Under-estimation of 210Pb in industrial radioactive scales.

Lead-210 (210Pb) can be present at high activity concentrations, in residues arising from the petroleum, mineral processing and chemical industries. Although 210Pb itself poses a low radiological risk, the nuclide decays via 210Bi to the alpha emitting and highly radiotoxic 210Po. Therefore, rapid, accurate determination of 210Pb is essential for assessing the radiological risk to plant operators and appropriate sentencing of waste. Unfortunately, direct measurement of 210Pb by gamma spectrometry is hindered by its weak gamma-ray emission at 46.5 keV, which is readily attenuated by mineral matrices. This paper demonstrates the extent to which 210Pb can be underestimated during routine analysis by an inter-laboratory exercise involving five accredited laboratories and a wide range of scales from diverse industrial sources. Two methods of addressing errors in 210Pb analysis are highlighted; the first, involving lithium tetraborate fusion prior to gamma spectrometry shows promise but is not suitable for all 210Pb-containing phases. The second method, requiring calculation of matrix attenuation factors for a representative fingerprint sample, was applied successfully to deposits from the steel and gas industries. However, its wider application depends on detailed chemical and mineralogical characterisation for each of the major categories of mineral scale found and at present, there is an acute lack of suitable certified reference materials.

Pre-concentration of naturally occurring radionuclides and the determination of (212)Pb from fresh waters.

A novel technique has been developed for determining the (212)Pb activity of fresh waters. This is of interest to environmental monitoring programmes that utilise gross α-activity methods to screen for anthropogenic radionuclides. The contribution from (212)Pb varies, and is difficult to experimentally measure due to its relatively short half-life (t(½) = 10.6 h) and low environmental activity (<0.1 Bq l(-1)). The use of a three-stage technique that encompasses a unique form of pre-concentration, separation and analysis by liquid scintillation counting allows a lower detection limit of 0.006 Bq l(-1) with a chemical yield of 92.5 ± 5.6%. The measurement can be obtained within 7 h of sample collection, and is calculated using the radioactive decay of (212)Bi. Other naturally occurring radionuclides may also be extracted using the pre-concentration stage of the technique, with efficiencies above 90% at a range of pH values.

Activity determination and nuclear decay data of (113m)Cd.

The radionuclide (113m)Cd was extracted from a Cd component, which has been irradiated in a research reactor during its routine operation. A validated separation procedure was then used to obtain a (113m)Cd solution of high radiochemical purity. The solution was measured by means of liquid scintillation counting for activity determination. To this end, the CIEMAT/NIST efficiency tracing method as well as the triple-to-double coincidence (TDCR) counting technique were used. Measurements in a low-background gamma-ray spectrometer were applied to identify any potential photon-emitting impurities and to measure the 263.7 keV photons from the isomer transition. A gamma emission probability of 0.01839(29)% was determined for this line. The liquid scintillation measurements were also used to evaluate the half-life of (113m)Cd. The decay was followed for about 11 months and a half-life T(1/2)=13.97(13) years was obtained.

Short-lived variations in the background gamma-radiation dose.

Sudden increases in the background gamma-radiation dose may occur due to the removal of (222)Rn and (220)Rn progeny from the atmosphere by wet deposition mechanisms. This contribution has been measured using a Geiger-Muller detector at the Atomic Weapons Establishment (Aldermaston, UK) during July 2005-April 2006. The results are approximated by a log-normal distribution and there were nine separate occurrences of the gamma-radiation dose exceeding 125% of the geometric mean value. The increases were associated with periods of heavy rainfall, although no correlation was evident between the dose rate and the amount of rainfall, as increased rainfall dilutes the activity further rather than increasing its atmospheric removal. The events were preceded by periods of fine weather and atmospheric stability that allow for the build-up of (222)Rn and (220)Rn progeny. Similar increases in gamma-radiation dose have been measured at a nearby monitoring station situated approximately 11 miles from Aldermaston. Increases in gamma-radiation dose during heavy rainfall have also been observed throughout the UK, that followed the trajectory of an air mass. All events decreased to typical values within 1-2 h as the water permeated into the ground below and the radioactivity decayed away.

Effective desorption of tritium from diverse solid matrices and its application to routine analysis of decommissioning materials.

Tritium extraction from materials is most commonly carried out using oxidative thermal desorption in purpose-built furnace systems and typically involves trapping the product in a water bubbler which is sampled for measurement using liquid scintillation counting (LSC). The performance of perhaps the most widely used commercial system, the Raddec Pyrolyser, has been evaluated for a broad range of sample types. Several parameters that were expected to affect tritium desorption and recovery were systematically studied. These included sample heating rates and end-point temperatures, carrier/oxidant gas flows, catalyst temperature, bubbler trapping and carry-over/memory effects. A catalyst such as platinised-alumina is used to ensure the quantitative oxidation of volatile combustion products to HTO and CO(2). This also ensures that the trapped decomposition products do not colourise the bubbler solutions that are subsequently sampled for LSC. Tritium evolution profiles were determined for a range of sample types and were obtained by systematically changing bubblers at a set of progressively increasing temperatures. These experiments showed the maximum heating temperature and total combustion time required for the complete recovery of tritium from samples was dependent on the sample matrix types and the (3)H form. These evolution profiles need only be determined once and are readily transferable to other Pyrolyser systems. For example tritiated water is rapidly liberated from samples at temperature around 100 degrees C whereas (3)H substituted for structural H in organic species can require a temperature in excess of 300 degrees C to be released. Higher temperatures (up to 900 degrees C) are needed to liberate (3)H originating from neutron capture reactions on trace Li or B within a material (e.g. reactor graphite or concrete). The furnace system investigated is highly effective at extracting tritium and (14)C from all sample types studied (soil, sediment, biota, wood, metal, plastic, concrete, graphite, etc.) and overall it demonstrates high and reproducible recoveries.

Spatial distribution of (241)Am, (137)Cs, (238)Pu, (239,240)Pu and (241)Pu over 17 year periods in the Ravenglass saltmarsh, Cumbria, UK.

Ninety five surface scrape samples were collected at the Ravenglass saltmarsh and analysed for radionuclides by alpha spectrometry ((238)Pu and (239,240)Pu), gamma spectrometry ((241)Am and (137)Cs) and liquid scintillation counting ((241)Pu). Both (241)Am and (137)Cs activities are compared with those reported by Horrill [1983. Concentrations and spatial distribution of radioactivity in an ungrazed saltmarsh. In: Coughtrey, P.J. (Ed.), Ecological Aspects of Radionuclide Release. British Ecological Society Special Publication No. 3. Blackwell, Oxford, pp. 119-215.] Significant decreases in activities for both radionuclides were observed which is caused by the declining levels of discharges from the Sellafield nuclear reprocessing plant since the 1980s. It has been concluded that the spatial distribution of these radionuclides are controlled by the tidal currents and the clay contents in the sediments. There is evidence of surface erosion of the saltmarsh and redistribution of radionuclides in the saltmarsh using isotopic ratios of measured Pu.

Effective determination of the long-lived nuclide 41Ca in nuclear reactor bioshield concretes: comparison of liquid scintillation counting and accelerator mass spectrometry.

The routine application of liquid scintillation counting to (41)Ca determination has been hindered by the absence of traceable calibration standards of known (41)Ca activity concentrations. The introduction of the new IRMM (41)Ca mass-spectrometric standards with sufficiently high (41)Ca activities for radiometric detection has partly overcome this although accurate measurement of stable Ca concentrations coupled with precise half-life data are still required to correct the certified (41)Ca:(40)Ca ratios to (41)Ca activity concentrations. In this study, (41)Ca efficiency versus quench curves have been produced using the IRMM standard, and their accuracy validated by comparison with theoretical calculations of (41)Ca efficiencies. Further verification of the technique was achieved through the analysis of (41)Ca in a reactor bioshield core that had been previously investigated for other radionuclide variations. Calcium-41 activity concentrations of up to 25 Bq/g were detected. Accelerator mass spectrometry (AMS) measurements of the same suite of samples showed a very good agreement, providing validation of the procedure. Calcium-41 activity concentrations declined exponentially with distance from the core of the nuclear reactor and correlated well with the predicted neutron flux.

Characterization of the NIST seaweed Standard Reference Material.

The National Institute of Standards and Technology (NIST) Standard Reference Material (SRM) for seaweed was developed through an interlaboratory comparison with 24 participants from 16 countries. After evaluating different techniques to calculate certified values for the radionuclides, the median method was found to be the most representative technique. The certified values were provided for 13 radionuclides and information values were given for 15 more radionuclides. Results for the natural decay series showed disequilibrium in both the uranium and thorium series.

A novel approach for the rapid decomposition of Actinide resin and its application to measurement of uranium and plutonium in natural waters.

A rapid and robust procedure is described for the decomposition of Actinide resin permitting the routine application of this resin as a preconcentrator. Although the classical Fe(OH)3 precipitation is effective in scavenging actinides, the need for careful handling to recover the sticky precipitate makes the new method much more attractive. The known difficulty of decomposing Actinide resin, which is required prior to the subsequent separation of adsorbed actinides, is innovatively overcome by using a borate fusion attack. This procedure effectively solves the normally encountered problem by safely and speedily decomposing the resin in minutes rather than hours. The alternative and apparently simpler technique of direct ashing of the Actinide resin is not used since it leads to a residue that is not readily leachable. The new technique has been incorporated into a procedure for the isolation of Pu and U from natural water samples and their subsequent quantification by alpha spectrometry. The efficiency of loading of the elements onto Actinide resin has been tested using both batch and column-based approaches. The integrated method involving Actinide resin preconcentration, borate fusion, anion and UTEVA chromatography and electrodeposition provides limits of detection of 0.001 BqL(-1) and chemical recoveries in excess of 80% from groundwater and seawater samples as large as 5L. Comparative data, presented for the analysis of independently analysed river, borehole and surface run-off waters using both the described procedure and other competing techniques, show very good agreement.

Penetration of tritium (as tritiated water vapour) into low carbon steel and remediation using abrasive cleaning.

The UKAEA Winfrith site is in a phase of accelerated decommissioning and de-licensing which will generate significant volumes of metal wastes some of which may be suitable for disposal as exempt wastes. If contamination is present, it is often confined within the surface layers of the metal. The UKAEA Winfrith site operates a shot-blast facility (WACM) that removes paint and surface contamination from low carbon steel enabling surface contaminated painted metal to be processed and therefore certified as exempt. A study was conducted to determine whether tritium (as tritiated water vapour) has penetrated into the metal to levels exceeding the Radioactive Substances Act (1993), Substances of Low Activity (SoLA) Exemption Order criteria, and whether processing via the WACM removes sufficient tritium contamination that the SoLA Exemption Order criteria can be met. The results of sampling and analysis show that the tritium is mainly held in the paint or outer 40 microm layer of the metal and that processing through the WACM removes these layers along with sufficient tritium to meet the SoLA Exemption Order criteria.

Radiochemical determination of 241Am and Pu(alpha) in environmental materials.

Americium-241 and plutonium determinations will become of greater importance over the coming decades as 137Cs and 241Pu decay. The impact of 137Cs on environmental chronology has been great, but its potency is waning as it decays and diffuses. Having 241Am and Pu as unequivocal markers for the 1963 weapon fallout maximum is important for short time scale environmental work, but a fast and reliable procedure is required for their separation. The developed method described here begins by digesting samples using a lithium borate fusion although an aqua regia leachate is also effective in many instances. Isolation of the Am and Pu is then achieved using a combination of extraction chromatography and conventional anion exchange chromatography. The whole procedure has been optimized, validated, and assessed for safety. The straightforwardness of this technique permits the analysis of large numbers of samples and makes 241Am-based techniques for high-resolution sediment accumulation rate studies attractive. In addition, the technique can be employed for the sequential measurement of Pu and Am in environmental surveillance programs, potentially reducing analytical costs and turnround times.

The uptake of iron-55 by marine sediment, macroalgae, and biota following discharge from a nuclear power station.

Significant quantities of 55Fe, an activation product of stable iron, have been released into the environment following the atmospheric testing of nuclear weapons (mainly in the 1950s and 1960s) as well as through authorized discharges of radioactivity from nuclear power and reprocessing sites. Although some studies have been performed on the behavior of weapons' fallout-derived 55Fe in the environment and subsequent impact on humans, little has been published on the behavior of 55Fe released as a point source discharge from nuclear sites. This study presents data on the concentration and temporal variation of 55Fe in fucoid seaweeds, shellfish, crab, and lobster collected from Weymouth Bay and adjacent coastal areas, southern England. These areas have received authorized discharges of radionuclides originating from the operation of a now-decommissioned steam-generating, heavy water-type reactor at AEE Winfrith. The highest activities of 55Fe are found associated with marine sediments collected near the discharge pipeline and a rapid decline occurs away from the pipeline. This is consistent with rapid sorption of 55Fe by the sediment, and the data show there is only limited reworking and remobilization. Activities of 55Fe in biota generally decreased over time, due to a reduction in the amount of 55Fe discharged. The variation of 55Fe activity, revealed from the monthly sampling of seaweed, does not reflect the short-term fluctuations seen in the patterns of discharged 55Fe activity. Although discharges of 55Fe from AEE Winfrith exceeded other radionuclides, the radiological impact on local seafood consumers is considerably less than for other key radionuclides such as 60Co and 65Zn but of comparable magnitude to the global average population dose arising from fallout-derived 55Fe.

Reactivity of reverse transcriptase toward (s4U,U)n copolymers and spin-labeled nucleic acid lattices.

Spin-labeled copolymers of 4-thiouridine and uridine (ls4U,U)n] that contain various amounts of spin label (l) were synthesized by either (i) chemical alkylation of the 4-thiouridine-uridine copolymers (s4U,U)n prepared by copolymerizing 4-thiouridine 5'-diphosphate (s4UDP) and UDP or (ii) copolymerization of spin-labeled s4UDP with UDP using polynucleotide phosphorylase. The effect of (s4U,U)n and (ls4U,U)n on avian myeloblastosis virus (AMV) RNA-dependent DNA polymerase (RNA-dependent DNA nucleotidyltransferase, EC 2.7.7.7; reverse transcriptase) was studied to determine whether the presence of potentially reactive thiol groups or spin labels enhances the inhibitory properties of the copolymers as compared to (U)n. Inhibition by (s4U,U)n gradually increases as the percentage of thiolation increases. Enhanced inhibition by (s4U,U)n appears to be due to the interaction of the thiol groups of (s4U,U)n with the thiol group(s) of the polymerase, because inhibition by (s4U,U)n (8% thiolated) in the presence of dithiotreitol resembles that by (U)n. In contrast, inhibition by (ls4U,U)n containing 3% spin label resembles that by (U)n; however, increasing the spin label to 6% or 12% results in enhanced inhibition by (ls4U,U)n as compared to that by (U)n, and dithiothreitol has no effect on enhanced inhibition by (ls4U,U)n. These results suggest that the mechanism of inhibition observed with (ls4U,U)n with a ls4U:U ratio > 1:33 differs from the mechanism for (s4U,U)n and involves complex formation between the spin label and the essential Zn2+ of RNA-dependent DNA polymerase.

Reverse transcriptase: a monitor for perturbation effects of spin labels covalently bound to nucleic acids.

The sensitive biological assay for reverse transcriptase was used to monitor potential perturbation effects of spin labels covalently bound to various nucleic acids or nucleic acid analogs to the extent of about one label per 100 residues. The inhibitory properties of the spin labeled and unlabeled biopolymers were compared for evaluating possible interference of the reporter group in protein-nucleic acid interaction studies. The amount of inhibitor required for 50% inhibition (ED50) was determined for the competitive inhibitors (U)n, l(U)n, (RUGT,U)n, (Um)n, (A)n, (Am)n, and l(A)n as well as for thenon- or uncompetitive inhibitors (dUfl)n, l(dUfl)n, (dUz)n, and l(dUz)n. The most pronounced inhibition was observed with spin labeled and unlabeled (dUfl)n. The results indicate that the ED50 and the kinetic patterns of inhibition are similar for the spin labeled and unlabeled inhibitors studied. Thus, the presence of a limited number of spin labels in a nucleic acid matrix has little effect, if any, on reverse transcriptase-nucleic acid complexes and most likely on other protein-nucleic acid complexes.

Modification of the cysteine residue of streptococcal dihydrofolate reducatse.

Modification of the single cysteine residue of streptococcal dihydrofolate reducatase with 5,5'-dithiobis (2-nitrobenzoic acid) results in virtually complete inactivation of the enzyme. Reduction of the enzyme-S-nitrobenzoate mixed disulfide with dithiothreitol indicates that 1.0 cysteine has been modified and approximately 70 percent of the original enzyme activity restored. Circular dichroic and fluorescence studies suggest that a localized conformational change involving aromatic residues, possibly tryptophan, has occurred following modification. In addition, nearly stoichiometric amounts of p-hydroxymercuribenzoate lead to complete inactivation of the reducatas. It is suggested that the S-nitrobenzoate moiety bound to the cysteine residue of the enzyme may perturb one or more aromatic side chains and lead to a distortion of the hydrophobic substrate binding site.