Comparison of dissolved iodine measurements in seawater between inductively coupled plasma mass spectrometry and voltammetry.

Two analytical methods, inductively coupled plasma mass spectrometry (ICP-MS) combined with high-performance liquid chromatography (HPLC) and voltammetry (VM), for three chemical species of dissolved iodine (iodide, iodate, and total dissolved iodine: TDI) were compared for dozens of coastal seawater samples owing to the compatibility of data between both methods. The median differences in the measured concentrations of TDI, total inorganic dissolved iodine (TII, the sum of iodide and iodate), and iodate between ICP-MS and VM were equivalent to 9.2, 13, and 14%, respectively. These differences were within the ranges that could be explained by the repeated-measurement precision of each measurement method for TDI, TII, and iodate. The difference for iodide was 19%, which was larger than the value based on the repeated-measurement precision for both methods. This is considered to be caused by the chemical instability and lower concentrations of iodide compared to other iodine species in seawater, in addition to the heterogeneity of natural samples. Finally, both methods provided reasonable measurement values for the iodine concentration in natural seawater samples.

Investigation of changes in the iodine concentrations of oceanic sediment and terrestrial soil samples after thermal drying.

To certify the suitability of pretreatment by thermal drying to measure iodine concentrations of oceanic sediment and terrestrial soil samples, changes in iodine concentrations after drying (50, 80 or 85, and 110 °C for 48 h) were examined using the samples in addition to a terrestrial plant (pine needles), which was selected as an intact organic sample. The iodine concentrations per wet weight of the sediment and soil samples processed by thermal drying were comparable to those of the raw samples at all temperatures. However, the concentrations of the plant samples dried at 85 and 110 °C were lower than those of the raw samples. The lower concentrations of the plant samples at higher temperatures were considered to be derived from the volatilization of a part of the plant's organic matter. Finally, these results suggested that the iodine concentrations in oceanic sediment and terrestrial soil samples scarcely change after thermal drying at 110 °C, although the concentrations may decrease when these samples include high contributions of fresh organic matter.

DISTRIBUTION OF RADIOCESIUM IN BLACK PINE TREE FORESTS IN ROKKASHO, AOMORI, JAPAN.

Since the Fukushima Dai-ichi Nuclear Power Plant (FDNNP) accident in 2011, 134Cs had been detected in atmospheric deposition samples collected in Rokkasho and Aomori in Japan, located ~400-km north of the FDNNP, during March 2011-May 2015. To study the distribution of radiocesium (134, 137Cs) in a Japanese black pine tree forest, we measured the activity concentration of 134, 137Cs in whole black pine trees, including roots collected during 2017-19 along with soil samples in 2015 and 2017-19. The results show that most of the deposited 134Cs was retained in the forest floor in 2015, with depth distribution different from that of the weapon testing fallout. Proportions of the weapon fallout 137Cs in trunks, branches, needles and roots were 44, 17, 13 and 26%, respectively, indicating that >50% of 137Cs in above-ground part existed in the trunks. The total inventories of 134Cs and 137Cs in the forest were estimated to be 8.9 and 2.5·103 Bq m-2, respectively, and ~4.8% of 137Cs inventory was originated from the accident. Inventory of 134Cs in the forest-including the black pine trees-was 1.6 times larger than cumulative deposition outside of the forest due to the canopy effect.

Ten-year radiocesium fluvial discharge patterns from watersheds contaminated by the Fukushima nuclear power plant accident.

After the Fukushima Dai-ichi nuclear power plant accident in March 2011, the fluvial discharge of 137Cs from watersheds to rivers was analyzed between 2011 and 2021. The concentrations of dissolved and particulate 137Cs were measured in river water samples collected from two rivers (the Hiso and Wariki rivers, mainly draining farmlands and forests, respectively) draining approximately 4-7 km2 watersheds in a montane area (the areal deposition of 134+137Cs; 1-3 MBq·m-2 in March 2011) of Iitate Village, Fukushima. Over the 10 yr analysis, the particulate 137Cs concentrations in the Hiso and Wariki rivers decreased by 70 and 50 times, respectively, and that of the dissolved form decreased by 150 and 130 times, respectively. Moreover, the apparent Kd (distribution coefficient) of 137Cs for water samples from both rivers have increased gradually over these periods. In 2011, the 137Cs discharge rates through the Hiso and Wariki rivers were 0.63% and 0.46% per year of the total amount of 137Cs deposited in their catchments, respectively; however, by 2021, these rates had decreased to 0.09% and 0.03% per year. The cumulative 137Cs discharge rates over 10 yr in the farmland- and forest-dominated rivers were 1.95% and 1.33%, respectively. These rates of the farmland-dominated river were ∼1.4-fold greater than those of the forest-dominated river. Moreover, ∼90% of the of the discharge occurred in particulate form while the remaining ∼10% was in the dissolved form. Thus, 137Cs deposited within these watersheds due to the accident was gradually discharged by the rivers over the 10-yr period; however, the majority remains stored in soils and litters etc. of the catchment area. These results indicate that 137Cs outflow from land-to-ocean will be limited in the future, as the river export of 137Cs is expected to continue decreasing.

240Pu/239Pu and 242Pu/239Pu atom ratios of Japanese monthly atmospheric deposition samples during 1963-1966.

Global fallout plutonium isotopic ratios from the 1960s are important for the use of Pu as environmental tracers. We measured the 240Pu/239Pu and 242Pu/239Pu atomic ratios of monthly atmospheric deposition samples collected in Tokyo and Akita, Japan during March 1963 to May 1966. To our knowledge, our results represent the first data measured for actual atmospheric deposition samples collected continuously during the 1960s. Both atomic ratios increased rapidly from March 1963 to June 1963, followed by a gradual increase until September 1963. Then, both ratios declined with a half-life of approximately 5.6 months. The observed temporal changes of the ratios were likely caused by the upper-stratospheric input of nuclear debris from high-yield atmospheric nuclear weapon testing during 1961-62, followed by its downward transport to the troposphere.

Regional and global contributions of anthropogenic iodine-129 in monthly deposition samples collected in North East Japan between 2006 and 2015.

We measured the monthly atmospheric deposition flux of 129I at Rokkasho, Aomori, Japan-the location of a commercial spent nuclear fuel reprocessing plant-from 2006 to 2015 to assess the impact of the plant on environmental 129I levels. The plant is now under final safety assessment by a national authority after test operation using actual spent nuclear fuel. During cutting and chemical processing in test operations from April 2006 to October 2008, 129I was discharged to the atmosphere and detected in our deposition samples. 129I deposition fluxes largely followed the discharge pattern of 129I from the plant to the atmosphere, and most of the deposited 129I originated from the plant. In and after 2009, 129I deposition fluxes decreased dramatically to reach the background level; the 129I deposition fluxes at Rokkasho were almost the same as those at Hirosaki, where an additional sampling point was set up as a background site 85 km from the plant in 2011. The background 129I deposition fluxes showed seasonal variation-high in winter and low in the other seasons-at both Rokkasho and Hirosaki. The results of a backward trajectory analysis of the air mass at Rokkasho suggested that reprocessing plants in Europe were the origins of the high 129I flux in winter. The contribution of 129I released from the Fukushima Dai-ichi Nuclear Power Plant accident to the 129I deposition flux at Rokkasho in 2011 was small on the basis of the 129I/131I activity ratio.

Vertical distribution of radiation dose rates in the water of a brackish lake in Aomori Prefecture, Japan.

Seasonal radiation dose rates were measured with glass dosemeters housed in watertight cases at various depths in the water of Lake Obuchi, a brackish lake in Aomori Prefecture, Japan, during fiscal years 2011-2013 to assess the background external radiation dose to aquatic biota in the lake. The mean radiation dose in the surface water of the lake was found to be 27 nGy h(-1), which is almost the same as the absorption dose rate due to cosmic ray reported in the literature. Radiation dose rates decreased exponentially with water depth down to a depth of 1 m above the bottom sediment. In the water near the sediment, the dose rate increased with depth owing to the emission of γ-rays from natural radionuclides in the sediment.

Effects of radiocesium inventory on (137)Cs concentrations in river waters of Fukushima, Japan, under base-flow conditions.

To investigate the behavior of nuclear accident-derived (137)Cs in river water under base-flow conditions, concentrations of dissolved and particulate (137)Cs were measured at 16 sampling points in seven rivers of Fukushima Prefecture, Japan, in 2012 and 2013. The concentration of dissolved (137)Cs was significantly correlated with the mean (137)Cs inventory in the catchment area above each sampling point in both sampling years. These results suggest that the concentration of dissolved (137)Cs under base-flow conditions is primarily determined by the (137)Cs inventory of the catchment area above the sampling point. However, the concentration of particulate (137)Cs did not show a clear relationship with either the mean (137)Cs inventory or the dissolved (137)Cs concentration, thus indicating that particulate and dissolved forms do not effectively interact in rivers. To evaluate the contribution of the (137)Cs inventory within catchment areas, we analyzed relations between the (137)Cs concentration and the mean (137)Cs inventory over the area within certain flow path lengths that were traced along the river and slope above the sampling point. Coefficients of determination for dissolved (137)Cs concentrations were highest for the longest flow path, i.e., the whole catchment area, and lower for shorter flow paths. Coefficients of determination for particulate (137)Cs concentrations were only moderately high for the shortest flow path in 2012, whereas the values were quite low for all flow paths in 2013. These results suggest that dissolved (137)Cs can originate from a larger area of the catchment even under base-flow conditions; however, particulate (137)Cs did not show such behavior. The results also show that under base-flow conditions, dissolved and particulate (137)Cs behave independently during their transport from river catchments to the ocean.

Daily radionuclide ingestion and internal radiation doses in Aomori prefecture, Japan.

To assess internal annual dose in the general public in Aomori Prefecture, Japan, 80 duplicate cooked diet samples, equivalent to the food consumed over a 400-d period by one person, were collected from 100 volunteers in Aomori City and the village of Rokkasho during 2006­2010 and were analyzed for 11 radionuclides. To obtain average rates of ingestion of radionuclides, the volunteers were selected from among office, fisheries, agricultural, and livestock farm workers. Committed effective doses from ingestion of the diet over a 1-y period were calculated from the analytical results and from International Commission on Radiological Protection dose coefficients; for 40K, an internal effective dose rate from the literature was used. Fisheries workers had significantly higher combined internal annual dose than the other workers, possibly because of high rates of ingestion of marine products known to have high 210Po concentrations. The average internal dose rate, weighted by the numbers of households in each worker group in Aomori Prefecture, was estimated at 0.47 mSv y-1. Polonium-210 contributed 49% of this value. The sum of committed effective dose rates for 210Po, 210Pb, 228Ra, and 14C and the effective dose rate of 40K accounted for approximately 99% of the average internal dose rate.

Fluvial discharges of radiocaesium from watersheds contaminated by the Fukushima Dai-ichi Nuclear Power Plant accident, Japan.

A large amount of radiocaesium, (134)Cs and (137)Cs, was released to the atmosphere and Pacific Ocean from the Tokyo Electric Power Company's Fukushima Dai-ichi Nuclear Power Plant (FDNPP) that was damaged by the tsunami caused by the Tohoku earthquake on 11 March 2011. Radiocaesium deposited on the ground is now the most important consideration in assessing the risk to people in the vicinity of the FDNPP and remediating the contaminated area. Transfer of radiocaesium from the ground through rivers is an important factor in the downstream contamination of irrigation waters, paddy fields, lakes, and the sea. We estimated the transport of radiocaesium through two small rivers, the Hiso River and Wariki River, that traverse mountainous areas in Fukushima Prefecture. Areal depositions of radiocaesium in their watersheds (catchments) were high (1-3 MBq m(-2)). Water samples were collected from the rivers twice during each of two baseflow and two flood stages in 2011 and analysed for radiocaesium in particulate and dissolved forms. The radiocaesium concentrations depended strongly on the rates of water discharge. Maximum activities of radiocaesium in the samples from the Hiso River and Wariki River when there was precipitation or flooding (July and September) were 25 ± 0.31 and 35 ± 0.25 Bq L(-1), respectively. Particulate radiocaesium during periods of flooding contributed over 90% of the total radiocaesium activity in the samples. The discharge of radiocaesium from the catchments during 2011 was estimated to be 0.5% and 0.3% of the total amount of radiocaesium deposited on the catchments of the Hiso River and Wariki River, respectively. It is considered that the most of the radiocaesium deposited in the catchment remains on the soil surface.

Concentrations of 137Cs, 90Sr, 108m Ag, 239+240 Pu and atom ratio of 240Pu/239Pu in tanner crabs, Chionoecetes japonicus and Chionoecetes opilio collected around Japan.

The anthropogenic radionuclides, (137)Cs, (90)Sr, (108m)Ag, (239+240)Pu, were measured in two Chionoecetes species, red queen crab (Chionoecetes japonicus) and snow crab (Chionoecetes opilio) collected around Japan during 1996-2007. There was no increase in the concentrations of these radionuclides and no large variation of the atom ratio of (240)Pu/(239)Pu during this research period. These results indicated that the source of the radionuclides was not the radioactive wastes dumped by the former USSR and Russia and originated from past nuclear weapon tests. The higher atom ratio in the crab species than that from global fallout would be contributed by the Pacific Proving Grounds close-in fallout. The variability of the concentration of radionuclides in the crab species would result from the variability of the composition and quantity in the diet. However, the decrease in the concentration of radionuclides with sampling depth would depend on the concentration in the seawater and diet.

Uranium isotopes in well water samples as drinking sources in some settlements around the Semipalatinsk Nuclear Test Site, Kazakhstan.

Radiochemical results of U isotopes (234U, 235U and 238U) and their activity ratios are reported for well waters as local sources of drinking waters collected from the ten settlements around the Semipalatinsk Nuclear Test Site (SNTS), Kazakhstan. The results show that 238U varies widely from 3.6 to 356 mBq/L (0.3-28.7 µg/L), with a factor of about 100. The 238U concentrations in some water samples from Dolon, Tailan, Sarzhal and Karaul settlements are comparable to or higher than the World Health Organization's restrictive proposed guideline of 15 µg (U)/L. The 234U/238U activity ratios in the measured water samples are higher than 1, and vary between 1.1 and 7.9, being mostly from 1.5 to 3. The measured 235U/238U activity ratios are around 0.046, indicating that U in these well waters is of natural origin. It is probable that the elevated concentration of 238U found in some settlements around the SNTS is not due to the close-in fallout from nuclear explosions at the SNTS, but rather to the intensive weathering of rocks including U there. The calculated effective doses to adults resulting from consumption of the investigated waters are in the range 1.0-18.7 µSv/y. Those doses are lower than WHO and IAEA reference value (100 µSv/y) for drinking water.

Inventories of 239+240Pu, 137Cs, and excess 210Pb in sediments from freshwater and brackish lakes in Rokkasho, Japan, adjacent to a spent nuclear fuel reprocessing plant.

We investigated the vertical profiles of (239+240)Pu, (137)Cs, and excess (210)Pb ((210)Pb(ex)) in sediment core samples obtained from two freshwater lakes and two brackish lakes situated near the first commercial spent nuclear fuel reprocessing plant in Rokkasho, Japan, before the final test of the plant using actual spent nuclear fuel. The inventory of (239+240)Pu in those lakes was larger than that in soil in Rokkasho, which indicated the inflow of (239+240)Pu from the catchment area in addition to direct deposition on the lake surfaces. The (137)Cs inventory in sediments of the brackish lakes was lower than that in the soil, which showed that part of the (137)Cs was removed from the sediments by the brackish water or that it was not deposited into the sediments, because of the high solubility of Cs in brackish water. The (137)Cs inventory in sediments of the freshwater lakes was higher than that of the brackish lakes, and comparable with that in soil except for one core sample out of four. The (239+240)Pu/(137)Cs ratio in freshwater lake sediments was higher than that in soil, and that indicated that part of the (137)Cs was lost from the sediments. The low inventory of (137)Cs may be attributable to competition for absorption sites in sediments with ammonium ions formed in the reducing environment which occurs from summer to fall in the sediments. Those data will be used as background data on the artificial radionuclides in the lakes to assess the effect of released radionuclides on their concentrations.

Deposition of 137Cs in Rokkasho, Japan and its relation to Asian dust.

Biweekly atmospheric depositions of (137)Cs were measured in Rokkasho, Aomori, Japan from March 2000 to March 2006 to study recent (137)Cs deposition. Although the deposition level was generally lower than the detectable limit, deposition samples collected in spring occasionally had measurable levels of (137)Cs. The annual (137)Cs deposition from 2001 to 2005 was 0.04-0.69 Bq m(-2) with a mean value of 0.27 Bq m(-2). Depositions of insoluble Al, Fe and Ti were strongly correlated with the (137)Cs deposition, suggesting that suspension of soil particles was the main source of the recent (137)Cs deposition. Asian dust events were coincident with some of the significant (137)Cs depositions in spring. It was found that the ratios of (137)Cs/Al and Fe/Al could be used as indices for discriminating Asian dust from suspension of the local surface soil. Backward trajectory analysis suggested southern Mongolian and northeastern China regions as sources of the significant (137)Cs depositions.

Rapid method for the analysis of plutonium isotopes in a soil sample within 60 min.

A rapid method for the determination of Pu isotopes in a soil sample within 60 min of starting sample pretreatment was developed. The large reduction in the analysis time was attained by the rapid and perfect digestion of the sample using an alkaline fusion method with an induction heating machine. Pu concentrations were then determined by flow injection/ICP-MS using a solid extraction resin after preconcentration by batch extraction with a chelate resin. The limits of detection for 239Pu and 240Pu were 9.2 fg and 4.3 fg, corresponding to 0.03 and 0.05 Bq kg(-1), respectively, under our analytical conditions, which satisfy the lower detection limits (0.5 Bq kg(-1) of 239Pu, and 2 Bq kg(-1) of 240Pu) required for rapid analysis techniques by the Ministry of Education, Culture, Sports, Science and Technology, Japan. This method provides a powerful and practical technique for emergency monitoring in and around nuclear facilities that handle large amounts of plutonium.

Development of rapid plutonium analysis for environmental samples by isotope dilution/inductively coupled plasma mass spectrometry with on-line column.

This paper describes our development of a rapid on-line column/ID-ICP-MS technique for the analysis of plutonium (Pu) in environmental samples using an UTEVA extraction chromatograph resin (UTEVA resin) column. It took only 40 min to separate and measure Pu in the sample solution, including the time for conditioning the resin column for the next analysis. In our method, Pu in a 3 M nitric acid solution was fed to the UTEVA resin, and then eluted from the resin by reducing Pu to Pu(III) with 3 M nitric acid mixed with 0.01 M ascorbic acid after washing the resin. The outflow from the resin column was directly introduced to an ICP-MS system. The low concentration of ascorbic acid and the small volume of the eluting solution (0.6 mL) made successive stable analysis possible without any skimmer cone clogging. The chemical recovery of Pu during column operation was 70%, and typical lower detection limits for 239Pu, 240Pu and 242Pu were 9.2, 4.3 and 7.5 fg (21, 36 and 1.1 microBq), respectively. We analyzed five international standard materials for Pu, and obtained good results.