On the solubility of radium sulfate and carbonate
Radium is one of the most toxic elements and its concentration in different human activities and migration from man-made wastes provokes a strong interest in environmental science. To be able to model the migration process, reliable experimental thermodynamic data of radium compounds are needed.
In this work details of the safe radium source disassembly which were previously used in brachytherapy are described and different methods for conversion of RaSO4 into aqueous solution are reviewed. The method of choice included three cycles of RaSO4 heating in 1.5 M Na2CO3 up to 85 oC, cooling and subsequent removal of supernatant. X-ray diffraction studies showed that the method allows the synthesis of amorphous RaCO3, which can be dissolved in mineral acid. Gamma spectrometric measurements showed that most of the initial RaSO4 was converted into solution and that 7 ± 1 % of the initial 210Pb was co-precipitated with RaCO3. Synthesized RaCO3 was dissolved in HCl to prepare a radium stock solution. 
The radium stock solution was used to determine the solubility of pure RaSO4 and RaCO3 from oversaturation using Na2SO4 and Na2CO3 as a source of sulfate and carbonate ions. The solubility was determined at 25.1 oC as a function of ionic strength using NaCl media. The concentration of radium was measured by gamma spectrometry after separation of the aqueous phase from the solid phase using ultracentrifugation. The extended specific ion interaction theory was used to extrapolate solubility product constants to zero ionic strength (log10 Ksp° = -10.16 ± 0.05 for RaSO4 and log10 Ksp° = -7.73 ± 0.56 for RaCO3) and to calculate ion interaction coefficients.
A comparison of the shapes of the radium solubility curves for both anions with the shapes of corresponding barium solubility curves demonstrates the similarity of the behaviour of radium and barium salts in saline solutions. It can be supposed that due to the similarity of the radium and barium effective ionic radii, and the same charge, these ions undergo similar specific ion interactions in NaCl media.
Gross alpha/beta radioactivity and radiation dose in thermal and non-thermal spas groundwaters
Gross alpha and gross beta activities have been determined in thermal and non-thermal spas groundwaters (75) occurring at São Paulo and Minas Gerais states in Brazil as they are ingested in public places, bottled and used for bathing purposes, among other. The samples provided from springs and pumped tubular wells drilled at different aquifer systems inserted in Paraná and Southeastern Shield hydrogeological provinces. The WHO guideline reference value proposed in 2011 for the drinking water quality was never reached for the gross alpha activity (0.5 Bq/L) but it was exceeded in 13 groundwater samples for the gross beta activity (1 Bq/L). Available activity concentration data of the natural radionuclides 40K, 228Ra (232Th-daughter), 238U and descendants (234U, 226Ra, 222Rn, 210Pb, 210Po) allowed calculate the total Committed Effective Dose (CED) based on a drinking water ingestion rate of 2 L/day. The WHO reference level of 0.1 mSv per year for the CED was surpassed in a high number of water sources (62 (83%) or 41 (55%), disregarding radon), denoting the relevance of the radiological surveys detailing as much as possible the dissolved radionuclides present in potable waters, despite the analytical difficulties and costs involved.
An Ultrasensitive Analytical Method Based on Chemiluminescence Sensing Electrochemical Parallel Catalytic Reaction Event
An ultrasensitive electrochemiluminescence (ECL) method on the combination of electrochemical parallel catalytic reaction and chemiluminesence signal sensing was proposed for improving ECL analytical characteristics using vanadate(V) as a representative. Vanadate(V) could be electrochemically reduced to generate vanadate(II) which could be chemically oxidized by potassium periodate to regenerate vanadate(V) and give parallel catalytic wave effect. Then, the reduced product of potassium periodate could react with butyl-rhodamine B to emit a sensitive chemiluminescence signal. The chemiluminescence intensity was correlative with vanadate(V) concentration. The investigation on the electrochemical reaction rate constant (k0) confirmed that the speed of electrochemical reaction was faster than that of the subsequent chemiluminescence reaction. The possibility of the combination of electrochemical parallel catalytic reaction with chemiluminescence signal sensing was proved. The similar ECL behaviors could be observed at zirconia nanowires-Nafion modified electrode. Because of the separation and enrichment effect of the modified electrode on vanadate(V), the selectivity and sensitivity was further improved greatly. Based on these findings, a new concept on the combination of electrochemical parallel catalytic reaction and chemiluminesence signal sensing was proposed and an ultrasensitive ECL method for the determination of vanadate(V) was developed at zirconia nanowires-Nafion modified electrode. Under the optimum experimental conditions, the ECL intensity was linear with the concentration of vanadate(V) in the range of 2.0×10−12 mol/L–2.0×10−10 mol/L. The detection limit was 8.0×10−13 mol/L, which was more than 6 orders of magnitude lower than that observed by electrochemical current transduction for electrochemical parallel catalytic reaction at zirconia nanowires-Nafion modified electrode.