Multi-element isotopic analysis of hot particles from Chornobyl.

Microscopic fuel fragments, so-called "hot particles", were released during the 1986 accident at the Chornobyl nuclear powerplant and continue to contaminate the exclusion zone in northern Ukraine. Isotopic analysis can provide vital information about sample origin, history and contamination of the environment, though it has been underutilized due to the destructive nature of most mass spectrometric techniques, and inability to remove isobaric interference. Recent developments have diversified the range of elements that can be investigated through resonance ionization mass spectrometry (RIMS), notably in the fission products. The purpose of this study is to demonstrate the application of multi-element analysis on hot particles as relates to their burnup, particle formation in the accident, and weathering. The particles were analysed with two RIMS instruments: resonant-laser secondary neutral mass spectrometry (rL-SNMS) at the Institute for Radiation Protection and Radioecology (IRS) in Hannover, Germany, and laser ionization of neutrals (LION) at Lawrence Livermore National Laboratory (LLNL) in Livermore, USA. Comparable results across instruments show a range of burnup dependent isotope ratios for U and Pu and Cs, characteristic of RBMK-type reactors. Results for Rb, Ba and Sr show the influence of the environment, retention of Cs in the particles and time passed since fuel discharge.

Imaging of I, Re and Tc plant uptake on the single-cell scale using SIMS and rL-SNMS.

In radioecological studies, there is a significant need for understanding the plant uptake of radionuclides on a cellular level. The present work applies mass spectrometry to image the radionuclide distribution within the cellular structures of plants at varying concentrations. In a first step, plants of Daucus carota and Pisum sativum labelled with iodine and rhenium were examined, at concentrations in the range of 10 mM. Cross sections of several plant parts were imaged by secondary ion mass spectrometry (SIMS) after cryogenation in order to preserve cell structure. In a second step, the distribution of 99Tc in the two plant species was determined. For radiological reasons, a concentration three orders of magnitude lower was used, rendering measurements with SIMS impossible. Therefore, resonant laser secondary neutral mass spectrometry (rL-SNMS) was used for the first time to image 99Tc with suppression of molecular isobaric interferences. The measurement of only about 1010 atoms of 99Tc atoms is demonstrated and the distribution of 99Tc within a single epidermal cell is imaged.

New horizons in microparticle forensics: Actinide imaging and detection of 238Pu and 242mAm in hot particles.

Micrometer-sized pollutant particles are of highest concern in environmental and life sciences, cosmochemistry, and forensics. From their composition, detailed information on origin and potential risks to human health or environment is obtained. We combine secondary ion mass spectrometry with resonant laser ionization to selectively examine elemental and isotopic composition of individual particles at submicrometer spatial resolution. Avoiding any chemical sample preparation, isobaric interferences are suppressed by five orders of magnitude. In contrast to most mass spectrometric techniques, only negligible mass is consumed, leaving the particle intact for further studies. Identification of actinide elements and their isotopes on a Chernobyl hot particle, including 242mAm at ultratrace levels, proved the performance. Beyond that, the technique is applicable to almost all elements and opens up previously unexplored scientific applications.

Temperature-dependent luminescence spectroscopic and mass spectrometric investigations of U(VI) complexation with aqueous silicates in the acidic pH-range.

In this study the complexation of U(VI) with orthosilicic acid (H4SiO4) was investigated between pH 3.5 and 5 by combining electrospray ionization mass spectrometry (ESI-MS) and laser-induced luminescence spectroscopy. The ESI-MS experiments performed at a total silicon concentration of 5 · 10-3M (exceeding the solubility of amorphous silica at both pH-values) revealed the formation of oligomeric sodium-silicates in addition to the UO2OSi(OH)3+ species. For the luminescence spectroscopic experiments (25 °C), the U(VI) concentration was fixed at 5 · 10-6M, the silicon concentration was varied between 1.3 · 10-4-1.3 · 10-3M (reducing the formation of silicon oligomers) and the ionic strength was kept constant at 0.2 M NaClO4. The results confirmed the formation of the aqueous UO2OSi(OH)3+ complex. The conditional complexation constant at 25 °C, log *ß = -(0.31 ± 0.24), was extrapolated to infinite dilution using the Davies equation, which led to log *ß0 = -(0.06 ± 0.24). Further experiments at different temperatures (1-25 °C) allowed the calculation of the molal enthalpy of reaction ΔrHm0 = 45.8 ± 22.5 kJ·mol-1 and molal entropy of reaction ΔrSm0 = 152.5 ± 78.8 J·K-1·mol-1 using the integrated van't Hoff equation, corroborating an endothermic and entropy driven complexation process.

Complex formation between UO22+ and α-isosaccharinic acid: insights on a molecular level.

Cellulosic materials present as tissue, paper, wood, or filter materials in low and intermediate level waste will degrade under alkaline conditions if water ingresses in a cementitious backfilled repository. The main degradation product is isosaccharinic acid. Complex formation with isosaccharinic acid may adversely affect the retention of radionuclides by the sorption or formation of solid phases. Hence, this compound is of particular concern in the context of nuclear waste disposal. Structural information of complexes is limited to spherical metal centers and little is known about the interaction of uranyl (UVIO22+) with isosaccharinic acid. Therefore, the interaction of UO22+ with α-isosaccharinate (ISA) was studied under acidic conditions focusing particularly on the structural characterization of the formed complexes. Attenuated total reflection Fourier-transform infrared (ATR-FTIR), nuclear magnetic resonance (NMR), UV-Vis, extended X-ray absorption fine structure (EXAFS) spectroscopy and electrospray-ionization mass spectrometry (ESI-MS) were combined with theoretical calculations to obtain a process understanding on the molecular level. The dominant binding motifs in the formed complexes are 5- and 6-membered rings involving the carboxylic group as well as the α- or ß-hydroxy group of ISA. Two concentration dependent complex formation mechanisms were identified involving either mono- ([UO2(ISA)(H2O)3]+) or binuclear ([(UO2)2(ISA)(H2O)6]3+) species. Furthermore, this study unveils the interaction of UO22+ with the protonated α-isosaccharinic acid (HISA) promoting its transformation to the corresponding α-isosaccharinate-1,4-lactone (ISL) and inhibiting the formation of polynuclear UO22+-ISA species. Future studies on related systems will benefit from the comprehensive knowledge concerning the behavior of ISA as a complexing agent gained in the present study.

Calcium binding to a disordered domain of a type III-secreted protein from a coral pathogen promotes secondary structure formation and catalytic activity.

Strains of the Gram-negative bacterium Vibrio coralliilyticus cause the bleaching of corals due to decomposition of symbiotic microalgae. The V. coralliilyticus strain ATCC BAA-450 (Vc450) encodes a type III secretion system (T3SS). The gene cluster also encodes a protein (locus tag VIC_001052) with sequence homology to the T3SS-secreted nodulation proteins NopE1 and NopE2 of Bradyrhizobium japonicum (USDA110). VIC_001052 has been shown to undergo auto-cleavage in the presence of Ca2+ similar to the NopE proteins. We have studied the hitherto unknown secondary structure, Ca2+-binding affinity and stoichiometry of the "metal ion-inducible autocleavage" (MIIA) domain of VIC_001052 which does not possess a classical Ca2+-binding motif. CD and fluorescence spectroscopy revealed that the MIIA domain is largely intrinsically disordered. Binding of Ca2+ and other di- and trivalent cations induced secondary structure and hydrophobic packing after partial neutralization of the highly negatively charged MIIA domain. Mass spectrometry and isothermal titration calorimetry showed two Ca2+-binding sites which promote structure formation with a total binding enthalpy of -110 kJ mol-1 at a low micromolar Kd. Putative binding motifs were identified by sequence similarity to EF-hand domains and their structure analyzed by molecular dynamics simulations. The stoichiometric Ca2+-dependent induction of structure correlated with catalytic activity and may provide a "host-sensing" mechanism that is shared among pathogens that use a T3SS for efficient secretion of disordered proteins.