Radium-Bearing Waters In Coal Mines: Occurence, Methods Of Measurement And Radiation Hazard

INTRODUCTION Radioactive deposits were observed in 1972 in some of the Upper Silesian coal mines. They were located mainly in the drains in galeries and on the inside surfaces of water pipes. They also caused some problems by accumulating in water pumps. It has been postulated that the deposits are produced by natural radioactive waters seeping from the rocks. Investigations were initiated to answer the following questions: - What is the composition and the amount of radioactivity in the deposits? - What radioisotopes are present in the water? - How are the radioactive deposits formed? - Do the radioactive waters also occur in other mines? - How does the radioactivity of the water depend on chemical composition? - What is the origin of the radioactive water? - Does the water and the deposits cause radiation hazards for miners? -How can the radiation hazard be reduced? METHODS OF MEASUREMENT Determination of Radium Isotopes in Water The commonly used methods of radium determination in water are either based on measurements of the radioactivity of 222Rn which is in equilibrium with 226Ra, or on the detection of alpha particles of the radium radioisotopes after chemical separation of radium from the water sample. The method based on radon activity measurements is very sensitive and does not require any chemical Separation, but it can be used for determination of 226Ra from the uranium series only, because the thorium daughter 220Rn has too short a half-life (55s to yield the required accuracy. The method developed by Goldin, 1961 [2] involved alpha-particle measurements in thin layers of RaS04 and BaS04 separated from the water. This method is not convenient for saline water and water with high barium concentration because the amount of barium carrier in this case is too large to obtain a thin layer of precipitate with sufficient activity. The Upper Silesian carboniferous waters are often saline with high barium content, so the method described by Goldin was not convenient for this case and it was necessary to change the detection system and modify the chemical preparation. The procedure developed by the authors for the determination of radium isotopes in water was as follows: - Depending on the Ba2+ content and the required sensitivity of measurement, a water sample of 200 cm3 to 3 dm3 was taken. - 10 cm3 of 0.25 M citric acid and 5 cm3 15M ammonia was added to form complex Ba2+ ions and avoid the immediate precipitation of BaSO4. (This was repeated as long as the addition of BaC12 did not form a precipitate.) - 1 cm3 of 1N solution of Pb(N03)2 as a carrier for radioactive isotopes of lead and 10 cm3 of 0.1 N BaC12 as a carrier for radium were added. - The sample was heated to the boiling point and the precipitation of RaS04, BaSO4 and PbS04 with 50% H2SO4 was carried out. - After several hours the sample was centrifuged and the precipitate was purified by washing with nitric acid and distilled water. - The precipitate was then redisolved in 20 cm3 0.125 M Na2EDTA and 3 cm3 6M ammonia and reprecipitated from the solution by dropwise addition of acetic acid to d pH of 4.5. At this value of pH, precipitation occurs only for the barium and radium sulfates, while lead and all other radioactive elements remain in the solution. The date and time of deposit precipitation was recorded. - The final barium-radium sulfate mixture was washed with distilled water and transferred to standard measurement vials. - Each vial containing a deposit had 6 cm3 of distilled water added and was then shaken vigorously. 12 cm3 of liquid gelling scintillator (INSTA-GEL UNISOLV-1 type) was then added and the vi 1 was shaken again. After a while the scintillator turns into a milky gel in which the deposit is uniformly distributed. - The standard sample of 226Ra was prepared in the same way. - The activity of the samples was measured using a liquid scintillation spectrometer. (In this case the TRICARB 3320 produced by Packard Instruments, was used). Tests run on standard radium solutions provided by Amersham Radiochemical Centre indicated that this method of measurement enables one to achieve an efficiency of almost 100% (within measurement error). For alpha particles no quenching effect was observed for the BaS04 concentration in the range up to 80 mg of BaS04 per 1 cm3 of liquid scintillator coctail (Fig. 1). This provides a sensitive determination of radium in water with high barium content and also in saline water. In saline water the solubility of barium sulfate is much higher than in