Thermodynamic study of the complexation of protactinium(V) with diethylenetriaminepentaacetic acid.

The complex formation of protactinium(V) with DTPA was studied at different temperatures (25-50 °C) and ionic strengths (0.1-1 M) with the element at tracer scale. Irrespective of the temperature and ionic strength studied, only one neutral complex with (1:1) stoichiometry was identified from solvent extraction and capillary electrophoresis coupled to ICP-MS (CE-ICP-MS) experiments. Density Functional Theory (DFT) calculations revealed that two complexes can be considered: Pa(DTPA) and PaO(H2DTPA). The associated formation constants were determined from solvent extraction data at different ionic strengths and temperatures and then extrapolated to zero ionic strength by SIT methodology. These constants are valid, regardless of complex form, Pa(DTPA) or PaO(H2DTPA). The standard thermodynamic data determined with these extrapolated constants revealed a very stable complex formed energetically by an endothermic contribution which is counter balanced by a strong entropic contribution. Both, the positive enthalpy and entropy energy terms suggest the formation of an inner sphere complex.

New insights into formation of trivalent actinides complexes with DTPA.

Complexation of trivalent actinides with DTPA (diethylenetriamine pentaacetic acid) was studied as a function of pcH and temperature in (Na,H)Cl medium of 0.1 M ionic strength. Formation constants of both complexes AnHDTPA(-) and AnDTPA(2-) (where An stands for Am, Cm, and Cf) were determined by TRLFS, CE-ICP-MS, spectrophotometry, and solvent extraction. The values of formation constants obtained from the different techniques are coherent and consistent with reinterpreted literature data, showing a higher stability of Cf complexes than Am and Cm complexes. The effect of temperature indicates that formation constants of protonated and nonprotonated complexes are exothermic with a high positive entropic contribution. DFT calculations were also performed on the An/DTPA system. Geometry optimizations were conducted on AnDTPA(2-) and AnHDTPA(-) considering all possible protonation sites. For both complexes, one and two water molecules in the first coordination sphere of curium were also considered. DFT calculations indicate that the lowest energy structures correspond to protonation on oxygen that is not involved in An-DTPA bonds and that the structures with two water molecules are not stable.

Using biofilms for monitoring metal contamination in lotic ecosystems: The protective effects of hardness and pH on metal bioaccumulation.

Biofilms can make good bioindicators and biomarkers, offering a convenient tool to monitor metal contamination in streams that results from mine tailing sites. Biofilm metal content (Cu, Zn, Cd, Pb) as well as diatom diversity and the presence of teratologies (diatom abnormalities) were determined for biofilms from rivers with a variety of physicochemical properties across a metal contamination gradient. The results of metal accumulation were highly consistent from year to year, with significant relationships between calculated free metal ion concentrations and biofilm metal contents for samples from different rivers. This indicates the "universal nature" of the metal accumulation process in biofilms. The authors observed that protons and major cations protected against metal accumulation. A very low number of diatom taxa were found at the most contaminated sites, and the highest proportions of deformities were observed at these sites. However, it was difficult to distinguish the effect of metal contamination from the effect of other parameters, especially pH. The results suggest that the development of biofilm-based proxies for metal bioavailability is useful and that incorporation of the effects of hardness and pH in this metal contamination monitoring tool is important. Environ Toxicol Chem 2016;35:1489-1501. © 2015 SETAC.