Vertical distribution of 241Am in the southern Baltic Sea sediment profiles.

The contamination of the Baltic Sea with radioactive substances occurred due to the global fallout of atmospheric nuclear weapon tests and the Chernobyl disaster. The knowledge of 241Am in the sediments of the Baltic Sea is limited. Thus, this study aimed to determine 241Am in sediment cores collected from the southern Baltic Sea. Time-based distributions were derived from age-depth profiles using the 210Pb dating method and further corroborated by 137Cs profiles. The activities of 241Am were measured by alpha spectrometry after radiochemical purification. The results show divergences in the concentrations of 241Am at the local level, varying from 0.017 ± 0.001 Bq·kg-1 at the Gotland Basin station to 3.19 ± 0.23 Bq·kg-1 in the Gdansk Basin. These findings enhance our understanding of the radioactive contamination levels in the Baltic Sea and serve as a crucial reference dataset for future assessments and management strategies to mitigate the environmental impact of radionuclides in the region.

Half-century trends of radioactivity in fish from Danish areas of the North Sea, Kattegat, and Baltic Sea.

This work reports comprehensive time-series datasets over the past 50 years for natural (210Po) and anthropogenic (134Cs and 137Cs) radionuclides in three fish species (cod, herring and plaice) from Danish marine areas covering the North Sea, Kattegat, and Baltic Sea. Impact from the global fallout of atmospheric nuclear weapons testing, radioactive discharges from the European nuclear reprocessing plants and release from Chernobyl accident are clearly detected in the fish samples. While 210Po concentrations in each fish species demonstrated comparable levels across the three regions without notable temporal trends, significantly higher median 210Po concentration was observed in the lower trophic level fish, namely herring and plaice, compared to cod. In contrast, 137Cs concentrations in all three species steadily decrease over time after the Chernobyl-attributed peaks in late 1980s in the entire study area, whereas 137Cs always demonstrated higher concentrations in cod than herring and plaice. Our calculated concentration factors (CFs) for 137Cs in this work indicate that the mean CFs for 137Cs over the past 50 years are significantly different across the three species, following the order of cod < herring < plaice. Based on the time-series data, ecological half-lives (Teco) of 137Cs in fish from Danish marine areas were estimated to evaluate the long-term impact of anthropogenic radioactive contamination in different regions. Our results indicate no significant difference in Teco across different fish species, whereas the weighted mean Teco for fish in the Baltic Sea (29.3 ± 3.9 y) is significantly longer than those of the North Sea (9.8 ± 0.9 y) and Kattegat (11.7 ± 1.2 y), reflecting the strong 'memory effect' of the Baltic Sea due to its slow water renewal. However, the dose assessment demonstrates that the contribution of the natural radionuclide 210Po to ingestion dose from fish consumption is 1-2 order of magnitude higher compared to that of 137Cs.

Simultaneous determination of femtogram levels of 237Np, 239Pu, and 240Pu in environmental solid samples using extraction chromatography and ICP-MS/MS.

An analytical method based on triple quadrupole inductively coupled plasma mass spectrometry (ICP-MS/MS) was developed for simultaneous determination of femtogram levels of 237Np, 239Pu, and 240Pu in environmental samples. By carefully controlling the valence states of Np and Pu in the entire separation procedure using a simple single extraction chromatographic column (TK200), the consistent behavior of Np and Pu was achieved, allowing for the reliable application of 242Pu as the chemical yield tracer for 237Np, 239Pu, and 240Pu. A high decontamination factor of 3.2 × 107 for the most critical interfering element, uranium, was achieved in the chemical separation step. The interferences of 238U1H+ and peak tailing of 238U+ during the measurement of plutonium isotopes were effectively eliminated by utilizing 7.5 mL/min He-1.1 mL/min CO2 as reaction gases in the octupole collision/reaction cell and employing sequential quadrupole mode for mass separation in ICP-MS/MS. Specifically, the interference of 238U1H+ was reduced to 10-6 and the peak tailing of 238U+ to 10-10, surpassing the performance of measurement method without reaction gases by 3 orders of magnitude. The developed method enables the accurate determination of femtogram levels of 237Np, 239Pu, and 240Pu in the samples with U/Np and U/Pu atom ratios of up to 1017 and 1012, respectively. The developed method was validated by analyzing standard reference materials and spiked soil samples.

Long-term environmental risks of the Baltic Sea's "memory effect" revealed by ocean modeling and observation of reprocessing-derived radiotracers.

Although previous research indicated that the Baltic Sea has a strong "memory effect" for trapping pollutants/nutrients, the associated environmental risks are not well understood due to the knowledge gaps in the long-term hydrodynamics-driven exchange of pollutants/nutrients between the North Sea and the Baltic Sea. In this work, we exploited 99Tc and 129I released from the two European nuclear reprocessing plants as oceanic tracers and pollutant proxies, and performed a five-decade hindcast simulation to quantitatively estimate the fluxes and timescales of marine transport of pollutants/nutrients in the North-Baltic Sea. Modeling results underline two potential environmental risks of the Baltic Sea's "memory effect": (1) ∼26 years of environmental half-life for any existing water-soluble pollutants/nutrients in the Baltic Sea driven by its hydrodynamics; (2) the Baltic Sea as a pollutant reservoir continuously exporting 3 % of contaminations per year to the downstream areas after any pollution event. Our findings provide fundamental knowledge for understanding the long-term hydrodynamics-driven pollutant/nutrient transport in the North-Baltic Sea, facilitating the future regional management of the marine environment.

Distribution of Anthropogenic 129I in the Western South China Sea and Its Application for Tracing the Sources and Movement of Pollution.

Anthropogenic 129I has been dispersed all over the world and could be utilized as an oceanographic tracer based on its conservative nature in the ocean. The first datasets of 129I and 127I were obtained by analysis of seawater of 36 water columns collected in the western South China Sea during August-September 2018. The measured 129I concentrations decreased with depth from (0.93-1.61) × 107 atoms/L in the upper 200 m to (0.04-0.14) × 107 atoms/L at 1500 m, indicating a clear anthropogenic source in the upper layer, mainly originated from the global fallout. The riverine input of the deposited 129I on the catchment area of the Mekong River is an important source besides the direct deposition in the seas. The water mass with high 129I from the Mekong River water moves to the east at 11°N by the North Nansha Current in the surface layer (2-25 m). The exponentially decreasing 129I level with depth indicates that the vertical dispersion of 129I from the upper to the lower layer was mainly through slow diffusion, and the deep water at more than 1500 m was not significantly contaminated by the upper layer water at least in the past 70 years.

Determination of 93Mo in Radioactive Samples of Sulfuric Acid Media from Nuclear Facilities.

93Mo is an important radionuclide in view of radioactive waste repository because of its long half-life and high mobility in the environment. 93Mo decays by electron capture without any measurable gamma ray emission. The concentration of 93Mo in most of the radioactive waste is many orders of magnitude lower than the major activation product radionuclides, which makes the accurate determination of 93Mo a big challenge. A new analytical method for the determination of 93Mo in sulfuric acid media from nuclear power reactor was developed. 93Mo was separated from most of the radionuclides by cation exchange chromatography followed by the removal of sulfate by CaSO4 precipitation. A further purification of 93Mo, especially from anion species of 51Cr and 125Sb, was achieved by anion exchange chromatography and a short alumina column separation. The chemical yield of 93Mo in the entire separation procedure reached about 75%, and the decontamination factors for all potential interfering radionuclides were 1.5 × 106-1.6 × 108. The purified 93Mo was measured by liquid scintillation counting through counting its low-energy Auger electrons. A detection limit of 2 mBq/g for 93Mo in 50 g sample was achieved by this method, which enables the quantitative determination of 93Mo in most of the radioactive samples in the decommissioning waste and coolant water of nuclear power reactors. The developed method has been successfully applied to determine 93Mo in coolant water of nuclear power reactors, providing a robust analytical approach of 93Mo for the radiological characterization of radioactive wastes.

Tracing Atlantic water transit time in the subarctic and Arctic Atlantic using 99Tc-233U-236U.

The pathway and transport time of Atlantic water passing northern Europe can be traced via anthropogenic radioisotopes released from reprocessing of spent nuclear fuels at Sellafield (SF) and La Hague (LH). These reprocessing derived radioisotopes, with extremely low natural background, are source specific and unique fingerprints for Atlantic water. This study explores a new approach using 99Tc-233U-236U tracer to estimate the transit time of Atlantic water in the coast of Greenland. We isolate the reprocessing plants (RP) signal of 236U (236URP) by incorporating 233U measurements and combine this with 99Tc which solely originates from RP, to estimate the transit time of Atlantic water circulating from Sellafield to the coast of Greenland-Iceland-Faroe Islands. Both being conservative radioisotopes, the temporal variation of 99Tc/236URP ratio in Atlantic water is only influenced by their historic discharges from RP, thus 99Tc/236URP can potentially be a robust tracer to track the transport of Atlantic water in the North Atlantic-Arctic region. Based on our observation data of 99Tc-233U-236U in seawater and the proposed 99Tc/236URP tracer approach, Atlantic water transit times were estimated to be 16-22, 25 and 25 years in the coast of Greenland, Iceland and Faroe Island, respectively. Our estimates from northeast Greenland coastal waters agree with earlier results (17-22 years). Therefore, this work provides an independent approach to estimate Atlantic water transit time with which to compare estimates from ocean modelling and other radiotracer approaches.

Understanding source terms of anthropogenic uranium in the Arctic Ocean - First 236U and 233U dataset in Barents Sea sediments.

This work reports the first dataset of 236U and 233U in sediment cores taken from the Barents Sea, with the aim to better understand the source terms of anthropogenic uranium in the Arctic region. Concentrations of 236U and 233U along with 137Cs, and 233U/236U atomic ratio were measured in six sediment profiles. The cumulative areal inventories of 236U and 233U obtained in this work are (3.50-12.7) × 1011 atom/m2 and (4.92-21.2) × 109 atom/m2, with averages values of (8.08 ± 2.93) × 1011 atom/m2 and (1.08 ± 0.56) × 1010 atom/m2, respectively. The total quantities of 236U and 233U deposited in the Barents Sea bottom sediments were estimated to be 507 ± 184 g and 7 ± 3 g, respectively, which are negligible compared to the total direct deposition of 236U (6000 g) and 233U (40-90 g) from global fallout in the Barents Sea. The integrated atomic ratios of 233U/236U ranging in (0.98-1.57) × 10-2 reflect the predominant global fallout signal of 236U in the Barents Sea sediments and the highest reactor-236U contribution accounts for 30 ± 14 % among the six sediment cores. The reactor-236U input in the Barents Sea sediments is most likely transported from the European reprocessing plants rather than related to any local radioactive contamination. These results provide better understanding on the source term of anthropogenic 236U in the Barents Sea, prompt the oceanic tracer application of 236U for studying the dynamics of the Atlantic-Arctic Ocean and associated climate changes. The 236U-233U benchmarked age-depth profiles seem to match reasonably well with the reported input function history of radioactive contamination in the Barents Sea, indicating the high potential of anthropogenic 236U-233U pair as a useful tool for sediment dating.

Determination of 241Am in Environmental Samples: A Review.

The determination of 241Am in the environment is of importance in monitoring its release and assessing its environmental impact and radiological risk. This paper aims to give an overview about the recent developments and the state-of-art analytical methods for 241Am determination in environmental samples. Thorough discussions are given in this paper covering a wide range of aspects, including sample pre-treatment and pre-concentration methods, chemical separation techniques, source preparation, radiometric and mass spectrometric measurement techniques, speciation analyses, and tracer applications. The paper focuses on some hyphenated separation methods based on different chromatographic resins, which have been developed to achieve high analytical efficiency and sample throughput for the determination of 241Am. The performances of different radiometric and mass spectrometric measurement techniques for 241Am are evaluated and compared. Tracer applications of 241Am in the environment, including speciation analyses of 241Am, and applications in nuclear forensics are also discussed.

Plutonium isotopes in the northwestern South China Sea: Level, distribution, source and deposition.

The spatial distribution of plutonium isotopes (239Pu, 240Pu) in the surface sediments collected from the northwestern South China Sea (SCS) in 2018 was investigated. The 239,240Pu concentrations in surface sediments vary from 0.048 to 0.960 mBq/g (with mean of 0.282 ± 0.242 mBq/g) depending on the geographical feature of the sampling location such as the river estuary, continental shelf, slope and deep basin. Higher 240Pu/239Pu atomic ratios (0.24-0.31) in the surface sediment of the SCS compared to the global fallout value of 0.18 were observed, this is attributed to the input of close-in fallout of the Pacific Proving Ground (PPG) transported by the North Equatorial Current and Kuroshio Current to the northern SCS. The contribution of the PPG derived plutonium in the SCS sediment was estimated to be 39%-78% using a simple two-end member mixing model based on the measured 240Pu/239Pu atomic ratios in the sediment. Besides the soluble 239,240Pu level in seawater, load of suspended particulate matter from the river runoff and biological debris, hydrographic and hydrodynamic conditions are key parameters influencing the deposition process of plutonium to the sediment.

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.

Deciphering anthropogenic uranium sources in the equatorial northwest Pacific margin.

This work reports the first high-resolution deposition records of anthropogenic uranium (236U and 233U) in a sediment core taken at the continental slope of the Philippine Sea off Mindanao Island in the equatorial northwest Pacific Ocean. Two notable peaks were observed in both profiles of 236U and 233U concentrations, with a narrower peak in 1951-1957 corresponding to close-in Pacific Proving Grounds (PPG) signal, and a broader peak in 1960s-1980s corresponding to the global fallout from nuclear weapons testing. 236U and 233U areal cumulative inventories in the studied sediment core are (2.79 ± 0.20) ∙ 1012 atom ∙ m-2 and (3.12 ± 0.41) ∙ 1010 atom ∙ m-2, respectively, about 20-30% of reported 233U and 236U inventories from the direct global fallout deposition. The overall 233U/236U atomic ratios obtained in this work vary within (0.3-3.5) âˆ™ 10-2, with an integrated 233U/236U atomic ratio of (1.12 ± 0.17) âˆ™ 10-2. The contribution from global fallout and close-in PPG fallout to 236U in the sediment core is estimated to be about 69% and 31%, respectively. We believe the main driving process for anthropogenic uranium deposition in the Philippine sediment is continuous scavenging of dissolved 236U from the surface seawater by sinking particles.

High-Resolution Tritium Profile in an Ice Core from Camp Century, Greenland.

We measure 3H in an ice core from Camp Century. The temporal distribution of 3H concentration in the ice core corresponds generally well with the historical record of explosive yields of atmospheric nuclear weapons tests. Maximum 3H values observed in 1962-1963 are comparable to those in ice core or precipitation in many other locations in the Northern Hemisphere. There is no indication that significant 3H contamination was locally released into the air during the operation of the Camp Century reactor. It is, however, somewhat surprising that several prominent 3H peaks are still observed after 1980. We suggest that these are associated with airborne 3H releases from the civil nuclear industry. A wavelet analysis during 1970-2017 indicates the primary frequency of variability in the 3H record is annual 3H peaks. These annual peaks can be combined with the 3H spikes from global fallout of known nuclear weapons tests to benchmark and evaluate theoretical ice core dating scales back to the 1950s. A positive correlation is observed between annual 3H average concentration and variability of Arctic Oscillation (AO). This highlights the value of 3H as a potential tracer for air masses and airborne pollutants in the Arctic.

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.

Determination of low-level 135Cs and 135Cs/137Cs atomic ratios in large volume of seawater by chemical separation coupled with triple-quadrupole inductively coupled plasma mass spectrometry measurement for its oceanographic applications.

Radioisotopes of cesium are powerful tracer for oceanographic studies. In this work, a novel method was developed for determination of ultra-low level 135Cs and 137Cs in seawater using triple-quadrupole inductively coupled plasma mass spectrometry (ICP-MS/MS). Cesium was pre-concentrated from up to 45 L seawater samples using ammonium molybdophosphate (AMP) adsorption, following a selective leaching of cesium using Sr(OH)2. The cesium was further purified from interfering elements using AMP-PAN and cation-exchange chromatography. Sr(OH)2 leaching was found to be an effective approach for selective exchange of cesium from the AMP sorbent without dissolution, which avoids the problem of separation of huge amount of NH4+ and MoO42- in the following steps. The decontamination factors for barium and rubidium with the developed method were more than 4 × 107 and 800, respectively. The separated 135Cs and 137Cs were measured using ICP-MS/MS by employing N2O as reaction gas to further elimination of isobaric (i.e. 135Ba and 137Ba) and polyatomic ions interferences. A detection limit of 1.5 × 10-16 g L-1 for 135Cs in seawater was achieved. The concentrations of 135Cs in seawater from Baltic Sea, Danish straits and Roskilde Fjord were determined using the developed method to identify the sources of 135Cs, the water masses exchange in this region was investigated using 135Cs and 137Cs.

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.

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.

Determination of 135Cs concentration and 135Cs/137Cs ratio in waste samples from nuclear decommissioning by chemical separation and ICP-MS/MS.

Determination of 135Cs concentration and 135Cs/137Cs atomic ratio is of great importance in characterization of radioactive waste from decommissioning of nuclear facilities. In this work, an effective analytical method was developed for simultaneously determination of 135Cs and 137Cs in different types of waste samples (steel, zirconium alloy, reactor coolant, ion exchange filter paper and spent ion exchange resin) by coupling AMP-PAN, AG MP-1M and AG 50 W-X8 chromatographic separation with ICP-MS/MS measurement. Decontamination factors of 7.0 × 106 for Co, 6.0 × 106 for Ba, 4.2 × 105 for Mo, 3.2 × 105 for Sn and 2.1 × 105 for Sb were achieved using the chemical separation procedure. The overall chemical yields of cesium were higher than 85%. A detection limit of 3.1 × 10-14 g/g for 135Cs was achieved for 0.2 g stainless steel sample or spent resin. The developed method was validated by analysis of standard reference materials (IAEA-375) and successfully applied for analysis of zirconium alloy, steel, ion exchange filter paper and spent ion exchange resin from nuclear power reactors. The obtained 135Cs can be used to evaluate the long-term environmental impact and provide useful information for waste disposal. The measured 135Cs/137Cs ratio in reactor coolant, as a characteristic information, might be useful for source identification and localization of leaked fuel element. The neutron flux of the leaked fuel element can be estimated based on the measured 135Cs/137Cs atomic ratios in the reactor coolant water. The developed method is simple and rapid (8 samples/day) for the determination of 135Cs concentrations and 135Cs/137Cs ratios in various waste samples from nuclear decommissioning.

Plutonium isotopes in Northern Xinjiang, China: Level, distribution, sources and their contributions.

Plutonium in the environment has drawn significant attentions due to its radiotoxicity in high concentration and source term linked with nuclear accidents and contaminations. The isotopic ratio of plutonium is source dependent and can be used as a fingerprint to discriminate the sources of radioactive contaminant. 239Pu, 240Pu and 137Cs in surface soil and soil cores collected from Northern Xinjiang were determined in this work. The concentrations of 239,240Pu and 137Cs are in the range of 0.06-1.20 Bq kg-1, and <1.0-31.4 Bq kg-1 (decay corrected to Sep. 2017), respectively, falling in the ranges of global fallout in this latitude zone. The 240Pu/239Pu atomic ratios of 0.118-0.209 and 239,240Pu/137Cs activity ratios of 0.039-0.215 were measured. Among the investigated sites, distinctly lower 240Pu/239Pu atomic ratios of 0.118-0.133 and higher 239,240Pu/137Cs activity ratios of 0.065-0.215 compared to the global fallout values were observed in the northwest part, indicating a significant contribution from other source besides the global fallout. This extra source is mainly attributed to the releases of atmospheric nuclear weapons testing at Semipalatinsk Nuclear Test Site, which was transported by the west and northwest wind through the river valley among mountains in this region. This contribution is estimated to account for 28-43% of the global fallout in the northwest part of Northern Xinjiang. The contribution from the Chinese atmospheric nuclear weapons testing to this region is negligible due to the lack of appropriate wind direction to transport the radioactive releases to this region.