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A method for rapid and sensitive determination of thorium in urine by inductively coupled plasma mass spectometry (ICP-MS) is described. The method is sufficiently sensitive to detect 1 ng/L 232Th in urine without any sample preparation. The mean urinary 232Th excretion in 23 unexposed subjects was 6.2 +/- 3.3 ng/d.
Spectrophotometric determination of microgram amounts of U(VI) with 2-(5-Bromo-2-Pyridylazo)-5-diethylaminophenol (Br-PADAP), originally developed by Johnson and Florence has been modified to enable the determination of U(VI) in the presence of a large excess of Th(IV). The effects of thorium, tri-n-butyl phosphate (TBP) and ethanol on the estimation of uranium have been studied in detail and are presented in this paper. This modified method can be applied for the analysis of U(VI) both in aqueous and organic samples containing a large excess of Th(IV) (Th:U = 10000:1).
The influence of addition order and contact time in the system hematite (alpha-Fe2O3)-humic acid (HA)-thorium(IV) (Th(IV)) was studied in batch experiments. Th(IV) is considered here as a chemical analogue of other actinides (IV). The sorption isotherms were acquired varying pH in the range 2-10 and HA concentration in the range 1-100 mg/L. As already observed by numerous authors, Th(IV) retention was hindered when HA and hematite were equilibrated beforehand during 24 h. As it has been observed in a previous study, this effect was drastic when the ratio between humic and surface (iron oxide) sites exceeds a critical value. However, when HA was added after a 24-h equilibration of the hematite-Th(IV) system, Th(IV) was barely desorbed from the iron oxide surface. Furthermore, no drastic effect of the ratio between humic and surface sites could be evidenced, as the increase of HA concentration only results in a slight monotonic decrease in Th(IV) retention. Increasing contact time between components of the systems only indicated slight Th(IV) retention variation. This was interpreted as a consequence of slow kinetic controls of both the Th(IV)-HA complexation and HA-hematite sorption.
The Kyrghyz Republic, located in the southeastern region of the former Soviet Union, maintains a population of more than one-half-million persons and is heavily dependent on Lake Issyk-Kyol, both to draw tourists to the area and for its utilization by some as a food and recreation source. Historical surveys, conducted primarily for geological exploration, have indicated that localized areas of shoreline on Lake Issyk-Kyol have relative radiation levels in excess of ambient background by as much as a factor often. Uranium mining operations in the mountains bordering the lake to the south may have resulted in the contamination of a number of areas on the lake's southern shore. Concentrations of naturally occurring uranium, thorium, and potassium are present in these soils in elevated quantities. This paper presents the results of an investigation of soil concentrations along the shoreline of Lake Issyk-Kyol relative to previously discovered areas of high exposure rate.
Samples of tree bark were collected from four locations in Northern England (a typical rural site, a coal-fired power station, a uranium (isotopic) enrichment plant and a nuclear fuel fabrication facility), to assess the nature and extent of airborne uranium and thorium contamination. The U and Th concentrations of bark were determined by inductively coupled plasma mass spectrometry after conventional nebulisation of bark digests, whilst measurement of 235U/238U isotopic ratio utilised high efficiency nebulisation. Uranium concentrations varied between and within the sites (range, 0.01-12 micrograms g-1), with maximum values recorded within 1 km of the nuclear fuel fabrication plant (Springfields). In comparison, the concentration of Th in bark was low (mean, 0.018 microgram g-1) at all sites with the exception of the area affected by coal combustion (0.2-0.8 microgram g-1). The U/Th ratio varied from 0.5 to 3900 compared with the average crustal ratio of 0.3. Low values (< 2) were recorded at the 'coal' and 'rural' sites whilst Capenhurst and Springfields showed high values indicating the relative magnitude of uranium elevation. Significant enrichment of the natural 235U/238U ratio (0.00725) was observed near the nuclear installations, in particular, the enrichment plant (Capenhurst).
The high-yield synthesis, spectroscopic and structural determination of three new uranium(IV) and thorium(IV)ate complexes supported by three different diamido ether ligands are reported. The reaction of Li2[2,6-iPr2PhN(CH2CH2)]2O (Li2[DIPPNCOCN]) with 1 equiv. of UCl4 in THF generates [DIPPNCOCN]UCl3Li(THF)2(1), while reaction in toluene/ether gives salt-free [DIPPNCOCN]UCl2.1/2C7H8(2), which was identified by paramagnetically shifted 1H NMR. Reaction of 0.5 equiv. of {[tBuNON]UCl2}2([tBuNON]=[(CH3)3CN(Si(CH3)2)]2O2-) with 3.5 equiv. LiI in toluene and a minimal amount of THF results in [tBuNON]UI3Li(THF)2(3) and is very similar in structure to 1. {[MesNON]ThCl3Li(THF)}2(4), a dimeric complex with a Th2Li2Cl6 core, is prepared by reaction of Li2[2,4,6-Me3PhN(Si(CH3)2)]2O (Li2[MesNON]) with ThCl4 in THF. The analogous reaction in toluene did not yield the salt-free complex but rather a sterically crowded diligated compound, [MesNON]2Th (5), which was also structurally characterized. Complex 5 was prepared rationally by reacting 2 equiv. Li2[MesNON] with ThCl4 in toluene. The reaction of 1 and 3 with 2 equiv. of LiCH2Si(CH3)3 generates the stable, salt-free organoactinides [DIPPNCOCN]U(CH2Si(CH3)3)2(6) and [tBuNON]U(CH2Si(CH3)3)2(7). Complex 6 was structurally characterized. These reactions illustrate the viability of ate complexes as useful synthetic precursors.
Mast cells from the peritoneal cavity of the rat were obtained at various times following in situ injection of a colloidal thorium dioxide preparation (Thorotrast). They were prepared for electron microscopy by aldehyde fixation, osmium tetroxide postfixation, and embedding in Epon. Thorotrast was rapidly taken up by mast cells through enhanced or newly elicited surface specializations. It was confined at first to large vesicles which moved to the Golgi area. Subsequently, in a matter of a few hours only, it became associated with progressively more mature granules, including "fully" mature ones. In addition to demonstrating a further phagocytic or pinocytotic activity of mast cells, the findings suggest that mast cell granules share a common membranous investment, and that substances from the tissue environment may theoretically percolate over and interact with the granules. Mast cell function could thus be served primarily by absorptive rather than secretory processes.
The aim of this work was to investigate the biokinetics of thorium dioxide in animals for the purpose of assessing intakes of the compound by workers and the resulting doses. The results imply that measurements of the decay products in the chest or extrapolations from urine analysis data are unlikely to be of value for doses below 20 mSv. Even higher doses should be interpreted with caution as a consequence of uncertainties in particle size distribution and variations in dietary excretion.
A Series of comparisons were conducted to test the capabilities of a range of metrological techniques and analytical laboratories engaged in the assay of thorium in the workplace. The results of these exercises are presented together with the decision criteria used to determine whether results are significantly different from the true value. The discussion highlights those aspects which warrant closer and further attention.
Following the use of in vivo measurements of 210Pb to estimate retrospectively radon exposure, interest has been expressed in the use of in vivo measurements of 208Tl to estimate thorium intake. To aid with calibration and to determine the optimum part of the body on which in vivo measurements should be made, the distribution of 208Tl and 228Ac amongst different human bones was measured in the underground laboratory HADES. The 208Tl activity was determined by the 2614.5 keV and the 583.2 keV gamma ray lines. The 225Ac activity was determined by the 911.2 keV and the 969.0 keV gamma ray lines. The background under those peaks when measured on the 106% relative efficiency coaxial HPGe detector in HADES is of the order of 1 d(-1), resulting in detection limits in the order of 1 mBq for both radionuclides for a typical 10 g bone sample and for a measuring time of I week.
An overview is given of the models recommended by the International Commission on Radiological Protection (ICRP) for assessing intakes and doses, and summarises biokinetic data obtained after the deposition of different chemical compounds of thorium in the rat lung. The results emphasise the importance of using material-specific data rather than default reference values for absorption into blood. The limitations of external monitoring of the chest or urine analysis are discussed, and comments made on alternative strategies for radiological protection of the worker.
Data on the daily urinary excretion of thorium (Th) was obtained from 15 non-exposed adult German subjects. A radiochemical neutron activation analysis method was developed and standardised especially for this purpose. The daily urinary excretion of 232Th was found to be in the range 1.9-14.9 microBq d(-1) with a mean (+/-SD) value of 6.5 (+/-4.3) microBq d(-1). Using this excretion value and reported data on dietary intake of Th for a similar German population, the gastrointestinal absorption factor (f1 value) proposed by the International Commission on Radiological Protection (ICRP) was tested. Although the daily excretion of 232Th observed in the present study was comparable to some of the currently reported values in certain other countries, it was higher than the excretion value calculated by applying the biokinetic model of Th proposed by ICRP for the dietary intake values. The study showed that the default ICRP values of the f1 factor for diet-incorporated Th may not be applicable.
The concentrations of natural alpha-emitting isotopes of thorium (228Th, 230Th and 232Th) have been determined in 22 sets of human tissue samples obtained at autopsy from Grand Junction, CO and in 10 sets from Washington, DC. Tissues included lung, pulmonary lymph nodes, liver, kidney, bone, a few gonads, spleen and thyroid. Personal data on each individual's age, sex, smoking history and occupation were obtained whenever possible. The concentrations of 228Th, 230Th and 232Th were highest in lymph nodes for both populations with 2.6 and 5.1 pCi/kg of 228Th, 4.60 and 11.10 pCi/kg of 230Th, and 2.8 and 7.8 pCi/kg of 232Th in Washington, DC and Grand Junction, CO, respectively. The order of concentrations of all three isotopes in all other organs for both populations was as follows: (formula; see text) The data suggest that the non-mining residents who lived in the vicinity of uranium mine tailings do not have elevated 230Th concentrations in their lungs, when compared to the residents of Washington, DC who are not exposed to such tailings. However, 230Th concentration in bone of Grand Junction subjects was just significantly higher (at p less than 0.1) than that for Washington, DC subjects after suitable age adjustments. The data also suggest that 230Th is more available for accumulation in skeleton than would be supposed from its relative geochemical abundance.
Theoretical calculations are presented for partially enclosed uranium- and thorium-bearing subterranean environments, such as tunnels and underground uranium mines. The variables of practical interest considered here are the 222Rn and 220Rn concentrations in the wall, and the flux densities of the same radioactive gases in the wall and at the wall/air interface of these underground sites. Calculations have been conducted based on a plane, semi-infinite geometry model (commonly used to predict radiation levels in mines) and a cylindrical (i.e., tunnel) geometry model. The 220Rn flux density, J(220Rn), calculated according to the plane and cylindrical geometries agree with each other within 5% for wall media of porosity equal to or greater than about 2%, even for tunnels of small radii. However, for 222Rn the cylindrical geometry gives values for the 222Rn flux density, J(222Rn), substantially higher (by a factor of 1.4 to approximately 3) than those predicted by the plane semi-infinite geometry. A practical difficulty arises in the experimental verification of the models in underground environments. The results are relevant for predicting radioactivity levels (222Rn, 220Rn, and their progeny) in underground environments such as uranium mines. Health Phys.
A general method for solving first-order compartmental models (recycling and nonrecycling) with any number of radioactive progeny is described and a heuristic proof of the method is provided. The method can be applied to any system where the progeny are assumed to behave isokinetically with the parent, as is the case with the biokinetic models currently recommended by the ICRP. The method is simple to apply, and its application to the modeling of radioactive progeny in the lungs following inhalation of thorium oxides is illustrated. The new ICRP respiratory tract model is used for this illustration.
Thoriated electrodes are used in TIG welding. TIG welders, along with persons who grind thoriated electrodes and persons located near relevant welding and grinding sites, might be at risk of thorium intake. The isotopes of radiological relevance are 232Th, 230Th, and 228Th. The studies described in the literature do not provide a consistent picture of the actual hazards, and changes in European and German radiological protection laws have now made it necessary to determine the risks. To accomplish this, a field test was conducted under real working conditions in 26 different welding shops. The airborne activity generated through welding, and through grinding of electrodes, was measured using personal air samplers. Stationary samplers were also used. The filters' samples were evaluated by means of direct alpha spectrometry with proportional counting and by means of gamma spectrometry following neutron activation. The results clearly showed that considerable intake can occur during both alternating-current welding and electrode grinding, if no suction systems are used. The range of 232Th intakes to welders were estimated from 0.1 Bq y(-1) to 144 Bq y(-1) during welding and from 0.02 Bq y(-1) to 30.2 Bq y(-1) during grinding. In 6 of the 26 cases the recent annual limit on intake derived from the most recent ICRP publications was exceeded--in the worst case it was exceeded by a factor of 10--if it is assumed that the persons studied were not exposed workers (not routinely monitored for radiation exposure). When the significantly more restrictive German limits are applied, the amounts by which the limits were exceeded were even greater. Because many qualified welders have very long careers, the risks can thus be considerable. The paper also discusses parameters that influence exposure, and it presents a catalogue of recommended measures for dosage reduction.
A 74-year-old man complained of anorexia and weight loss. Twenty-six years earlier he had received an injection of Thorotrast. A needle biopsy of the liver showed thorium dioxide granules and periportal fibrosis. On laparotomy, a hepatoma of the left lobe of the liver was discovered. Hepatic malignancy should be suspected in any patient with abnormal results of liver function tests, particularly an elevated level of alkaline phosphatase, who previously has had an injection of Thorotrast.
Patients who have received thorium dioxide (Thorotrast) are at risk for hepatic and other malignancies. Because of the need to identify and carefully follow up these patients, we have presented three cases with the characteristic radiologic findings on plain films so that physicians unfamiliar with this appearance will now be aware of it.