Authors:Kamalika Sen, Wouter Breeman, and H. Wolterbeek
The present article describes the probable speciation of 68Ga radionuclide just before labeling to DOTA peptides for PET imaging. The 68Ga eluted from an anion exchange column after its purification was analyzed for its elemental composition and pH at several
stages. Neutron activation analysis of the eluted fractions yields the concentrations of Na and Cl, pH measurements indicate
the concentration of free H+ ions in the medium and specific activity calculations indicate the concentration of 68Ga in the solution. Using all these information we get the idea of speciation of no carrier added Ga in the eluted fractions
from CHEAQS programme. The estimations indicate that Ga is mostly present as GaCl2+ in the total MiliQ eluate. However, just before labeling of DOTA the pH of the Ga-containing eluate is adjusted to ~3.5 using
HEPES buffer and at that condition Ga remains as Ga3+ species which is responsible for a successful and efficient labeling. The MilliQ eluate collected before actual labeling
was estimated for trace elements using inductively coupled plasma atomic emission spectrometry was found to contain a few
ppb of Al, Co, Pd and Pt that did not interfere in the actual labeling. A clear idea about the prerequisite of 68Ga species before labeling to a peptide might be of special interest for its judicious application as a radiopharmaceutical.
Authors:Nils Baumann, Thuro Arnold, and Martin Lonschinski
In situ leaching of uranium ores with sulfuric acid during active uranium mining activity on the Gessenheap has caused longstanding
environmental problems of acid mine drainage and elevated concentrations of uranium. To study there remediation measures the
test site Gessenwiese, a recultivated former uranium mining heap near Ronnenburg/East Thuringia/Germany, was installed as
a part of a research program of the Friedrich-Schiller University Jena to study, among other techniques, the phytoremediation
capacity of native and selected plants towards uranium. In the first step the uranium speciation in surface seepage and soil
pore waters from Gessenwiese, ranging in pH from 3.2 to 4.0, were studied by time-resolved laser-induced fluorescence spectroscopy
(TRLFS). Both types of water samples showed mono-exponential luminescence decay, indicating the presence of only one major
species. The detected emission bands were found at 477.5, 491.8, 513.0, 537.2, 562.3, and 590.7 nm in case of the surface
water samples, and were found at 477.2, 493.2, 513.8, 537.0, 562.4, and 590.0 nm in case of the soil water samples. These
characteristic peak maxima together with the observed mono-exponential decay indicated that the uranium speciation in the
seepage and soil pore waters is dominated by the uranium (VI) sulfate species UO2SO4(aq). Due to the presence of luminescence quenchers in the natural water samples the measured luminescence lifetimes of the UO2SO4(aq) species of 1.0–2.6 μs were reduced in comparison to pure uranium sulfate solutions, which show a luminescence lifetime of
4.7 μs. These results convincingly show that in the pH range of 3.2–4.0 TRLFS is a suitable and very useful technique to study
the uranium speciation in naturally occurring water samples.
Authors:Věra Jedináková-Křížová, Josef Zeman, Hana Vinšová, and Eduard Hanslík
The contribution is focused on chemical, geochemical and mineralogical research of bentonite stability with the aim to determine
the effect of saturation medium composition and loading by heat on bentonite stability. The main part of the research is directed
to the experimental results of bentonite and bentonite leachate samples obtained for the bentonite interaction under laboratory
experiments. Computer-modeling methods were used to calculate equilibrium thermodynamic principles, the distributions of predominant
aqueous species, and potential solubility controls for the environmentally important oxidation states of each investigated
radioactive contaminants. The Eh–pH diagrams of individual chemical species of the tested radionuclides were calculated by
the geochemical software tool Geochemist’s Workbench that included the actual chemical compositions of the solid–liquid systems
under the given experimental conditions. It was confirmed that smectites are transformed to more stable silicate phases, such
as illite/smectite mixed layers, illite. The data obtained from the model calculations conform with experimental results.
The effect of the variable aqueous phase composition on bentonite stability using Ca–Mg and Na–Ca bentonites for the experiments
was studied. The synthetic granitic waters with the higher concentration of the K+ and Mg2+ cations were applied for the study of bentonite stability.
Knowledge of the oxidation state distribution of plutonium in natural waters is necessary in modeling its behavior in environmental systems. The redox speciation of plutonium is complicated by such effects as hydrolysis, complexation, disproportionation, solubility, and redox interchange reactions. The insolubility of Pu(OH)4 is often the limiting factor of the net solubility of plutonium in oxic natural waters where Pu(V)O
is the most stable oxidation state. Perturbations to the oxidation state speciation due to the complexation chemistry of the different oxidation states of plutonium and to the insolubility of plutonium(IV) in neutral aquatic systems are discussed. The merits and limitations of some chemical separation techniques used to study redox speciation of plutonium are presented, and recommendations made for obtaining reliable oxidation state distribution data.
The application of UV-Vis and time-resolved laser-induced fluorescence (TRLF) spectroscopies to direct speciation of uranium(VI) in environmental samples offers various prospects that have, however, serious limitations. While UV-Vis spectroscopy is probably not sensitive enough to detect uranium(VI) species in the majority of environmental samples, TRLFS is principially able to speciate uranium(VI) at very low concentration levels in the nanomol range. Speciation by TRLFS can be based on three parameters: excitation spectrum, emission spectrum and lifetime of the fluorescence emission process. Due to quenching effects, the lifetime may not be expected to be as characteristic as, e.g., the emission spectrum. Quenching of U(VI) fluorescence by reaction with organic substances, inorganic ions and formation of carbonate radicals is one important limiting factor in the application of U(VI) fluorescence spectroscopy. Fundamental photophysical criteria are illustrated using UV-Vis and fluorescence spectra of U(VI) hydrolysis and carbonato species as examples.
Authors:Iisa Outola, Kenneth Inn, Robert Ford, Steve Markham, and Petri Outola
The environmental mobility/availability behavior of radionuclides in soils and sediments depends on their speciation. Experiments
have been carried out to develop a simple but robust radionuclide sequential extraction method for identification of radionuclide
partitioning in sediments and soils. The sequential extraction protocol was optimized for temperature, concentration of reagents
and reaction time. Optimum extraction conditions were chosen based on the release of 239,240Pu, 238U and stable elements. Results from the experiments with lake sediment (SRM 4354) are compared to the previous trials where
the sequential extraction protocol was optimized with the ocean sediment (SRM 4357). Based on these two trials the NIST standard
sequential extraction protocol is established for defined extraction settings for temperature, reagent concentration and time.
Nuclear test explosions and nuclear reactor wastes and accidents have released large amounts of radioactivity into the environment.
Actinideions in waters often are not in a state of thermodynamic equilibrium and their solubility and migration behavior is
related to the form in which the nuclides are introduced into the aquatic system. Chemical speciation, oxidation state, redox
reactions, and sorption characteristics are necessary in predicting solubility of the different actinides, their migration
behaviors and their potential effects on marine biota. The most significant of these variables is the oxidation state of the
metal ion as the simultaneous presence of more than one oxidation state for some actinides in a solution complicates actinide
environmental behavior. Both Np(V)O2+ and Pu(V)O2+, the most significant soluble states in natural oxic waters, are relatively noncomplexing and resistant to hydrolysis and
subsequent precipitation. The solubility of NpO2+ can be as high as 10−4M while that of PuO2+ is much more limited by reduction to the insoluble tetravalent species, Pu(OH)4, (pKsp≥56) but which can be present in the pentavalent form in aqautic phases as colloidal material. The solubility of hexavalent
UO22+ in sea water is relatively high due to formation of carbonate complexes. The insoluble trivalent americium hydroxocarbonate,
Am(OH)(CO3) is the limiting species for the solubility of Am(III) in sea water. Thorium(IV) is present as Th(OH)4, in colloidal form. The chemistry of actinide ions in the environment is reviewed to show the spectrum of reactions that
can occur in natural waters which must be considered in assessing the environmental behavior of actinides. Much is understood
about sorption of actinides on surfaces, the mode of migration of actinides in such waters and the potential effects of these
radioactive species on marine biota, but much more understanding of the behavior of the actinides in the environment is needed
to allow proper and reliable modeling needed for disposition of nuclear waste over many thousands of years.
The dynamic features of metal ion speciation in complex aqueous systems are defined in terms of the pertaining association/dissociation rate parameters. Subsequently, the role of complex species in the supply of free-metal towards a consuming interface is analysed. Limiting cases are those of inert and labile complexes. For each category the steady-state metal uptake by organisms can be described by a basic two-parameter flux equation. This allows a detailed interpretation of experimentally observed bioconversion rates. As an example, the uptake of radiocobalt(II) by carp from various types of complex media is reconstructed on the basis of the flux characteristics.
The migration of radionuclides with groundwater into the environment of a radioactive waste repository is an important aspect in evaluating the safety assessment of such repositories. The potential transport and fate of these radioactive species are dependent upon their speciation and the geochemical behavior of the predominant ones. The speciation of different valence states of neptunium [Np(IV, V and VI)] and their migration behavior are investigated. The data revealed that the uptake is highly dependent upon pH and the distribution coefficient (Kd) is depressed by the presence of organic ligands. The relative migration velocities (Vn) of the valence states relative to that of groundwater, in the concerned area, clarified that Np(V) is the most mobile species and their transport rates are highly accelerated by the presence of humic acid. Also, a radionuclide dispersion model was applied to elucidate the migration behavior of these radioactive species in the selected site and to quantitatively predict their concentrations at different distances in both x and z directions over long time scales.