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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. [ABSTRACT FROM AUTHOR]

Quantitative understanding of the stability of sorbed radionuclides in smectite is necessary to assess the performance of engineering barriers used for nuclear waste disposal. Our previous study demonstrated that the spatial organization of the smectite platelets triggered by the divalent cations led to the apparent fixation of intrinsic Cs in smectite, because some Cs is retained inside the formed tactoids. Natural water is usually a mixture of Na+ and divalent cations (Ca2+ and Mg2+). This study therefore investigated the desorption behavior of intrinsic Cs in Na-smecite in mixed Na+-divalent cation solutions under widely various cation concentrations using batch experiments, grain size measurements, and cation exchange modeling (CEM). Results show that increased Na+ concentrations facilitate Cs desorption because Na+ serves as the dispersion agent. A linear relation was obtained between the logarithm of the Na+ fraction and the accessible Cs fraction in smectite. That relation enables the prediction of accessible Cs fraction as a function of solution cationic compositions. The corrected CEM considering the effects of the spatial organization suggests that the stability of intrinsic Cs in the smectite is governed by the Na+ concentration, and suggests that it is almost independent of the concentrations of divalent cations in natural water. [ABSTRACT FROM AUTHOR]

The enrichment of Cs and Rb relative to Ba, Sr, and K in three soils representing a range of soil maturities was determined to investigate the long-term sorption behavior of these elements in upland soils of the Savannah River Site (SRS). Elemental mass fractions normalized to upper continental crust (UCC) decreased in the order Cs > Rb > Ba > K > Sr in the soil fine fractions. Only the UCC-normalized amount of Cs was greater than unity. The UCC-normalized amounts in strong-acid extracts decreased as Cs > Rb > Ba > K ≈ Sr. In all three soil cores, the trends of the UCC-normalized amounts of acid-extractable metals were similar to trends of cation-exchange capacity (CEC) calculated from synchrotron-X-ray diffractometry measurements of soil mineralogy. Consequently, the relative enrichment of Cs and Rb is largely controlled by selective sorption to micaceous minerals, including hydroxy-interlayered vermiculite, that dominate the CEC. Where high clay content had caused retention of soil solution, amounts of acid extractable K, Sr, and Ba were enhanced. The retention of natural Cs by these three soils, which developed over many thousands of years, is a strong indicator that radiocesium will likewise be retained in SRS soils. [ABSTRACT FROM AUTHOR]

We report here a pressure-driven metathesis reaction where Ag-exchanged natrolite (Ag16Al16Si24O80·16H2O, Ag-NAT) is pressurized in an aqueous CsI solution, resulting in the exchange of Ag+ by Cs+ in the natrolite framework forming Cs16Al16Si24O80·16H2O (Cs-NAT-I) and, above 0.5 GPa, its high-pressure polymorph (Cs-NAT-II). During the initial cation exchange, the precipitation of AgI occurs. Additional pressure and heat at 2 GPa and 160 °C transforms Cs-NAT-II to a pollucite-related, highly dense, and water-free triclinic phase with nominal composition CsAlSi2O6. At ambient temperature after pressure release, the Cs remains sequestered in a now monoclinic pollucite phase at close to 40 wt % and a favorably low Cs leaching rate under back-exchange conditions. This process thus efficiently combines the pressure-driven separation of Cs and I at ambient temperature with the subsequent sequestration of Cs under moderate pressures and temperatures in its preferred waste form suitable for long-term storage at ambient conditions. The zeolite pollucite CsAlSi2O6·H2O has been identified as a potential host material for nuclear waste remediation of anthropogenic 137Cs due to its chemical and thermal stability, low leaching rate, and the large amount of Cs it can contain. The new water-free pollucite phase we characterize during our process will not display radiolysis of water during longterm storage while maintaining the Cs content and low leaching rate. [ABSTRACT FROM AUTHOR]

Transport processes of particulate radiocesium were investigated using a sediment trap deployed at about 100 km east of the Fukushima Daiichi Nuclear Power Plant. A sediment trap was installed at 873 m depth of the station (119 m above the bottom), and time-series sampling of sinking particles was carried out from August, 2011 to June, 2013. The accident-derived radiocesium was detected from sinking particles over two years after the accident. Observed 137Cs flux was highest in September 2011 (98 mBq m-2 day-1: decay-corrected to March 11, 2011), and decreased over time with seasonal fluctuations. Particulate fluxes of radiocesium were mainly affected by two principal processes. One was the rapid sinking of radiocesium-bound particles (moderate mode). This mode was dominant especially in the early postaccident stage, and was presumed to establish the distribution of radiocesium in the offshore seabed. Another mode was observed in winter, and secondary transport of particles attributed to turbulence near the seabed increased fluxes of particulate radiocesium (turbulence mode). Although the latter process would not drastically change the distribution of sedimentary radiocesium in the short term, attention should be paid as this key process redistributing the accident-derived radiocesium may cumulatively affect the long-term distribution. [ABSTRACT FROM AUTHOR]

Fine clay particles have functioned as transport media for radiocesium in terrestrial environments after nuclear accidents. Because radiocesium is expected to be retained in clay minerals by a cation-exchange reaction, ascertaining trace cesium desorption behavior in response to changing solution conditions is crucially important. This study systematically investigated the desorption behavior of intrinsic Cs (13 nmol/g) in well-characterized Na-montmorillonite in electrolyte solutions (NaCl, KCl, CaCl2, and MgCl2) under widely differing cation concentrations (0.2 mM to 0.2 M). Batch desorption experiments demonstrated that Cs+ desorption was inhibited significantly in the presence of the environmental relevant concentrations of Ca2+ and Mg2+ (>0.5 mM) and high concentrations of K+. The order of ability for Cs desorption was Na+ = K+ > Ca2+ = Mg2+ at the highest cation concentration (0.2 M), which is opposite to the theoretical prediction based on the cation-exchange selectivity. Laser diffraction grain-size analyses revealed that the inhibition of Cs+ desorption coincided with the increase of the clay tactoid size. Results suggest that radiocesium in the dispersed fine clay particles adheres on the solid phase when the organization of swelling clay particles occurs because of changes in solution conditions caused by both natural processes and artificial treatments. [ABSTRACT FROM AUTHOR]

TEPCO's Fukushima Daiichi Nuclear Power Plant (FDNPP) accident of March 2011 caused the discharge of a considerable quantity of radionuclides, including 137Cs. Because of its long half-life (30.17 years), the fate of 137Cs in the marine biota is of great interest. This study aims to evaluate, using food monitoring data, ecological half-lives (Teco) of 137Cs in marine biota caught offshore of Fukushima. The data were categorized into two regional groups (north and south) with respect to the FDNPP site, and the regional 137Cs concentration trend and estimated Teco in the marine biota were appraised. Although the 137Cs concentration in the seawater in the south was higher than that in the north, Teco values remained relatively consistent among common species of both regions. Teco was then compared to biological half-life (Tb) estimated in laboratory settings. The ratios of Teco/Tb were inconsistent among different groups of marine species. The ratios of Teco/Tb for brown seaweed and bivalves were approximately 1, and the ratios of Teco/Tb for demersal fish ranged from 4.4 to 16.1. The reasons for different ratios of Teco and Tb values may be attributed to environmental and ecological factors, such as different trophic levels. [ABSTRACT FROM AUTHOR]

The earthquake and the subsequent tsunami that occurred offshore of Japan resulted in an important loss of life and a serious accident at the nuclear facility of Fukushima. The "hot spots" of the release are evaluated here applying the model LMDZORINCA for 137Cs. Moreover, an assessment is attempted for the population and the environment using the dosimetric scheme of the WHO and the interactive tool ERICA, respectively. Cesium-137 was deposited mostly in Pacific and Atlantic Oceans and North Pole (80%), whereas the rest in the continental areas of North America and Eurasia contributed slightly to the natural background (0.5-5.0 kBq m-2). The effective dose from 137Cs and 134Cs (radiocesium) irradiation during the first 3 months was estimated between 1-5 mSv in Fukushima and the neighboring prefectures. In the rest of Japan, the respective doses were found to be less than 0.5 mSv, whereas in the rest of the world it was less than 0.1 mSv. Such doses are equivalent with the obtained dose from a simple X-ray; for the highly contaminated regions, they are close to the dose limit for exposure due to radon inhalation (10 mSv). The calculated dose rates from radiocesium exposure on reference organisms ranged from 0.03 to 0.18 μGy h-1, which are 2 orders of magnitude below the screening dose limit (10 μGy h-1) that could result in obvious effects on the population. However, these results may underestimate the real situation, since stable soil density was used in the calculations, a zero radiocesium background was assumed, and dose only from two radionuclides was estimated, while more that 40 radionuclides have been deposited in the vicinity of the facility. When monitoring data applied, much higher dose rates were estimated certifying ecological risk for small mammals and reptiles in terms of cytogenetic damage and reproduction. [ABSTRACT FROM AUTHOR]

Colloid-sized particles are commonly detected in vadose- zone pore waters and are capable of binding chemicals with sorptive affinities for geologic materials. Published research demonstrates that colloids are capable of facilitating the transport of sorptive contaminants under conditions of steady pore water flow, when volumetric moisture content and pore water velocity are constant Less is known about the role of colloids in governing contaminant mobility under transient-flow conditions, which are characteristic of natural vadose-zone environments. The objective of this study is to elucidate the influences of flow transients on the mobilization and transport of in situ colloids and colloid-associated contaminants. We conducted column experiments in which the mobilization of in situ colloids and 137Cs was induced by transients associated with the drainage and imbibition of 137Cs contaminated-sediments. Our results demonstrate that substantial quantities of in situ colloids and colloid-associated 137Cs are mobilized as volumetric moisture content declines during porous-medium drainage and as volumetric moisture content increases during porous- medium imbibition. We also find that the colloid-effect on 137Cs transport is sensitive to changes in pore water ionic strength. That is, the quantities of colloids mobilized and the capacity of the these colloids to bind 137Cs decrease with increasing ionic strength, leading to a decrease of the mass of 137Cs eluted from the columns during porous-medium drainage and imbibition. [ABSTRACT FROM AUTHOR]

Cationic surfactants modified clays exhibit high sorptive capability toward anionic radionuclides but retention of cationic radionuclides was concurrently reduced. In this study, organoclays were synthesized by intercalating a variety of primary/quaternary alkylammonium species (NH2R/(CH3)3N+RBr-, where R = benzyl, dodecyl, and octadecyl) into bentonite MX-80. The effect of surfactant's properties on enhancing or limiting cationic sorption capability was investigated by performing Cs sorption experiments. Experimental results were analyzed using the MINEQL+ software by considering Cs uptake by structural and edge sorption sites. Bentonites that were intercalated with primary alkylammonium surfactants had a higher sorptive capacity than those intercalated with quaternary alkylammonium surfactants. Samples intercalated with octadecyl-bearing surfactants had the lowest sorption rate. XRD and FTIR analyses revealed that each organoclay had a characteristic arrangement of alkyl chains. The cation retention of organoclays was dominated by the extent of hydrophobic interactions affected by the local distribution and arrangement of surfactants. The intercalated primary alkylammoniun surfactants tended to transform into local clusters with a high packing density, leaving more structural sites available for Cs uptake. In contrast, the NH3R+-surfactants tended to form a denser monolayer over clay surface, inhibiting the retention of Cs at structural sites. [ABSTRACT FROM AUTHOR]

Tracer tests were performed in distinct biogeochemical zones of a sand and gravel aquifer in Cape Cod, MA, to study the redox chemistry (I) and transport (Cs, I) of cesium and iodine in a field setting. Injection of iodide (I-) into an oxic zone of the aquifer resulted in oxidation of I- to molecular iodine (I2) and iodate (IO3-) over transport distances of several meters. Oxidation is attributed to Mn-oxides present in the sediment. Transport of injected IO3- and Cs+ was retarded in the mildly acidic oxic zone, with retardation factors of 1.6-1.8 for IO3- and 2.3-4.4 for Cs. Cs retardation was likely due to cation exchange reactions. Injection of IO3- into a Fe-reducing zone of the aquifer resulted in rapid and complete reduction to I- within 3 m of transport. The nonconservative behavior of Cs and I observed during the tracer tests underscores the necessity of taking the redox chemistry of I as well as sorption properties of I species and Cs into account when predicting transport of radionuclides (e.g., 129I and 137Cs) in the environment. [ABSTRACT FROM AUTHOR]

Clay minerals may be an important unrecognized sorptive phase for dioxins in soils and clay deposits. Smectites, especially Cs-saponite, effectively adsorbed dibenzo-p-dioxin (DD) from water, reaching 0.8% (wt/wt). Adsorption was promoted by exchangeable cations with low hydration energies, and negative charge in the smectite arising from the tetrahedral siloxane sheets. X-ray diffraction measurements revealed that as DD loading increased to ≥8000 mg/kg the clay basal spacing increased abruptly from 12.3 to 15.2 Å demonstrating DD intercalation. The 12.3 Å spacing provides an interlayer distance that closely matches the molecular thickness of DD. In this configuration DD is essentially dehydrated as it interacts with the opposing hydrophobic siloxane sheets and with coplanar Cs+ via one of the dioxin ring oxygens. Ab initio calculations suggest that geometrical structures form at higher loadings in which intercalated DD molecules adopt a butterfly geometry sandwiched between dehydrated interlayer Cs+ and the siloxane surface, consistent with the 15.2 Å spacing, wherein Cs+ interacts with dioxin ring oxygens and benzene ring π-electrons. Fourier transformation infrared measurements confirm that adsorbed DD is present in orientations that are not parallel with the interlayer planar siloxane surfaces of smectite. [ABSTRACT FROM AUTHOR]