Gaseous Ruthenium Research Articles

Release Behavior of Gaseous Ruthenium Tetroxide During Heating of High-Level Liquid Waste Simulant During Simulated Accident Conditions

A malfunction of the cooling system of high-level liquid waste (HLLW) and the failure of countermeasures may lead to the evaporation to dryness due to the loss of cooling functions (EDLCF) of the HLLW. In the EDLCF, ruthenium (Ru) can be released at a greater fraction to the initial amount than the other elements in HLLW by forming gaseous Ru. It is important to identify the chemical form of the released gaseous Ru to achieve a comprehensive understanding of the events impacting the source term assessment of Ru in this accident, such as particle formation, gas absorption, and deposition on migration pathways. In this study, we observed the ultraviolet/visible spectroscopy of the off-gas generated during the heating of a HLLW simulant. Employing a program that allows for the separation and quantification of known components within the spectrum [ruthenium tetroxide (RuO4), nitrogen dioxide, and nitric acid], we attempted to analyze the composition of gaseous Ru within the generated off-gas. Our findings revealed RuO4 as the main component of the gaseous Ru in the off-gas after comparing the total amount of released Ru and the RuO4 released amount obtained via spectroscopic analysis.

Capture and immobilization of gaseous ruthenium tetroxide RuO4 in the UiO-66-NH2 metal-organic framework.

106Ru is a radioactive isotope usually generated by the nuclear industry within power plant reactors. During a nuclear accident, 106Ru reacts with oxygen, leading to the production of highly volatile ruthenium tetroxide RuO4. The combination of volatility and radioactivity makes 106RuO4, one of the most radiotoxic species and justifies the development of a specific setup for its capture and immobilization. In this study, we report for the first time the capture and immobilization of gaseous RuO4 within a porous metal-organic framework (UiO-66-NH2). We used specific installation for the production of gaseous RuO4 as well as for the quantification of this gas trapped within the filtering medium. We proved that UiO-66-NH2 has remarkable affinity for RuO4 capture, as this MOF exhibited the worldwide highest RuO4 decontamination factor (DF of 5745), hundreds of times higher than the DF values of sorbents daily used by the nuclear industry (zeolites or activated charcoal). The efficiency of UiO-66-NH2 can be explained by its pore diameters well adapted to the capture and immobilization of RuO4 as well as its conversion into stable RuO2 within the pores. This conversion corresponds to the reactivity of RuO4 with the MOF organic sub-network, leading to the oxidation of terephthalate ligands. As proved by powder X-ray diffraction and NMR techniques, these modifications did not decompose the MOF structure.

Gaseous phase above Ru–O system: A thermodynamic data assessment

The present study is a critical assessment of thermochemical data for gaseous ruthenium oxides based on available experimental data. A full critical analysis and a reinterpretation of data are presented with a proposition for new accurate standard formation enthalpies values: Δf H°298(RuO4, g) = −197.6 ± 5.5 kJ mol−1, Δf H°298(RuO3, g) = −53.0 ± 10 kJ mol−1, Δf H°298(RuO2, g) = 158 ± 20 kJ mol−1 and Δf H°298(RuO, g) = 301 ± 28 kJ mol−1.

Decomposition behavior of gaseous ruthenium tetroxide under atmospheric conditions assuming evaporation to dryness accident of high-level liquid waste

ABSTRACT Emphasis has been placed on the behavior of ruthenium (Ru) in the evaporation to dryness accident due to the loss of cooling functions (EDLCF) of high-level liquid waste in fuel reprocessing plants. It is because Ru would form volatile compounds such as ruthenium tetroxide (RuO4) and could be released into the environment with other coexisting gasses such as nitric acid (HNO3), water (H2O). To contribute to the safety evaluation of this accident, we experimentally evaluated the decomposition and chemical change behavior of the gaseous RuO4 (RuO4(g)) under the various atmospheric conditions: temperature and composition of coexisting gasses. As a result, the behavior of the RuO4(g) was diverse depending on the atmospheric conditions. In the experiments with the dry air or H2O vapor, decomposition of RuO4(g) was observed. In the experiment with the mixed gas which containing HNO3, almost no decomposition of the RuO4(g) was observed, and chemical form of the RuO4(g) was retained.

Filtration tests of gaseous ruthenium tetroxide by sand bed and metallic filters

This work presents laboratory tests on gaseous RuO4 filtration carried out at IRSN in Cadarache. The objective is to determine if gaseous ruthenium tetroxide can be trapped by metallic filter and sand bed filter, both elements being used in filtered containment venting systems implemented on French pressurized water reactors. The results show no ruthenium tetroxide trapping by physical or chemical adsorption but certain retention is observed resulting from its thermal decomposition into solid ruthenium dioxide. A thermodynamic analysis of the system tends to confirm this conclusion. Chemical stability of RuO4(g) has to be considered as it strongly impacts potential filtration and so potential releases.

A DFT study of RuO4 interactions with porous materials: metal-organic frameworks (MOFs) and zeolites.

Radioactive gaseous ruthenium tetroxide (RuO4) can be released into the environment in the case of a severe nuclear accident. Using periodic dispersion corrected density functional theory calculations, we have investigated for the first time the adsorption behavior of RuO4 into prototypical porous materials, Metal-Organic Frameworks (MOFs) and zeolites, with the aim of mitigating ruthenium releases to the outside. For the MOFs, we have screened a set of six structures (MIL-53(Al), MIL-120(Al), HKUST-1(Cu), UiO-66(Zr), UiO-67(Zr) and UiO-68(Zr)), while for the zeolites two structures have been selected: mordenite (MOR) with Si/Al ratios of 11 and 5, and faujasite (FAU) with a Si/Al ratio of 2.4. The DFT calculations show that the nature of the porous materials does not have a significant effect on the adsorption energy of RuO4 compounds and that the main interaction is due to the formation of hydrogen bonds. For the tested materials, computational results show that the interaction energies of RuO4 reach their maximum with the hydrated form of HKUST-1(Cu) (-114 kJ mol-1) due to the presence of strong hydrogen bonds between the water molecules and the oxygen atoms of RuO4.

Ruthenium transport in an RCS with airborne CsI

Ruthenium is one of the most radiotoxic fission products which can be released from fuel as ruthenium oxides in an air ingress accident at a nuclear power plant. In this study it was found that the transport of the released ruthenium oxides through a reactor coolant system into the containment building is significantly affected by the atmospheric conditions. Airborne CsI increased the transport of gaseous ruthenium compared with that in a pure air atmosphere. The overall transport of ruthenium increased with temperature. In order to understand the behaviour of ruthenium in accident conditions, it is important to widen the experimental conditions from pure air/steam atmospheres to more realistic mixtures of prototypic gases and aerosols.

Impact of Ag and NOx compounds on the transport of ruthenium in the primary circuit of nuclear power plant in a severe accident

Ruthenium is a semi-volatile element originating as a fission product in nuclear reactors that can be released in case of a severe nuclear accident. In this work, the impact of atmosphere composition on the transport of ruthenium through the primary circuit was examined. The effects of silver nanoparticles representing aerosols and NO2 gas as a product of air radiolysis were studied. Quantification of ruthenium transported both as gas and aerosol was performed. Chemical composition of ruthenium species was evaluated. The transport of gaseous ruthenium through the facility increased significantly when NO2 gas was fed into the atmosphere. When both silver aerosols and NO2 were fed into the atmosphere, the transport of ruthenium in gaseous and aerosol forms was promoted. It was concluded that the composition of atmosphere in the primary circuit will have a notable effect on the speciation of ruthenium transported into the containment building during a severe accident and thus on the potential radioactive release to the environment.

Thermochemistry of Ruthenium Oxyhydroxide Species and Their Impact on Volatile Speciations in Severe Nuclear Accident Conditions

Literature thermodynamic data of ruthenium oxyhydroxides reveal large uncertainties in some of the standard enthalpies of formation, motivating the use of high-level relativistic correlated quantum chemical methods to reduce the level of discrepancies. Reaction energies leading to the formation of all possible oxyhydroxide species RuOx(OH)y(H2O)z have been calculated for a series of reactions combining DFT (TPSSh-5%HF) geometries and partition functions, CCSD(T) energies extrapolated to the complete basis set limits. The highly accurate ab initio thermodynamic data were used as input data of thermodynamic equilibrium computations to derive the speciation of gaseous ruthenium species in the temperature, pressure and concentration conditions of severe nuclear accidents occurring in pressurized water reactors. At temperatures lower than 1000 K, gaseous ruthenium tetraoxide is the dominating species, between 1000 and 2000 K ruthenium trioxide becomes preponderant, whereas at higher temperatures gaseous ruthenium oxide, dioxide and even Ru in gaseous phase are formed. Although earlier studies predicted the formation of oxyhydroxides in significant quantities, the use of highly accurate ab initio thermodynamic data for ruthenium gaseous species leads to a more reliable inventory of gaseous ruthenium species in which gaseous oxyhydroxide ruthenium molecules are formed only in negligible amounts.

Transport of ruthenium in primary circuit conditions during a severe NPP accident

Ruthenium species, volatilized from damaged fuel during a severe accident in a nuclear power plant, are radiotoxic and can be transported to the containment atmosphere in gaseous form. To limit the possible source term to the environment, it is of interest to understand the behaviour of Ru after it has been released from fuel and the phenomena taking place within the decreasing temperature section of the reactor coolant system. This was investigated in the framework of EC SARNET and SARNET2 projects, as a part of the Source Term work package, with several separate-effect tests on the transport and speciation of Ru in primary circuit conditions considering the influence of other fission products as well. The source of Ru was metallic Ru, RuO2 powder or gaseous RuO4. The large-scale integral tests of the Phébus FP program were conducted with real irradiated fuel, and more realistic analysis on the release and transport of Ru could be performed. Experimental studies proved that the transport of ruthenium to the containment atmosphere took mainly place as RuO2 particles when Ru source was oxidized above 1250°C. The fraction of Ru transported in gaseous form was at its highest when ruthenium was oxidized at approx. 1000–1100°C. A major part of the released Ru was deposited at the decreasing temperature area of the circuit as RuO2. Revaporisation of the deposited Ru at low temperature was a significant source of gaseous ruthenium. In order to understand the behaviour of ruthenium in these tests, the analysis work was extensive and several simulations were carried out. As an outcome, the observed transport and deposition of ruthenium was explained. The simulation studies gave also an insight into the performance of the ASTEC code and some model improvements for Ru transport through the reactor coolant system have been identified.

Ruthenium release modelling in air and steam atmospheres under severe accident conditions using the MAAP4 code

In a nuclear power plant (NPP), a severe accident is a low probability sequence that can lead to core fusion and fission product (FP) release to the environment (source term). For instance during a loss-of-coolant accident, water vaporization and core uncovery can occur due to decay heat. These phenomena enhance core degradation and, subsequently, molten materials can relocate to the lower head of the vessel. Heat exchange between the debris and the vessel may cause its rupture and air ingress. After lower head failure, steam and air entering in the vessel can lead to degradation and oxidation of materials that are still intact in the core. Indeed, Zircaloy-4 cladding oxidation is very exothermic and fuel interaction with the cladding material can decrease its melting temperature by several hundred of Kelvin. FP release can thus be increased, noticeably that of ruthenium under oxidizing conditions. Ruthenium is of particular interest because of its high radio-toxicity due to 103Ru and 106Ru isotopes and its ability to form highly volatile compounds, even at room temperature, such as gaseous ruthenium tetra-oxide (RuO4). It is consequently of great need to understand phenomena governing steam and air oxidation of the fuel and ruthenium release as prerequisites for the source term issues. A review of existing data on these phenomena shows relatively good understanding. In terms of oxygen affinity, the fuel is oxidized before ruthenium, from UO2 to UO2+x. Its oxidation is a rate-controlling surface exchange reaction with the atmosphere, so that the stoichiometric deviation and oxygen partial pressure increase. High temperatures combined with the presence of oxygen in the atmosphere lead to fuel expansion and formation of cracks. In these conditions, intra- and inter-granular diffusions of ruthenium in the fuel matrix are so enhanced that it is possible to consider an instantaneous volatilisation of ruthenium oxides at the fuel surface. Based on these considerations, a completely new model has been implemented in the EDF local version of the MAAP4.07 severe accident code (Modular Accident Analysis Program), owned by EPRI (Electric Power Research Institute). The fuel oxidation modelling takes into account many kinds of atmospheres (steam and/or air and/or hydrogen), the stoichiometric evolution and the oxygen partial pressure of the fuel matrix. The release of ruthenium oxides is calculated considering their particular reaction constants. The model was assessed by the simulation of different CEA-VERCORS experiments in air, steam and mixed atmospheres. These experiments are specifically designed to study FP release from fuel under different atmospheres and temperatures. This paper deals with the main results obtained with MAAP4.07 when simulating these tests.

ChemInform Abstract: Gas-Phase Electron Diffraction Study of Ruthenium(V) Fluoride and Osmium(V) Fluoride.

The molecular structures of the constituents of gaseous ruthenium(V) fluoride and osmium(V) fluoride at approximately 120 o C have been determined by electron diffraction. At this temperature, for both RuF 5 and OsF 5 , the main constituents are trimeric molecules together with smaller amounts of dimeric species. The trimeric molecules contain three six-coordinate metal atoms each of which are bonded to four terminal fluorine atoms and to two further ring fluorine atoms in a bridging manner

Recent advances in understanding ruthenium behaviour under air-ingress conditions during a PWR severe accident

In a hypothetical severe accident in a Pressurised Water Reactor (PWR), Fission Products (FPs) can be released from the overheated nuclear fuel and partially transported by gases, composed of a mixture of superheated steam and hydrogen, to the reactor containment. Subsequent air ingress into a damaged reactor core may lead to enhanced fuel oxidation, affecting some FP release, especially that of ruthenium. Ruthenium is of particular interest because of its high radiotoxicity and its ability to form very volatile oxides. In the reactor containment, such volatile forms are very hazardous as they are much less efficiently trapped than particulate forms by emergency filtered venting. In the four and a half years of SARNET, collaborative research dedicated to the “ruthenium story” has been performed by several partners. This paper presents the main achievements over the whole project period. Starting from experimental observations showing that fuel could be extensively oxidised by air to, and that a significant fraction of ruthenium inventory can be released, rather satisfactory models have been developed. In addition, the effect of the air interaction with Zircaloy cladding, as well as with UO 2 itself, has been studied. Experiments on the complex transformations of ruthenium oxides upon cooling through the reactor circuit have been performed. An unexpectedly large effect of temperature on the decomposition rate of gaseous ruthenium compounds has been found, as well as effects of the nature of circuit internal surfaces and other FP deposits. So it has been highlighted that various forms of ruthenium can reach the containment, but the most probable gaseous species under these conditions is ruthenium tetroxide. Preliminary analysis of ruthenium transport supports these conclusions. Experiments and analysis have also been launched on the radio-chemical reactions undergone by these ruthenium oxides in the reactor containment. Competing effects of gaseous decomposition to solid particles and re-volatilization from these ruthenium deposits have been demonstrated and modelled. The paper concludes by identifying the remaining work needed to achieve full resolution of the ruthenium source term issue. Recommendations are made for future research activities in the follow-up programme SARNET2.

Deposition of RuO 4 on various surfaces in a nuclear reactor containment

During a severe nuclear reactor accident with air ingress, ruthenium can be released from the nuclear fuel in the form of ruthenium tetroxide. Hence, it is important to investigate how the reactor containment is able to reduce the source term of ruthenium. The aim of this work was to investigate the deposition of gaseous ruthenium tetroxide on aluminium, copper and zinc, which all appear in relatively large amounts in reactor containment. The experiments show that ruthenium tetroxide is deposited on all the metal surfaces, especially on the copper and zinc surfaces. A large deposition of ruthenium tetroxide also appeared on the relatively inert glass surfaces in the experimental set-ups. The analyses of the different surfaces, with several analytical methods, showed that the form of deposited ruthenium was mainly ruthenium dioxide.

Radiolytic Oxidation of Ruthenium Oxide Deposits

In the case of a hypothetical severe accident in a nuclear pressurized water reactor, the formation of radiotoxic RuO4(g) may occur in the reactor containment building, resulting from the interactions of ruthenium oxide deposits with the oxidizing medium induced by air radiolysis. Consequently, this gaseous ruthenium tetroxide may be dispersed into the environment; therefore, the determination of the ruthenium deposits behavior is of primary impo rtance for nuclear safety studies. An experimental study, performed by the French Institut de Radioprotection et de Sûrete Nucleaire (IRSN), using a gam ma irradiator cell (EPICUR facility at IRSN/Cadarache) has been carried out in order to obtain experimental data on these interactions. The results showed that radiolytic oxidation of ruthenium oxide deposits leads to the formation of gaseous ruthenium tetroxide to a significant extent. A comparison between the revolatilized Ru fractions obtained experimentally and those obtained by calculations based on the rate laws modeling ozone irradiation effect, established in previous studies, is presented. The disagreement observed is discussed. It appears that the oxidation resulting from air/steam radiolysis products is enhanced in comparison with pure ozone effect.

Oxidation of ruthenium oxide deposits by ozone

Summary During a hypothetical severe accident on a nuclear Pressurized Water Reactor (PWR), the formation of highly radiotoxic RuO4(g) may occur in the reactor containment building, resulting from the interactions of ruthenium oxide deposits with the oxidising medium induced by air radiolysis. Consequently, there is a risk that the gaseous ruthenium tetroxide could be dispersed into the environment through containment leakages; therefore data concerning the behaviour of ruthenium oxide deposits is of primary importance for safety studies. An experiment has been designed to study the interactions of ruthenium oxide deposits with ozone, formed by air radiolysis. Experimental results have shown that the oxidation reaction leading to the formation of RuO4(g) occurred to a large extent. An oxidation kinetic rate law has been determined, in dry and moist air, for ruthenium deposited onto painted substrates, representative of the inner surfaces of PWR's. This law, combined with tetroxide stability data [Mun, C., Cantrel, L., Madic, C.: Study of RuO4 decomposition in dry and moist air. Radiochim. Acta 95(11), 1 (2007)], will allow a first evaluation of ruthenium revolatilisation phenomenon, possibly occurring in the containment during a severe accident.

On the transport and speciation of ruthenium in high temperature oxidising conditions

Summary In this paper, the transport and speciation of ruthenium under conditions simulating an air ingress accident was studied. Ruthenium dioxide was exposed to an oxidising environment at high temperatures (>1200 °C) in a tubular flow furnace. At these conditions, volatile ruthenium species were formed. A major part of the released ruthenium was deposited in the tube as RuO2. Depending on the experimental conditions, 12–35 wt. % of the released ruthenium was trapped in the outlet filter as RuO2 particles. At completely dry conditions using stainless steel tubes, only 0.1–0.2 wt. % of the released ruthenium reached the trapping bottle as gaseous RuO4. However, when alumina was applied as tube material or the atmosphere contained some water vapour and silver seed particles, the fraction of gaseous ruthenium reaching the trapping bottle increased to 5 wt. % which is close to thermodynamic equilibrium. This indicates that RuO2 does not catalyse the decomposition of RuO4.

Trapping characteristics of volatile ruthenium oxides by Y2O3 filter

Yttria filter has been suggested as a trapping agent for gaseous oxides of ruthenium volatilized during DUPIC fuel fabrication process. Experiments were performed to evaluate the trapping characteristics of gaseous ruthenium oxides by yttria ceramic foam filters in the two-zone furnace under air condition. Yttria filter is expected to offer stable material in which the volatility of the ruthenium can be effectively trapped because of its incorporation into a lattice of high stability over 900 ‡C under air condition. The XRF result of ruthenium trapped on an yttria filter under air condition showed that concentrations of ruthenium on the back and the front faces of the filter decreased linearly with increasing superficial air velocity, and the back face concentration of filter was lower than the front face concentration by about 30-45%. The TGA result of ruthenium trapped on an yttria filter indicates that there is weight loss of 5.8 wt% up to 1,400 ‡C, which is believed to be due to the fact that the thermally stable Y2Ru2O7 phase was formed on an yttria filter.

Gas-phase electron diffraction study of ruthenium(V) fluoride and osmium(V) fluoride

The molecular structures of the constituents of gaseous ruthenium(V) fluoride and osmium(V) fluoride at approximately 120 o C have been determined by electron diffraction. At this temperature, for both RuF 5 and OsF 5 , the main constituents are trimeric molecules together with smaller amounts of dimeric species. The trimeric molecules contain three six-coordinate metal atoms each of which are bonded to four terminal fluorine atoms and to two further ring fluorine atoms in a bridging manner

Absorption Behaviour of Gaseous Ruthenium into Water

Absorption Behaviour of Gaseous Ruthenium into Water