Dose effect for South Serbians due to 238U in natural drinking water

The use of depleted uranium ammunition in South Serbia during the 1999 Kosovo conflict raised a great deal of public concern in the Balkans. Radioactivity levels of 238U in 20 wells and lake water samples were checked from the viewpoint of internal radiation exposure for South Serbian subjects. We have measured 238U concentration using inductively coupled plasma mass spectrometry, whereas thermal ionisation mass spectrometry has been used for the measurement of isotope ratios, e.g. 234U/238U and 235U/238U. The concentration of uranium in water samples varies in the range 1.37-63.18 mBq/L. 234U belongs to the 238U natural radioactive decay series, and at secular equilibrium, the abundance ratio, 234U/238U, corresponds to the ratio of their half-lives. The 234U/238U activity ratio varies in the range 0.88-2.2 and 235U/238U isotope ratio varies from 0.00698 to 0.00745. These findings indicate that uranium in water was a mixture of natural and anthropogenic origin. The annual effective dose due to 238U was estimated to be in the range 9.2 x 10(-5)-2.1 x 10(-3) mSv.     

Isotopic analysis of uranium in tree bark by ICP mass spectrometry: a strategy for assessment of airborne contamination

Isotopic analysis of uranium in tree bark by ICP mass spectrometry is proposed as a new measurement strategy for monitoring airborne contamination and for discrimination of nuclear and nonnuclear emission sources. A quadrupole-based ICP mass spectrometer equipped with a microconcentric nebulizer and membrane desolvator was used to provide high-sensitivity measurement. The limit of detection for uranium (238U) was 0.004 ng L(-1). Measurement precision (235U/238U) was between 0.2 and 0.5% RSD for isotopic SRMs (U005 and U015; concentration, 1 microg L(-1)) and ranged from 0.4 to 3.1% RSD for tree bark extracts (U concentration, 0.03-0.08 microg L(-1)). Bark samples collected from the Peak District National Park in Derbyshire (U.K.) exhibited a natural 235U/238U isotope ratio value (0.0072) whereas samples from Sellafield, West Cumbria (U.K.) showed depletion in 235U (235U/238U = 0.0053-0.0064).     

Determination of 234U/238U ratio: comparison of multi-collector ICPMS and ICP-QMS for water, hair and nails samples, and comparison with alpha-spectrometry for water samples

The (234)U/(238)U ratio in water, hair and nails samples was determined by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) and inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) and by alpha-spectrometry for the water samples only. A correlation of 0.99 was found between the two ICPMS methods and of 0.98 with alpha-spectrometry. The range of activity ratios was between 0.9 and 2.6 according to the MC-ICPMS measurements. The reproducibility of both ICPMS techniques was better than 4% for water samples containing 1 mug l(-1) of uranium and a (234)U/(238)U atom ratio of 54.9 x 10(-6). Sample preparation for the ICPMS consisted of dilution of water samples containing >10 microg l(-1) of uranium and measurement time was approximately 1 min, while alpha-spectrometry involved pre-concentration and separation of the uranium and counting times of 1,000 min.     

Uranium isotopes in public drinking water and dose assessment for man in Poland

238U, 234U and 235U were determined in tap water from municipal water pipes that drew their supply from surface water or ground water in various locations in Poland. Average activity concentrations of 238U, 234U and 235U in tap water from surface water were 9.6 +/- 7.1, 12.8 +/- 9.7 and 0.41 +/- 0.31 Bq m(-3), respectively, whereas from ground water they were 4.5 +/- 6.0, 5.7 +/- 6.9 and 0.19 +/- 0.27 Bq m(-3), respectively. Activity concentrations of 234U were higher than 238U. Ratios of 234U/238U ranged from 1.07 to 2.60, indicating the lack of equilibrium between these isotopes. The average 235U/238U ratio was 0.043 +/- 0.008, being close to 0.046 for natural uranium. Average annual intake with water and food was 7.6 +/- 5.1 Bq for 238U and 9.5 +/- 6.6 Bq for 234U. Annual committed effective doses calculated from these intakes for adults were 0.34 +/- 0.23 and 0.47 +/- 0.32 microSv, respectively; 235U contributed to the total dose from the uranium isotopes by about 2%.     

Ultratrace uranium fingerprinting with isotope selective laser ionization spectrometry

Uranium isotope ratios can provide source information for tracking uranium contamination in a variety of fields, ranging from occupational bioassay to monitoring aftereffects of nuclear accidents. We describe the development of isotope selective laser ionization spectrometry for ultratrace measurement of the minor isotopes (234)U, (235)U, and (236)U with respect to (238)U. The inherent isotopic selectivity of three-step excitation with single-mode continuous wave lasers results in measurement of the minor isotopes at relative abundances below 1 ppm and is not limited by isobaric interferences such as (235)UH(+) during measurement of (236)U. This relative abundance limit is attained without mass spectrometric analysis of the laser-created ions. Uranyl nitrate standards from an international blind comparison were used to test analytical performance for different isotopic compositions and with quantities ranging from 11 ng to 10 microg total uranium. Isotopic ratio determination was demonstrated over a linear dynamic range of 7 orders of magnitude with a few percent relative precision and detection limits below 500 fg for the minor isotopes.     

Determination of depleted uranium in urine via isotope ratio measurements using large-bore direct injection high efficiency nebulizer-inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS), coupled with a large-bore direct injection high efficiency nebulizer (LB-DIHEN), was utilized to determine the concentration and isotopic ratio of uranium in 11 samples of synthetic urine spiked with varying concentrations and ratios of uranium isotopes. Total U concentrations and (235)U/(238)U isotopic ratios ranged from 0.1 to 10 microg/L and 0.0011 and 0.00725, respectively. The results are compared with data from other laboratories that used either alpha-spectrometry or quadrupole-based ICP-MS with a conventional nebulizer-spray chamber arrangement. Severe matrix effects due to the high total dissolved solid content of the samples resulted in a 60 to 80% loss of signal intensity, but were compensated for by using (233)U as an internal standard. Accurate results were obtained with LB-DIHEN-ICP-MS, allowing for the positive identification of depleted uranium based on the (235)U/(238)U ratio. Precision for the (235)U/(238)U ratio is typically better than 5% and 15% for ICP-MS and alpha-spectrometry, respectively, determined over the concentrations and ratios investigated in this study, with the LB-DIHEN-ICP-MS system providing the most accurate results. Short-term precision (6 min) for the individual (235)U and (238)U isotopes in synthetic urine is better than 2% (N = 7), compared to approximately 5% for conventional nebulizer-spray chamber arrangements and >10% for alpha-spectrometry. The significance of these measurements is discussed for uranium exposure assessment of Persian Gulf War veterans affected by depleted uranium ammunitions.     

Levels of depleted uranium in Kosovo soils

The United Nations Environment Programme (UNEP) has performed a field survey at 11 sites located in Kosovo, where depleted uranium (DU) ammunitions were used by the North Atlantic Treaty Organization (NATO) during the last Balkans conflict (1999). Soil sampling was performed to assess the spread of DU ground contamination around and within the NATO target sites and the migration of DU along the soil profile. The 234U/238U and 235U/238U activity concentration ratios have been used as an indicator of natural against anthropogenic sources of uranium. The results show that levels of 238U activity concentrations in soils above 100 Bq x kg(-1) can be considered a 'tracer' of the presence of DU in soils. The results also indicate that detectable ground surface contamination by DU is limited to areas within a few metres from localised points of concentrated contamination caused by penetrator impacts. Vertical distribution of DU along the soil profile is measurable up to a depth of 10-20 cm. This latter aspect is of particular relevance for the potential risk of future contamination of groundwater.     

Dissolution behaviour of 238U, 234U and 230Th deposited on filters from personal dosemeters

Kinetics of dissolution of (238)U, (234)U and (230)Th dust deposited on filters from personal alpha dosemeters was studied by means of a 26-d in vitro dissolution test with a serum ultrafiltrate simulant. Dosemeters had been used by miners at the uranium mine 'Dolní Rozínka' at Rozná, Czech Republic. The sampling flow-rate as declared by the producer is 4 l h(-1) and the sampling period is typically 1 month. Studied filters contained 125 +/- 6 mBq (238)U in equilibrium with (234)U and (230)Th; no (232)Th series nuclides were found. Half-time of rapid dissolution of 1.4 d for (238)U and (234)U and slow dissolution half-times of 173 and 116 d were found for (238)U and (234)U, respectively. No detectable dissolution of (230)Th was found.     

Assessment of uranium exposure from total activity and 234U:238U activity ratios in urine

Radiation workers at Atomic Weapons Establishment (AWE) are monitored for uranium exposure by routine bioassay sampling (primarily urine sampling). However, the interpretation of uranium in urine and faecal results in terms of occupational intakes is difficult because of the presence of uranium due to intakes from environmental (dietary) sources. For uranium in urine data obtained using current analytical techniques at AWE, the mean, median and standard deviation of excreted uranium concentrations were 0.006, 0.002 and 0.012 μg per g creatinine, respectively. These values are consistent with what might be expected from local dietary intakes and the knowledge that occupational exposures at AWE are likely to be very low. However, some samples do exceed derived investigation levels (DILs), which have been set up taking account of the likely contribution from environmental sources. We investigate how the activity and isotopic composition of uranium in the diet affects the sensitivity of uranium in urine monitoring for occupational exposures. We conclude that DILs based on both total uranium in urine activity and also (234)U:(238)U ratios are useful given the likely variation in dietary contribution for AWE workers. Assuming a background excretion rate and that the enrichment of the likely exposure is known, it is possible to assess exposures using (234)U:(238)U ratios and/or total uranium activity. The health implications of internalised uranium, enriched to <5-8 % by mass (235)U, centre on its nephrotoxicity; the DILs for bioassay samples at AWE are an order of magnitude below the conservative recommendations made by the literature.     

Chemically assisted laser ablation ICP mass spectrometry

A new laser ablation technique combined with a chemical evaporation reaction has been developed for elemental ratio analysis of solid samples using an inductively coupled plasma mass spectrometer (ICPMS). Using a chemically assisted laser ablation (CIA) technique developed in this study, analytical repeatability of the elemental ratio measurement was successively improved. To evaluate the reliability of the CLA-ICPMS technique, Pb/U isotopic ratios were determined for zircon samples that have previously been analyzed by other techniques. Conventional laser ablation for Pb/U shows a serious elemental fractionation during ablation mainly due to the large difference in elemental volatility between Pb and U. In the case of Pb/U ratio measurement, a Freon R-134a gas (1,1,1,2-tetrafluoroethane) was introduced into the laser cell as a fluorination reactant. The Freon gas introduced into the laser cell reacts with the ablated sample U, and refractory U compounds are converted to a volatile U fluoride compound (UF6) under the high-temperature condition at the ablation site. This avoids the redeposition of U around the ablation pits. Although not all the U is reacted with Freon, formation of volatile UF compounds improves the transmission efficiency of U. Typical precision of the 206Pb/238U ratio measurement is 3-5% (2sigma) for NIST SRM 610 and Nancy 91500 zircon standard, and the U-Pb age data obtained here show good agreement within analytical uncertainties with the previously reported values. Since the observed Pb/U ratio for solid samples is relatively insensitive to laser power and ablation time, optimization of ablation conditions or acquisition parameters no longer needs to be performed on a sample-to-sample basis.     

Application of nanosecond-UV laser ablation-inductively coupled plasma mass spectrometry for the isotopic analysis of single submicrometer-size uranium particles

For the first time, laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) was used to carry out isotopic measurement on single submicrometer-size uranium particles. The analytical procedure was applied on two particle-containing samples already analyzed in the same laboratory by established techniques for particle analysis: combination of the fission track technique with thermo-ionization mass spectrometry (FT-TIMS) and secondary ion mass spectrometry (SIMS). Particles were extracted from their initial matrix with ethanol and deposited on a polycarbonate disk where they were fixed in a layer of an organic compound (collodion). Prior to the isotopic analysis, particles were precisely located on the disk's surface by scanning electron microscopy (SEM) for one sample and using the fission track technique for the other sample. Most of the particles were smaller than 1 μm, and their (235)U content was in the femtogram range. (235)U/(238)U ratios were successfully analyzed for all located particles using a nanosecond-UV laser (Cetac LSX 213 nm) coupled to a quadrupole-based ICPMS (Thermo "X-Series II"). LA-ICPMS results, although less precise and accurate (typically 10%) than the ones obtained by FT-TIMS and SIMS due to short (20-40 s), transient, and noisy signals, are in good agreement with the certified values or with the results obtained with other techniques. Thanks to good measurement efficiency (~6 × 10(-4)) and high signal/noise ratio during the analysis, LA-ICPMS can be considered a very promising technique for fast particle analysis, provided that uranium-bearing particles are fixed on the sample holder and located prior to isotope measurement.     

Isotopic measurements of uranium using inductively coupled plasma cavity ringdown spectroscopy

Inductively coupled plasma cavity ringdown spectroscopy (ICP-CRDS) is applied to isotopic measurements of uranium. We have successfully obtained the isotopic-resolved spectra of uranium at three different atomic/ionic transition lines, 286.57, 358.49, and 409.01 nm. Of the three lines, the largest isotope shift of approximately 9 pm was measured at the 286.57 ionic line. Isotopic-resolved spectra were recorded in ratio of 1:1 (235U/238U, 2.5 micrograms/mL) and at the natural abundance ratio of 0.714% (235U/238U, 1.25 micrograms/mL 235U). The smallest measurable isotope shift of approximately 3 pm was determined for the 409.01 nm ion spectral line. Detection limits (DL) were obtained under optimized ICP operating conditions to be in the range of 70-150 ng/mL, except for the 238U component of the 286.57 nm line (300 ng/mL). This latter result was determined to be due to a strong, previously unreported, absorption interference from the argon plasma. The 235U isotope component (DL 70 ng/mL) was found to be unaffected. This work demonstrates the applicability of ICP-CRDS for uranium isotopic measurements. The potential of development of a field-deployable, on-line uranium isotope monitor using plasma-CRDS is discussed.     

A Method for Determining the Isotope Composition of U, Pu, Am, and Cm in "Hot" Particles and Spent Nuclear Fuel

A method was proposed for determining the content of ^234-238U, ^238-242Pu, ^241-243Am, and ^242-244Cm in "hot" fuel particles and spent nuclear fuel. The method is based on high-precision measurement of the -activity in the sample and calculation of the relative contributions of individual nuclides or radionuclide groups to the total activity. Partitioning of U, Pu, Am, and Cm was carried out by ion-exchange chromatography. The contents of ²³⁴U, ²³⁶U, ²³⁸U, ²³⁸Pu, ^239+240Pu, ²⁴²Pu, ²⁴¹Am, ^242mAm, ²⁴³Am, ²⁴²Cm, and ²⁴⁴Cm in "hot" particles sampled in the Chernobyl area were reported. The applicability of the method proposed to determining the radionuclide composition of spent nuclear fuel was discussed.     

Resonance and nonresonant laser ionization of sputtered uranium atoms from thin films and single microparticles: evaluation of a combined system for particle trace analysis

The resonance and nonresonant laser ionization of uranium atoms sputtered from thin metal films and individual micrometer-size uranium oxide particles, respectively, was studied to evaluate a new setup for the analysis of actinide-containing micrometer-size particles. Experiments using nonresonant (193-nm) ionization of atoms and molecules sputtered from micrometer-size uranium oxide particles have shown that the uranium detection efficiencies for sputtered neutral atoms are approximately 2 orders of magnitude higher than for secondary ions. In uranium particles of 0.5-microm diameter, 6 x 10(6) atoms of 235U were easily detected and the isotopic ratio of 235U/238U = 0.0048 +/- 4.6% is in excellent agreement with the certified value. The use of two-color, two-step resonance ionization of the sputtered neutral uranium atoms from thin films was investigated. Several excitation schemes were tested, and a significant population of several low-lying metastable states after ion sputtering was observed. Autoionizing states for double-resonant ionization were determined, and the high selectivity of ionization schemes involving these autoionizing states was illustrated by comparing the flight-time distributions of different sputtered species obtained both by resonance and nonresonant multiphoton (355-nm) laser postionization. Ideally, the options for resonance as well as nonresonant ionization would be combined in a single setup, to obtain a large gain in sensitivity and selectivity. Thus, information about the main components as well as specific isotopic information of a trace element could be obtained from the same single particle.     

High precision measurements of non-mass-dependent effects in nickel isotopes in meteoritic metal via multicollector ICPMS

We measured the Ni isotopic composition of metal from a variety of meteorite groups to search for variations in the 60Ni abundance from the decay of the short-lived nuclide 60Fe (t(1/2) = 1.49 My) and for possible nucleosynthetic effects in the other stable isotopes of Ni. We developed a high-yield Ni separation procedure based on a combination of anion and cation exchange chromatography. Nickel isotopes were measured on a single-focusing, multicollector, inductively coupled mass spectrometer (MC-ICPMS). The external precision on the mass-bias-corrected 60Ni/58Ni ratio (+/-0.15 epsilon; 2sigma) is comparable to similar studies using double-focusing MC-ICPMS. We report the first high-precision data for 64Ni, the least abundant Ni isotope, obtained via MC-ICPMS. The external precision on the mass-bias-corrected 64Ni/58Ni ratio (+/-1.5 epsilon; 2sigma) is better than previous studies using thermal ionization mass spectrometry. No resolvable excesses relative to a terrestrial standard in the mass-bias-corrected 60Ni/58Ni ratio were detected in any meteoritic metal samples. However, resolvable deficits in this ratio were measured in the metal from several unequilibrated chondrites, implying a 60Fe/56Fe ratio of approximately 1 x 10(-6) at the time of Fe/Ni fractionation in chondritic metal. A 60Fe/56Fe ratio of (4.6 +/- 3.3) x 10(-7) is inferred at the time of Fe/Ni fractionation on the parent bodies of magmatic iron meteorites and pallasites. No clearly resolvable non-mass-dependent anomalies were detected in the other stable isotopes of Ni in the samples investigated here, indicating that the Ni isotopic composition in the early solar system was homogeneous (at least at the level of precision reported here) at the time of meteoritic metal formation.     

Assessment of annual effective dose from 238U and 226Ra due to consumption of foodstuffs by inhabitants of Tehran city, Iran

The concentrations of (238)U and (226)Ra were determined in different foodstuffs purchased from markets in Tehran. Determinations of the radionuclides have been carried out using alpha spectrometry technique, on samples of egg, lentil, potato, rice, soya, spinach, tea and wheat. Average concentrations of natural radionuclides and foodstuff consumption rate were used to assess annual intake and based on intake values, the annual effective ingestion dose has been estimated for Tehran city residents. The measurement results show that soya has the maximum concentration of (238)U equal to 15.6 +/- 2.6 mBq kg(-1) and tea has the maximum concentration of (226)Ra equal to 1153.3 +/- 265.3 mBq kg(-1). Besides, the maximum annual effective dose from (238)U and (226)Ra were assessed to be 2.88 x 10(-2) +/- 7.20 x 10(-3) and 2.15 +/- 0.54 muSv, respectively, from wheat samples.     

Sequential Radiochemical Procedure for Isotopic Analysis of Uranium and Thorium in Egyptian Monazite

Radiochemistry - Gamma and alpha spectrometry techniques were applied to determine the activity concentrations of 238U and 232Th (Bq kg–1) as well as the 234U/238U and 230Th/234U isotopic...     

Precise determination of element/calcium ratios in calcareous samples using sector field inductively coupled plasma mass spectrometry

A new method was developed for rapid and precise simultaneous determination of Mg/Ca, Sr/Ca, Mn/Ca, Cd/Ca, Ba/Ca and U/Ca ratios in foraminiferal shells using sector field inductively coupled plasma mass spectrometry (ICPMS). Element/calcium ratios were determined directly from intensity ratios using external, matrix-matched standard to correct for instrumental mass discrimination. Because of large differences in the abundance of chemical constituents of the foraminiferal shell, major elemental ratios were determined in analog mode (using (24)Mg, (43)Ca, (44)Ca, (55)Mn, and (88)Sr) whereas trace elemental ratios were determined in pulse-counting mode (using (111)Cd, (138)Ba, (238)U, and the low-abundance (46)Ca isotope). Matrix-induced variations in mass discrimination over a calcium concentration range of 2.0-24.5 mM were observed only for Mg/Ca and Cd/Ca ratios. However, these effects are negligible if the samples and standard calcium concentration are within a factor of 2-3. Multiratio method reproducibility was better than previously reported for other ICPMS methods yielding precision (1σ) of Sr/Ca = 0.45%; Mg/Ca = 0.45%, Mn/Ca = 0.8%, Cd/Ca = 1.7%, Ba/Ca = 0.7%, and U/Ca = 1.4% for foraminifera samples as small as 25 μg. Using this approach for a single-ratio analysis, Sr/Ca ratios were determined with precision of 0.06% (1σ) on carbonate samples as small as a single foraminifera shell (<10 μg). The new method is more sensitive, more precise, and simpler to use than previously available ICPMS techniques. It provides an efficient tool for simultaneous determination of several elemental ratios of paleoceanographic interest in a single foraminiferal sample, thereby reducing overall sample size requirement and analysis time.     

Determination of 238U, 234U, 232Th, 228Th, 228Ra, 226Ra and 210Pb concentration in excreta samples of inhabitants of a high natural background area

The high concentration of uranium and thorium in certain Brazilian areas provides an opportunity to evaluate the radiation exposure due to intake of radionuclides by the populations that live and work in areas with a high natural radiation background. Buena, where this study was conducted, is a small village on the coast in the northern part of Rio de Janeiro State, characterised by the presence of a large deposit of monazite sand. In this paper, the concentrations of 238U, 234U, 232Th, 228Th, 228Ra, 226Ra and 210Pb in faecal samples from inhabitants of this area were determined by a sequential analytical method. The results of the average concentrations in faeces of inhabitants of Buena are 9.4 +/- 3.4 mBq g(ash)(-1) for 238U, 9.2 +/- 4.0 mBq g(ash)(-1) for 234U, 7.0 +/- 4.2 mBq g(ash)(-1) for 232Th, 256.1 +/- 134.6 mBq g(ash)(-1) for 228Th, 335.5 +/- 192.8 mBq g(ash)(-1) for 228Ra, 156.6 +/- 74.1 mBq g(ash)(-1) for 226Ra and 66.7 +/- 17.7 mBq g(ash)(-1) for 210Pb. The results were compared with background concentrations from faecal samples from individuals living in Rio de Janeiro City. For most of the radionuclides analysed, the average concentration in faeces from inhabitants of the high natural radiation background was higher than the concentration found in Rio de Janeiro, considered a 'normal' background area.     

Separation and measurement techniques for the determination of 228Th, 230Th and 232Th in various matrices

Three analytical techniques are presented which are used at PSI for determination of U and Th isotopes (234U, 235U, 238U, 228Th, 230Th, 232Th) in different materials, i.e. environmental samples (soils, minerals) and dental ceramics as well as in urine for in vitro monitoring of potentially exposed workers. Depending on the sample quantity available and/or required detection limits the measurements are performed either directly via gamma spectrometry or via alpha particle counting with preceding separation chemistry. The separation methods applied are based on either extraction chromatography or on sorption of U and Th on actinide selective resin. Following sample digestion, chemical yield spike additions (232U, 225Th or 225Th), chemical purification and electro-depositional source preparation, alpha particle measurement is carried out using low-level alpha spectrometry. This technique allows detection limits of less than 0.2 mBq per counting source if the assay lasts over a few days and is therefore suitable for determination of trace quantities of short-lived 225Th that can be hardly detected by means of mass spectrometric techniques.