Spontaneous and photo-induced decay processes of WF5 - and HfF5 - molecular anions in a cryogenic storage ring.

Spontaneous and photo-induced decay processes of HfF5 - and WF5 - molecular anions were investigated in the Double ElectroStatic Ion Ring ExpEriment (DESIREE). The observation of these reactions over long time scales (several tens of ms) was possible due to the cryogenic temperatures (13 K) and the extremely low residual gas pressure (∼10-14 mbar) of DESIREE. For photo-induced reactions, laser wavelengths in the range 240 to 450 nm were employed. Both anion species were found to undergo spontaneous decay via electron detachment or fragmentation. After some ms, radiative cooling processes were observed to lower the probability for further decay through these processes. Photo-induced reactions indicate the existence of an energy threshold for WF5 - anions at about 3.5 eV, above which the neutralization yield increases strongly. By contrast, HfF5 - ions exhibit essentially no enhanced production of neutrals upon photon interaction, even for the highest photon energy used in this experiment (∼5.2 eV). This suppression will be highly beneficial for the efficient detection, in accelerator mass spectrometry, of the extremely rare isotope 182Hf using the 182HfF5 - anion while effectively reducing the interfering stable isobar 182W in the analyte ion 182WF5 -. The radionuclide 182Hf is of great relevance in astrophysical environments as it constitutes a potential candidate to study the events of nucleosynthesis that may have taken place in the vicinity of the solar system several million years ago.

Correction: Novel 90Sr analysis of environmental samples by Ion-Laser InterAction Mass Spectrometry.

Correction for 'Novel 90Sr analysis of environmental samples by Ion-Laser InterAction Mass Spectrometry' by Maki Honda et al., Anal. Methods, 2022, 14, 2732-2738, https://doi.org/10.1039/D2AY00604A.

Novel 90Sr analysis of environmental samples by Ion-Laser InterAction Mass Spectrometry.

The sensitive analysis of 90Sr with accelerator mass spectrometry (AMS) was developed to advance environmental radiology. One advantage of AMS is the ability to analyze environmental samples with 90Sr/88Sr atomic ratios of 10-14 in following a simple chemical separation. Three different IAEA samples with known 90Sr concentrations (moss-soil, animal bone, Syrian soil: 1 g each) were analyzed to assess the validity of the chemical separation and the AMS measurement. The 90Sr measurements were conducted on the AMS system VERA combined with the Ion Laser InterAction Mass Spectrometry (ILIAMS) setup at the University of Vienna, which has excellent isobaric separation performance. The isobaric interference of 90Zr in the 90Sr AMS was first largely removed by chemical separation. The separation factor of Zr in two-step column chromatography with Sr resin and anion exchange resin was 106. The 90Zr remaining in the sample was effectively suppressed by ILIAMS. This procedure achieved a limit of detection <0.1 mBq in the 90Sr AMS, which is lower than typical ß-ray detection. The agreement between AMS measurements and nominal values for the 90Sr concentrations of IAEA samples indicated that the new highly-sensitive 90Sr analysis in the environmental samples with AMS is reliable.

Deciphering sources of U contamination using isotope ratio signatures in the Loire River sediments: Exploring the relevance of 233U/236U and stable Pb isotope ratios.

A broad range of contaminants has been recorded in sediments of the Loire River over the last century. Among a variety of anthropogenic activities of this nuclearized watershed, extraction of uranium and associated activities during more than 50 years as well as operation of several nuclear power plants led to industrial discharges, which could persist for decades in sedimentary archives of the Loire River. Highlighting and identifying the origin of radionuclides that transited during the last decades and were recorded in the sediments is challenging due to i) the low concentrations which are often close or below the detection limits of routine environmental surveys and ii) the mixing of different sources. The determination of the sources of anthropogenic radioactivity was performed using multi-isotopic fingerprints (236U/238U, 206Pb/207Pb and 208Pb/207Pb) and the newly developed 233U/236U tracer. For the first time 233U/236U data in a well-dated river sediment core in the French river Loire are reported here. Results highlight potential sources of contamination among which a clear signature of anthropogenic inputs related to two accidents of a former NUGG NPP that occurred in 1969 and 1980. The 233U and 236U isotopes were measured by recent high performance analytical methods due to their ultra-trace levels in the samples and show a negligible radiological impact on health and on the environment. The determination of mining activities by the use of stable Pb isotopes is still challenging probably owing to the limited dissemination of the Pb-bearing material marked by the U-ore signature downstream to the former U mines.

Anthropogenic 236U and 233U in the Baltic Sea: Distributions, source terms, and budgets.

The Baltic Sea receives substantial amounts of hazardous substances and nutrients, which accumulate for decades and persistently impair the Baltic ecosystems. With long half-lives and high solubility, anthropogenic uranium isotopes (236U and 233U) are ideal tracers to depict the ocean dynamics in the Baltic Sea and the associated impacts on the fates of contaminants. However, their applications in the Baltic Sea are hampered by the inadequate source-term information. This study reports the first three-dimensional distributions of 236U and 233U in the Baltic Sea (2018-2019) and the first long-term hindcast simulation for reprocessing-derived 236U dispersion in the North-Baltic Sea (1971-2018). Using 233U/236U fingerprints, we distinguish 236U from the nuclear weapon testing and civil nuclear industries, which have comparable contributions (142 ± 13 and 174 ± 40 g) to the 236U inventory in modern Baltic seawater. Budget calculations for 236U inputs since the 1950s indicate that, the major 236U sources in the Baltic Sea are the atmospheric fallouts (∼1.35 kg) and discharges from nuclear reprocessing plants (> 211 g), and there is a continuous sink of 236U to the anoxic sediments (589 ± 43 g). Our findings also indicate that the limited water renewal endows the Baltic Sea a strong "memory effect" retaining aged 236U signals, and the previously unknown 236U in the Baltic Sea is likely attributed to the retention of the mid-1990s' discharges from the nuclear reprocessing plants. Our preliminary results demonstrate the power of 236U-129I dual-tracer in investigating water-mass mixing and estimating water age in the Baltic Sea, and this work provides fundamental knowledge for future 236U tracer studies in the Baltic Sea.

70-Year Anthropogenic Uranium Imprints of Nuclear Activities in Baltic Sea Sediments.

A strongly stratified water structure and a densely populated catchment make the Baltic Sea one of the most polluted seas. Understanding its circulation pattern and time scale is essential to predict the dynamics of hypoxia, eutrophication, and pollutants. Anthropogenic 236U and 233U have been demonstrated as excellent transient tracers in oceanic studies, but unclear input history and inadequate long-term monitoring records limit their application in the Baltic Sea. From two dated Baltic sediment cores, we obtained high-resolution records of anthropogenic uranium imprints originating from three major human nuclear activities throughout the Atomic Era. Using the novel 233U/236U signature, we distinguished and quantified 236U inputs from global fallout (45.4-52.1%), Chernobyl accident (0.3-1.8%), and discharges from civil nuclear industries (46.1-54.3%) to the Baltic Sea. We estimated the total release of 233U (7-15 kg) from the atmospheric nuclear weapon testing and pinpointed the 233U peak signal in the mid-to-late 1950s as a potential time marker for the onset of the Anthropocene Epoch. This work also provides fundamental 236U data on Chernobyl accident and early discharges from civil nuclear facilities, prompting worldwide 233U-236U tracer studies. We anticipate our data to be used in a broader application in model-observation interdisciplinary research on water circulation and pollutant dynamics in the Baltic Sea.

An unknown source of reactor radionuclides in the Baltic Sea revealed by multi-isotope fingerprints.

We present an application of multi-isotopic fingerprints (i.e., 236U/238U, 233U/236U, 236U/129I and 129I/127I) for the discovery of previously unrecognized sources of anthropogenic radioactivity. Our data indicate a source of reactor 236U in the Baltic Sea in addition to inputs from the two European reprocessing plants and global fallout. This additional reactor 236U may come from unreported discharges from Swedish nuclear research facilities as supported by high 236U levels in sediment nearby Studsvik, or from accidental leakages of spent nuclear fuel disposed on the Baltic seafloor, either reported or unreported. Such leakages would indicate problems with the radiological safety of seafloor disposal, and may be accompanied by releases of other radionuclides. The results demonstrate the high sensitivity of multi-isotopic tracer systems, especially the 233U/236U signature, to distinguish environmental emissions of unrevealed radioactive releases for nuclear safeguards, emergency preparedness and environmental tracer studies.

On the Quality Control for the Determination of Ultratrace-Level 236U and 233U in Environmental Samples by Accelerator Mass Spectrometry.

Our recent attempt to determine ultratrace-level 236U and 233U in small-volume seawater samples was challenged by high and unstable procedure blanks in our environmental radioactivity laboratory, which used to be a spent fuel research facility. Through intercomparison experiments with different laboratories and background checks on the chemical reagents and laboratory dust, the resuspended U-bearing dust was identified as the dominating source of the 236U and 233U contamination. With the implementation of background control (especially dust control) measures, the procedure blanks and detection limits of 236U and 233U for the radiochemical separation procedure have been significantly improved by three orders of magnitudes. With well-controlled blanks, the analytical precision for 236U and 233U predominantly relies on the AMS counting statistics. Background check and dust control are strongly recommended before the analyses of environmental-level long-lived radionuclides (such as 236U and 233U) that are conducted in the former or active nuclear facilities, even if clearance of radioactivity relevant for radioprotection was achieved.

Pushing Limits of ICP-MS/MS for the Determination of Ultralow 236U/238U Isotope Ratios.

Determination of uranium isotope ratios is of great expedience for assessing its origin in environmental samples. In particular, the 236U/238U isotope ratio provides a powerful tool to discriminate between the different sources of uranium (uranium ore, geochemical background, and uranium from anthropogenic activities). However, in the environment, this ratio is typically below 10-8. This low abundance of 236U and the presence in large excess of major isotopes (mainly 238U and 235U) complicates the accurate detection of 236U signal by mass spectrometry and thus highly sensitive analytical instruments providing high abundance sensitivity are required. This work pushes the limits of triple quadrupole-based ICP-MS technology for accurate detection of 236U/238U isotope ratios down to 10-10, which is so far mainly achievable by AMS. Coupled with an efficient desolvating module, N2O was used as the reaction gas in the collision reaction cell of the ICP-MS/MS. This configuration allows a significant decrease of the uranium polyatomic interferences (235UH+ ions) and an accurate determination of low 236U/238U isotope ratios. This new methodology was successfully validated through measurements of certified reference material from 10-7 to 10-9 and then through comparisons with AMS measurement results for ratios down to 10-10. This is the first time that 236U/238U isotope ratios as low as 10-10 were determined by ICP-MS/MS. The possibility of measuring low 236U/238U isotope ratios can offer a large variety of geochemical applications in particular for the determination of uranium sources in the environment.

Limits on Supernova-Associated

We searched for the presence of ^{26}Al in deep-sea sediments as a signature of supernova influx. Our data show an exponential dependence of ^{26}Al with the sample age that is fully compatible with radioactive decay of terrigenic ^{26}Al. The same set of samples demonstrated a clear supernova ^{60}Fe signal between 1.7 and 3.2 Myr ago. Combining our ^{26}Al data with the recently reported ^{60}Fe data results in a lower limit of 0.18_{-0.08}^{+0.15} for the local interstellar ^{60}Fe/^{26}Al isotope ratio. It compares to most of the ratios deduced from nucleosynthesis models and is within the range of the observed average galactic ^{60}Fe/^{26}Al flux ratio of (0.15±0.05).

Multiactinide Analysis with Accelerator Mass Spectrometry for Ultratrace Determination in Small Samples: Application to an in Situ Radionuclide Tracer Test within the Colloid Formation and Migration Experiment at the Grimsel Test Site (Switzerland).

The multiactinide analysis with accelerator mass spectrometry (AMS) was applied to samples collected from the run 13-05 of the Colloid Formation and Migration (CFM) experiment at the Grimsel Test Site (GTS). In this in situ radionuclide tracer test, the environmental behavior of 233U, 237Np, 242Pu, and 243Am was investigated in a water conductive shear zone under conditions relevant for a nuclear waste repository in crystalline rock. The concentration of the actinides in the GTS groundwater was determined with AMS over 6 orders of magnitude from ∼15 pg/g down to ∼25 ag/g. Levels above 10 fg/g were investigated with both sector field inductively coupled plasma mass spectrometry (SF-ICPMS) and AMS. Agreement within a relative uncertainty of 50% was found for 237Np, 242Pu, and 243Am concentrations determined with the two analytical methods. With the extreme sensitivity of AMS, the long-term release and retention of the actinides was investigated over 8 months in the tailing of the breakthrough curve of run 13-05 as well as in samples collected up to 22 months after. Furthermore, the evidence of masses 241 and 244 u in the CFM samples most probably representing 241Am and 244Pu employed in a previous tracer test demonstrated the analytical capability of AMS for in situ studies lasting more than a decade.

Anthropogenic 236U in Danish Seawater: Global Fallout versus Reprocessing Discharge.

This work focuses on the occurrence of 236U in seawater along Danish coasts, which is the sole water-exchange region between the North Sea-Atlantic Ocean and the Baltic Sea. Seawater collected in 2013 and 2014 were analyzed for 236U (as well as 238U and 137Cs). Our results indicate that 236U concentrations in Danish seawater are distributed within a relatively narrow range of (3.6-8.2) × 107 atom/L and, to a certain extent, independent of salinity. 236U/238U atomic ratios in Danish seawater are more than 4 times higher than the estimated global fallout value of 1× 10-9. The levels of 236U/238U atomic ratios obtained are comparable to those reported for the open North Sea and much higher than several other open oceans worldwide. This indicates that besides the global fallout input, the discharges from the two major European nuclear reprocessing plants are dominating sources of 236U in Danish seawater. However, unexpectedly high 236U/238U ratios as well as high 236U concentrations were observed at low-salinity locations of the Baltic Sea. While this feature might be interpreted as a clue for another significant 236U input in the Baltic Sea, it may also be caused by the complexity of water currents or slow turnover rate.

Plutonium Isotopes (239-241Pu) Dissolved in Pacific Ocean Waters Detected by Accelerator Mass Spectrometry: No Effects of the Fukushima Accident Observed.

The concentration of plutonium (Pu) and the isotopic ratios of 240Pu to 239Pu and 241Pu to 239Pu were determined by accelerator mass spectrometry (AMS) in Pacific Ocean water samples (20 L each) collected in late 2012. The isotopic Pu ratios are important indicators of different contamination sources and were used to identify a possible release of Pu into the ocean by the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident. In particular, 241Pu is a well-suited indicator for a recent entry of Pu because 241Pu from fallout of nuclear weapon testings has already significantly decayed. A total of 10 ocean water samples were prepared at the Radiochemie München of the TUM and analyzed at the Vienna Environmental Research Laboratory (VERA). Several samples showed a slightly elevated 240Pu/239Pu ratio of up to 0.22 ± 0.02 compared to global fallout (240Pu/239Pu = 0.180 ± 0.007), whereas all measured 241Pu-to-239Pu ratios were consistent with nuclear weapon fallout (241Pu/239Pu < 2.4 × 10-3), which means that no impact from the Fukushima accident was detected. From the average 241Pu-to-239Pu ratio of 8-2+3 ×10-4 at a sampling station located at a distance of 39.6 km to FDNPP, the 1-σ upper limit for the FDNPP contribution to the 239Pu inventory in the water column was estimated to be 0.2%. Pu, with the signature of weapon-grade Pu was found in a single sample collected around 770 km off the west coast of the United States.

Method for (236)U Determination in Seawater Using Flow Injection Extraction Chromatography and Accelerator Mass Spectrometry.

An automated analytical method implemented in a flow injection (FI) system was developed for rapid determination of (236)U in 10 L seawater samples. (238)U was used as a chemical yield tracer for the whole procedure, in which extraction chromatography (UTEVA) was exploited to purify uranium, after an effective iron hydroxide coprecipitation. Accelerator mass spectrometry (AMS) was applied for quantifying the (236)U/(238)U ratio, and inductively coupled plasma mass spectrometry (ICPMS) was used to determine the absolute concentration of (238)U; thus, the concentration of (236)U can be calculated. The key experimental parameters affecting the analytical effectiveness were investigated and optimized in order to achieve high chemical yields and simple and rapid analysis as well as low procedure background. Besides, the operational conditions for the target preparation prior to the AMS measurement were optimized, on the basis of studying the coprecipitation behavior of uranium with iron hydroxide. The analytical results indicate that the developed method is simple and robust, providing satisfactory chemical yields (80-100%) and high analysis speed (4 h/sample), which could be an appealing alternative to conventional manual methods for (236)U determination in its tracer application.

Accelerator Mass Spectrometry of Actinides in Ground- and Seawater: An Innovative Method Allowing for the Simultaneous Analysis of U, Np, Pu, Am, and Cm Isotopes below ppq Levels.

(236)U, (237)Np, and Pu isotopes and (243)Am were determined in ground- and seawater samples at levels below ppq (fg/g) with a maximum sample size of 250 g. Such high sensitivity was possible by using accelerator mass spectrometry (AMS) at the Vienna Environmental Research Accelerator (VERA) with extreme selectivity and recently improved efficiency and a significantly simplified separation chemistry. The use of nonisotopic tracers was investigated in order to allow for the determination of (237)Np and (243)Am, for which isotopic tracers either are rarely available or suffer from various isobaric mass interferences. In the present study, actinides were concentrated from the sample matrix via iron hydroxide coprecipitation and measured sequentially without previous chemical separation from each other. The analytical method was validated by the analysis of the Reference Material IAEA 443 and was applied to groundwater samples from the Colloid Formation and Migration (CFM) project at the deep underground rock laboratory of the Grimsel Test Site (GTS) and to natural water samples affected solely by global fallout. While the precision of the presented analytical method is somewhat limited by the use of nonisotopic spikes, the sensitivity allows for the determination of ∼10(5) atoms in a sample. This provides, e.g., the capability to study the long-term release and retention of actinide tracers in field experiments as well as the transport of actinides in a variety of environmental systems by tracing contamination from global fallout.

Sequential injection method for rapid and simultaneous determination of 236U, 237Np, and Pu isotopes in seawater.

An automated analytical method implemented in a novel dual-column tandem sequential injection (SI) system was developed for simultaneous determination of (236)U, (237)Np, (239)Pu, and (240)Pu in seawater samples. A combination of TEVA and UTEVA extraction chromatography was exploited to separate and purify target analytes, whereupon plutonium and neptunium were simultaneously isolated and purified on TEVA, while uranium was collected on UTEVA. The separation behavior of U, Np, and Pu on TEVA-UTEVA columns was investigated in detail in order to achieve high chemical yields and complete purification for the radionuclides of interest. (242)Pu was used as a chemical yield tracer for both plutonium and neptunium. (238)U was quantified in the sample before the separation for deducing the (236)U concentration from the measured (236)U/(238)U atomic ratio in the separated uranium target using accelerator mass spectrometry. Plutonium isotopes and (237)Np were measured using inductively coupled plasma mass spectrometry after separation. The analytical results indicate that the developed method is robust and efficient, providing satisfactory chemical yields (70-100%) of target analytes and relatively short analytical time (8 h/sample).

Iodine-129 in seawater offshore Fukushima: distribution, inorganic speciation, sources, and budget.

The Fukushima nuclear accident in March 2011 has released a large amount of radioactive pollutants to the environment. Of the pollutants, iodine-129 is a long-lived radionuclide and will remain in the environment for millions of years. This work first report levels and inorganic speciation of (129)I in seawater depth profiles collected offshore Fukushima in June 2011. Significantly elevated (129)I concentrations in surface water were observed with the highest (129)I/(127)I atomic ratio of 2.2 × 10(-9) in the surface seawater 40 km offshore Fukushima. Iodide was found as the dominant species of (129)I, while stable (127)I was mainly in iodate form, reflecting the fact that the major source of (129)I is the direct liquid discharges from the Fukushima NPP. The amount of (129)I directly discharged from the Fukushima Dai-ichi nuclear power plant to the sea was estimated to be 2.35 GBq, and about 1.09 GBq of (129)I released to the atmosphere from the accident was deposited in the sea offshore Fukushima. A total release of 8.06 GBq (or 1.2 kg) of (129)I from the Fukushima accident was estimated. These Fukushima-derived (129)I data provide necessary information for the investigation of water circulation and geochemical cycle of iodine in the northwestern Pacific Ocean in the future.

Light induced suppression of sulfur in a cesium sputter ion source.

New techniques for suppression of atomic isobars in negative ion beams are of great interest for accelerator mass spectrometry (AMS). Especially small and medium-sized facilities can significantly extend their measurement capabilities to new interesting isotopes with a technique independent of terminal voltage. In a new approach, the effect of continuous wave laser light directed towards the cathode surface in a cesium sputter ion source of the Middleton type was studied. The laser light induced a significant change in oxygen, sulfur and chlorine negative ion production from a AgCl target. Approximately 100 mW of laser light reduced the sulfur to chlorine ratio by one order of magnitude. The effect was found to depend on laser power and ion source parameters but not on the laser wavelength. The time constant of the effect varied from a few seconds up to several minutes. Experiments were first performed at the ion beam facility GUNILLA at University of Gothenburg with macroscopic amounts of sulfur. The results were then reproduced at the VERA AMS facility with chemically cleaned AgCl targets containing ∼1 ppm sulfur. The physical explanation behind the effect is still unclear. Nevertheless, the technique has been successfully applied during a regular AMS measurement of 36Cl.