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.
Dissociation constants of radium-organic acid complexes measured by ion exchange.
In neutral media the cations of the alkaline earth elements form partially dissociated complex ions with many weak organic acids, particularly those involved in the tricarboxylic acid cycle. Quantitative measurements of the extent of this association are fundamental for the elucidation of the chemical, biochemical, and metabolic behavior of the alkaline earth and other elements. The dissociation constants of Mg, Ca, Sr, and Ba complexes with citrate or numerous other organic acids have been determined by methods such as the frog heart preparation (l), solubility, potentiometric titrations, and other electromotive force procedures. As far as we can ascertain, no measurements of the dissociation constants of radium complexes have been reported. This is understandable in view of the hazardous and destructive action of the radiations emitted by high radium concentrations. These difficulties are avoided in the ion exchange method (2) for measuring dissociation constants because less than microcurie quantities of one of the components is required. The ion exchange technique has been used for studying the citrate and tartrate complexes of alkaline earth and rare earth elements (3-5). In this paper we shall report on the stability of the complexes formed between radium and several organic acids. In addition, we shall present an improved formulation of the equations used for calculating dissociation constants from ion exchange equilibria.
Electrochemical detection of copper(II) at a gold electrode modified with a self-assembled monolayer of penicillamine
A penicillamine (PCA) self-assembled monolayer (SAM) was prepared on a gold electrode. It has been found that the modified electrode exhibited a selective response to copper ions. As demonstrated by cyclic voltammetric experiments, the SAM-based electrode showed an attractive ability to preconcentrate efficiently traces of copper(II) from solutions. Under optimum conditions, the anodic peak current was proportional to the concentration of Cu(II) in the range from 8.0 × 10−7 to 1.0 × 10−4 M with a detection limit of 4.0 × 10−7 M. Moreover, this modified gold electrode is also characterized by excellent repeatability, showing a relative standard deviation of 3.2% for nine successive measurements of 1.0 × 10−5 M Cu(II). The PCA/Au SAM gold electrode was used for the determination of Cu(II) in a tap water sample and the results showed a good agreement with the data obtained by atomic emission spectrometry.