Research on the Transport and Chemistry of Fission Products in Primary Circuit and Containment Conditions at VTT

Research on the Transport and Chemistry of Fission Products in Primary Circuit and Containment Conditions at VTT Nuclear 2012, Pitesti, Romania, 17.5.2012 Teemu Kärkelä 1, Jarmo Kalilainen 1, P. Rantanen 1, Ari Auvinen 1, Jorma Jokiniemi 1,2 1 VTT Technical Research Centre of Finland 2 University of Eastern Finland

2 Introduction During a severe accident in a nuclear power plant (NPP), in which the normal core cooling is lost and the fuel rods are melting, the release of fission products (FPs) from fuel will take place. In that event it is possible, that FPs are transported from the damaged fuel rods into the primary circuit and further to the containment building.

3 Introduction The released fission products, such as ruthenium and iodine, are radiotoxic and they may form gaseous compounds. Therefore, it is important to know in which form (gas, aerosol) the released FPs are transported in severe accident conditions.

4 Background The release and transport of fission products have internationally been one of the main interests in a field of nuclear safety research. The objectives of the studies have been to gather information on the behaviour of FPs and utilize it in the validation of severe accident simulation codes.

5 Background Phebus-FP has been one of the largest experimental programs where the release of FPs from the real fuel rods, with various burnups, has been studied [2]. These large scale experiments have resulted in a wide database. M. Schwarz, G. Hache, P. von der Hardt PHÉBUS FP: a severe accident research programme for current and advanced light water reactors Nucl. Eng. Des. 187, 47-69 (1999) H. Allelein, A. Auvinen, J. Ball, S. Guntay, L. E. Herranz, A. Hidaka, A. V. Jones, M. Kissane, D. Powers, G. Weber, State-Of-Art-Report on Nuclear Aerosols. Nuclear safety NEA/CSNI/R(2009)5, November 2009.

6 Background However, there are still open questions e.g. on the behaviour of iodine. In the Phebus-FP experiments, the gas phase concentration of iodine was found to be on a stable level in a long term, regardless of the experimental conditions and the water chemistry in a sump. The chemical processes for the observed generation and depletion of gaseous iodine in the containment are not known.

7 Background While the processes leading to this are not known the following hypothesis has been formulated * : Gaseous iodine and particulate iodine swept to painted condensers by steam condensation Iodide ion (or some other soluble chemical form of iodine) rapidly absorbs from water film onto paint before water film can drain and be discharged to sump Iodine on paint desorbs as a volatile species whether a water film is present or not Gaseous iodine species radiolytically destroyed to form fine particulate iodine oxides or iodine nitrogen oxides Iodine particulate sediments from containment atmosphere * R.Y. Lee and M. Salay, Phébus-FP Findings on Iodine Behaviour in Design Basis and Severe Accidents, Presented to the Advisory Committee on Reactor Safeguards 8.5.2008, U.S.NRC

8 Background In addition to large-scale facilities, there are several intermediate and small scale facilities which are dedicated on studying the various phenomena taking place in the primary circuit and the containment building during a severe accident. Studies at VTT have focused on the transport and chemistry of FPs at described conditions. In recent years the interest in experiments has been on ruthenium and iodine, because of their high radiotoxicity.

9 Experiments at VTT Ruthenium transport in primary circuit Iodine transport in primary circuit Radiolytical oxidation of iodine in containment conditions Desorption of iodine from IOx deposition on painted surface

10 Ruthenium transport in primary circuit In experiments the formation and transport of volatile ruthenium oxides was studied by exposing RuO 2 powder to diverse oxidising atmospheres at a relatively high temperature. Varied parameters: Temperature 1100-1700 K Oxygen volume fraction in flow 6-21 % Steam volume fraction in flow 0-50 % Total flow rate 5 10 l/min

11 Ruthenium transport in primary circuit

12 Ruthenium transport in primary circuit 25 20 15 10 Release rate (mg/min) 21 / 0 5 19 / 4 Oxygen volume fraction and steam volume fraction (%) 6 / 10 6 / 50 10 lpm, 6 / 25 1100 K 1300 K 1500 K 1700 K Temperature (K) 0 1100 K 1300 K 1500 K 1700 K

13 Ruthenium transport in primary circuit 9 > 8 7 6 RuO 2 transport rate [mg/min] 5 4 Transport (mg/min) 21 / 0 19 / 4 3 6 / 10 6 / 50 2 10 lpm, 6 / 25 revap. 19/4 1 revap. 6/10 Oxygen volume fraction and steam volume fraction (%) 1100 K 1300 K 1500 K Temperature (K) 1100 K 1300 K 1500 K 1700 K 1700 K 0

Transport [mg/min] 31/05/2012 14 Ruthenium transport in primary circuit RuO 4 transport rate [mg/min] 0.035 0.030 0.025 0.020 0.015 0.010 0.005 0.000 1100 K 1300 K 1500 K 1700 K Temperature [K]

(%/cm) of released Ru 31/05/2012 15 Ruthenium transport in primary circuit 7 Ru deposition profile in the facility 6 5 Furnace outlet (0 cm) 4 3 2 Ceramic furnace tube End of ceramic furnace tube Stainless steel tube connector - no data Stainless steel tube 1 0-25 -20-15 -10-5 0 5 10 15 20 25 30 35 40 45 50 55 60 Distance (cm) Exp 6 1500K Air saturated Exp 7 1300K 10% steam Exp 8 1300K 50% steam Exp 9 1300K Dry air Exp 16 1500K Air sat + RuO4 Exp 17 1500K Air sat + RuO4

16 Ruthenium transport in primary circuit It was noticed that a very large fraction of ruthenium may be transported in gaseous form. At 1300 K ruthenium was primarily transported in gaseous form (as high as 89% of transported Ru) and increasing steam partial pressure increased the fraction of gaseous ruthenium. At 1500 K and above, ruthenium transport took place almost entirely as aerosol particles (~99% of transported Ru). Gaseous ruthenium seemed to react on the surface of the stainless steel tube, on top of which RuO 2 particles had been deposited.

17 Iodine transport in primary circuit Reactions of deposited fission products on primary circuit surfaces can modify the amount, composition and timing of fission product release to the containment. Studies to investigate the effects of reactions with primary circuit surfaces on transport of iodine have been conducted. The effects of different precursor mixtures on iodine transport have been investigated with EXSI PC facility

18 Iodine transport in primary circuit Caesium iodide (CsI) was used as the source of iodine in all experiments. Silver, molybdenum oxide and boron oxide were used as additives. Reaction furnace temperature was varied between 400 and 650 C in order to determine the effect of temperature in the release of gaseous and aerosol phase iodine. Each experiment contained three different atmosphere conditions, with different fractions of steam, argon and hydrogen

Mass conc. [mg/m 3 ] 31/05/2012 19 100 10 CsI + Ag 650 C 1 0.1 0.01 A B C A B C A B C A B Iodine Cesium Silver Molyb. Aerosol Gaseous Addition of silver to the CsI precursor at 650 C decreased the release of iodine as well as the fraction of gaseous iodine. C

Mass conc. [mg/m 3 ] 31/05/2012 20 1000 100 CsI + Ag 400 C 10 1 0.1 0.01 A B C A B C A B C A B Iodine Cesium Silver Molyb. Aerosol Gaseous At 400 C, Ag + CsI as well as Ag + MoO 3 + CsI precursor significantly increased the release of gaseous iodine, where almost no aerosol particles were released. C

Mass conc. [mg/m 3 ] 31/05/2012 21 1000 100 CsI + Ag + MoO 3, 400 C 10 1 0.1 0.01 A B C A B C A B C A B C Iodine Cesium Silver Molyb. Aerosol Gaseous At 400 C, Ag + CsI as well as Ag + MoO 3 + CsI precursor significantly increased the release of gaseous iodine, where almost no aerosol particles were released.

22 Iodine transport in primary circuit Generally in the experiments, it was observed that the hydrogen in the atmosphere decreased the fraction of released gaseous iodine. As the temperature was lowered, less iodine was released, but the fraction of gaseous iodine from the overall released iodine was increased.

23 Radiolytical oxidation of iodine in containment conditions During a severe accident, iodine may react with painted surfaces of containment to form organic iodine species. These organic species are a possible source of volatile iodine, which may increase the fraction of iodine in the gas phase. Therefore, it is important to study the transport of organic iodine in containment conditions. Another question is, whether the organic iodides are transported as gaseous molecules or as aerosol particles resulting from reactions with air radiolysis products.

24 Radiolytical oxidation of iodine in containment conditions In experiments methyl iodide was fed into the EXSI CONT facility in an air mixture. In some experiments the flow contained also humidity. The reactions took place in a quartz tube heated either to 50 C, 90 C or 120 C. UV-light was used as a source of radiation to produce ozone from oxygen. A separate generator was also applied to reach higher ozone concentrations.

25 Radiolytical oxidation of iodine in containment conditions EXSI CONT facility

26 Radiolytical oxidation of iodine Irradiation of oxygen molecules in air leads to the subsequent formation of ozone, which is keen to react with other substances. Both gaseous elemental and organic iodine tends to react with air radiolysis product ozone and form iodine oxide aerosol particles. Air radiolysis: UV (185nm) + O2 -> O + O O + O2 -> O3 I2 + O3 -> final products: e.g. I2O5, I4O9 aerosols

00:00 00:15 00:30 00:45 01:00 01:15 01:30 01:45 02:00 02:15 02:30 02:45 03:00 03:15 03:30 03:45 04:00 04:15 04:30 04:45 05:00 Particle concentration [#/cm 3 ] 31/05/2012 27 Radiolytical oxidation of iodine 1E+08 9E+07 8E+07 7E+07 6E+07 5E+07 4E+07 3E+07 2E+07 1E+07 0E+00 CPC 3775 SMPS Time [mm:ss]

28 Radiolytical oxidation of iodine

29 Radiolytical oxidation of iodine

30 Desorption of iodine from IOx deposition on painted surface

The fraction of iodine desorpted [%] 31/05/2012 31 4 The effect of radiation dose on the desorption of iodine from IOx on paint 3.5 3 2.5 2 1.5 1 0.5 Humid flow 0 0 0.5 1 1.5 2 2.5 3 3.5 Gamma radiation dose [kgy]

32 Conclusions A siginificant fraction of ruthenium and iodine may transport as gas to the containment atmosphere. The radiolytical oxidation of iodine in the air atmosphere produces IOx particles. Gaseous iodine releases from the IOx particles deposited on the painted surface of containment. This work was funded by the Finnish Research Programme on Nuclear Power Plant Safety (SAFIR2010 and SAFIR2014), Nordic Nuclear Safety Research (NKS-R), European Commission / EU SARNET2 programmes.