Determination of 22 elements in geological samples by instrumental neutron activation analysis

An instrumental neutron activation analysis (INAA) method has been developed for multi-element determination in geological samples. The INAA method consists of irradiation of samples for 90 sec at a flux of 1.0·10¹² n·cm⁻²·sec⁻¹ and determination of 12 elements by using their short-lived nuclides. Samples have been re-irradiated for 3 hrs for measuring concentrations of another 10 elements. Precision and accuracy of the INAA method have been evaluated by analysing samples and USGS standard reference materials. Precision and accuracy are within±15% and ±10%, respectively.     

Instrumental neutron activation analysis of monomineral fractions of sulfide minerals and quartzes

A method has been worked out of multi-elemental instrumental neutron-activation analysis INAA of small weights some mg of monomineral fractions of sulfide minerals pyrites, galenites, chalcopyrites, arsenopyrites, bornites, chalcosines and quartzes. The samples were irradiated in a nuclear reactor under a flux of 1.3·10¹³ n·cm⁻²·s⁻¹. For measuring the gamma radiation of the exposed samples Ge(Li) gamma-spectrometers with semiconductor detectors were used. Determined in sulfide monofractions were the elements: Co, Sc, Ag, Se, Sb, Cr, Fe, Zr; rare-earth elements: Ce, Sm, Eu and others at content levels of 10⁻¹−10⁻⁴%. In quartzes they were: Mn, Na, Sb, Cr, Sc, Fe, Co at content levels of 10⁻⁵−10⁻⁷% and Au to n×10⁻⁹%. A special method has been worked out for the determination of In in sulfides with the irradiation of samples in a cadmium screen. An example is cited of using the method for studying some peculiar features of the genetics of copper pyrite deposits. The data on the distribution of admixture elements in sulfide monofractions produced in this work made it possible to conclude that the oreformation in the deposits has a stage-by-stage character.     

Rare-earth elemental analysis of banded iron-formations by instrumental neutron activation analysis

Representative banded iron-formations (BIFs) from various locations of the eastern Indian geological belt were investigated by instrumental neutron activation analysis (INAA). After pre-concentration, irradiation was carried out using a neutron flux of 5.1·10¹⁶ m⁻²·s⁻¹, 1.0·10¹⁵ m⁻²·s⁻¹ and 3.7·10¹⁵ m⁻²s⁻¹, with thermal, epi-thermal and fast neutrons, respectively. The activities in these samples were measured by a HPGe detector. Ten rare-earth elements, such as La, Ce, Nd, Sm, Eu, Tb, Ho, Tm, Yb and Lu, have been qualitatively identified and quantitatively estimated in these samples. The present investigation is an example of employing a pre-concentration method for high iron-containing ores prior to neutron activation analysis.     

Determination of chlorine distribution in silicon dioxide by neutron activation

A neutron activation method for the determination of chlorine distribution in silicon dioxide on the surface of Si wafers has been developed. After irradiation of the sample with a standard, successive layers are removed from the oxide surface by chemical etching and the chlorine content in the solutions obtained is determined gamma-spectrometrically. Using a Ge(Li) detector, a lower limit of determination of 1.0·10⁻⁷ g was obtained. This limit can be improved by using a NaI(Tl) detector. The error of chlorine determination is discussed.     

Determination of lithium by instrumental neutron activation analysis

The fast transfer system in the DR 2 reactor for irradiation at a thermal neutron flux density of 10¹³ n·cm⁻²·sec⁻¹ was used for the determination of lithium by the⁷Li(n, γ)⁸Li reaction. β-counting with a large perspex Cerenkov detector begun at 0.3 s after the end of irradiation, and multi-scaler data was accumulated in 300 channels at 0.1 s per channel. With a suitable choice of discrimination level only¹⁶N and background interfere, and the 0.84 s half-life of⁸Li was resolved by the method of weighted least squares. Results are presented for 36 international geochemical reference materials, and for a few biological samples, including BOWEN's kale and the NBS Standard Reference Material 1571 Orchard Leaves.     

Halogen speciation in the rat thyroid: Simultaneous determination of bromine and iodine by short-term INAA

The study describes a mode of non-destructive simultaneous determination of bromine and iodine concentrations, by reactor instrumental neutron activation analysis (INAA) in the regime of short-term activation. Under the conditions of 1-minute activation in the neutron flux of 8.0·10¹³ n·cm⁻²·s⁻¹, it was possible to determine reliably as little as 5·10⁻⁸ g bromine and about 10⁻⁷ g iodine in matrices of a given type and of the mass of about 5 mg dry weight. We applied this method for the determination of Br and I concentrations in the whole rat thyroid gland as well as for the halogen speciation in fractions separated from this organ.     

Characterization and use of the new NIST rapid pneumatic tube irradiation facility

Recently a new rapid pneumatic tube facility was inserted into a long unused location in the NIST 20 MW nuclear reactor. This facility was designed and constructed specifically for rapid INAA using short lived activation products. Included is a computer controlled console which uses fast sensors to accurately measure the irradiation capsule flight time, and a loss-free counting system connected to a 32% efficient PHGe detector with a transistor reset preamplifier. Measurement of travel, times from end-of-irradiation to detector were 473±8 ms. Measurement of the thermal neutron fluence rate was 5.0·10¹³ n·cm⁻²·s⁻¹. The other three pneumatic tubes in the NIST reactor have transfer times of 3 to 15 seconds, and no timing capability more accurate than human response. This new facility substantially improves our ability to accurately determine activation products with half-lives from 1 to 100 seconds. Characterization information reported on this new irradiation facility includes absolute fluence measurements, fluence rate variations within the capsule and variations with time, and determination of analytical sensitivities for fluorine-20 selenium-77m, and silver-110g.     

Characterization of Brazilian commercial milks by instrumental neutron activation analysis

Aiming at the determination of toxic and essential elements in Brazilian commercial bovine milk, 25 ultra high temperature (UHT) milk samples were acquired in the local market of Piracicaba, SP. The samples were freeze-dried and analyzed by instrumental neutron activation analysis (INAA) allowing the determination of Br, Ca, Co, Cs, Fe, K, Na, Rb and Zn. When the results were expressed as concentration (mg·l⁻¹) no significant differences were found. However, considering the dry matter, results showed a clear difference between the mass fractions (mg·kg⁻¹ d.w.) of skim milk and whole milk for the elements Br, Ca, K, Na, Rb and Zn, indicating that the removal of fat caused a concentration effect in the dry matter of skim milks. Discrepancies were found between the concentrations of Ca and Na measured by INAA and the values informed in the labels. Ca showed variations within 30% for most samples, while concentrations of Na were up to 190% higher than informed values. The sample preparation and the INAA procedure were appropriate for the determination of Br, Ca, Co, Cs, Fe, K, Na, Rb and Zn in milk samples.     

Determination of trace elements in high purity copper by INAA, GFAAS and ICP/AES

Trace impurity elements in high purity copper metal (4 mine class) put on the market were analyzed by Instrumental Neutron Activation Analysis (INAA) and the results compared with those from Graphite Furnace Atomic Absorption Spectrophotometry (GFAAS) and Inductively Coupled Plasma Atomic Emission Spectrophotometry (ICP-AES). The sample irradiation was done at the irradiation facilities (thermal neutron flux, 5·10¹² n·cm⁻²·s⁻¹) of the TRIGA Mark-III research reactor in the Korea Atomic Energy Research Institute. Four unalloyed copper standards (NIST SRM # 393, 394, 395 and 398) were used to identify the accuracy and precision of the analytical procedure. The homogeneity of samples was assessed by means of the elements such as Ag, As, Co, Sb, Se and Zn. The analytical results of INAA, GFAAS and ICP-AES were in good agreement within expected uncertainties each other and showed the possibility of using them for the analytical quality control.     

Determination of certain elements in human serum albumin by neutron activation analysis

Instrumental activation analysis was used to determine the contents of certain elements in human serum albumin (HSA). Sample irradiation was performed with a thermal neutron flux of 1.5·10¹³ n·cm⁻²·sec⁻¹ in the RA nuclear reactor of the Boris Kidrič Institute, Vinča. Measurements were performed on a 4096-channel analyser with a high-resolution Ge(Li) detector. The Na, Cu, Br, Au, Hg, Cr, Fe, Ag, Sc, Ba and Co contents were determined in HSA produced by the Institute for Blood Transfusion, Belgrade.     

Detection limits of Au using fast and thermal neutron activation analyses

The applicability of fast and thermal neutron activation analyses for the determination of gold in rock samples has been studied. Using a Ge/Li/ detector limit of 0.45 mg g⁻¹ was obtained for a fast neutron flux of 8.10⁷ n cm⁻².s⁻¹. With a thermal neutron flux of 6.10⁵ n cm⁻².s⁻¹ and the same detector a value of 35 μg g⁻¹ was obtained. Using a NaI/Tl/ crystal a sensitivity of 14 μg g⁻¹ was attained at the same thermal flux. This work was supported in part by the Hungarian Academy of Sciences.     

Aktivierungsanalytische Bestimmung von Nickel in Ionenaustauschern

A method for the determination of nickel in ion exchange resins has been elaborated. It is based on the⁵⁸Ni(n, p)⁵⁸Co reaction. Samples of 500 mg are irradiated for 90 h in a fission neutron flux of 10¹³ n·cm⁻²·s⁻¹. After decomposing by HNO₃/HClO₄ mixture the radiochemical separation is carried out by extraction of the Co-DDTC-complex in chloroform. Measuring by a 23 cm³ Ge(Li) detector for 15 h provides a detection limit of 10 ppb. Radiochemical yield is determined by⁵⁷Co as radioactive indicator. Limitations by⁶⁰Co are reduced by Cd-screened activation and by anticoincidence measuring technique.      

Determination of natural uranium in biological samples using the solid state nuclear track detector method

For the solution of most of the problems which are connected to the biological and physiological role of natural uranium in plants and animal organisms about 10⁻¹⁴ g uranium should be determined. However most of the physico-chemical methods for the determination of natural uranium in biomaterials are time-consuming and possess considerable error. On the basis of addition and inner standard methods a version of Solid State Nuclear Track Detectors (SSNTD) method has been developed in order to determine the natural uranium in biospecimens. According to the experimental data simple relations have been obtained for the calculation of uranium concentration in biomaterial and minium uranium concentration in biosolution which can be measured by the detector used. Under irradiation of SSNTD at a thermal neutron flux of (3–5)·10¹⁵n·cm⁻² the detector sensitivity is 2.30·10⁻⁹ g U/ml for glass detectors; 9.60·10⁻¹⁰g U/ml for the detectors made from artificial mica.     

Determination of isotopic composition of lithium by neutron activation analysis; comparison with mass spectrometry

An activation analysis method is described for routine determination of⁶Li-abundances in various lithium compounds on the basis of the reaction sequence⁶Li(n,α)T and¹⁶O(t, n)¹⁸F and the measurement of¹⁸F. Irradiations of diluted equeous solutions of samples containing CrO₃ as internal flux monitor were carried out at a thermal neutron flux density of ϕ≤10¹¹ n·cm⁻²·sec⁻¹. Interferences from variations in neutron self-shielding oxygen concentration and triton range do not exceed 0.5% when using the dilution technique. The results for⁶Li abundances from 3.52 to 7.60% with standard deviations of 1 to 2.5% were confirmed by mass spectrometric measurements.     

Trace element distributions in man-made fibers

A preliminary study to evaluate the use of neutron activation analysis for the characterization of six groups of man-made fibers for forensic purposes has been made. A total of 81 samples of acetate, acrylic, modacrylic, nylon, polyester and rayon were analyzed. Small samples, approximately the size typically found during a crime scene search, were analyzed using a Ge(Li) detector system following a 20 min irradiation at a flux of 5·10¹³ n·cm⁻²·sec⁻¹. The following elements were determined quantitatively in one or more of the samples: Ti, Sr, Au, Zn, Sb, Br. Mn, Mg, Cu, In, Co, Cu, V, K, Al, Cl, Na, Ca, and S. Significant qualitative and quantitative differences were found both between and within the six groups. However, within certain groups some fibers from different manufacturers showed marked similarities in qualitative and quantitative composition.     

Trace element content of medicinal plants from Algeria

Neutron activation analysis (INAA) has been applied to multielemental determination of eleven medicinal plants used to cure the urinary tract diseases observed in Algeria. These plants include Androgena Citratus, Ceratonia Siliquata, Punica Granatum, Glyryrrhiza Glabra, Lausaunia Alba, Fragaria Vesca, Arbutus Unedol, Hordeum Vulgaris, Papieteria Officinalis, Zea Mays L, and Davallia Seae. Concentrations of twenty elements Ba, Br, Ca, Cl, Co, Cu, Cr, Fe, I, Mn, Na, Mg, Rb, Sb, Se, Sc, Sr, Ti, V, and Zn have been determined by short, and long irradiation times with a thermal and epithermal flux of 1.4·10¹² n·cm⁻²·s⁻¹ and 1.4·10¹¹ n·cm⁻²·s⁻¹, respectively. These analyses were performed in conjunction with Compton suppression. In almost herbs studied the Co, Cr, Cu, Rb, Sb, Sc, Se and V are found to be present at trace levels, Br, Mn, and Zn at the minor level, and Ca, Cl, Fe, Mg and Na are generally at the major level. The accuracy of the measurements has been evaluated by analyzing NIST-botanical references materials.     

Further investigating the determination of phosphorus in plants by INAA using<Emphasis Type="Italic"> bremsstrahlung</Emphasis> measurement

Phosphorus is an essential element for plants and animals, playing a fundamental role in the production of biochemical energy. Despite its relevance, phosphorus is not commonly determined by instrumental neutron activation analysis (INAA), because ³²P does not emit gamma-rays in its decay. There are alternative methods for the determination of phosphorus by INAA, such as the use of beta counting or the measurement of bremsstrahlung originated from the high energy beta particle from ³²P. Here the determination of phosphorus in plant materials by measuring the bremsstrahlung production was further investigated, to optimize an analytical protocol for minimizing interferences and overcoming the poor specificity. Eight certified reference materials of plant matrices with phosphorus ranging between 171 and 5,180 mg kg⁻¹ were irradiated at a thermal neutron flux of 9.5 × 10¹² cm⁻² s⁻¹ and measured with a HPGe detector at decay times varying from 7 to 60 days. Phosphorus solutions added to a certified reference material at three levels were used for calibration. Counts accumulated in the baseline at four different regions of the gamma-ray spectra were tested for the determination of phosphorus, with better results for the 100 keV region. The Compton scattering contribution in the selected range was discounted using an experimental peak-to-Compton factor and the net areas of all peaks in the spectra with energies higher than 218 keV, i.e. Compton edge above 100 keV. Amongst the interferences investigated, the production of ³²P from sulfur, and the contribution of Compton scattering should be considered for producing good results.     

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.     

Determination of phosphorus in polymers by INAA

An INAA technique employing beta spectrometry was developed for the determination of phosphorus in polymers. The (n,γ) reaction on phosphorus produces³²P, half-life 14.3 days, a pure beta emitter with end-point energy 1.71 MeV. Polymer samples in the form of powders, films and pellets are irradiated and then counted with a plastic scintillator. The beta spectrum is corrected for interferences (especially Sb, Zn and Br which are quantified by gamma spectrometry) and for energy loss in the thick sample. Samples must also be analyzed for S and Cl which cause nuclear interferences. With an irradiation time of 4 hours at a neutron flux of 5·10¹¹ n·cm^{−2 s −1}, decay time 10 days and counting time 10 minutes, the sensitivity is 520 counts/μg phosphorus and the detection limit is typically 2μg/g.