Monitoring atmospheric 85Kr by atom counting.

Radioactive 85Kr is a major gaseous fission product emitted into the air by the nuclear fuel reprocessing industry. Measuring atmospheric 85Kr has applications in environmental monitoring, atmospheric transport model validation and dating of environmental water samples, including groundwater, sea water and glacier ice. We present an ultra-sensitive method for fast analysis of atmospheric 85Kr at 10-5 parts per trillion level. This method is based on laser cooling and trapping and is capable of counting individual 85Kr atoms. Measurements at the 3% precision level can be made on krypton extracted from 1L STP of air with a turnaround time of 1.5 h. Moreover, we have realized a system for continuous air sampling over days to weeks. Based on this atom-counting technology and a portable air sample integrator we have realized atmospheric 85Kr baseline monitoring in Hefei, China, for over 20 months. The technological advances presented in this work lay the ground for a global atmospheric 85Kr monitoring network.

Evaluating 5 decades of atmospheric 85Kr measurements in the southern hemisphere to derive an input function for dating water and ice with implications for interhemispheric circulation and the global 85Kr emission inventory.

In July 2015, the currently only active monitoring station for atmospheric 85Kr measurements in the southern hemisphere went operational at the Commonwealth Scientific and Industrial Research Organization (CSIRO) in Adelaide, Australia. Here, this new data is presented and combined with measurements from historic monitoring stations, to generate a85Kr input function for the southern hemisphere which is crucial for the application of 85Kr as a dating tracer for water and ice. After a linear increase in atmospheric 85Kr concentrations between 1980 and 2005, concentrations stabilized yielding mean 85Kr activity concentration during the Adelaide monitoring period of 1.3 ± 0.15 Bq/m³ air with slight variations indicating seasonal effects. Data from three northern hemispheric monitoring stations Schauinsland, Freiburg and Jungfraujoch of the German Federal Office for Radiation Protection (BfS), located in Central Europe are used to calculate an interhemispheric exchange time of 1.25 ± 0.24 years, using a simple box model approach. Furthermore, it is investigated whether a southern hemispheric 85Kr input function can be calculated from the baseline of the northern hemispheric data set. A comparison between the calculated and the fitted input function shows that analytical techniques can just resolve the concentration differences, emphasising the need of southern hemispheric monitoring stations for 85Kr. Analysing the decay-corrected input function and taking the current detection limit of low-level counting and Atom Trap Trace Analysis of 0.05 Bq/m³ air, a maximum apparent 85Kr tracer age of 40 years can be determined in the southern hemisphere. Finally, the 85Kr measurements are used to derive global 85Kr emission rates which are found to be in good agreement with published emissions from nuclear reprocessing plants.

Using isotope data to characterize and date groundwater in the southern sector of the Guaraní Aquifer System.

The Guaraní Aquifer System (SAG) is the largest transboundary aquifer in Latin America, extending beneath parts of Brazil, Paraguay, Argentina, and Uruguay. This paper presents the results of recent hydrogeological studies in the southern portion of the SAG. Locally, the abundance of surface water bodies precluded the use of conventional hydrological tools to characterize groundwater flows. Geological, hydrochemical and environmental isotope investigations were integrated to postulate a revised hydrogeological conceptual model. The revised geological model has provided a better definition of the geometry of the aquifer units and outlined the relevance of regional faults in controlling flow patterns. The new potentiometric map is consistent with groundwater flow from the SAG outcrops to the centre of the Corrientes Province, where upwards flows were identified. Hydrochemical and isotope data confirmed the widespread occurrence of mixing. Noble gas isotopes dissolved in groundwater (4He and 81Kr/Kr) provided residence times ranging from recent recharge up to 770 ± 130 ka. Groundwater age modelling confirmed the role of the geological structures in controlling groundwater flow. The southern sector of the SAG is a multilayer aquifer system with vertical flows and deep regional discharge near the Esteros del Iberá wetland area and along the Paraná and Uruguay rivers.

Half a century of Krypton-85 activity concentration measured in air over Central Europe: Trends and relevance for dating young groundwater.

For almost half a century weekly samples for the measurement of krypton-85 (85Kr) activity concentrations in surface air have been collected by the Bundesamt für Strahlenschutz (BfS), Germany. Sampling started at Freiburg (230m asl) in 1973, Mt Schauinsland (1205m asl) in 1976 and Mt Jungfraujoch in Switzerland (3454 asl) in 1990. Distinct maxima in the time series of atmospheric 85Kr activity concentration are caused by emissions from nuclear reprocessing plants in Europe, mainly the La Hague, France, and Sellafield, UK, reprocessing plants. Between 1970 and 1990 peak activity concentrations measured in winter along the Rhine Rift in Freiburg are often higher than at Mt Schauinsland, due to emissions from the operating pilot reprocessing plant in Karlsruhe - approximately 130 km to the north - and large-scale inversions that inhibit exchange of air masses within the Rhine Rift with those at higher altitudes. From the early 1990s onwards, after the shut-down of the pilot plant, differences between Freiburg and Schauinsland are much smaller. Activity concentrations measured at Jungfraujoch are generally lower and close to baseline levels, due to its location in the free troposphere. Weekly baseline and average 85Kr activity concentration in the atmosphere in Central Europe were modelled from almost 12,000 individual measurements at 11 stations. The baseline and average have continuously increased, interrupted by a relatively stable period between 2009 and the end of 2014 with a baseline activity concentration of about 1.39 Bq/m3. Depending on the geographical location and hydrological conditions, the modelled baseline or average 85Kr activity concentration time series can be used as input functions for the dating of young groundwater.

Simulating the mesoscale transport of krypton-85.

Due to its half-life, chemical inertness and low solubility in water, radioactive 85Kr is a valuable tracer for testing the performance of atmospheric dispersion models in simulating long-range transport of pollutants. This paper evaluates the capability of simulating the dispersion of radiokrypton emitted by a nuclear fuel reprocessing plant in north-west France. Three time periods during which elevated activity concentrations of 85Kr in ground level air were detected in south-west Germany are chosen. Simulations have been performed using the HYSPLIT code and the European Centre for Median-Range Weather Forecasts (ECMWF) data base. Although their results show a slight trend of underestimating the measured 85Kr concentrations, there is a significant correlation and moderate scatter between observations and simulations with about 50% of the results being within a factor of two of the measured concentrations. The simulated travel time distributions provided a valuable tool for providing additional insight into the dispersion of the tracer radionuclides and for identifying potential causes of deviations between measured and calculated concentrations.

Present and future potential of krypton-85 for the detection of clandestine reprocessing plants for treaty verification.

Burnup calculations are applied to determine the amount of krypton-85 that is produced during the irradiation of nuclear fuel. Since krypton-85 is most likely released into the atmosphere during reprocessing to separate plutonium, atmospheric transport modeling is used to calculate the worldwide distribution of krypton-85 concentrations stemming from emissions from declared reprocessing plants. The results are the basis for scenarios in which emissions from clandestine reprocessing facilities have to be detected against various background levels. It is concluded that today's background imposes heavily on the ability to detect small and medium plutonium separation rates; only high separation rates of 1 SQ per week and higher have a chance to be detected with feasible outlay. A fixed network of monitoring stations seems too costly; instead the high number of samples that are required rather calls for mobile sampling procedures, where air samples are collected at random locations over the world and are analyzed in regional laboratories for their krypton-85 concentration. Further, it is argued that krypton-85 emissions from declared reprocessing activities have to be significantly lowered to enable a worldwide verification of the absence of even smaller clandestine reprocessing. For each scenario the number of samples that have to be taken for probable detection is calculated.

Estimation of 85Kr dispersion from the spent nuclear fuel reprocessing plant in Rokkasho, Japan, using an atmospheric dispersion model.

The spent nuclear fuel reprocessing plant of Japan Nuclear Fuel Limited (JNFL) located in Rokkasho, Japan, discharged small amounts of (85)Kr into the atmosphere during final tests of the plant with actual spent fuel from 31 March 2006 to October 2008. During this period, the gamma-ray dose rates due to discharged (85)Kr were higher than the background rates measured at the Institute for Environmental Sciences and at seven monitoring stations of the Aomori prefectural government and JNFL. The dispersion of (85)Kr was simulated by means of the fifth-generation Penn State/NCAR Mesoscale Model and the CG-MATHEW/ADPIC models (ver. 5.0) with a vertical terrain-following height coordinate. Although the simulated gamma-ray dose rates due to discharged (85)Kr agreed fairly well with measured rates, the agreement between the estimated monthly mean (85)Kr concentrations and the observed concentrations was poor. Improvement of the vertical flow of air may lead to better estimation of (85)Kr dispersion.

Near-field krypton-85 measurements in stable meteorological conditions around the AREVA NC La Hague reprocessing plant: estimation of atmospheric transfer coefficients.

The aim of this work was to study the near-field dispersion of (85)Kr around the nuclear fuel reprocessing plant at La Hague (AREVA NC La Hague - France) under stable meteorological conditions. Twenty-two (85)Kr night-time experimental campaigns were carried out at distances of up to 4 km from the release source. Although the operational Gaussian models predict for these meteorological conditions a distance to plume touchdown of several kilometers, we almost systematically observed a marked ground signal at distances of 0.5-4 km. The calculated atmospheric transfer coefficients (ATC) show values (1) higher than those observed under neutral conditions, (2) much higher than those proposed by the operational models, and (3) higher than those used in the impact assessments.

Krypton-81 in groundwater of the Culebra Dolomite near the Waste Isolation Pilot Plant, New Mexico.

The Waste Isolation Pilot Plant (WIPP) in New Mexico is the first geologic repository for disposal of transuranic nuclear waste from defense-related programs of the US Department of Energy. It is constructed within halite beds of the Permian-age Salado Formation. The Culebra Dolomite, confined within Rustler Formation evaporites overlying the Salado Formation, is a potential pathway for radionuclide transport from the repository to the accessible environment in the human-disturbed repository scenario. Although extensive subsurface characterization and numerical flow modeling of groundwater has been done in the vicinity of the WIPP, few studies have used natural isotopic tracers to validate the flow models and to better understand solute transport at this site. The advent of Atom-Trap Trace Analysis (ATTA) has enabled routine measurement of cosmogenic (81)Kr (half-life 229,000 yr), a near-ideal tracer for long-term groundwater transport. We measured (81)Kr in saline groundwater sampled from two Culebra Dolomite monitoring wells near the WIPP site, and compared (81)Kr model ages with reverse particle-tracking results of well-calibrated flow models. The (81)Kr model ages are ~130,000 and ~330,000 yr for high-transmissivity and low-transmissivity portions of the formation, respectively. Compared with flow model results which indicate a relatively young mean hydraulic age (~32,000 yr), the (81)Kr model ages imply substantial physical attenuation of conservative solutes in the Culebra Dolomite and provide limits on the effective diffusivity of contaminants into the confining aquitards.

Variability of atmospheric krypton-85 activity concentrations observed close to the ITCZ in the southern hemisphere.

Krypton-85 activity concentrations in surface air have been measured at Darwin, which is located in northern Australia and is influenced by seasonal monsoonal activity. Measurements between August 2007 and May 2010 covered three wet seasons. The mean activity concentration of krypton-85 measured during this period was 1.31±0.02Bqm(-3). A linear model fitted to the average monthly data, using month and monsoon as predictors, shows that krypton-85 activity concentration measured during the sampling period has declined by 0.01Bqm(-3) per year. Although there is no statistically significant difference in mean activity concentration of krypton-85 between wet and dry season, the model implies that activity concentration is higher by about 0.015Bqm(-3) during months influenced by the monsoon when a north westerly flow prevails. Backward dispersion runs using the Lagrangian particle dispersion model Hysplit4 highlight possible source regions during an active monsoon located deep in the northern hemisphere, and include reprocessing facilities in Japan and India. However, the contribution of these facilities to krypton-85 activity concentrations in Darwin would be less than 0.003Bqm(-3).

Monte Carlo modelling of 90Sr/90Y and 85Kr beta fields for Hp(3) measurements.

In support of research aimed at developing a thermoluminescence dosemeter capable of accurately measuring ionising radiation doses to the lens of the eye, Monte Carlo modelling of a standard beta exposure set-up has been performed. It was found that electrons with an energy distribution corresponding to the beta emission spectrum from (85)Kr deposit negligible doses at a depth of 3 mm in tissue, but doses from (90)Sr/(90)Y are significant; free in air and fluence-to-Hp(3,θ°) and -Hp(0.07,θ°) conversion coefficient data were found for this field for exposures at 0°, 30° and 60° angles of incidence, and the response characteristics of the new eye dosemeter were evaluated. It was shown that the results were not affected greatly by the shape of the calibration phantom. However, it was demonstrated that the presence of intermediating air and beam flattening filters hardens the energy distribution of the field at the point of test, relative to a raw (90)Sr/(90)Y source, and this impacts dose depositions.

Comparison of RIMPUFF, HYSPLIT, ADMS atmospheric dispersion model outputs, using emergency response procedures, with (85)Kr measurements made in the vicinity of nuclear reprocessing plant.

The Institut de Radioprotection et de Sureté Nucléaire (IRSN) performed a series of (85)Kr air sampling campaigns at mesoscale distances (18-50 km) from the AREVA NC La Hague nuclear reprocessing plant (North West France) between 2007 and 2009. The samples were collected in order to test and optimise a technique to measure low krypton-85 ((85)Kr) air concentrations and to investigate the performance of three atmospheric dispersion models (RIMPUFF, HYSPLIT, and ADMS), This paper presents the (85)Kr air concentrations measured at three sampling locations which varied from 2 to 8000 Bq m(-3), along with the (85)Kr air concentrations output by the dispersion models. The dispersion models made reasonable estimates of the mean concentrations of (85)Kr field measurements during steady wind conditions. In contrast, the models failed to accurately predict peaks in (85)Kr air concentration during periods of rapid and large changes in wind speed and/or wind direction. At distances where we made the comparisons (18-50 km), in all cases, the models underestimated the air concentration activities.

Analysis of 85Kr: a comparison at the 10 -14 level using micro-liter samples.

The isotopic abundance of (85)Kr in the atmosphere, currently at the level of 10(-11), has increased by orders of magnitude since the dawn of nuclear age. With a half-life of 10.76 years, (85)Kr is of great interest as tracers for environmental samples such as air, groundwater and ice. Atom Trap Trace Analysis (ATTA) is an emerging method for the analysis of rare krypton isotopes at isotopic abundance levels as low as 10(-14) using krypton gas samples of a few micro-liters. Both the reliability and reproducibility of the method are examined in the present study by an inter-comparison among different instruments. The (85)Kr/Kr ratios of 12 samples, in the range of 10(-13) to 10(-10), are measured independently in three laboratories: a low-level counting laboratory in Bern, Switzerland, and two ATTA laboratories, one in Hefei, China, and another in Argonne, USA. The results are in agreement at the precision level of 5%.

High resolution monitoring system for IRE stack releases.

The main activity of IRE (Institute for Radio-Element) is radioisotope production of bulk (99)Mo and (131)I for medical application (diagnosis and therapy). Those isotopes are chemically extracted from HEU (High Enriched Uranium) targets activated in reactors. During this process, fission products are released from the targets, including noble gases isotopes (Xe and Kr). Like any nuclear plant, IRE has release limits which are given by the Belgium authority and moreover IRE is in the process of continuously reducing the level of its releases. To achieve this mission, the need of an accurate tool is necessary and IRE has developed a specific monitoring system using a high resolution detector in order to identify and accurately estimate its gaseous releases. This system has a continuous air sampling system in the plant main stack. The sampled gases cross charcoal cartridges where they are slowed down and concentrated for higher detection efficiency. In front of those cartridges is installed an HPGe detector with a detection chain connected to a specific analysis system allowing on-line spectrum analysis. Each isotope can be separately followed without interferences, especially during the production process where high activity can be released. Due to its conception, the system also allows to measure iodine isotopes by integration on the charcoal cartridges. This device is of great help for accurately estimate IRE releases and to help for understanding specific releases and their origin in the production or maintenance process.

Update and improvement of the global krypton-85 emission inventory.

Krypton-85 is mainly produced in nuclear reactors by fission of uranium and plutonium and released during chopping and dissolution of spent fuel rods in nuclear reprocessing facilities. As noble gas it is suited as a passive tracer for evaluation of atmospheric transport models. Furthermore, research is ongoing to assess its quality as an indicator for clandestine reprocessing activities. This paper continues previous efforts to compile a comprehensive historic emission inventory for krypton-85. Reprocessing facilities are the by far largest emitters of krypton-85. Information on sources and calculations used to derive the annual krypton-85 emission is provided for all known reprocessing facilities in the world. In addition, the emission characteristics of two plants, Tokai (Japan) and La Hague (France), are analysed in detail using emission data with high temporal resolution. Other types of krypton-85 sources are power reactors, naval reactors and isotope production facilities. These sources contribute only little or negligible amounts of krypton-85 compared to the large reprocessing facilities. Taking the decay of krypton-85 into account, the global atmospheric inventory is estimated to about 5500 PBq at the end of 2009. The correctness if the inventory has been proven by meteorological simulations and its error is assumed to be in the range of a few percent.

Half-life determination of 88Kr and 138Xe.

The half-lives of (88)Kr and (138)Xe have been determined with two high purity germanium (HPGe) detectors by the position relay method. Data have been recorded at regular time intervals during measurements covering more than nine times the respective half-lives. This article describes in detail the principle and process of the position relay method with two HPGe detectors. The determined half-lives of (88)Kr and (138)Xe are 2.804±0.015 h and 14.18±0.10 min, respectively.

Comparison of two different types of LiF:Mg,Cu,P thermoluminescent dosimeters for detection of beta rays (beta-TLDs) from 90Sr/90Y, 85Kr and 147Pm sources.

Targeted radionuclide therapies in nuclear medicine departments increasingly depend on using unsealed beta radiation sources in the labeling of peptides and antibodies. Monitoring doses received by the fingers and hands during these procedures is best accomplished with TLD dosimeters that can be located at the fingertips. The present study examines the response of two TLD dosimeters (MCP-Ns and GR200A) to 90Sr/90Y, 85Kr, and 147Pm. The dosimeters were supplied by two different services, and all irradiations were performed at the PTB Institute in Germany. Each dosimetry service evaluated the dosimeters without knowledge that they had been purposefully irradiated. The accuracy and precision of the dosimeters were evaluated as a function of delivered dose, energy of beta particles and angular incidence. The results are compared to performance measures recommended by the IEC. Both dosimeter types displayed significant energy dependence. Angular dependence was moderate. Accuracy and precision as a function of dose (linearity) differed between the two systems, with the MCP-Ns being noticeably better than the GR200A. The superior precision makes the MCP-Ns much more useful for extremity dose measurements. The differences between these two dosimeter systems reinforce the need to evaluate a dosimeter carefully before using it in the daily work routine.

A study of the atmospheric dispersion of a high release of krypton-85 above a complex coastal terrain, comparison with the predictions of Gaussian models (Briggs, Doury, ADMS4).

Atmospheric releases of krypton-85, from the nuclear fuel reprocessing plant at the AREVA NC facility at La Hague (France), were used to test Gaussian models of dispersion. In 2001-2002, the French Institute for Radiological Protection and Nuclear Safety (IRSN) studied the atmospheric dispersion of 15 releases, using krypton-85 as a tracer for plumes emitted from two 100-m-high stacks. Krypton-85 is a chemically inert radionuclide. Krypton-85 air concentration measurements were performed on the ground in the downwind direction, at distances between 0.36 and 3.3 km from the release, by neutral or slightly unstable atmospheric conditions. The standard deviation for the horizontal dispersion of the plume and the Atmospheric Transfer Coefficient (ATC) were determined from these measurements. The experimental results were compared with calculations using first generation (Doury, Briggs) and second generation (ADMS 4.0) Gaussian models. The ADMS 4.0 model was used in two configurations; one takes account of the effect of the built-up area, and the other the effect of the roughness of the surface on the plume dispersion. Only the Briggs model correctly reproduced the measured values for the width of the plume, whereas the ADMS 4.0 model overestimated it and the Doury model underestimated it. The agreement of the models with measured values of the ATC varied according to distance from the release point. For distances less than 2 km from the release point, the ADMS 4.0 model achieved the best agreement between model and measurement; beyond this distance, the best agreement was achieved by the Briggs and Doury models.

Krypton gas cylinders as a source of radiation.

A standard 40 foot shipping container with a cargo of pressurized krypton gas in 159 steel cylinders, which had triggered a radiation alarm, was investigated to address radiation safety and illicit nuclear trafficking concerns. The investigation included contamination and dose rate measurements as well as in situ high resolution gamma spectroscopy. The dose rate measurements gave a maximum value of 0.07 microSv h(-1) above background (0.08 to 0.11 microSv h(-1)) on the cylinder surface and no detectable increase above background at distances of 1 m and higher. Contamination monitor readings showed a similar relative increase (plus 8 cpm) above background (about 12 cpm) to the dose rate readings. Quantitative gamma spectroscopy revealed a contamination of the gas with 85Kr at a level of 3.5 x 10(5) Bq kg(-1). This value was found to be consistent with analytical and numerical estimates based on current data for atmospheric 85Kr, which is captured from ambient air together with stable krypton during the production process. This incident demonstrates an apparent lack of radiation-related knowledge by those who handle krypton gas, as well as by border control personnel and emergency responders. We therefore propose to improve labeling and documentation standards for such shipments. This effort may be facilitated by introducing the new category of "technically enhanced artificial radioactive material," or "TEARM" (similar to the existing "naturally occurring radioactive material" or "NORM" and "technically enhanced naturally occurring radioactive material" or "TENORM" categories).

An improved method for 85Kr analysis by liquid scintillation counting and its application to atmospheric 85Kr determination.

Atmospheric (85)Kr concentration at Fukuoka, Japan was determined by an improved (85)Kr analytical method using liquid scintillation counting (LSC). An average value of 1.54 +/- 0.05 Bq m(-3) was observed in 2008, which is about two times that measured in 1981 at Fukuoka, indicating a 29 mBq y(-1) rate of increase as an average for these 27 years. The analytical method developed involves collecting Kr from air using activated charcoal at liquid N(2) temperature and purifying it using He at dry ice temperature, followed by Kr separation by gas chromatography. An overall Kr recovery of 76.4 +/- 8.1% was achieved when Kr was analyzed in 500-1000 l of air. The Kr isolated by gas chromatography was collected on silica gel in a quartz glass vial cooled to liquid N(2) temperature and the activity of (85)Kr was measured with a low-background LS counter. The detection limit of (85)Kr activity by the present analytical method is 0.0015 Bq at a 95% confidence level, including all propagation errors, which is equivalent with (85)Kr in 1.3 l of the present air under the analytical conditions of 72.1% counting efficiency, 0.1597 cps background count rate, and 76.4% Kr recovery.