Nuclear methods of analysis applied to quantitation in laser microprobe mass spectrometry

Laser microprobe mass spectrometry (LMMS) detection limits for mercury have been determined using mercury-doped Spurr's tissue embedding medium. Actual mercury concentrations were confirmed via INAA. Procedures have also been developed to measure lithium and indium concentrations in thin films of polymerized Spurr's samples via PIGE and PIXE. These elements are currently being investigated as laser power density internal standards in the analysis of human tissue for studies of trace element involvement in neurological diseases.     

Simultaneous determination of low Z elements in barium borosilicate glass samples by in situ current normalized particle induced gamma-ray emission methods

Particle induced gamma-ray emission (PIGE) method using 4 MeV proton beam was utilized to analyze two types of barium borosilicate glass (BaBSG) samples for quantification of concentrations of low Z elements. The in situ current normalization method was applied in the analysis of eight samples containing varying concentration of F along with Si, B and Na. Charge normalized PIGE method was applied to determine concentrations of above low Z elements including Li and Al in samples having simulated nuclear waste from reprocessing of thoria spent fuel. Synthetic samples and NIST SRMs were used for method validation.     

Environmental Monitoring at Terra Nova Bay Station From 1989 to 1991

Abstract

Monitoring was carried on in the Italian Antarctic Station Terra Nova Bay. Airborne particulate matter was sampled at different Base locations during the Italian expeditions; samples were then analyzed at the ENEA laboratories for chemical characterization. The analyses were carried out by INAA (Instrumental Neutron Activation Analysis) for the determination of major, minor and trace elements (Na, K, Cs, Sc, V, Mn, Fe, Co, Zn, La) and by gas chromatography-mass spectrometry for the determination of PAH compounds. Data from the 1989–1990 and 1990–1991 campaigns are reported and discussed. Moreover, isokinetic samplings were carried out at the Base incinerator; the filters were analyzed by INAA; the V, Cr, Cu, Zn, Cd, Sb concentrations are reported.     

Trace element characterization of medieval and post-medieval glass objects by means of INAA and EPMA

Instrumental neutron activation analysis (INAA) was applied to create a database for minor and trace elements in medieval and post-medieval glassware in order to establish a methodology for estimating the origin of the glass objects. First, general characterization of glass types was done on the basis of the results obtained by the use of electron probe microanalysis (EPMA). Information received by the use of INAA provided the additional valuable data reflecting to some extent the method of preparation or the differentiation of various sources of certain raw materials. Several glass samples and a set of various reference glass materials were used for our experiments.     

Variability of total and mobile element contents in ash derived from biomass combustion

Seven samples of the ash derived from biomass, representing both fly and bottom ash, were analysed for a wide spectrum of total and mobile contents of nutrient and potentially risk elements. Several techniques, X-ray fluorescence (XRF) spectrometry, instrumental neutron activation analysis (INAA), proton-induced gamma-ray emission (PIGE) and proton induced X-ray emission (PIXE), inductively coupled plasma-atomic emission spectrometry (ICP-OES), and flame atomic absorption spectrometry (F-AAS) were compared. The results showed fairly good agreement between the XRF and INAA results, where the correlation coefficients (r) varied between 0.96 and 0.98. Lower contents documenting insufficient dissolution of the ash samples in the applied acid mixture were observed for both ICP-OES and AAS. In this case, weaker correlation with the INAA results not exceeding r = 0.7 were obtained. Therefore, the sample decomposition step is a bottleneck of the accurate analysis of this type of materials. For the assessment of plant-available portions of the elements in the ash samples, the Mehlich III extraction procedure and the extraction with a 0.11 mol L^?1 solution of CH₃COOH were applied. The results showed relatively low mobility of the elements (especially micronutrients) in the ash samples regardless of their source and composition, suggesting limited immediate effect of direct ash application as a fertilizer.     

Ion beam analysis of elemental signatures in uranium dioxide samples: importance for nuclear forensics

In this paper the suitability of two non-destructive analytical techniques for identification of elemental signatures in samples containing uranium of different enrichments was studied. The measurements were based on particle induced X-ray emission (PIXE) and particle induced gamma-ray emission (PIGE) methods. The samples were irradiated by 3 and 5 MeV protons at the 3 MV Tandetron™ of Horia Hulubei National Institute for Physics and Nuclear Engineering. The characteristic X and gamma rays were measured using high purity germanium (HPGe) detectors. The GUPIX software was applied for processing the PIXE spectra, while a relative standardization was applied for PIGE analysis by using certified comparator standards and proton stopping powers calculated by SRIM.

     

Comparison of neutron activation analysis with conventional detection techniques for the evaluation of trace elemental contamination in Mallard (<Emphasis Type="Italic">Anas platyrhynchos</Emphasis>) feathers

Instrumental neutron activation analysis (INAA) was used to determine trace elemental contamination in bird feathers. Primary feathers from twelve mallard (Anas platyrhynchos) ducks, migrating through the Thousand Islands region of Ontario, Canada, were analyzed for selenium, mercury, chromium, arsenic and antimony. Certified reference materials were used to assess the quality of the analytical procedure. Quantification of chemical elements was performed using Ortec Gamma Vision software. Five chemical elements were quantified, with corresponding analytical uncertainties of less than 20%. Results indicated the presence of As (max = 0.13 mg kg⁻¹), Cr (max = 2.6 mg kg⁻¹), Hg (max = 7.7 mg kg⁻¹), Sb (max = 0.31 mg kg⁻¹) and Se (max = 1.31 mg kg⁻¹). To assess the validity of using INAA as a quantitative analytical technique for feather samples, two standard reference materials were examined and mercury results were compared to those obtained from both direct mercury analysis (DMA) and cold vapour atomic absorption spectroscopy (CVAAS). Several CVAAS results differed significantly from the INAA results; in many instances CVAAS appeared to under-report when compared to INAA, with relative percent difference values as high as 126%. Conversely, results obtained using DMA compared favourably with INAA. For all samples, RPD values were within 30%. This is the first study to use INAA to examine feather contamination in Canadian migratory waterfowl and the first to corroborate INAA feather results by comparing them to those obtained using CVAAS and DMA.     

Instrumental neutron activation analysis of carbonatites from Panda Hill and Oldoinyo-Lengai, Tanzania

Twenty nine (major and trace) elements including nine rare earth elements (REE) in African carbonatite samples were determined by instrumental neutron activation analysis (INAA). The geochemical behavior of trace elements in carbonatites, especially REE pattern (chondrite normalized), and the efficiency of neutron activation analysis compared to other methods are discussed in this study.     

Non-destructive compositional analysis of sol–gel synthesized lithium titanate (Li2TiO3) by particle induced gamma-ray emission and instrumental neutron activation analysis

Lithium titanate, one of the important tritium breeding materials in D–T based fusion reactor under ITER programme, was synthesized through sol–gel route. For chemical quality control of finished product, it was necessary to quantify the lithium and titanium contents. As this ceramic sample is difficult to dissolve, non-destructive analytical methods are preferred for compositional analysis. In the present work, two non-destructive nuclear analytical methods namely particle induced gamma-ray emission (PIGE) using proton beam and instrumental neutron activation analysis (INAA) using reactor neutrons were standardized for the determination of lithium and titanium concentrations, respectively and applied to eleven samples of lithium titanate. To the best of our knowledge, Li quantification in lithium titanate sample is being reported for the first time using PIGE. For quantifications of Li and Ti, 478 keV prompt gamma-ray from ⁷Li (p, p′γ) ⁷Li and 320 keV gamma-ray from ⁵⁰Ti (n,γ) ⁵¹Ti were measured, respectively, by high resolution gamma-ray spectrometry. The PIGE and INAA methods were validated using several synthetic samples containing lithium and titanium, respectively. Concentrations of lithium and titanium and Li/Ti mole ratios were evaluated and compared with the stoichiometric concentration of Li₂TiO₃.     

Trace element analysis of turkey vulture (Cathartes aura) feathers

Ten feather samples, including primary and secondary flight and tail feathers, were analysed for the trace element composition of vane and rachis structures using instrumental neutron activation analysis (INAA), inductively coupled plasma-mass spectrometry (ICP-MS), and cold vapour atomic absorption spectroscopy (CVAAS). Five environmentally significant elements, Cr, As, Se, Sb and Hg, were analysed by INAA and ICP-MS/CVAAS. A further seventeen elements were analysed by ICP-MS. The majority data obtained by INAA and ICP-MS/CVAAS were not statistically significantly different (p = 0.05), although the removal of isobaric interferences using dynamic reaction cell technology was essential to produce ICP-MS data that were consistent with INAA for Cr, As and Se. Significantly higher trace element concentrations were observed for vane relative to rachis for all elements, except Cu and Hg. These elements displayed vane/rachis ratios of 0.7 ± 0.2 and 1.0 ± 0.2, respectively. In general, vane and rachis subgroups afforded data that were consistent with a normal distribution, with RSDs in the range (12–83) % for INAA analyses. A total of 18 outliers were noted amongst the various feather, structure, element combinations, with 14 outliers being observed in the vane and/or rachis structures of the same tail feather. Given the significant differences in vane and rachis concentrations observed for many elements, the large RSDs reported for elements and the potential for outliers, the determination of environmental trace element burden using feathers is significantly enhanced by the analysis of multiple feathers using INAA.     

Use of neutron activation analysis for the characterization of single-wall carbon nanotube materials

Instrumental neutron activation analysis (INAA) and prompt gamma neutron activation analysis (PGAA) were used to characterize a variety of single-wall carbon nanotube (SWCNT) materials from different principal production processes, as well as a material containing SWCNTs together with other carbon species, catalyst residues, and trace element contaminants to be issued by the National Institute of Standards and Technology for characterization and distribution as Standard Reference Material SRM 2483 Carbon Nanotube Soot. INAA proved to be well suited for the direct determination of catalyst and contaminant trace elements requiring only minimal sample preparation. PGAA complemented the INAA data in particular with determinations of the light elements. Carbon and hydrogen results provided information on the materials purity and storage properties. Strategies for the quality assurance of the measurements in these new materials were developed. INAA and PGAA data were provided for the value assignment of mass fractions of catalyst and trace elements in the candidate SRM and a systematic overview was obtained of the catalyst and trace element contaminants associated with each of the major production routes.     

Comparison of fluorine determination in biological and environmental samples by NAA, PAA and PIXE

Capabilities of instrumental neutron activation analysis (INAA), photon activation analysis with radiochemical separation (RPAA) and proton induced γ-ray emission (PIGE) for determination of fluorine in biological and environmental materials are compared in terms of detection limits, nuclear and other interferences. The lowest detection limit of 0.5 μg^.g^-1 was achieved by RPAA, the detection limit of the non destructive and interference-free PIGE method was by one order of magnitude higher, whereas two to three orders of magnitude higher detection limits compared to RPAA were obtained in INAA. A satisfactory agreement was found between the results obtained in this work and reference, mostly information values for several biological and environmental materials. However, higher values of two orders of magnitude were determined by RPAA and PIGE in NIST RM-8414 Bovine Muscle compared to the fluorine information value. The reason for this difference is the contamination of this material with Teflon, which occurred on its preparation and has not been taken into account in establishing the information value. This revised version was published online in August 2006 with corrections to the Cover Date.     

Trace and major element compositions of Black Sea aerosol

Instrumental neutron activation analysis (INAA), flame atomic absorption spectrometry (FAAS), flame atomic emission spectrometry (FAES), graphite furnace atomic absorption spectrometry (GF-AAS), ion chromatography (IC) and visible spectrometry (VIS) were used to determine the composition of atmospheric aerosols, collected at a rural site in the Western Black Sea Coast of Turkey. A total of 354 daily aerosol samples were analyzed for 46 trace and major elements and ions. Sample preparation, quality control procedures, instrumental operating conditions for INAA and source apportionment work is presented.     

Trace elemental composition of Nigerian coal measured by neutron activation analysis

The instrumental neutron activation analysis (INAA) technique has been used to determine 17 major, minor, and trace elements in samples of the three major sources of Nigerian coal. The NBS Standard Reference Material, Coal SRM 1632, was also analyzed, for the purpose of verifying the accuracy of the method. The results obtained with it were in good agreement with the NBS certified values. The concentrations of the major elements determined for the Nigerian coal were found to be much lower than the mean values of those reported for coal samples from other parts of the world.     

Role of diet and trace elements in lithogenesis of renal calculi

Twenty eight stones were characterized for chemical composition and structure. The concentrations of trace elements were determined using INAA while EDXRF was used for determining the calcium contents of the stones. Twenty stones were found to be mainly composed of calcium, six were mixed type and the remaining two were of uric acid type. The concentrations of trace elements namely Zn, Sr, Fe and Cr were lower in uric acid stones as compared to calcium based stones. Diet analysis of 310 patients who were treated for renal stones showed a diet rich in calcium and oxalate and decreased water consumption.

     

Determination of rare earth and other trace element abundances in human kidney stones and brain tissue by instrumental neutron activation analysis

We have used INAA to analyze more than 30 minor and trace elements in 10 human kidney stones (phosphate and oxalate types). In addition we also analyzed human brain tissue samples for trace elements by INAA to determine the limitations of the method. Samples were taken from the temporal and frontal cortex of the brain of a patient that suffered from dialysis encephalopathy (where an increased Al content is expected), as well as a number of control samples. Trace elements were analyzed to study possible compositional differences other than the Al content. The analyses were done using large volume HPGe detectors; because of the low abundances, accuracy and precision vary between 3–80% for individual elements. We found a difference between the rare earth element (REE) patterns for apatite and oxalate kidney stones, and a fractionation compared to typical REE contents in plants. For the brain samples there is evidence for differences between the dialysis patient and the control samples not only for Al, but also for some other elements including the REEs, but most differences are minimal, and may not be significant.     

Major and trace element assessment of Tietê river sediments, São Paulo, Brazil

The objective of this study was to quantify major and trace elements present in sediments collected from the one of Brazil’s most important rivers, Tietê River. Sediments from 5 different sampling points (P₀–P₄), in 3 campaigns (2008/2009), from the headwaters to Suzano County upstream from São Paulo city were collected. X-ray fluorescence was applied for measuring total concentration of major elements and instrumental neutron activation analysis (INAA) for trace elements. The elements Cd, Hg and Pb were determined by atomic absorption spectrometry after digestion using the US EPA 3,051 procedure. These metal concentrations were compared to the PEL and TEL oriented values from CCME. The sampling sites P₃ and P₄, near industrialized areas, showed the highest concentrations for potentially bioavailable metals, mainly Pb and Hg. The results obtained by INAA were compared to upper continental crust values. A strong enrichment was found for the elements As, Br, Sb, Th, U and Zn. These results evidenced contamination by industrial effluents and sewage even relatively close to the Tietê River headwaters. The worst biological effects (acute toxicity) on benthonic organism Hyalella azteca were also observed at P₃ and P₄.     

Characteristics of the aerosol particulates in the atmosphere in an urban environment at Faisalabad, Pakistan

Summary The deposition of trace and major elements from the atmosphere to the ground is an important factor for plants, animals and humans as well. Total suspended particulate matter was measured by a standard gravimetric technique. A scanning electron microscope was used for the evaluation of the size distribution and morphological structures of the aerosol particulates trapped on the surface of filter paper. The aerosol particulates were studied by a scanning electron microscope at various magnification. The trace elemental composition in the atmosphere of Faisalabad was studied by using instrumental neutron activation analysis (INAA) and atomic absorption spectrometry (AAS). Concentrations of 23 trace elements and a major one were determined in samples of aerosol particulates collected during a longe sampling period in the atmosphere at Faisalabad, Pakistan. Their amount was two times higher than the limits adopted by the U.S. Environmental Protection Agency for the urban environment.     

Nigerian coal analysis by PIXE and RBS techniques

PIXE and RBS techniques were employed for the measurement of the concentrations of the major, minor and trace elements in Nigerian coal samples from a major deposit. The samples were irradiated with 2.55 MeV protons from the 3 MeV tandem accelerator (NEC 3 UDH) in Lund. The PIXE results are reported and compared with an earlier work on Nigerian coal using FNAA and INAA analytical techniques while the RBS results are compared with ASTM previous results. The results show that Nigerian coals have a low (0.82–0.99)% sulfur content. This is quite important for pollution control reasons.     

Feasibility of ETV-ICP-OES for Characterization of Archaeological Glasses

In the present study the possibilities of electrothermal vaporization inductively coupled plasma optical emission spectrometry (ETV-ICP-OES) for characterization of archaeological glasses were investigated. The objects of our research were fragments of a colorless late antique Roman flat window glass (fifth century A.D.) and colored medieval glass bracelets (eleventh–twelfth century A.D.) excavated in the region of Pernik (West Bulgaria).

The finely ground glass samples were analyzed directly and CHF₃ was used as evaporation and transport modifier. Dried aqueous standard solutions and certified reference materials with different matrix (glass, fly ash, and stream sediment) were used as calibration standards. No matrix effects were observed by the optimized conditions. Measurements were performed using common calibration curves obtained with all appropriate calibration standards and major, minor, and trace element concentrations were determined. ETV-ICP-OES analytical data were used to establish the type of glass, the fluxing agents, the typical coloring and decoloring elements, and the recipe norm.