Instrumental Neutron Activation Analysis Method Research Articles

Optimization and Applications of Instrumental and Preconcentration Neutron Activation Analysis Methods for Rapid Determination of Selected REE by Utilizing their Short‐Lived Activation Products**

AbstractDetermination of Rare Earth Elements (REEs) using spectroscopic methods is challenging. Conventional Instrumental Neutron Activation Analysis (INAA) method utilizing Pneumatic Carrier Facility (PCF) of Dhruva research reactor has been optimized with the short‐lived isotopes such as 161Gd, 165mDy and 153/155Sm for quantification of Gd, Dy and Sm respectively. Such isotopes are difficult to observe by conventional INAA with longer cooling periods owing to their very short half‐lives (1–3 mins). In this work, such isotopes are not only observed but also utilized as activation product for rapid determination of these REEs. The standardized method has been utilized for the first time in liquid samples involving nuclear fuel like U3O8 wherein TBP/n‐dodecane has been applied for chemical separation of Uranium prior to analysis. The INAA method has also been applied for validating the stoichiometry of Gd in Gd3+ co‐doped Zn2P2O7:Tb3+ green emitting solid‐state phosphors, which plays a very pivotal role in sensitizing the terbium ion in its performance for solid state lighting. We believe with huge current demand of REEs in research, science and technology; INAA can be a game changer wherever needed for quantification with high precision and accuracy and can also be extended to other REEs of interest.

Features of determining organometallic compounds in organic matters of black shale using diffuse reflectance infrared Fourier transform spectroscopy

Relevance. The problem of studying organometallic compounds in carbonized and carbonaceous substances is part of the global problem of the structure of natural materials from plant remains and manifestation of ore genesis in organic sedimentary deposits. This problem covers a number of issues. The most pressing one among them is the form of occurrence of finely dispersed gold in the form of organometallic compounds in metal-bearing coals and shales. This is especially true for large gold deposits of black shale strata. Aim. To study the relationship between sedimentation of organic formations and ore genesis in black shale deposits using the example of the Verninskoe deposit (Patom Highlands, Yakutia). Using the SKAUFV hardware and software complex together with ICP-MS and INAA methods, which allow one to assess the degree of Au concentration in organic matter, to substantiate the possibility of determining organometallic compounds of gold that are significant in the processes of sedimentogenesis, lithogenesis and epigenesis. Methods. IR spectroscopy, instrumental neutron activation analysis (INAA) and inductively coupled plasma mass spectrometry (ICP-MS). Results. The authors have determined that the SKAUFV hardware and software complex, together with the ICP-MS and INAA methods, makes it possible to establish the role of organic matter in metasomatism and to identify temperature zonality and the associated gold concentration in the ore zone. To determine the organometallic compounds of Au, structural and genetic indicators  (Pm, Ko, PVt+L, PI) were selected. These indicators reflect the significance of sedimentation, diagenesis, catagenesis and epigenesis on Au concentration of in organic matter. These indicators made it possible to assess the level of temperature impact on sedimentary deposits of regional metamorphism and near-ore metasomatism. In this regard, subzones of Au concentration were established in the ore zone, determined by temperature zoning in the form of a manifestation of local metasomatism. The latter was influenced by the protein-fat composition of plants that form organic matter.

Rapid and non-destructive quantification of trace to minor concentrations of Uranium in ores, minerals and reference materials by instrumental neutron activation analysis using high-flux pneumatic carrier facility of Dhruva reactor

ABSTRACT Rapid and non-destructive determination of trace quantities of Uranium in “as received” solid samples using a suitable analytical method is a challenging task. Uranium can be quantified by Instrumental Neutron Activation Analysis (INAA) using both short lived (239U) and medium-lived (239Np from decay of 239U) activation products. In the present work, INAA method has been optimised in terms of sample mass, duration of irradiation, lesser decay period and faster counting to acquire reasonable counts (peak area) under the peak of interest. Pneumatic Carrier Facility (PCF), high neutron flux (5 × 1013 n/cm2 /s at 50 MW power) at Dhruva research reactor, has been advantageously utilised for short duration irradiation (1 min) of the samples. Quantification of Uranium utilising 239U short-lived activation product (23.5 min half-life) formed after short irradiation, makes the methodology faster without any longer decay time. Immediately after 1 min of irradiation, the short-lived 239U activation product showed higher analytical sensitivity compared to that of medium-lived activation product (239Np) having gamma-rays at 106 and 277 keV. The detection limit of uranium was found to be much lower when it was calculated using 239U activation product. A comparative study was carried out between the short and medium lived activation products of 238U. The method was applied for determination of trace quantities of total Uranium in ores and minerals like Zircon, Ilmenite and Rutile having complex matrices. INAA method was validated by analysing USGS CRMs like STM-1, RGM-1 and AGV-1 and IAEA RM RGU-1. The detection limit was found to be around 1 ppb for the analysed solid samples (ores and minerals).

Determination of Chromium Mineral in Foodstuffs in Indonesia using INAA Method

The concentration of the element chromium (Cr) was determined in 76 types of food ingredients from four provinces in Indonesia. The element Cr is one of the essential elements needed by the human body for physiological processes. Although the amount needed for Cr is relatively small, this mineral is very important for the insulin hormone to function properly. Chromium deficiency can result in decreased insulin sensitivity, glucose intolerance and an increased risk of diabetes. The Cr element was determined using the Instrumental Neutron Activation Analysis (INAA) method in the GA. Siwabessy Multipurpose Research Reactor. The reactor which is located in the Puspiptek area has a thermal neutron flux of around 5.47 x 1013 n.cm-2s-1 . Bombardment Cr-50 in foodstuffs samples by thermal neutrons will produce Cr-51 through the n, nuclear reaction. The radiosotope Cr-51. The radiosotope Cr-51 which is the result of thermal neutron activation has a half-life of 27.7 days. The single energy peak of the Cr- 51 gamma-ray can be observed at 320.08 keV. The results showed that cassava leaves, melinjo leaves, watercress, sweet potato leaves, papaya leaves, ipomoea aquatica, kenikir, pumpkin leaves, spinach and mushrooms are foodstuffs rich in Cr compared to other foodstuffs. Foodstuffs from Pandeglang Regency-Banten Province have relatively higher Cr concentrations than other three locations.The concentration of Cr in foodstuffs ranges from 0.039 to 5.244 µg/g.

Determination of Fe and Tb concentrations in geological and environmental samples using the instrumental neutron activation analysis method combined with the γ − γ coincidence technique

The instrumental neutron activation analysis (INAA) method was combined with the γ − γ coincidence technique to measure Iron (Fe) and Terbium (Tb) concentrations in geological (Montana II Soil) and environmental (Coal Fly Ash) standard materials. The measured concentrations, which agree well with the corresponding certified values, are compared with those obtained from the traditional INAA method. It is demonstrated that employing the γ − γ coincidence technique slightly improves the accuracy of the analysis. Furthermore, the coincidence technique enhances the detection limits of Tb by ∼4.5 and ∼5.5 times in environmental and geological samples, respectively, but has almost no enhancement in those of Fe. The γ − γ coincidence technique therefore does not always promote the analysis quality of the INAA method, but it is effective for analyzing elements whose characteristic γ rays sustain a high Compton background and/or are overlapped with other γ rays.

Content of Fifty Trace Elements in Thyroid Benign Nodules and Thyroid Tissue adjacent to Nodules investigated using Neutron Activation Analysis and Inductively Coupled Plasma Mass Spectrometry

Thyroid benign nodules (TBNs) are the most common diseases of this endocrine gland and are common worldwide. The etiology and pathogenesis of TBNs must be considered as multifactorial. The present study was performed to clarify the role of some trace elements (TEs) in the etiology of these thyroid disorders. Thyroid tissue levels of fifty TEs were prospectively evaluated in nodular tissue and tissue adjacent to nodules of 79 patients with TBNs. Measurements were performed using a combination of non-destructive instrumental neutron activation analysis and destructive method such as inductively coupled plasma mass spectrometry. Results of the study were additionally compared with previously obtained data for the same TEs in “normal” thyroid tissue. This study provides evidence on many TEs level alteration in nodular and adjacent to nodule tissue and shows the necessity to continue TEs research of TBNs.

Content of 31 trace elements in thyroid malignant nodules and thyroid tissue adjacent to nodules investigated using neutron activation analysis and inductively coupled plasma mass spectrometry

Thyroid malignant nodules (TMNs) are the most common endocrine cancer and the fifth most frequently occurring type of malignancies. Women are at particular risk for this thyroid disease The etiology and pathogenesis of TMNs must be considered as multifactorial. The present study was performed to clarify the role of some trace elements (TEs) in the etiology of these thyroid disorders. Thyroid tissue levels of silver (Ag), aluminum (Al), boron (B),, beryllium (Be), bismuth (Bi), cadmium (Cd), cerium (Ce), cobalt (Co), chromium (Cr), cesium (Cs), iron (Fe), gallium (Ga), mercury (Hg), lanthanum (La), lithium (Li), manganese (Mn), molybdenum (Mo), neodymium (Nd), nickel (Ni), lead (Pb), praseodymium (Pr), rubidium (Rb), antimony (Sb), scandium (Sc), selenium (Se), samarium (Sm), tin (Sn), thallium (Tl), uranium (U), yttrium (Y), and zinc (Zn) were prospectively evaluated in malignant tumor and thyroid tissue adjacent to tumor of 41 patients with TMNs. Measurements were performed using a combination of non-destructive instrumental neutron activation analysis and destructive method such as inductively coupled plasma mass spectrometry. Results of the study were additionally compared with previously obtained data for the same TEs in “normal” thyroid tissue. It was observed that main characteristics of TMNs in comparison with “normal” thyroid were significantly elevated levels of Ag, Al, B, Bi, Ce, Cr, Hg, Mn, Mo, Ni, Pb, Rb, Sm, and Tl. Furthermore, the TEs composition of thyroid tissue adjacent to tumor did not equal TEs contents of “normal” thyroid. Moreover, contents of such elements as Ag, Hg, and Se in adjacent tissue were higher than in tumor. Thus, from results obtained, it was possible to conclude that at least the excessive accumulation of Ag, Hg, and Se by thyroid tissue is likely to precede the TMNs origination and development. Elevated levels of Ag, Al, B, Bi, Ce, Cr, Hg, Mn, Mo, Ni, Pb, Rb, Sm, and Tl in nodular tissue could possibly be explored for differential diagnosis of benign and malignant thyroid nodules.

Determination of Fe and Tb Concentrations in Geological and Environmental Samples Using the Instrumental Neutron Activation Analysis Method Combined with the Γ−Γ Coincidence Technique

Determination of Fe and Tb Concentrations in Geological and Environmental Samples Using the Instrumental Neutron Activation Analysis Method Combined with the Γ−Γ Coincidence Technique

Ore Minerals and Metal Distribution in Tailings of Sediment-Hosted Stratiform Copper Deposits from Poland and Kazakhstan

This study, carried out in tailings from two sediment-hosted stratiform copper deposits in the Lublin-Głogów Copper District in Poland (Kupferschiefer-type deposit) and Zhezkazgan (cupriferous sandstone-type deposit) in Kazakhstan, analysed the mineralogy of copper, zinc, and lead minerals as related to metal accumulation in sediments. Microscopic study in reflected light and SEM–EDS (Scanning Electron Microscope—Energy Dispersive Spectrometer) analysis, as well as chemical diversity in the used INAA (Instrumental Neutron Activation Analysis), ICP (Inductively Coupled Plasma), and AAS (Atomic Absorption Spectroscopy) methods in 35 samples from Kazakhstan and 35 from Poland were examined due to their diversity. In both tailing deposits in Kazakhstan and Poland, heavy fractions were dominated by copper sulphides: chalcopyrite (CuFeS2), bornite (Cu5FeS4). and chalcocite (Cu2S). Moreover, sphalerite, galena, and cerussite have been recognized as a carriers of Zn and Pb. Their geochemistry was dominated by Cu, showing a mean content of 2500 ppm, in both Poland and Kazakhstan. Zinc and lead also occurred, showing a content of approximately 200 ppm and 500 ppm in Poland, and 1500 ppm Zn and 2500 ppm Pb in Kazakhstan, respectively. Grain size analysis indicated that the dominant grain size in both districts corresponded to the silt and fine sands fractions. Copper, zinc and lead sulphides accumulated in fine fractions in tailings from Kazakhstan (in sandstones and quartz grains), and mainly in coarse fractions in Poland (within carbonates, sandstones, and black shales). Mineralogical and geochemical features should be taken into consideration when assessing potential metal sources of technogenic materials.

Intercomparison studies of Instrumental Neutron Activation Analysis using singles and gamma–gamma coincidence spectrometry for trace element determination in sodalime glass and sediment matrices and utilization of coincidence method for rapid automobile glass forensics

Instrumental Neutron Activation Analysis (INAA) using research reactor neutrons is a powerful nuclear analytical technique for multi-elemental determination in diverse matrices. In the present work, two different matrix samples namely sodalime glass and sediment samples have been analyzed by INAA using neutrons from research reactors at BARC. Samples were assayed by γ-γ coincidence spectrometry besides conventional (singles) counting using HPGe detector systems due to the presence of higher background from medium and long-lived activation products including 24Na. Accuracies of both the methods were evaluated by analyzing geological Certified Reference Material USGS CRM G2. INAA method with singles counting could give trace elemental concentrations of sixteen elements with about 10 days cooling period compared to nine elements by γ-γ coincidence method with a minimum of 4 days cooling period. Results of elemental concentrations are reported by both the methods along with experimental detection limits. Five automobile (sodalime) glass fragments were analyzed by INAA using γ-γ coincidence method for forensic applications utilizing seven trace elements of interest in grouping study. Concentrations of Sc and elemental concentration ratios like La/Sc indicated that five glasses fall into two major groups, which was confirmed by statistical cluster analysis. Though both the approaches of INAA are authentic for forensic applications for provenance study utilizing determined concentrations of trace elements, γ-γ coincidence INAA is helpful for giving results with less turnaround time of analysis.

АНАЛИТИЧЕСКИЕ ПОДХОДЫ К КОЛИЧЕСТВЕННОМУ ОПРЕДЕЛЕНИЮ СОДЕРЖАНИЙ ХИМИЧЕСКИХ ЭЛЕМЕНТОВ В УГЛЯХ И УГЛИСТЫХ ПОРОДАХ С ИСПОЛЬЗОВАНИЕМ МЕТОДОВ ИСП-МС И ИНАА

Актуальность исследования обусловлена значительным интересом ученых, работающих в области угольной геологии, и специалистов химико-аналитических лабораторий, практикующих элементный количественный анализ объектов окружающей среды, к проблематике высокоточного определения низких содержаний химических элементов в углях и угольных материалах для последующего применения полученных данных при решении научных и различных технологических задач. Цель: рассмотреть и обобщить наиболее часто используемые методические подходы к определению химических элементов в широком диапазоне их содержаний в углях (угольных материалах), а также оценить правильность и точность результатов метода ИСП-МС после открытого кислотного разложения проб и их сплавления с метаборатом лития, сопоставлением получаемых данных с результатами метода ИНАА и статистической обработкой данных. Объекты: угли, углистые алевролиты и углефицированная древесина месторождения германия Спецугли, расположенного на юго-западной окраине Ханкайского массива в восточной части Павловской угленосной впадины, Приморский край. Методы: масс-спектрометрия с индуктивно-связанной плазмой (ИСП-МС), применённая после перевода исследуемых образцов в растворенную форму, и неразрушающий метод количественного инструментального нейтронно-активационного анализа (ИНАА). Для обработки полученных результатов были использованы методы математической статистики. Результаты. Получены результаты ИСП-МС анализа трех стандартных образцов утвержденного типа (СО) состава золы уноса угля КАТЭКа ГСО 9237-2008 (ЗУК-2), золы бурого угля Азейского месторождения ГСО 7177-95 (ЗУА-1) и битуминозного угля CLB-1 Геологической службы США, представленные в виде данных об их микроэлементном составе в сравнении с аттестованными и рекомендованными значениями. Результаты определения части элементов, приведенные нами, дополняют представленные в паспорте данные по этим СО. Проведено сопоставление ИСП-МС результатов анализа для проб углей и углистых пород после различных способов химической пробоподготовки: методики открытого кислотного разложения и сплавления с метаборатом лития. Изучено поведение отдельных элементов во время этих процессов. Выполнено сравнение полученных данных по ИСП-МС и ИНАА методам. Все результаты обработаны метрологически, и показано их допустимое расхождение.

Comparing INAA and pXRF analytical methods for ceramics: A case study with Classic Maya wares

In order to develop more rigorous methods for ceramic-specific chemical composition analyses using a portable X-ray fluorescence (pXRF), this article compares pXRF and instrumental neutron activation analysis (INAA) analyses on Classic period (ca. 300–1000 CE) ceramics from 10 Maya Lowland archeological sites. Our comparative study indicates that pXRF analyses are capable of identifying the same region-level paste composition groups identified by INAA when using the same suite of elements. In addition, experimentation of different sample preparation techniques using a pXRF underscores the advantages and disadvantages of powdered samples versus the targeting of cleaned interior, exterior, and cross-section surfaces. As such, pXRF analyses provide an efficient way of looking at macro-scale ceramic production and exchange relationships in the Southern Maya Lowlands.

Macro-, micro-, and trace element distributions in areca nut, husk, and soil of northeast India.

In areca nut and husk, 14 elements (As, Ca, Cd, Cl, Co, Cu, K, Mg, Mn, Na, Rb, Sb, and Zn) were determined, while 34 elements including rare earth elements were detected in the corresponding soil samples using instrumental neutron activation analysis and atomic absorption spectrometry methods, whereas the concentration levels of Hg in tested samples are negligible, perhaps, below the detection limits. No rare earth elements were detected in edible areca nut. The concentration levels of various essential elements and heavy elements such as As, Cd, and Cu present in areca nut are within the permissible levels, whereas Pb content is relatively higher than FAO/WHO's permissible levels. The order of bioaccumulation index for heavy metals in areca nut was Cd > Sb > Cu > Zn ≥ Mn ≥ Co > Pb ≥ As. Bioaccumulation index values are indicating that areca palm may not be able to accumulate other heavy elements in the edible areca nut, except for Cd. On the basis of pollution indices, Northeast Indian soil may be relatively unpolluted.

Combination of Instrumental Neutron Activation Analysis with X-Ray Fluorescence Spectrometry for the Determination of Rare-Earth Elements in Geological Samples

A combined use of comparator instrumental neutron activation analysis (INAA) including the internal standard method and energy-dispersive X-ray fluorescence spectrometry (EDXRF) for the determination of 14 rare-earth elements (REE) in geological samples at the level of their clarke concentrations is studied. A rapid analysis with the determination of light REE from La to Sm with Fe as an internal standard is performed using a portable RLP-21T energy-dispersive X-ray fluorescence spectrometer (Republic of Kazakhstan) with the excitation of K-series lines of characteristic radiation of a sample with a low-power (10 W) X-ray tube with a tungsten anode and the maximum voltage 70 kV. The neutron activation analysis of other REE was performed using a WWR-K nuclear research reactor. Based on the analysis of ten certified reference materials of geological samples, a possibility of using a complex of INAA and EDXRF methods for routine qualitative analyses of REE in the III accuracy class in accordance with the branch standard OST41-08-212-04 is shown. Examples of using a complex of INAA and EDXRF methods for solving geochemical problems and determining REE in out-of-balance ores of the Kundybay deposit are presented.

Experimental design and z-score results are useful tools for optimizing instrumental neutron activation analysis procedures

In this study 2k experimental designs were used for the optimization of an instrumental neutron activation analysis method for the determination of bromine, chlorine, magnesium, manganese, potassium, sodium and vanadium in biological matrix materials. Depending on radionuclide half-lives, 23 or 24 experimental designs were used with irradiation time, sample–detector distance, counting time and sample decay time as factors. Gamma ray spectrometer, comparator mass fraction and sample mass were kept constant. Optimized irradiation and measurement conditions were established based on the experimental design results that used z-scores as response on a reference material for the various elements and experimental conditions.

Assessment of heavy metals pollution in the sediment of Ciliwung river

Thirteen (13) rivers flowing in the city of Jakarta and Ciliwung is one of them. This river flows through residential, offices, industrial and factories. Activities that exist around the river can cause rivers to become polluted. River sediments act as a potential sink for many hazardous chemicals that can be used as indicators for pollution monitoring of the river. The objective of this study is to assess the heavy metal contamination in the Ciliwung river sediment based on single and combination indices. For the assessment of the Ciliwung sediment quality, measurements of metal concentration in river sediments have been performed. Sampling was carried out at four sampling locations, namely in Kelapa Dua, Kalibata, Condet, and Depok. Analysis of heavy metals in the sample was carried out using instrumental neutron activation analysis method. The analysis result shows that the detected elements in sediment include: Br, Al, As, Ca, Ce, Cr, Co, Cs, Mg, Mn, Na, Sb, Eu, Fe, Hf, K, Sc, Sm, Ta, Tb, Th, Yb, and Zn. The assessment based on the value of the enrichment factor indicates that there has been an increase in the concentration of heavy metals As, Cr, Sb, and Zn in moderate levels due to anthropogenic factors. Based on the geo accumulation index value, it is known that the sampling area is not polluted to moderate contamination. Heavy metals As, Cr, Sb, and Zn in sediments provide a low level of ecological risk to the aquatic environment. Based on the pollution load index value (PLI), all sampling locations are in no pollution conditions. From the evaluation, it can be seen that even for some heavy metals namely As, Cr, Sb, and Zn has been an increase in the concentration value but has not yet reached the polluted level and the ecological risk of heavy metals in the sediments also still provides a low ecological risk.

Application of the INAA methods for KRISS infant formula CRM analysis: standardization of INAA at KRISS

We have established an instrumental neutron activation analysis (INAA) method, including k0-based INAA, at the Korea Research Institute of Standards and Science (KRISS) for the certification of reference materials. As part of establishing INAA measurements, KRISS infant formula certified reference material was analysed for multiple elements at three different metrological institutes: KRISS and NIST for the standard comparator method, and JSI for the k0-INAA method. The mass fraction of most elements was consistent within expanded uncertainty (k = 2). In addition, the results were used to verify the validity of elemental analysis of Zn using the standard comparator INAA at KRISS, and spreadsheet-based INAA calculations were evaluated.

Chemical characterization of soda-lime glass samples by in situ current normalised PIGE and conventional INAA methods for forensic applications

Nuclear analytical methods namely in situ current normalised Particle Induced Gamma Ray Emission (PIGE) and conventional Instrumental Neutron Activation Analysis (INAA) were utilized for determining major, minor and trace concentrations of eighteen elements in five soda-lime (automobile) glass samples. Concentration of four major elements (Si, Na, Mg and Al) by PIGE and fourteen elements including ten trace elements by INAA were determined. For forensic application, major elements were used for confirming the class of glass samples, whereas concentration results of trace elements like transition and rare earth elements were utilized for finding similarity or differences among the glass samples.

Исследование состава мха – естественного биоиндикатора для мониторинга воздуха Восточно-Казахстанской области

Here are the results of determining the chemical composition of moss in the East Kazakhstan region. The following research stages were carried out: harvesting plant materials; methods of taking samples of the studied material for analysis; determination of the concentration of elements by inductively coupled plasma mass spectrometry (ICP-MS). Developed methods for dry and wet ashing bioindicator. The results of the analysis of moss obtained by the ICP-MS method and the instrumental neutron activation analysis (INAA) method are compared. The reliability of the results of the analysis by the method of additives and photometric determination of the concentration of elements was determined.

Determination of mass fractions of 12 elements in more common apple varieties in Iran by instrumental neutron activation analysis

In this study, the amount of 12 elements in five widespread varieties of apples (Malus pumila) used in the Arak markets in Iran (Uromieh golden apple—Maragheh golden apple—Semirom golden apple, Semirom green apple, Semirom red apple) were determined using the instrumental neutron activation analysis method. In this work, the Tehran research reactor was used as a source of thermal neutron flux. The highest concentrations of Cl, K, Mg, Na and Zn were detected in Maragheh golden apple which indicates that from the point of view of nutrition, the best cultivar of studied apples is Maragheh golden apple.