Disproportionately High Contributions of 60 Year Old Weapons-137Cs Explain the Persistence of Radioactive Contamination in Bavarian Wild Boars.

Radionuclides released from nuclear accidents or explosions pose long-term threats to ecosystem health. A prominent example is wild boar contamination in central Europe, which is notorious for its persistently high 137Cs levels. However, without reliable source identification, the origin of this decades old problem has been uncertain. Here, we target radiocesium contamination in wild boars from Bavaria. Our samples (2019-2021) range from 370 to 15,000 Bq·kg-1 137Cs, thus exceeding the regulatory limits (600 Bq·kg-1) by a factor of up to 25. Using an emerging nuclear forensic fingerprint, 135Cs/137Cs, we distinguished various radiocesium source legacies in their source composition. All samples exhibit signatures of mixing of Chornobyl and nuclear weapons fallout, with 135Cs/137Cs ratios ranging from 0.67 to 1.97. Although Chornobyl has been widely believed to be the prime source of 137Cs in wild boars, we find that "old" 137Cs from weapons fallout significantly contributes to the total level (10-68%) in those specimens that exceeded the regulatory limit. In some cases, weapons-137Cs alone can lead to exceedances of the regulatory limit, especially in samples with a relatively low total 137Cs level. Our findings demonstrate that the superposition of older and newer legacies of 137Cs can vastly surpass the impact of any singular yet dominant source and thus highlight the critical role of historical releases of 137Cs in current environmental pollution challenges.

Identification of a chemical fingerprint linking the undeclared 2017 release of 106Ru to advanced nuclear fuel reprocessing.

The undeclared release and subsequent detection of ruthenium-106 (106Ru) across Europe from late September to early October of 2017 prompted an international effort to ascertain the circumstances of the event. While dispersion modeling, corroborated by ground deposition measurements, has narrowed possible locations of origin, there has been a lack of direct empirical evidence to address the nature of the release. This is due to the absence of radiological and chemical signatures in the sample matrices, considering that such signatures encode the history and circumstances of the radioactive contaminant. In limiting cases such as this, we herein introduce the use of selected chemical transformations to elucidate the chemical nature of a radioactive contaminant as part of a nuclear forensic investigation. Using established ruthenium polypyridyl chemistry, we have shown that a small percentage (1.2 ± 0.4%) of the radioactive 106Ru contaminant exists in a polychlorinated Ru(III) form, partly or entirely as ß-106RuCl3, while 20% is both insoluble and chemically inert, consistent with the occurrence of RuO2, the thermodynamic endpoint of the volatile RuO4 Together, these findings present a clear signature for nuclear fuel reprocessing activity, specifically the reductive trapping of the volatile and highly reactive RuO4, as the origin of the release. Considering that the previously established 103Ru:106Ru ratio indicates that the spent fuel was unusually young with respect to typical reprocessing protocol, it is likely that this exothermic trapping process proved to be a tipping point for an already turbulent mixture, leading to an abrupt and uncontrolled release.

Determination of Characteristic vs Anomalous 135Cs/137Cs Isotopic Ratios in Radioactively Contaminated Environmental Samples.

A contamination with the ubiquitous radioactive fission product 137Cs cannot be assigned per se to its source. We used environmental samples with varying contamination levels from various parts of the world to establish their characteristic 135Cs/137Cs isotope ratios and thereby allow their distinction. The samples included biological materials from Chernobyl and Fukushima, historic ashed human lung tissue from the 1960s from Austria, and trinitite from the Trinity Test Site, USA. After chemical separation and gas reaction shifts inside a triple quadrupole ICP mass spectrometer, characteristic 135Cs/137Cs isotope signatures (all as per March 11, 2011) were obtained for Fukushima- (∼0.35) and Chernobyl-derived (∼0.50) contaminations, in agreement with the literature for these contamination sources. Both signatures clearly distinguish from the characteristic high ratio (1.9 ± 0.2) for nuclear-weapon-produced radiocesium found in human lung tissue. Trinitite samples exhibited an unexpected, anomalous pattern by displaying a low (<0.4) and nonuniform 135Cs/137Cs ratio. This exemplifies a 137Cs-rich fractionation of the plume in a nuclear explosion, where 137Cs is a predominant species in the fireball. The onset of 135Cs was delayed because of the longer half-life of its parent nuclide 135Xe, causing a spatial separation of gaseous 135Xe from condensed 137Cs, which is the reason for the atypical 135Cs/137Cs fractionation in the fallout at the test site.

Separation of Ultratraces of Radiosilver from Radiocesium for Environmental Nuclear Forensics.

The presence of environmental radiosilver and the investigation of the 108mAg/110mAg isotopic ratio in the aftermath of a nuclear power plant accident provide valuable information on the condition of the control rods of pressurized water reactors. However, the detection of minute amounts of the γ-emitting radiosilver isotopes is often thwarted by the presence of concomitant and dominating γ emitters, primarily 137Cs, which results in increased detection limits in the γ spectra. We developed a rapid and robust separation protocol for trace silver extraction in the presence of overwhelming activities of 137Cs via the autodepostion of silver on a copper plate. This method achieved a quantitative removal of interfering 137Cs in the deposition product and proved to be very efficient (yields >70% for aqueous samples), rapid (results within 4 h), and robust with respect to varying salinities and composition of the water samples. The autodeposition approach is also applicable for organic samples after acid-assisted microwave digestion. By applying the established sequential extraction protocols for soil, the fate of freshly deposited radiosilver and radiocesium in soil was investigated. Silver showed a high affinity to the soil with a pronounced (>90%) accumulation in the residual fraction after the sequential extraction, whereas radiocesium exhibited higher mobility, allowing for the extraction of major fractions in the first extraction steps. The composition of the aqueous contamination matrix (CaCl2 or Ca(NO3)2) had a significant influence on the binding properties of cesium on soil.

Patterning of Nanoparticle-Based Aerogels and Xerogels by Inkjet Printing.

Nanoparticle-based voluminous 3D networks with low densities are a unique class of materials and are commonly known as aerogels. Due to the high surface-to-volume ratio, aerogels and xerogels might be suitable materials for applications in different fields, e.g. photocatalysis, catalysis, or sensing. One major difficulty in the handling of nanoparticle-based aerogels and xerogels is the defined patterning of these structures on different substrates and surfaces. The automated manufacturing of nanoparticle-based aerogel- or xerogel-coated electrodes can easily be realized via inkjet printing. The main focus of this work is the implementation of the standard nanoparticle-based gelation process in a commercial inkjet printing system. By simultaneously printing semiconductor nanoparticles and a destabilization agent, a 3D network on a conducting and transparent surface is obtained. First spectro-electrochemical measurements are recorded to investigate the charge-carrier mobility within these 3D semiconductor-based xerogel networks.

Non-natural ruthenium isotope ratios of the undeclared 2017 atmospheric release consistent with civilian nuclear activities.

Understanding the circumstances of the undeclared 2017 nuclear release of ruthenium that led to widespread detections of the radioisotope 106Ru in the Eurasian region, and whether it derives from a civilian or military source, is of major importance for society and future improvements in nuclear safety. Until now, the released nuclear material has merely been studied by analyzing short-lived radioisotopes. Here, we report precise measurements of the stable isotopic composition of ruthenium captured in air filters before, during, and after the nuclear release, and find that the ruthenium collected during the period of the 2017 nuclear release has a non-natural isotopic composition. By comparing our results with ruthenium isotopic compositions of spent nuclear fuels, we show that the release is consistent with the isotopic fingerprints of a civilian Russian water-water energetic reactor (VVER) fuel at the end of its lifetime, and is not related to the production of plutonium for nuclear weapons.

Chemical and radioanalytical investigations of 106Ru-containing air filters from Vienna in 2017: searching for stable element anomalies.

Related to the recent nuclear release of radioactive ruthenium isotopes in fall 2017, we analyzed air filters from Vienna for irregularities in the (stable) elemental composition of particulate matter from this period. Methods were SEM/EDXS and INAA. For comparison, a reference filter from 2007 and blank filters were used. The chemical fingerprint encompassed 28 elements. The results show no indication for a considerable change in the elemental composition of the suspended matter. For example, no anomalies in the abundance of platinum group elements were found. The results suggest that the release of 106Ru had not been accompanied by a release of detectable amounts of (activatable) stable elements.