Seiya Nagao

Factors affecting vertical distribution of Fukushima accident-derived radiocesium in soil under different land-use conditions

The Fukushima Dai-ichi nuclear power plant accident in Japan, triggered by a big earthquake and the resulting tsunami on 11 March 2011, caused a substantial release of radiocesium ((137)Cs and (134)Cs) and a subsequent contamination of soils in a range of terrestrial ecosystems. Identifying factors and processes affecting radiocesium retention in these soils is essential to predict how the deposited radiocesium will migrate through the soil profile and to other biological components. We investigated vertical distributions of radiocesium and physicochemical properties in soils (to 20 cm depth) at 15 locations under different land-use types (croplands, grasslands, and forests) within a 2 km × 2 km mesh area in Fukushima city. The total (137)Cs inventory deposited onto and into soil was similar (58.4±9.6 kBq m(-2)) between the three different land-use types. However, aboveground litter layer at the forest sites and herbaceous vegetation at the non-forested sites contributed differently to the total (137)Cs inventory. At the forest sites, 50-91% of the total inventory was observed in the litter layer. The aboveground vegetation contribution was in contrast smaller (<35%) at the other sites. Another remarkable difference was found in vertical distribution of (137)Cs in mineral soil layers; (137)Cs penetrated deeper in the forest soil profiles than in the non-forested soil profiles. We quantified (137)Cs retention at surface soil layers, and showed that higher (137)Cs retention can be explained in part by larger amounts of silt- and clay-sized particles in the layers. More importantly, the (137)Cs retention highly and negatively correlated with soil organic carbon content divided by clay content across all land-use types. The results suggest that organic matter inhibits strong adsorption of (137)Cs on clay minerals in surface soil layers, and as a result affects the vertical distribution and thus the mobility of (137)Cs in soil, particularly in the forest ecosystems.

Comparison of the vertical distributions of Fukushima nuclear accident radiocesium in soil before and after the first rainy season, with physicochemical and mineralogical interpretations

Effect of intense rainfall on the distribution of Fukushima-accident-derived (137)Cs in soil was examined. Inventories and vertical distributions of (137)Cs in soils were determined at 15 locations (including croplands, grasslands, and forests) in Fukushima city in the post-rainy season, approximately 4.5months after the accident, and were compared with those in the pre-rainy season determined in our former study. The (137)Cs inventory levels scarcely changed between points in time spanning the first rainy season after the accident. Moreover, the majority of (137)Cs remained stored in the aboveground vegetation and in the upper 5cm of soil layer at undisturbed locations in the post-rainy season. A more quantitative analysis with the characterization of the vertical profile of (137)Cs using the relaxation length confirmed that the vertical profile was almost unchanged at most locations. Accordingly, it is concluded that rainfall during the rainy season had a limited effect on (137)Cs distribution in the soil, indicating the very low mobility. Chemical extraction of (137)Cs from selected soil samples indicated that (137)Cs in the soil was barely water soluble, and even the fraction extracted with 1M ammonium acetate was only approximately 10%. This further supports the low mobility of (137)Cs in our soils. Soil mineralogical analyses, which included the identification of clay minerals, suggested that smectite and mica could lower the exchangeable fraction of (137)Cs. However, no direct relationship was obtained between mineral composition and (137)Cs retention in the upper soil layer. In contrast, positive correlations were observed between (137)Cs extractability and soil properties such as pH, organic matter content, finer-sized particle content, and cation-exchange capacity. These results suggest that the mineralogical effect on the firm fixation of (137)Cs on soil constituents may be masked by the non-specific adsorption offered by the physicochemical properties of the soils.

Characteristics of humic substances in the Kuji River waters as determined by high-performance size exclusion chromatography with fluorescence detection

Direct measurement by high-performance size exclusion chromatography with fluorescence detection was applied to the characterization of humic substances in river waters from the Kuji River system, which runs through forest hills and an agricultural plain in Japan. The monitoring wavelength of excitation 320 nm and emission 430 nm corresponds to the fluorescence maxima for aquatic fulvic acid. Chromatograms of the river waters showed four peaks; each peak position was in good agreement among these samples. Peak height ratios for the samples from the upstream Kuji River and its tributaries were different from those of the midstream and downstream sections of the Kuji River, which may reflect differences in the characteristics of humic substances and other organic materials supplied from soil to river.

134Cs and 137Cs activities in coastal seawater along Northern Sanriku and Tsugaru Strait, northeastern Japan, after Fukushima Dai-ichi Nuclear Power Plant accident

A total of 37 seawater samples were collected at 10 sites along the coastline of the Northern Sanriku and Tsugaru Strait, 250-450 km north of the Fukushima Dai-ichi Nuclear Power Plant in April-December 2009 and May-June 2011, and analyzed for (134)Cs and (137)Cs activities using low-background γ-spectrometry. The (134)Cs and (137)Cs activities measured in these samples in May 2011 were found to be 2-3 mBq/L and 2.5-4 mBq/L, respectively. By June, these values had decreased by 25-45%/month and 5-30%/month, respectively. These results can be plausibly explained by surface infusion of these isotopes into the sea by atmospheric transport from Fukushima and their subsequent reduction by water migration to off-shore and deeper regions.

Lateral variation of 134Cs and 137Cs concentrations in surface seawater in and around the Japan Sea after the Fukushima Dai-ichi Nuclear Power Plant accident.

A total of 82 surface seawater samples was collected in the Japan Sea and the southwestern Okhotsk Sea before and after the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident. Analysis of (134)Cs and (137)Cs concentrations using low-background γ-spectrometry revealed that the (137)Cs concentration of the samples collected in June 2011 was 1.5-2.8mBq/L, which is approximately 1-2 times higher than the pre-accident (137)Cs level, while the (134)Cs concentration was less than detectable to 1mBq/L. In addition to (134)Cs being clearly detected (∼1mBq/L), (137)Cs concentration in water samples from the northeastern Japan Sea (2-2.8mBq/L) was also higher than that from the coast in the southwestern Japan Sea (∼1.5mBq/L). These higher concentrations in the northeastern Japan Sea could be ascribed to the atmospheric transport of nuclides from the FDNPP as aerosols and subsequent transport and dilution after delivery to the sea surface.

Effects of humic acid on the sorption of neptunium(V) on kaolinite

Abstract The sorption coefficient of Np(V), K d , on kaolinite was measured at pH 6 to 11 and in humic acid concentrations of 0 to 40 mg dm −3 at the ionic strength of 0.1 M. The K d value increased with pH both with and without humic acid. The K d value increased slightly with increasing concentration of humic acid in the pH range below 8 and decreased not more than an order of magnitude with increasing concentrations of humic acid in the pH region above 8. Below pH 8, Np(V) sorption is considered to be enhanced by the sorption of humic acid on the kaolinite to form Np(V)-humate complexes. Above 8, it is probable that the desorption of humic acid and formation of Np(V)-humate in solution result in the decrease of K d . The behavior of Np(V) sorption on kaolinite with humic acid is described by a simple model.

Particulate and dissolved elemental loads in the Kuji River related to discharge rate.

In order to investigate influences of discharge rates on fluvial transport behavior of elements in the Kuji River, Japan, suspended and dissolved phase concentrations in the river water were measured together with the water flow rates. The concentrations of suspended particulate matter (SPM) increased by two or three orders of magnitude with the water discharge, and also had seasonal variations. Adsorptive elements or heavy metal elements, which tend to form insoluble compounds, were present generally as suspended forms in the river waters, and their dissolved form concentrations tended to increase with the water discharge. On the other hand, non-adsorptive elements such as alkali and alkaline-earth elements were present as dissolved forms under a normal flow rate condition, but equivalent quantity of suspended species also occurred under a high flow condition. In this case, the dissolved form concentrations decreased with the water discharge. Characterization of SPM with analyses of chemical compositions, scanning electron microscopy (SEM) and X-ray diffractometry (XRD) indicated that clay mineral such as montmorillonite would be the main carrier material of trace and major elements during the fluvial transport in the Kuji River. Variations of contents of selected elements in SPM with the water discharge indicated that river bottom sediments, which are probably potential sources of SPM added due to high water flow rates, would be different in chemical compositions from SPM floating under a normal flow condition. Variations of chemical compositions of SPM as well as of suspended or dissolved form concentrations of elements in the river waters were formulated as a function of the water discharge rates.

The factors controlling vertical color variations of North Atlantic Madeira Abyssal Plain sediments

Abstract Colors of Madeira Abyssal Plain sediments, North East Atlantic were determined with a simple colorimeter and described in the second CIE 1976 color space ( L∗a∗b∗ color space). L∗a∗b∗ values of the original sediment core and the powdered sediments vary sharply with depth and these variations were found to be due to changes in the contents of calcium carbonate, organic matter, iron and manganese. The vertical color profiles are essentially conserved after drying and powdering. These results suggest that this rapid measurement method with the colorimeter can be used in quantitative color determination of marine sediments aboardship. As a result of quantitative studies among L∗a∗b∗ values, calcium carbonate, organic carbon, iron and manganese contents of powdered sediment samples, the following conclusions were obtained: (1) L∗ value (psychometric lightness) is controlled by calcium carbonate for whitish color and by organic matter for blackish color. The redox fronts can be easily characterized by a sharp decrease in L∗ value; (2) a∗ value (psychometric red-green chromaticness) is controlled by iron for pelagic sediments, by manganese carbonate and iron oxide and hydroxide for calcareous turbidites and turbidite G and by pigments and iron(II)-bearing minerals for greenish and grayish turbidites; (3) b∗ value (psychometric yellow-blue chromaticness) is controlled by iron contents probably in the form of hydroxides for calcareous turbidites.

Pattern of oxidation products derived from tetrabromobisphenol A in a catalytic system comprised of iron(III)-tetrakis(p-sulfophenyl)porphyrin, KHSO5 and humic acids

Tetrabromobisphenol A (TBBPA), a commercially used brominated flame retardant, also functions as an endocrine disruptor and is of serious concern in terms of environmental pollution. TBBPA has been detected in leachates from landfills, because hydrophobic interactions with humic acids (HAs) result in an increase in its solubility. In the present study, the oxidation of TBBPA was examined using a biomimetic catalytic system comprised of a combination of iron(III)-tetrakis(p-sulfophenyl)porphyrin (FeTPPS) and KHSO(5). Although more than 90% of TBBPA was oxidized at pH 8 in the absence and presence of HAs, no debromination was observed. An analysis of the oxidation products by GC/MS indicated that 4-(2-hydroxyisopropyl)-2,6-dibromophenol was the main byproduct. However, only about 6-12% of the TBBPA was degraded. In the presence of HAs, the remaining byproducts from TBBPA may be incorporated into HAs via a variety of interactions. Thus, HA fractions in the reaction mixture were separated, and analyzed for their Br content. Based on the analyses, the majority of the Br species (70-80%) were found to be incorporated into HAs after oxidation with TBBPA. In addition, coupling compounds between brominated intermediates from TBBPA and phenolic moieties in HAs were detected by pyrolysis-GC/MS. These results lead to the conclusion that the oxidation of TBBPA in the presence of HAs via catalytic oxidation using FeTPPS resulted in the incorporation of brominated intermediates into the polymeric structures of HAs.

The transfer capability of long-lived Chernobyl radionuclides from surface soil to river water in dissolved forms

Hydrologic runoff is one of the main processes in which radionuclides deposited in the surface environment migrate widely in both particulate and dissolved forms. This paper focuses on the transfer capability of long lived Chernobyl radionuclides from surface soil to river water in dissolved forms. First, concentration and speciation of radioactive Cs, Sr and transuranic isotopes, such as Pu and Am, were examined in undisturbed surface soil along the river in the exclusion zone (30 km zone) near the Chernobyl Nuclear Power Plant (NPP) in order to validate the radioactive contamination characteristics. Almost all radioactivities exist in the very top surface in the undisturbed soil layer. Sr-90 in the soil was estimated to be highest in the water soluble and exchangeable fractions, which were easily accessible to river water as a dissolved fraction. Pu isotopes and Am-241 are major radionuclides in free humic and free fulvic acid fractions. Secondly, surface soil near the Sahan River was extracted with distilled water, as an analogue of rain water, to estimate the dissolved fraction in runoff components from surface soil to river water. After a filtration procedure, extracted water was treated with ultra filtration techniques separating the molecular weight fractions of beyond and below 10,000 Da. Each fraction was measured for the radioactivity and the characteristics of organic materials including humic substances. Most Pu and Am exist in the molecular weight fractions beyond 10,000 Da, in spite of the fact that most of the dissolved organic fractions exist below 10,000 Da. This means that transuranic elements such as Pu and Am are associated with mobile high molecular weight materials like fulvic acids in water leachates.