Temporal variation of particulate organic carbon flux at the mouth of Tokyo Bay.

A sediment trap experiment was conducted at a depth of 750 m at the mouth of Tokyo Bay to clarify the quantity and transport process of particles from the bay to the open ocean. The high total mass flux (8.7 ± 4.5 g m-2 d-1) suggests that the particles not only originate in the surface layer right above the trap, but are also focused in Uraga Channel and discharged into the bay mouth. The organic carbon and nitrogen isotope ratios (δ13Corg, δ15N) of the trapped particles were like those of the surface sediment in the bay, that is, a mixture of particles in rivers and suspended particles in the surface layer of the bay. Compared with the results of the experiment conducted in 1995-2002, the average total mass flux was reduced by 70% and organic carbon content was reduced by 50%. The δ13Corg values of trapped particles were also lower than those observed in the previous experiment, indicating a lower contribution from surface-suspended particles with high δ13Corg values in the bay. These results could partly reflect a decrease of the concentration of the suspended particulate carbon in the bay by half over 20 years. Another factor contributing to the decrease of the flux at the bay mouth would be that the intrusion of Kuroshio coastal water into the bay, which pushes particles out to the bay mouth, has not occurred in recent years.

A modeling study on the oceanic dispersion and sedimentation of radionuclides off the coast of Fukushima.

We developed a three-dimensional prognostic oceanic dispersion model that accounted for the phase transfer of radionuclides between seawater, suspended particles, and seabed sediments with multiscale grain sizes. A detailed hindcast of 137Cs in the seabed sediment off the Fukushima coast was conducted to investigate the transfer mechanism of dissolved 137Cs derived from the Fukushima Daiichi Nuclear Power Plant (FNPP1) accident toward the seabed sediment. Extensive model-data comparison demonstrated that the model could satisfactorily reproduce the oceanic structure and 137Cs concentrations in the seawater and seabed sediment. The model successfully reproduced the major features of the observed spatial variation of the 137Cs activities in the sediment, which represented more than 90% of the sedimentary radiocesium existing in the coastal area off Fukushima several months after the accident. Shear stress associated with the resuspension of the seabed sediment was induced by waves near the shore and by current velocity offshore of the study area. The adsorption of 137Cs on the seabed sediment differed depending on the particle size, with adsorption on clay being the most substantial. The distribution of 137Cs in the sediment off the Fukushima coast was formed mainly owing to adsorption from the dissolved phase by June 2011, when the impact of the direct oceanic 137Cs release from FNPP1 was remarkable. After June 2011, seabed sediment became a source of 137Cs released to the seawater owing to resuspension with and desorption from the sediment.

Spatiotemporal change of cesium-137 in the Pacific coast of Tohoku, Japan: The mussel watch approach.

We measured radiocesium in mussel tissue collected from the Pacific coast of Tohoku from 2011 to 2015 to investigate the temporal and spatial dynamics of radiocesium in the coastal area. Radioactive 137Cs was detected in all the samples collected in 2011, but it was not found in samples from localities north of Sendai after 2012. In contrast, 137Cs was detected in many sites in the Fukushima area even from 2012 to 2015. The fluctuation of 137Cs concentration in mussel tissue seems to reflect the 137Cs concentration in suspended particles in the seawater, suggesting that there was an influx of soil deposition and resuspension of seabed sediment. These results suggest that the 137Cs concentration in mussel tissue sensitively indicates the 137Cs concentration in the environment, and that the "mussel watch" approach is an effective way to understand the dynamics of radiocesium concentrations in coastal areas.

First isolation and analysis of caesium-bearing microparticles from marine samples in the Pacific coastal area near Fukushima Prefecture.

A part of the radiocaesium from the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident was emitted as glassy, water-resistant caesium-bearing microparticles (CsMPs). Here, we isolated and investigated seven CsMPs from marine particulate matter and sediment. From the elemental composition, the 134Cs/137Cs activity ratio, and the 137Cs activity per unit volume results, we inferred that the five CsMPs collected from particulate matter were emitted from Unit 2 of the FDNPP, whereas the two CsMPs collected from marine sediment were possibly emitted from Unit 3, as suggested by (i) the presence of calcium and absence of zinc and (ii) the direction of the atmospheric plume during the radionuclide emission event from Unit 3. The presence of CsMPs can cause overestimation of the solid-water distribution coefficient of Cs in marine sediments and particulate matter and a high apparent radiocaesium concentration factor for marine biota. CsMPs emitted from Unit 2, which were collected from the estuary of a river that flowed through a highly contaminated area, may have been deposited on land and then transported by the river. By contrast, CsMPs emitted from Unit 3 were possibly transported eastward by the wind and deposited directly onto the ocean surface.

Distribution and Evolution of Fukushima Dai-ichi derived 137Cs, 90Sr, and 129I in Surface Seawater off the Coast of Japan.

The Fukushima Dai-ichi Nuclear Power Plants (FDNPPs) accident in 2011 led to an unprecedented release of radionuclides into the environment. Particularly important are 90Sr and 137Cs due to their known health detriments and long half-lives (T1/2 ≈ 30 y) relative to ecological systems. These radionuclides can be combined with the longer-lived 129I (T1/2 = 15.7 My) to trace hydrologic, atmospheric, oceanic, and geochemical processes. This study seeks to evaluate 137Cs, 90Sr, and 129I concentrations in seawater off the coast of Japan, reconcile the sources of contaminated waters, and assess the application of 137Cs/90Sr, 129I/137Cs, and 129I/90Sr as oceanic tracers. We present new data from October 2015 and November 2016 off the coast of Japan, with observed concentrations reaching up to 198 ± 4 Bq·m-3 for 137Cs, 9.1 ± 0.7 Bq·m-3 for 90Sr, and (114 ± 2) × 10-5 Bq·m-3 for 129I. The utilization of activity ratios suggests a variety of sources, including sporadic and independent releases of radiocontaminants. Though overall concentrations are decreasing, concentrations are still elevated compared to pre-accident levels. In addition, Japan's Environment Minister has suggested that stored water from the FDNPPs may be released into the environment and thus continued efforts to understand the fate and distribution of these radionuclides is warranted.

Behavior of Radiocesium in Sediments in Fukushima Coastal Waters: Verification of Desorption Potential through Pore Water.

Concentrations of 137Cs in seawater, seabed sediment, and pore water collected from the area around Fukushima were investigated from 2015 to 2018, and the potential of coastal sediments to supply radiocesium to the bottom environment was evaluated. The 137Cs concentration in the pore water ranged from 33 to 1934 mBq L-1 and was 10-40 times higher than that in the overlying water (seawater overlying within 30 cm on the seabed). At most stations, the 137Cs concentrations in the overlying water and the pore water were approximately proportional to those in the sediment. The conditional partition coefficient between pore water and sediment was [0.9-14] × 102 L kg-1, independent of the year of sampling. These results indicated that an equilibrium of 137Cs between pore water and sediment has been established in a relatively short period, and 137Cs in the pore water is gradually exported to seawater near the seabed. A simple box model estimation based on these results showed that 137Cs in the sediment decreased by about 6% per year by desorption/diffusion of 137Cs from the seabed.

Distribution and fate of 129I in the seabed sediment off Fukushima.

In this study, seabed sediment was collected from 26 stations located within 160 km from the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) during the 2 years which followed the FDNPP accident of March 2011 and the concentrations of 129I and 137Cs were measured. By comparing the distribution of these two radionuclides with respect to their different geochemical behaviors in the environment, the transport of accident-derived radionuclides near the seafloor is discussed. The concentration of 129I in seabed sediment recovered from offshore Fukushima in 2011 ranged between 0.02 and 0.45 mBq kg-1, with 129I/137Cs activity ratios of (1.9 ±â€¯0.5) × 10-6 Bq Bq-1. The initial deposition of 129I to the seafloor in the study area was 0.36 ±â€¯0.13 GBq, and the general distribution of sedimentary 129I was established within 6 months after the accident. Although iodine is a biophilic element, the accident-derived 129I negligibly affects the benthic ecosystem. Until October 2013, a slight increase in activity of 129I in the surface sediment along the shelf-edge region (bottom depth: 200-400 m) was observed, despite that such a trend was not observed for 137Cs. The preferential increase of the 129I concentrations in the shelf-edge sediments was presumed to be affected by the re-deposition in the shelf-edge sediments of 129I desorbed from the contaminated coastal sediment. The results obtained from this study indicate that 129I/137Cs in marine particles is a useful indicator for tracking the secondary transport of accident-derived materials, particularly biophilic radionuclides, from the coast to offshore areas.

Tracking the Fate of Particle Associated Fukushima Daiichi Cesium in the Ocean off Japan.

A three year time-series of particle fluxes is presented from sediment traps deployed at 500 and 1000 m at a site 115 km southeast of Fukushima Daiichi Nuclear Power Plant (FDNPP). Results show a high fraction of lithogenic material and mass flux peaks that do not align between the trap depths, suggesting a lateral source of sediments. Fukushima cesium-137 and cesium-134 were enhanced in flux peaks that, given variations in trap (137)Cs/(210)Pbex ratios, are characteristic of material derived from shelf and slope sediments found from <120 to >500 m. These lateral flux peaks are possibly triggered by passing typhoons. The Cs fluxes are an order of magnitude higher than were previously reported for the trap located 100 km due east of FDNPP. We attribute this large difference to the position of our trap under the southeasterly currents that carry contaminated waters and resuspended sediments away from FDNPP and into the Pacific. These higher Cs sedimentary fluxes offshore are still small relative to the inventory of Cs currently buried nearshore. Consequently, we do not expect them to effect any rapid decrease in Cs levels for the coastal sediments near FDNPP that have been linked to enhanced Cs in demersal fish.

Vertical and lateral transport of particulate radiocesium off Fukushima.

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.

Speciation of iodine isotopes inside and outside of a contaminant plume at the Savannah River Site.

A primary obstacle in understanding the fate and transport of the toxic radionuclide (129)I (a thyroid seeker) is an accurate method to distinguish it from the stable isotope, (127)I, and to quantify the various species at environmentally relevant concentrations (~10(-8) M). A pH-dependent solvent extraction and combustion method was paired with accelerator mass spectrometry (AMS) to measure ambient levels of (129)I/(127)I isotope ratios and iodine speciation (iodide (I(-)), iodate (IO3(-)), and organo-I (OI)) in aquatic systems. The method exhibited an overall uncertainty of 10% or less for I(-) and IO3(-), and less than 30% for OI species concentrations and enabled (129)I measurements as low as 0.001 Bq/L (1 Bq/L=10(-13) M). The method was used to analyze groundwater from the Savannah River Site (SRS), South Carolina, USA, along a pH, redox potential (Eh), and organic carbon gradient (8-60 µM DOC). The data confirmed that the (129)I/(127)I ratios and species distribution were strongly pH dependent and varied in a systematic manner from the strongly acidic source. While (129)I speciation in plume samples containing total I concentrations >1.7 Bq/L was similar whether measured by AMS or GC-MS ([I(-)]≫[IO3(-)]=[OI]), AMS enabled (129)I speciation measurements at much lower concentrations than what was possible with GC-MS. AMS analyses demonstrated that groundwater samples minimally impacted by the plume were still orders of magnitude higher than ambient (129)I concentrations typically found elsewhere in the USA groundwaters and rivers. This is likely due to past atmospheric releases of volatile (129)I species by SRS nuclear reprocessing facilities near the study site. Furthermore, the results confirmed the existence of (129)I not only as I(-), but also as OI and IO3(-) species.

Radiocesium derived from the Fukushima Daiichi Nuclear Power Plant accident in seabed sediments: initial deposition and inventories.

Since the accident at Fukushima Daiichi Nuclear Power Plant (1FNPP), significant levels of anthropogenic radionuclides have been detected in seabed sediments off the east coast of Japan. In this paper, the approximate amount of accident-derived radiocesium in seabed sediments off Fukushima, Miyagi and Ibaraki prefectures was estimated from a sediment integration algorithm. As of October 2011, about half a year after the accident, the total amount of sedimentary 134Cs was 0.20±0.06 PBq (decay corrected to March 11, 2011) and more than 90% of the radiocesium was accumulated in the regions shallower than 200 m depth. The large inventory in the coastal sediments was attributed to effective adsorption of dissolved radiocesium onto suspended particles and directly to sediments in the early post-accident stage. Although rivers are also an important source to supply radiocesium to the coastal regions, this flux was much lower than that of the above-mentioned process within half a year after the accident.

Sedimentation and remobilization of radiocesium in the coastal area of Ibaraki, 70 km south of the Fukushima Dai-ichi Nuclear Power Plant.

Sedimentation and remobilization processes of radiocesium were investigated from time-series observations at nine stations in the coastal area of Ibaraki, 70-110 km south of the Fukushima Dai-ichi Nuclear Power Plant (1FNPP). Sediment samples were collected four times between June 2011 and January 2012, and concentrations of radiocesium as well as sediment properties such as grain size and elemental compositions were analyzed. Cumulative inventory of (137)Cs in sediment (0-10 cm) ranged between 4 × 10(3) and 3 × 10(4) Bq/m(2) as of January 2012. This amount was generally higher at stations nearer 1FNPP and has remained at the same level since August 2011. From these results, it can be inferred that dissolved radiocesium advected southward from the region adjacent to the 1FNPP and was deposited to the sediment of the study area in the early stage after the accident. The incorporation of radiocesium into sediments was almost irreversible, and higher concentrations of (137)Cs were obtained from the finer-grained fraction of sediments. In the northern offshore stations, resuspension of the fine-grained sediments formed a high-turbidity layer 10-20 m above the seabed. These results indicate that radiocesium-enriched fine particles were transported from the coast to offshore regions through the bottom high-turbidity layer.

Collection of lanthanides and actinides from natural waters with conventional and nanoporous sorbents.

Effective collection of trace-level lanthanides and actinides is advantageous for recovery and recycling of valuable resources, environmental remediation, chemical separations, and in situ monitoring. Using isotopic tracers, we have evaluated a number of conventional and nanoporous sorbent materials for their ability to capture and remove selected lanthanides (Ce and Eu) and actinides (Th, Pa, U, and Np) from fresh and salt water systems. In general, the nanostructured materials demonstrated a higher level of performance and consistency. Nanoporous silica surface modified with 3,4-hydroxypyridinone provided excellent collection and consistency in both river water and seawater. The MnO(2) materials, in particular the high surface area small particle material, also demonstrated good performance. Other conventional sorbents typically performed at levels below the nanostructured sorbents and demonstrate a larger variability and matrix dependency.

Bacterial production of organic acids enhances H2O2-dependent iodide oxidation.

To develop an understanding of the role that microorganisms play in the transport of (129)I in soil-water systems, bacteria isolated from subsurface sediments were assessed for iodide oxidizing activity. Spent liquid medium from 27/84 bacterial cultures enhanced iodide oxidation 2-10 fold in the presence of H(2)O(2). Organic acids secreted by the bacteria were found to enhance iodide oxidation by (1) lowering the pH of the spent medium, and (2) reacting with H(2)O(2) to form peroxy carboxylic acids, which are extremely strong oxidizing agents. H(2)O(2)-dependent iodide oxidation increased exponentially from 8.4 to 825.9 µM with decreasing pH from 9 to 4. Organic acids with ≥2 carboxy groups enhanced H(2)O(2)-dependent iodide oxidation (1.5-15-fold) as a function of increasing pH above pH 6.0, but had no effect at pH ≤ 5.0. The results indicate that as pH decreases (≤5.0), increasing H(2)O(2) hydrolysis is the driving force behind iodide oxidation. However, at pH ≥ 6.0, spontaneous decomposition of peroxy carboxylic acids, generated from H(2)O(2) and organic acids, contributes significantly to iodide oxidation. The results reveal an indirect microbial mechanism, organic acid secretion coupled to H(2)O(2) production, that could enhance iodide oxidation and organo-iodine formation in soils and sediments.

Sequestration and remobilization of radioiodine (129I) by soil organic matter and possible consequences of the remedial action at Savannah River Site.

In order to investigate the distributions and speciation of (129)I (and (127)I) in a contaminated F-Area groundwater plume of the Savannah River Site that cannot be explained by simple transport models, soil resuspension experiments simulating surface runoff or stormflow and erosion events were conducted. Results showed that 72-77% of the newly introduced I(-) or IO(3)(-) were irreversibly sequestered into the organic-rich riparian soil, while the rest was transformed by the soil into colloidal and truly dissolved organo-iodine, resulting in (129)I remobilization from the soil greatly exceeding the 1 pCi/L drinking water permit. This contradicts the conventional view that only considers I(-) or IO(3)(-) as the mobile forms. Laboratory iodination experiments indicate that iodine likely covalently binds to aromatic structures of the soil organic matter (SOM). Under very acidic conditions, abiotic iodination of SOM was predominant, whereas under less acidic conditions (pH ≥5), microbial enzymatically assisted iodination of SOM was predominant. The organic-rich soil in the vadose zone of F-Area thus acts primarily as a "sink," but may also behave as a potentially important vector for mobile radioiodine in an on-off carrying mechanism. Generally the riparian zone provides as a natural attenuation zone that greatly reduces radioiodine release.

Factors controlling mobility of 127I and 129I species in an acidic groundwater plume at the Savannah River Site.

In order to quantify changes in iodine speciation and to assess factors controlling the distribution and mobility of iodine at an iodine-129 ((129)I) contaminated site located at the U.S. Department of Energy's Savannah River Site (SRS), spatial distributions and transformation of (129)I and stable iodine ((127)I) species in groundwater were investigated along a gradient in redox potential (654 to 360 mV), organic carbon concentration (5 to 60 µmol L(-1)), and pH (pH 3.2 to 6.8). Total (129)I concentration in groundwater was 8.6±2.8 Bq L(-1) immediately downstream of a former waste seepage basin (well FSB-95DR), and decreased with distance from the seepage basin. (127)I concentration decreased similarly to that of (129)I. Elevated concentrations of (127)I or (129)I were not detected in groundwater collected from wells located outside of the mixed waste plume of this area. At FSB-95DR, the majority (55-86%) of iodine existed as iodide for both (127)I and (129)I. Then, as the iodide move down gradient, some of it transformed into iodate and organo-iodine. Considering that iodate has a higher K(d) value than iodide, we hypothesize that the production of iodate in groundwater resulted in the removal of iodine from the groundwater and consequently decreased concentrations of (127)I and (129)I in downstream areas. Significant amounts of organo-iodine species (30-82% of the total iodine) were also observed at upstream wells, including those outside the mixed waste plume. Concentrations of groundwater iodide decreased at a faster rate than organo-iodine along the transect from the seepage basin. We concluded that removal of iodine from the groundwater through the formation of high molecular weight organo-iodine species is complicated by the release of other more mobile organo-iodine species in the groundwater.

Detection and temporal variation of (60)Co in the digestive glands of the common octopus, Octopus vulgaris, in the East China Sea.

(60)Co were detected in common octopus specimens collected in the East China Sea in 1996-2005. The source of (60)Co has remained unclear yet. Stable isotope analyses showed that there was no difference in stable Co concentrations between octopus samples with (60)Co and without (60)Co. This result showed that the stable Co in the digestive gland of octopus potentially did not include a trace amount of (60)Co and the source of (60)Co existed independently. Furthermore, investigations of octopus in other area and other species indicated that the origin of the source of (60)Co occurred locally in the restricted area in the East China Sea and not in the coastal area of Japan. Concentrations of (60)Co have annually decreased with shorter half-life than the physical half-life. This decrease tendency suggests that the sources of (60)Co were identical and were temporary dumped into the East China Sea as a solid waste.