Tetra-µ3-selen-ido-1:2:3κ3Se;1:2:4κ3Se;1:3:4κ3Se;2:3:4κ3Se-tetrakis-[(η5-methyl-cyclo-penta-dien-yl)molybdenum(III)](6 Mo-Mo).

The title cluster compound, [Mo4(η5-C5H4Me)4(µ3-Se)4], was synthesized from the reaction of [Mo(η5-C5H4Me)(CO)3]2 with grey selenium in refluxing xylene solution under a nitro-gen atmosphere. The complete cluster is generated by a crystallographic twofold axis and contains an Mo4Se4 cubane-like core surrounded by four η5-methylcyclo-pentadienyl ligands. In the core, the four molybdenum atoms are connected to each other to form a tetra-hedron, with a selenium atom capping each face. The Mo-Mo bond lengths vary from 2.9857 (5) to 3.0083 (3) Šand the Mo-Se separations range from 2.4633 (4) to 2.4693 (5) Å.

Crystallographic evidence for the stereoselective substitution of equatorial pyridyl ligands in ruthenium(III) complexes.

Mononuclear Ru complexes catalyze dioxygen formation via water splitting; therefore, a detailed investigation into their water-oxidation process is necessary. In this study, we synthesized a series of Ru(III) complexes containing a dianionic tridentate ligand with three pyridine groups (one coordinated to Ru while the other two are "free") and investigated their substitution reactions in a water/acetonitrile mixture. Among the monodentate pyridyl ligands, the one at the equatorial position was crystallographically proven to be selectively substituted. Therefore, our results experimentally demonstrate the proposed coordination geometry for an intermediate during water oxidation over Ru complexes.

Effect of radioactive cesium-rich microparticles on radioactive cesium concentration and distribution coefficient in rivers flowing through the watersheds with different contaminated condition in Fukushima.

Radioactive cesium-rich microparticles (CsMPs) derived from the Fukushima Daiichi Nnuclear Power Plant accident were detected from soils and river water around Fukushima Prefecture, Japan. Because CsMPs are insoluble and rich in radioactive cesium (RCs), they may cause the overestimation of solid-water distribution coefficient (Kd) for RCs in the water. Previous studies showed the proportion of RCs derived from CsMPs on RCs concentration in soils collected from areas with different contaminated levels. Because the proportion of RCs concentration derived CsMPs to the RCs concentration of soils in the less contaminated areas is higher than that in the highly contaminated areas, the effect of CsMPs on particulate RCs concentration in river water may be larger in the less contaminated areas. However, the difference in the effects of CsMPs on the particulate RCs concentration and Kd in river water flowing through watersheds with different contaminated levels has not been clarified. In this study, we investigated the effect of CsMPs on the particulate RCs concentration and Kd in two rivers, Takase River and Kami-Oguni River, flowing through the watersheds with different RCs contaminated levels in Fukushima Prefecture. CsMPs might enter rivers due to soil erosion because they were detected only in some samples collected from both rivers during flood events. CsMPs accounted for more than half of particulate RCs concentration in some water samples collected in the flood condition. In particular, the proportion of CsMPs in particulate RCs for the Kami-Oguni River was greater than that for the Takase River. However, when evaluating for the entire water sampling in the flood condition, a proportion of RCs concentration derived from CsMPs in the average RCs concentrations per unit mass of SS in both river waters collected in the flood condition was not large. CsMPs might temporarily increase the particulate RCs concentration and Kd in the flood event, but CsMPs did not significantly affect them when evaluated throughout the event.

Preparation of Highly Concentrated Uniform-Sized Silver Nanoparticles via Use of Thermoresponsive Zwitterionic Surfactants.

Despite the popular use of citrate for the reduction of silver ions, this process suffers from slow crystal growth and broad size distribution. The rapid and effective synthesis of highly concentrated and stable spherical silver nanoparticles (AgNPs) confined in the surfactant-rich phase of thermoresponsive 3-(alkyldimethylammonio)-propyl sulfate surfactants obtained after reaction with citrate ions at high temperature is described. The present approach using the zwitterionic surfactant offers an alternative rapid approach for production of AgNPs and an in situ phase separation step that serves to "extract" and concentrate the AgNPs in the surfactant-rich phase. Almost all (synthetic yield 99.9%, extraction efficiency 98.6%) of the synthesized AgNPs with a diameter of 21.0 ± 2.5 nm were incorporated into the phase-separated surfactant-rich phase at pH 11, and the capacity (maximum concentration) was 3.4 × 1013 particles/mL. The AgNPs were stable upon long-term storage (at least 3 months).

Isolation and structural comparison of RuII-dnp complexes [dnp = 2,6-bis-(1,8-naphthyridin-2-yl)pyridine] with axially or equatorially coordinating NCS ligands.

The mol-ecular and crystal structures of two ruthenium(II) complexes, viz. cis-aqua-[2,6-bis-(1,8-naphthyridin-2-yl)pyridine-κ3 N,N',N''](thio-cyanato-κN)(tri-phen-yl-phosphine-κP)ruthenium(II) hexa-fluorido-phosphate-acetone-water (1/0.5/1), [Ru(NCS)(C21H13N5)(C18H15P)(H2O)]PF6·0.5C3H6O·H2O (I) and trans-[2,6-bis-(1,8-naphthyridin-2-yl)pyridine-κ3'N,N',N'']bis-(pyridine-κN)(thiocyanato-κN)ruthenium(II) thio-cyanate, [Ru(NCS)(C21H13N5)(C5H5N)2]NCS (II), with an N-coordinating thio-cyanato group and a tridentate polypyridyl supporting ligand, are reported. The RuII atom in each of the cationic complexes adopts a distorted octa-hedral coordination sphere, defined by an N atom of the thio-cyanato ligand, three N atoms from the tridentate polypyridyl ligand, and an O and P atom in (I) or two pyridine-N atoms in (II) derived from monodentate ligands. The thio-cyanato ligand in (I) coordinates in an axial manner to the {Ru-dnp} unit [dnp = 2,6-bis-(1,8-naphthyridin-2-yl)pyridine], whereas it coordinates in an equatorial manner in (II). In the crystal structure of compound (I), intra-molecular C-H⋯O, C-H⋯N and O-H⋯N hydrogen bonds as well as π-π contacts are present, in addition to inter-molecular C-H⋯F, C-H⋯O and O-H⋯O hydrogen bonds. In the crystal structure of compound (II), intra-molecular C-H⋯N hydrogen bonds are observed along with inter-molecular C-H⋯N and C-H⋯S hydrogen bonds as well as a π-π inter-action.

Radiocaesium accumulation and fluctuating asymmetry in the Japanese mitten crab, Eriocheir japonica, along a gradient of radionuclide contamination at Fukushima.

The 2011 Tohoku earthquake-tsunami and the subsequent nuclear accident at the Fukushima Dai-ichi Nuclear Power Station (FDNPS) led to large-scale radionuclide contamination of the marine and freshwater environment. Monitoring studies of marine food products in the Fukushima region have generally demonstrated a declining trend in radiocaesium concentrations. However, the accumulation and elimination of radiocaesium and potential biological effects remain poorly understood for freshwater biota inhabiting highly contaminated areas at Fukushima. Consequently, the present study aimed to assess radiocaesium accumulation and developmental effects on the commercially important catadromous Japanese mitten crab, Eriocheir japonica. E. japonica were collected from four sites along a gradient of radionuclide contamination 4-44 km in distance from the FDNPS in 2017. To determine potential developmental effects, fluctuating asymmetry (FA) was used as a measure of developmental stability. Combined 134Cs and 137Cs values for whole E. japonica from highly contaminated sites 4 and 16 km in distance from the FDNPS were 3040 ± 521 and 2250 ± 908 Bq kg-1 wet weight respectively, 30 and 22 times greater than the Japanese standard limit of 100 Bq kg-1. Estimated total dose rates based on radiocaesium concentrations in whole crabs and sediment ranged from 0.016 to 37.7 µGy h-1. No significant relationship between radiocaesium accumulation and FA was recorded, suggesting that chronic radiation exposure at Fukushima is not inducing developmental effects in E. japonica as measured using fluctuating asymmetry. Furthermore, estimated dose rates were below proposed regulatory limits where significant deleterious effects are expected. The present study will aid in the understanding of the long-term consequences of radiation exposure for non-human biota and the management of radioactively contaminated environments.

Evaluation of DNA damage and stress in wildlife chronically exposed to low-dose, low-dose rate radiation from the Fukushima Dai-ichi Nuclear Power Plant accident.

The health effects associated with chronic low-dose, low-dose rate (LD-LDR) exposures to environmental radiation are uncertain. All dose-effect studies conducted outside controlled laboratory conditions are challenged by inherent complexities of ecological systems and difficulties quantifying dose to free-ranging organisms in natural environments. Consequently, the effects of chronic LD-LDR radiation exposures on wildlife health remain poorly understood and much debated. Here, samples from wild boar (Sus scrofa leucomystax) and rat snakes (Elaphe spp.) were collected between 2016 and 2018 across a gradient of radiation exposures in Fukushima, Japan. In vivo biomarkers of DNA damage and stress were evaluated as a function of multiple measurements of radiation dose. Specifically, we assessed frequencies of dicentric chromosomes (Telomere-Centromere Fluorescence in situ Hybridization: TC-FISH), telomere length (Telo-FISH, qPCR), and cortisol hormone levels (Enzyme Immunoassay: EIA) in wild boar, and telomere length (qPCR) in snakes. These biological parameters were then correlated to robust calculations of radiation dose rate at the time of capture and plausible upper bound lifetime dose, both of which incorporated internal and external dose. No significant relationships were observed between dicentric chromosome frequencies or telomere length and dose rate at capture or lifetime dose (p value range: 0.20-0.97). Radiation exposure significantly associated only with cortisol, where lower concentrations were associated with higher dose rates (r2 = 0.58; p < 0.0001), a relationship that was likely due to other (unmeasured) factors. Our results suggest that wild boar and snakes chronically exposed to LD-LDR radiation sufficient to prohibit human occupancy were not experiencing significant adverse health effects as assessed by biomarkers of DNA damage and stress.

Hydroquinone/quinone electro- and photochemical interconversion in isolable polypyridylruthenium(II) complexes.

Quinone derivatives and their metal complexes are well-known molecules that participate in electron-transfer reactions relevant to diverse fields. However, the fundamental knowledge on the unique reactivity of redox-active quinone complexes is limited by the difficulty in their isolation. Herein, the synthesis of isolable mononuclear polypyridylruthenium(ii) complexes containing both hydroquinone and quinone units is described. Three types of monodentate ligands are conveniently used to control the electronic states of the complexes. Both reduced (hydroquinone) and oxidised (quinone) forms are successfully isolated and characterised by spectroscopic and crystallographic analysis, allowing direct comparisons of their properties. The redox-rich and visible light-responsive nature of the ruthenium complexes enables to investigate the quinone/hydroquinone interconversion induced by electron transfer, photoirradiation and photoswitching based on ligand substitution reactions. These results demonstrate the occurrence of synergistic effects between metal complexes and redox-active organic compounds.

Radiocesium distribution and mid-term dynamics in the ponds of the Fukushima Dai-ichi nuclear power plant exclusion zone in 2015-2019.

This study analyzes the 137Cs behavior in the ponds of Okuma Town from 2015 to 2019 in the Fukushima Dai-ichi nuclear power plant (FDNPP) exclusion zone. A decline in both particulate and dissolved 137Cs activity concentrations was revealed. The decline rate constants for the particulate 137Cs activity concentration were found to be higher than for the dissolved 137Cs activity concentration. In terms of seasonality the dissolved 137Cs concentrations were higher from June to October, depending on the specific pond and year, most likely due to temperature dependence of 137Cs desorption from frayed edge sites of micaceous clay minerals. The apparent Kd(137Cs) in the studied ponds, in absolute value, appeared to be much higher than that for closed and semi-closed lakes of the Chernobyl contaminated area; however, these were comparable to the values characteristic of the rivers and reservoirs of the FDNPP contaminated area. The apparent Kd(137Cs) in the suspended sediment-water system was observed to decrease over time. It was hypothesized that this trend was associated with the decomposition of glassy hot particles. Relying on the theory of selective sorption and fixation, the exchangeable radiocesium interception potential, RIPex(K) was estimated using data on 137Cs speciation in the surface bottom-sediment layer and its distribution in the sediment-water system. For the studied ponds, RIPex(K) was on the average 2050 mEq/kg, which is within the range of values measured in laboratory studies reported in the literature.

Effects of Chemically-Modified Polypyridyl Ligands on the Structural and Redox Properties of Tricarbonylmanganese(I) Complexes.

Carbonyl complexes with manganese(I) as the central metal are very attractive catalysts. The introduction of redox-active ligands, such as quinones and methyl viologen analogs into these catalysts, would be expected to lead to superior catalyst performances, since they can function as excellent electron carriers. In this study, we synthesized four tricarbonylmanganese(I) complexes containing typical bidentate polypyridyl ligands, including 1,10-phenanthroline (phen) and 2,2'-bipyridine (bpy) frameworks bound to redox-active ortho-quinone/catechol or methyl viologen-like units. The molecular structures of the resulting complexes were determined by X-ray crystallography to clarify their steric features. As expected from the infrared (IR) data, three CO ligands for each complex were coordinated in the facial configuration around the central manganese(I) atom. Additionally, the structural parameters were found to differ significantly between the quinone/catechol units. Electrochemical analysis revealed some differences between them and their reference complexes, namely [MnBr(CO)3(phen)] and [MnBr(CO)3(bpy)]. Notably, interconversions induced by two-electron/two-proton transfers between the quinone and catechol units were observed in the phenanthroline-based complexes. This work indicated that the structural and redox properties in tricarbonylmanganese(I) complexes were significantly affected by chemically modified polypyridyl ligands. A better understanding of structures and redox behaviors of the present compounds would facilitate the design of new manganese complexes with enhanced properties.

Synthesis and crystal structures of manganese(I) carbonyl complexes bearing ester-substituted α-di-imine ligands.

The crystal structures of two manganese(I) complexes with ester-substituted bi-pyridine or bi-quinoline supporting ligands are reported, namely, fac-bromido-tricarbon-yl(diethyl 2,2'-bi-pyridine-4,4'-di-carboxyl-ate-κ2 N,N')mangan-ese(I), [MnBr(C16H16N2O4)(CO)3], I, and fac-bromido-tricarbon-yl(diethyl 2,2'-bi-quinoline-4,4'-di-carboxyl-ate-κ2 N,N')manganese(I), [MnBr(C24H20N2O4)(CO)3], II. In both complexes, the manganese(I) atom adopts a distorted octa-hedral coordination sphere defined by three carbonyl C atoms, a Br- anion and two N atoms from the chelating α-di-imine ligand. Both complexes show fac configurations of the carbonyl ligands. In I, the complex mol-ecules are linked by C-H⋯Br hydrogen bonds and aromatic π-π contacts. In II, intra-molecular C-H⋯O hydrogen bonds are present as well as inter-molecular C-H⋯O and C-H⋯Br hydrogen bonds and π-π inter-actions.

Selective synthesis and crystal structures of manganese(I) complexes with a bi- or tridentate terpyridine ligand.

The crystal structures of two manganese(I) complexes with a different coordination mode of the supporting ligand are reported: fac-bromido-tricarbon-yl(4'-phenyl-2,2':6',2''-terpyridine-κ2 N,N')manganese(I), [MnBr(C21H15N3)(CO)3], I, and cis-bromido-dicarbon-yl(4'-phenyl-2,2':6',2''-terpyridine-κ3 N,N',N'')manganese(I), [MnBr(C21H15N3)(CO)2], II. In both complexes, the manganese(I) atom is coordinated by terminal carbonyl ligands, a bromide ion, and a 4'-phenyl-2,2':6',2''-terpyridine ligand within a distorted octa-hedral environment. In I, the metal ion is facially coordinated by three carbonyl ligands and the terpyridine ligand binds in a bidentate fashion. The non-coordinating nitro-gen atom in the terpyridine ligand is positioned on the side opposite to the bromido ligand. In II, the metal ion is coordinated by two carbonyl ligands in a cis configuration and the terpyridine ligand binds in a tridentate fashion; notably, one carbonyl and the trans bromido ligand are mutually disordered over two positions. In I, the complex mol-ecules are linked by C-H⋯Br hydrogen bonds. In II, aromatic π-π contacts are present, as well as pairs of C-H⋯Br and C-H⋯O hydrogen bonds.

Radiocesium concentrations and GPS-coupled dosimetry in Fukushima snakes.

One of the largest releases of radioactive contamination in history occurred at Japan's Fukushima Daiichi Nuclear Power Plant (FDNPP). Although the accident happened in 2011, questions still persist regarding its ecological impacts. For example, relatively little is known about radiocesium accumulation in snakes, despite their high trophic status, limited home range sizes, and close association with soil where many radionuclides accumulate. This study presents one of the most comprehensive radioecological studies of snakes published to date using a combination of whole-body radiocesium analyses, GPS transmitters, and optically stimulated luminescence (OSL) dosimeters. The objectives were to: 1) quantify whole-body radiocesium activity concentrations and internal dose rates among several common species of snakes within and around the Fukushima Exclusion Zone (FEZ), 2) determine effects of species, sex, and body size on radiocesium activity concentrations, 3) measure external dose rates using GPS-coupled dosimeters deployed on free-ranging snakes, 4) compare field-derived empirical dose rates to those generated by computer simulation software (i.e., the ERICA tool), and 5) determine if incorporating snake behavior into computer models improve simulated estimates of external dose. Whole-body radiocesium levels for snakes were highly variable among individuals (16 to 25,000 Bq/kg, FW), but were influenced more by levels of local contamination than species, sex, or size. Doses recorded by OSL dosimeters on snakes, as well as modeling in ERICA, suggest that individual movements and behavior have a substantial influence on dose rates to snakes. However, dose estimates produced with ERICA were comparable to dose received by tracked snakes. The average external plus internal dose rate for snakes captured in the FEZ was 3.6-3.9 µGy/h, with external dose contributing 80% to the total. Further research regarding reptile-specific benchmark dose rates would improve risk assessment for reptiles in radiologically contaminated areas.

Coordination Chemistry of Ru(II) Complexes of an Asymmetric Bipyridine Analogue: Synergistic Effects of Supporting Ligand and Coordination Geometry on Reactivities.

The reactivities of transition metal coordination compounds are often controlled by the environment around the coordination sphere. For ruthenium(II) complexes, differences in polypyridyl supporting ligands affect some types of reactivity despite identical coordination geometries. To evaluate the synergistic effects of (i) the supporting ligands, and (ii) the coordination geometry, a series of dicarbonyl-ruthenium(II) complexes that contain both asymmetric and symmetric bidentate polypyridyl ligands were synthesized. Molecular structures of the complexes were determined by X-ray crystallography to distinguish their steric configuration. Structural, computational, and electrochemical analysis revealed some differences between the isomers. Photo- and thermal reactions indicated that the reactivities of the complexes were significantly affected by both their structures and the ligands involved.

Formation and stability of the mixed-chelator complexes of Sr2+, Mg2+, Ca2+, Ba2+, and Y3+ in solution with bio-relevant chelators.

The formation and equilibria of Sr2+, Mg2+, Ca2+, Ba2+, and Y3+ (M) complexes with a mixed-chelator comprising two biodegradable chelators (GLDA, LG, 2-[bis(carboxymethyl)amino] pentanedioic acid; HIDS, LH, 2-(1,2-dicarboxyethylamino)-3-hydroxy-butanedioic acid) in an aqueous matrix was evaluated. The potentiometric measurement results (ionic strength, 0.10 M; temperature, 25 ±â€¯0.1 °C) confirmed the formation of 1:1:1 (M:LG:LH) complexes and the experimental data sets were further used to derive the equilibrium constants for the ternary complexes. The [MHLGLH]5- complex was the dominant ternary complex with Sr2+, Mg2+, Ca2+, and Ba2+, while Y3+ formed [M(OH)2LGLH]7- as the principal ternary species. The trend in the overall formation constants of the MLmix (Lmix, LG:LH = 1:1) complexes was in the order: Y3+ > Ca2+ > Mg2+ > Sr2+ > Ba2+. The ternary complexation trend was interpreted using the corresponding atomic radii and solution-phase electronegativities of the elements. The modes of interaction between the chelators and cations in the MLmix systems were subsequently deduced, and evaluated by using Gaussian 16W program. The relative stabilities of the ternary complexes (ΔlogK) were interpreted by comparison with the stabilities of the corresponding binaries, with negative ΔlogK values observed for all the MLmix complexes.

Use of different surface covering materials to enhance removal of radiocaesium in plants and upper soil from orchards in Fukushima prefecture.

The effectiveness of a decontamination methodology whereby herbaceous plants were grown through different materials covering the soil surface followed by subsequent removal of the material, associated plant tissues and attached soil on 137Cs removal from soil was evaluated. Revegetation netting sown with Kentucky bluegrass and white clover had a high effectiveness in 137Cs removal when rolling up the plants, roots, and rhizosphere soil approximately 6 months after sowing. The removal rate was lower when there was higher 137Cs vertical migration down the soil profile. The maximum removal effectiveness of 93.1% was observed by rolling up fertilized Kentucky bluegrass with a well-developed root mat without netting, indicating that applying nutrients to encourage the development of roots or root mats in the 3 cm topsoil rhizosphere is an efficient technology to increase the decontamination effect of plant removal in orchards. Netting and weeding were able to remove up to 80% of 137Cs in the soil without the use of heavy machinery. There was a significant relationship between the removal ratio and the removed soil weight per area. Using the relationship on the site below the canopy, removal of 14.3 kg m-2 DW soil would achieve a removal ratio of 80%. The effectiveness of the technique will decrease with time as radiocaesium migrates down the soil profile but this would be expected to occur slowly in many soils.

A comparison of methods to derive aggregated transfer factors using wild boar data from the Fukushima Prefecture.

Aggregated transfer factors (Tag; m2 kg-1) are often used to predict radionuclide activity concentrations in biota (Bq kg-1) from soil contamination levels (Bq m-2). Inherently large uncertainties in Tag values severely limit their predictive power. Many published Tag values have been derived from radionuclide deposition onto soil following weapons fallout, or the accidents at Chernobyl and Fukushima. In many cases the soil data used to derive a Tag value were collected for other purposes, and the spatial resolution of the soil data is much less than that of the biota data to which it is paired. We hypothesized that this disassociation and imprecision in paring deposition density and biota data may contribute to the large variations observed in Tag values. We tested the hypothesis by deriving Tag values for Japanese wild boar in two ways. One method used paired deposition density-biota contamination levels, with the soil data collected from each boar trap site. The second method used a soil radioactivity density map, of relatively low spatial resolution, generated by the Japanese government agency MEXT for fallout from the Fukushima accident. We hypothesized that Tag values derived from the method using paired deposition density-wild boar data would have less variation. Initial statistical test suggested significant differences in the predictive power of the two methods. However, removal of suspected outliers in the MEXT data set decreased the statistical differences and indicated that collecting 137Cs soil deposition density measurements in the field did not reduce the large variation in our Tag values. More importantly, both methods revealed that soil contamination levels are a poor predictor of radiocesium concentrations in boar (r2 < 0.23). The inadequacies of Tag to predict wild boar 137Cs concentrations is an ominous indication of the lack of applicability of the Tag model as a rigorous research parameter. Tag values are best suited for their original intended purpose: upper tier, screening level computations. Further studies on how to reduce uncertainty when predicting 137Cs concentrations in biota are needed to thoroughly understand the transfer of radiocesium within the environment.

Crystal structure of a dinuclear ruthenium(II) complex with a bent CO22- bridge.

The mol-ecular and crystal structures of a CO22--bridged dinuclear ruthenium complex is reported, namely, µ-carbonito-κ2C:O-bis-[bis(2,2'-bi-pyridine-κ2N,N')carbon-ylruthenium(II)] bis-(hexa-fluorido-phosphate)-aceto-nitrile-diethyl ether (1/1/0.5), [Ru2(CO)2(C10H8N2)4(µ:κ2-C:O-CO2)](PF6)2·CH3CN·0.5C4H10O. The complex cation in the title compound consists of two {Ru(CO)(bpy)2}2+ units (bpy = 2,2'-bi-pyridine) singly bridged by a µ:κ2-C:O carbonite anion, resulting in an unsymmetrical dinuclear structure. Some of the inter-atomic C⋯O distances involving the carbonyl ligands are shorter than the sum of the van der Waals radii. There are intra-molecular C-H⋯O and aromatic π-π contacts in the cationic complex. In the crystal, the cations are linked by pairs of C-H⋯F hydrogen bonds in addition to weak C-H⋯F inter-actions between the solvent mol-ecules and PF6- counter-anions. The equatorial F atoms of one of the PF6- anions are disordered over two sets of sites with an occupancy ratio of 0.908 (7):0.092 (7) while the central O atom of the diethyl ether solvent mol-ecule is disordered over an inversion centre.

Radioactive and stable cesium isotope distributions and dynamics in Japanese cedar forests.

Dynamics of the Fukushima-derived radiocesium and distribution of the natural stable isotope 133Cs in Japanese cedar (Cryptomeria japonica D. Don) forest ecosystems were studied during 2014-2016. For the experimental site in Yamakiya, Fukushima Prefecture, we present the redistribution of radiocesium among ecosystem compartments during the entire observation period, while the results obtained at another two experimental site were used to demonstrate similarity of the main trends in the Japanese forest ecosystems. Our observations at the Yamakiya site revealed significant redistribution of radiocesium between the ecosystem compartments during 2014-2016. During this same period radionuclide inventories in the aboveground tree biomass were relatively stable, however, radiocesium in forest litter decreased from 20 ± 11% of the total deposition in 2014 to 4.6 ± 2.7% in 2016. Radiocesium in the soil profile accumulated in the 5-cm topsoil layers. In 2016, more than 80% of the total radionuclide deposition in the ecosystem resided in the 5-cm topsoil layer. The radiocesium distribution between the aboveground biomass compartments at Yamakiya during 2014-2016 was gradually approaching a quasi-equilibrium distribution with stable cesium. Strong correlations of radioactive and stable cesium isotope concentrations in all compartments of the ecosystem have not been reached yet. However, in some compartments the correlation is already strong. An increase of radiocesium concentrations in young foliage in 2016, compared to 2015, and an increase in 2015-2016 of the 137Cs/133Cs concentration ratio in the biomass compartments with strong correlations indicate an increase in root uptake of radiocesium from the soil profile. Mass balance of the radionuclide inventories, and accounting for radiocesium fluxes in litterfall, throughfall and stemflow, enabled a rough estimate of the annual radiocesium root uptake flux as 2 ± 1% of the total inventory in the ecosystem.

Behavior of 137Cs in ponds in the vicinity of the Fukushima Dai-ichi nuclear power plant.

137Cs activity concentration in the water of four ponds, Suzuuchi (SU), Funasawa (FS), Inkyozaka (IZ), and Kashiramori (KM), that are within 10 km of the Fukushima Dai-ichi nuclear power plant were observed from April 2015 to August 2016. 137Cs inventories in soils surrounding SU, FS, IZ, and KM were 6.4, 2.9, 2.1, and 0.9 MBq m-2, respectively. 137Cs inventories in the bottom sediments of SU, FS, IZ, and KM were 13, 8.9, 1.6, and 1.1 MBq m-2, respectively. Higher 137Cs inventories in bottom sediment than those of soil in SU and FS suggest that 137Cs was delivered to and accumulated in these ponds. Mean total 137Cs activity concentrations in SU, FS, IZ, and KM were 41, 13, 9.5, and 1.4 Bq L-1, respectively. Particulate 137Cs concentration accounted for 71-90% of total 137Cs in the water samples, on average. The mean distribution coefficient, Kd, in SU, FS, IZ, and KM was 1.3 × 105, 2.1 × 105, 1.7 × 105, and 6.2 × 105 L kg-1, respectively. These Kd values were higher than the Kd values observed in the Chernobyl area by 1-2 orders of magnitude. Although no significant decreasing trends were found, dissolved 137Cs activity concentration tended to be low during winter in all four ponds. Dissolved 137Cs activity concentrations were proportional to K+ and DOC concentrations in all the ponds. The results from principal component analysis performed for 137Cs activity concentration and water chemistry data sets suggested that there were different mechanisms behind variability of dissolved 137Cs activity concentrations for each pond. Continuous monitoring is required to reveal temporal trends in 137Cs activity concentrations of these waters and controlling factors of such in closed water systems in Fukushima.