Revaporization Behavior of Cesium and Iodine Compounds from Their Deposits in the Steam-Boron Atmosphere.

This paper presents our investigation on cesium and iodine revaporization from cesium iodide (CsI) deposits on stainless steel type 304L, which were initiated by boron and/or steam flow. A dedicated basic experimental facility with a thermal gradient tube (TGT) having a temperature range of 1000-400 K was used for simulating the phenomena. In the absence of boron, it was found that the initially deposited CsI at 850 K could be revaporized as CsI vapor/aerosol or reacted with the carrier gas and stainless steel (Cr2O3 layer) to form Cs2CrO4. The latter mechanism consequently released gaseous iodine that was later accumulated downstream. After introducing boron to the steam flow, a severe revaporization occurred. This, in addition to the revaporized CsI vapor/aerosol, was caused by cesium borate (Cs2B4O7 and CsB5O8) formation, which then largely released gaseous iodine that was capable of reaching the TGT outlet (<400 K). In the case of a nuclear severe accident, our study has demonstrated that an increase of gaseous iodine in the colder region of a reactor could occur after late release of boron or a subsequent steam flow after refloods of the reactor, thus posing its inherent risk once leaked to the environment.

Uranium Dioxides and Debris Fragments Released to the Environment with Cesium-Rich Microparticles from the Fukushima Daiichi Nuclear Power Plant.

Trace U was released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) during the meltdowns, but the speciation of the released components of the nuclear fuel remains unknown. We report, for the first time, the atomic-scale characteristics of nanofragments of the nuclear fuels that were released from the FDNPP into the environment. Nanofragments of an intrinsic U-phase were discovered to be closely associated with radioactive cesium-rich microparticles (CsMPs) in paddy soils collected ∼4 km from the FDNPP. The nanoscale fuel fragments were either encapsulated by or attached to CsMPs and occurred in two different forms: (i) UO2+X nanocrystals of ∼70 nm size, which are embedded into magnetite associated with Tc and Mo on the surface and (ii) Isometric (U,Zr)O2+X nanocrystals of ∼200 nm size, with the U/(U+Zr) molar ratio ranging from 0.14 to 0.91, with intrinsic pores (∼6 nm), indicating the entrapment of vapors or fission-product gases during crystallization. These results document the heterogeneous physical and chemical properties of debris at the nanoscale, which is a mixture of melted fuel and reactor materials, reflecting the complex thermal processes within the FDNPP reactor during meltdown. Still CsMPs are an important medium for the transport of debris fragments into the environment in a respirable form.

Isotopic signature and nano-texture of cesium-rich micro-particles: Release of uranium and fission products from the Fukushima Daiichi Nuclear Power Plant.

Highly radioactive cesium-rich microparticles (CsMPs) released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) provide nano-scale chemical fingerprints of the 2011 tragedy. U, Cs, Ba, Rb, K, and Ca isotopic ratios were determined on three CsMPs (3.79-780 Bq) collected within ~10 km from the FDNPP to determine the CsMPs' origin and mechanism of formation. Apart from crystalline Fe-pollucite, CsFeSi2O6 · nH2O, CsMPs are comprised mainly of Zn-Fe-oxide nanoparticles in a SiO2 glass matrix (up to ~30 wt% of Cs and ~1 wt% of U mainly associated with Zn-Fe-oxide). The 235U/238U values in two CsMPs: 0.030 (±0.005) and 0.029 (±0.003), are consistent with that of enriched nuclear fuel. The values are higher than the average burnup estimated by the ORIGEN code and lower than non-irradiated fuel, suggesting non-uniform volatilization of U from melted fuels with different levels of burnup, followed by sorption onto Zn-Fe-oxides. The nano-scale texture and isotopic analyses provide a partial record of the chemical reactions that occurred in the fuel during meltdown. Also, the CsMPs were an important medium of transport for the released radionuclides in a respirable form.

Caesium-rich micro-particles: A window into the meltdown events at the Fukushima Daiichi Nuclear Power Plant.

The nuclear disaster at the Fukushima Daiichi Nuclear Power Plant (FDNPP) in March 2011 caused partial meltdowns of three reactors. During the meltdowns, a type of condensed particle, a caesium-rich micro-particle (CsMP), formed inside the reactors via unknown processes. Here we report the chemical and physical processes of CsMP formation inside the reactors during the meltdowns based on atomic-resolution electron microscopy of CsMPs discovered near the FDNPP. All of the CsMPs (with sizes of 2.0-3.4 µm) comprise SiO2 glass matrices and ~10-nm-sized Zn-Fe-oxide nanoparticles associated with a wide range of Cs concentrations (1.1-19 wt% Cs as Cs2O). Trace amounts of U are also associated with the Zn-Fe oxides. The nano-texture in the CsMPs records multiple reaction-process steps during meltdown in the severe FDNPP accident: Melted fuel (molten core)-concrete interactions (MCCIs), incorporating various airborne fission product nanoparticles, including CsOH and CsCl, proceeded via SiO2 condensation over aggregates of Zn-Fe oxide nanoparticles originating from the failure of the reactor pressure vessels. Still, CsMPs provide a mechanism by which volatile and low-volatility radionuclides such as U can reach the environment and should be considered in the migration model of Cs and radionuclides in the current environment surrounding the FDNPP.

Radioactive Cs in the estuary sediments near Fukushima Daiichi Nuclear Power Plant.

The migration and dispersion of radioactive Cs (mainly (134)Cs and (137)Cs) are of critical concern in the area surrounding the Fukushima Daiichi Nuclear Power Plant (FDNPP). Considerable uncertainty remains in understanding the properties and dynamics of radioactive Cs transport by surface water, particularly during rainfall-induced flood events to the ocean. Physical and chemical properties of unique estuary sediments, collected from the Kuma River, 4.0km south of the FDNPP, were quantified in this study. These were deposited after storm events and now occur as dried platy sediments on beach sand. The platy sediments exhibit median particle sizes ranging from 28 to 32µm. There is increasing radioactivity towards the bottom of the layers deposited; approximately 28 and 38Bqg(-1) in the upper and lower layers, respectively. The difference in the radioactivity is attributed to a larger number of particles associated with radioactive Cs in the lower part of the section, suggesting that radioactive Cs in the suspended soils transported by surface water has decreased over time. Sequential chemical extractions showed that ~90% of (137)Cs was strongly bound to the residual fraction in the estuary samples, whereas 60~80% of (137)Cs was bound to clays in the six paddy soils. This high concentration in the residual fraction facilitates ease of transport of clay and silt size particles through the river system. Estuary sediments consist of particles <100µm. Radioactive Cs desorption experiments using the estuary samples in artificial seawater revealed that 3.4±0.6% of (137)Cs was desorbed within 8h. More than 96% of (137)Cs remained strongly bound to clays. Hence, particle size is a key factor that determines the travel time and distance during the dispersion of (137)Cs in the ocean.