Radionuclide concentration variations in the fuel and residues of oil shale-fired power plants: Estimations of the radiological characteristics over a 2-year period.

Several multi-day samplings were conducted over a 2-year period from an oil shale-fired power plant operating with pulverized fuel type of boilers that were equipped with either novel integrated desulphurization system and bag filters or with electrostatic precipitators. Oil shale, bottom ash and fly ash samples were collected and radionuclides from the 238U and 232Th series as well as 40K were determined. The work aimed at determining possible variations in the concentrations of naturally occurring radionuclides within the collected samples and detect the sources of these fluctuations. During the continuous multi-day samplings, various boiler parameters were recorded as well. With couple of exceptions, no statistically significant differences were detected (significance level 0.05) between the measured radionuclide mean values in various ash samples within the same sampling. When comparing the results between multiple years and samplings, no statistically significant variations were observed between 238U and 226Ra values. However, there were significant differences between the values in the fly ashes when comparing 210Pb, 40K, 228Ra and 232Th values between the various samplings. In all cases the radionuclide activity concentrations in the specific fly ash remained under 100 Bq kg-1, posing no radiological concerns when using this material as an additive in construction or building materials. Correlation analysis between the registered boiler parameters and measured radionuclide activity concentrations showed weak or no correlation. The obtained results suggest that the main sources of variations are due to the characteristics of the used fuel. The changes in the radionuclide activity concentrations between multiple years were in general rather modest. The radionuclide activity concentrations varied dominantly between 4% and 15% from the measured mean within the same sampling. The relative standard deviation was however within the same range as the relative measurement uncertainty, suggesting that the main component of fluctuations is derived from the measurement method and approach. The obtained results indicate that representativeness of the data over a longer time period is valid only when a fuel with a similar composition is used and when the combustion boilers operate with a uniform setup (same boiler type and purification system). The results and the accompanying statistical analysis clearly demonstrated that in order to obtain data with higher reliability, a repeated multi-day sampling should be organized and combined with the registered boiler technical and operational parameters.

Pb-210 and fly ash particles in ombrotrophic peat bogs as indicators of industrial emissions.

Peat cores were collected from a Sphagnum-dominated Selisoo bog, which is located about 40 km from the large oil shale-fired power plants (PPs) in Estonia. These PPs have been operational from the 1960's and had the largest negative impact on the surrounding environment during the 1970's and 1980's. Nearby ombrotrophic peatlands are good indicators of atmospheric pollution due to their properties of effectively adsorbing mineral matter and pollutants. Collected peat cores (S1 and S2) from Selisoo peat bog were sliced into 1 cm thick layers and measured gamma spectrometrically. In addition, spherical fly ash particles (SFAP) originating from the combustion of the PPs were counted. The maximum concentrations (particles per cm3) of the SFAP remained between 7 and 12 cm for core S1 and between 11 and 17 cm for core S2. The concentration profiles of the SFAP reflect the combustion and emission history of the PPs. Pb-210 activity concentrations have the maximum values up to 500 Bq kg-1 and 413 Bq m-2 for S1 and for the S2 the values are 441 Bq kg-1 and 535 Bq m-2 (dry weight). The unsupported 210Pb inventory is around 4250 Bq m-2. This represents a 210Pb deposition flux of 133 Bq m-2 y-1. The estimated 210Pb deposition via fly ash from the PPs at Selisoo area remains between 0.2 and 2.2 Bq m-2 y-1. Considering the annual 210Pb deposition from the atmosphere (with a precipitation rate of 600 mm y-1) between 92 and 133 Bq m-2, which is regarded as the natural background value, we show that the radiological burden due to the power plants at these distances is negligible. As the peat cores exhibit noticeable differences from each other (in terms of radionuclide concentration distribution), the SFAP can provide a good additional parameter to improve the validity of results obtained only from radiometric methods in the chronological studies. SFAP can also act as a possible tool to estimate the radionuclide deposition rate via fly ash in the vicinity of the PPs.

Behaviour mechanisms and correlation between lead (Pb) and its isotope (210)Pb in industrial residue as an indicator for waste characterization.

Total lead and (210)Pb concentrations were determined in various ash fractions (collected from two of the world's largest oil shale-fired power plants) by inductively coupled plasma mass-spectrometry (ICP-MS) and gamma spectrometry. Results show a clear increase in total lead (values up to 193 ppm in filter ashes) and (210)Pb (values up to 148 Bq kg(-1) in filter ashes) concentrations in the ash fractions from the furnace towards the filter ashes. A strong positive linear correlation (Pearson's bivariate correlation remained between 0.86 and 0.99) was determined between total lead concentration (ppm) and (210)Pb activity concentration (Bq kg(-1)) within all the boilers under observation. The constant concentration ratio between total lead and (210)Pb remained around one (with minor exceptions), independent of the sampling location and the used combustion technology. The determined concentration ratio can be applicable as an indicative tool in waste material characterization. It also provides multiple additions to the general material characterization approach, by integrating radiological and elemental studies and providing an option to rapidly obtain initial indicative information about the residues. This in turn helps to generate the initial information to work out the next steps in waste material management.

The enrichment behavior of natural radionuclides in pulverized oil shale-fired power plants.

The oil shale industry is the largest producer of NORM (Naturally Occurring Radioactive Material) waste in Estonia. Approximately 11-12 million tons of oil shale containing various amounts of natural radionuclides is burned annually in the Narva oil shale-fired power plants, which accounts for approximately 90% of Estonian electricity production. The radionuclide behavior characteristics change during the fuel combustion process, which redistributes the radionuclides between different ash fractions. Out of 24 operational boilers in the power plants, four use circulating fluidized bed (CFB) technology and twenty use pulverized fuel (PF) technology. Over the past decade, the PF boilers have been renovated, with the main objective to increase the efficiency of the filter systems. Between 2009 and 2012, electrostatic precipitators (ESP) in four PF energy blocks were replaced with novel integrated desulphurization technology (NID) for the efficient removal of fly ash and SO2 from flue gases. Using gamma spectrometry, activity concentrations and enrichment factors for the (238)U ((238)U, (226)Ra, (210)Pb) and (232)Th ((232)Th, (228)Ra) family radionuclides as well as (40)K were measured and analyzed in different PF boiler ash fractions. The radionuclide activity concentrations in the ash samples increased from the furnace toward the back end of the flue gas duct. The highest values in different PF boiler ash fractions were in the last field of the ESP and in the NID ash, where radionuclide enrichment factors were up to 4.2 and 3.3, respectively. The acquired and analyzed data on radionuclide activity concentrations in different PF boiler ashes (operating with an ESP and a NID system) compared to CFB boiler ashes provides an indication that changes in the fuel (oil shale) composition and boiler working parameters, as well as technological enhancements in Estonian oil shale fired power plants, have had a combined effect on the distribution patterns of natural radionuclides in the oil shale combustion products.

The enrichment of natural radionuclides in oil shale-fired power plants in Estonia--the impact of new circulating fluidized bed technology.

Burning oil shale to produce electricity has a dominant position in Estonia's energy sector. Around 90% of the overall electric energy production originates from the Narva Power Plants. The technology in use has been significantly renovated - two older types of pulverized fuel burning (PF) energy production units were replaced with new circulating fluidized bed (CFB) technology. Additional filter systems have been added to PF boilers to reduce emissions. Oil shale contains various amounts of natural radionuclides. These radionuclides concentrate and become enriched in different boiler ash fractions. More volatile isotopes will be partially emitted to the atmosphere via flue gases and fly ash. To our knowledge, there has been no previous study for CFB boiler systems on natural radionuclide enrichment and their atmospheric emissions. Ash samples were collected from Eesti Power Plant's CFB boiler. These samples were processed and analyzed with gamma spectrometry. Activity concentrations (Bq/kg) and enrichment factors were calculated for the (238)U ((238)U, (226)Ra, (210)Pb) and (232)Th ((232)Th, (228)Ra) family radionuclides and for (40)K in different CFB boiler ash fractions. Results from the CFB boiler ash sample analysis showed an increase in the activity concentrations and enrichment factors (up to 4.5) from the furnace toward the electrostatic precipitator block. The volatile radionuclide ((210)Pb and (40)K) activity concentrations in CFB boilers were evenly distributed in finer ash fractions. Activity balance calculations showed discrepancies between input (via oil shale) and output (via ash fractions) activities for some radionuclides ((238)U, (226)Ra, (210)Pb). This refers to a situation where the missing part of the activity (around 20% for these radionuclides) is emitted to the atmosphere. Also different behavior patterns were detected for the two Ra isotopes, (226)Ra and (228)Ra. A part of (226)Ra input activity, unlike (228)Ra, was undetectable in the solid ash fractions of the boiler. Most probably it is released to the surrounding environment.