Determination of ultra-trace levels of uranium and thorium in electrolytic copper using radiochemical neutron activation analysis.

Uranium and thorium as natural radioactive elements are present everywhere in the environment. Their trace levels are also present in various materials, such as copper, used as a shielding material in gamma-ray spectrometry, usually located very close to the detector. Ultra-low levels of uranium and thorium in electrolytic copper were determined in this study using radiochemical neutron activation analysis (RNAA) via their induced nuclides U-239/Np-239 and Pa-233, respectively. After irradiation of copper together with uranium and thorium standards, various techniques were used for their separation from the matrix. To isolate of short-lived U-239, solvent extraction in a combination of tributyl phosphate (TBP) in toluene was used. To separate Np-239 and Pa-233, extraction chromatography using TEVA and TK-400 resins was applied. Special attention was paid to the estimation of radiochemical recovery, which was determined in each sample aliquot using U-235, Np-238 and Pa-231 tracers. For quantification of induced nuclides and tracers used in the experiment, gamma-ray spectrometry was used. Obtained results showed that electrolytic copper samples contained impurities of uranium and thorium in ultra-trace levels: up to 45 pg/g (550 nBq/g) for uranium and up to 80 pg/g (330 nBq/g) for thorium. The electrolytic copper also contained impurities of Ag, As, Au, Sb, Se and Zn as observed using the k0-INAA technique.

Epiphytic lichens as biomonitors of atmospheric pollution in Slovenian forests.

Two country-wide surveys using epiphytic lichens as biomonitors of atmospheric pollution carried out during 2000 and 2001 in Slovenia were compared with surveys in 1991 and 1992. In the first survey, epiphytic lichen cover was studied in more than 500 plots of the 4 x 4 km national grid carried out within the framework of forest decline inventories. In the second survey, the epiphytic lichen Hypogymnia physodes (L.) Nyl., was collected on a 16 x 16 km bioindication grid and analysed for S, N, As, Br, Ce, Cd, Cr, K, La, Mo, Rb, Sb, Th, U and Zn contents. Only 'forested area' sampling points were included in the present study. Lichen cover was low, with about 70% of plots with less than 10% foliose lichen cover. No relationship was found between Hypogymnia trace element, N and S concentrations and foliose epiphytic lichen cover.

Estimation of 99Mo production rates from natural molybdenum in research reactors.

Molybdenum-99 is one of the most important radionuclides for medical diagnostics. In 2015, the International Atomic Energy Agency organized a round-robin exercise where the participants measured and calculated specific saturation activities achievable for the 98Mo(n,γ)99Mo reaction. This reaction is of interest as a means to locally, and on a small scale, produce 99Mo from natural molybdenum. The current paper summarises a set of experimental results and reviews the methodology for calculating the corresponding saturation activities. Activation by epithermal neutrons and also epithermal neutron self-shielding are found to be of high importance in this case.

Atmospheric heavy metal pollution in Slovenia derived from results for epiphytic lichens.

In 1992, a monitoring survey has been started on the national scale in Slovenia using the epiphytic lichen Hypogymnia physodes (L.) Nyl. The primary aim has been to analyse lichens using the k(0)-based INAA method to obtain information about the levels of elements in the atmosphere and to identify significant pollution sources. Monte Carlo-Assisted Factor Analysis was applied to a data set of the 28 elements As, Ag, Ba, Br, Ce, Cd, Co, Cr, Cs, Fe, Ga, Hf, Hg, K, La, Mo, Na, Rb, Sb, Sc, Se, Sr, Sm, Tb, Th, U, W and Zn, which have been selected from the elements determined as the most important ones for the identification of pollution sources. A Monte Carlo approach has been used to give more insight into the uncertainties and significance levels of the factor analysis results. It has been found that concentration patterns in lichens yielded 9 factors (source types) which are presented and discussed in detail. The geographical patterns of the contributions of all factors are also shown.

Lichens as integrating air pollution monitors.

In this work an attempt to combine the results of lichen mapping with the quantitative levels of certain trace elements in Hypogymnia physodes (L.) Nyl. collected on a national scale is presented. An Index of Atmospheric Purity (IAP) was calculated using a simple method of mapping lichens based on the assessment of the cover and frequency of crustose, foliose and fruticose lichens on different tree species. For determination of trace elements in lichens k0-instrumental neutron activation analysis was used. From the IAP results it can be concluded that the epiphytic lichen flora look quite poor with more than 70% of the territory in the fourth and third classes, which represent highly polluted and moderately polluted air. By comparing IAP results with elemental levels in H. physodes using multivariate statistical methods it was found that the elemental levels do not have a direct negative effect on the diversity of lichens but can help in identification of the type of possible pollution sources and their origin.

Determination of trace elements in standard reference materials by the ko-standardization method.

The ko-standardization method is suitable for routine multielement determinations by reactor neutron activation analysis (NAA). Investigation of NIST standard reference materials SRM 1571 Orchard Leaves, SRM 1572 Citrus Leaves, and SRM 1573 Tomato Leaves showed the systematic error of 12 certified elements determined to be less than 8%. Thirty-four elements were determined in NIST proposed SRM 1515 Apple Leaves.

Effect of arsenic trioxide on metallothionein and its conversion to different arsenic metabolites in hen liver.

The metabolism of arsenic, its affinity to metallothionein (MT), its influence on selenium levels, and its biotransformation to different metabolites in the liver tissue of laying hens exposed to arsenic trioxide (As2O3) was investigated. The experiment was performed with two groups of hens fed for 19 d with either a standard diet or with the same diet enriched in arsenic (30 microg/g). The major findings were as follows: 1. After 19 d exposure, about 65% of the total liver As was found in the water-soluble phase (100,000g centrifuged supernatant). In liver supernatant, As binding was found mostly in the range of very low-molecular-weight proteins (Mr < 10,000). Although after exposure the amount of MT-like proteins increased, the As bound to it was only in trace amounts. The protein was identified by convential procedures as Zn,Cu-thionein with traces of selenium and arsenic. 2. Arsenic exposure resulted in almost unchanged Se levels regarding its tissue concentrations and distribution between supernatant and pellet, where about 10% of total Se was found in the supernatant. On the contrary, As exposure did affect Cd levels. Tissue Cd concentration was slightly diminished, but the percentage of tissue Cd found in the water-soluble phase was increased from 20% to 40%. 3. In methanol extracts of tissue and supernatant of the As-exposed group, only two arsenic compounds were detected, As(III) and dimethylarsinic acid (DMA), the latter prevailing.

Installation and calibration of Kayzero-assisted NAA in three Central European countries via a Copernicus project.

An account is given of the installation and calibration of k0-based NAA--assisted by the DSM Kayzero/Solcoi software package--at the KFKI-AEKI, Budapest, the NPI, Rez and the IJS, Ljubljana. Not only the calibration of the Ge-detectors and the irradiation facilities are discussed, but also other important topics such as gamma-spectrometric hard- and software, QC/QA of the IRMM-530 Al-Au flux monitor and the upgrade of the Kayzero/Solcoi code. The work was performed in the framework of a European Copernicus JRP, coordinated by the Laboratory of Analytical Chemistry, Gent, with DSM Research, Geleen, as the industrial partner.

Determination of trace elements in some copper minerals by k0-neutron activation analysis.

Trace element contents in two copper minerals [brochantite [Cu(4)SO(4)(OH)(6)] and native Cu] using k(0)-NAA were determined before and after quantitative removal of copper. The distribution of 44 elements in the studied minerals was investigated. An important advantage of the proposed method is the possibility to determine the content of several elements (Al, Dy, Mg, Mn and V) via their short-lived nuclides after the electrolytic removal of Cu due to the elimination of matrix interferences.

k0-INAA quality assessment by analysis of soil reference material GBW07401 using the comparator and neutron flux monitor approaches.

It is possible to apply the k(0)-method using a simplified equation for concentration calculations using Excel spreadsheet, using comparators without making corrections. The objective of this study was to confirm that the k(0)-standardization method is more efficient and accurate than this "k(0)-comparator" procedure, applying suitable software that takes into account several corrections. The reference material GBW07401 soil was analyzed in this study. Relative Bias and u-score tests were used in order to evaluate the overall results.

Analysis of neutron flux distribution for the validation of computational methods for the optimization of research reactor utilization.

In order to verify and validate the computational methods for neutron flux calculation in TRIGA research reactor calculations, a series of experiments has been performed. The neutron activation method was used to verify the calculated neutron flux distribution in the TRIGA reactor. Aluminium (99.9 wt%)-Gold (0.1 wt%) foils (disks of 5mm diameter and 0.2mm thick) were irradiated in 33 locations; 6 in the core and 27 in the carrousel facility in the reflector. The experimental results were compared to the calculations performed with Monte Carlo code MCNP using detailed geometrical model of the reactor. The calculated and experimental normalized reaction rates in the core are in very good agreement for both isotopes indicating that the material and geometrical properties of the reactor core are modelled well. In conclusion one can state that our computational model describes very well the neutron flux and reaction rate distribution in the reactor core. In the reflector however, the accuracy of the epithermal and thermal neutron flux distribution and attenuation is lower, mainly due to lack of information about the material properties of the graphite reflector surrounding the core, but the differences between measurements and calculations are within 10%. Since our computational model properly describes the reactor core it can be used for calculations of reactor core parameters and for optimization of research reactor utilization.

Mercury and other elements in lichens near the INA Naftaplin gas treatment plant, Molve, Croatia.

This paper describes the use of epiphytic lichens as bioindicators for spatial monitoring of mercury and other elements in air near the natural gas treatment facilities at Molve, Croatia. It is well known that at this location the concentration of mercury in natural gas is very high and therefore it has to be removed from natural gas before further processing in order to prevent technological and environmental problems. In order to monitor the efficiency of an industrial facility for removal of mercury from natural gas, mercury measurements in air and lichens were performed during 9 months in 1997/1998. In situ lichens Parmelia sulcata, Xantoria parientina and Hypogymnia physodes and transplanted lichen species Hypogymnia physodes were used. A good correlation between mercury concentrations in air and lichens was found. The concentrations of barium and bromium were also significantly elevated in transplanted lichens, most probably related to technological process at the gas treatment plant and/or other geological factors. It was confirmed that lichens can successfully be used as bioindicators, provided a careful experiment is designed, particularly the amount of lichens transplanted, the duration of exposure and the initial levels and homogeneity of transplanted lichens.

Applicability of neutron activation analysis (NAA) in quantitative determination of some essential and toxic trace elements in food articles.

Accurate and reliable data on microgram and nanogram quantities of some essential and toxic elements in most food articles are very scarce. Neutron activation analysis (NAA), with its essentially blankfree advantage, is a valuable approach in the field of determination of trace elements in different foodstuffs and diets. Accordingly, various radiochemical (RNAA) and instrumental (INAA) approaches have been developed in our laboratory for the element As, Cd, Co, Cu, Hg, I, Mo, Ni, Sb, Se, Sn, Th, U, V, and others, and verified by the analysis of compositionally appropriate certified reference materials.

The validation of Kayzero-assisted NAA in Budapest, Rez, and Ljubljana via the analysis of three BCR certified reference materials.

After installation and calibration of k0-assisted NAA in three Central European research institutes (AEKI-Budapest, NPI-Rez, and IJS, Ljubljana), its validation was established via the analysis of three BCR certified reference materials. The matrices of choice were: CRM 277 estuarine sediment, CRM 038 coal fly ash from pulverized coal, and CRM 101 spruce needles. For some elements, e.g. Zn, Cd, and Hg, the analyses were not only performed instrumentally (INAA), but also in the radiochemical mode (RNAA). The work was performed in the framework of a European Copernicus Project.