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For the quality control in determining transuranic nuclides in fallout samples, this work first reported the 237 Np activity concentration in a reference fallout material and further calculated the activity ratios of 237 Np/ 239+240 Pu and 237 Np/ 241 Am, and the atom ratio of 237 Np/ 239 Pu in it. The reference fallout material prepared by the Meteorological Research Institute was collected at 14 stations throughout Japan in 1963-1979. The 237 Np and Pu isotopes ( 239 Pu and 240 Pu) were separated and purified using AG MP-1M anion-exchange resin, quantified using 242 Pu as an isotope dilution tracer, and determined by the SF-ICP-MS. The analytical method was validated by the analysis of 4 sediment reference materials. The activity concentrations of 237 Np, 239 Pu and 240 Pu were (25.9 ± 0.6) × 10 -3 , 4.10 ± 0.01 and 2.89 ± 0.04 Bq/kg, respectively, in the investigated reference fallout material. The activity ratio of 237 Np/ 239+240 Pu (3.7 ± 0.1) × 10 -3 was consistent with the global fallout evaluation value. The 237 Np/ 239 Pu atom ratio of 0.561 ± 0.014 was higher than the average global fallout value of 0.41 ± 0.010, indicating the necessity of establishing regional characteristic global fallout value of 237 Np/ 239 Pu atom ratio for assessment of radioactive contamination. Comparison of the 237 Np/ 239+240 Pu activity ratios between in the reference fallout material and in soils over several decades indicated that 237 Np has stronger migration capability than Pu isotopes in soils because 237 Np was depleted compared to reference fallout material., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Neptunium-237 and 239 Pu are important radionuclides in the safety assessment related to geological disposal of radioactive waste because of the possibility of long-term exposure to humans. Mobilities of these radionuclides in the environment are of particular importance for their radiation dose evaluation; therefore, in this study, we have made the assessment of the soil-soil solution distribution coefficient (K d , L/kg) using global fallout 237 Np and 239 Pu in Japanese upland soils. The K d values were determined by extracting these radionuclides from 24 soil samples using a laboratory batch method. The desorption K d values of 237 Np ranged from 3.3 × 10 2 to 1.0 × 10 4  L/kg, and their geometric mean (GM) and arithmetic mean (AM) were 1.7 × 10 3  L/kg and 2.6 × 10 3  L/kg, respectively. The desorption K d values of 239 Pu were found to vary from 9.4 × 10 3 to 7.1 × 10 4  L/kg, and their GM and AM were 3.3 × 10 4  L/kg and 4.0 × 10 4  L/kg, respectively. In Japanese upland soils, the K d value of 239 Pu was one order of magnitude higher than that of 237 Np., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

A high sensitivity analytical method for 237 Np analysis was developed and applied to groundwater samples from the Nevada National Security Site (NNSS) using short-lived 239 Np as a yield tracer and HR magnetic sector ICP-MS. The 237 Np concentrations in the vicinity of the Almendro, Cambric, Dalhart, Cheshire, and Chancellor underground nuclear test locations range from <4 × 10 −4 to 2.6 mBq/L (6 × 10 −17 –4.2 × 10 −13 mol/L). All measured 237 Np concentrations are well below the drinking water maximum contaminant level for alpha emitters identified by the U.S. EPA (560 mBq/L). Nevertheless, 237 Np remains an important indicator for radionuclide transport rates at the NNSS. Retardation factor ratios were used to compare the mobility of 237 Np to that of other radionuclides. The results suggest that 237 Np is less mobile than tritium and other non-sorbing radionuclides ( 14 C, 36 Cl, 99 Tc and 129 I) as expected. Surprisingly, 237 Np and plutonium ( 239,240 Pu) retardation factors are very similar. It is possible that Np(IV) exists under mildly reducing groundwater conditions and exhibits a retardation behavior that is comparable to Pu(IV). Independent of the underlying process, 237 Np is migrating downgradient from NNSS underground nuclear tests at very low but measureable concentrations. [ABSTRACT FROM AUTHOR]

Two solid phase extraction resins (SPER) were prepared by impregnating solutions of two diglycolamide-functionalized calix[4]arenes in 10% isodecanol in n-dodecane into Chromosorb W, as the stationary phase. While SPER-I contained n-propyl functionalized calix[4]arene, SPER-II contained the calix[4]arene with isopentyl groups at the carboxamide nitrogen atoms. The SPERs were characterized by SEM, TGA, FTIR, etc. and were used for the batch uptake of neptunium(IV) from nitric acid feed solutions. While the uptake of Np(IV) was extremely high with SPER-I (K d : 47,544 at 3 M nitric acid, ca. 8% extractant loading), SPER-II displayed a significantly lower extraction efficiency (K d : 13,724 under identical conditions) as indicated by the batch uptake studies. Sorption isotherm studies were carried out which indicated good fitting to the Langmuir model suggesting uptake conforming to monolayer sorption. Fitting to the D-R isotherm model conformed to a chemisorption model. Column studies were also carried out and the elution profiles, obtained with solutions of oxalic acid and nitric acid indicated very sharp peaks suggesting that the column can be used for the separation of Np(IV) from acidic radioactive feeds., Competing Interests: Declaration of Competing Interest The authors have no conflict of interest to declare., (Copyright © 2021. Published by Elsevier B.V.)

In this study, the distribution and migration of 237 Np and 239+240 Pu in soils in the vicinity (<5 km) of Qinshan and Tianwan Nuclear Power Plants in China were studied, which is the first specific study of global fallout 237 Np in Chinese soils. The 237 Np and 239+240 Pu concentrations in surface soils showed large spatial inhomogeneity. A remarkable 239+240 Pu concentration (4.783 mBq/g) was observed in a surface soil near Qinshan NPP and stands for the ever reported highest value in the Chinese soils. The inventories of 239+240 Pu in two Qinshan and Tianwan soil cores were estimated to be 128.8 Bq/m 2 and 121.0 Bq/m 2 , respectively; while the 237 Np inventories were 0.039 Bq/m 2 and 0.035 Bq/m 2 at these sites, respectively. The 240 Pu/ 239 Pu atomic ratios in these soils indicated that the global fallout is the main source of Pu in these regions. However, the non-isotopic 237 Np/ 239 Pu atomic ratio in environmental soil is not a sensitive indicator for source identification. Furthermore, we conducted pilot study on the migration behaviors of 237 Np and 239+240 Pu in soil core at Qinshan site with the Convection-Dispersion Equation (CDE) model. The obtained apparent dispersion coefficients of 237 Np (2.82 ± 2.06 cm 2 /y) was 5 times higher than that of 239+240 Pu (0.57 ± 0.16 cm 2 /y), proving that 237 Np has stronger migration ability than Pu isotopes in the Qinshan soil. Finally, we predicted that with the increase of migration time, both 237 Np and 239+240 Pu concentration in the soil will gradually become more evenly distributed among different soil layers due to the dominant dispersion effects., Competing Interests: Declaration of competing interest None., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The rate constants k of the reduction of 5 × 10 -5  M Np(V) to Np(IV) by hydroxylamine hydrochloride (HAHCl) in 1 M HCl have been determined by CE-ICP-MS in the temperature range of ϑ = 30-70°C and with varying concentrations of HAHCl from 1 to 7.2 M. The reaction was found to have (pseudo)first order kinetics with respect to HAHCl. The experimental results for k ranged from 0.0029(1) min -1 (ϑ = 40°C, c(HAHCl) = 3 M) to 0.039(7) min -1 (ϑ = 60°C, c(HAHCl) = 7.2 M). The activation energy of the reaction was determined as E A  = (72 ± 10) kJ/mol. These results and a comparison with literature data show that the coupling of CE to ICP-MS provides a powerful analytical tool for the investigation of the kinetic aspects of redox reactions of actinides at low concentrations. On the basis of this proof-of-principle study, the method presented here can be extended to the investigation of the kinetic parameters of other redox systems containing different actinides (or transition metals) and oxidants/reductants., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The implementation of the one-pass-through separation technique using two stacked chromatography columns of TEVA - TRU resins for the separation of 237 Np, 241 Am, thorium, plutonium and uranium from environmental and urine samples was investigated. The sequential separation technique proved to be successful and gave similar results to those obtained when using individual separations. The analysis time was considerably improved. The amount of chemical waste was also reduced by 50% and the use of HClO 4 was avoided. The technique of ICP-MS was also investigated as a complementary technique to alpha-spectrometry., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Environmental 237 Np analyses are challenged by low 237 Np concentrations and lack of an available yield tracer; we report a rapid, inexpensive 237 Np analytical approach employing the short lived 239 Np (t 1/2  = 2.3 days) as a chemical yield tracer followed by 237 Np quantification using inductively coupled plasma-mass spectrometry. 239 Np tracer is obtained via separation from a 243 Am stock solution and standardized using gamma spectrometry immediately prior to sample processing. Rapid digestions using a commercial, 900 W "Walmart" microwave and Parr microwave vessels result in 99.8 ± 0.1% digestion yields, while chromatographic separations enable Np/U separation factors on the order of 10 6 and total Np yields of 95 ± 4% (2σ). Application of this method to legacy soil samples surrounding a radioactive disposal facility (the Subsurface Disposal Area at Idaho National Laboratory) reveal the presence of low level 237 Np contamination within 600 m of this site, with maximum 237 Np concentrations on the order of 10 3 times greater than nuclear weapons testing fallout levels., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

An optimized method was developed to analyze environmental soil and sediment samples for (237)Np, (239)Pu, and (240)Pu by ICP-MS using a (242)Pu isotope dilution standard. The high yield, short time frame required for analysis, and the commercial availability of the (242)Pu tracer are significant advantages of the method. Control experiments designed to assess method uncertainty, including variation in inter-element fractionation that occurs during the purification protocol, suggest that the overall precision for measurements of (237)Np is typically on the order of ± 5%. Measurements of the (237)Np concentration in a Peruvian Soil blank (NIST SRM 4355) spiked with a known concentration of (237)Np tracer confirmed the accuracy of the method, agreeing well with the expected value. The method has been used to determine neptunium and plutonium concentrations in several environmental matrix standard reference materials available from NIST: SRM 4357 (Radioactivity Standard), SRM 1646a (Estuarine Sediment) and SRM 2702 (Inorganics in Marine Sediment)., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Seawater contains radionuclides at environmental levels; some are naturally present and others come from anthropogenic nuclear activity. In this report, the molecular speciation in seawater of uranium(VI) and neptunium(V) at a concentration of 5 × 10(-5) M has been investigated for the first time using a combination of two spectroscopic techniques: Time-resolved laser-induced fluorescence (TRLIF) for U and extended X-ray absorption fine structure (EXAFS) for U and Np at the LIII edge. In parallel, the theoretical speciation of uranium and neptunium in seawater at the same concentration is also discussed and compared to spectroscopic data. The uranium complex was identified as the neutral carbonato calcic complex UO2(CO3)3Ca2, which has been previously described in other natural systems. In the case of neptunium, the complex identified is mainly a carbonato complex whose exact stoichiometry is more difficult to assess. The knowledge of the actinide molecular speciation and reactivity in seawater is of fundamental interest in the particular case of uranium recovery and more generally regarding the actinide life cycle within the biosphere in the case of accidental release. This is the first report of actinide direct speciation in seawater medium that can complement inventory data.

We report (237)Np Mössbauer measurements on NpFeAsO. The Np atoms were found to occupy only one crystallographic site. The value of the isomer shift (δ ∼ 9.1 mm s(-1) versus NpAl2) indicates a 5f(4) electronic configuration (Np(3+) ions). The magnetic ordering of the Np sublattice below 60 K is established and the saturated ordered magnetic moment is determined to be 1.73μB at 3.6 K. The unique set of hyperfine parameters exclude a modulated magnetic structure or spin waves on the Np site. The neptunium magnetic moments μNp are found to lie along the tetragonal c-axis.

An automated multisample processing flow injection (FI) system was developed for simultaneous determination of technetium, neptunium, plutonium, and uranium in large volume (200 L) seawater. Ferrous hydroxide coprecipitation was used for the preliminary sample treatment providing the merit of simultaneous preconcentration of all target radionuclides. Technetium was separated from the actinides via valence control of technetium (as Tc(VII)) in a ferric hydroxide coprecipitation. A novel preseparation protocol between uranium and neptunium/plutonium fractions was developed based on the observation of nearly quantitative dissolution of uranium in 6 mol/L sodium hydroxide solution. Automated extraction (TEVA for technetium and UTEVA for uranium) and anion exchange (AGMP-1 M for plutonium and neptunium) chromatographic separations were performed for further purification of each analyte within the FI system where four samples were processed in parallel. Analytical results indicate that the proposed method is robust and straightforward, providing chemical yields of 50-70% and improved sample throughput (3-4 d/sample). Detection limits were 8 mBq/m(3) (0.013 pg/L), 0.26 μBq/m(3) (0.010 fg/L), 23 μBq/m(3) (0.010 fg/L), 84 μBq/m(3) (0.010 fg/L) and 0.6 mBq/m(3) (0.048 ng/L) for (99)Tc, (237)Np, (239)Pu, (240)Pu and (238)U for 200 L seawater, respectively. The unique feature of multiradionuclide and multisample simultaneous processing vitalizes the developed method as a powerful tool in obtaining reliable data with reduced analytical cost in both radioecology studies and nuclear emergency preparedness.

The National Laboratory for Metrology of Ionizing Radiation (LNMRI)/Brazil acquired (166m)Ho and (243)Am/(239)Np solutions from commercial suppliers in order to realize primary standardization and therefore reducing the associated uncertainties. The method used in the standardization was the live-timed 4πβ(LS)-γ(ΝaI(Tl)) anticoincidence counting. The live-timed anticoincidence system is operated since 2006 in LNMRI and is composed of two MTR2 modules donated by Laboratoire National Henri Becquerel (LNE-LNHB)/France. The data acquisition system uses a homemade LabView program and an Excel file for calculus. These systems have been used for primary standardization at LNMRI for many radionuclides and recently took part in the (124)Sb and (177)Lu International Key Comparisons with good performance., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Nuclear waste disposal concepts developed worldwide foresee the use of cementitious materials for the immobilization of long-lived intermediate level waste (ILW). This waste form may contain significant amounts of neptunium-237, which is expected to be present as Np(IV) under the reducing conditions encountered after the closure of the repository. Predicting the release of Np(IV) from the cementitious near field of an ILW repository requires a sufficiently detailed understanding of its interaction with the main sorbing components of hardened cement paste (HCP). In this study, the uptake of Np(IV) by calcium silicate hydrates (C-S-H) and HCP has been investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy. The EXAFS studies on Np(IV)-doped C-S-H and HCP samples reveal that Np(IV) is predominantly incorporated in the structure of C-S-H phases having different Ca:Si ratios. The two main species identified correspond to Np(IV) in C-S-H with a Ca:Si mol ratio of 1.65 as in fresh cement and with a Ca:Si mol ratio of 0.75 as in highly degraded cement. The local structure of Np(IV) changes with the Ca:Si mol ratio and does not depend on pH. Furthermore, Np(IV) shows the same coordination environment in C-S-H and HCP samples. This study shows that C-S-H phases are responsible for the Np(IV) uptake by cementitious materials and further that incorporation in the interlayer of the C-S-H structure is the dominant uptake mechanism.

A new rapid separation method was developed for the measurement of plutonium and neptunium in urine samples by inductively-coupled plasma mass spectrometry (ICP-MS) and/or alpha spectrometry with enhanced uranium removal. This method allows separation and preconcentration of plutonium and neptunium in urine samples using stacked extraction chromatography cartridges and vacuum box flow rates to facilitate rapid separations. There is an increasing need to develop faster analytical methods for emergency response samples. There is also enormous benefit to having rapid bioassay methods in the event that a nuclear worker has an uptake (puncture wound, etc.) to assess the magnitude of the uptake and guide efforts to mitigate dose (e.g., tissue excision and chelation therapy). This new method focuses only on the rapid separation of plutonium and neptunium with enhanced removal of uranium. For ICP-MS, purified solutions must have low salt content and low concentration of uranium due to spectral interference of (238)U(1)H(+) on m/z 239. Uranium removal using this method is enhanced by loading plutonium and neptunium initially onto TEVA resin, then moving plutonium to DGA resin where additional purification from uranium is performed with a decontamination factor of almost 1×10(5). If UTEVA resin is added to the separation scheme, a decontamination factor of ~3 × 10(6) can be achieved.

Neptunium(V) ions are unstable in acid media, which limits their extraction on chromatographic resins. We developed a novel analytical method to measure Np by either α-spectrometry or inductively coupled plasma mass spectrometry (ICP-MS) after extraction chromatography as Np(VI). We investigated the reactivity of various oxidizing reagents, and determined the retention capacity of Np(IV, V, and VI) on various extraction chromatographic supports. A simple method using two UTEVA resins was used to rapidly detect Np in soil and sediment samples., (Copyright 2010 Elsevier Ltd. All rights reserved.)

After the disintegration of the USSR in end of 1991, it became possible for foreign scientists to visit Kazakhstan, in order to investigate the radiological consequences of nuclear explosions that had been conducted at the Semipalatinsk nuclear test site (SNTS). Since the first visit in 1994, our group has been continuing expeditions for soil sampling at various areas around SNTS. The current level of local fallout at SNTS was studied through γ-spectrometry for (137)Cs as well as α-spectrometry for (239,240)Pu. Average values of soil inventory from wide areas around SNTS were 3,500 and 3,700 Bq m(-2) for (137)Cs and (239,240)Pu, respectively, as of January 1, 2000. The average level of (137)Cs is comparable to that in Japan due to global fallout, while the level of (239,240)Pu is several tens of times larger than that in Japan. Areas of strong contamination were found along the trajectories of radioactive fallout, information on which was declassified after the collapse of the USSR. Our recent efforts of soil sampling were concentrated on the area around the Dolon village heavily affected by the radioactive plume from the first USSR atomic bomb test in 1949 and located 110 km east from ground zero of the explosion. Using soil inventory data, retrospective dosimetry was attempted by reconstructing γ-ray exposure from fission product nuclides deposited on the ground. Adopting representative parameters for the initial (137)Cs deposition (13 kBq m(-2)), the refractory/volatile deposition ratio (3.8) and the plume arrival time after explosion (2.5 h), an absorbed dose in air of 600 mGy was obtained for the 1-year cumulative dose in Dolon village, due to the first bomb test in 1949. Considering possible ranges of the parameters, 350 and 910 mGy were estimated for high and low cases of γ-ray dose in air, respectively. It was encouraging that the deduced value was consistent with other estimations using thermal luminescence and archived monitoring data. The present method can be applied to other settlements affected by local fallout from SNTS.

The sorption and diffusion behavior of 8 x 10(-6) M Np(V) in Opalinus Clay (OPA) with synthetic pore water (pH 7.6) as mobile phase was studied under ambient conditions by batch and diffusion experiments, respectively. The Kd value determined by batch experiments with OPA suspensions is equal to 0.025 +/- 0.005 m3/kg. The diffusion-accessible porosity epsilon of intact OPA as determined by through- and out-diffusion experiments with tritiated water (HTO) is equal to 0.15 +/- 0.01. The diffusion coefficient De and the rock capacity factor alpha of 22Na+ in OPA were measured by through-, out-, and in-diffusion experiments and asserted the reliability of these diffusion techniques. For the diffusion of Np(V) in synthetic pore water, the capillary method gave Dw = (6.0 +/- 1.0) x 10(-10) m/s. Due to the strong sorption of Np(V) on CPA, the diffusion of Np(V) was investigated bythe in-diffusiontechnique.The diffusion parameters for Np(V) in OPA are De = (6.9 +/- 1.1) x 10(-12) m2/s and alpha = 243 +/- 4. This corresponds to Kd = 0.10 +/- 0.01 m3/kg for the sorption of Np(V) in intact OPA.

Direct determination of the stability constants of some pentavalent actinides (Np and Pu) with carbonate ligands was investigated by CE-ICP-sector field MS (SFMS). The high sensitivity of ICP-SFMS coupled with the high separation power of CE makes it possible to determine the mobility of each species as well as the stability constants with good accuracy. A procedure for preparing pentavalent plutonium at trace level has been successfully tested enabling the study of Pu(V) complexation by CE-ICP-SFMS. Stability constants beta1, beta2 and beta3 have been obtained at 25 +/- 1 degrees C at a constant ionic strength of 0.37 M in NaClO4 for K1 and NaCl for beta2 and beta3. The results were extrapolated to zero ionic strength and compared with data available in the literature for Np(V). The following stability constants were obtained for a Pu(V)/CO3 system: logbeta(1)(0) = 4.95 +/- 0.10, logbeta(2)(0) = 6.34 +/- 0.10, and logbeta(3)(0) = 5.61 +/- 0.16.

A method to analyse Pu and Np was optimised to achieve low detection limits and high sample throughput. Soil and sediment samples were ashed and digested with a borate fusion. After dissolving the melt in nitric acid, Pu and Np were separated on a TEVA extraction chromatopraphy column. It was measured with a sector field ICP-MS. Detection limits in soils and sediments as low as 1x10(-15)g/g for Pu and Np were achieved. The method was applied to reference materials, soil profiles from Switzerland and sediment samples from the river Yenisei (RU), where radioactive nuclides have been discharged.

The potential use of direct high-resolution alpha spectrometry to identify the presence of transactinium elements in air samples is illustrated in the case when alpha-particle-emitting radionuclides are incorporated in nuclear fuel particles. Alpha particle energy spectra are generated through Monte Carlo simulations assuming a nuclide composition similar to RBMK (Chernobyl) nuclear fuel. The major alpha-particle-emitting radionuclides, in terms of activity, are 242Cm, 239Pu and 240Pu. The characteristics of the alpha peaks are determined by fuel particle properties as well as the type of the air filter. It is shown that direct alpha spectrometry can be readily applied to membrane filter samples containing nuclear fuel particles when rapid nuclide identification is of relevance. However, the development of a novel spectrum analysis code is a prerequisite for unfolding complex alpha spectra.

Metaschoepite, [(UO2)8O2(OH)12] x 10H2O, and metastudtite, UO4 x 4H2O, are alteration phases anticipated in a spent nuclear fuel repository following the moist oxidation of UO2 on a geologic time scale. Dissolved concentrations and hence potential mobility of other radionuclides in the fuel, such as the neptunyl cation (NpO2+), will likely be determined by the extent of their partitioning into these U(VI) solids. 237Np is of particular interest due to its potential high mobility and long half-life (2.1 x 10(6) years.) In this study, metaschoepite has been precipitated and subsequently transformed to studtite in the presence of dissolved Np. The metaschoepite and studtite solids that formed initially contained <10 and 6500 ppm Np, respectively. Batch dissolution studies of these solids at pH 6 demonstrate release of Np that exceeds congruent dissolution of U from metastudtite; furthermore, the released Np cation remains in solution. Thus, although the Np partitions into the metastudtite solid initially, it is released to solution over time, indicating that metastudtite is not likely to serve as a host solid for Np incorporation or sorption of the neptunyl cation on long time scales.

The long-lived anthropogenic radionuclides (237)Np, (239)Pu and (240)Pu were determined in marine environmental samples (seaweed and seawater) collected from Swedish-Danish waters and the North Atlantic Ocean at various locations on different occasions during the period 1991-2001. The measurements were performed with sector field Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and conventional alpha spectrometry. The (237)Np activity concentrations in Fucus vesiculosus and surface seawater from the Swedish west coast and Danish waters ranged from 0.16+/-0.02 to 1.02+/-0.09 mBq kg(-1) (dry weight) and 0.65+/-0.02 to 1.69+/-0.02 mBq m(-3), respectively, depending on the location and sampling year. Most of the (237)Np in these waters is believed to originate from the Sellafield nuclear reprocessing plant, with some contribution from global fallout. The (240)Pu/(239)Pu atomic ratios in F. vesiculosus samples are reported in this study with an overall average of 0.17+/-0.03. The (237)Np and (239)Pu activity concentrations observed in surface seawater collected in North Atlantic waters ranged from 0.16+/-0.01 to 0.62+/-0.08 mBq m(-3) and from 0.64+/-0.05 to 4.27+/-0.08 mBq m(-3), respectively, and the (237)Np/(239)Pu atomic ratios were a good indicator of conservative behaviour of Np in marine waters.

A study has been made of X- and gamma-ray emission from 237Np in equilibrium with 233Pa using the full response function method. This analysis process is characterised by photon spectrometry in which the entire spectrum is modelled in a pseudo-empirical way by means of elementary functions describing the total absorption and escape peaks, the Compton diffusion internal and external to the detector and the peaks resulting from detection of internal conversion electrons. This method has been applied to determine the L X-, K X- and gamma-rays emission probabilities in 237Np and 233Pa decay studies.

A procedure for determination of 237Np, 238Pu, 239,240Pu and 241Pu in environmental samples is described. Neptunium-237 is determined using radiochemical neutron activation analysis with pre- and post-irradiation chemistry based on solvent extraction and extraction chromatography. 238Pu, 239,240Pu is determined using alpha spectrometry and 241Pu by liquid scintillation spectrometry. The vertical profiles of 237Np, 238Pu, 239,240Pu in bottom sediments from the Black Sea are presented.

Technetium, uranium and neptunium may all occur in the environment in more than one oxidation state (IV or VII, IV or VI and IV or V respectively). The surface of mackinawite, the first-formed iron sulfide phase in anoxic conditions, can promote redox changes so a series of laboratory experiments were carried out to explore the interactions of Tc, U and Np with this mineral. The products of reaction were characterised using X-ray absorption spectroscopy. Technetium, added as TcO4(-), is reduced to oxidation state IV and forms a TcS(2)-like species. On oxidation of the mackinawite in air to form goethite, Tc remains in oxidation state IV but in an oxide, rather than a sulfide environment. At low concentrations, uranium forms uranyl surface complexes on oxidised regions of the mackinawite surface but at higher concentrations, the uranium promotes surface oxidation and forms a mixed oxidation state oxide phase. Neptunium is reduced to oxidation IV and forms a surface complex with surface sulfide ions. The remainder of the Np coordination sphere is filled with water molecules or hydroxide ions.

The activity concentrations of (237)Np and the two Pu isotopes, (239)Pu and (240)Pu, were determined in lichen samples (Cladonia stellaris) contaminated by fallout from atmospheric nuclear test explosions and the Chernobyl accident. The samples were collected at 18 locations in Sweden, from north to south, between 1986 and 1988 and analysed with high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) and alpha spectrometry. Data on the activity ratios (238)Pu/(239+240)Pu and (134)Cs/(137)Cs measured previously were also included in this study for comparison. The (237)Np activity concentration ranged from 0.08 +/- 0.01 to 2.08 +/- 0.17 MBq kg(-1), depending on the location of the sampling site and time of collection. The (239+240)Pu activity concentration ranged from 0.09 +/- 0.01 to 4.09 +/- 0.15 Bq kg(-1), with the (240)Pu/(239)Pu atomic ratio ranging between 0.16 +/- 0.01 and 0.44 +/- 0.03, the higher ratios indicating a combination of weapons test fallout and Chernobyl fallout. The (237)Np/(239)Pu atomic ratios ranged between 0.06 +/- 0.01 and 0.42 +/- 0.04, the lower ratios indicating combination of weapons test fallout and Chernobyl fallout. At a well-defined sampling site at Lake Rogen (62.32 degrees N, 12.38 degrees E), additional lichen samples were collected between 1987 and 1998 to study the distribution of Np and Pu in different layers. The concentrations of the two elements follow each other quite well in the profile.

Radioecological studies carried out in a joint co-operation between Russian, Ukrainian and Danish Laboratories are reported. The environmental impact of routine, discharges as well as accidental events, notably the Kyshtym accident in 1957 and the Karachay wind dispersion in 1968 have been studied. From measurements and based on model assumptions it has been estimated that the Ob river system outside Mayak, i.e. first of all the Techa and Iset rivers and their floodplains contain 0.1 PBq 90Sr, 0.3 PBq 137Cs and 0.8 TBq 239, 240Pu. The uncertainty of these estimates is a factor of 3-4. The present contamination from the Kyshtym accident outside the Mayak area is calculated to 0.1-0.5 PBq 90Sr and from the Karachay incident the contamination is 0.05-0.1 Bq 137Cs. The environmental contaminations with Pu from these two events are in the order of 1 TBq. The occurrence of 99Tc, 129I and 237Np in highly contaminated Techa river sediments collected outside Mayak is for the first time reported.

Electret ion chambers are inexpensive, lightweight, robust, commercially available, passive, charge-integrating devices for accurate measurement of different ionizing radiations. In an earlier work a chamber of dimensions larger than the range of alpha particles having aluminized Mylar windows of different thickness was used for measurement of alpha radiation. Correlation between electret mid-point voltage, alpha particle energy, and response was developed and it was shown that this chamber could be used for estimating the effective energy of an unknown alpha source. In the present study, the electret ion chamber is used in the windowless mode so that the alpha particles dissipate their entire energy inside the volume, and the alpha particle energy is determined from the first principles. This requires that alpha disintegration rate be accurately known or measured by an alternate method. The measured energies were within 1 to 4% of the true values for different sources (230Th, 237Np, 239Pu, 241Am, and 224Cm). This method finds application in quantitative determination of alpha energy absorbed in thin membrane and, hence, the absorbed dose.

Neptunium is a transuranium element, produced in tonne quantities in nuclear reactors. Because it has access to a range of oxidation states, neptunium may undergo redox transformations in the environment and these can have far-reaching effects on its environmental mobility. Here, the reaction of NpO2+ (the soluble and thermodynamically stable neptunium species in oxic systems) with microcrystalline mackinawite is studied. Uptake of neptunium from solution is relatively low (approximately 10% of the total initially present in solution) and independent of initial solution concentration over the range 0.27-2.74 mM and of equilibration time. X-ray absorption spectroscopy (XAS) of the solid sulfide samples indicates nearest neighbor oxygen atoms at distances around 2.25-2.26 A, sulfur atoms at around 2.61-2.64 A, and two more distant shells fitted with iron, at 3.91-3.95 A and 4.15-4.16 A. These observations suggest that on interaction with the sulfide surface reduction of Np(V) to Np(IV) occurs, accompanied by loss of axial oxygen atoms. Neptunium coordinates directly to surface sulfide atoms, in contrast to the behavior previously observed for uranium under similar conditions. These results demonstrate the importance and variability of the speciation of redox sensitive actinides under anoxic conditions.

A combination of experimental, analytical, and modeling investigations shows that an anaerobic, sulfate-reducing consortium reduced Np(V) to Np(IV), with subsequent precipitation of a Np(IV) solid. Precipitation of Np(IV) during growth on pyruvate occurred before sulfate reduction began. H2 stimulated precipitation of Np(IV) when added alone to growing cells, but it slowed precipitation when added along with pyruvate. Increasing concentrations of pyruvate also retarded precipitation. Accumulation of an intermediate pyruvate-fermentation product--probably succinate--played a key role in retarding Np(IV) precipitation by complexing the Np(IV). Hydrogen appears to have two roles in controlling Np precipitation: donating electrons for Np(V) reduction and modulating intermediate levels. That Np(V) is microbially reduced and subsequently precipitated under anaerobic conditions has likely beneficial implications for the containment of Np on lands contaminated by radionuclides, but complexation by fermentation intermediates can prevent immobilization by precipitation.

Isotopic ratios of Pu and Np measured in sediment cores from 5 locations in the Ob River drainage basin show clear evidence of input from sources other than global fallout (non-fallout sources). Historical contaminant records obtained by combining isotopic ratio information with chronological information indicate that non-fallout inputs are from several sources that have varied significantly over the past 50 years. Unique isotopic signatures observed in sediments from tributaries that drain areas containing known or suspected sources of non-fallout contamination are used to identify the source of materials in sediments collected at downstream locations. These data can lead to a better understanding of the transport behavior, fate, and relative importance of particle reactive, weapons related contaminants originating from the nuclear facilities Mayak. Tomsk-7, and Semipalitinsk, which lie within the drainage basin. From our work to date, we draw the following conclusions: (1) Persistent non-fallout contamination is observed in the Ob River above its confluence with the Irtysh River, indicating contamination from the Tomsk-7 facility. (2) Non-fallout contamination in the Tobol River above its confluence with the Irtysh River indicates contamination from the Mayak facility. (3) Non-fallout contamination in the Irtysh River above its confluence with the Tobol River indicates contamination from the Semipalitinsk weapons test site. (4) The occurrence of isotopic ratios in Ob Delta sediments that are similar to those observed in source tributaries suggests that contamination from at least two sources has been transported along the length of the river system. (5) Global fallout, a result of high-yield atmospheric weapons tests conducted by the FSU and USA primarily, is the dominant source of Pu and Np to the region; however, there have been brief periods when inputs from non-fallout sources exceeded those from global fallout.

Accelerator mass spectrometry (AMS) was used to measure 237Np in environmental water samples extracted from Irish Sea sediments. The samples were of limited volume (approximately 700 ml) and of low activity (0.06-0.79 mBq l-1; 2.30-30.3 pg l-1). AMS proved to have the required sensitivity for measuring these samples, and was in principle capable of measuring much smaller amounts, as low as 0.4 microBq (3.9 x 10(7) atoms). However, the background level in the procedural blanks showed that there was a systematic low level 237Np contamination of each sample, arising from the 239Np yield monitor used in the separations procedure, which effectively increased the detection limit of these analyses.

Inventories and compositions of Pu isotopes and 237Np in archived soil samples collected in the 1970s from 54 locations around the world were determined to provide regional baselines for recognizing possible future environmental inputs of non-fallout Pu and Np. As sample sizes used in this work were small (typically 1 g), inhomogeneities in Pu and Np concentrations were easily recognizable and, as a result, we were able to determine that atypical debris in South America, from French testing in the South Pacific, is more widely and uniformly distributed than previously supposed. From our results we conclude that fallout 237Np/239Pu atom ratios are generally lower in the Southern Hemisphere (approximately 0.35) than in the Northern Hemisphere (approximately 0.47.) Moreover, 237Np/239Pu atom ratios are more device-dependent, hence more variable, than counterpart 240Pu/239Pu atom ratios. Given predictable trends caused by sample inhomogeneities, with only two exceptions, the Pu results of this work are entirely consistent with (and in several instances improve on) results previously reported for these same samples. However, unlike earlier interpretations used to explain these results, we recommend that fallout isotopic signatures be represented by mixing lines, rather than averages, to better reflect regional variations of stratospheric fallout inventories relative to tropospheric fallout inventories, and provide the theoretical basis for doing so. Finally, the Np results of this work constitute one of the largest single compilations of such data reported to date.

Heavy metals and rare earth elements in two types of cigarettes were studied. The contents of trace elements were determined by using delayed neutron activation analysis. In the present study 11 elements have been detected in popular and fine brand cigarettes marketed in Egypt. Evaluation of these elements with their potential hazards for smokers is briefly discussed. The material balance (source and sink) for each element was determined. Also the ratio of element recovery to the total amount was assessed.

Electret ion chambers are inexpensive, light-weight, commercially available, passive charge-integrating devices for accurate measurement of different radiations. Performance of electret ion chambers for surface alpha contamination measurement was evaluated. Ion chambers of two types and electrets of three thicknesses were used for the study. Calibration of the electret ion chambers was performed using reference alpha standards of different energies and radioactivities. Effects of various parameters such as chamber dimensions, electret thickness, alpha particle energy, position of alpha source from the chamber centerline, source localized or uniformly distributed, level of alpha contamination, Mylar window covering the chamber, and ambient radon and gamma radiation on the response of the electret ion chambers were determined. Suitable combinations of chambers and electrets to measure surface alpha contamination were determined.

As part of the Hanford Environmental Dose Reconstruction Project, an unsteady flow hydraulic model, modified to include radionuclide decay, was used to simulate the transport of radionuclides released to the Columbia River from Hanford. The model was applied to the river from Priest Rapids Dam to the vicinity of Portland, Oregon, for the period from January 1950 through January 1971. Model output consisted of monthly-average water concentrations for 24Na, 32P, 65Zn, 76As, and 239Np. Model validation was accomplished by comparing computed water depths and 51Cr concentrations to measured field data. This paper discusses the modeling approach and compares the results to historical river monitoring data collected during the peak years of operation.

The alpha radioactive components in the Hemp-palm of Bontenchiku were determined with emphasis on the measurement low-level 237Np by alpha-ray spectrometry after chemical separation. Bontenchiku is a kind of fishing gear for long-line fishing used by the Fifth Fukuryu-Maru (Lucky Dragon). This gear was exposed to fallout from the second thermonuclear test explosion (Bravo) at Bikini Atoll in March 1954. The 237Np content in the Bontenchiku sample was determined to be 11.5 +/- 0.8 mBq g(-1), with an activity ratio of 237Np:239,240Pu and an atom ratio of 237Np:239Pu estimated to be (2.2 +/- 0.2) x 10(-3) and 0.42 +/- 0.04, respectively. The data showed the existence of a chain reaction of 238U and its ratio to be 237Np:239Pu, as well as the presence of 237U at the time of fallout from Bravo event in March 1954.

The vertical distribution of weapons testing fallout 237Np has been determined in an undisturbed grassland soil (Alfisol). By using a compartmental model for multi-layered soils, the mean residence half-times of 237Np in each soil layer were calculated and compared with results on weapons fallout 239 + 240Pu, 241Am and 137Cs in the same soil. The results show that the mobility of 237Np was in most soil horizons either equal or slightly enhanced as compared to that of Pu, Am, and radiocesium.

Iodine-131, ruthenium-103, and neptunium-239 are present as contaminants in the eluate of 99Mo-99mTc generators loaded with 99Mo prepared by thermal-neutron irradiation of enriched 98Mo. The elution pattern of each of these contaminants is determined, together with the amounts found in the eluate of all generators tested over a 7-month period.