Enrichment of naturally occurring radionuclides and trace elements in Yatagan and Yenikoy coal-fired thermal power plants, Turkey.

Coal, residues and waste produced by the combustion of the coal contain naturally occurring radionuclides such as 238U, 226Ra, 210Pb, 232Th and 40K and trace elements such as Cd, Cr, Pb, Ni and Zn. In this work, coal and its combustion residues collected from Yatagan and Yenikoy coal fired thermal power plants (CPPs) in Turkey were studied to determine the concentrations of natural radionuclides and trace elements, and their enrichments factors to better understand the radionuclide concentration processes within the combustion system. In addition, the utilization of coal fly ash as a secondary raw material in building industry was also studied in terms of radiological aspects. Fly ash samples were taken at different stages along the emission control system of the thermal power plants. Activity concentrations of naturally occurring radionuclides were determined with Canberra Broad Energy Germanium (BEGe) detector BE3830-P and ORTEC Soloist PIPS type semiconductor detector. The particle size distribution and trace elements contents were determined in various ash fractions by the laser scattering particle size distribution analyzer and inductively coupled plasma (ICP-OES). From the obtained data, natural radionuclides tend to condense on fly ash with and the activity concentrations increase as the temperature drop in CPPs. Measured 210Pb and 210Po concentration varied between 186 ± 20-1153 ± 44 Bq kg-1, and 56 ± 5-1174 ± 45 Bq kg-1, respectively. The highest 210Pb and 210Po activity concentrations were determined in fly ash taken from the temporary storage point as 1153 ± 44 Bq kg-1 and 1174 ± 45 Bq kg-1, respectively. There were significant differences in the activity concentrations of some natural radionuclide and trace elements (Pb and Zn) contents in ash fractions among the sampling point inside both of the plants (ANOVA, p < 0.001). Coal and ash sample analysis showed an increase activity concentration and enrichment factors towards the electrostatic precipitators for both of the power plants. The enrichment factors for Zn follow a similar trend as Pb, increasing in value towards the end of the emission control system. The calculated activity indexes were above 1.0 value for both of the power plants, assuming the utilization of fly ash at 100%. It can be concluded that the reuse of fly ash as a secondary raw material may not be hazardous depending on the percentage of utilization of ash.

Long-term monitoring of water treatment technology designed for radium removal-removal efficiencies and NORM formation.

A drinking water treatment plant in Viimsi, Estonia, was monitored over three years for iron, manganese, radium-226, radium-228, as well as their daughter nuclides, in order to determine the efficiency of the treatment process, gain an insight into the removal mechanisms and interactions between radium, iron, and manganese, and assess the overall longevity and performance of the technology along with the possible build-up of NORM in the treatment process. During the study, samples were collected from raw water, first and second stage filtrate, consumer water, backwash water and filter materials. The results show consistent removal efficiency for iron and manganese, as well as an average of over 85% removal for radium with a slight decline over time. The backwash process has been optimised for maximum radium removal from the filters, while keeping concentrations in the backwash water below exemption levels. However, the accumulation of radium and thorium occurs in the filter material, exceeding exemption levels in the top layer of the filter columns in less than a year. By the end of the observation period, activity concentrations in the top layer of the columns were above 30 000 Bq kg-1 for Ra-226 and Ra-228, and around 15 000 Bq kg-1 for Th-228. Radionuclides are not homogenously distributed in the filter columns. In order to estimate the average activity concentrations in the filter media, the height distribution of radionuclides has to be accounted for. Two years and two months after commissioning the treatment plant, the average activity concentrations of Ra isotopes in the filter columns were in the range 10 000 Bq kg-1, while Th-228 activity concentration was roughly 3500 Bq kg-1.

Long-term monitoring of a water treatment technology designed for radium removal - removal efficiencies and NORM formation.

A drinking water treatment plant in Viimsi, Estonia was monitored over three years for iron, manganese, radium-226, radium-228, and their daughter nuclides in order to determine the efficiency of the treatment process, get an insight of the removal mechanisms and interactions between radium, iron, and manganese, and assess the overall longevity and performance of the technology and possible build-up of NORM from the treatment process. During the study, samples were collected from raw water, first and second stage filtrate, consumer water, backwash water, and filter materials. The results show a consistent removal efficiency for iron and manganese, as well as an average of over 85% removal for radium with a slight decline with time. Backwash process has been optimized for maximum radium removal from the filters, while keeping the radium concentrations in the backwash water below exemption levels. However, accumulation of radium and thorium occurs in the filter material, exceeding exemption levels in the top layer of the filter columns in less than a year. By the end of the observation period, activity concentrations in the top layer of the columns were above 30 000 Bq/kg for Ra-226 and Ra-228, and around 15 000 Bq/kg for Th-228. Radionuclides are not homogenously distributed in the filter columns. In order to estimate the average activity concentrations in the filter media, the height distribution of radionuclides has to be accounted for. Two years and two months after commissioning of the treatment plant average activity concentrations of Ra isotopes in the filter columns were in a range of 10 000 Bq/kg while Th-228 activity concentration was roughly 3500 Bq/kg.

Long-term modelling of fly ash and radionuclide emissions as well as deposition fluxes due to the operation of large oil shale-fired power plants.

Two of the world's largest oil shale-fired power plants (PPs) in Estonia have been operational over 40 years, emitting various pollutants, such as fly ash, SOx, NOx, heavy metals, volatile organic compounds as well as radionuclides to the environment. The emissions from these PPs have varied significantly during this period, with the maximum during the 1970s and 1980s. The oil shale burned in the PPs contains naturally occurring radionuclides from the 238U and 232Th decay series as well as 40K. These radionuclides become enriched in fly ash fractions (up to 10 times), especially in the fine fly ash escaping the purification system. Using a validated Gaussian-plume model, atmospheric dispersion modelling was carried out to determine the quantity and a real magnitude of fly ash and radionuclide deposition fluxes during different decades. The maximum deposition fluxes of volatile radionuclides (210Pb and 210Po) were around 70 mBq m-2 d-1 nearby the PPs during 1970s and 1980s. Due to the reduction of burned oil shale and significant renovations done on the PPs, the deposition fluxes were reduced to 10 mBq m-2 d-1 in the 2000s and down to 1.5 mBq m-2 d-1 in 2015. The maximum deposition occurs within couple of kilometers of the PPs, but the impacted area extends to over 50 km from the sources. For many radionuclides, including 210Po, the PPs have been larger contributors of radionuclides to the environment via atmospheric pathway than natural sources. This is the first time that the emissions and deposition fluxes of radionuclides from the PPs have been quantified, providing the information about their radionuclide deposition load on the surrounding environment during various time periods.

Pb-210 and Po-210 atmospheric releases via fly ash from oil shale-fired power plants.

During high temperature processes in the furnace volatile and semi-volatile elements and radionuclides are partially emitted to the environment, depending on their chemical form in the original fuel, the technological set-up of the combustion system, and the prevailing combustion conditions. Two of the world's largest oil shale-fired power plants (PPs) have been operational in Estonia from the 1960s, during which time creation of significant environmental emissions and waste containing naturally occurring radionuclides has occurred. Pb-210 and 210Po are considered natural radionuclides with the highest emission rates from PPs and possess elevated potential radiation exposure risks to humans and the environment. These radionuclides have the highest activity concentration values in fine ash fractions, especially in fractions remaining below 2.5 µm. To determine the activity concentrations of 210Pb and 210Po in the PPs' outlet, sampling was conducted from boilers operating on pulverized fuel (PF) technology with novel integrated desulphurization (NID) system and bag filters as well as with electrostatic precipitators (ESPs). The 210Pb and 210Po activity concentrations remained around 300 Bq kg-1 for the NID system compared to 60-80 Bq kg-1 in the ESP system. The dominant ash fraction in both systems was PM2.5, constituting over 50% of the fly ash mass collected from the outlet. The authors estimate that the total atmospherically emitted activity for the modernized PPs remains dominantly below 1% of the activity that is inserted via fuel. The implementation of higher efficiency purifications systems has significantly reduced the negative effect of these PPs. Based on annually emitted fly ash and boilers' working hours, the 210Pb and 210Po activity released relative to energy production were up to 68.3 kBq GWhel-1 for 210Pb and 64.6 kBq GWhel-1 for 210Po. These values are 1 to 2 orders of magnitude lower compared to the situation in the 1980s. These findings represent the first publicly available quantitative results estimating the 210Po emissions from large oil shale-fired PPs.

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.