Natural radionuclides and radiological risk assessment in the stream and river sediments of a high background natural radiation area Kanyakumari, India.

The Kanyakumari coast is known to be a high background natural radiation area due to the placer deposits of heavy minerals such as ilmenite, monazite, and rutile. The Kanyakumari river sediments that could be the source of the elevated amounts of natural radionuclides in the coastal sands have been studied in this paper. The activity concentrations of primordial radionuclides 226Ra, 232Th, and 40K were determined using high-purity germanium (HPGe) gamma-ray spectrometry. The mean activity concentrations of 226Ra, 232Th, and 40K were found to be 75 Bq kg-1, 565 Bq kg-1, and 360 Bq kg-1, respectively. The mean absorbed dose rate was 395 nGy h-1. Radiological hazard parameters were studied and compared with the world average values. The contribution of 232Th to the total dose rate was found to be higher than that of the two other radionuclides. The high mean ratio of 232Th/226Ra suggested an enrichment of 232Th and the occurrence of 226Ra leaching due to an oxidizing environment. Principal component analysis (PCA) was carried out for the radionuclides in order to discriminate the source of the sediments. This study provides new insights into the distribution of natural radionuclides in sediments of rivers and streams.

ICP-MS Measurement of Trace and Rare Earth Elements in Beach Placer-Deposit Soils of Odisha, East Coast of India, to Estimate Natural Enhancement of Elements in the Environment.

Inductively coupled plasma mass spectrometry (ICP-MS) has been used to measure the concentration of trace and rare earth elements (REEs) in soils. Geochemical certified reference materials such as JLk-1, JB-1, and JB-3 were used for the validation of the analytical method. The measured values were in good agreement with the certified values for all the elements and were within 10% analytical error. Beach placer deposits of soils mainly from Odisha, on the east coast of India, have been selected to study selected trace and rare earth elements (REEs), to estimate enrichment factor (EF) and geoaccumulation index (Igeo) in the natural environment. Enrichment factor (EF) and geoaccumulation index (Igeo) results showed that Cr, Mn, Fe, Co, Zn, Y, Zr, Cd and U were significantly enriched, and Th was extremely enriched. The total content of REEs (Æ©REEs) ranged from 101.3 to 12,911.3 µg g-1, with an average 2431.1 µg g-1 which was higher than the average crustal value of ΣREEs. A high concentration of Th and light REEs were strongly correlated, which confirmed soil enrichment with monazite minerals. High ratios of light REEs (LREEs)/heavy REEs (HREEs) with a strong negative Eu anomaly revealed a felsic origin. The comparison of the chondrite normalized REE patterns of soil with hinterland rocks such as granite, charnockite, khondalite and migmatite suggested that enhancement of trace and REEs are of natural origin.

Precise Measurement of Tellurium Isotope Ratios in Terrestrial Standards Using a Multiple Collector Inductively Coupled Plasma Mass Spectrometry.

Precise tellurium (Te) isotope ratio measurement using mass spectrometry is a challenging task for many decades. In this paper, Te isotope ratio measurements using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) in terrestrial Te standards have been reported. Newly developed Faraday cup with 1012 Ω resistor is used to measure low abundance 120Te, whereas the 1011 Ω resistor is used to measure other Te isotopes. The relative standard deviation obtained for Te isotope ratio measurement by Faraday cups of 120Te/128Te [0.002907(05)], 122Te/128Te [0.079646(10)], 123Te/128Te [0.027850(07)], 125Te/128Te [0.221988(09)], 126Te/128Te [0.592202(20)], and 130Te/128Te [1.076277(30)] were 0.140%, 0.014%, 0.026%, 0.005%, 0.004%, and 0.004%, respectively. The measured isotope ratio results are compared with previous results obtained by thermal ionization mass spectrometry (TIMS), negative thermal ionization mass spectrometry (N-TIMS), and MC-ICP-MS, showing an improvement in the precision about one order of magnitude for 120Te/128Te ratio. The present study shows better precision for Te isotope ratios compared to earlier studies.

A Microwave Digestion Technique for the Analysis of Rare Earth Elements, Thorium and Uranium in Geochemical Certified Reference Materials and Soils by Inductively Coupled Plasma Mass Spectrometry.

Two different digestion methods-microwave digestion (Mw) and Savillex digestion (Sx)-were used to evaluate the best quality control for analysis of the rare earth elements, Th and U in the geochemical certified reference material JSd-2, supplied by the Geological Survey of Japan (GSJ). The analysis of trace elements was carried out using inductively coupled plasma mass spectrometry (ICP-MS). The digestion recovery was > 90% for almost all elements by both methods. Mw-4 (four repeats of the microwave digestion) was found to be more effective and faster than Sx. In order to evaluate the efficiency of Mw-4, three other GSJ certified reference materials, JLk-1, JB-1 and JB-3, as well as five different soil samples from Belarus, Japan, Serbia and Ukraine were also analyzed. The Mw-4 method was seen to be promising for complete digestion and recovery of most of the elements. The U/Th ratio showed some heterogeneity for Ukraine and Serbia soils affected by Chernobyl nuclear power plant accident and depleted uranium contamination, respectively. This method can be successfully applied to any type of soils for elemental analyses.

Chemical Separation of Uranium and Precise Measurement of 234U/238U and 235U/238U Ratios in Soil Samples Using Multi Collector Inductively Coupled Plasma Mass Spectrometry.

A new chemical separation has been developed to isolate uranium (U) using two UTEVA columns to minimize iron and thorium interferences from high background area soil samples containing minerals like monazites and ilmenite. The separation method was successfully verified in some certified reference materials (CRMs), for example, JSd-2, JLk-1, JB-1 and JB-3. The same method was applied for purification of U in Fukushima soil samples affected by the Fukushima dai-ichi nuclear power station (FDNPS) accident. Precise and accurate measurement of 234U/238U and 235U/238U isotope ratios in chemically separated U were carried out using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS). In this mass spectrometric method, an array of two Faraday cups (1011 Ω, 1012 Ω resistor) and a Daly detector were simultaneously employed. The precision of U isotope ratios in an in-house standard was evaluated by replicate measurement. Relative standard deviation (RSD) of 234U/238U and 235U/238U were found to be 0.094% (2σ) and 0.590% (2σ), respectively. This method has been validated using a standard reference material SRM 4350B, sediment sample. The replicate measurements of 234U/238U in SRM shows 0.7% (RSD). This developed method is suitable for separation of U and its isotope ratio measurement in environmental samples.

Method for 90Sr Analysis in Environmental Samples Using Thermal Ionization Mass Spectrometry with Daly Ion-Counting System.

In this work, a new 90Sr analysis method was developed using the Isotopx Ltd., Phoenix X62 thermal ionization mass spectrometer (TIMS). Excellent ion beam sensitivity was demonstrated with the detection of 1 mBq (0.2 fg) 90Sr on a Daly ion-counting system. The abundance sensitivity for the 90Sr/88Sr ratio was 2.1 × 10-10, and this could ensure measurement of 100 Bq·kg-1 (19 fg·g-1) 90Sr in an environmental sample with 100 µg·g-1 stable strontium concentration. For analytical method validation, 90Sr was determined in two certified reference materials, for example, wild berry (IRMM-426) and freshwater lake sediment (NIST-4354), for the first time in the history of TIMS. This mass spectrometry method is faster than conventional radiometric techniques; however, interference from 90Zr and peak tailing on the higher mass side from 88Sr must be considered for a reliable 90Sr determination.

Radiation dose due to radon and thoron progeny inhalation in high-level natural radiation areas of Kerala, India.

In order to evaluate internal exposure to radon and thoron, concentrations for radon, thoron, and thoron progeny were measured for 259 dwellings located in high background radiation areas (HBRAs, outdoor external dose: 3-5 mGy y-1) and low background radiation areas (control areas, outdoor external dose: 1 mGy y-1) in Karunagappally Taluk, Kerala, India. The measurements were conducted using passive-type radon-thoron detectors and thoron progeny detectors over two six-month measurement periods from June 2010 to June 2011. The results showed no major differences in radon and thoron progeny concentrations between the HBRAs and the control areas. The geometric mean of the annual effective dose due to radon and thoron was calculated as 0.10 and 0.44 mSv, respectively. The doses were small, but not negligible compared with the external dose in the two areas.

Simultaneous sampling of indoor and outdoor airborne radioactivity after the Fukushima Daiichi nuclear power plant accident.

Several studies have estimated inhalation doses for the public because of the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident. Most of them were based on measurement of radioactivity in outdoor air and included the assumption that people stayed outdoors all day. Although this assumption gives a conservative estimate, it is not realistic. The "air decontamination factor" (ratio of indoor to outdoor air radionuclide concentrations) was estimated from simultaneous sampling of radioactivity in both inside and outside air of one building. The building was a workplace and located at the National Institute of Radiological Sciences (NIRS) in Chiba Prefecture, Japan. Aerosol-associated radioactive materials in air were collected onto filters, and the filters were analyzed by γ spectrometry at NIRS. The filter sampling was started on March 15, 2011 and was continued for more than 1 year. Several radionuclides, such as (131)I, (134)Cs, and (137)Cs were found by measuring the filters with a germanium detector. The air decontamination factor was around 0.64 for particulate (131)I and 0.58 for (137)Cs. These values could give implications for the ratio of indoor to outdoor radionuclide concentrations after the FDNPP accident for a similar type of building.

Distribution of strontium-90 in soils affected by Fukushima dai-ichi nuclear power station accident in the context of cesium-137 contamination.

90Sr and 137Cs activity concentrations were determined by radiometric methods in 76 soil samples (soil, litter, rain gutter deposit, and roadside sediment samples) affected by the Fukushima Dai-ichi Nuclear Power Station (FDNPS) accident and collected from the Fukushima exclusion zone. The 90Sr and 137Cs activity concentrations were in the range of 3 to 1050 Bq kg-1 (median 82 Bq·kg-1) and 0.7 to 6770 kBq·kg-1 (median 890 kBq·kg-1), respectively (decay correction date: March 15, 2011). A strong positive correlation was found between 90Sr and 137Cs activity concentration and higher mobility of 90Sr was confirmed in Japanese soil samples. The activity ratio of 90Sr/137Cs in 85% of all samples was in the range of 5.0 × 10-5 to 5.0 × 10-4 with a median of 1.2 × 10-4. From the activity ratio values it was concluded that the 90Sr released to the atmosphere was only around 0.0003-0.02 PBq which is negligible compared to the Chernobyl accident (∼10 PBq) or other nuclear accident contaminations. From the standpoints of radioecology and radiation safety, 137Cs remains the primary pollutant of the FDNPS accident.

Improvement of spectral analysis using a NaI(Tl) scintillation spectrometer to evaluate ambient gamma dose rates from primordial radionuclides.

In-situ measurements by gamma-ray spectrometry using a NaI(Tl) scintillation spectrometer are performed to discriminate primordial and artificial radionuclides contributing to ambient gamma dose rates in the living environment to quantify prolonged influence of nuclear accidents. However, low energy resolution of the spectrometer causes poor discrimination in the measurements at high-dose-rate points, which leads to overestimation of ambient gamma dose rate from the primordial radionuclides. The present study clarified that photon fluxes originating from 40K and 214Bi were affected by the presence of 134Cs, whereas those from 208Tl were independent of it. In addition, the absorbed dose rates in air were strongly correlated with the 208Tl photon fluxes. These findings indicate that 208Tl photon fluxes can be used to evaluate absorbed dose rates in air from the primordial radionuclides. When estimated from the 208Tl photon fluxes only, the absorbed dose rates in air in Namie Town and Okuma Town, locations affected by the Fukushima Dai-ichi Nuclear Power Plant accident, were 19-71 and 20-47 nGy h-1, respectively.

ACTIVITY RATIO OF URANIUM IN FUKUSHIMA SOIL SAMPLES USING MULTI-COLLECTOR INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY.

The Fukushima soils have been collected from Namie and Futaba areas for the radiocaesium and uranium isotope ratio studies. The 137Cs activity concentration of soil samples ranged from 6 ± 1 to 756 ± 14 kBq/kg. The uranium isotope ratios are measured using multi collector inductively coupled plasma mass spectrometry. The activity ratio (234U/238U) of the Fukushima soils is calculated from the measured 234U/238U isotope ratio. Activity ratio varied from 0.98 to 1.02 which indicates that 234U and 238U are in secular equilibrium. The 235U/238U atomic ratio of the Fukushima soils did not show any heterogeneity compared with the natural terrestrial ratio even with high level of 137Cs in soils.

Measurements and future projections of Gd-based contrast agents for MRI exams in wastewater treatment plants in the Tokyo metropolitan area.

Large amounts of Gd-based contrast agents are used in magnetic resonance imaging (MRI) that are then excreted in urine. These agents are subsequently discharged into the environment because they are difficult to remove by usual sewage treatment techniques. In this study, changes of the Gd anomaly during wastewater treatment processes were determined by analyzing wastewater samples and the possibility for future prediction of the changes was evaluated based on the relationship between the Gd anomaly and the number of MRI devices in use. After the wastewater treatment processes, the values of final effluent were increased 1.8 times compared to those of influent, and the Gd anomaly of effluent had a positive correlation to the number of MRI devices. The finding suggested that the changes of environmental impact were predictable based on the number of MRI devices.

Effect of operating variables on the separation of radiostrontium from aqueous matrices with ion-selective solid-phase extraction systems.

Radiostrontium (r-Sr: 90Sr) is one of the primary fission products in nuclear power plants and generates liquid radioactive waste when intermixed to the aqueous matrix. Therefore, separation or preconcentration of r-Sr from the aqueous matrices is necessary for environmental monitoring or nuclear forensics. The solid-phase extraction (SPE) approach is prevalently used for r-Sr isolation and to design matrix-specific methods, while generalized SPE-assisted operating protocols are not proposed by far. In the current work, four different SPEs, namely AnaLig Sr-01, Eichrom Sr, Triskem TK100, and Eichrom DGA, were evaluated for selective separation of Sr from aqueous matrices. Operating variables, e.g., solution acidity, washing solvent, eluent-type or volume, loading or elution flow-rate, were varied to optimize the SPEs performance. The objective was to ascertain the operating variables for maximum Sr-separation yield from aqueous environmental samples with the SPEs mentioned above. In addition, the Sr-separation efficiency of SPEs was evaluated by calculating the separation factor (SFSr/M) between Sr and interfering elements to r-Sr (M = Ca, Mg, Ba, or Y), and the Sr-retention capacity of the SPEs was determined. Finally, the optimized operating variables for the evaluated SPEs were used to construct protocols for r-Sr separation from aqueous matrices. Real 90Sr contaminated aqueous samples from the Chernobyl nuclear power plant cooling pond were treated by those protocols, and the results are validated comparing with the IAEA-recommended classical protocol. All the SPEs were able to isolate Sr at varying extents from matrices at the optimum conditions, even at much higher contents of interfering elements. Eichrom Sr or AnaLig Sr-01 showed better Sr-retention capability among the SPEs, while Triskem TK100 showed superiority over other SPEs regarding Sr-selectivity.

Geochemical behavior of uranium and thorium in sand and sandy soil samples from a natural high background radiation area of the Odisha coast, India.

Owing to their natural radioactivity, uranium (U) and thorium (Th) play significant roles in environmental sciences for monitoring radiation dose and in geological sciences for understanding sedimentary processes. The Odisha coastal area, in eastern India, is a well-known high background radiation area that is rich in monazites and rutile. This area was selected to study geochemical characteristics of U and Th in sand and sandy soil samples. The concentrations of U and Th were measured using inductively coupled plasma mass spectrometry (ICP-MS). The median, geometric mean, and standard deviation for U were determined to be 6, 4.5, and 2.5 µg/g and for Th were 186, 123.3, and 3.1 µg/g, respectively. Major element concentrations were evaluated using X-ray fluorescence spectroscopy to get the mineralogical composition and state of chemical weathering. The ratios of Th/U and Th/K varied from 4 to 37 and from 13 to 1058, respectively. These results clearly indicate that the samples from the coastal region were formed in an oxidizing and intense chemical weathering terrestrial environment with an enrichment of radiogenic heavy minerals (monazites and zircon) and clay mineral association. Since the majority of the samples have undergone moderate to intense weathering in the oxidizing environment, U is leached from the soil and sand matrix. Eventually, Th resides in the matrix and becomes a major source for radiation exposure in the environment. The high ratios of Th/U, along with the strong positive correlation between Th and P2O5, evidence the enrichment of the Th-bearing radioactive mineral, monazite, in these samples.

Impact on gadolinium anomaly in river waters in Tokyo related to the increased number of MRI devices in use.

The Gd-based contrast agents utilized in magnetic resonance imaging are difficult to remove by usual sewage treatment technology, and they enter rivers in the discharges from waste water treatment plants. Gd anomaly in rivers has been considered depends on used amount of Gd-based contrast agents. In this study, variation of Gd anomaly in rivers of Tokyo was determined by comparisons to previously reported values. The range of anthropogenic Gd was 0.1-138.8 ppt with an average value of 35.5 ppt (n = 40); in particular, the anthropogenic Gd was significantly changed depending on the location of the waste water treatment plants, and the measurement revealed significant increases in the Gd anomaly in the range of 5.0-6.6 times compared to data obtained 22 years ago. This study highlights the necessary of continuous research in setting new public policies for medical practices.

Determination of (129)I and (127)I concentration in soil samples from the Chernobyl 30-km zone by AMS and ICP-MS.

A large amount of radioiodine isotopes (mainly (131)I, t(1/2) = 8 days) was released from the accident at Chernobyl Nuclear Power Plant (CNPP) in April-May 1986. An increase in childhood-thyroid cancer in the contaminated areas in Belarus, Russia and the Ukraine was demonstrated to be caused by radioiodine released at the time of the accident. However, there is a lack of quantitative data on the (131)I levels in the local environment (e.g. air, plant, soil). At this point, a long-lived iodine isotope, (129)I (t(1/2) = 15.7 million years), also released with a certain ratio to (131)I from CNPP, could be used for estimating the (131)I levels in the environment. In this paper we present analytical results of the (129)I concentrations and (129)I/(127)I atom ratios in soil samples collected from the CNPP exclusion zone (30-km zone), with the aim of assessing current contamination levels and distribution patterns. For the analysis of the iodine fraction in the investigated soil samples, the pyrohydrolysis method was utilized for separation of (127)I and (129)I nuclides, and subsequently their concentration was determined using inductively coupled plasma mass spectrometry (ICP-MS) and accelerator mass spectrometry (AMS), respectively. The concentration of (129)I and the (129)I/(127)I atom ratio in the surface soil samples in the 30 km-zone of CNPP ranged from 4.6 to 170 mBq/kg, and from 1.4 x 10(-6) to 13 x 10(-6), respectively. These values are significantly higher than those from global (129)I fallout, indicating that most of the measured (129)I was due to the deposition of the accident. Stable iodine concentrations in this area were found to be very low (below 1 ppm) for most of the samples, suggesting the environmental iodine levels in this area to be potentially low. The (129)I/(137)Cs activity ratio in surface and sub-surface soils was not so constant, i.e., in the range (7.3-20.2) x 10(-7). This might be due to the different behavior of deposition and/or migration of these nuclides in soil. These results suggest the obtained data of (129)I to be useful for the reconstruction of the (131)I deposition in the contaminated areas.

Ultra low-dose radiation: stress responses and impacts using rice as a grass model.

We report molecular changes in leaves of rice plants (Oryza sativa L. - reference crop plant and grass model) exposed to ultra low-dose ionizing radiation, first using contaminated soil from the exclusion zone around Chernobyl reactor site. Results revealed induction of stress-related marker genes (Northern blot) and secondary metabolites (LC-MS/MS) in irradiated leaf segments over appropriate control. Second, employing the same in vitro model system, we replicated results of the first experiment using in-house fabricated sources of ultra low-dose gamma (gamma) rays and selected marker genes by RT-PCR. Results suggest the usefulness of the rice model in studying ultra low-dose radiation response/s.

Accurate and precise determination of 90Sr at femtogram level in IAEA proficiency test using Thermal Ionization Mass Spectrometry.

A novel method for the determination of ultra-trace level 90Sr has been recently developed applying thermal ionization mass spectrometry (TIMS). The method includes the chemical separation of Zr (isobaric interference of 90Zr) from the samples followed by determination of 90Sr/88Sr abundance  sensitivity (2.1 × 10-10). The analytical performance of this method was assessed in the IAEA-TEL 2017-3 worldwide open proficiency test. For 90Sr determination, tap water and milk powder samples were distributed amongst the participant laboratories with reference values of 11.2 ± 0.3 Bq kg-1 (2.2 ± 0.1 fg g-1) and 99.9 ± 5.0 Bq kg-1 (19.5 ± 1.0 fg g-1), respectively. The stable Sr concentrations were 39.4 ± 0.9 ng g-1 and 2.5 ± 0.1 µg g-1 while the 90Sr/88Sr isotope ratios were 6.47 ± 0.17 × 10-8 and 9.04 ± 0.45 × 10-9 in the tap water and milk powder samples, respectively. For TIMS measurement, 50 mL water and 1 g milk powder samples were taken for analysis. This TIMS method demonstrated an impressive accuracy (relative bias of 4.2% and -2.1%, respectively) and precision (relative combined uncertainty of 4.1% and 7.6%, respectively) when compared with radiometric techniques. For the first time in the history of inorganic mass-spectrometry, 90Sr analysis using a TIMS instrument is confirmed by an independent proficiency test.

Strontium-90 activity concentration in soil samples from the exclusion zone of the Fukushima daiichi nuclear power plant.

The radioactive fission product (90)Sr has a long biological half-life (˜18 y) in the human body. Due to its chemical similarity to calcium it accumulates in bones and irradiates the bone marrow, causing its high radio-toxicity. Assessing (90)Sr is therefore extremely important in case of a nuclear disaster. In this work 16 soil samples were collected from the exclusion zone (<30 km) of the earthquake-damaged Fukushima Daiichi nuclear power plant, to measure (90)Sr activity concentration using liquid scintillation counting. (137)Cs activity concentration was also measured with gamma-spectroscopy in order to investigate correlation with (90)Sr. The (90)Sr activity concentrations ranged from 3.0 ± 0.3 to 23.3 ± 1.5 Bq kg(-1) while the (137)Cs from 0.7 ± 0.1 to 110.8 ± 0.3 kBq kg(-1). The fact that radioactive contamination originated from the Fukushima nuclear accident was obvious due to the presence of (134)Cs. However, (90)Sr contamination was not confirmed in all samples although detectable amounts of (90)Sr can be expected in Japanese soils, as a background, stemming from global fallout due to the atmospheric nuclear weapon tests. Correlation analysis between (90)Sr and (137)Cs activity concentrations provides a potentially powerful tool to discriminate background (90)Sr level from its Fukushima contribution.

Long-term measurements of residential radon, thoron, and thoron progeny concentrations around the Chhatrapur placer deposit, a high background radiation area in Odisha, India.

The Chhatrapur placer deposit is found in a high background radiation area which has been recently identified on the southeastern coast of India. Previously, some geochemical studies of this area were carried out to assess external dose from radionuclides-bearing heavy mineral sands. In this study, radon, thoron and thoron progeny concentrations were measured in about 100 dwellings during three seasons (autumn-winter, summer, and rainy) in a 10- to 12-month period and annual doses due to inhalation of them were evaluated. The measurements were made by passive-type radon-thoron discriminative detectors and thoron progeny detectors in which solid state nuclear track detectors were deployed. The results show that radon and thoron concentrations differ by one order of magnitude depending on exposure periods, while thoron progeny concentration is nearly constant throughout the year. Since thorium-rich sand is distributed in the studied area, exposure to thoron is equal to, or exceeds, exposure to radon and is not negligible for dose evaluation. Based on the measurements, doses due to inhalation of radon and thoron are evaluated as 0.1-1.6 mSv y-1 and 0.2-3.8 mSv y-1, respectively. The total dose is 0.8-4.6 mSv y-1, which is the same order of magnitude as the worldwide value.