Proton-induced prompt gamma-ray emission for determination of light elements in human bone

Proton-induced prompt gamma-ray emission (PIGE) analysis has been used for the determination of light elements in human dense bone samples. Li, B, N, O, F, Na, Mg, Al, P and Ca peaks were detected. Smoothed, freeze-dried samples were irradiated in vacuo by 2.4 MeV protons and the induced prompt gamma rays recorded with a 110 cm³ Ge(Li) detector. Absolute concentrations were calculated on the basis of both calibration standards and pure element gamma-ray yields. The mean (±1 S. D.) concentrations as ppm or weight % obtained for 15 dense bone samples were: B 8.0 (3.3)ppm, N 12.2 (0.8)%, O 34.8 (2.3)%, F 639 (417)ppm, Na 5763 (371)ppm, Mg 2078 (290)ppm, P 9.26 (0.50)% and Ca 20.4 (1.3)%. The detection limits obtained without any prior concentration of the bone samples were: 0.3 ppm for Li, 2.0 ppm for B, 1.0% for N, 1.0% for O, 1.0 ppm for F, 3.0 ppm for Na, 50 ppm for Mg, 22 ppm for Al, 600 ppm for P and 0.8% for Ca. Detection limits for other light elements (4≤Z≤21) have also been estimated.     

Sulfur determination in coal by 14 MeV neutron activation analysis

A procedure involving the irradiation of coal samples with 14 MeV neutrons and subsequent gamma-ray spectrometry of the irradiated sample for the estimation of solfur in coal, has been outlined. The samples were irradiated with 14MeV neutrons from a Cockroft-Walton type generator for one minute and then subjected to gamma-ray spectrometry for another minute using an automated transfer cyclic system. Ten such cycles were repeated for accumulating events under the 2130 keV gamma ray photopeak belonging to³⁴P (T=12.4 s) produced by the³⁴S(n, p)³⁴P reaction for assessing the lower level of detection, LLD, of Sulfur. Interferences due to the presence of other elements in coal were also determined. Sulfur can be determined at LLD of 0.25% in coal provided a 5 g sample of the coal is irradiated with a neutron flux of 5·10⁹ n·cm⁻²·sec⁻¹ assayed with a gamma ray spectrometer having a large hollow core Ge(Li) detector and an anti-Compton shield.     

Ultrahigh energy resolution gamma-ray spectrometers for precision measurements of uranium enrichment

Superconducting gamma-ray detectors offer an order of magnitude higher energy resolution than conventional high-purity germanium detectors. This can significantly increase the precision of non-destructive isotope analysis for nuclear samples where line overlap affects the errors of the measurement. We have developed gamma-detectors based on superconducting molybdenum-copper sensors and bulk tin absorbers for nuclear science and national security applications. They have, depending on design, an energy resolution between ∼50 and ∼150 eV FWHM at ∼100 keV. Here, we apply this detector technology to the measurement of uranium isotope ratios, and discuss the trade-offs between energy resolution and quantum efficiency involved in detector design.     

Trace element study of human bone by X-ray emission analysis using an external proton beam

A simple proton beam (PIXE) arrangement developed for a low energy accelerator was used for the determination of absolute concentrations of nine trace elements in human bone samples. The 2.4 MeV proton beam was externalized through a thin (2 μm) aluminiummylar foil. Using an air cooling system, the foil withstood a high current (0.5–1 μA) for a long time. The samples were cooled to prevent damage and volatilization of elements. The induced X-rays were detected with a Si(Li) detector and the external beam was monitored with a second detector, measuring K X-rays induced in atmospheric argon. The mean (SD) trace element levels (ppm) measured in dense bone by comparison with hydroxyapatite/standard mixtures were: Cr<2.0, Mn<2.3, Fe 7.58 (1.55), Ni<2.4, Cu 3.58 (2.16), Zn 144 (27), Pb 12.2 (2.5), Br 12.4 (5.5) and Sr 47.7 (14.3). The detection limits for these elements achieved in this work were about 1 ppm when rather short measuring times (∼10 min) were used. The coefficient of variation of a single measurement, e.g. for Zn, was 3–4%. Because of the slow turnover of dense bone, such measurements provide a means of monitoring long term trace element exposure.     

Determination of bromine and iodine in biological and environmental materials using epithermal neutron activation analysis

Epithermal neutron activation analysis (ENAA) was applied to the determination of the contents of bromine and iodine in 40 biological and environmental standard reference materials and Chinese diets. Boron nitride (BN) for solid samples and BN+Cd for liquid samples were adopted as shield material. Irradiation was carried out in inner and outer irradiation sites in a Miniature Source Reactor (MNSR) for solid and liquid samples, respectively. The 443 keV photopeak of ¹²⁸I and the 616 keV photopeak of ⁸⁰Br were used. The precision of measurement (relative standard deviation) is 2∼6% for contents of iodine of more than 100 ng/g and 8∼12% in the 20∼100 ng/g range in solid samples, and 12∼18% at less than 100 ng/ml in liquid samples. For bromine, the precision of measurement is 2–8% for solid samples and lower than 13% for liquid samples. The detection limits under experimental conditions varied between 10∼30 ng/g, 55∼95 ng/g and 25∼68 ng/g for iodine and 50∼150 ng/g, 200∼450 ng/g and 100∼300 ng/g for bromine in ENAA with BN shield in inner irradiation sites, with Cd shield and BN+Cd shield in outer irradiation sites, respectively. Received: 13 June 1996 / Revised: 2 September 1996 / Accepted: 19 September 1996     

Analytical use of neutron-capture gamma-rays

Certain elements which are not possible to detect with conventional neutron activation analysis can be measured using thermal neutron-capture gamma-ray analysis. The use of a curved neutron guide at the High Flux Reactor, Grenoble, with a thermal neutron flux of 1.5·10¹⁰n·cm⁻²·sec⁻¹ and the advantage of a low-background counting system (Ge(Li) detector) far from the reactor core are described. Experimental detection limits of a number of elements are given for the low-energy and the high-energy regions. Some applications of the capture gamma-ray method in the whole energy range are studied and are briefly discussed.     

Measurement of the ash content of iron-rich coals by gamma-ray irradiation

Ash contents of some coal samples from Enugu mines in Nigeria were measured using gamma-ray irradiation technique. The method employed gamma-ray energies of 0.060, 0.662 and 1.33 MeV of²⁴¹Am,¹³⁷Cs and⁶⁰Co, respectively, and a counting system with a scintillation detector, to obtain empirical relationships between the conventionally determined ash content and the measured gamma-attenuation coefficient in the sample. The sensitivity of the method was observed to decrease drastically with increase in ash content above 35% ash, and with increase in energy of the gamma-ray. Further analyses showed that the error in the ash content determination was due to iron content which was not constant, but increased with ash content, with vidth variation above a mean value of ±0.64% Fe₂O₃.     

Analysis of glass by simultaneous spectrometry of scattered alpha particles and prompt protons

The energy spectrum of alpha particles scattered from a beam of 4 MeV was used to determine heavy elements and oxygen and silicon in glass. Simultaneously, but with a separate detector, the energy spectrum of prompt protons from (α, p) reactions were used to determine boron, sodium and aluminium. Both detectors were placed at 135° to the direction of the beam, but the proton detector was covered with an absorber to stop backscattered alpha particles, Glass samples analysed by other methods and standard glass powders from the U. S. Bureau of Standards were used as references.     

Radioactivity levels of <Superscript>238</Superscript>U and <Superscript>232</Superscript>Th,the α and β activities and associated dose rates from surface soil in Ulu Tiram,Malaysia

A survey was carried out to determine terrestrial gammaradiation dose rates, the concentration level of ²³⁸U and ²³²Th and α and β activities for the surface soil in Ulu Tiram, Malaysia A 125 measurements were performed using a NaI(T1) gamma-ray detector with crystal size of 1″ × 1″ on 15 soil samples collected from the site area about 102 km^{2 238}U and ²³²Th concentrations were determined in soils by using hyper pure germanium (HPGe) gamma-ray spectrometry. The activity of α and β from the surface soil was counted by using alpha beta counting system. The average value of ²³⁸U and ²³²Th concentrations in soil samples collected are 3.63±0.39 ppm within the range of 1.74±0.20 to 4.58±0.48 and 43.00±2.31 ppm within the range of 10.68±0.76 to 82 10±4.01 ppm, respectively. The average estimate of α and β activity in soil samples collected are 0.65±0.09 Bqg⁻¹ and 0.68±0.08 Bqg⁻¹, respectively. The average of terrestrial gamma-radiation dose rates measured in Ulu Tiram was found to be 200 nGy h⁻¹, within the range of 96 to 409 nGy h⁻¹. The population weighted outdoor annual effective dose was 1.2 mSv.     

Development of a process for routine production of123I using the127I(p, 5n)123Xe→123I reaction

The object of this paper is to give details of a production method for¹²³I, now in routine use at Harwell. We employ the (p, 5n) reaction, irradiating a liquid target of di-iodomethane (CH₂I₂) spiked with additional iodine, with 58 MeV protons. A yield of ∼9 mCi/μAh is obtained; the only detectable radionuclidic impurity is¹²⁵I, present to the extent of ∼0.15% by activity at the time of separation of Xe from I.     

Towards routine NAA of materials rich in heavy elements with iterative gamma-ray attenuation and neutron self-shielding calculations

Solids and powders can be analysed directly and with good accuracy by neutron activation analysis without sample preparation because of the excellent penetrating powers of neutrons and gamma rays. However, if the sample contains high concentrations of gamma-absorbing heavy elements or neutron-absorbing elements, the analysis results must be corrected for neutron self-shielding and gamma-ray attenuation. These effects are coupled and depend on the chemical composition of the sample, which is the final result of the analysis. Thus, the correction calculation must be iterative. In this work we performed the first coupled iterative corrections of the two effects. Six test samples were prepared by mixing powders containing compounds of Cd, a neutron absorber, and the rare-earth elements Ce, Pr and Nd with concentrations as high as 47 %. The samples were irradiated in the SLOWPOKE research reactor and counted with a germanium gamma-ray detector. In the samples with the highest heavy element concentrations, the uncorrected Neutron activation analysis results were in error by as much as 55 %. The results were corrected iteratively using the neutron self-shielding model coupled with the gamma-ray attenuation model, and the final corrected results were accurate to 5 % or better.     

High resolution prompt (n,γ) spectroscopy using a down hole logging tool

A down-hole logging tool is described utilising a 5 Ci²⁴¹Am–Be neutron source and intrinsic germanium gamma-ray detector. The tool was used to measure the prompt gamma-ray response from the irradiation of 4 well characterised coal samples. The correlation between the count-rate into the 2380 keV line arising from sulphur and the sulphur concentration as determined by chemical analysis is described. A depression in the count rate into the sulphur peak of interest is modelled using the neutron transport code ANISN and compares well with measurement. The influence of borehole diameter and the presence of borehole fluid upon logging performance is assessed.     

Direct determination of parts-per-billion levels of germanium in botanical samples and coal fly ash by graphite furnace atomic absorption spectrometry

 Parts-per-billion levels of germanium can be determined directly by graphite furnace atomic absorption spectrometry (GFAAS) using palladium plus strontium as a mixed modifier resulting in pyrolysis temperatures up to 1400 °C without loss of germanium. At this temperature the matrix effect including the most troublesome sulfate interference can be eliminated. Palladium plus strontium nitrate is advantageous compared to palladium alone or palladium plus magnesium nitrate; an amount of 15 μg of sulfate does not show any interference on the determination of 1 ng of germanium. The method was successfully applied to the determination of ng/g levels of germanium in botanical samples and coal fly ash after thermal decomposition of the samples in a mixture of acids using a pressure bomb. The results were consistent with the reference values given for botanical samples and coal fly ash with a recovery range of 96.4∼103.4% Received: 16 September 1996/Revised: 10 December 1996/Accepted: 14 January 1997     

Growth of hair and the trace element profile a study by sectional analysis

Correlations between the growth of hair and the trace element profile have been investigated by non-destructive neuron activation analysis through gamma-ray speetrometry using NaI(Tl) as well as Ge(Li) detectors. After preliminary investigations to establish the experimental errors, the effect of washing procedures and in-person variations, hair samples belonging to ladies with known case histories, particularly with regard to dietary habits, health and profession, were examined. Scalp-hair samplex 50–100 cm in length, representing an average time span of ∼5–10 years were collected by combing. Samples in their non-anagen phase, differentiated by their roots, were analysed in 10 cm sections. The concentrations of the following elements were determined: Na, Cl, Mn, Co, Cu, Zn, As, Se, Ag, I, Au and Hg. Absolute values for the concentrations are reported for most of the elements, while for the rest relative values for the various sections are given. The values for the different sections vary by large factors for many elements although for some elements, like Cu and Mn, the variations are not appreciable. The unusually large concentrations of elements like Se ang Hg are in broad agreement with the case histories. However, detailed examination of the results with regard to time-dependent variations seem to pose serious problems in the applications to forensic science.     

COHN analysis: Body composition measurements based on the associated particle imaging and prompt-gamma neutron activation analysis techniques

The measurement of the body’s carbon (C), oxygen (O), hydrogen (H), and nitrogen (N) content can be used to calculate the relative amounts of fat, protein, and water. A system based on prompt-gamma neutron activation analysis (PGNAA), coupled with the associated particle imaging (API) technique, is being developed for this purpose. A compact D, T neutron generator (∼10⁷ n/s output) with an internal alpha-particle detector is used. The counting system consists of 6 shielded bismuth germanate (BGO) detectors (10.2 cm × 10.2 cm × 10.2 cm) operated with fast-timing electronics to detect only gamma-rays within a 100 ns time window following a trigger pulse generated by the alpha detector. The body can be scanned from the shoulders to the knees within about 30 min, with the equivalent whole-body dose <0.4 mSv. The cumulative gamma-ray spectra in the 2 MeV to 8 MeV region is collected and analyzed for multiple peaks attributed to body C,O,H, and N. Measurement precision for each element, based on tissue-equivalent phantoms, are in the 2–5% range, which are sufficient for population studies in adults. Further improvements are needed to extend the measurements to pediatric clinical research studies.     

Determination of the hydrogen concentration in coal and titanium alloy by prompt gamma neutron activation analysis

The determination of the hydrogen concentrations in coal and metal samples were investigated by using the PGAA system at the HANARO Research Reactor, KAERI. The calibration curve of the hydrogen concentration was obtained from a standard sample and the effects of the interference peaks near the gamma-energy region of hydrogen were investigated. The background in the hydrogen peak of a prompt gamma-ray spectrum was measured for the sample chamber and shielding materials of an atmospheric state. The combined uncertainties estimated for the analysis procedure were in the range of 4–5%. Two kinds of certified reference materials, NIST SRM 1632c (Coal), NIST SRM 173c (Titaniumbase Alloy) and NIST SRM 2453 (Titanium Alloy) were used to verify the accuracy and precision of the measurement. The relative error was in the range of 3–6% and the relative standard deviation were less than 4%.     

Prompt Gamma Neutron Activation Analysis of 316-L Stainless Steel

Prompt gamma-rays from thermal neutron capture reaction have been used to measure the concentrations of the main constituents namely Fe, Ni and Cr in 316-L stainless steel using recently established prompt gamma neutron activation analysis (PGNAA) facility at Pakistan Institute of Nuclear Science and Technology (PINSTECH). High resolution, high purity germanium detector with 40% relative efficiency was employed for the gamma-ray spectroscopy of the samples. The interference-free full energy gamma-ray peaks of the elements of interests were selected in the high energy low background region (5.0–9.0 MeV). The efficiency calibration of the detector was performed using ultra pure standards of chromium and chlorine obtained respectively from Merck and Alpha Inorganics. This paper describes, in addition, the salient features as well as the background of establishing PGNAA facility at the Institute.     

The use of an activation detector in the determination of beryllium by photon activation

The determination of traces of beryllium in large samples by the (γ, n) reaction, using a¹²⁴Sb gamma-source, is in general hampered by the rather high handling costs when a BF₃ counter is used for the neutron detection. When manganese dioxide is used as an activation detector, the analysis is possible with a simple facility which can be stored in a water basin. The lower limit of the determination is ∼ 1 μg/g for a sample weight of 50 g.     

Development of an accurate,sensitive, and robust isotope dilution laser ablation ICP-MS method for simultaneous multi-element analysis (chlorine,sulfur, and heavy metals) in coal samples

A method for the direct multi-element determination of Cl, S, Hg, Pb, Cd, U, Br, Cr, Cu, Fe, and Zn in powdered coal samples has been developed by applying inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with laser-assisted introduction into the plasma. A sector-field ICP-MS with a mass resolution of 4,000 and a high-ablation rate laser ablation system provided significantly better sensitivity, detection limits, and accuracy compared to a conventional laser ablation system coupled with a quadrupole ICP-MS. The sensitivity ranges from about 590 cps for ³⁵Cl⁺ to more than 6 × 10⁵ cps for ²³⁸U⁺ for 1 μg of trace element per gram of coal sample. Detection limits vary from 450 ng g⁻¹ for chlorine and 18 ng g⁻¹ for sulfur to 9.5 pg g⁻¹ for mercury and 0.3 pg g⁻¹ for uranium. Analyses of minor and trace elements in four certified reference materials (BCR-180 Gas Coal, BCR-331 Steam Coal, SRM 1632c Trace Elements in Coal, SRM 1635 Trace Elements in Coal) yielded good agreement of usually not more than 5% deviation from the certified values and precisions of less than 10% relative standard deviation for most elements. Higher relative standard deviations were found for particular elements such as Hg and Cd caused by inhomogeneities due to associations of these elements within micro-inclusions in coal which was demonstrated for Hg in SRM 1635, SRM 1632c, and another standard reference material (SRM 2682b, Sulfur and Mercury in Coal). The developed LA-ICP-IDMS method with its simple sample pretreatment opens the possibility for accurate, fast, and highly sensitive determinations of environmentally critical contaminants in coal as well as of trace impurities in similar sample materials like graphite powder and activated charcoal on a routine basis. Figure LA-ICP-IDMS allows direct multi-element determination in powdered coal samples     

Determination of total fluorine in five coal reference materials by proton-induced gamma-ray emission spectrometry

The direct non-destructive proton-induced gamma-ray emission (PIGE) technique with a germanium detector was applied to the determination of total fluorine concentration in five coal reference materials (BCR 40, NIST 1632b, NIST 1635, SARM 20 and USGS CLB-1). Duplicate analyses were made from five randomly selected bottles of each coal. Individual data are presented and some problems (calibration, proton stopping power, effects of sample heating by the proton beam, background estimation) which were encountered during this study are discussed. Sensitivity and reproducibility of the determinations, and homogeneity of the coal samples with respect to fluorine contents by analysis of variance were investigated. The present data are also compared with the few published values for these reference samples, including other PIGE data. The use of synthetic standards and spiked samples in the present study suggested that the PIGE method was more accurate than other techniques.