Extending NAA to materials with high concentrations of neutron absorbing elements

Summary The recently discovered universal functions for thermal and epithermal neutron self-shielding were adapted to NAA of cylindrical samples, expressing the magnitude as the product of a nuclear factor, a geometrical factor and the amount of the neutron absorbing element. The theory was tested and the nuclear factors were measured for 1 ml samples containing the halogens Cl, Br and I. Tests on samples containing these elements at a priori unknown concentrations, irradiated in a mixed thermal and epithermal neutron spectrum, showed that self-shielding as high as 30% could be corrected with an accuracy of about 1%, except in cases with significant epithermal shielding of one element by another.     

Determination of sodium and chlorine in pure water by neutron activation analysis

Neutron activation analysis was applied to determine sodium and chlorine in high purity water samples. After irradiation of the sample,³⁸Cl was purified from⁸²Br and other nuclides by carbon tetrachloride extraction and silver chloride precipitation, and²⁴Na was separated from other alkali elements and other nuclides by adsorption of²⁴Na on HAP. The activities of both elements were measured by conventional G.M. counter. The contamination of the elements from container walls during neutron irradiation and the interference with³⁸Ar(n, p)³⁸Cl reaction on argon dissolved in water were also examined. Water samples containing 3 ppb of chlorine could not be determined accurately, owing to the above mentioned interfering reaction.     

Determination of Chlorine in Plastics via SrCl by Solid-Sampling High-Resolution Continuum Source Graphite Furnace Molecular Absorption Spectrometry

Solid sampling high resolution continuum source molecule absorption spectrometry (SS-HR-CS MAS) was applied for the determination of chlorine in plastic using the strontium monochloride (SrCl) molecule. For this purpose, 10?µL of 20?g L^?1 strontium (prepared from Sr(NO₃)₂) solution were pipetted with aqueous Cl standards or 0.05 to 4?mg of slivered plastic samples on a platform and introduced into the furnace. Chlorine was determined with the molecular absorption of SrCl at 635.862?nm using 1100?°C and 2200?°C for the pyrolysis and vaporization temperatures, respectively. Aqueous standards were used for calibration. The accuracy of the method was evaluated using a certified polyethylene reference material. The limit of detection and characteristic mass values of the method were 2.5?ng and 0.4?ng, respectively. The chlorine concentrations in various polyethylene beverage containers were determined.     

Neutron activation analysis of manganese in Japanese iron reference standard materials, with large amounts of manganese

Effects of pile-up and neutron self-shielding were experimentally corrected in INAA of manganese and vanadium in iron and ferro- and silicon manganese samples supplied by the Japan Iron and Steel Federation. A pile-up correction curve was drawn as a function of total gamma count rate for each Ge detector by a ⁶⁰Co source set at a fixed position and ²⁴Na and ¹³⁷Cs sources moved to vary the gamma-ray intensities. The neutron self-shielding effect was examined by varying the weight of irradiated samples. The effect was negligible for iron samples containing a few percent manganese when samples of less than 0.2 g were irradiated. Good results were obtained for silicon and ferro-manganese by repeated analyses of samples less than 0.02 g in order to avoid the influence of the neutron self-shielding and sample inhomogeneity. A good result can be also obtained from the maximum point of a quadratic equation derived from the relationship between apparent manganese concentrations and sample weight in the range clearly affected by self-shielding. The water dilution after acid dissolution was also effective for samples of high manganese content if special caution was given to regulate the concentration of chloride having a large neutron absorption cross section.     

Determination of 2,4-D in aqueous solution by neutron activation analysis

A method based on neutron activation analysis was developed for the determination of fractions of milligrams of 2,4-D (2,4-dichlorophenoxy acetic acid) in aqueous solution in laboratory tests. The indirect determination of 2,4-D was based on the quantification of chlorine,³⁸Cl, produced by neutron activation. The range of application was 0.01–100 mg l⁻¹. No loss of³⁸Cl by chemical effects of the nuclear reaction was found. The advantages of the proposed method include high precision and sensitivity of determination. Results were compared with those obtained by UV-Vis spectrophotometry, where concentrations less than 1 mg·l⁻¹ were not detected.     

Determination of chlorine in silicate rocks by neutron activation analysis

A simple radiochemical neutron activation analysis scheme has been developed for the determination of chlorine in silicate rocks. The method involves a 15-min thermal neutron irradiation of rock powder followed by a quick separation of ³⁸Cl as AgCl, and Ge(Li) spectrometry. Chemical yield, normally ranging between 95% and 100%, is monitored gravimetrically through the recovery of AgCl. The procedure has been tested on several geochemical standards to assess its accuracy and precision. The values obtained for standard rocks agree with the literature values. At the 100-ppm level, the analytical precision for chlorine is within ±5% (2σ).     

Applications of gamma-spectrometry in determining chlorine in aqueous solutions

A method is described for the radioanalytical determination of traces of chlorine in aqueous solutions without radiochemical separation or purification. Using a gamma-spectrometer with monocrystal scintillator, the sensitivity of the analysis is about 1·10⁻⁸ g of chlorine/ml, the time of analysis being 15 minutes. For the selective determination of chlorine in aqueous solutions containing a large amount of impurities, a bicrystal scintillation sum-coincidence spectrometer was employed with 120×100 mm NaI(Tl) crystals and thus the³⁸Cl cascade radiation could be used. Application of the sum-coincidence spectrometer allowed a reliable determination of 1·10⁻⁷ g of Cl/ml against a background of 1·10⁻⁵ g of Na/ml.     

Application de l’Analuyse par Radioactivation Neutronique et du Calcul Electronique au Dosage non Destructif de Traces de Chlore dans les Silices-alumines

A method applicable for serial determination of traces of chlorine in SiO₂−Al₂O₃ catalysts by neutron activation is described. The results are evaluated by means of a computer. The³⁸Cl activity is subtracted from the activity of the interfering components (⁵⁶Mn,²⁴Na) and this enables a direct γ-spectrometric determination. In praxis ten samples should be irradiated simultaneously and for this reason 3 standards are irradiated together with the samples to correct for the fluxus gradient. The reproducibility of the method is better than 2 per cent for 10–300 mg samples with a Cl content of 10 ppm.      

Experimental evaluation of epithermal neutron self-shielding for 96Zr and 98Mo

In a previous work we experimentally tested some neutron self-shielding calculations methods for thermal absorbers, from which the semi-empirical “sigmoid method” gave the most accurate results. In this work we aim at evaluating the accuracy of this method on the epithermal self-shielding phenomena as compared to the analytical “MatSSF method”. Metallic foils of Zr and Mo were compactly stacked together into small cylinders (or disks) of different thickness, allowing for up to 20 % epithermal self-shielding when irradiated on two channels of the BR1 reactor. A 2 % relative difference between calculated and experimental self-shielding factors was obtained from the MatSSF method when a perpendicular source-sample axial configuration was assumed, while the isotropic or the co-axial configuration alternatives gave up to 10 % relative differences. On the other hand, the sigmoid method gave relative differences of up to 6 % that can be reduced to just 2 % by applying the “effective” epithermal absorption cross-sections for ⁹⁸Mo and ⁹⁶Zr proposed in this work.     

Determination of 36Cl in environmental samples collected in the JCO by AMS

Long-lived chlorine, ³⁶Cl (T_1/2 = 301,000 y) in environmental samples has been measured by the AMS system installed in Tandem Accelerator Center, University of Tsukuba. A tri-carbon-molecular ¹²C₃ ^- pilot beam method is used to stabilize the terminal voltage of the tandem. A small amount of pure carbon graphite is well mixed into a AgCl target material for creating Cl^- and ¹²C₃ ^- in the ion source. A ³⁶S isobaric interference in the system is eliminated to determine ³⁶Cl in environmental samples by chemical procedure. Some samples containing chlorine such as soil, chemical reagents and table salt have been collected in the JCO criticality accident site and analyzed to detect neutron-induced ³⁶Cl. The experimental result has been compared with a theoretical calculation.     

Determination of trace amounts of chlorine in hydraulic fluid by Instrumental Neutron Activation Analysis

A procedure has been developed for the determination by thermal neutron activation analysis of trace amounts of total chlorine in the Electro-Hydraulic-Control /EHC/ fluid used by the Hadera Power Station in various hydraulic systems. Irradiation for 1 min near the core of a nuclear reactor is followed by high resolution gamma-ray spectrometry using a Ge/Li/ detector. Chlorine amount is quantitatively determined by measuring the gamma-ray photopeaks of the radioactive nuclide³⁸Cl. The system response is linear in the concentration ranges investigated. Chlorine concentration in a fresh hydraulic fluid sample was found to be 17.6±0.5 ppm. The limit of detection, when assaying a 1 cm³ sample of fluid under the present experimental conditions, is 1 g of chlorine and the corresponding concentration is 1 ppm.     

The application of NAA with irradiation at reduced temperature for the study of element losses during pretreatment of biological samples

The neutron capture gamma-ray spectroscopy facility assembled at the Institute of Radiochemistry, KfK (for analytical purposes) using a²⁵²Cf neutron source with a strength of 6·10⁷ n/s, has been used to check its applicability and sensitivity for quantitative analyses of ores. The analysis of Sm, Cd and Mn in phosphate and monazite rock samples has been carried out. The results from this study show a variation of about 25% from the values determined by RNAA method. This discrepancy could be mainly due to the low signal-to-background ratio observed which is caused by (i) scattering of the source gammarays by the target, and (ii) interference from the 2223.1 keV neutron capture hydrogen gamma-rays produced by the moderated materials and from their compton scattering in the detector. To overcome these difficulties we suggest to introduce a 2.5 cm thick polyethylene sheet between the detector⁶Li-cap shielding and the target as well as to increase the detection solid angle. Also the strength of the²⁵²Cf neutron source should be increased by an order of magnitude and the neutron beam should be collimated to obtain the optimal thermal neutron flux with a low level of²⁵²Cf gamma-rays. This can be achieved by setting up between the neutron source and the target a conical polyethylene collimator with a thickness of 10 cm containing a 1 cm thick lead sheet.     

Measurement of the 238U(n,γ)239U reaction cross sections in the energy range of 2.0–5.0 MeV by using a neutron activation technique

The neutron capture cross-sections of ²³⁸U at the neutron energies of 4.38?±?0.05 MeV, 3.02?±?0.49 MeV and 2.04?±?0.26 MeV have been measured using the activation method and off-line gamma-ray spectrometric technique. The effects of neutron flux fluctuation, multiple scattering, flux self-shielding and gamma-ray self-absorption were corrected. The excitation function of the ²³⁸U(n,γ)²³⁹U reaction was also calculated using the TALYS-1.9 code. The experimental results were compared with the evaluated data, the theoretical data and the previous experimental data.

     

Measurement of <Superscript>36</Superscript>Cl in nuclear wastes and effluents: Validation of a radiochemical protocol with an in-house reference sample

Summary ³⁶Cl is a beta-emitter with a very low specific activity. It is produced during the irradiation of nuclear fuel, in the reactor core of power plants, from neutron capture by stable ³⁵Cl that may be present at trace level in any part of the irradiated material. Due to its long half-life (T_1/2 = 3.01 ^. 10⁵ y), ³⁶Cl may be significant in impact assessment studies of disposal sites of nuclear wastes. Considering these different elements, the National Radioactive Waste Management Agency (Andra-France) requests information on the ³⁶Cl content of the waste packages destined to be stored at Andra sites. As for other halogens, the measurement of ³⁶Cl is a difficult analytical task in view of its potential losses during the different chemical steps and also because of the lack of international certified reference material needed to validate the chemical and measurement procedures. This paper describes the methodology processed to constitute an in-house solid reference sample with a known content of stable and radioactive chlorine. The original radiochemistry developed to extract ³⁶Cl from solid samples and purify it before a liquid scintillation counting is explained. The comparison of the results given by this radiochemical protocol and other methods allow its validation. The replication of the measurements on the constituted reference materials gives a repeatability around 8% at a confidence level of 95% that is very close to the calculated combined uncertainty value.     

Recoil chlorine reactions with ethylene

The reactions of recoil³⁸Cl atoms produced through the³⁷Cl(n,)³⁸Cl process in the CF₃Cl–C₂H₄ gas phase are described in this work. The CF₃Cl is a chlorine source as well as moderator. Scavengers, such as O₂ and H₂S, were added to the system to discriminate the reactions induced by energetic and/or thermal chlorine atoms. The radioactive³⁸Cl-labeled products were separated using gas-chromatogarphic technique followed by an external proportional counter for quantitative determination of the product yeids. The mechanisms of the chemical reactions are predicted to account for the formation of these organic compounds.     

A new reflector structure for facility thermalizing D–T neutrons

A facility for thermalization of fast neutrons (14.2 MeV) emitted by compact deuterium–tritium (D–T) neutron generators (NGs) for thermal neutron activation analysis is proposed. Its final design is based on Monte Carlo calculations (MCNP5). To maximize the ratio between the thermal neutron flux and the total neutron flux and simultaneously to ensure the highest possible value of the thermal neutron flux at the output surface, the facility should consist of a two-layer reflector [tungsten (W)—the inner part, molybdenum—the outer part], a two-layer multiplier (W followed by lead), a moderator (polyethylene followed by magnesium fluoride) and a collimator (molybdenum and nickel near the output surface). For the D–T NG producing the maximum available neutron yield 10¹⁵ n s^?1, the facility provides the thermal neutron flux 2.0 × 10¹¹ n cm^?2 s ^?1 and a slightly higher fast neutron flux 2.3 × 10¹¹ n cm^?2 s^?1. To improve the ratio of the thermal neutron flux to the fast neutron flux (above 2.7) an addition of a silicon layer to the moderator and especially a proper adjustment and a threefold increase of the multiplier thickness is necessary.     

Determination of the fission averaged cross sections of some threshold reactions induced on chlorine, potassium, and calcium, and their role in the development of self-validated methods of neutron activation analysis

The feasibility of validating data obtained in the determination of chlorine, potassium, and calcium by neutron capture activation analysis, through their determination using threshold reactions has been studied. To this purpose the authors experimentally determined the following fission neutron spectrum averaged cross sections (in mb):³⁷Cl(n,p)³⁷S, 0.234±0.015;⁴¹K(n,α)³⁸Cl, 0.740±0.044;⁴²Ca(n,p)⁴²K, 3.09±0.22;⁴³Ca(n,p)⁴³K, 2.27±0.12;⁴⁴Ca(n,p)⁴⁴K, 0.074±0.013. The application of these values to the analysis of some reference materials are presented. Also, the problem of mutual interferences has been addressed for the following pairs:³⁶S(n,Γ)³⁷S and³⁷Cl(n,p)³⁷S;³⁷Cl(n,Γ)³⁸Cl and⁴¹K(n,α)³⁸Cl;⁴¹K(n,ψ)⁴²K and⁴²Ca(n,p)⁴²K.     

Prompt gamma-ray neutron activation analysis methodology for determination of boron from trace to major contents

Prompt gamma ray neutron activation analysis methodologies were standardized using a reflected neutron beam and Compton suppressed γ-ray spectrometer to quantify boron from trace to major concentrations. Neutron self-shielding correction factors for higher boron contents (0.2–10 mg) in samples were obtained from the sensitivity of chlorine by irradiating KCl with and without boron. This method was validated by determining boron concentrations in six boron compounds and applied to three borosilicate glass samples with boron contents in the range of 1–10 mg. Low concentrations of boron (10–58 mg kg⁻¹) were also determined in two samples and five reference materials from NIST and IAEA.     

A Study of Transition‐Metal Organometallic Complexes Combining 35Cl Solid‐State NMR Spectroscopy and 35Cl NQR Spectroscopy and First‐Principles DFT Calculations

A series of transition‐metal organometallic complexes with commonly occurring metal? chlorine bonding motifs were characterized using ³⁵Cl solid‐state NMR (SSNMR) spectroscopy, ³⁵Cl nuclear quadrupole resonance (NQR) spectroscopy, and first‐principles density functional theory (DFT) calculations of NMR interaction tensors. Static ³⁵Cl ultra‐wideline NMR spectra were acquired in a piecewise manner at standard (9.4 T) and high (21.1 T) magnetic field strengths using the WURST‐QCPMG pulse sequence. The ³⁵Cl electric field gradient (EFG) and chemical shielding (CS) tensor parameters were readily extracted from analytical simulations of the spectra; in particular, the quadrupolar parameters are shown to be very sensitive to structural differences, and can easily differentiate between chlorine atoms in bridging and terminal bonding environments. ³⁵Cl NQR spectra were acquired for many of the complexes, which aided in resolving structurally similar, yet crystallographically distinct and magnetically inequivalent chlorine sites, and with the interpretation and assignment of ³⁵Cl SSNMR spectra. ³⁵Cl EFG tensors obtained from first‐principles DFT calculations are consistently in good agreement with experiment, highlighting the importance of using a combined approach of theoretical and experimental methods for structural characterization. Finally, a preliminary example of a ³⁵Cl SSNMR spectrum of a transition‐metal species (TiCl₄) diluted and supported on non‐porous silica is presented. The combination of ³⁵Cl SSNMR and ³⁵Cl NQR spectroscopy and DFT calculations is shown to be a promising and simple methodology for the characterization of all manner of chlorine‐containing transition‐metal complexes, in pure, impure bulk and supported forms.