Boron concentration measurements by prompt gamma activation analysis: Application on miocene-quaternary volcanics of the Carpathian-Pannonian Region

Prompt gamma activation analysis is a highly powerful analytical method in geology, due to its applicability to determine the concentration of all major and few trace elements in whole rock samples. Furthermore, the boron concentration can be determined with proper accuracy without time consuming sample preparation. The reliability of this method was checked on geological standards and on other volcanic rocks, which were analyzed previously by XRF and TIMS for many major and trace element components and Sr-isotopes. Boron concentrations of volcanic rock samples from the East Carpathian Volcanic Field (Eastern-Central Europe) are reported here for the first time. The boron concentrations were measured for an improved definition of the petrogenezis of these rocks and to understand the fluid addition processes during subduction-related volcanism in this region.     

Combining prompt gamma activation analysis and off-line counting

The off-line γ-counting of in-beam activated radionuclides has been explored to extend the detection capabilities of prompt gamma activation analysis (PGAA). Such combination of the prompt measurement with a subsequent decay-counting is feasible if radionuclides with half-lives of minutes or hours are produced in the sample during neutron irradiation. Thanks to the simpler spectrum and the higher counting efficiency of decay counting, both selectivity and sensitivity can be improved. The pros and cons of the proposed method have been demonstrated on a series of industry-related measurements.     

Progress of prompt gamma activation analysis in Korea

Summary The new PGAA facility using diffracted neutron beam was developed in Korea. The basic characteristics of the facility were studied in detail. A general formalism of the k₀ factor as extended to non-1/v absorber and arbitrary neutron spectrum was discussed and the actual data for Cd, Sm, Eu, Gd have been measured and determined successfully owing to the simple nature of the diffracted neutron spectrum. The k₀ factors for B, N, Si, P, S and Cl were also determined and showed consistent results with previously reported ones. At an early stage, feasibility of boron concentration analysis and measurement of thermal neutron capture cross sections has been studied. The PGAA facility is now open to users. A considerable amount of beam time is already dedicated to studies on the elemental analysis.     

Neutron activation analysis of some volcanic rocks

INNA has been adopted for multielemental study of an acidic rock (OH-121) and three basic rocks (EH-121, WH-121 and SI-121) collected from Al-Madina in the Western Region of the Kingdom of Saudi Arbia. The basic rocks have higher concentrations of the transition elements Ti, V, Cr, Mn and Co, as compared to the acidic rock.     

Xenon diffusion studies with prompt gamma activation analysis

Developing a better understanding of xenon transport through porous systems is critical to predicting how this gas will enter the atmosphere after a below ground nuclear weapons test. Radioxenon monitoring is a vital part of the Comprehensive Nuclear-Test-Ban Treaty (CTBT) International Monitoring System. This work details the development of prompt gamma activation analysis for measuring the diffusion rates of xenon and argon gases through a porous medium. The University of Texas at Austin maintains a prompt gamma activation analysis facility with a peak neutron flux of ~1.5 × 10⁷ cm⁻² s⁻¹ and a beam diameter of 1 cm. Due to the relatively large prompt gamma cross sections of many stable xenon isotopes at thermal and sub-thermal neutron energies, prompt gamma activation analysis is a suitable technique for in situ non-destructive analysis of natural xenon. A test chamber has been designed and constructed to utilize prompt gamma activation analysis to measure xenon and argon diffusion through geological materials (e.g., sand, soil, etc.). Initial experiments have been conducted to determine the detection limits for stable gas measurements. The results from these experiments will be utilized to benchmark parts of a xenon transport model that is being used to determine diffusion coefficients for xenon and argon.     

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%.     

Recent developments of prompt gamma activation analysis at Budapest

The PGAA facility at the Budapest Research Reactor has been continually upgraded and developed since its start-up in 1996, as a result of which its performance has improved considerably. The installation of the cold neutron source, the partial change to supermirror neutron guides and their realignment increased the flux by almost two orders of magnitude. The data acquisition has been modernized as well; digital spectrometers were tested and implemented in novel forms of gamma-ray spectrum collection. This year a higher-efficiency HPGe detector and a new data acquisition module were put into operation. Most recently all the neutron guides were changed to supermirror-coated ones to further increase the neutron flux. The improved evaluation software makes possible a more reliable elemental analysis of the samples. In this progress report these developments are critically reviewed. The characteristics of the latest system are also described. It is the first time that a set of new partial gamma-ray production cross sections are presented, which are based on the new intensity values of ¹⁴N(n,γ)¹⁵N calibration standard.     

Analyses of oxyanion materials by prompt gamma activation analysis

Prompt gamma activation analysis (PGAA) has been used to analyze metal ion oxyanion materials that have multiple applications, including medicine, materials, catalysts, and electronics. The significance for the need for accurate, highly sensitive analyses for the materials is discussed in the context of quality control of end products containing the parent element in each material. Applications of the analytical data for input to models and theoretical calculations related to the electronic and other properties of the materials are discussed.     

Determination of boron and other elements in volcanic rocks by prompt gamma-ray analysis: An application to magma genesis in Kyushu island,SW-Japan

Neutron induced prompt gamma-ray activation analysis (PGAA) is applied for determining boron contents in volcanic rocks, which is an important element in the discussion of material circulation in volcanic arc systems. To evaluate the recycling of oceanic crust in Kyushu, we analyzed boron and other trace element contents in basaltic rocks from the area. The basalts from volcanic front have high B/Nb (2.9–3.7), B/Zr (0.1–0.2) and B/Sm (2.8–6.0) ratios, whereas those ratios in the basalts from backarc are extremely low (<0.5; <0.1; 0.5–1.7), respectively. This indicates that the recycling of subducted oceanic crust to the arc crust is limited in the volcanic front.     

Upgrade of the prompt gamma activation analysis and the neutron-induced prompt gamma spectroscopy facilities at the Budapest research reactor

The Budapest Research Reactor’s Prompt Gamma Activation Analysis (PGAA) and Neutron-Induced Prompt gamma Spectroscopy (NIPS) facilities were significantly upgraded during the last few years. The higher neutron flux, achieved by the partial replacement and realignment of the neutron guides, made feasible the automation and specialization of the two experimental stations. A new neutron flux monitor, computer-controlled beam shutters and a low-level counting chamber have been put into operation to assist with in-beam activation experiments. An automatic sample changer has been installed at the PGAA station, while the NIPS station was redesigned and upgraded with a Compton suppressor to use for the non-destructive analysis of bulky samples. In the near future the latter setup will be completed with a neutron tomograph and a moving table, to turn it into a Neutron Radiography/Tomography-driven PGAA equipment.     

Cold neutron prompt gamma activation analysis at NIST: A progress report

An instrument for prompt gamma-ray activation analysis is now in operation at the NIST Cold Neutron Research Facility (CNRF). The cold neutron beam is relatively free of contamination by fast neutrons and reactor gamma rays, and the neutron fluence rate is 1.5·10⁸ cm^–2·s^–1 (thermal equivalent). As a result of a compact target-detector geometry the sensitivity is better by a factor of as much as seven than that obtained with an existing thermal instrument, and hydrogen background is a factor of 50 lower. We have applied this instrument to multielement analysis of the Allende meteorite and other materials.     

Combined application of Monte Carlo method and neural networks to simulate qualitative prompt gamma neutron activation analysis

Prompt gamma spectrum produced by thermal neutron absorption and fast neutron inelastic scattering is simulated using Monte Carlo code MCNP4C. The simulated spectrum is analyzed with artificial neural network techniques. The neural network in our study is trained based on back-propagation algorithm with 138 gamma ray spectra. Elements existing in the 20 different substances are specified. The ANN could identify elements correctly in 96% of input cases.     

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).     

Accurate and efficient determination of boron content in volcanic rocks by neutron induced prompt gamma-ray analysis

An accurate and efficient analytical method using neutron-induced prompt γ-ray was developed for the determination of boron contents in volcanic rocks. We corrected the effect of sample geometry and flux fluctuation by using silicon as an internal standard. However, we found that the slopes of the calibration line vary among volcanic samples with different matrix. Because the increase of boron activity correlates positively with γ-ray count rate of hydrogen (water), we call this as the hydrogen effect. The hydrogen effect was confirmed by our experiment in which the boron activities showed systematic increase with the amount of added hydrogen (water). Most volcanic rocks, however, contain little water (<2 wt.%) to show this effect. We determined boron contents in various volcanic rocks in order to confirm the validity of the procedure that we established. The analyzed boron contents agreed well with the previous reported values. For efficient PGA of boron in volcanic rocks, we recommend JB-2 (GSJ standard rock) as a single geochemical standard, because of its high boron content (31.2 ppm).     

Performance of the University of Texas cold-neutron prompt gamma activation analysis facility

The University of Texas cold-neutron prompt gamma-activation analysis (PGAA) facility is operational at the 1-MW UT TRIGA research reactor. The UT-PGAA facility utilizes a guided cold neutron beam produced by the Texas Cold Neutron Source. The cold neutrons are transported to the PGAA chamber via a 6-m long curved neutron guide followed by an 80-cm long converging neutron guide. A program of testing, optimizing, and calibrating the UT-PGAA facility is currently underway. Preliminary results for the sensitivities and detection limits of boron, hydrogen, and silicon in semiconductor materials are given.     

Neutron self-shielding correction for prompt gamma neutron activation analysis of large samples

Summary Facilities and methods for INAA of large samples (up to 30 kg) have been developed and successfully tested at IRI, Delft. The methods encompass corrections for neutron self shielding in an isotropic neutron field and gamma self-absorption. The sample’s neutron absorption and scattering characteristics are determined by monitoring the neutron fluence rate around the sample and comparing the neutron densities measured with unperturbed fluence rates. We report on the possibility of developing similar methods for PGNAA. Relative self-shielding factors were measured as well as obtained from Monte Carlo computations. The agreement is good except for the most extreme case, with respect to absorption, attempted (CCl₄).     

Combinatorial study of thin film metal hydride by prompt gamma activation analysis

Cold neutron prompt gamma activation analysis (PGAA) was used to determine the mass of hydrogen in Mg hydride thin films with varying hydrogenation times. The results suggest that hydrogenation of the Mg thin films remains unsaturated even after 48 h of treatment, contrary to the indications of inferential hydrogen measurement methods. To demonstrate PGAA as an effective combinatorial methodology for hydride thin films, a continuously varying composition gradient of thin Mg_yTi_(1−y) hydride film with y ranging from 0.65 to 0.94 was prepared and analyzed by both PGAA and instrumental neutron activation analysis (INAA). The variation in the molar ratio of Mg, Ti, and H was obtained for nine 5 mm wide segments of the film.     

Analysis of boron in biological reference materials using prompt gamma activation analysis

Summary A prompt gamma activation analysis facility has been constructed on the ST1 horizontal beam port at the HANARO research reactor, KAERI in 2003. The detector system consists of a high-purity Ge detector surrounded by BGO/NaI(Tl) scintillators as an annulus type to reject the Compton scattered photons. Detection sensitivity for boron was obtained from the prompt gamma-ray spectra of boric acid, B(OH)₃, containing 0.1-65 μg boron. The net peak for the calculation of the boron concentration was obtained by eliminating the sodium 472 keV peak, involved in the boron 478 keV peak. The biological samples used are NIST SRMs such as Peach Leaves, Apple Leaves, Tomato Leaves, Spinach Leaves, Total Diet, Typical Diet, Oyster Tissue and Corn Bran, etc. The measured values for high boron concentration showed up to a 3% of the relative, but in a low concentration below 5 ppm, present values were higher than the certified ones.