Previous research has shown that burning oil shale in the large power plants causes these radionuclides to become enriched in different ash fractions and be partially emitted to the atmosphere via fly ash and flue gases. The activity concentrations (Bq/kg) of these nuclides in different oil shale ash fractions vary significantly. This is influenced by the boiler parameters and combustion conditions - prevailing temperatures, pressure, ash circulating mechanisms, fly ash particle size, chemical composition of ash and coexistence of macro and micro components. As with radionuclides, various heavy metals remain concentrated in the ash fractions and are released to the atmosphere (over 20 tons of Pb per year from Estonian oil shale power plants). Lead is a heavy metal with toxic influence on the nervous system, reproductive system and different organs in human body. Depending on the exposure pathways, lead could pose a long term health hazard. Ash samples are highly heterogeneous and exhibit great variability in composition and particle size. Determining the lead concentration in ash samples by modern methods like inductively coupled plasma mass spectroscopy (ICP-MS), flame atomic absorption spectrometry (FAAS), graphite furnace atomic absorption spectroscopy (GFAAS) and other techniques often requires time consuming, multistage and complex chemical sample preparation. The list of possible methods to use is lengthy, but it is a challenge to choose a suitable one to meet measurement needs and practical considerations. The detection limits, capital costs and maintenance expenses vary between the instruments. This work presents the development of an alternative measurement technique for our oil shale ash samples. Oil shale ash was collected from different boilers using pulverized fuel (PF) and circulating fluidized bed (CFB) firing technology. These samples were analyzed to determine macro and trace elements by the ICP-MS method. The same samples were also measured with a high-purity germanium detector (planar BSI GPD-50400) to determine the activity concentrations of natural radionuclides. The lead concentrations and Pb-210 activity concentrations were determined, and the correlation between the corresponding values was analyzed. Initial results demonstrate a strong positive linear relationship between these values, with the coefficient of determination (R2) over 94. The correlation coefficient (Pearson's, 'r') had a value over 0.95. Both Pb and Pb-210 values had an increasing trend from the bottom ash towards electrostatic precipitator (ESP) ashes. The strong linear correlation between Pb concentrations and Pb-210 activity concentrations gives a credible indication that lead can be measured in ash samples using its radioactive isotope Pb-210. Especially in situations where there are higher concentrations of Pb, for example in the case of wastes from the metallurgic and energy industries, this method could be used to detect the lead concentration quickly and with no chemical processing of the sample. Document available in abstract form only. (authors)