Atmospheric deposition of heavy metals in northern Serbia and Bosnia-Herzegovina studied by the moss biomonitoring, neutron activation analysis and GIS technology

The results on atmospheric deposition of heavy metals and other trace elements using the moss biomonitoring technique in the northern part of Serbia and some areas of Bosnia-Herzegovina are presented. Samples of Hypnum cupressiforme along with some other moss types were collected at 92 sites during the summer of 2000. A total of 44 elements were determined by INAA using epithermal neutrons. High values of Cl and V content in the moss samples at certain areas are suspected to be associated with fires in oil refineries damaged during the 1999 NATO military action.     

Rapid analysis of biological reference materials by instrumental neutron activation

Summary Instrumental neutron activation analysis (INAA) was applied to the rapid determination of cadmium and other elements in the IAEA biological reference material horse-kidney (H-8). Nuclear reactor neutrons and epithermal neutrons were used as neutron sources. Cadmium, bromide, iodine and phosphorus were determined by epithermal neutron activation analysis. Aluminum was determined by reactor neutron activation analysis taking into account the contribution of phosphorus to the ²⁸Al activity.     

atmospheric deposition of heavy metals around the lead and copper-zinc smelters in Baia Mare, Romania, studied by the moss biomonitoring technique, neutron activation analysis and flame atomic absorption spectrometry

The mosses Pleurozium schreberi, Pseudoscleropodium purumandRhytidiadelphus squarrosus were used as biomonitors to study the atmospheric deposition of metals around the lead and copper-zinc smelters in Baia Mare. Samples representing the last three years" growth of moss or its green part, collected on the ground at 28 sites located 2-17 km from the source area, were analyzed by instrumental neutron activation analysis using epithermal neutrons (ENAA) and by flame atomic absorption spectrometry (FAAS). A total of 31 elements were determined, including most of the heavy metals characteristic of emissions from this kind of industry. The observed data for Pb, As, Cu, and Cd are all high compared with those observed in other regions of Europe with similar industries, but the concentrations in moss approach regional background levels at a distance of about 8 km from the main source area. Factor analysis of the data distinguishes two industrial components, one characterized by Pb, Cu, As, and Sb, and another one by Zn and Cd. A strong crustal component including five major elements (Na, Mg, Al, Ti, Fe) and an additional number of trace elements (Sc, V, Cr, Cs, Ba, REE, Th) also appears to be derived mainly from industrial sources. The mean I value in the present material is 5 times lower than the corresponding level in moss in Norway, and also consistently lower than elsewhere in Europe, a fact which evidences the endemic character of the examined area due to iodine depletion.     

Evaluation of atmospheric airborne particles in Lisbon, Portugal using neutron activation analysis

Summary We have employed Compton supression neutron activation analysis in conjunction with thermal and epithermal neutrons to detemine trace elements in airborne particulate matter in Lisbon, Portugal. As a result of the proximity of ocean marine, elements such as sodium and chlorine can signficantly decrease the analytical sensitivities of many elements of interest due ot the high backgrounds arising from ³⁸Cl and ²⁴Na. Compton suppression has resulted in the increase of the analytical sensitivities using thermal neutrons of Al, Ba, Ce, Cr, Cu, Ni, Rb, Se, Th, Ti, V, and Zn. The use of Compton suppression and epithermal neutrons significantly reduced the detection limits for As, I, K, Si, and W, while the utilization of solely epithermal neutrons improved the analyses of In.     

Determination of selected elements in red, brown and green seaweed species for monitoring pollution in the coastal environment of Ghana

Summary The concentrations of 23 elements, namely Al, As, Br, Ca, Cd, Cl, Co, Cr, Cu, Fe, Hf, Hg, I, K, La, Mg, Mn, Na, Ni, Sc, Sm, V, and Zn, in seven Rhodophyta (red), three Phaeophyta (brown) and five Chlorophyta (green) seaweed species from different areas along the coast of Ghana were determined using instrumental neutron activation analysis (INAA). These species can be potentially used as biomonitors. The INAA method involved irradiations using thermal and epithermal neutrons at the Dalhousie University SLOWPOKE-2 Reactor (DUSR) facility followed by conventional and anti-coincidence g-ray spectrometry. The precision in terms of relative standard deviation was within ±4%. The accuracy of the methods was evaluated by analyzing four reference materials. Our results were within ±3% of the certified or information values in all cases.     

Atmospheric trace metal characterization in industrial area of Lisbon, Portugal

Summary A set of 15 atmospheric aerosol samples was collected in an industrial area of Lisbon, Portugal and then analyzed by instrumental neutron activation analysis (INAA). Both fine and coarse aerosol samples were collected during November and December 2001 on polycarbonate filters with Gent samplers. The INAA methodology utilized both thermal and epithermal neutron irradiations. Compton suppressed and normal gamma-ray spectra were acquired simultaneously for each measurement and the elemental concentrations of 30 elements were determined. Enrichment factors, wind speed comparison and receptor modeling techniques were applied to obtain the different source contributions of the aerosols. Crustal, marine and anthropogenic sources were identified. The anthropogenic elements have origin mainly in the area close to the sampling site (<5 km), with the exception of Ca and V. A direct relationship was observed between the anthropogenic atmospheric aerosol concentrations and wind speed.     

Application of epithermal neutron activation in multielement analysis of silicate rocks employing both coaxial Ge(Li) and low energy photon detector systems

The instrumental activation analysis of silicate rocks using epithermal neutrons has been studied using both high resolution coaxial Ge(Li) detectors and low energy photon detectors, and applied to the determination of 23 elements in eight new U.S.G.S. standard rocks. The analytical use X-ray peaks associated with electron capture or internal conversion processes has been evaluated. Of 28 elements which can be considered to be determinable by instrumental means, the epithermal activation approach is capable of giving improved sensitivity and precision in 16 cases, over the normal INAA procedure. In eleven cases the use of the low energy photon detector is thought to show advantages over convertional coaxial Ge(Li) spectroscopy.     

Moss as monitor of heavy metal deposition: Comparison of different multi-element analytical techniques

Instrumental activation analysis (INAA) based on irradiations in a nuclear reactor with particularly high relative fluxes of resonance and fast neutrons has been shown to open new possibilities for multi-element surveys of mosses used as monitors of atmospheric deposition. Comparison is made with data obtained by inductively coupled plasma-mass spectrometry (ICP-MS) and conventional INAA. Data for 15 elements not previously investigated in routine moss studies are presented, e.g., Zr, Sn, Hf, Ta, W, Au, Th, and the rare earth elements Ce, Nd, Eu, Gd, Tb, Tm, Yb, Lu. Other elements particularly well determined by this approach are Sc, Co, As, Ag, Sb, Cs, La, Sm, Th, and the non-metallic trace elements Se, Br, and I. Advantages and drawbacks with the high fast neutron component are discussed.     

Intercomparison of moss reference material by different multi-element techniques

An intercomparison of data obtained for a moss reference material (Hylocomium splendens) used as biomonitor of atmospheric deposition by different multi-element techniques is presented. In total 43 elements (Na, Mg, Al, Cl, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Zr, Ag, Sn, Sb, I, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Tm, Yb, Lu, Hf, Ta, W, Au, Th, U) were determined using inductively coupled plasma-mass spectrometry (ICP-MS), conventional instrumental neutron activation analysis (INAA), epithermal neutron activation analysis (ENAA) and as well as shorttime neutron activation analysis without and with a⁶LiD-converter. Advantages and drawbacks of each method are discussed. The introduction of moss reference materials for atmospheric multi-element deposition studies involving nuclear analytical techniques is strongly recommended.     

Activation analysis of alkaline rocks. A comparison between destructive and non-destructive methods

The United States Geological Survey reference sample AGV-1 andesite, and three alkaline rocks from the apatite mine of Jacupiranga, Brasil, were analyzed by thermal neutron activation analysis using destructive and non-destructive methods, and high resolution Ge(Li) gamma-ray detectors. One of the rocks, a carbonatite, was also analyzed by instrumental activation analysis with epithermal neutrons. A greater number of elements can be determined using the radiochemical separation, but the precision and accuracy attained by INAA and RNAA were of the same order for most of the elements analyzed. Epithermal activation was more advantageous for tantalum, terbium and holmium. Comparison of the analytical results for USGS reference sample (AGV-1) with the data published by others gave good agreement. Statistical tests used for comparison of the results of destructive and non-destructive methods, as well as other results are presented.     

William D. Ehmann, radioanalytical chemist and radiochemistry educator

Copper (Cu) is an essential element and is incorporated in many biomolecules that are involved in protecting the brain from oxidative damage. Many brain regions strongly affected by neurodegene rative diseases are small. A sensitive nondestructive procedure to determine Cu is desirable to preserve samples for additional studies. Copper is not easily determined by instrumental neutron activation analysis (INAA) due to high activity levels produced by major abundance elements such as sodium (Na) and chlorine (Cl), which produce a high Compton background. An INAA method involving a short epithermal neutron irradiation and counting with a Compton suppression system was developed to determine Cu in brain, via 5.1-min⁶⁶Cu. These short irradiation results are compared to those based on coincidence spectrometry of annihilation photons from positron emitting 12.7-h⁶⁴Cu after a long irradiation.     

Determination of zinc in geological samples using Compton suppression with thermal and epithermal instrumental neutron activation analysis

The determination of Zn in geological samples using instrumental neutron activation analysis is usually done using the ⁶⁴Zn(n,γ)⁶⁵Zn reaction and its 244 day half-life. However this analysis has proven to be potentially difficult. This is due to its relatively low neutron absorption cross section and gamma ray intensity, and the relatively high neutron absorption cross section and gamma intensity of ⁴⁶Sc, which has an energy peak that is only 5 keV greater than ⁶⁵Zn. The use of a high resolution detector makes it possible to differentiate between the ⁶⁵Zn and ⁴⁶Sc photopeaks peaks. However, the dominating ⁴⁶Sc gamma ray can even make peak fitting routines unsuccessful in the proper determination of ⁶⁵Zn. The use of a Compton suppression system suppresses the ⁴⁶Sc peak, which has two coincident gamma-rays, and this greatly improves the ratio of the height of the ⁴⁶Sc 1120.5 keV photopeak to the ⁶⁵Zn 1115.4 keV photopeak. Irradiating the sample with epithermal neutrons also improves the measurement since ⁶⁵Zn has a higher cross section for epithermal neutrons rather than thermal neutrons, whereas ⁴⁶Sc has a higher thermal cross section. Another technique to determine zinc is the use of ⁶⁸Zn(n,γ)^69mZn reaction with its 13 h half-life using epithermal neutrons and Compton suppression INAA. However, the 438 keV gamma ray of ^69mZn has no interference with any adjoining photopeak. A critical comparison of these two methods is given.     

Instrumental neutron activation analysis of geological and pedological samples. Further investigation of epithermal neutron activation analysis using monostandard method

A comparative study is presented on neutron activation analysis of rock and soil samples using whole reactor neutron spectrum and epithermal neutrons with both relative and monostandard procedures. The latter procedure used with epithermal neutron activation analysis of soil samples necessitated the use of the “effective resonance integrals” which were determined experimentally. The incorporation of the β factor, representing deviation of reactor epithermal neutron flux from 1/E law, is developed in the present work. The main criteria for the choice of one or more of the procedures studied for a given purpose are also indicated. Analysis of 15 trace elements, Ca and Fe in the standard Japanese granite JC-1 using monostandard epithermal neutron activation gave results in good agreement with the average literature values. This paper is dedicated to the 80th birthday of Professor Dr. Robert Klement, University of Munich.     

Determination of some elements by epithermal neutron activation analysis for the Arctic aerosol

Summary We have determined nineteen trace elements in 685 aerosol filter samples collected during 1964-1978 in northern Finland by the Finnish Meteorological Institute. In this paper we present some procedures and results for very short (~25 s), short (~3-54 min), and medium (12-35 h) lived isotopes as determined by epithermal NAA in conjunction with and without Compton suppression. Elements with a I_γ/σthratio are favorable to be determined by epithermal NAA. Silver was determined by a one minute epithermal irradiation because of a very short ¹¹⁰Ag half-life. Antimony, arsenic, cobalt, bromine, indium, iodine, potassium, silicon, tin, tungsten, and zinc were determined by a ten minute epithermal irradiation. For silver determination, samples were counted without transferring the filter from the irradiated vial, however, for ten minute irradiation all samples were transferred to a non-irradiated vial and counted both in the normal and Compton mode by the HPGe gamma-spectrometry system with a decay time of about 10 minutes and counting time of 15 minutes. Each day a maximum of 16 samples were irradiated and immediately following the short counting, these samples were loaded into an automatic sample changer in sequence of irradiation and counted for an hour in both normal and Compton modes. This has proven to be an extremely cost effective measure thus reducing the need to employ long-lived NAA to analyze other elements such as Ag, Co, Sn and Zn and Ag for air pollution source receptor modeling.     

Chemical characterization of graphite by instrumental neutron activation analysis

Nuclear and commercial grade graphite samples were analysed by instrumental neutron activation analysis (INAA) using high flux reactor neutrons. Eleven elements (Na, K, As, Sc, Fe, Cr, Co, Zn, La, Ce, and Sm) were determined in eight samples of graphite (two nuclear grade and six commercial grade) by irradiating at a neutron flux of 3?×?10¹³ cm^?2 s^?1 in CIRUS reactor and assaying the activity by high-resolution gamma ray spectrometry using 40% relative efficiency HPGe detector coupled to an MCA. Concentrations of elements were determined by relative method of INAA. Results of both types of graphites as well as detection limits achieved by INAA method are discussed in the paper.     

Characterization of simulated vitrified highly active waste and its leachates by neutron activation

Neutron activation analysis (NAA) methods have been developed for the simultaneous determinations of multielement concentrations in various types of glass and their leachates. The epithermal instrumental NAA (EINAA) method involves the irradiation of samples in a Cd-shielded site for 2–5 min in order to determine levels of of up to 13 elements through their short-lived nuclides. Another 15 elements can be measured via their long-lived nuclides using conventional instrumental NAA (INAA). Accuracy of the methods have been evaluated by analyzing certified reference materials. The limits of detection for all elements are reported. The methods have been applied to sodium borosilicate and sodium calcium aluminosilicate glass samples in order evaluate their suitability as a host matrix for immobilizing high level radioactive waste.     

Determination of concentrations of chromium and other elements in soil and plant samples from leather tanning area by Instrumental Neutron Activation Analysis

Chromium, one of the toxic elements, along with other elements has been determined in samples of soil and plant (leaves and seeds) from Jajmau Area, Kanpur district, India, which is irrigated with effluent waste water from leather tanning industries. Soil and plant samples were collected from these areas and analyzed by Instrumental Neutron Activation Analysis (INAA) using high flux reactor neutrons and high resolution gamma-ray spectrometry. Concentrations of fifteen elements in soil and five elements in plant samples were determined by relative method. Chromium concentrations were found to be in range of 45–3,900 mg kg^?1in soil samples and 14–83 mg kg^?1 in plant samples. This study showed that Cr is present in significant amounts, in the soil as well as in the plant samples, near to the leather tanning area. As a part of quality control work, IAEA reference material (RM) SL-3 and NIST standard reference material (SRM) 1645 were analyzed and the quality of the results has been evaluated by calculating % deviations from recommended/literature/certified values.     

Instrumental neutron activation analysis of lunar samples and the identification of primary matter in the Lunar Highlands

We describe the scheme of sequential neutron activation which was developed in our laboratory especially for the analysis of lunar samples and in which more than 50 elements are determined. Irradiations with 14 MeV, epithermal and thermal neutrons and both instrumental techniques and radiochemical separations were applied. It is shown that the achieved accuracy can compete with the best available analytical methods for most major and many trace elements. Besides the observation of “correlated elements”, the discovery of primary matter of the last accretion stage of the moon in samples from the lunar highlands is discussed in some detail.     

57Fe Mössbauer spectroscopy of banded iron formations from eastern India

Samples of the mosses Hylocomium splendens and Pleurozium schreberi, collected in the summer of 1998, were used to study the atmospheric deposition of heavy metals and other toxic elements in the Chelyabinsk Region situated in the South Urals, one of the most heavily polluted industrial areas of the Russian Federation. Samples of natural soils were collected simultaneously with moss at the same 30 sites in order to investigate surface accumulation of heavy metals and to examine the correlation of elements in moss and soil samples in order to separate contributions from atmospheric deposition and from soil minerals. A total of 38 elements (Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Rb, Sr, Zr, Mo, Sb, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Yb, Hf, Ta, W, Au, Th, U) in soil and 33 elements Na, Mg, Al, Cl, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Br, Rb, Ag, Sb, Cs, Ba, La, Ce, Sm, Tb, Yb, Hf, Ta, W, Au, Th, U) were determined by epithermal neutron activation analysis. The elements Cu, Cd and Pb (in moss samples only) were obtained by atomic absorption spectrometry. VARIMAX rotated principal component analysis was used to identify and characterize different pollution sources and to point out the most polluted areas.     

Determination of concentrations of U and Th in their mixed oxides by INAA methods

Uranium and thorium mixed oxides are being prepared using natural U and Th for studies on fuels for Advanced Heavy Water Reactors, wherein composition of U and Th is specific and requires strict control in terms their contents and homogeneity. Chemical quality control necessitates accurate and precise compositional characterization of the fuel material by a suitable analytical method. Among various analytical methods for U and Th, instrumental neutron activation analysis (INAA) is one of the best methods for their simultaneous determination without chemical dissolution and separation. INAA methods using reactor neutrons namely thermal NAA and epithermal NAA were standardized for the determination of U and Th in their mixed oxides. Standards, synthetic samples and U–Th mixed oxide samples, prepared in cellulose matrix, were irradiated at pneumatic carrier facility of Dhruva reactor as well as at self serve facility of CIRUS reactor under cadmium cover (0.5 mm). Radioactive assay was carried out using a 40% relative efficiency HPGe detector. Both activation and daughter products of ²³⁸U (²³⁹U and ²³⁹Np) and ²³²Th (²³³Th and ²³³Pa) were used for their concentration determination. The method was validated by analyzing synthetic samples of 6–48%U–Th mixed oxides. The standardized method was used for the concentration determination of U and Th in 4–30%U–Th mixed oxide samples. Results of U and Th concentrations including associated uncertainties obtained from the INAA methods are presented in this paper.