Nickel Retention on Callovo-Oxfordian Clay: Applicability of Existing Adsorption Models for Dilute Systems to Real Compact Rock.

In a waste management context, predicting the mobility of contaminants is essential. A key issue entails assessing the applicability of current knowledge on adsorption processes to natural systems. Such is the focus herein for nickel in interaction with Callovo-Oxfordian (COx) clay rock, a formation selected in France for possible radioactive waste disposal. The challenge is to link predictive modeling results with the experimental data characterizing the behavior of the labile and naturally occurring Ni fraction by implementing a new simple method. Retention studies on compact systems serve to complete this work. Combined electron microprobe and laser ablation high-resolution inductively coupled plasma mass spectrometry data show that natural Ni (∼39 mg kg-1) is homogeneously distributed within the clay matrix, which corresponds to the main reservoir (∼70%). Data interpretation of desorption tests yields an in situ Kd value of ∼80 L kg-1 and a labile Ni amount of ∼5 mg kg-1, that is, ∼13% of the Ni inventory. Predictive modeling explains the sorption data in considering that only weak clay fraction sites take part in the adsorption. The role of the clay matrix in Ni retention is confirmed by analyzing the Ni-spiked compact COx samples, whereby an increase of the Ni content in the clay fraction is observed following the retention experiment.

Thermodynamic data of adsorption reveal the entry of CH4 and CO2 in a smectite clay interlayer.

The ability of smectite clays to incorporate gases in their interlayers is shown to be conditioned by interlayer spacing, depending, in turn, on phyllosilicate layer composition and effective size of the charge-balancing cations. As illustrated by earlier in situ X-ray diffraction and spectroscopic characterization of the gas/clay interface, most smectites with small-size charge-balancing cations, such as Na+ or Ca2+, accommodate CO2 and CH4 in their interlayers only in a partially hydrated state resulting in the opening of the basal spacing, above a certain critical value. In the present study CH4 and CO2 adsorption isotherms were measured for Na- and Mg-exchanged montmorillonite up to 9 MPa using a manometric technique. The process of dehydration of these clays was thoroughly characterized by thermogravimetric analysis and powder X-ray diffraction. A dramatic decrease in specific surface area and methane and carbon dioxide adsorption capacities for fully dehydrated samples in comparison to partially dehydrated ones is assigned to the shrinkage of interlayer spacing resulting in its inaccessibility for the entry of CH4 and CO2 molecules. This observation is direct evidence of CH4 and CO2 adsorption capacity variation depending on the opening of smectite clay interlayer spacing.

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.

Novel Method of Quantifying Radioactive Cesium-Rich Microparticles (CsMPs) in the Environment from the Fukushima Daiichi Nuclear Power Plant.

Highly radioactive cesium-rich microparticles (CsMPs) were released from the Fukushima Daiichi nuclear power plant (FDNPP) to the surrounding environment at an early stage of the nuclear disaster in March of 2011; however, the quantity of released CsMPs remains undetermined. Here, we report a novel method to quantify the number of CsMPs in surface soils at or around Fukushima and the fraction of radioactivity they contribute, which we call "quantification of CsMPs" (QCP) and is based on autoradiography. Here, photostimulated luminescence (PSL) is linearly correlated to the radioactivity of various microparticles, with a regression coefficient of 0.0523 becquerel/PSL/h (Bq/PSL/h). In soil collected from Nagadoro, Fukushima, Japan, CsMPs were detected in soil sieved with a 114 µm mesh. There was no overlap between the radioactivities of CsMPs and clay particles adsorbing Cs. Based on the distribution of radioactivity of CsMPs, the threshold radioactivity of CsMPs in the size fraction of <114 µm was determined to be 0.06 Bq. Based on this method, the number and radioactivity fraction of CsMPs in four surface soils collected from the vicinity of the FDNPP were determined to be 48-318 particles per gram and 8.53-31.8%, respectively. The QCP method is applicable to soils with a total radioactivity as high as ∼106 Bq/kg. This novel method is critically important and can be used to quantitatively understand the distribution and migration of the highly radioactive CsMPs in near-surface environments surrounding Fukushima.

Simulant molten core-concrete interaction experiments in view of understanding Fukushima Daiichi Nuclear Power Station Cs-bearing particles generation mechanism.

The Fukushima Daiichi accident resulted in the release of a novel form of radioactive Cs contamination into the environment, called Cs-bearing microparticles (CsMP). CsMPs constitute a substantial portion of the radioactive pollution near the nuclear power station and traveled beyond several hundred kilometers. Extensive characterization of the CsMPs revealed an amorphous silica matrix, along with Cs and other minor or trace elements such as Fe and Zn. This study explores the unclear generation mechanism of CsMPs by conducting experimental molten core concrete interactions (MCCI) as a source of Si and analyzing the resultant aerosols. The findings demonstrate that MCCI is in capacity to produce spherical submicronic and micronic particles, primarily composed of amorphous silica and incorporating elements akin to CsMPs. A humid atmosphere is found to favour an even closer chemical composition. Examination of the internal structure of the synthesized particles unveils pores and numerous crystalline nanoinclusions possibly serving as nucleation sites for CsMP formation through the condensation of Si-rich vapors.

"Invisible" radioactive cesium atoms revealed: Pollucite inclusion in cesium-rich microparticles (CsMPs) from the Fukushima Daiichi Nuclear Power Plant.

Understanding radioactive Cs contamination has been a central issue at Fukushima Daiichi and other nuclear legacy sites; however, atomic-scale characterization of radioactive Cs in environmental samples has never been achieved. Here we report, for the first time, the direct imaging of radioactive Cs atoms using high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). In Cs-rich microparticles collected from Japan, we document inclusions that contain 27 - 36 wt% of Cs (reported as Cs2O) in a zeolite: pollucite. The compositions of three pollucite inclusions are (Cs1.86K0.11Rb0.19Ba0.22)2.4(Fe0.85Zn0.84X0.31)2.0Si4.1O12, (Cs1.19K0.05Rb0.19Ba0.22)1.7(Fe0.66Zn0.32X0.41)1.4Si4.6O12, and (Cs1.27K0.21Rb0.29Ba0.15)1.9(Fe0.60Zn0.32X0.69)1.6Si4.4O12 (X includes other cations). HAADF-STEM imaging of pollucite, viewed along the [111] zone axis, revealed an array of Cs atoms, which is consistent with a simulated image using the multi-slice method. The occurrence of pollucite indicates that locally enriched Cs reacted with siliceous substances during the Fukushima meltdowns, presumably through volatilization and condensation. Beta radiation doses from the incorporated Cs are estimated to reach 106 - 107 Gy, which is more than three orders of magnitude less than typical amorphization dose of zeolite. The atomic-resolution imaging of radioactive Cs is an important advance for better understanding the fate of radioactive Cs inside and outside of nuclear reactors damaged by meltdown events.

Microbially formed Mn(IV) oxide as a novel adsorbent for removal of Radium.

Radioactivity of Ra isotopes in natural waters is of serious concern. Control of 226Ra concentrations in tailings ponds, which store waste from U ore extraction processes, is an important issue in mill tailings management. In this study, we tested microbially formed Mn(IV) oxide as an adsorbent for removal of Ra in water treatment. Biogenic Mn(IV) oxide (BMO) was prepared using a Mn(II)-oxidizing fungus, Coprinopsis urticicola strain Mn-2. First, adsorption experiments of Sr and Ba, as surrogates for Ra, onto BMO were conducted in aqueous NaCl solution at pH 7. Distribution coefficients for Ba and Sr were estimated to be ∼106.5 and ∼104.3 mL/g, respectively. EXAFS analysis indicated that both Sr and Ba adsorbed in inner-sphere complexes on BMO, suggesting that Ra would adsorb in a similar way. From these findings, we expected that BMO would work effectively in removal of Ra from water. Then, BMO was applied to remove Ra from mine water collected from a U mill tailings pond. Just 7.6 mg of BMO removed >98% of the 226Ra from 3 L of mine water, corresponding to a distribution coefficient of 107.4 mL/g for Ra at pH ∼7. The obtained value was convincingly high for practical application of BMO in water treatment. At the same time, the high distribution coefficient indicates that Mn(IV) oxide can be an important carrier and host phase of Ra in the environment.

Occurrence of radioactive cesium-rich micro-particles (CsMPs) in a school building located 2.8 km south-west of the Fukushima Daiichi Nuclear Power Plant.

Radioactive Cs-rich microparticles (CsMPs) released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) are a potential health risk through inhalation. Little has been documented on the occurrence of CsMPs, particularly their occurrence inside buildings. In this study, we quantitatively analyze the distribution and number of CsMPs in indoor dust samples collected from an elementary school located 2.8 km to the southwest of FDNPP. The school had remained deserted until 2016. Then, using a modified version of the autoradiography-based "quantifying CsMPs (mQCP) method," we collected samples and determined the number of CsMPs and Cs radioactive fraction (RF) values of the microparticles (defined as total Cs activity from CsMPs/bulk Cs activity of the entire sample). The numbers of CsMPs ranged from 653 to 2570 particles/(g dust) and 296-1273 particles/(g dust) on the first and second floors of the school, respectively. The corresponding RFs ranged between 6.85 - 38.9% and 4.48-6.61%, respectively. The number of CsMPs and RF values in additional outdoor samples collected near the school building were 23-63 particles/(g dust or soil) and 1.14-1.61%, respectively. The CsMPs were most abundant on the school's first floor near to the entrance, and the relative abundance was higher near the stairs on the second floor, indicating a likely CsMP dispersion path through the building. Additional wetting of the indoor samples combined with autoradiography revealed that indoor dusts had a distinct absence of intrinsic, soluble Cs species, such as CsOH. These combined observations indicate that a significant amount of poorly soluble CsMPs were likely contained in initial radioactive airmass plumes from the FDNPP and that the microparticles penetrated buildings. CsMPs could still be abundant at the location, with locally high Cs activity in indoor environments near to openings.

Volatilization of B4C control rods in Fukushima Daiichi nuclear reactors during meltdown: B-Li isotopic signatures in cesium-rich microparticles.

Boron carbide control rods remain in the fuel debris of the damaged reactors in the Fukushima Daiichi Nuclear Power Plant, potentially preventing re-criticality; however, the state and stability of the control rods remain unknown. Sensitive high-resolution ion microprobe analyses have revealed B-Li isotopic signatures in radioactive Cs-rich microparticles (CsMPs) that formed by volatilization and condensation of Si-oxides during the meltdowns. The CsMPs contain 1518-6733 mg kg-1 of 10+11B and 11.99-1213 mg kg-1 of 7Li. The 11B/10B (4.15-4.21) and 7Li/6Li (213-406) isotopic ratios are greater than natural abundances (~4.05 and ~12.5, respectively), indicating that 10B(n,α)7Li reactions occurred in B4C prior to the meltdowns. The total amount of B released with CsMPs was estimated to be 0.024-62 g, suggesting that essentially all B remains in reactor Units 2 and/or 3 and is enough to prevent re-criticality; however, the heterogeneous distribution of B needs to be considered during decommissioning.

Radiocesium in Shiitake mushroom: Accumulation in living fruit bodies and leaching from dead fruit bodies.

In this paper, cesium (Cs) accumulation by the saprophytic fungus Lentinula edodes (Shiitake) was investigated to contribute to the elucidation of radiocesium-cycling mechanisms in forest environments. Although the 137Cs in the mushroom bed before culture was bioavailable, the transfer factor (TF) of Cs (133Cs and 137Cs) from the mushroom bed to fruit bodies was low (approximately 1) and the TFs of K (5) and Na (1.5) were higher. Cs and K concentrations in fruit bodies at different maturity stages were almost constant. The concentration ratio of Cs/K is constant in the pileus regardless of the pileus tissues. These results demonstrate that Shiitake non-specifically accumulates Cs while accumulating the essential element K and provide evidence that no selective Cs accumulation (or binding) sites exist within the Shiitake fruit body. Furthermore, the present results show that most accumulated Cs quickly leaches out from the dead fruit body with exposure to water. The leached Cs was largely adsorbable on clay minerals, suggesting that the Shiitake fruit body likely contains Cs in the cation form.

Effect of bacterial siderophore on cesium dissolution from biotite.

In this study, the adsorption of cesium (Cs) on biotite and dissolution of Cs from Cs-bearing biotite using a siderophore were investigated aiming to contribute to the elucidation of radiocesium migration mechanisms in the soil environment. Thus, a siderophore was extracted and purified from the culture medium of Pseudomonas sp., and the purified siderophore was used in five consecutive dissolution experiments of biotite samples. Prior to the dissolution experiments, Cs was adsorbed on a hardly weathered biotite powder sample. The major components of the biotite (Al, Fe, and Mg) were dissolved almost stoichiometrically, strongly suggesting that the siderophore selectively dissolves the broken edges of the biotite. The amount of the dissolved Cs decreased by increasing the repetition times of the dissolution experiment. Therefore, the Cs adsorbed on the broken edges was dissolved rapidly as the siderophore dissolved the broken edges, and then, the Cs adsorbed on the outer planar surface of the biotite particles was slowly dissolved because the siderophore did not directly dissolve the outer planar surface of the biotite but dissolved the surface edge.

New highly radioactive particles derived from Fukushima Daiichi Reactor Unit 1: Properties and environmental impacts.

A contaminated zone elongated toward Futaba Town, north-northwest of the Fukushima Daiichi Nuclear Power Plant (FDNPP), contains highly radioactive particles released from reactor Unit 1. There are uncertainties associated with the physio-chemical properties and environmental impacts of these particles. In this study, 31 radioactive particles were isolated from surface soils collected 3.9 km north-northwest of the FDNPP. Two of these particles have the highest particle-associated 134+137Cs activity ever reported for Fukushima (6.1 × 105 and 2.5 × 106 Bq per particle after decay-correction to March 2011). The new, highly-radioactive particle labeled FTB1 is an aggregate of flaky silicate nanoparticles with an amorphous structure containing ~0.8 wt% Cs, occasionally associated with SiO2 and TiO2 inclusions. FTB1 likely originates from the reactor building, which was damaged by a H2 explosion, after adsorbing volatilized Cs. The 134+137Cs activity in the other highly radioactive particle labeled FTB26 exceeded 106 Bq. FTB26 has a glassy carbon core and a surface that is embedded with numerous micro-particles: Pb-Sn alloy, fibrous Al-silicate, Ca-carbonate or hydroxide, and quartz. The isotopic signatures of the micro-particles indicate neutron capture by B, Cs volatilization, and adsorption of natural Ba. The composition of the micro-particles on FTB26 reflects the composition of airborne particles at the moment of the H2 explosion. Owing to their large size, the health effects of the highly radioactive particles are likely limited to external radiation during static contact with skin; the highly radioactive particles are thus expected to have negligible health impacts for humans. By investigating the mobility of the highly radioactive particles, we can better understand how the radiation dose transfers through environments impacted by Unit 1. The highly radioactive particles also provide insights into the atmospheric conditions at the time of the Unit 1 explosion and the physio-chemical phenomena that occurred during reactor meltdown.

Non-disturbing characterization of natural organic matter (NOM) contained in clay rock pore water by mass spectrometry using electrospray and atmospheric pressure chemical ionization modes.

We have investigated the composition of the mobile natural organic matter (NOM) present in Callovo-Oxfodian pore water using electrospray ionization mass spectrometry (ESI-MS), atmospheric pressure chemical ionization mass spectrometry (APCI-MS) and emission-excitation matrix (EEM) spectroscopy. The generation of knowledge of the composition, structure and size of mobile NOM is necessary if one wants to understand the interactions of these compounds with heavy metals/radionuclides, in the context of environmental studies, and particularly how the mobility of these trace elements is affected by mobile NOM. The proposed methodology is very sensitive in unambiguously identifying the in situ composition of dissolved NOM in water even at very low NOM concentration, due to innovative non-disturbing water sampling and ionization (ESI/APCI-MS) techniques. It was possible to analyze a quite exhaustive inventory of the small organic compounds of clay pore water without proceeding to any chemical treatment at naturally occurring concentration levels. The structural features observed were mainly acidic compounds and fatty acids as well as aldehydes and amino acids.

Discrepancies in thorium oxide solubility values: study of attachment/detachment processes at the solid/solution interface.

The solubility of thorium under oxide and/or hydroxide forms has been extensively studied for many years. Nevertheless, a large discrepancy in the solubility values is noticed in the literature. We study Th atom exchange between thorium oxide surfaces and various aqueous solutions (0.01 mol·L(-1) NaCl for 0.0 < pH < 5.2) to address this issue. By solid-state characterization [X-ray photoelectron spectroscopy (XPS), scanning electron microscopy, and atomic force microscopy], we determined that 80% of the XPS accessible near the surface region of sintered thorium oxide is represented by the less reactive ThO(2)(cr) grains. The remaining 20% corresponds to ThO(x)(OH)(y)(H(2)O)(z), which is largely associated with grain boundaries. Only the latter fraction is involved in solid/solution exchange mechanisms. Local conditions (thorium concentrations, pH values, etc.) in grain boundaries lead to an adjustment of the "local solubility constraints" and explain the thorium concentration measured in our experiments. For pH <5.2, the thorium concentration and pH gradient between the bulk solution and grain-boundary regions imply that the solubility values mainly depend on the availability and accessibility of ThO(x)(OH)(y)(H(2)O)(z). We have performed two solubility experiments with a (232)ThO(2)(cr) solid in a 0.01 mol·L(-1) NaCl solution for 300 days. In a first experiment, we measured (232)Th concentrations in dissolution experiments in order to determine the detachment rates of Th atoms from the solid surface. In a subsequent step, we added (229)Th to the solution in order to measure the surface attachment rate for dissolved Th atoms. This allowed an assessment of the net balance of Th atom exchange at the solid/solution interface. The empirical solubility data do not correspond to the thermodynamic bulk phase/solution equilibrium because measured solution concentrations are controlled by site-specific exchange mechanisms at the solid/solution interface. Therefore, for sparingly soluble solids, one needs to quantify site-specific surface attachment and detachment rates if one wants to assess solubility constraints.

Particulate plutonium released from the Fukushima Daiichi meltdowns.

Traces of Pu have been detected in material released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) in March of 2011; however, to date the physical and chemical form of the Pu have remained unknown. Here we report the discovery of particulate Pu associated with cesium-rich microparticles (CsMPs) that formed in and were released from the reactors during the FDNPP meltdowns. The Cs-pollucite-based CsMP contained discrete U(IV)O2 nanoparticles, <~10 nm, one of which is enriched in Pu adjacent to fragments of Zr-cladding. The isotope ratios, 235U/238U, 240Pu/239Pu, and 242Pu/239Pu, of the CsMPs were determined to be ~0.0193, ~0.347, and ~0.065, respectively, which are consistent with the calculated isotopic ratios of irradiated-fuel fragments. Thus, considering the regional distribution of CsMPs, the long-distance dispersion of Pu from FNDPP is attributed to the transport by CsMPs that have incorporated nanoscale fuel fragments prior to their dispersion up to 230 km away from the Fukushima Daiichi reactor site.

Abundance and distribution of radioactive cesium-rich microparticles released from the Fukushima Daiichi Nuclear Power Plant into the environment.

The abundance and distribution of highly radioactive cesium-rich microparticles (CsMPs) that were released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) during the first stage of the nuclear disaster in March 2011 are described for 20 surface soils collected around the FDNPP. Based on the spatial distribution of the numbers (particles/g) and radioactive fraction (RF) of the CsMPs in surface soil, which is defined as the sum of the CsMP radioactivity (in Bq) divided by the total radioactivity (in Bq) of the soil sample, three regions of particular interest have been identified: i.) near-northwest (N-NW), ii.) far-northwest (F-NW), and iii.) southwest (SW). In these areas, the number and RF of CsMPs were determined to be 22.1-101 particles/g and 15.4-34.0%, 24.3-64.8 particles/g and 36.7-37.4%, and 0.869-8.00 particles/g and 27.6-80.2%, respectively. These distributions are consistent with the plume trajectories of material released from the FDNPP on March 14, 2011, in the late afternoon through to the late afternoon of March 15, 2011, indicating that the CsMPs formed only during this short period. Unit 3 is the most plausible source of the CsMPs at the beginning of the release based on an analysis of the sequence of release events. The lower RF values in the N-NW region indicate a larger influence from subsequent plumes that mainly consisted of soluble Cs species formed simultaneously with precipitation. The quantitative map of the distribution of CsMPs provides an important understanding of CsMP dispersion dynamics and can be used to assess risks in inhabited regions.

Smectite fraction assessment in complex natural clay rocks from interlayer water content determined by thermogravimetric and thermoporometry analysis.

The smectite content is a key parameter to be determined for various applications of clays and clay-rich rocks. The quantity of interlayer water characteristic of swelling domains can be used to assess the smectite content in clays. We propose in this study to use a simple approach to determine water distribution in clays (mainly between pores and interlayers) by means of thermoporometry and thermogravimetric analysis. Provided the interlayer water does not freeze at low temperature upon thermoporometry experiments, the difference between water quantities determined by the two techniques is assigned to interlayer water. Single-phase model clays and complex natural clay rocks and their composites in water-saturated state are characterized by this approach. The open question is the application of available thermoporometry models developed for simple pore geometry to characterize the complex pore network of clays. Depending on the approach used, different pore sizes were obtained highlighting the limit of a simplified model to describe the complex porous network. The results are more coherent when quantifying the amount of interlayer water, further used for smectite content estimation. Good agreement was obtained between smectite fraction contents deduced from the results of thermal analysis and those measured by conventional mineralogical techniques.

Size Distribution of Droplets in a Two Liquid-phase Mixture Compared between Liquid Spraying and Mechanical Stirring.

A new liquid-liquid extraction method, called the "emulsion flow" method, is expected to realize an ideal liquid-liquid extraction by controlling the emulsion generation and separation using liquid spraying, only by solution sending. In order to understand the mechanism of emulsion control in the emulsion flow method, the size distribution of droplets in two liquid-phase mixtures was compared by using originally designed apparatuses 1) for the case of liquid spraying and 2) for the case of mechanical stirring. We demonstrated that the size distribution of droplets generated near a mixing device (a nozzle for liquid spraying or an impeller head for mechanical stirring) determines the phase-separation property.

Dissolution of radioactive, cesium-rich microparticles released from the Fukushima Daiichi Nuclear Power Plant in simulated lung fluid, pure-water, and seawater.

To understand the chemical durability of highly radioactive cesium-rich microparticles (CsMPs) released from the Fukushima Daiichi Nuclear Power Plant in March 2011, we have, for the first time, performed systematic dissolution experiments with CsMPs isolated from Fukushima soils (one sample with 108 Bq and one sample with 57.8 Bq of 137Cs) using three types of solutions: simulated lung fluid, ultrapure water, and artificial sea water, at 25 and 37 °C for 1-63 days. The 137Cs was released rapidly within three days and then steady-state dissolution was achieved for each solution type. The steady-state 137Cs release rate at 25 °C was determined to be 4.7 × 103, 1.3 × 103, and 1. 3 × 103 Bq·m-2 s-1 for simulated lung fluid, ultrapure water, and artificial sea water, respectively. This indicates that the simulated lung fluid promotes the dissolution of CsMPs. The dissolution of CsMPs is similar to that of Si-based glass and is affected by the surface moisture conditions. In addition, the Cs release from the CsMPs is constrained by the rate-limiting dissolution of silicate matrix. Based on our results, CsMPs with ∼2 Bq, which can be potentially inhaled and deposited in the alveolar region, are completely dissolved after >35 years. Further, CsMPs could remain in the environment for several decades; as such, CsMPs are important factors contributing to the long-term impacts of radioactive Cs in the environment.

Mobile fission and activation products in nuclear waste disposal.

When disposing nuclear waste in clay formations it is expected that the most radiotoxic elements like Pu, Np or Am move only a few centimetres to meters before they decay. Only a few radionuclides are able to reach the biosphere and contribute to their long-term exposure risks, mainly anionic species like I129, Cl36, Se79 and in some cases C14 and Tc99, whatever the scenario considered. The recent OECD/NEA cosponsored international MOFAP workshop focussed on transport and chemical behaviour of these less toxic radionuclides. New research themes have been addressed, such as how to make use of molecular level information for the understanding of the problem of migration at large distances. Diffusion studies need to face mineralogical heterogeneities over tens to hundreds of meters. Diffusion rates are very low since the clay rock pores are so small (few nm) that electrostatic repulsion limits the space available for anion diffusion (anion exclusion). The large volume of traversed rock will provide so many retention sites that despite weak retention, even certain of these "mobile" nuclides may show significant retardation. However, the question how to measure reliably very low retention parameters has been posed. An important issue is whether redox states or organic/inorganic speciation change from their initial state at the moment of release from the waste during long term contact with surfaces, hydrogen saturated environments, etc.