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.     

Nuclear spectrometric determination of uranium isotopes without use of radiochemical yield monitors

A method is described for the determination of uranium isotopes in solid samples without the use of radiochemical yield monitors. The analytical procedure employs direct determination of ²³⁸U via the 63.3 keV gamma emission of its first daughter, ²³⁴Th. The measurement of this emission requires that corrections must be made for the gamma-ray attenuation and for contribution due to the 63.9 keV ²³²Th photoemission for samples rich in natural thorium. Isotopic ratios are determined by alpha-particle spectrometric assay of the uranium fraction purified by an anion-exchange technique. The method provides reliable analytical measurements for samples containing widely different amounts of natural uranium and thorium.     

Assessment of exposure to depleted uranium

In most circumstances, measurement of uranium excreted in urine at known times after exposure is potentially the most sensitive method for determining the amount of depleted uranium (DU) incorporated. The problems associated with this approach are that natural uranium is always present in urine because of the ingestion of natural uranium in food and drink, and that the uncertainties in the intakes as assessed from excretion measurements can be quite large, because many assumptions concerning the exposure characteristics (time pattern of exposure, route of intake, chemical form, solubility, biokinetics within the body) must be made. Applying currently available methods and instruments for the measurement of uranium in urine samples, DU incorporations of levels relevant with respect to potential health hazards can be detected reliably, even a long time after exposure.     

Use of group monitoring data in lung dose estimation for intakes of uranium

This paper describes an internal dosimetry program developed for Canadian uranium processing facilities. The recently adopted recommendations of ICRP Publication 60 have made it extremely difficult to detect intakes of insoluble forms of natural uranium by in vivo methods (lung counting). A type S intake of UO2 corresponding to a 20 mSv effective dose has a lung burden that is a factor of 2-3 lower than the MDA, 6 months after the intake occurred. A new methodology, approved in principle by the Canadian Nuclear Safety Commission, has been designed to overcome this problem by summing sequential, but separate, lung counts for an individual, or summing lung counts from a group of workers performing similar tasks. This summing technique effectively increases the counting time and, therefore, reduces the MDA to a value below the dose limit. Doses will be assigned to the individual or work group based on the average lung burden.     

Solid-phase extraction of ultratrace uranium(VI) in natural waters using octadecyl silica membrane disks modified by tri-n-octylphosphine oxide and its spectrophotometric determination with dibenzoylmethane

A simple and reliable method for rapid extraction and determination of uranium in natural waters using octadecyl-bonded silica membrane disks modified with tri-n-octylphosphine oxide (TOPO) and spectrophotometry with dibenzoylmethane is presented. Extraction efficiency and the influence of sample matrix, type, and optimum amount of extractant, flow rates, and type and minimum amount of organic eluent were evaluated. The maximal capacity of the membrane disks modified by 50 mg of TOPO was found to be 4033 micrograms of uranium. The limit of detection of the proposed method is 100 ng/1000 mL. The method was applied to the extraction and determination of uranium in natural waters.     

Assessment of occupational exposure to uranium by indirect methods needs information on natural background variations

Urine monitoring is the preferred method to determine exposure to soluble compounds of uranium in workplaces. The interpretation of uranium contents in workers bioassay samples requires knowledge on uranium excretion and its dependence on intake by diet. Exceptionally high concentrations of natural uranium in private drinking water sources have been measured in the granite areas of Southern Finland. Consequently, high concentrations of natural uranium have been observed in the urine and hair samples of people using water from their own drilled wells. Natural uranium content in urine and hair samples of family members, who use uranium-rich household water, have been analyzed by using ICP-MS. The uranium concentrations both in urine and hair samples of the study subjects were significantly higher than the world-wide average values. In addition, gammaspectrometric methods have been tested for determining uranium in hair samples. This method can be used only for samples with highly elevated uranium concentrations.     

The airborne natural radioactivity in the uranium mine Rožná I

The knowledge of the behaviour of radioactive aerosol particles in the uranium mine atmosphere is very important due to the evaluation of the effective dose for uranium miners. During the research of the project SUJ200402-'Study of behaviour of natural long-lived radionuclides in the mine atmosphere', several measurement campaigns were performed in the last active Central Europe uranium mine Rozna I. The main purpose of this paper is characterisation the radionuclides which creating the main part of the airborne radioactivity in the uranium mine atmosphere. The present paper introduces results of the measurements of airborne radioactivity in stopes of the uranium mine Rozna I. The measurements were performed at the 21st floor at a depth of ～1100 m under the ground. In addition to the concentration of (222)Rn, its progenies, long-lived radionuclides and also the concentration of aerosol particles were measured.     

Verification of U mass content in nuclear fuel plates by an absolute method

Nuclear Safeguards is referred to a verification System by which a State can control all nuclear materials (NM) and nuclear activities under its authority. An effective and efficient Safeguards System must include a system of measurements with capabilities sufficient to verify such NM. Measurements of NM using absolute methods could eliminate the dependency on NM Standards, which are necessary for other relative or semi-absolute methods. In this work, an absolute method has been investigated to verify the ²³⁵U mass content in nuclear fuel plates of Material Testing Reactor (MTR) type. The most intense gamma-ray signature at 185.7 keV emitted after -decay of the ²³⁵U nuclei was employed in the method. The measuring system (an HPGe-spectrometer) was mathematically calibrated for efficiency using the general Monte Carlo transport code MCNP-4B. The calibration results and the measured net count rate were used to estimate the ²³⁵U mass content in fuel plates at different detector-to-fuel plate distances. Two sets of fuel plates, containing natural and low enriched uranium, were measured at the Fuel Fabrication Facility. Average accuracies for the estimated ²³⁵U masses of about 2.62% and 0.3% are obtained for the fuel plates containing natural and low enriched uranium; respectively, with a precision of about 3%.     

Sizing particles of natural uranium and nuclear fuels using poly-allyl-diglycol carbonate autoradiography

Theoretical and experimental methods were developed to assess the size distribution of alpha-emitting particles captured on air-sampler filters. The particle size of oxides of low enriched, depleted and natural uranium and also aged plutonium in mixed oxide reactor fuels of known composition was determined using poly-allyl-diglycol carbonate (PADC) autoradiography, the commercial product TASTRAK((R)), solid-state nuclear track detectors. The exposed PADC was chemically etched to reveal clusters of tracks, radially dispersing from central points. A theoretical model was developed which converted the number of tracks in a track cluster to the hot particle diameter. The diameters of 26 particles of natural uranium oxide were measured (4-130 microm) using an optical microscope. There was a good agreement between these particle size measurements and a theoretical assessment based on the track cluster count.     

Sodium dodecyl sulfate coated alumina modified with a new Schiff's base as a uranyl ion selective adsorbent

A simple and selective method was used for the preconcentration and determination of uranium(VI) by solid-phase extraction (SPE). In this method, a column of alumina modified with sodium dodecyl sulfate (SDS) and a new Schiff's base ligand was prepared for the preconcentration of trace uranyl(VI) from water samples. The uranium(VI) was completely eluted with HCl 2M and determined by a spectrophotometeric method with Arsenazo(III). The preconcentration steps were studied with regard to experimental parameters such as amount of extractant, type, volume and concentration of eluent, pH, flow rate of sample source and tolerance limit of diverse ions on the recovery of uranyl ion. A preconcentration factor more than 200 was achieved and the average recovery of uranyl(VI) was 99.5%. The relative standard deviation was 1.1% for 10 replicate determinations of uranyl(VI) ion in a solution with a concentration of 5 μg mL(-1). This method was successfully used for the determination of spiked uranium in natural water samples.     

Content of uranium in urine of uranium miners as a tool for estimation of intakes of long-lived alpha radionuclides

Uranium in the urine of 10 uranium miners (hewers), 27 members of general population and 11 family members of miners was determined by the High-Resolution ICP-MS method. Concentration of uranium in urine of the miners was converted to daily excretion of (238)U under the assumption that the daily excretion of urine is 2 l and compared with the modelled excretion of (238)U. Daily excretion of (238)U was modelled using input data from personal dosemeters from a component for measurement of intake of long-lived alpha radionuclides. A reasonable agreement between evaluated and measured values was found. The uncertainty of inhalation intakes, derived from measurements of filters from personal dosemeters, and uncertainty of concentration of uranium in urine are discussed.     

Minimum detectable annual dose calculation for routine individual monitoring programme in case of plutonium and uranium contamination of the workplace

An example of a numerical method application for minimum detectable annual dose calculation that can be guaranteed by the operating monitoring programmes for plutonium and uranium is presented. The method analyses the frequency distribution for a total number of counts obtained in n measurements performed during n monitoring intervals that are inside the calendar year. Urine sample radiometric measurement technique for plutonium and uranium operating monitoring programmes is investigated, showing dependences of the detection limits on the frequency of measurements, on number of calendar years under observation and on the activity median aerodynamic diameter (AMAD). Only a probability density function (PDF), for the background number of counts, stochastic variability of urine excretion and uncertainty of the intake pattern were taken into account as the main variables influencing the calculated detection limits. But there is no limitation for the proposed method to include the variability of other influencing model parameters in the calculation procedure.     

Extended survey of indoor and outdoor terrestrial gamma radiation in Greek urban areas by in situ gamma spectrometry with a portable Ge detector

The results obtained from more than 1000 indoor and outdoor in situ gamma spectrometry measurements in 41 towns (from all geographic subdivisions) of the Greek mainland (not islands) are presented. From the in situ gamma spectra the absorbed dose rate in air due to uranium series, thorium series, 40K and 137Cs are derived and discussed.     

Spatial distribution of thorium fission rate in a fast spallation and fission neutron field: An experimental and Monte Carlo study

The Energy plus Transmutation (EpT) set-up of the Joint Institute for Nuclear Research (JINR), Dubna, Russia is composed of a lead spallation target surrounded by a blanket of natural uranium. The resultant neutron spectrum is a combination of spallation and fission spectra, modified by a reflective external layer of polyethylene and an internal absorbing layer of cadmium. The EpT set-up was irradiated with a beam of 4 GeV deuterons from the Nuclotron Accelerator at JINR. The spatial distribution of thorium fission rate within the assembly was determined experimentally, using a fission track detector technique, and compared with Monte Carlo predictions of the MCNPX code. Contributions of neutrons, protons, deuterons, photons and pions to total fission were taken into account. Close agreement between the experimental and calculated results was found.     

Measuring complete isotopomer distribution of aspartate using gas chromatography/tandem mass spectrometry

We have developed a simple and accurate method for determining the complete positional isotopomer distribution of aspartate carbon atoms by gas chromatography/tandem mass spectrometry for (13)C-metabolic flux analysis. First, we screened tandem mass spectrometry (MS) spectra of the tert-butyldimethylsilyl (TBDMS) derivative of aspartate for daughter fragments with the necessary carbon atom fragmentations to fully resolve all 16 isotopomers of aspartate. Tandem MS scanning parameters were optimized for each daughter fragment, and the accuracy of tandem MS measurements were evaluated. We selected five accurate fragments that provided a redundant set of 47 labeling measurements to quantify the complete isotopomer distribution of aspartate by least-squares regression. The validity of the approach was demonstrated using six (13)C-labeled aspartate standards and natural aspartate.     

Alpha-particle emission from contaminants in counter materials

Energy spectra of surface activities from thorium and uranium contaminants have been investigated for typical counter materials. Soft-tempered stainless steel with a rate of 1.2 ± 0.1 α-particles emitted per 100 cm² in one hour was found better than other stainless steel and far better than brass and aluminum. Energy spectra provide information about the contaminating activity and about its depth profile. Thorium, uranium and ²¹⁰Pb contamination was also observed for thin sources of other materials including isotopically enriched materials.     

Comparative study of femtosecond and nanosecond laser-induced breakdown spectroscopy of depleted uranium

We present spectra of depleted uranium metal from laser plasmas generated by nanosecond Nd:YAG (1064 nm) and femtosecond Ti:sapphire (800 nm) laser pulses. The latter pulses produce short-lived and relatively cool plasmas in comparison to the longer pulses, and the spectra of neutral uranium atoms appear immediately after excitation. Evidence for nonequilibrium excitation with femtosecond pulses is found in the dependence of spectral line intensities on the pulse chirp.     

Daily uranium excretion in German peacekeeping personnel serving on the Balkans compared to ICRP model prediction

An investigation was performed to assess a possible health risk of depleted uranium (DU) for residents and German peacekeeping personnel serving on the Balkans. In order to evaluate a possible DU intake, the urinary uranium excretions of volunteers were collected and analysed using inductively coupled plasma mass spectrometry (ICP-MS). In total, more than 1300 urine samples from soldiers, civil servants and unexposed controls of different genders and ages were analysed to determine uranium excretion parameters. All participating volunteers, aged 3-92 y, were grouped according to their gender and age for evaluation. The results of the investigation revealed no significant difference between the unexposed controls and the peacekeeping personnel. In addition, the geometric means of the daily urinary excretion in peacekeeping personnel, ranging from 3 to 23 ng d(-1) for different age groups, fall toward the lower end of renal uranium excretion values published for unexposed populations in literature. The measured data were compared with the International Commission on Radiological Protection prediction for the intake of natural uranium by unexposed members of the public. The two data sets are in good agreement, indicating that no relevant intake of additional uranium, either natural or DU, has appeared for German peacekeeping personnel serving on the Balkans.     

Sensitivity of a low energy Ge detector system for in vivo monitoring in the framework of ICRP 78 applications

In in vivo detection of internal contamination by actinides the minimum detectable activities (MDAs) correspond to significant doses, so the sensitivity of the detection system is the key to establishing adequate individual monitoring programmes for internal exposure to these radionuclides. The whole body counting (WBC) faculty at CIEMAT uses a low-energy Ge detector system with different available counting geometries to estimate the retention of actinides in the lungs and evaluate 125I in thyroid and 241Am in bone (skull and knee). A study of the factors and uncertainties involved in estimations of MDA is presented for lung and thyroid monitoring. The dependence of detection limits on counting efficiency in the measurement of low-energy emitters in the lungs has been carefully studied, carrying out a comparison among different biometric equations obtained by ultrasound techniques for estimations of chest wall thickness. Dosimetric implications of the estimated MDAs are taken into account in the framework of ICRP 78 application and considering Spanish regulations. The main interest in lung measurements is for the assessment of occupational exposure. This work confirms the low-energy Ge detector system to be an adequate in vivo technique for the routine monitoring of internal exposure to most insoluble uranium compounds (detection of 3% enriched uranium in lungs), and also to be useful in special monitoring programmes or in the case of incidents when the detection of 241Am is required.     

Surface-enhanced Raman spectroscopy for in situ measurements of signaling molecules (autoinducers) relevant to bacteria quorum sensing

Autoinducer (AI) molecules are used by quorum sensing (QS) bacteria to communicate information about their environment and are critical to their ability to coordinate certain physiological activities. Studying how these organisms react to environmental stresses could provide insight into methods to control these activities. To this end, we are investigating spectroscopic methods of analysis that allow in situ measurements of these AI molecules under different environmental conditions. We found that for one class of AIs, N-acyl-homoserine lactones (AHLs), surface-enhanced Raman spectroscopy (SERS) is a method capable of performing such measurements in situ. SERS spectra of seven different AHLs with acyl chain lengths from 4 to 12 carbons were collected for the first time using Ag colloidal nanoparticles synthesized via both citrate and borohydride reduction methods. Strong SERS spectra were obtained in as little as 10 seconds for 80 microM solutions of AI that exhibited the strongest SERS response, whereas 20 seconds was typical for most AI SERS spectra collected during this study. Although all spectra were similar, significant differences were detected in the SERS spectra of C4-AHL and 3-oxo-C6-AHL and more subtle differences were noted between all AHLs. Initial results indicate a detection limit of approximately 10(-6)M for C6-AHL, which is within the limits of biologically relevant concentrations of AI molecules (nM-microM). Based on these results, the SERS method shows promise for monitoring AI molecule concentrations in situ, within biofilms containing QS bacteria. This new capability offers the possibility to "listen in" on chemical communications between bacteria in their natural environment as that environment is stressed.