THESIS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY A Chemical Perspective on the Tellurium Source Term in the Context of Severe Nuclear Power Plant Accidents Fredrik J. C. Espegren Department of Chemistry and Chemical Engineering CHALMERS UNIVERSITY OF TECHNOLOGY Gothenburg, Sweden 2020 A Chemical Perspective on the Tellurium Source Term in the Context of Severe Nuclear Power Plant Accidents Fredrik J. C. Espegren ISBN 978-91-7905-352-9 © Fredrik Jonny Christoffer Espegren, 2020. Doktorsavhandlingar vid Chalmers tekniska högskola Ny serie nr 4819 ISSN 0346-718X Nuclear Chemistry Department of Chemistry and Chemical Engineering Chalmers University of Technology SE-412 96 Gothenburg Sweden Telephone + 46 (0)31-772 1000 Cover: Samples of tellurium and sodium chloride heated to increasingly higher temperature. Chalmers Reproservice Gothenburg, Sweden 2020 A Chemical Perspective on the Tellurium Source Term in the Context of Severe Nuclear Power Plant Accidents Fredrik J.C. Espegren Department of Chemistry and Chemical Engineering Nuclear Chemistry and Industrial Materials Recycling Chalmers University of Technology Abstract In the event of a severe nuclear accident, one of the biggest concerns is the release of radioactive nuclides. Typically, the most volatile is likely to be released. One that is considered among the most volatile is tellurium. Additionally, health implications towards the public by tellurium can be by itself or the decay product iodine. Several aspects concerning the volatility under mainly oxidizing (e.g., air ingress) and inert (injection of inert gas preventing hydrogen explosion) conditions of the tellurium source term from a chemical perspective have been explored. These aspects are the consequence of seawater as an emergency cooling medium, the effect of cesium iodide on the transport on and interaction in the reactor coolant system (RCS), and the effect of surfaces located inside a boiling water reactor (BWR). Finally, the effectiveness of the containment spray system (CSS) using different solutions was investigated. Under oxidizing conditions, tellurium was noticeably affected by all aspects. The seawater experiments showed that tellurium was enhanced by sodium chloride. From the RCS experiments, the addition of cesium iodide decreased the transported amount of tellurium and a new tellurium species was observed, but uncertain if it was correlated to cesium. Regarding the BWR surfaces, only zinc was removed from the surface by the tellurium when humidity was high. However, neither if this enhanced the volatility or if a new compound formed were clear. Finally, high removal efficiency was observed of the spray system under all conditions. The investigation of tellurium under inert conditions had less of the investigated aspect affecting the volatility. The seawater experiment showed no change to the volatilization of tellurium. However, in the RCS the addition of cesium iodide resulted in both an increase in transported tellurium and new tellurium species, potentially correlated to cesium. None of the BWR surfaces had any effect on tellurium. Finally, the effectiveness of the CSS was lower than under oxidizing conditions but still above 50%. However, the addition of cesium iodide considerably enhanced the removal. Therefore, indicating a change of the tellurium speciation. From this work, it is clear that the chemistry concerning the volatility of tellurium still needs further attention. Under an air ingress scenario, using seawater would enhance the release of tellurium. Opposed to the cesium iodide, that would reduce it. In the containment, tellurium would interact with surfaces made out of zinc. For a scenario when inert gas has been injected, the use of seawater would have less impact if any and the presence of cesium iodide would enhance the transport of tellurium. No surface in the BWR containment would interfere. However, under both scenarios, an intact containment and a functional CSS would effectively trap the tellurium in the sump. Keywords: Tellurium, Cesium Telluride, Nuclear Accident, Fission Products, Seawater Cooling, Reactor Coolant System, Containment, Containment Spray System Thesis for the degree of Doctor of Philosophy Espegren, F. List of Publications The thesis is based on the work found in the publications stated below and the contribution by the author of this thesis is included: I. Espegren, F., Glanneskog,¨ H., Foreman, M.R.S., Ekberg, C. ”Chemical interaction be- tween sea-salt and tellurium, between 300 and 1180 K”. In: ”Journal of Radioanalytical and Nuclear Chemistry” 317 (2018), pp. 535–543 DOI: 10.1007/s10967-018-5922-1 Contribution: Main author, all experimental work, all data acquisition and interpre- tation. II. Espegren, F. and Ekberg, C. ”Potential tellurium deposits in the BWR containment during a severe nuclear accident”. In: ”Annals of Nuclear Energy” 146 (2020), pp. 107629, ISSN: 0306-4549, DOI: 10.1016/j.anucene.2020.107629 Contribution: Main author, all experimental work, all data acquisition and interpre- tation. III. Espegren, F., Karkel¨ a,¨ Pasi, A.E., Tapper, U., Kucera,ˇ J., Lerum, V.L., Omtvedt, J.P., Ekberg, C. ”Tellurium Transport in the RCS under conditions relevant for severe nuclear accidents”. Submitted to: ”Progress in Nuclear Energy” Contribution: Main author, collaborated on all experimental work, part of data acquisition and interpretation. IV.K arkel¨ a,¨ Pasi, A.E., Espegren, F., Sevon, T., Tapper, U., Ekberg, C. ”Tellurium Reten- tion by Containment Spray System”. Manuscript to be submitted in September. Input from other authors still missing. Journal aim: ”Nuclear Engineering and Technology”, ”Progress in Nuclear Energy”, ”Annals of Nuclear Energy”, or ”Nuclear Technology”. Contribution: Editing of article, participation in most of the experimental work, part of data acquisition and interpretation. V. Kucera,ˇ J., Pasi, A.E., Espergen, F., Karkel¨ a,¨ T., Lerum, H.V., Omtvedt, J.P., Ekberg, C. ”Tellurium determination by three modes of instrumental neutron activation anal- ysis in aerosol filters and trap solutions for the simulation of a severe nuclear acci- dent”. In: ”Microchemical Journal” 58 (2020), pp. 105139, ISSN: 0026-265X, DOI: 10.1016/j.microc.2020.105139 Contribution: Editing of article concerning the TETRA part, participated in the analysis. Thesis for the degree of Doctor of Philosophy Espegren, F. Contents 1 Introduction 1 2 Background 2 2.1 Accident - General . .3 2.2 Accident - Fukushima Daiichi . .4 2.3 Radionuclides . .6 2.4 Fission Products . .7 2.5 Tellurium - Radioactivity and Fission yield . .7 2.6 Tellurium - Health Concerns . .8 3 Theory 9 3.1 Reactiveness and Expected Chemical Species . .9 3.1.1 State of Tellurium in the Fuel . .9 3.1.2 Cladding Interaction with Tellurium . 10 3.1.3 Tellurium within the Reactor Coolant System . 11 3.1.4 Containment Enclosure Aspects of Tellurium . 16 4 Experimental 19 4.1 Seawater-Tellurium Experiments . 19 4.2 Reactor Coolant System Experiment . 20 4.3 Containment Experiments . 21 4.4 Containment Spray Experiments . 22 4.5 Analytical Methods . 25 4.5.1 Quantification - Morphology, Elemental, Speciation . 25 4.5.2 Quantification - Amounts on Filters and Traps, Online Monitoring dur- ing Experiments . 26 5 Results and Discussion 29 5.1 Seawater-Tellurium Experiment . 29 5.1.1 Inert Conditions . 29 5.1.2 Oxidizing Conditions . 31 5.1.3 Visualization of Samples through Furnace Experiments . 32 5.2 Reactor Coolant System experiment . 35 5.2.1 Initial Observations and Quantification . 35 5.2.2 Detailed Quantification . 36 5.2.3 Chemical Speciation . 38 5.2.4 Online Measurements . 40 5.2.5 Morphology and Elemental Composition . 42 5.3 Containment Experiment . 44 5.3.1 Oxidizing Conditions . 45 5.3.2 Inert Conditions . 48 5.3.3 Reducing Conditions . 51 5.4 Spray Experiment . 54 6 Summary 58 Thesis for the degree of Doctor of Philosophy Espegren, F. 7 Conclusions 60 8 Future Work 61 9 Acknowledgments 62 Thesis for the degree of Doctor of Philosophy Espegren, F. 1 Introduction Starting from 2007 and continuing through to 2017, the global primary energy consumption was increased by an average of 1.5% per year. The following year of 2018, the global energy consumption exceeded this by doubling the average of prior years to 2.9%. To meet such an increase in demand for energy, several sources were expanded over the 10-year period as well as during the year 2018 [1]. Among these sources were fossil, hydro, renewables, and nuclear. The corresponding individual annual increase for these sources can be found in Table 1. Table 1. The global energy production increase of some of the primary energy sources. Values given are for 2007-2017 average annual increase and the 2018-year increase. Renewable includes solar and wind production [1]. Energy source Coal Oil Natural gas Nuclear Hydro Renewable 2007-2017 0.7% 1.0% 2.2% -0.4% 2.8% 16.4% 2018 1.4% 1.2% 5.3% 2.4% 3.1% 14.5% A major concern associated with energy production today is the CO2-emission [2]. According to the Intergovernmental Panel on climate change [3] and the European Union [4], one energy source that can deliver low emission of CO2 energy is nuclear power and as shown in Table 1, was expanded during 2018. Using nuclear power comes with some drawbacks and these are operational safety, waste management, and fissile material proliferation. Therefore, if nuclear power is to be part of the future energy mix of any country, these aforementioned drawbacks need to be mitigated and research. During a nuclear accidents, one of the biggest issues is the release of radionuclides. On this topic a considerable effort has already been made. Still, if the safe use of nuclear power is to be continued, more is needed. Historically, such research has been carried out in large fission prod- uct release research programs such as e.g., VERCORS [5, 6, 7], VERDON [8, 9, 10], PHEBUS´ [11, 12, 13, 14, 15]. In such programs, a large number of radionuclides, phenomena, and pa- rameters have been investigated simultaneously and as such closer mimics an actual nuclear power plant accident scenario.